DE29917230U1 - Dispensing device for a detergent tablet - Google Patents

Description

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Dispensing device for a detergent tablet Jacky Pierre DUQUET Technical area

The present invention relates to devices for dispensing a detergent composition in tablet form.

Background of the invention

Tablets are used particularly in the field of machine dishwashing or the field of machine washing of laundry to facilitate the handling of a detergent composition compared to alternative forms such as powder, granules, liquids or a paste. However, in order to maintain the dispersion characteristics of a detergent composition in tablet form when compared to the above-mentioned alternative forms, it is preferred to use a special device for dispensing the detergent composition in tablet form.

It is known, for example, from WO 98/40550 to use a dispensing device for a detergent tablet, the device being at least partially formed from a flexible, water-permeable material, the device comprising at least one wall, and the wall comprising an opening for inserting the tablet.

Among the advantages of detergent tablet dispersing devices is their ability to improve the dispersion properties of the tablet, which may result from an increase in mechanical disintegration.

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While having these and other advantages, devices for dispersing a detergent tablet have disadvantages. For example, such devices typically include closure means to prevent the tablet from escaping from the device during the wash, such closure means making the device more complex to manufacture and more difficult to use.

The invention aims to provide a device of the above-mentioned type which makes it possible to prevent the tablet from escaping from the device during washing and which is less complex to manufacture and easier to use.

Summary of the invention

According to the invention, this object is achieved with a device of the aforementioned type, characterized in that the device further comprises a flap, the flap being folded over the opening and the flap remaining folded over the opening.

A device formed in accordance with the invention has a number of advantages. Since the flap is folded over the opening and is retained, the tablet can remain in the device during washing. This simple arrangement eliminates the need to attach complex closure means to the device.

Detailed description of the invention

The invention relates to a dispensing device for a detergent tablet. By dispensing device should be understood a device which is used to dispense the tablet in an aqueous solution, the dispensing being normally facilitated by the use of the dispensing device. Dispensing devices already exist for detergent powder, as proposed for example in EP-A-343069 or EP-A-343070. Dispensing devices

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There are also similar devices for liquid cleaning agents, as proposed for example in FR-A-2563250. Depending on the form of the cleaning agent, the dispensing devices have different special features.
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The dispensing device according to the invention relates to a detergent tablet. A detergent tablet is typically obtained by compressing a detergent powder. A detergent tablet may or may not be coated and may have one or more layers. Detergent tablets are currently sold. Typical detergent tablets are described, for example, in EP-A-846755.

The device according to the invention is at least partially formed of a flexible, water-permeable material. By flexible should be understood that the material is not rigid. Typically, a material is considered flexible if it collapses when subjected to its own weight. Such a property of the material normally leads to an improved disintegration of the tablet due to the mechanical crushing effect exerted by the deformation of the flexible material during a normal wash, such deformation being due, for example, to collisions between the device and the laundry to be washed, or to collisions between the device and a wall of a washing machine. Typical flexible materials include, for example, synthetic polymeric (nylon, polyolefin) materials or vegetable (cotton, cellulosic) materials. The flexible material is also water-permeable. By this should be understood that liquid water is not prevented from flowing through the material. This property allows to facilitate the dispersion of a tablet by allowing the inflow or outflow of the aqueous medium in which the tablet is dispersed.

Tablet dispersion is used here as a general description,

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which includes equivalent expressions such as tablet disintegration or tablet dissolution.

The device comprises at least one wall. In fact, the device comprises a part typically in the form of a pocket, the pocket being suitable for receiving one or more detergent tablets. The device comprises at least one wall, but may also comprise more than one wall, for example to be more robust. The wall comprises an opening for inserting the tablet. By "opening for inserting the tablet" is meant an opening having dimensions that allow a tablet to be inserted without entailing permanent deformation of the device.

It is preferred that the device comprises only one opening for insertion of the tablet. It is to be noted that this preferred device may also comprise further openings, such further openings typically being smaller than the opening for insertion of the tablet, so that the other openings are not openings as far as the tablet itself is concerned.

The device according to the invention further comprises a flap. By flap should be understood a flat part which is hinged on another part of the device. The flap is folded over the opening so that it covers the opening in its missing position. This means that the part of the wall of the device which directly surrounds the opening is covered by an extra wall which is formed by the flap. Furthermore, the flap remains folded over the opening. In this way, the flap is designed so that the opening remains substantially closed by the flap and thus prevents a tablet located in the device from escaping from the device through the opening.

The flap can remain permanently folded over the opening, for example

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by means of a thread or by welding or sealing. By permanently remaining should be understood that the flap cannot be removed from the retained position without significant effort (e.g. unstitching the thread). Further preferably the flap remains folded in such a way that a tablet can be inserted under the flap while the flap remains folded over the opening. This can be achieved, for example, by stringing the flap onto the opening except along a length, this string-free length forming an opening opposite the area covered by the flap and enabling insertion of the tablet into the area covered by the flap. In such a case it is preferred that the opening opposite the area covered by the flap is not located directly above the opening in the wall of the device so that the flap still covers the opening in the wall of the device and thus operates according to the invention.

