EP1019486A1 - Composition for use in a washing machine - Google Patents

Composition for use in a washing machine

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Publication number
EP1019486A1
EP1019486A1 EP19990939398 EP99939398A EP1019486A1 EP 1019486 A1 EP1019486 A1 EP 1019486A1 EP 19990939398 EP19990939398 EP 19990939398 EP 99939398 A EP99939398 A EP 99939398A EP 1019486 A1 EP1019486 A1 EP 1019486A1
Authority
EP
Grant status
Application
Patent type
Prior art keywords
ƒ
da
characterized
composition according
composition
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.)
Ceased
Application number
EP19990939398
Other languages
German (de)
French (fr)
Inventor
Manuela Bosco
Enric Carbonell
Joan Clotet
Antonio Cordellina
Giorgio Franzolin
Paul W. Robinson
Guido Wäschenbach
Ralf Wiedemann
Dora Zamuner
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.)
Reckitt Benckiser NV
Original Assignee
Benckiser NV
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

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0091Dishwashing tablets

Abstract

A composition for use in a washing machine, characterized by a basic composition in the form of a tablet acting essentially during the main wash cycle of the washing machine and by at least one particle that is made up of at least one nucleus comprising at least one substance that acts mainly during the rinsing processes of the washing machine in addition to a coat that fully surrounds the nucleus or nuclei and comprises at least one compound whose solubility increases when the concentration of a specific ion in the ambient medium is reduced. At least one particle is arranged in or on the tablet, whereby the surface of the particle or particles comes into direct contact with the surface of the basic composition surrounding said particle or particles until the tablet dissolves to a quasi-total extent, whereby the envelope is prevented from dissolving or the envelope is prevented from detaching itself from the nucleus (or nuclei) in a substantial manner. The invention also relates to a method for carrying out a wash cycle in a washing machine using the inventive composition.

Description

A composition for use in a washing machine

The present invention relates to a composition for use in a washing machine and a method for their use.

Although modern washing machines have in most cases a plurality of different washing programs which differ in duration and temperature of each wash and rinse cycles, are all washing programs consist essentially of the following basic steps: pre-wash cycle; Main wash; a plurality of rinse cycles; and spin. While the actual detergent, which is to exhibit the cleaning effect at the start of the main washing cycle (or possibly at the beginning of Vorwaschganges) was added, special means with different functions can be used in the rinse cycles. These special funds for rinses should bring further benefits mainly for the laundry treatment with it. includes a non-exhaustive list of such agents are not limited to: fragrances (pleasant smell of the laundry), softener (softness of the wash), antistatic agents (reduce or prevent the build up of static electricity in the wash), means to restore the ability of the linen wet-pickup, mild acids (breakdown of incrustations or neutralization of alkalinity), bleach, either oxygen or chlorine-based (improve the cleaning effect), disinfectants, preparations for lasting protection for both the laundry and the person's underwear bearing from insects or mites means for the improved removal of greasy soils, means for finishing with anti-crease agents, optical brighteners, ironing aids (for ease of Bügeins of the laundry), means for inhibiting dye transfer, enzymes such as cellulases, lipases, etc., for special purposes.

The various features described so far are (if any) is achieved by metering of different products, partly via separate dosing devices, and dosing at different times.

Object of the present invention was the cleaner function and the function (s) to unite the to be added in the rinse cycles substance (s), at a constant power as possible compared to the results that can be achieved with a separate dosage, in a product or to allow dosing of other substances in the rinse cycles.

Detergent shaped bodies for use as detergents are known from German Offenlegungsschriften 20 65 153 and 20 07 4 13 in which is provided, inter alia, to combine two components with different functionality. It is an assembly of a coating pan, which is composed for example of two shell halves, which consist of a detergent, and a space enclosed by the shells cavity, the additives containing, such as plasticizers, whitening agents, etc., are provided.

British Patent Specification 1,390,503 discloses a liquid detergent containing capsules, which are insoluble in the composition, but release their contents when the composition is diluted with water. This object is achieved in that the capsules are coated with a substance having a poor solubility in water solutions with high ionic strength, but is soluble when the ionic strength is lowered by dilution. It should be noted that this technique can be applied in order to include materials in the liquid detergent, which are themselves unstable in liquid detergent, or would generate instability when you zusetzte directly. It is also proposed to use the technology to delay the release of a specific substance. The use in detergents is addressed. The encapsulated material is within 2 minutes after dilution of the detergent with water, that is already released in the main wash.

In US Patent 4,082,678 a fabric conditioning product is described which comprises a closed container containing a releasable agent that serves a disposed in the container inner container, which is normally water-soluble or water-gierbar, water insoluble or non-dispersible for make, wherein the inner container contains a Gewebekonditioniemngsmittel. The inner container consists of a substance whose solubility is highly dependent on the ionic strength or of the pH value of the medium in water, and the agent serves to make the inner container is insoluble, is a means to control the pH, or the ionic strength. Japanese Patent Application KOKAI 60-141705, 61-28440, 61-28441, 61-28596, 61- 28597, and 61-28598 describe a method for the production of pH-sensitive micro krokapseln for use in detergents. The pH sensitive coating is a co-polymer of the following monomers:

A) at least one basic monomer of formula I:

in which R is hydrogen or a methyl group, R 1 and R 2 are each an alkyl group having 1-3 carbon atoms, and x is an integer from 1-4;

B) at least one monomer which is insoluble or poorly soluble in water, and

C) at least one water soluble monomer.

It is stated that the described polymers are insoluble at a pH value of 9.5 or more, and are soluble at a pH value of 8.5 or less. It describes different ingredients of detergent compositions that can be coated with success and benefit by the described polymers. The aim of the invention described therein is to substances which are to exert their function only in the rinse cycle to protect up to its beginning and then release without delay.

A disadvantage of the solution described in this Japanese patent application that the coated particles are at the beginning of the wash cycle in direct contact with non-alkaline wash water, which may have a dissolution of the protective casing result.

From the Japanese Patent KOKAI 50-77406, a washing aid is known which is surrounded by a water soluble enclosure, the dialkylaminoacetat by mixing polyvinyl acetal is obtained and at least one organic acid which is solid at room temperature. This protective cover is designed to protect the detergent during the main wash cycle and release during the rinse cycles. The conjunction described responds to the change in the pH value between the main wash cycle and

Rinse cycles. The appropriately coated particles are combined with conventional powdery

Detergent mixed. Here, too, there is the disadvantage of the possible dissolution of the

Protective covering at the beginning of the wash cycle.

