EP1019486A1

EP1019486A1 - Composition for use in a washing machine

Info

Publication number: EP1019486A1
Application number: EP99939398A
Authority: EP
Inventors: Guido Wäschenbach; Ralf Wiedemann; Enric Carbonell; Antonio Cordellina; Manuela Bosco; Giorgio Franzolin; Joan Clotet; Dora Zamuner; Paul W. Robinson
Original assignee: Benckiser NV
Current assignee: Reckitt Benckiser NV
Priority date: 1998-07-29
Filing date: 1999-07-23
Publication date: 2000-07-19
Also published as: WO2000006683A1; US6660704B1; CA2304526A1; AU5371399A

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

Composition for use in a washing machine

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

Although modern washing machines in most cases have a large number of different washing programs, which differ in the duration and temperature of the individual washing and rinsing cycles, all washing programs essentially consist of the following basic steps: pre-wash cycle; Main wash cycle; several rinses; and spin cycle. While the actual detergent, which is supposed to have a cleaning effect, is added at the beginning of the main wash cycle (or possibly at the start of the pre-wash cycle), special detergents with different functions can be used in the rinse cycles. These special rinse aid agents should primarily bring additional laundry treatment benefits. A non-exhaustive list of such agents includes, but is not limited to: fragrances (pleasant smell of laundry), fabric softener (softness of laundry), antistatic agents (reducing or preventing the build-up of static electricity in laundry), agents to restore the ability of the laundry Laundry to absorb moisture, mild acids (breakdown of incrustations or neutralization of alkalinity), bleaching agents, either on an oxygen or chlorine basis (improving the cleaning effect), disinfectants, agents for the long-term protection of both the laundry and the person wearing the laundry against insects or mites , Agents for improved removal of grease soiling, agents for providing anti-crease, optical brighteners, ironing aids (to facilitate ironing of the laundry), agents for inhibiting dye transfer, enzymes such as cellulases, lipases, etc., for special purposes.

The different functionalities described have so far (if at all) been achieved by metering in different products, in some cases via separate metering devices, and metering in at different times.

The aim of the present invention was to compare the cleaning function and the function (s) of the substance (s) to be added in the rinse cycles, with the performance being as constant as possible the results, which can be achieved with a separate dosage, in one product or to allow the addition of further substances in the rinse cycles.

From the German laid-open documents 20 65 153 and 20 07 4 13 detergent tablets for use as detergents are known, in which, among other things, it is provided to combine two components with different functionality. In this case, a structure is provided from an enveloping shell, which is composed, for example, of two shell halves, which consist of a cleaning agent, and a cavity enclosed by the shells, which contains additives such as plasticizers, whitening agents, etc.

British Patent 1,390,503 discloses a liquid detergent which contains capsules which are insoluble in the composition but which release their contents when the composition is diluted with water. This goal is achieved in that the capsules are coated with a substance which has poor solubility in water solutions with high ionic strength, but becomes soluble when the ionic strength is reduced by dilution. It is pointed out that this technique can be used to include materials in the liquid detergent that are unstable in the liquid detergent itself, or would create instability if added directly. It is also suggested to use the technique to delay the release of a specific substance. The use in detergents is addressed. The encapsulated material is removed within 2 minutes after diluting the detergent with water, i.e. already released in the main wash cycle.

US Pat. No. 4,082,678 describes a fabric conditioning product which comprises a closed container which contains a releasable agent which serves to insoluble or non-dispersible an inner container arranged in the container, which is normally water-soluble or water-dispersible make, wherein the inner container contains a tissue conditioning agent. The inner container consists of a substance whose solubility in water is strongly dependent on the ionic strength or the pH of the medium, and the agent which serves to render the inner container insoluble is a means of controlling 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 process for producing pH-sensitive microcapsules for use in detergents. The pH-sensitive coating is a copolymer of the following monomers:

A) at least one basic monomer of the formula I:

in which R is hydrogen or a methyl group, R ¹ and R ^{2 are} each an alkyl group with 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.

The polymers described are said to be insoluble at pH 9.5 or more and to become soluble at pH 8.5 or less. Different ingredients of detergent compositions are described, which can be coated successfully and effectively by the polymers described. The aim of the invention described there is to protect substances that are only supposed to develop their function in the rinse cycle until the beginning and then to release them as soon as possible.

A disadvantage of the solution described in these Japanese patent applications is that the coated particles are in direct contact with non-alkaline wash water at the start of the washing cycle, which can result in the protective coating becoming detached.

From Japanese patent KOKAI 50-77406 a washing aid is known which is surrounded by a water-soluble coating which is obtained by mixing polyvinyl acetal dialkylaminoacetate and at least one organic acid which is solid at room temperature. This protective covering is intended to protect the washing aid during the main wash cycle and to release it during the rinse cycles. The described Binding reacts to the change in pH between the main wash cycle and the

Rinse cycles. The correspondingly coated particles are powdered with conventional

Detergent mixed. Here too there is the disadvantage of possible resolution of the

Protective cover at the beginning of the washing cycle.