The flap may alternatively be left removably folded over the opening. In this case, a tablet may be inserted into the area covered by the flap by lifting the flap, after which the flap is re-fixed to remain folded over the opening. Such removability may be achieved, for example, by using a button arrangement.

In a preferred embodiment, the device is formed by folding a single piece of the flexible material. This enables the manufacture of a device according to the invention by means of a simple process.

In a preferred embodiment, the flexible, water-permeable material is a mesh material. Such a material can be, for example, woven, extruded or non-woven. Preferably, the material should be resistant to the high temperature of machine washing, to detergent compositions and to use through multiple cycles. Furthermore, it is preferred that the material does not

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is rasive to avoid damaging textiles.

In a preferred embodiment, the device is formed in part from a flexible, water-impermeable material. A water-permeable material is impermeable to screens, so that liquid water cannot pass through such a material. The presence of such impermeable to screens material enables the passage of even the smallest solid particles which may be separated from the tablet by, for example, friction to be prevented. Therefore, when a user grips such a device by placing the fingers on the impermeable to screens material, contact between such solid particles or even direct skin contact with the tablet is avoided.

In a further preferred embodiment, the device has a part opposite the opening, the part opposite the opening being made of the flexible, water-impermeable material. A part opposite the opening should be understood to mean a part which is located at the bottom of the device when the opening is at the top of the device. It is preferred that the part opposite the opening is made of the flexible, water-impermeable material in order to prevent minute solid particles which can be separated from the tablet, for example by friction, from being sieved through and deposited on a support for the device before the device is inserted into a washing machine. Indeed, a user will typically place the empty device on a support surface, with the part opposite the opening in contact with the support surface, and insert a tablet into the device through the opening, which tablet may be inserted together with solid particles which may be separated from the tablet, for example by friction, such solid particles being prevented from contaminating the support surface by means of the impermeable material forming the part opposite the opening.

* &iacgr;&iacgr;&zgr; I * * i.i»

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In a further preferred embodiment, the part of the device formed of flexible, water-impermeable material is in the form of a band. Typically, such a band is arranged around the device to enable the potential user to place his fingers on the band when holding the device and thus in particular to minimise potential direct skin contact with the detergent tablet.

The device is formed at least partially from a flexible, water-permeable material and also partially from a flexible, water-impermeable material. In essence, the device is preferably formed entirely from the addition of the flexible, water-permeable material and the flexible, water-impermeable material, although it may additionally comprise optional elements such as closure means or structural means. The flexible material forming the device has a total surface area. The total surface area of the flexible material is preferably formed from more than 50% of the permeable material and less than 50% of the impermeable material. More preferably, the total surface area of the flexible material is formed from more than 60% of the permeable material and less than 40% of the impermeable material. Still more preferably, the total surface area of the flexible material is formed from more than 75% of the permeable material and less than 25% of the impermeable material. Most preferably, the total surface area of the flexible material is made up of more than 90% of the permeable material and less than 10% of the impermeable material. Furthermore, the flexible impermeable material should preferably cover a surface area of at least half the total external surface area of a laundry detergent tablet. Typically, the flexible impermeable material should have a surface area of at least 10 cm^, more preferably at least 15 cm^, even more preferably at least 20 cm^, and most preferably at least 30 cm^.

The invention is applicable to a method for dispersing a

··

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Detergent tablet in an aqueous solution in a washing machine, comprising a first step of providing a detergent tablet and a device according to the invention, a second step of inserting the tablet into the device, and a third step of inserting the device containing the tablet into the washing machine.

The invention is particularly advantageous with a tablet having a tensile strength of at least 30 kPa. Indeed, it has been found that a tablet having a high tensile strength requires improved dispersion by means of an apparatus compared to a tablet having a low tensile strength. More preferably, the invention is applied to a tablet having a tensile strength of at least 40 kPa, even more preferably of at least 50 kPa.

It should be noted that the method is preferable when two or more tablets are inserted into the device. In fact, inserting more than one tablet may increase the disintegration due to mechanical friction between the different tablets.

Furthermore, for an equivalent total amount of product, the surface activity of two tablets is normally higher than the surface activity of just one tablet.

The invention also relates to a kit comprising a device according to the invention and further comprising a plurality of detergent tablets, the device and the plurality of detergent tablets being provided in a package. Typically the package is a cardboard box, the cardboard box containing the detergent tablets which may be contained in secondary packaging such as flow wraps, the device preferably being collapsible and arranged at the top of the box.

Specific information about detergent tablets is provided in the following paragraphs.

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The tablets may comprise components such as perfume, surfactants, enzymes, detergent, etc. Typical tablet compositions for the preferred embodiment of the present invention are described, for example, in the applicant's copending European applications 96 203 471.6, 96 203 462.5, 96 203 473.2 and 96 203 464.1. Elements which typically find their way into the composition of detergent tablets or other forms of detergents such as liquids or granules are explained in more detail in the following paragraphs.
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Highly soluble compounds

The tablet may contain a highly soluble compound. Such a compound could be formed from a mixture or from a single compound. A highly soluble compound is defined as follows:

A solution is prepared as follows, comprising deionized water and 20 grams per liter of a specific compound:
1. 20 g of the specific compound are placed in a Sotax beaker. This beaker is placed in a constant temperature bath set at 10°C. A stirrer with a ship's propeller is inserted into the beaker so that the bottom of the stirrer is 5 mm above the bottom of the Sotax beaker. The mixer is set to a rotation speed of 200 revolutions per minute.