From European Patent Application EP 0284191 A2 and 0284334 A2 a water-soluble polymer film in the release of wash additives in the rinse cycle of washing machines is known, which remains intact during normal washing cycle over a range of typical temperatures and rapidly dissolves in the rinse cycle. The applications should be noted that although the use of pH-sensitive coatings is well known, these movies but usually are also temperature sensitive so that they are not reliable stable during the different temperatures in the wash. The proposed solution, a pH-dependent material (which undesirably also a positive temperature-dependent dissolution behavior shows) with a material to combine, showing a negative temperature dependent solubility behavior. This combination is intended to guarantee that the coatings at the high temperatures at the start of the wash cycle (in particular the very high temperatures occurring in American machines) will not solve.

The European patent application EP 0481547 Al discloses multilayer dishwashing detergent tablets having a core, a separating layer surrounding the core and an outer layer for the sequential release of the ingredients of the different layers. With this tablet two tasks to be solved in principle, namely 1) incompatible materials can be formulated together and are released at different times in order to avoid mutual interference in a single tablet; and 2) compositions which are to exert their functions at different times, may be formulated in a single tablet.

One of the disadvantages of the above described prior art is that the sequential pressing of the individual steps is described as a single manufacturing process. This creates the danger that the core and / or the wrapping of the core are deformed, which on the one hand to damage (and thus reducing the protective effect) may cause the wrapper of the core to the other (Zung, depending on the composi- of the core) to a "bleeding" of the core into the material of the coating and the base composition. in addition, the intimate full surface contact between the individual layers can cause reactions to occur in the boundary layers, which are undesirable, in particular between the sheath and the base composition.

The second major disadvantage of the prior art is that the temperature is used as a causative factor for the initiation of dissolution of the coating layer, that is, temperature-sensitive materials are used for the material of the envelope. Since the temperature / time profile in washing machines can be very different depending on the selected program, it would be difficult, if not impossible, to select a material for the sheath that can be used for all kinds of programs modern washing machines. EP 0481547 Al acknowledges itself (page 7, lines 37-43) that the selection of the material of the coating layer gerate- and must take into account program-specific features. The practical applicability of the described products is therefore considerably restricted. One use for washing machines is not mentioned in the citation.

The PCT application WO 95/29982 discloses a dishwashing detergent with delayed release of a rinse aid in the form of a nonionic surfactant, said nonionic surfactant forms a core particle together with an inorganic builder salt, which is provided with a wax-like enclosure for the delayed ensure release. This envelope is a substance which does not melt at the operating temperatures encountered in the cleaning operation, but is chemically disintegrated so gradually at alkaline pHs that even an effective amount of the rinse aid remains at the end of the main cleaning cycle and is transferred to the rinse cycle. One use for washing machines is not mentioned in the citation.

A disadvantage of the embodiment shown in this reference solution in that the sheathing is solubilized by chemical stranding at alkaline pHs, so that the timing at which the rinse aid is released from the core, is a function of both the temperature and the length of the main cleaning cycle , The patent application does not teach how a product is to be formulated with which the rinse aid is released in all wash programs each device type in the rinse cycle. Finally, the product is a mixture of granular detergent and rinse agent granular.

The object of the present invention is in view of the prior art seeks to provide a generic composition which is suitable for most washing programs of various types of equipment of washing machines and in each of these cases, the substance (s) that their action substantially only in the rinse cycles to develop (s), and only in these releases. It is desirable to do this without substantial restriction on the choice for the employed detergent, the inserted (s) substance (s) for the rinses and other ingredients of the composition to achieve.

According to the invention this object is achieved with a generic composition, which is characterized by a base composition evolving its function substantially in the main wash cycle of the washing machine in the form of a tablet; and at least one particle with at least one core comprising at least one substance evolving its function substantially in the rinse cycles of the washing machine, and the (the) core (e) substantially completely surrounding envelope which comprises at least one compound whose solubility increases with decreasing concentration of a specific ion in the surrounding medium increases; wherein the at least one particle is arranged in or on the tablet that the surface of (the) particle (particle) at most partially in direct contact with the surface of this surrounding (these) based composition and local concentration of the specific ion in the vicinity of (the) particle (particle) until substantially complete dissolution of the tablet is sufficiently high to prevent substantial dissolution of the envelope or a significant detachment of the envelope from the core (of the nuclei).

It is preferably provided that the or all the particles is received in at least one completely surrounded by the basic composition of the tablet or cavity are having a larger volume than the or all the particle or received in the respective cavity or are. It can (can not) in an alternative, the particles may be arranged loosely inside the cavity or, in another alternative, fixed (s). In the case of fixing the inside of the cavity, this is preferably effected by an adhesive.

In a particularly preferred embodiment of the invention, the cavity is disposed substantially centrally in the interior of the tablet.

The invention further provides that the tablet has a single substantially spherical cavity in which a single, substantially spherical particle is preferably, whose external diameter is smaller than the inner diameter of the cavity.

In an alternative embodiment of the invention may be provided, the or all the particles is received in at least one cavity of the tablet and are, which is only partially surrounded by the basic composition.

In this case, the cavity is preferably a depression in one of the surfaces of the tablet, in which the (s) is at least partially accommodated particles (are).

In this case is (are) the (s) particles are preferred so received in the cavity or in the recess, that it (they) do not have the surface (s) of the tablet protrudes (protrude).

In one embodiment of the invention it is provided that the cavity or recess parallel to one of the surfaces to which it opens or in which it is located, has a substantially circular cross-sectional area.

The invention proposes in a particular embodiment in that the cavity or recess to the (s) surface (s) is open only so far that the (the) ^) received therein particles do not (by the Öffhung s) of the cavity or can pass through the recess (can). It is preferably provided that the (s) of particles in the cavity or in the recess is loosely (are) arranged.

but it can also be provided that the (s) is fixed to particles in the cavity or in the recess (are), wherein this fixing can be made preferably with an adhesive.

The invention provides preferred that the base composition comprises a composition at least selected from the group consisting of a detergent composition, a water-softening composition and a wash intensifier composition.