From European patent applications EP 0 284 191 A2 and 0 284 334 A2 a water-soluble polymer film for releasing washing additives in the washing cycle of washing machines is known, which remains intact during the normal washing cycle over a range of typical temperatures and dissolves quickly in the washing cycle. The applications point out that although the use of pH-sensitive coatings is well known, these films are normally also temperature-sensitive, so that they are not reliably stable during different wash cycle temperatures. As a solution, it is proposed to combine a pH-dependent material (which undesirably also shows a positive temperature-dependent dissolution behavior) with a material which shows a negative temperature-dependent solution behavior. This combination is intended to guarantee that the coatings will not come off at the high temperatures at the beginning of the wash cycle (especially the very high temperatures that occur in American machines).

The European patent application EP 0 481 547 AI discloses multi-layer dishwasher tablets with a core, a separating layer surrounding the core and an outer layer for the sequential release of the ingredients of the different layers. Basically, two tasks are to be solved with this tablet, namely 1) incompatible materials can be formulated together in a single tablet and released at different times in order to avoid mutual interference; and 2) Compositions that are designed to perform their functions at different times can be formulated in a single tablet.

One of the disadvantages of the prior art described above is that the successive pressing of the individual steps is described as the only manufacturing method. As a result, there is a risk that the core and / or the casing of the core will be deformed, which on the one hand can lead to damage (and thus a reduction in the protective effect) of the casing of the core, and on the other hand (depending on the composition). of the core) to a "bleeding" of the core into the material of the casing and the base composition. In addition, the intimate full-surface contact between the individual layers can lead to undesirable reactions occurring in the boundary layers, especially between the casing and the basic composition.

The second major disadvantage of the prior art is that the temperature is used as a triggering factor for the initiation of the dissolution of the cladding layer, i.e. temperature-sensitive materials are used for the material of the casing. Since the temperature / time course in washing machines can vary greatly depending on the program selected, it would be difficult, if not impossible, to select a material for the wrapping that can be used for all possible programs in modern washing machines. EP 0 481 547 AI itself admits (page 7, lines 37-43) that the selection of the material of the cladding layer must take into account device-specific and program-specific features. The practical usability of the products described is therefore clearly limited. Use in washing machines is not mentioned in the document.

PCT application WO 95/29982 discloses a delayed-release dishwashing detergent in the form of a non-ionic surfactant, this non-ionic surfactant, together with an inorganic builder salt, forming a core particle which is provided with a wax-like coating to compensate for the delayed release Ensure release. This coating is a substance that does not melt at the working temperatures that can be found in the cleaning cycle, but is chemically disintegrated so gradually at alkaline pH that an effective amount of the rinse aid remains at the end of the main cleaning cycle and is transferred into the rinse cycle. Use in washing machines is not mentioned in the document.

A disadvantage of the solution presented in this document is that the coating is made soluble by chemical stranding at alkaline pHs, so that the time at which the rinse aid substance is released from the core is a function of both the temperature and the length of the main cleaning cycle . The patent application contains no teaching on how to formulate a product with which the rinse aid is used in all washing programs each device type is released in the rinse cycle. After all, the product is a mixture of granular detergent and granular rinse aid particles.

In view of the prior art, the present invention is based on the object of creating a generic composition which can be used for most washing programs of various types of washing machine equipment and in each of these cases the substance (s) which have their effect essentially only in the rinse cycles should unfold, only in these releases. The aim is to achieve this without largely restricting the selection for the detergent used, the substance (s) used for the rinse cycles and other ingredients of the composition.

According to the invention, this object is achieved with a generic composition which is characterized by a basic composition, which unfolds its function essentially in the main washing cycle of the washing machine, in the form of a tablet; and at least one particle, having at least one core, which comprises at least one substance which functions essentially in the rinse cycles of the washing machine, and an envelope, which completely surrounds the core (s) and comprises at least one compound, whose solubility increases with decreasing concentration of a specific ion in the surrounding medium; wherein the at least one particle is arranged in or on the tablet such that the surface of the particle (s) is at most partially in direct contact with the surface of the base composition surrounding it and the concentration of the specific ion in the local one The area around the particle (s) is sufficiently high to substantially completely dissolve the tablet to prevent substantial disintegration of the envelope or substantial detachment of the envelope from the core (s).

It is preferably provided that the or all of the particles is or are received in at least one cavity of the tablet which is completely surrounded by the base composition and which has a larger volume than the or all of the particles which is or are received in the respective cavity or are. In one alternative, the particle (s) can be loosely arranged in the interior of the cavity or, in another alternative, can be fixed. In the case of fixation in the interior of the cavity, this is preferably done using an adhesive.

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

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

In an alternative embodiment of the invention it can be provided that the or all of the particles are or are received in at least one cavity of the tablet which is only partially surrounded by the base composition.

The cavity is preferably a depression in one of the surfaces of the tablet in which the particle (s) is (are) at least partially received.

The particle (s) is (are) preferably received in the cavity or in the depression such that it (they) do not protrude above the surface (s) of the tablet.