2. 980 g of deionized water are added to the Sotax beaker.

3. 10 s after the addition of water, the conductivity of the solution is measured using a conductivity meter.

4. Step 3 is repeated 20 s, 30 s, 40 s, 50 s, 1 min, 2 min, 5 min and 10 min after step 2.

5. The measurement taken at 10 min is used as the plateau value or maximum value.

The specific compound is highly soluble according to the invention if the conductivity of the solution reaches 80% of its maximum value in less than 10

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seconds, starting from the complete addition of the deionized water to the compound. When the conductivity is actually recorded in this manner, the conductivity reaches a plateau after a certain period of time, which plateau is considered to be the maximum value. Such a compound is preferably in the form of a flowable material consisting of solid particles at temperatures between 10 and 80 ⁰ C for ease of handling, but other forms may be used, such as a paste or a liquid.
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Examples of highly soluble compounds include sodium diisoalkylbenzenesulfonate (DIBS) or sodium toluenesulfonate.

Cohesion effect

The tablet may comprise a compound which exerts a cohesive effect on the particulate material of a detergent matrix forming the tablet. The cohesive effect on the particulate material of a detergent matrix forming the tablet or a layer of the tablet is characterized by the force required to break the tablet or layer apart when the detergent matrix being tested is compressed under controlled compression conditions. For a given compression force, a high tablet or layer strength indicates that the granules adhere strongly to one another when compressed so that a strong cohesive effect takes place. Means of assessing tablet or layer strength (also referred to as diametral fracture stress) are given in Pharmaceutical Dosage Forms: Tablets, Volume 1, Ed. H.A. Lieberman et al, published in 1989. The cohesive effect is measured by comparing the tablet or layer strength of the original base powder without any cohesive compound with the tablet or layer strength of a powder mixture comprising 97 parts of the original base powder and 3 parts of the cohesive compound. The cohesive compound is preferably added to the matrix in a form

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in which it is essentially anhydrous (water content below 10% (preferably below 5%)). The temperature of the addition is between 10 and 80 ⁰ C, more preferably between 10 and 40 ⁰ C.

A compound is defined according to the invention as having a cohesive effect on the particulate material if, for a given compaction force of 3000 N, for tablets weighing 50 g of particulate detergent material and having a diameter of 55 mm, their tablet tensile strength is increased by more than 30% (preferably 60 and more preferably 100%) by the presence of 3% of the compound having a cohesive effect in the particulate base material.

An example of a compound with a cohesive effect is sodium diisoalkylbenzenesulfonate.

When a highly soluble compound which also exerts a cohesive effect on the particulate material used for a tablet or layer is incorporated by compacting a particulate material comprising a surfactant, the dissolution of the tablet or layer in an aqueous medium or solution is significantly increased. In a preferred embodiment, at least 0.5% by weight of a tablet or layer is formed from the highly soluble compound, more preferably at least 0.75%, even more preferably at least 2%, and most preferably at least 4% by weight of the tablet or layer is formed from the highly soluble compound having a cohesive effect on the particulate material.

It is to be noted that a composition comprising a highly soluble compound and a surfactant is described in EP-A-0 524 075, which composition is a liquid composition.

A highly soluble compound with a cohesive effect on the particulate material allows a tablet with a higher tear

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strength at constant compaction force or an equal tear strength at lower compaction force, compared to conventional tablets. Typically a whole tablet has a tensile strength of more than 5 kPa, preferably more than 10 kPa, more preferably, particularly for laundry applications, more than 15 kPa, even more preferably more than 30 kPa, and most preferably more than 50 kPa, particularly for use in dishwashing or machine dishwashing applications; and a tear strength of less than 300 kPa, preferably less than 200 kPa, more preferably less than 100 kPa, even more preferably less than 80 kPa, most preferably less than 60 kPa. In fact, in the case of laundry applications the tablets should be less compacted than in the case of machine dishwashing applications where, for example, dissolution is more easily achieved, so that in the case of laundry applications the tear strength is preferably less than 30 kPa.

This allows the manufacture of tablets or layers having a strength and mechanical resistance comparable to the strength or mechanical resistance of conventional tablets, while providing a less compact tablet or layer which thus dissolves more easily. Furthermore, since the compound is highly soluble, the dissolution of the tablet or layer is further facilitated, resulting in a synergy which leads to facilitated dissolution for a tablet according to the invention.