The invention preferably provides that the enclosure comprises at least one compound which is in the concentration of the specific ion at the end of the main wash cycle of the washing machine does not or only slightly soluble and wherein the concentration of the specific ion in the rinse cycles shows a so sufficient solubility that it is so largely dissolved in the rinsing cycles, or from the core removed (from the cores) that an at least partial escape of the core material is made possible in the medium of the rinse cycles.

It is preferably provided that the solubility of the compound increases with decreasing OH - ion concentration and hence decreasing pH in the surrounding medium.

The invention proposes in a particularly preferred embodiment that the compound at a pH value above 10 shows little or no solubility, and at a pH value below 9 shows such a sufficient solubility that it largely dissolved in the rinse cycles so or from the core is replaced (by the cores) that an at least partial escape of the core material is made possible in the medium of the rinse cycles.

Preferably, this compound comprises a polymer, more preferably comprises a pH-sensitive polymer comprising at least one repeating unit having at least one basic function which is not part of the backbone chain of the polymer. In a preferred embodiment, the polymer comprises at least one repeating unit based on a compound selected from the group koholderivaten from Vinylal-, acrylates or alkyl acrylates, having said basic function.

In a particular embodiment of the invention, the polymer is a carbohydrate functionalised with said basic function.

The above-mentioned basic function is preferably an amine, particularly preferably a secondary or tertiary amine.

In one alternative, the repeating unit based on a compound having the following formula:

wherein G is a linking group selected from -COO-, -OCO-, -CONH-, - NHCO -, - NHCONH -, - NHCOO -, -OCONH - or - OCOO -, Ri is independently hydrogen or an alkyl group having is 1-3 carbon atoms, R 2 are independently hydrogen or an alkyl group having 1-5 carbon atoms, and x is an integer 1 to 6

Preferably, the repeating unit based on a compound of the formula TV:

wherein Rj is independently hydrogen or an alkyl group having 1-3 carbon atoms, R is independently hydrogen or an alkyl group having 1-5 carbon atoms, and x is an integer 1 to 6

In a further embodiment of the invention provides that the basic function is an imine or a basic aromatic N-containing group, preferably a pyridine group or an imidazole group.

In a further embodiment it is provided that the pH-sensitive polymer is a polymer derived from chitosan.

Finally, the invention proposes that the compound K-carrageenan.

In one embodiment of the invention it is provided that the (s) of core (s) comprises at least one material (cover) which is selected from the group sloppers from fragrances, plasticizers, anti-static agents, means to restore the ability of the laundry imitate the Feuchtigkeitsauf, mild acids, bleaches, disinfectants, means for lasting protection for both the laundry and the person's underwear bearing from insects or mites, means for improved removal of greasy soils, means for equipping with anti-crease, optical brighteners, ironing auxiliaries, agents for dye transfer inhibition and enzymes exists.

In one alternative, the core or at least part of the cores can be in the form of an encapsulated liquid. In another embodiment, the core or at least part of the cores is in a solid form.

The invention further relates to a method for carrying out a washing cycle in a washing machine, in which the composition of the invention at an appropriate time during the Vorwaschganges or main washing cycle for the washing machine located in medium is added.

In a particular embodiment of this process it is provided that, in the event that the base composition is not in a position in the form of the tablet, to provide after its dissolution in the medium until the end of the main washing cycle, a concentration of the specific ion in the medium is available, which is sufficiently high to prevent substantial dissolution of the envelope and a significant detachment of the envelope from the core (of the nuclei), these sufficient concentration of the specific ion to by the addition of another composition, such as a detergent composition, the medium of the main washing cycle a convenient time is provided.

The composition according to the invention is characterized in that it provides excellent results both in the main wash and in the rinse cycles of a washing machine. The tablet is dissolved during the main washing cycle, and can their corresponding intended effect (cleaning, water softening, washing amplification, etc.). The arranged in or on the tablet particles as the core material contains that substance or those substances which are to exert their primary function in the rinse cycles of the washing machine. These substance (s) is (are) protected by a sheath which is stable at the concentration of ions, such as the pH and temperature of the main washing cycle and not or only slightly move up or peel off.

After the main wash cycle and the pumping of the wash liquor a dilution effect occurs in the rinse cycles on by repeated entry of fresh water, so that the ion concentration or the pH drops significantly. Of course, the actual profile of the ion concentration or pH profile depends Waschzylus a washing machine in a large extent on the composition of the detergent used. The following large extent on the composition of the detergent used. The following Table 1 shows an example of a pH-profile was measured at a washing machine CANDY Activa 80 Plus, conventional in a 60 ° C washing program with 3 kg of normally soiled fabric and 3 40 g detergent tablets as (below Example 4 ) are described in more detail.

Table 1

It is clear that during the entire main washing cycle, a relatively high pH value from 10.25 to 10.35 is present, which drops to a value of 8.50 to the fourth wash. The solubility of the coating material must therefore be so greatly reduced at pH values ​​of preferably less than 9, that this move up quickly or detaches and the actually effective core material into the surrounding medium, that is, the rinsing water releases.

Provided that the metered addition is not provided through special dosing, which may hold back the erfmdungs- according particles, particles of the invention should be chosen so large that they are at least not discharged to any significant extent during the evacuation after the main wash cycle and the first rinse cycles of the washing machine , For the inventive solution, it is essential that the surface of the particle at most partially in direct contact with the surface of this surrounding base composition of the tablet. This can be done concretely described in this application and illustrated species, but also in any other way in which the intended purpose is achieved. Examples are the loose arrangement of a smaller particle in a larger cavity as well as the fixation of a smaller particle in a larger cavity in such a manner that no or only a partial contact between the particle and the base composition of the tablet is, etc ..

This constellation provides over the prior art that in the manufacturing process, such as the taking place in successive steps pressing of the individual components, deformation and possibly consequent damage to the core (cores) and / or the sheath is reliably avoided to advantage, by the a reduction in the protective action of the sheath of the core could (the cores) occur. By preventing that pressure is applied to the particles at any stage of the manufacturing process can be reliably prevented that at a given composition of the core (cores) to a "bleeding" of the same in the material of the envelope and the outer layer into comes. Finally, it may in certain compositions of the enclosure and the base composition may be advantageous to avoid intimate full surface contact, as otherwise might occur reactions in the boundary layers, which are undesirable.