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

In a particular embodiment, the invention proposes that the cavity or the depression only opens to the surface (s) to such an extent that the particle (s) accommodated therein does not pass through the opening (s) of the cavity or the depression can pass through. It is preferably provided that the particle (s) is (are) loosely arranged in the cavity or in the depression.

However, it can also be provided that the particle (s) is (are) fixed in the cavity or in the depression, this fixing preferably being carried out with an adhesive.

The invention preferably provides that the base composition comprises at least one composition selected from the group consisting of a detergent composition, a water softener composition and a washing enhancer composition.

The invention preferably provides that the covering comprises at least one compound which is insoluble or only slightly soluble at the concentration of the specific ion at the end of the main washing cycle of the washing machine and which is sufficiently soluble at the concentration of the specific ion in the rinse cycles that it is largely dissolved in the rinse cycles or detached from the core (from the cores) in such a way that an at least partial escape of the core material into the medium of the rinse cycles is made possible.

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

In a particularly preferred embodiment, the invention proposes that the compound shows no or only a low solubility at a pH above 10 and that it has sufficient solubility at a pH below 9 that it is largely dissolved in the rinse cycles or is detached from the core (s) so that an at least partial escape of the core material into the medium of the rinse cycles is made possible.

This compound preferably comprises a polymer, particularly preferably a pH-sensitive polymer which comprises at least one repeating unit which has 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 which is based on a compound which is selected from the group consisting of vinyl alcohol derivatives, acrylates or alkyl acrylates which comprise said basic function.

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

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

In an alternative, the repeating unit is based on a connection with the following formula:

where G is a linking group which is selected from -COO-, -OCO-, -CONH-, - NHCO -, - NHCONH -, - NHCOO -, -OCONH - or - OCOO -, Ri independently of one another hydrogen or an alkyl group with Is 1-3 carbon atoms, R _{2 is} independently hydrogen or an alkyl group of 1-5 carbon atoms and x is an integer from 1 to 6.

The repetition unit is preferably based on a compound with the following formula TV:

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

In a further embodiment of the invention it is provided 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 comprise K-carrageenan.

In one embodiment of the invention it is provided that the core (s) comprise (s) at least one material selected from the group consisting of fragrances, fabric softeners, antistatic agents, agents for restoring the ability of the laundry for moisture absorption, mild acids, bleaching agents, disinfectants, agents for the long-term protection of both the laundry and the person wearing the laundry from insects or mites, agents for improved removal of grease soiling, agents for providing anti-crease, optical brighteners, ironing aids, agents for There is inhibition of dye transfer and enzymes.

In an 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 some of the cores are 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 according to the invention is added to the medium in the washing machine at a suitable point in time during the prewash or main wash cycle.

In a special embodiment of this method it is provided that, in the event that the base composition in the form of the tablet is not able to provide a concentration of the specific ion in the medium after its dissolution in the medium until the end of the main wash cycle, which is sufficiently high to prevent substantial disintegration of the coating and substantial detachment of the coating from the core (s), this sufficient concentration of the specific ion by adding another composition, such as a detergent composition, to the medium of the main wash cycle is provided at a suitable time.

The composition according to the invention is characterized in that it delivers excellent results both in the main wash cycle and in the rinse cycles of a washing machine. The tablet is released during the main wash cycle and can develop its intended effect (cleaning, water softening, washing intensification, etc.). The particle arranged in or on the tablet contains, as the core material, that substance or substances which are intended to unfold their main function in the washing cycles of the washing machine. This substance (s) is (are) protected by a sheath which, at the ion concentration, e.g. the pH value and the temperature of the main wash cycle are stable and do not dissolve or dissolve only insignificantly.

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

Table 1

It is clear that a relatively high pH of 10.25 to 10.35 is present during the entire main wash cycle, which drops to a value of 8.50 by the fourth wash cycle. The solubility of the cladding material must therefore be reduced so much at pH values, preferably below 9, that it quickly dissolves or dissolves and the actually effective core material dissolves in the surrounding medium, i.e. the rinse water, releases.

Unless the metering is provided by means of special metering aids which can hold back the particles according to the invention, the particles according to the invention should be chosen so large that they are at least not discharged from the washing machine to a significant extent during the pumping out after the main wash cycle and the first rinse cycle . It is essential for the solution according to the invention that the surface of the particle is at most partially in direct contact with the surface of the basic composition of the tablet surrounding it. This can be done in the ways specifically described and illustrated in this application, but also in any other way with which the intended purpose is achieved. Examples are the loose arrangement of a smaller particle in a larger cavity and the fixing of a smaller particle in a larger cavity in such a way that there is no or only partial contact between the particle and the basic composition of the tablet, etc.

This constellation offers the advantage over the prior art that in the manufacturing process, e.g. the pressing of the individual components in successive steps, deformation and possibly consequent damage to the core (the cores) and / or the covering, which could reduce the protective effect of the covering of the core (the cores), can be reliably avoided. By preventing pressure on the particle at any stage in the manufacturing process, it can also be reliably prevented from "bleeding" into the material of the cladding and the outer layer at a given composition of the core (s) is coming. Finally, it can be advantageous to avoid intimate full-surface contact with certain compositions of the covering or the base composition, since otherwise undesirable reactions could occur in the boundary layers.