Tablet production

The tablet may comprise several layers. For the purpose of producing a single layer, the layer itself may be considered a tablet. Detergent tablets can be prepared simply by mixing the solid components and compressing the mixture in a conventional tablet press, such as is used in the pharmaceutical industry. Preferably, the

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Main ingredients, particularly gelling surfactants, are used in particulate form. Any liquid ingredients, for example surfactant or suds suppressor, may be incorporated into the solid particulate ingredients in a conventional manner. In particular for detergent tablets, the ingredients such as builder and surfactant may be spray dried in a conventional manner and then compacted at a suitable pressure. Preferably, the tablets according to the invention are compressed using a force of less than 100,000 N, more preferably less than 50,000 N, even more preferably less than 5,000 N, and most preferably less than 3,000 N. Indeed, the most preferred embodiment is a laundry tablet which has been compressed using a force of less than 2,500 N, but machine dishwashing tablets, for example, may also be considered, such machine dishwashing tablets being normally more highly compressed than laundry tablets.

The particulate material used to make a tablet may be prepared by any particle formation or granulation process. An example of such a process is spray drying (in a co-current or counter-current spray drying tower) which typically gives low bulk densities of 600 g/l or lower. Higher density particulate materials may be prepared by granulation and compaction in a batch high shear mixer/granulator or by a continuous granulation and compaction process (for example using Lodige® CB and/or Lodige® KM mixers). Other suitable processes include fluid bed processes, compaction processes (for example roll compaction), extrusion and any particulate material prepared by any chemical process such as flocculation, crystallization sintering etc. Individual particles may also be any other particles, granules, beads or grains.

The components of the particulate material may be

• · ♦

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a conventional device. A batch operation is suitable, for example in a concrete mixer, Nauta mixer, ribbon mixer or any other. Alternatively, the mixing process can be carried out continuously by metering each component by weight onto a moving belt and mixing them in one or more rollers or mixers. Non-gelling binder can be sprayed onto the mixture of some or all of the components of the particulate material. Other liquid ingredients can also be sprayed onto the mixture of components, either separately or in a pre-mixed state. For example, perfume and optical brightener slurries can be sprayed. A finely divided flow aid (powdering agents such as zeolites, carbonates, silicas) can be added to the particulate material after the binder has been sprayed on, preferably towards the end of the process, to make the mixture less sticky.

The tablets may be prepared using any compaction process such as tabletting, briquetting or extrusion, preferably tabletting. Suitable equipment includes a standard single stroke or a rotary press (such as Courtoy®, Korch®, Manesty® or Bonais®). The tablets prepared according to the invention preferably have a diameter of between 20 mm and 60 mm, preferably at least 35 and up to 55 mm, and a weight of between 25 and 100 g. The height to diameter (or width) ratio of the tablets is preferably greater than 1:3, more preferably greater than 1:2. In another preferred embodiment, the tablets have a square cross-section of 45 mm x 45 mm and are 25 mm high. The compaction pressure used to produce these tablets must not exceed 100,000 kN/m ² , preferably not exceed 30,000 kN/m ² , more preferably not exceed 5,000 kN/m ² , even more preferably not exceed 3,000 kN/m ² , and most preferably not exceed 1,000 kN/m ² . In a preferred embodiment according to the invention, the tablet has a density of at least 0.9 g/cm^2, more preferably at least

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1.0 g/cm ³ , and preferably less than 2.0 g/cm ³ , more preferably less than 1.5 g/cm ³ , even more preferably less than 1.25 g/cm ³ , and most preferably less than 1.15 g/cm ³ .

Multilayer tablets are typically formed in rotary presses by feeding the particulate material of each layer, one at a time, into force-feeding pistons. As the process progresses, the layers of particulate material are then compressed together in the pre-compression and compression stations to form the multilayer tablet. In some rotary presses, it is also possible to compress the first layer of feed material before the entire tablet is compressed.

Hydrotropic compound

A highly soluble compound having a cohesive effect can be incorporated into a detergent tablet, which compound is also a hydrotropic compound. Such a hydrotropic compound can be generally used to promote surfactant dissolution while avoiding gelation. A specific compound is defined as hydrotropic as follows (see SE Friberg and M. Chiu, J. Dispersion Science and Technology, 9(5&6), pp. 443 to 457, (1988-1989)):
1. A solution is prepared comprising 25% by weight of the specific compound and 75% by weight of water.

2. Octanoic acid is then added to the solution in a ratio of 1.6 times the weight of the specific compound in solution, with the solution at a temperature of 20°C. The solution is mixed in a Sotax beaker using a marine propeller stirrer, with the propeller positioned approximately 5 mm above the bottom of the beaker and the mixer set at a rotation speed of 200 revolutions per minute.

3. The particular compound is hydrotropic when the octanoic acid is completely solubilized, that is, when the solution has only one phase, which phase is a liquid phase.

■it* ·

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It is to be noted that in a preferred embodiment of the invention the hydrotropic compound is a flowable material prepared from solid particles at operating conditions between 15 and 60 ^° C.

Hydrotropic compounds include the compounds listed below:

A list of commercial hydrotropes can be found in McCutcheon's Emulsifiers and Detergents, published by the McCutcheon Division of the Manufacturing Confectioners Company. Compounds of interest also include:

1. Non-ionic hydrotrope of the following structure:

RO- (CH ₂ CH ₂ O) _x (CH - CH ₂ O) _y H

_CH3
15

wherein R is a Cs-CjO'alkyl chain, χ is in the range of 1 to 15, and y is 3 to 10.