The term "local environment", as used in connection with the inventive particles intended to refer to the immediate area around this particles around. The ion concentration in the local environment of the particle is the determining factor for its stability. The products of this invention is the ion concentration determined in this local environment at least until substantially complete dissolution of the tablet through of these ions in solution is preferably the origin of the "specific ion" therefore -., at least in the initial phase of the main washing cycle - one compound selected from the tablet-forming base composition or . produced by this in the surrounding medium. Most typically these are in the customary basic detergents to OH "ions, the concentration can be expressed as pH.

Detergent composition is provided as a basic composition is not a (basic, for example) is used, but for example, a water-softening or laundry booster composition is the protection of the envelope of the particle may be provided by a sufficiently high ion concentration in the local environment of the particle only until the tablet is completely dissolved , namely in the cases that the base composition of the tablet to be unable to provide a sufficiently high ion concentration in the wash liquor disposal. In these cases, the sufficiently high ion concentration in the wash liquor and thus also in the local environment of the (the) particle (particle) by the resolution of the actual washing agent (or of another particular additive) is reached.

The invention will now be described in more detail by the following examples and drawings. In the drawings:

1 shows a first embodiment of the composition according to the invention in cross-section.

Fig. 2 shows a second embodiment of the composition according to the invention in cross section;

3 shows a third embodiment of the composition according to the invention in cross-section.

FIG. 4a and b a fourth embodiment of the composition according to the invention in cross section and in plan view; and

Fig. 5 shows a fifth embodiment of the composition according to the invention in cross section.

Fig. 1 to Fig. 5 show possible embodiments of the composition according to the invention illustrate.

Fig. 1 shows a tablet 1, consisting of two half-tablets 2 and 3, which can have different or the same composition in both half-tablets to detect an approximately hemispherical recess 4 or 5 is approximately in the center, which in of assembled tablet 1 along an in approximately spherical

Cavity yield.

In this cavity, in the illustrated embodiment, a single particle is 6, consisting of pH or ion concentration-sensitive jacket 9, whose external diameter is slightly smaller from the core 8 and as the inner diameter of the

Cavity in the tablet. Both in the embodiment shown, in which the particles in the cavity is loosely received, and in one embodiment, where it is fixed by a fitted in the intermediate space glue, it is ensured that no continuous full-surface contact between the tablet material and the cladding of the particle is , This is an essential aspect of the present invention to prevent the one hand that the protective envelope is damaged around the core of the particle during the manufacturing process, and minimize the other possible interactions between the tablet material and the mentioned casing, both with the aim of up to the rinsing cycles to obtain the envelope reliably stable.

For fixation of the particle in the cavity, not only a conventional adhesive will of course be considered, but also other compositions and agents that serve the same purpose, for example, a mechanical fixing such as sufficient frictional engagement between tablet and particle at least at some points or a plug connection between tablet and particles. Moreover aufschmelzende or during the main washing cycle dissolving compounds as a fixing agent between the particle and the tablet are also preferably possible.

Of course, various other geometric shapes for the design of the cavity in the tablet or the particle received therein possible such as. Ellipsoid, cylinder, etc .. The shape and size of the cavity in the tablet and that of the particle received therein need not present correspond to each other. Thus, a cylinder-shaped particles may for example be received in a spherical cavity. All other possible combinations are possible within the scope of the present invention. Furthermore, it is possible not only the cavity with a

To fill particles but with a plurality of smaller particles.

In FIG. 2, a second embodiment of the composition according to the invention based on a conventional 2-layer tablet. 1 In this case, the upper half-tablet 3 consists of two parts, which provide both a sufficient cavity 5 for receiving the particle 6 as well as an opening to the side 11 of the tablet through to disposal. In this case, the particle 6 is not completely surrounded by the basic composition of the tablet 1 so that it is visible from the outside in the interior of the tablet. 1 Also in this case, the particles can be in the cavity 5 is either loose (be added if it is ensured by appropriate selection of the size of the particle 6 on the one hand and the size of the opening of the cavity 5 to the side 11 of the tablet that the particle or particles in the cavity not can pass through the opening or can) or in the interior of the cavity 5 may be fixed by appropriate means such as, adhesive.

A third possible embodiment is shown in FIG. 3. The basis is again a 2-layer tablet. In the upper layer 2 a recess 4 is formed by means of a suitable device. In this recess 4, the particles 6 is introduced, the one in this case, since the recess to the side 11 of the tablet 1 side is so far open that without fixing for instance with an adhesive 10 would be possible falling out of the particle from the recess, or fixing the intermediate layer or mechanically (eg by friction) is fixed in the recess. Of course, this principle is also applicable to single-layer tablets.

Also in this case various geometric embodiments are possible. Thus, the recess may, for example, parallel to the side 11 have a substantially circular cross-section. However, any number of other cross-sections is also conceivable, for example. any polygon. The captured in the recess 4 particles 6 can, as in the embodiment of FIG. 2 any (and the shape of the recess 4 independent) take form, such as. Ellipsoid, cylinder, cuboid, etc .. It may be because are thought 'through-going cylindrical hole 4' existing tablet body 1 'in one by one of a layer 2 to be fixed in an open on both sides of the cavity in the tablet, such as.' the particles 6, in which a corresponding cylindrical particles 6 ' is fixed (Fig. 4a and b).

Another possible embodiment is shown in FIG. 5. This is essentially constructed as the embodiment according to Fig. 3. In this case, the particle contains 6, however, "not only a core (as in Fig. 3), but a variety of cores 8 ", the total in a sheath 9 'are embedded. in this embodiment example, it is also possible to incorporate cores of different composition and different shape (encapsulated material or solid cores) in a particle 6".

In both the illustrated embodiments as well as other conceivable alternatives, it is essential that for the to be released in the rinse cycles (s) substance (s) containing the particles at least in the first phase of the main washing cycle a local environment with sufficient ionic concentration or pH who (which) acts as a "trigger" for the resolution of the envelope, is present, that is in a phase in which the detergent composition is not sufficiently dissolved, ie, the pH is still relatively low, ie, short-term in an area where would be given the increased solubility of the envelope. In this way it is ensured that the envelope up to the rinse cycles having a sufficient stability.

example 1

Preparing the core

a. Core for a particle for controlled release of acid in the rinse cycle

The release of an acid in the rinse cycles of a washing machine is to serve both of removal of incrustations and the neutralization of alkaline residues. Advantageously, amido weak acids are used for this purpose, such as. Sulphonic acid and / or maleic acid. Typically, it is these materials are solids that can be provided directly with the intended casing, wherein the coating method on the appropriate (s) substance (s) must be switched off if necessary.