The term “local environment”, as used in connection with the particle according to the invention, is intended to denote the immediate environment around this particle. The ion concentration in this local environment of the particle is the determining factor for its stability Ion concentration in this local environment is determined at least until the tablet dissolves essentially completely by ions dissolving from it. The origin of the "specific ion" is therefore - at least in the initial phase of the main wash cycle - a compound of the basic composition or tablet forming the tablet is generated by this in the surrounding medium. In the most typical case it is thereby in the case of the usual basic detergents around OH ^" ions, the concentration of which can be expressed as pH.

Unless a (e.g. basic) detergent composition is used as the base composition, but e.g. a water softener composition or washing booster composition, the protection of the coating of the particle by a sufficiently high ion concentration in the local environment of the particle may only be ensured until the tablet is completely dissolved, namely in cases where the basic composition of the tablet is not sufficient for this It is able to provide a sufficiently high concentration of ions in the wash liquor. In these cases, the sufficiently high ion concentration in the wash liquor and thus also in the local environment of the particle (s) is achieved by dissolving the actual detergent (or another special additive).

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

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

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;

4a and b show 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.

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

Fig. 1 shows a tablet 1, which consists of two half-tablets 2 and 3, which may have different or the same composition A roughly hemispherical recess 4 or 5 can be seen approximately in the center of both half-tablets, which, when the tablet 1 is assembled, together has an approximately spherical one

Reveal cavity.

In the illustrated embodiment, a single particle 6, consisting of the core 8 and the coating 9 sensitive to pH or ion concentration, is accommodated in this cavity, the outer diameter of which is slightly smaller than the inner diameter of the

Cavity in the tablet. Both in the illustrated embodiment, in which the particle is loosely received in the cavity, and in an embodiment, where it is fixed by an adhesive provided in the intermediate space, it is ensured that there is no continuous, full-surface contact between the tablet material and the coating of the particle . This is an essential aspect of the present invention, on the one hand to prevent the protective covering around the core of the particle from being damaged during the manufacturing process, and on the other hand to minimize possible interactions between the tablet material and the mentioned covering, both with the aim of to keep the coating stable up to the rinse cycles.

Of course, not only a conventional adhesive can be used to fix the particle in the cavity, but also other compositions and agents that serve the same purpose, for example mechanical fixation, such as e.g. sufficient friction between the tablet and particles in at least some places or a plug connection between the tablet and particles. In addition, other compounds which preferably melt or dissolve during the main wash cycle are also possible as fixing agents between the particle and the tablet.

Of course, various other geometric shapes are possible for the design of the cavity in the tablet or the particle accommodated therein, such as, for example, ellipsoid, cylinder, etc. The shape and size of the cavity in the tablet and that of the particle accommodated therein do not have to be correspond with each other. For example, a cylindrical particle can be accommodated in a spherical cavity. All other possible combinations are within the present invention conceivable. It is also possible not to use only one cavity

Particles, but to fill with several smaller particles.

FIG. 2 shows a second embodiment of the composition according to the invention on the basis of a conventional 2-layer tablet 1. In this case, the upper half-tablet 3 consists of two parts which both provide a sufficient cavity 5 for receiving the particle 6 and an opening to the side 11 of the tablet. In this case, the particle 6 is therefore 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. In this case, too, the particle in the cavity 5 can either be loosely received (provided that 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 it is ensured that the particle or particles in the cavity do not pass through the opening can pass through) or be fixed in the interior of the cavity 5 by appropriate means, such as, for example, glue.

A third possible embodiment results from FIG. 3. The basis is again a two-layer tablet. A recess 4 is formed in the upper layer 2 by means of a suitable device. In this recess 4, the particle 6 is introduced, which in this case, since the recess on the side 11 of the tablet 1 is open to the extent that it would be possible for the particle to fall out of the recess without fixation, for example with an adhesive 10 or fixing intermediate layer or mechanically (for example by friction) in the recess. Of course, this principle can also be applied to single-layer tablets.

In this case too, a wide variety of geometric embodiments are possible. For example, the depression can have a substantially circular cross section parallel to side 11. However, any number of other cross sections is also conceivable, for example any polygon. As in the embodiment according to FIG. 2, the particle 6 accommodated in the depression 4 can assume any shape (such as ellipsoid, cylinder, cuboid, etc.) (and is independent of the shape of the depression 4). It can also be considered to fix the particle 6 'in a cavity open on both sides in the tablet, such as, for example, in a cylindrical hole 4' passing through a tablet body 1 'consisting of a layer 2', in which a corresponding hole cylindrical particle 6 'is fixed (Fig. 4a and b).

A further possible embodiment results from FIG. 5. This is essentially constructed in the same way as the embodiment according to FIG Cores 8 "which are embedded overall in a casing 9". In this embodiment it is also possible, for example, to incorporate cores of different composition and different shape (encapsulated material or solid cores) into a particle 6 ".