2. Anionic hydrotropes such as alkali metal arylsulfonates. These include alkali metal salts of benzoic acid, salicylic acid, benzenesulfonic acid and their numerous derivatives, naphthoic acid and various hydroaromatic acids. Examples of these are sodium, potassium and ammonium benzenesulfonate salts derived from toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, tetralinsulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, trimethylnaphthalenesulfonic acid. Further examples include salts of dialkylbenzenesulfonic acid such as salts of diisopropylbenzenesulfonic acid, ethylmethylbenzenesulfonic acid, alkylbenzenesulfonic acid with an alkyl chain length of 3 to 10 (preferably 4 to 9), linear or branched alkylsulfonates with an alkyl chain of 1 to 18 carbons.

3. Solvent hydrotropes such as alkoxylated glycerols and alkoxylated glycerides, esters of alkoxylated glycerols, alkoxylated fatty acids, esters of glycerin, polyglycerol esters. Preferred alkoxylated glycerols have the following structure:

&idigr;&iacgr;&idigr;··· · ·

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CH ₂ -Ol-CH ₂ CH-OI _n H
R

CH ₂ -Ot-CH ₂ CH-O-UI
R

O CHrOf-CH ₂ CH-OJ _n H

wherein 1, m and η are each a number from 0 to about 20, where 1+m+n = about 2 to about 60, preferably about 10 to about 45, and R is H, CH ₃ or C2H5.

Preferred alkoxylated glycerides have the following structure:
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H ₂ CR ₁

HC R ₂ R ₃
H ₂ CO-(CH ₂ CH-O)-H

wherein R ₁ and R ₂ are each C _n COO or -(CH ₂ CHR ₃ -O)IH, wherein R ₃ = H, CH ₃ or C ₂ H5, and 1 is a number from 1 to about 60, η is a number from about 6 to about 24.
4. Polymeric hydrotropes such as those described in EP 636 687:

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where E is a hydrophilic functional group,

R is H or a Cj-CjQ alkyl group or a hydrophilic functional group;

R ₁ is H or a lower alkyl group or an aromatic group,
R ₂ is H or a cyclic alkyl or aromatic group.

The polymer typically has a molecular weight between about 1,000 and 1,000,000.

5. Hydrotrope of unusual structure, such as δ-carboxy^-hexyl^-cyclohexen-1-yl-octanoic acid (Diaeid®).

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The use of such a compound in the invention would further increase the dissolution rate of the tablet, since a hydrotrope compound facilitates the dissolution of, for example, surfactants. Such a compound may be formed from a mixture or from a single compound.

Tensile or tear strength

For the purpose of measuring the tensile strength of a layer, the layer itself can be considered as a tablet. Depending on the composition of the starting material and the shape of the tablets, the compaction force applied can be adjusted so as not to affect the tensile strength and the break-up time in the washing machine. This method can be used to produce homogeneous or layered tablets of any size or shape. For a cylindrical tablet, the tensile strength corresponds to the diametrical fracture stress (CDFS), which is one way to express the strength of a tablet or layer and is determined according to the following equation:

Tensile strength = 2 F/nDt

where F is the maximum force (Newtons) to cause tensile failure (fracture) as measured using a VK 200 tablet hardness tester sold by Van Kell Industries, Inc.; D is the diameter of the tablet or layer, and t is the thickness of the tablet or layer. For a non-round tablet , πΔ can simply be replaced by the perimeter of the tablet.

(Method Pharmaceutical Dosage Forms: Tablets, Volume 2, pages 213 to 217).

A tablet with a diametral breaking stress of less than 20 kPa is considered fragile and is likely to have some broken tablets delivered to the consumer. A diametral breaking stress of at least 25 kPa is preferred. This applies equally to non-cylindrical tablets for the purpose of defining the tear strength, where the cross-section normal to the height of the tablet is not round, and

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wherein the force is applied along a direction perpendicular to the height direction of the tablet and normally to the side of the tablet, the side being perpendicular to the non-circular cross-section.

Tablet dispensing

The dispensing rate of a detergent tablet can be determined as follows:
Two tablets, nominally 50 g each, are weighed and then placed in the dispenser of a Bauknecht® WA9850 washing machine. The water supply to the washing machine is set to a temperature of 20 ⁰ C and a hardness of 21 grains per gallon, with the dispenser water inlet flow rate set to 8 l/min. The percentage of tablet residue remaining in the dispenser is checked by starting the wash and setting the wash cycle to wash program 4 (white/colored, short cycle). The percentage of dispense residue is determined as follows:

% Dispensing = Residue weight x 100/original tablet weight

The residue level is determined by repeating the procedure 10 times and calculating an average residue level based on the 10 individual measurements. In this challenge test, a residue of 40% of the initial tablet weight is considered acceptable. A residue of less than 30% is preferred and less than 25% is more preferred.