The manufacturing process is as follows:

A mixture of 1.05 g of sulfamic acid and 0.45 g of maleic acid are formed in a rotary press under a pressure of 890 kg / cm 2 into a tablet.

b. Core for a particle for controlled release of perfume in the rinse cycle

Taking into account similar considerations as in Example la, a corresponding core is prepared as follows:

0.1975 g perfume 0.0525 g are absorbed on finely divided silica to give a free flowing granular material. The resulting 0.25 g are mixed with 0.6 g of microcrystalline cellulose and 0.15 g of crosslinked polyvinylpyrrolidone. The mixture is tableted in a rotary press with an inner diameter of 10 mm under a pressure of 2900 kg / cm 2 to give an elliptical tablet having a height of 13.1 mm and a weight of about 1 g.

Alternatively, fragrances, which usually represent liquids, are also presented as the fragrance-containing capsules can.

c. Core for a particle for controlled release of chlorine bleach in the wash cycle

The use of chlorine bleach in the rinse cycle of a washing machine is used to improve the cleaning effect, while also having an additional disinfection.

Taking into account the considerations in Examples la and lb, such cores can be prepared as follows: 1 g chlorine bleach such as sodium dichloroisocyanurate pure, may be compressed into a tablet 2 in a suitable press under a pressure of 5,600 kg / cm.

d. Core for a particle for the controlled release of a Gewebekonditionierungsakti- tivity in the rinse cycle

In this example, the core comprises a plurality of substances to develop their respective effects in the rinse cycle of a washing machine. In the specific case, it is the combination of a fabric softener, an agent for reducing the buildup of static electricity in the tissue and an agent for improving the moisture re aufhahme through the tissue.

A slurry of 58% urea, 18% dimethyl (DMDSAC) (90%), 8% of a C. 9 11 alcohol ethoxylated with 9 moles of ethylene oxide, and 16% water was prepared. The slurry was spray-dried to obtain a granular material having a density of 580 g / 1 and the following composition: 68.8 wt .-% of urea, 19.2 wt .-% DMDSAC, 9.5 wt .-% non- -ionisches surfactant and 2.5 wt .-% water.

4 g of the granular composition were mixed with 1 g of cellulose. The mixture was tableted in a rotary press with an inner diameter of 25 mm and a pressure of 80 kg / cm 2 to obtain an elliptical tablet having a height of 14 mm and a weight of 5 g.

example 2

Screening method for wrapping materials

As stated above, it is for the present invention essential that the material for the cladding of the particle (the particle cores), the (s) comprising the substance (include) the evolving its function substantially in the rinse cycle, shows a solubility , which depends on the concentration of a specific selected ion. In this way, the enclosure is in the main wash cycle is substantially insoluble and is solubilized and separates from the particles when the ion concentration is lowered during the rinse cycles.

It has been observed that the dilution due to the pumping of the wash liquor and the inflow of fresh water occurring in the course of the various rinse cycles causes that the ion concentration is lowered is 20 to 200 times between the end of the main washing cycle and the last rinse ,

Based on this observation a method for screening the suitability of various polymers for their use has been developed as wrapping materials, which consists in the determination of the solubility of such polymers at two different ion concentrations at least 20 times, more preferably 200-fold to the apart.

The values ​​for the ionic concentration that should be used in the screening of the polymers depend on the formulation of the base composition of the tablet, in which the coated particles to be incorporated.

In fact, the value for the highest ion concentration, used for the screening procedure should correspond to the concentration of the selected ion which is to be found in the wash liquor, after the detergent is fully dissolved. Once this concentration is determined, the lower value for the ion concentration on the 20- to 200-fold higher than this value should be fixed.

With this information it is within the average skill and -Wissens a specialist mannses in this area to determine the values ​​for the ion concentration of the test solutions should be used in the test procedure described below.

Method for preparing the test solution and the implementation and evaluation of the tests

The test materials are dissolved in solvents in which they are readily soluble. The solutions are spread on glass slides and subsequently dried at room temperature until they show a constant weight. The glass plates are placed at a controlled temperature in a beaker containing the test solution. The solution is then stirred with a magnetic stirrer at a controlled stirring rate. After about 10 minutes the glass plates are removed from the beaker and dried at room temperature to constant weight. The results are expressed as weight loss [%].

Of course, the screening process must be adapted to the composition of the detergent, since it exerts the significant influence on the ion concentration or pH-profile in the wash cycle. The aim is in any case the check of the degree of solubility of the respective materials in different states, namely high (r) or low (r) ion concentration or pH.

Given this, it is obvious to a person skilled in this field only in its average ability to establish special test parameters for screening. Exemplary two screening methods are presented in the following, with which some of the possible materials for the envelope of the particles were tested.

Screening Method 1:

A screening method 1 was carried out with buffer solutions as the medium for simulating the wash liquor. To this end two buffer solutions were prepared as follows:

Stock solution: 7.507 g glycine (Merck 104169)

5.850 g NaCl made up with water to 1000 ml

pH 8 buffer solution: 500 ml stock solution least 500 ml. L H 2 O, 23 N NaOH gl

pH 10 buffer solution: 500 ml stock solution least 500 ml. H 2 O 32.6 g of 1 N NaOH. Screening Method 2:

A screening method 2 was carried out using the following detergent formulation in order to simulate the conditions in various stages of a wash cycle.