Both in the illustrated embodiments and in other conceivable alternatives, it is essential that for the particles containing the substance (s) to be released in the rinse cycles, at least in the first phase of the main wash cycle, there is a local environment with sufficient ion concentration or pH value , which serves as a "trigger" for the dissolution of the envelope, ie in a phase in which the detergent composition has not yet been sufficiently dissolved, i.e. the pH is still relatively low, i.e. briefly in an area in which there would be an increased solubility of the coating. This ensures that the casing has sufficient stability up to the rinse cycles.

example 1

Manufacture of the core

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

The release of an acid in the washing cycles of a washing machine is intended both to remove incrustations and to neutralize alkaline residues. Weak acids, such as amidosulfonic acid and / or maleic acid, are advantageously used for this purpose. These materials are usually Solids that can be provided directly with the intended coating, the coating process possibly having to be based on the corresponding substance (s).

The manufacturing process is as follows:

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

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

Taking into account similar considerations as in example la, a corresponding core is produced as follows:

0.1975 g of fragrance is absorbed onto 0.0525 g of finely divided silica to give a free-flowing granular material. The resulting 0.25 g is mixed with 0.6 g of microcrystalline cellulose and 0.15 g of cross-linked polyvinylpyrrolidone. The mixture is tableted in a round press with an inner diameter of 10 mm under a pressure of 2900 kg / cm ² to give an elliptical tablet with a height of 13.1 mm and a weight of approx. 1 g.

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

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

The use of chlorine bleach in the washing cycle of a washing machine improves the cleaning effect and at the same time has an additional disinfecting effect.

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

d. Core for a particle for the controlled release of tissue conditioning activity in the rinse cycle

In the present example, the core comprises several substances which are intended to develop their respective effects in the washing cycle of a washing machine. In the specific case, it is a combination of a fabric softener, an agent for reducing the build-up of static electricity in the fabric and an agent for improving the re-absorption of moisture by the fabric.

A slurry of 58% urea, 18% dimethyldistearylammonium chloride (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 with a density of 580 g / l and the following composition: 68.8% by weight urea, 19.2% by weight DMDSAC, 9.5% by weight not -ionic 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 round press with an inner diameter of 25 mm and a pressure of 80 kg / cm ² to obtain an elliptical tablet with a height of 14 mm and a weight of 5 g.

Example 2

Screening process for wrapping materials

As stated above, it is essential for the present invention that the material for the sheath of the particle core (s) comprising the substance (s) which function essentially in the rinse cycle shows solubility , which depends on the concentration of a specific ion selected. In this way, the cover in the main wash cycle is essentially insoluble and becomes soluble made and detaches from the particle when the ion concentration drops during the rinse cycles.

It has been observed that the dilution due to the pumping out of the wash liquor and the inflow of fresh water which occurs in the course of the various rinse cycles causes the ion concentration to drop 20 to 200 times between the end of the main wash cycle and the last rinse cycle .

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

The ion concentration values that should be used in the screening of the polymers depend on the formulation of the base composition of the tablet into which the coated particle is to be incorporated.

In fact, the highest ion concentration used for the screening process should correspond to the concentration of the selected ion that is found in the wash liquor after the detergent has completely dissolved. Once this concentration is determined, the lower value for the ion concentration should be set 20 to 200 times below this higher value.

With this information, it is within the average skill and knowledge of a person skilled in the art to determine the ion concentration values of the test solutions that should be used in the test procedures described below.

Procedure for preparing the test solution and for performing and evaluating the tests

The materials to be examined are dissolved in solvents in which they are easily soluble. The solutions are distributed on glass plates and then dried at room temperature until they have a constant weight. The glass plates are placed in a beaker with test solution at a controlled temperature. The solution is then stirred with a magnetic stirrer at a controlled stirring speed. After about 10 minutes, the glass plates are removed from the beaker and dried to constant weight at room temperature. The results are expressed as weight loss [%].

Of course, the screening methods must be adapted to the composition of the detergent, since this has the essential influence on the ion concentration or pH profile in the wash cycle. In any case, the aim is to check the degree of solubility of the corresponding materials under different conditions, namely high or low ion concentration or pH.

With these specifications, it is only within the skill of a person skilled in the art to set up special test parameters for the screening. Two screening methods are shown as examples below, with which some of the possible materials for the coating of the particles were tested.

Screening procedure 1:

Screening method 1 was carried out using buffer solutions as the medium for the simulation of the wash liquor. For this purpose, two buffer solutions were prepared as follows:

Stock solution: 7.507 g glycine buffer (Merck 104169)

5.850 g NaCl made up to 1000 ml with water

pH 8 buffer solution: 500 ml stock solution 500 ml dist. H ₂ O 1, 23 gl N NaOH

pH 10 buffer solution: 500 ml stock solution 500 ml dist. H ₂ O 32.6 g 1N NaOH. Screening procedure 2:

Screening Procedure 2 was performed on the following detergent formulation to simulate the conditions in different stages of a wash cycle.