It should be noted that the measurement of water hardness is given in the conventional unit "grains per gallon", where 0.001 moles per liter = 7.0 grains per gallon, which represents the concentration of Ca^ + ions in solution.

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Effervescent agents

Detergent tablets may further contain an effervescence agent. Effervescence as defined herein means the evolution of gas bubbles from a liquid as a result of a chemical reaction between a soluble acid source and an alkali metal carbonate to produce carbon dioxide gas, that is

C ₆ H ₈ O ₇ + 3NaHCO ₃ * Na ₃ CgHsO ₇ + 3CO ₂ t + 3H ₂ O
Further examples of acid and carbonate sources and other effervescence systems can be found in: (Pharmaceutical Dosage Forms: Tablets, Volume 1, pages 287 to 291).

An effervescent agent may be added to the tablet mixture in addition to the detergent ingredients. The addition of this effervescent agent to the detergent tablet improves the break-up time of the tablet. The amount is preferably between 5 and 20%, and most preferably between 10 and 20% by weight of the tablet. Preferably, the effervescent agent should be added as an agglomerate of the various particles or as a compact, rather than in the form of individual particles.

Due to the gas generated by effervescence in the tablet, the tablet can have a higher DFS and still have the same break-up time as a non-effervescent tablet. If the DFS of the effervescent tablet is kept the same as a non-effervescent tablet, the effervescent tablet will break up faster.

Furthermore, dissolution aid may be provided by using compounds such as sodium acetate or urea. A list of suitable dissolution aids can also be found in Pharmaceutical Dosage Forms: Tablets, Volume 1, 2nd Edition, edited by H.A. Lieberman, et al., ISBN 0-8247-8044-2.

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Coating

The solidity of a tablet can be improved by producing a coated tablet, where the coating covers an uncoated tablet, thereby improving the mechanical properties of the tablet. This applies very advantageously to multilayer tablets, where the mechanical properties of a more elastic layer can be transmitted through the coating to the rest of the tablet, thus combining the advantage of the coating with the advantage of the more elastic layer. In effect, mechanical stresses are transmitted through the coating, thereby improving the mechanical integrity of the tablet.

In one embodiment of the invention, the tablets may then be coated so that the tablet does not absorb moisture or absorbs moisture at only a very low rate. The coating is also resilient so that moderate mechanical shocks to which the tablets are subjected during handling, packaging and transportation result in no more than very low levels of breakage or abrasion. Finally, the coating is preferably brittle so that the tablet breaks apart rapidly when subjected to a more severe mechanical shock. Furthermore, it is advantageous if the coating material is dissolved under alkaline conditions or is easily emulsified by surfactants. This helps to prevent the problem of visible residue in the window of a front loading washing machine during the wash cycle and also prevents the deposition of undissolved particles or clumps of coating material on the laundry load.

Water solubility is measured following the test procedure of ASTM E1148-87 entitled "Standard Test Method for Measurement of Aqueous Solubility".

The coating material has a melting point of preferably

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40 ⁰ C to 200 ⁰ C. The coating can be applied in a variety of ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material.
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In a) the coating material is applied at a temperature above its melting point and solidifies on the tablet. In b) the coating is applied as a solution, the solvent being dried out to leave a coherent coating. The substantially insoluble material can be applied to the tablet by, for example, spraying or dipping. When the molten material is sprayed onto the tablet, it normally solidifies rapidly to form a coherent coating. When tablets are dipped into the molten material and then removed, rapid cooling in turn causes rapid solidification of the coating material. During the solidification phase, the coating is subject to some internal stress (e.g. shrinkage on cooling) and external stress (e.g. tablet relaxation). This can cause some cracks in the structure, such as edge chipping, if the coating material is too brittle to withstand this mechanical stress, which is often the case when a coating is made only from components which are solid at 25°C. In fact, it is preferred that the coating comprises a component which is liquid at 25°C. It is believed that this liquid component enables the coating to be more resilient and to absorb mechanical stress by making the coating structure more flexible. The component which is liquid at 25°C is preferably added to the coating materials in proportions of less than 10% by weight of the coating, more preferably less than 5% by weight, most preferably less than 3% by weight. The component which is liquid at 25°C is preferably added to the coating materials in proportions of more than 0.1% by weight of the coating, more preferably more than 0.3% by weight, and most preferably more than 0.5% by weight. More preferably, the addition

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of reinforcing fibers to the coating to further strengthen the structure.

Preferably, the coating comprises a crystallized structure. By crystallized should be understood that the coating comprises a material which is solid at ambient temperature (25°C) and has a structure which exhibits some order. This can typically be determined by conventional crystallography techniques, for example X-ray analysis, on the material itself. In a preferred embodiment, the material forming the crystallized structure does not crystallize simultaneously or only partially with the above-mentioned optional component which is liquid at 25°C. In fact, it is preferred that the optional component remains in the liquid state at 25 ^° C in the crystalline coating structure to impart flexibility and resistance to mechanical stress to the structure. In another embodiment, the component which is liquid at 25°C may advantageously have a laundry washing functionality, for example silicone oil which provides foam suppression benefits or perfume oil.