Detergent formulation:

First, a spray-dried base material with the following composition was prepared:

table 2

Ingredient wt .-%

sodium carbonate 7.43

Sodium LAS 40.0

zeolite 17.70

polymer 7.0

Sodium sulphate 9.61

Sodium silicate 7.00

soap 4.0

phosphonate 1.55

carboxymethylcellulose 1.01

Water and Other 4.7

This spray-dried base composition was mixed with the other ingredients following materials, to obtain the final formulation: Table 3

Ingredient wt .-%

spray-dried

Base material 22.6

sodium 20.0

sodium carbonate 19.58

Sodium tripolyphosphate 17.42 microcrystalline cellulose 6.0

alkyl sulfate 6.0

1.50 polymer crosslinked polyvinylpyrrolidone 1.80

enzymes 1.78

TAED 1.00

Polyethylene glycol 0, 18

Other water and 2.14

Screening Method 3:

Screening Method 3 is used to screen for compounds whose solubility varies depending on the concentration of potassium ions. The compounds identified by such screening methods may be used if the main wash cycle - as shown above - there is a correspondingly high concentration of potassium ions is reduced accordingly by dilution in the rinse cycles.

The screening process 3 was performed with the following formulation to simulate corresponding conditions. Formulation:

example 3

Selection of materials for the envelope of the particles

To those described in Example 2 screening method, various materials have been studied for their suitability as an envelope of the particles according to the present invention. One of these materials, hereinafter "Polymer 1" is a polymer as described in Japanese Patent Application KOKAI 61-28440, ie, a polymer of the general formula II with l / (l + m + n) = 0.35; m / (l + m + n) - 0.45; 1 + m + n = 1500-1800.

The polymer was produced in a conventional manner by bulk polymerization. The results of the screening tests were as follows:

Screening Method 1:

Films of polymer 1 were cast from a 10% solution is prepared in isopropanol.

Screening procedure 2 gave similar results.

The invention is of course not limited to this exemplary polymer, of course, already been given a great variation possibilities with regard to the mentioned in Japanese Patent Application KOKAI 60-141705, 61-28440, 61-28441, 61-28596, 61-28597 and 61- 28598 polymers is expanded or to compounds of the formula TV:

wherein Ri is independently hydrogen or an alkyl group having 1-3 carbon atoms, R 2 is independently hydrogen or an alkyl group having 1-5 carbon atoms, and x is an integer 1 to 6 In addition, are within the larger class of compounds with formula III:

wherein G is a linking group selected from -COO-, -OCO-, -CONH-, - NHCO-, -NHCONH-, -NHCOO-, -OCONH- or -OCOO-, R, are independently hydrogen or an alkyl group with 1-5 carbon atoms and x is an integer from 1 to 6, by way of example to use polymers with a repeating unit can be used which are based on a compound having the formula V

for example a pH-sensitive polymer. ( "Polymer 2") having the repeating unit VI, which is commercially available from Sankyo under the trade name AEA®

The above-described screening method 2 was also performed with "Polymer 2": 15 g of "Polymer 2" and 5 g of Mowiol 3-98 (Clariant) were dissolved in 200 ml of a mixture of water / ethanol / 1N HCl 12: 8: 1 solved. Films were formed and tested as described above. The results were comparable with those for "Polymer 1".

Other polymers which exhibit the desired properties or so can be modified in a simple manner that they are suitable for the purposes of the present invention are polymers of isomers or derivatives of pyridine, preferably copolymers with styrene or acrylonitrile, the following formulas VII and VIII, in which G is a substituent at any position of the pyridine ring.

A polymer according to the above formula VIII, namely poly (4-vinylpyridine-styrene) copolymer (Scientific Polymer Products, Inc.), "Polymer 3" was tested according to the above-described screening method 2:

10 g of "Polymer 3" were water in 230 ml / IN HC1 6.25: solved. 1 The formation of the films and the performance of the tests carried out as described above. The results were comparable with those for "Polymer 1" and "Polymer 2".

Other polymers (for example, statistical) polymers derived from chitosan, based on the following monomer units IX and X

In addition, it is also possible in the envelope of the core material to use substances or mixtures of substances which react with regard to their solubility to a change in the ion concentration, that is, ion concentration sensitive polymers. For this purpose, for example partially hydrolyzed polyvinyl acetates described in the publications EP 0284191 A2 and EP 0284334 A2 come (commercially available (under the trademark Mowiol® Clariant)) into consideration, in the presence of borates due to the complexation of borate with polyols show a corresponding ion concentration dependence. The first successful tests were carried out with the product Mowiol.RTM 56-88

Another ion concentration sensitive polymer, the polysaccharide is K-carrageenan, which in screening method 3 (see Example 2) as has been shown in its solubility of the potassium ion concentration in the surrounding medium dependent polymer. K-carrageenan is represented by the following formula XI:

This polymer is referred to as "Polymer 4", was tested according to the above-described screening method 3:

4 g of K-carrageenan was dissolved in 96 g of water. 10 g Mowiol 18-88 were dissolved in 90 g of water and both solutions were mixed. The resulting solution was used for the formation of the films and the performance of the tests, as described above. The following results were obtained:

The above list of compounds, which are suitable for the inventive sheath is of course not exhaustive. Other polymers that change their solubility by changing the pH or the ion concentration in the desired range are also conceivable or can be developed and fall under the scope of the present invention. Moreover, the appropriate envelope for the inventive substances are not limited to polymeric compounds, although such compounds are described herein as preferred embodiments.

Using the above screening methods or screening methods that are adapted to the measurement of an ion concentration sensitivity, various other commercially available or obtainable by simple modifications of materials may be examined for their suitability in the present invention. The selection of such polymers is in view of the clear target and the screening procedure given one for the skilled in the art without difficulties to be solved.

example 4

Preparation of a particle according to the invention

The different cores described in Example 1 were used as the basis for preparing inventive particles. These cores were in a device for applying a film coating, as is known from the pharmaceutical industry (eg. From the companies Loedige, Hüttlin, GS, Manesty and Driam), individually or in combination (Fig. 5) provided with a covering.

In the case that the (s) of core (s) comprises an ingredient (have) showing a certain incompatibility with the material of the envelope may (can) of (s) of core (s) prior to applying said sheath first with a protective coating be provided. For this purpose include various well-known from the prior art materials are suitable, such as, cellulose, cellulose derivatives, polyvinyl alcohol, polyvinyl alcohol derivatives and mixtures thereof. When using the cores of Example 1, such a barrier coating was deposited in the cases Ia, Ib and Ic used, where in this case was a 10 wt .-% aqueous solution of polyvinyl alcohol Mowiol 5-88 (Clariant) is used. In the case of Example la the core with 0.76 g of such a solution was coated, in the case of Example lb, 0.40 g of the same solution were used and in the case of Example lc, 0.29 g of the same solution was used.