Detergent formulation:

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

Table 2

Ingredient weight%

Sodium carbonate 7.43

Sodium LAS 40.0

Zeolite 17.70

Polymer 7.0

Sodium sulfate 9.61

Sodium silicate 7.00

Soap 4.0

Phosphonate 1.55

Carboxymethyl cellulose 1.01

Water and Others 4.7

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

Ingredient weight%

spray dried

Base material 22.6

Sodium percarbonate 20.0

Sodium carbonate 19.58

Sodium tripolyphosphate 17.42 microcrystalline cellulose 6.0

Alkyl sulfate 6.0

Polymer 1.50 cross-linked polyvinylpyrrolidone 1.80

Enzymes 1.78

TAED 1.00

Polyethylene glycol 0, 18

Water and Others 2.14

Screening procedure 3:

Screening method 3 is used to screen for compounds whose solubility changes depending on the concentration of potassium ions. The compounds determined using such screening methods can be used if, as described above, there is a correspondingly high concentration of potassium ions in the main wash cycle, which is correspondingly reduced by dilution in the rinse cycles.

The screening method 3 was carried out with the following formulation in order to simulate corresponding conditions. Formulation:

Example 3

Selection of materials for the coating of the particles

Using the screening methods described in Example 2, various materials were examined for their suitability as a coating for the particles according to the present invention. One of these materials, hereinafter referred to as "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 prepared in the customary manner by bulk polymerization. The results of the screening tests were as follows:

Screening procedure 1:

Polymer 1 films were made from a 10% solution in isopropanol.

Screening procedure 2 gave similar results.

The invention is of course not limited to this exemplary polymer, although there is of course already a large variation possibility with regard to the polymers mentioned in Japanese patent applications KOKAI 60-141705, 61-28440, 61-28441, 61-28596, 61-28597 and 61-28597 or can be extended to compounds of the formula TV:

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

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

for example a pH-sensitive polymer (“polymer 2”) with the repeating unit VI, which is commercially available from the company SANKYO under the brand name AEA®,

The screening method 2 described above was also carried out with “Polymer 2”: 15 g "Polymer 2" and 5 g Mowiol® 3-98 (Clariant) were dissolved in 200 ml of a mixture of water / ethanol / IN HC1 12: 8: 1. Films were formed and tested as described above. The results were comparable to those for "Polymer 1".

Other polymers which show the desired properties or can be modified in a simple manner so 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 represents a substituent at any point on the pyridine ring.

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

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

Other polymers are (e.g. statistical) polymers derived from chitosan based on the following monomer units IX and X

In addition, it is also possible to use substances or substance mixtures in the coating of the core material which react with regard to their solubility behavior to a change in the ion concentration, ie polymers which are sensitive to ion concentration. For this purpose, for example, the partially hydrolyzed polyvinyl acetates described in the publications EP 0 284 191 A2 and EP 0 284 334 A2 (commercially available under the brand name Mowiol® (Clariant)) come into consideration, which are due to the presence of borates the complexation of the borates with polyols shows a corresponding ion concentration dependence. The first successful tests were carried out with the Mowiol® 56-88 product

Another ion concentration-sensitive polymer is the polysaccharide K-carrageenan, which has been found in screening method 3 (see example 2) to be a polymer which is dependent on the potassium ion concentration in the surrounding medium in terms of its solubility. K-Carrageenan is represented by the following formula XI:

This polymer, designated "Polymer 4", was tested according to screening method 3 described above:

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

The above list of compounds which are suitable for the wrapping according to the invention is of course not exhaustive. Other polymers which change their solubility by changing the pH or the ion concentration in the desired range are conceivable or can be developed and are therefore within the scope of the present invention. Furthermore, the substances suitable for the coating according to the invention are not restricted to polymeric compounds, although such compounds are described here as preferred embodiments.

With the aid of the screening methods or screening methods specified above, which are adapted to the measurement of an ion concentration sensitivity, various other commercially available materials or materials which can be obtained by simple modifications can be examined for their suitability in the present invention. The selection of such polymers is a task which the average person skilled in the art can solve without difficulty, given the correspondingly clear target and the specified screening method.

Example 4

Production of a particle according to the invention

The different cores described in Example 1 were used as the basis for the production of particles according to the invention. These cores were provided individually or in groups (FIG. 5) with a covering in a device for applying a film coating, as is known from the pharmaceutical industry (for example from the companies Loedige, Huettlin, GS, Manesty and Driam).

In the event that the core (s) has an ingredient that shows a certain incompatibility with the material of the covering, the core (s) can (s) first apply a coating before applying this covering Protective cover can be provided. Various materials known from the prior art can be considered for this, such as, for example, cellulose, cellulose derivatives, polyvinyl alcohol, polyvinyl alcohol derivatives and mixtures thereof. When using the cores from Example 1, such a protective coating was used in cases 1a, 1b and 1c, a 10% strength by weight aqueous solution of the polyvinyl alcohol Mowiol® 5-88 (Clariant) being used here. In the case of example Ia, the core was coated with 0.76 g of such a solution, in the case of Example 1b, 0.40 g of the same solution was used and in the case of Example 1c, 0.29 g of the same solution was used.