The coating may also comprise other optional components. Suitable coating materials are, for example, dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from the group comprising oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof. Adipic acid is most preferred.

Substantially clearly insoluble materials with a melting point below 40 ⁰ C are often not sufficiently solid at ambient temperatures, and materials with a melting point above about 200 ⁰ C have been found to be practically inapplicable. Preferably, an acid with a melting point of more than 90 ⁰ C, such as azelaic acid, sebacic acid, dodecanedioic acid, is used. It is even more preferred,

-24-CM 2171 F

use an acid with a melting point above 145°C, such as adipic acid.

The "melting point" is the temperature at which the material turns into a clear liquid when slowly heated in, for example, a capillary tube.

A coating of any desired thickness can be applied in accordance with the present invention. For most purposes, the coating will constitute from 1 to 10%, preferably from 1.5 to 5%, of the tablet weight.

Tablet coatings are very hard and give additional strength to the tablet. Examples of optional components which are liquid at 25°C include polyethylene glycols, heat transfer oil, silicone oil, esters of dicarboxylic acids, monocarboxylic acids, paraffin, triacetin, perfumes or alkaline solutions. It is preferred that the structure of the components which are liquid at 25 ^° C be close to the material forming the crystallized structure so that the structure is not excessively disrupted. In a most preferred embodiment the crystallized structure is made from adipic acid, the component which is liquid at 25°C is available under the name Coasol™ from Chemoxy International which is a mixture of diisobutyl esters of glutaric, succinic and adipic acids. The advantage of using this component is that it is well dispersed in the adipic acid to provide flexibility. It should be noted that the disintegration of the adipic acid is further enhanced by the adipate content of Coasol™.

The breakage of the coating during washing can be improved by adding a disintegrating agent to the coating. The disintegrating agent swells after coming into contact with water and breaks the coating into small pieces. This improves the dissolution of the coating in the washing solution. The disintegrating agent is suspended in the coating melt in a proportion of up to 30%, preferably between 5 and 20%, most preferably between 5 and 10% by weight. Possible disintegrating agents

-25-CM 2171 F

are described in the Handbook of Pharmaceutical Excipients (1986). Examples of suitable disintegrants include starch; natural, modified or pregelatinized starch, sodium starch gluconate; gums: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose sodium, crospovidone, cellulose, carboxymethylcellulose, alginic acid and its salts including sodium alginate, silicon dioxide, clay, polyvinylpyrrolidone, soya polysaccharides, ion exchange resins, polymers with cationic (e.g. quaternary ammonium) groups, amine substituted polyacrylates, polymerized cationic amino acids such as poly-L-lysine, polyallylamine hydrochloride and mixtures thereof.

Preferably the coating comprises an acid having a melting temperature of at least 145°C, such as adipic acid, and clay, such as bentonite clay, the clay being used as a disintegrant and also to make the structure of the adipic acid more favorable for water penetration, thereby improving the dispersion of the adipic acid in an aqueous medium. Preferred are clays having a particle size of less than 75 μηη, more preferably less than 53 μα, in order to obtain the desired effect on the structure of the acid. Preferred are bentonite clays. In fact the acid has a melting point so that traditional cellulosic disintegrants undergo thermal degradation during the coating process, whereas such clays have been shown to be more heat stable. Furthermore, a traditional cellulosic disintegrant such as Nymcel™, for example, has been shown to turn brown at these temperatures.

In a further preferred embodiment, the coating further comprises reinforcing fibers. It has been found that such fibers further improve the resistance of the coating to mechanical stress and minimize the occurrence of splinter defects. Such fibers preferably have a length of at least 100 μια, more preferably at least 200 μιη, and most preferably at least

-26-CM 2171 F

at least 250 μιη to allow for structural reinforcement. Such fibers preferably have a length of less than 500 μιη, more preferably less than 400 μιη, and most preferably less than 350 μιη in order not to interfere with the dispersion of the coating in an aqueous medium. Materials which can be used for these fibers include viscose rayon, natural nylon, synthetic nylon (polyamide types 6 and 6,6), acrylics, polyesters, cotton, and derivatives of cellulose such as CMCs. Most preferred is a cellulosic material available under the trademark Solka-Floc™ from Fibers Sales & Development. It should be noted that such fibers do not normally require pre-compression to reinforce the coating structure. Such fibers are preferably added in a proportion of less than 5% by weight of the coating, more preferably less than 3% by weight. Such fibers are preferably added in a proportion of more than 0.5% by weight of the coating, more preferably more than 1% by weight.