The envelope can in principle be applied to the (s) of core (s) or the protective coating in any amount and thickness as long as it is ensured that the envelope log off fast enough in the rinsing cycles, or dissolves, so that in the core (in given by the cores) (s) substance (s) its effect (s) can unfold (can). In a preferred embodiment, onto the cores 1-10 wt .-%, preferably 4-8 wt .-% of Io nenkonzentrations-sensitive coating material (dry basis), based on the mass of the whole particle applied.

Preferably, particles of the invention should be of such a size that they are not or at least not discharged through the Abpumpvorgänge after the main wash or rinse cycles each to a considerable extent from the washing machine. This is usually a size of about 1 cm maximum diameter sufficient. but smaller or larger dimensions, may be granted as long as the operation is generally guaranteed.

For the other tests, "Polymer 1" of Example 3 was used as the sheath and as a 10% solution of the polymer in 0.055 N aqueous HC1 applied.

example 5

Manufacturing a tablet according to the invention particles

For example, the preparation of tablets according to the invention will be described with the following structure. Such tablets may be prepared by compressing the powdered ingredients in principle known from the prior art machines and using in principle known from the prior art operating parameters. The composition of such tablets is geared to commercial products.

By way of example, a detergent tablet, Wasserenthärtertablette and a washing intensifier tablet are described below.

detergent tablet

The mixture of the composition of a detergent tablet may for example be based on a detergent formulation, as it is shown in Example 2, Tables 2 and 3. FIG. The resulting granular composition has a bulk density of about 690 g / 1 and can be tableted, to give a half-tablet with a dimple, having a weight of about 20 g in a corresponding pressure under a pressure of 21 kg / cm.

One of the particles of the invention prepared according to Example 1 and 4 is placed in the recess of the half-tablet. Subsequently, a fixing substance such as an adhesive (for example, polyethylene glycol, polyvinyl ether, polyvinyl alcohol, silicate, preferably molten PEG 4000), is applied to the corresponding face of the half-tablet and possibly also on the particle and the second half-tablet on the first half-tablet with an inventive particles pressed. In this way, a detergent tablet is produced with a current commercial weighing about 40 g.

Wasserenthärtertablette

The following ingredients were mixed:

table 4

The resulting granular composition is tableted cm under a pressure of 150 kg / to give a half-tablet with recess, with a weight of about 8 g.

The completion to the invention the particles and the joining of the half-tablets is carried out as described above for the detergent tablet.

Washing amplifier tablet

Using the known technology for manufacturing a two-layer tablet, a washing amplifier tablet is prepared whose different heavy layers (26/74) having a different composition according to the following table: Table 5

a recess is formed as shown in Fig. 3 in the upper layer, first adhesive or the like in the particles and then to the invention is given.

The features disclosed in the foregoing description, the claims and the drawings, features of the invention may be material for realizing the invention in its various embodiments both individually and in any combination.