The covering can in principle be applied to the core (s) or the protective coating in any quantity and thickness, as long as it is ensured that the covering detaches or dissolves quickly enough in the rinsing cycles so that the core (in the substance (s) contained in the kernels can have their effect (s). In a preferred embodiment, 1-10% by weight, preferably 4-8% by weight, of the coating material (dry mass) sensitive to ion concentration, based on the mass of the entire particle, is applied to the cores.

The particles according to the invention should preferably have a size such that they are not, or at least not to a considerable extent, removed from the washing machine by the pumping-down processes after the main wash cycle or the individual rinse cycles. A size of approximately 1 cm in diameter is usually sufficient for this. Smaller or larger dimensions can of course be chosen as long as the functionality is guaranteed overall.

"Polymer 1" from Example 3 was used as the coating for the further tests and applied as a 10% strength solution of the polymer in 0.055 N aqueous HC1.

Example 5

Production of a tablet with particles according to the invention

The production of tablets with the structure according to the invention is described below by way of example. Tablets of this type can be produced by pressing the pulverulent ingredients in machines which are known in principle from the prior art and using operating parameters which are fundamentally known from the prior art. The composition of such tablets is based on commercially available products.

A detergent tablet, a water softener tablet and a washing intensifier tablet are described below by way of example.

Detergent tablet

The composition for a detergent tablet can be mixed, for example, on the basis of a detergent formulation as shown in Example 2, Tables 2 and 3. The resulting granular composition has a bulk density of approximately 690 g / l and can be tabletted in an appropriate compression under a pressure of 21 kg / cm to give a half-tablet, with a weight, of approximately 20 g.

One of the particles according to the invention produced according to Examples 1 and 4 is placed in the recess of the half-tablet. Then a fixing substance, e.g. an adhesive (for example, polyethylene glycol, polyvinyl ether, polyvinyl alcohol, silicate, preferably melted PEG 4000) is applied to the corresponding surface of the half tablet and, if appropriate, also to the particle, and the second half tablet is pressed onto the first half tablet with particles according to the invention. In this way, a detergent tablet with a current commercial weight of approx. 40 g is produced.

Water softener tablet

The following ingredients were mixed:

Table 4

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

The completion according to the particle according to the invention and the assembly of the half tablets takes place as previously described for the detergent tablet.

Washing intensifier tablet

Using the known technology for producing a two-layer tablet, a washing intensifier tablet is produced, the layers of different weights (26/74) having a different composition according to the following table: Table 5

As shown in FIG. 3, a depression is formed in the upper layer, into which first adhesive or the like and then the particle according to the invention is added.

The features of the invention disclosed in the above description, the claims and the drawings can be essential both individually and in any combination for realizing the invention in its various embodiments.

Claims

Expectations

1. Composition for use in a washing machine, characterized by

a basic composition (2, 3; 2 '), which unfolds its function essentially in the main washing 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 "), which comprises at least one substance that functions essentially in the rinse cycles of the washing machine, and

- a sheath (9; 9 '; 9 ") which substantially completely surrounds the core (s) and which comprises at least one compound whose solubility increases with decreasing concentration of a specific ion in the surrounding medium;

wherein the at least one particle (6; 6 '; 6 ") is arranged in or on the tablet (1; 1') such that the surface of the particle (s) (6; 6 '; 6") at most partly in direct contact with the surface of the base composition (2, 3; 2 ') surrounding it and the concentration of the specific ion in the local environment of the particle (s) until the tablet is essentially completely dissolved ( 1; 1 ') is sufficiently high to prevent a substantial dissolution of the covering or a substantial detachment of the covering from the core (from the cores).

Composition according to Claim 1, characterized in that the or all particles (6) are or are received in at least one cavity (4,5) of the tablet (1) which is completely surrounded by the base composition (2,3) and which is a larger one Has volume than the or all particles (6) which is or are received in the respective cavity.

3. Composition according to claim 2, characterized in that the (the) particle (6) inside the cavity (4,5) is loosely arranged (are).

4. Composition according to claim 2, characterized in that the (the) particles (6) in the interior of the cavity (4,5) is (are) fixed.

5. Composition according to claim 4, characterized in that the (the) particles (6) in the interior of the cavity (4,5) is (are) fixed by an adhesive.

*

6. Composition according to one of claims 2 to 5, characterized in that the cavity (4, 5) is arranged substantially centrally in the interior of the tablet (1).

7. Composition according to one of claims 2 to 6, characterized in that the tablet (1) has a single, substantially spherical cavity (4, 5).

8. The composition according to claim 7, characterized in that in the cavity (4, 5) a single, substantially spherical particle (6) is received, the outer diameter of which is smaller than the inner diameter of the cavity.

9. The composition according to claim 1, characterized in that the or all particles (6 '; 6 ") is or are received in at least one cavity (4') of the tablet (1 '), which is only partially from the basic composition ( 2 ') is surrounded.

10. The composition according to claim 9, characterized in that the cavity is a

Indentation (4 ^' ) in one of the surfaces (IT) of the tablet (1') in which the particle (s) (6 '; 6 ") is (are) at least partially received.

11. The composition according to claim 9 or 10, characterized in that the particle (s) (6 ^' ; 6 ") is (are) received in the cavity or in the recess (4') in such a way that it does not have the surface (s) (11 ') of the tablet (1') protrude (protrude).