Claims

Anspr├╝che
1. A composition for use in a washing machine, characterized by
a basic composition (2, 3; 2 '), the evolving its function substantially in the main wash cycle of the washing machine in the form of a tablet (1; 1'); and
at least one particle (6; 6 '; 6 "), with
- at least one core (8; 8 '; 8 "), the umfaßt at least one substance evolving its function substantially in the Spülgängen the washing machine, and
- one to (the) core (s) substantially surrounding vollständig Umhüllung (9; 9 '; 9 "), which umfaßt at least one compound whose Löslichkeit with decreasing concentration of a specific ion in the surrounding medium;
wherein the at least one particle (6; 6 '; 6 ") as in or on the tablet (1; 1') is arranged, the daß Oberfläche of (the) particle (particle) (6; 6 '; 6 ") höchstens partially in direct contact with the Oberfläche of this (these) surrounding the basic composition (2, 3; 2 ') is stopped and the concentration of the specific ion in the local environment of the (the) particle (particle) until substantially vollständigen Auflösung of the tablet (1; 1 ') is sufficiently high to prevent substantial Auflösung the Umhüllung or a substantial Ablösung the Umhüllung (from the core to prevent from the cores).
A composition according to claim 1, characterized in that the daß or all the particles (6) in at least one vollständig surrounded by the basic composition (2,3) the cavity (4,5) of the tablet (1) is received or are having a größeres volume than the or all the particles (6) which is received in the respective cavity or or are.
3. Composition according to claim 2, characterized in that the daß (s) of particles (6) inside the cavity (4,5) is loosely (are) arranged.
4. The composition according to claim 2, characterized in that the daß (s) of particles (6) inside the cavity (4,5) is fixed (are).
5. The composition according to claim 4, characterized in that the daß (s) of particles (6) inside the cavity (4,5) is fixed by an adhesive (are).
*
6. Composition according to one of Ansprüche 2 to 5, characterized in that daß the cavity (4, 5) substantially centrally in the interior of the tablet (1) is arranged.
7. A composition according to Ansprüche 2 to 6, characterized in that the tablet (1) daß a single, substantially kugelförmigen cavity (4, 5).
8. The composition according to claim 7, characterized in that daß in the cavity (4, 5) comprises a single, substantially kugelförmiges particles (6) is housed, whose Außendurchmesser is less than the inner diameter of the cavity.
9. The composition according to claim 1, characterized in that the daß or all the particles (6 '; 6 ") in at least one cavity (4') of the tablet (1 ') is or are added, which only partially from the basic composition (2 ') surrounding it.
10. The composition according to claim 9, characterized in that said cavity has a daß
Is depression (4 ') in one of the Oberflächen (IT) of the tablet (1') in which the (s) of particles (6 '; 6 ") at least partly accommodated is (are).
11. The composition of claim 9 or 10, characterized daß that (the) particles (6 '; 6 ") in the cavity or in the recess (4' is received) is (are), it daß ( it protrudes) are not (über the Oberfläche (s) 11 ') of the tablet (1') (protrude).
12. The composition according to any of Ansprüche 9 to 11, characterized in that the cavity or the recess (4 ') parallel to one of daß Oberflächen (IT) to which it itself or in öffnet which it is located, has a substantially kreisförmige Querschnittsfläche.
13. The composition according to any of Ansprüche 9 to 12, characterized in that the cavity or the recess (4 ') to the (the) Oberfläche (s) (IT) only so far daß öffnet can; '6 ") rather than by the Öffhung (s) of the cavity or the recess (4') pass (können), the (s) received therein ^) particles (6 daß.
14. The composition according to claim 13, characterized daß that (the) particles (6 '; 6 ") in the cavity or in the recess (4') is loosely (are) arranged.
15. Composition according to one of Ansprüche 9 to 13, characterized daß that (the) particles (6 '; 6 ") in the cavity or in the recess (4') is fixed (are).
16. The composition according to claim 15, characterized daß that (the) particles (6 '; 6 ") in the cavity or in the recess (4') with an adhesive (10 ') is fixed (are).
17. The composition according to any one of the preceding Ansprüche, characterized in that the base composition daß (2,3; 2 ') at least umfaßt a composition which is ausgewählt from the group consisting of a detergent composition, a Wasserenthärterzusammensetzung and a Waschverstärkerzusammensetzung there.
18. The composition according to any one of the preceding Ansprüche, characterized in that the daß Umhüllung (9; 9 '; 9 ") at least one compound umfaßt that in the concentration of the specific ion at the end of the main wash cycle machine little or not is löslich and shows such adequate Löslichkeit in the concentration of the specific ion in the Spülgängen, they daß in the Spülgängen so largely resolved öst or the core is abgelöst (of the nuclei), daß an at least partial escape of the core material into the medium of Spülgänge is ermöglicht.
19. The composition according to claim 18, characterized in that the daß Löslichkeit the compound increases with decreasing OH- ion concentration and hence decreasing pH in the surrounding medium.
20. The composition according to claim 19, characterized in that da├ƒ the compound at a pH above 10 shows little or no L├╢slichkeit and shows such adequate L├╢slichkeit at a pH below 9, da├ƒ it is so largely aufgel├╢st in the Sp├╝lg├ñngen or from the core abgel├╢st (of the nuclei), da├ƒ an at least partial escape of the core material into the medium of Sp├╝lg├ ñnge is erm├╢glicht.
21. The composition according to any of Ansprüche 18 to 20, characterized in that the compound is a polymer daß umfaßt.
22. The composition according to claim 21, characterized in that the connection daß a pH-sensitive polymer umfaßt that umfaßt at least one repeating unit having at least one basic function which is not part of the polymer Rückgratkette ,
23. The composition according to claim 22, characterized in that the polymer daß umfaßt at least a repeating unit based on a compound which is ausgewählt from the group consisting of vinyl alcohol derivatives, acrylates or alkyl acrylates, said basic function include.
24. The composition according to claim 22, characterized in that the polymer is a daß carbohydrate is functionalized with said basic function.
25. The composition according to any of Ansprüche 22 to 24, characterized in that the basic function is an amine daß.
26. A composition according to claim 25, characterized in that the basic function daß a sekundäres or tertiäres amine.
27. A composition according to claim 26, characterized in that the repeating unit daß on a compound having the formula III is based:
wherein G is a Verkn├╝pfungsgruppe which is ausgew├ñhlt from -COO-, -OCO-, -CONH-, - NHCO -, - NHCONH -, - NHCOO -, -OCONH - or - OCOO -, Ri unabh├ is ñngig represent hydrogen or an alkyl group having 1-3 carbon atoms, R 2 is unabh├ñngig represent hydrogen or an alkyl group having 1-5 carbon atoms, and x is an integer 1 to 6
28. A composition according to claim 27, characterized in that the repeating unit daß on a compound having the formula IV is based:
wherein Ri unabhängig represent hydrogen or an alkyl group having 1-3 carbon atoms, R 2 unabhängig represent hydrogen or an alkyl group having 1-5 carbon atoms, and x is an integer 1 to 6
29. A composition according to Ansprüche 22 to 24, characterized in that the basic function is an imine daß.
30. The composition according to any of claim 22 to 24, characterized in that the basic function daß a basic aromatic N-containing group.
31. A composition according to claim 30, characterized in that the basic function daß is a pyridine group.
32. A composition according to claim 30, characterized in that the basic function is daß an imidazole group.
33. A composition according to claim 24, characterized in daß the pH-sensitive polymer is a polymer derived from chitosan.
34. A composition according to claim 18, characterized in that the connection daß K- carrageenan umfaßt.
35. A composition according to any of the preceding Ansprüche, characterized in that the daß (s) of core (s) umfaßt at least one material (cover) which is ausgewählt from the group consisting of fragrances, Weichsp ülern, antistatic agents, agents for the restoration of the Fähigkeit Wäsche to Feuchtigkeitsauf imitate, mild Säuren, bleaches, disinfectants, means for lasting protection of both the Wäsche and the person carrying Wäsche ago insects and mites agents is for the improved removal of greasy soils, means for Ausrüsten with anti-crease agents, optical brighteners, Bügelhilfsmitteln, means for inhibiting the Farbstoffübertragung and enzymes.
36. A composition according to claim 35, characterized in that the core daß (8; 8 ') or at least part of the cores (8 ") is in the form of an encapsulated Flüssigkeit.
37. A composition according to claim 35, characterized in that the core daß (8; 8 ') or at least part of the cores (8 ") is in a solid form.
38. A method for Durchführung a washing cycle in a washing machine, characterized in that a composition according to one of daß Ansprüche 1 to 37 at an appropriate time während of Vorwaschganges or main washing cycle for washing machine located in the medium was added becomes.
39. The method according to claim 38, characterized in that daß, für the case, the base composition daß in shape of the tablet is not in a position, after their Auflösung in the medium until the end of the main washing cycle a to provide concentration of the specific ion in the medium for Verfügung, which is sufficiently high to prevent substantial Auflösung the Umhüllung and a substantial Ablösung the Umhüllung from the core (of the nuclei) to prevent these sufficient concentration of the specific ion is provided by addition of another composition, such as a detergent composition, the medium of the main washing cycle at a suitable time.
EP19990939398 1998-07-29 1999-07-23 Composition for use in a washing machine Ceased EP1019486A1 (en)

Priority Applications (3)

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DE19834179 1998-07-29
PCT/EP1999/005264 WO2000006683A1 (en) 1998-07-29 1999-07-23 Composition for use in a washing machine

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