12. The composition according to any one of claims 9 to 11, characterized in that the cavity or the recess (4 ') parallel to one of the surfaces (IT) to which it opens or in which it is arranged, a substantially circular Has cross-sectional area.

13. Composition according to one of claims 9 to 12, characterized in that the cavity or the recess (4 ') opens to the surface (s) (IT) only to such an extent that the (s) accommodated therein ) Particles (6 '; 6 ") cannot (can) pass through the opening (s) of the cavity or of the depression (4').

14. The composition according to claim 13, characterized in that the (the) particle (6 '; 6 ") in the cavity or in the recess (4') is loosely arranged.

15. Composition according to one of claims 9 to 13, characterized in that the particle (s) (6 '; 6 ") is (are) fixed in the cavity or in the recess (4').

16. The composition according to claim 15, characterized in that the (the) particle (6 '; 6 ") in the cavity or in the recess (4') with an adhesive (10 ') is (are) fixed.

17. The composition according to any one of the preceding claims, characterized in that the base composition (2,3; 2 ') comprises at least one composition which is selected from the group consisting of a detergent composition, a water softener composition and a washing enhancer composition.

18. Composition according to one of the preceding claims, characterized in that the covering (9; 9 '; 9 ") comprises at least one compound which is not or only slightly soluble at the concentration of the specific ion at the end of the main washing cycle of the washing machine and at The concentration of the specific ion in the rinse cycles shows such a sufficient solubility that it is so largely dissolved in the rinse cycles or detached from the core (s) that an at least partial leakage of the core material into the medium of the rinse cycles is made possible.

19. The composition according to claim 18, characterized in that the solubility of the compound increases with falling OH ^' ion concentration and thus decreasing pH in the surrounding medium.

20. The composition according to claim 19, characterized in that the compound shows no or only a low solubility at a pH above 10 and shows a sufficient solubility at a pH below 9 that it is so largely dissolved in the rinse cycles or is detached from the core (s) so that an at least partial escape of the core material into the medium of the rinse cycles is made possible.

21. The composition according to any one of claims 18 to 20, characterized in that the compound comprises a polymer.

22. The composition according to claim 21, characterized in that the compound comprises a pH-sensitive polymer which comprises at least one repeating unit which has at least one basic function which is not part of the backbone chain of the polymer.

23. The composition according to claim 22, characterized in that the polymer comprises at least one repeating unit based on a compound selected from the group consisting of vinyl alcohol derivatives, acrylates or alkyl acrylates, which comprise said basic function.

24. The composition according to claim 22, characterized in that the polymer is a carbohydrate which is functionalized with said basic function.

25. Composition according to one of claims 22 to 24, characterized in that the basic function is an amine.

26. The composition according to claim 25, characterized in that the basic function is a secondary or tertiary amine.

27. The composition according to claim 26, characterized in that the repeating unit is based on a compound having the following formula III:

28. The composition according to claim 27, characterized in that the repeating unit is based on a compound having the following formula IV:

wherein Ri is independently hydrogen or an alkyl group with 1-3 carbon atoms, R _{2 is} independently hydrogen or an alkyl group with 1-5 carbon atoms and x is an integer from 1 to 6.

29. The composition according to any one of claims 22 to 24, characterized in that the basic function is an imine.

30. The composition according to any one of claims 22 to 24, characterized in that the basic function is a basic aromatic N-containing group.

31. The composition according to claim 30, characterized in that the basic function is a pyridine group.

32. Composition according to claim 30, characterized in that basic function is an imidazole group.

33. Composition according to claim 24, characterized in that the pH-sensitive polymer is a polymer derived from chitosan.

34. Composition according to claim 18, characterized in that the compound comprises K-carrageenan.

35. Composition according to one of the preceding claims, characterized in that the core (s) comprises (s) at least one material selected from the group consisting of fragrances, fabric softeners, antistatic agents, agents for restoring the ability of the laundry to absorb moisture, mild acids, bleaches, disinfectants, agents for the long-term protection of both the laundry and the person wearing the laundry against insects and mites, agents for improved removal of grease soiling, means to provide anti-crease, optical brighteners, ironing aids, means to inhibit dye transfer and enzymes.

36. Composition according to claim 35, characterized in that the core (8; 8 ') or at least part of the cores (8 ") is in the form of an encapsulated liquid.

37. Composition according to claim 35, characterized in that the core (8; 8 ') or at least part of the cores (8 ") is in a solid form.

38. A method for carrying out a washing cycle in a washing machine, characterized in that a composition according to one of claims 1 to 37 is added to the medium in the washing machine at a suitable time during the prewash or main wash cycle.

39. The method according to claim 38, characterized in that, in the event that the base composition in the form of the tablet is not able to provide a concentration of the specific ion in the medium after its dissolution in the medium until the end of the main wash cycle sufficiently high to prevent substantial disintegration of the cladding and substantial detachment of the cladding from the core (s), this sufficient concentration of the specific ion by the addition of another composition, such as a detergent composition, to the medium of the main wash cycle is provided at an appropriate time.