Detergents

Surfactants are typically included in a detergent composition. The dissolution of surfactants is promoted by the addition of the highly soluble compound. Non-limiting examples of surfactants typically useful herein at levels of about 1 to about 55 wt.% include the conventional C^-C^ alkylbenzenesulfonates ("LAS") and primary, branched chain and random C ₁ OC ₂ O-alkylsulfates ("AS"), the secondary (2,3) C ₁₀ -C ₁₈ alkyl sulfates of the formula CH ₃ (CH ₂ ) _X (CHOSO3_M ⁺ ) CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ .M ⁺ ) CH ₂ CH ₃ , wherein &khgr; and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C ₁ QC ₁ S alkylalkoxysulfates ("AE _x S"; especially EO 1-7 ethoxysulfates), C ₁₀ -C ₁₈ alkylalkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates), the C ₁ Q- C ₁ 3 glycerol ethers, the C^-Cj^ alkylpolyglycosides and their corresponding sulfated polyglycosides, and alpha-sulfonated C ₁₂ -

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C ^'Fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the Cj^-Cis-alkyl ethoxylates ("AE") including the so-called narrow peak distribution alkyl ethoxylates and Cj2-C18"alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Cj2-C18" ^{betaines and} sulfobetaines ("sultaines"), C jq-C ^-amine ^oxides and the like can also be included in the overall compositions. The CjQ-Cis-N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the Cj2- ^c 18- ^{N -Methn} y ¹ S ^lucamides · See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides such as Cio-Ci8- ^N -( ³ - ^{Meth ox} yP ^ro Pyl) ^glucamide · The N-propyl to N-hexyl Ci2"Ci8 glucamides may be used for low foaming. Conventional CiQ-C20' soaps may also be used. If high foaming is desired, the branched chain Cio-Ci6' soaps may be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventional suitable surfactants are listed in standard textbooks. In a preferred embodiment, the tablet comprises at least 5% by weight of a surfactant, more preferably at least 15% by weight, even more preferably at least 25% by weight, most preferably between 35 and 45% by weight of surfactant.

Non-gelling binders

Non-gelling binders may be incorporated into detergent compositions to further facilitate dissolution. When non-gelling binders are used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers. The Handbook of Pharmaceutical Excipients, 2nd Edition, has the following binder classification: acacia, alginic acid, carbomer, carboxymethylcellulose sodium, dextrin, ethylcellulose, gelatin, guar gum, hydrogenated vegetable oil type I, hydroxyethylcellulose, hydroxypropylmethylcellulose, liquid glucose, magnesium aluminum silicate,

·*♦*♦*

CM 2171 F

cat, maltodextrin, methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein. The most preferred binders also have an active cleaning function when washing laundry, such as cationic polymers, i.e. ethoxylated hexamethylenediamine quaternary compounds, bishexamethylenetriamines or others such as pentaamines, ethoxylated polyethyleneamines, maleic acrylic polymers.
Non-gelling binder materials are preferably sprayed on and therefore have a suitable melting point temperature below 90°C, preferably below 70 ^° C, and even more preferably below 50 ^° C, so as not to damage or degrade the other active ingredients in the matrix. Most preferred are non-aqueous liquid binders (i.e. not in aqueous solution) which can be sprayed in molten form. However, they can also be solid binders which are introduced into the matrix by dry addition but which have binder properties within the tablet.

Non-gelling binder materials are preferably used in an amount within the range of 0.1 to 15% of the composition, more preferably below 5%, and particularly in the case of a non-laundry active material, below 4% by weight of the tablet.

It is preferred that gelling binders such as non-ionic surfactants in their liquid or molten form are avoided. Non-ionic surfactants and other gelling binders are not excluded from the compositions, but it is preferred that these are incorporated into the detergent tablets as components of particulate materials rather than as liquids.
30

Builders

Detergent builders can optionally be included in the compositions mentioned here to help regulate the mineral hardness.

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Both inorganic and organic builders can be used. Builders are typically used in fabric washing compositions to assist in the removal of particulate soils. The level of builder can vary widely depending on the end use of the composition.

Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkaline ammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. In some regions, however, phosphate-free builders are required. It is important to emphasize that the compositions herein surprisingly function even in the presence of so-called "weak" builders (compared to phosphates), such as citrate, or in a so-called "underbuilt" situation which can occur with zeolite or layered silicate builders.

Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range of 1.6:1 to 3.2:1, and layered silicates such as those described in U.S. Patent 4,664,839 issued May 12, 1987 to HP Rieck. NaSKS-6 is the trademark for a crystalline layered silicate (commonly abbreviated herein as "SKS-6") sold by Hoechst. Unlike zeolite builders, the Na-SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2SiC>5 morphology form of layered silicate. It can be prepared by processes such as those described in DE-A-3 417 649 and DE-A-3 742 043. SKS-6 is a highly preferred layered silicate for use herein, however, other layered silicates may be used herein, such as those of the general formula NaMSi _x C^ _x+ χ T ¹ ^C" wherein M is sodium or hydrogen, χ is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and

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NaSKS-II, as the alpha, beta and gamma forms. As mentioned above, the delta-Na2SiO5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful, such as magnesium silicate, which can serve as an embrittlement agent in granular formulations, as a stabilizer for oxygen bleaches and as a component of foam control systems. Examples of carbonate builders are the alkaline earth and alkali metal carbonates as described in German Patent Application No. 2 321 001, published November 15, 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently sold heavy-duty granular detergent compositions, and they can also be an important builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
M _z [ (ZAlO ₂ Jy] -XH ₂ O

wherein ζ and y are integers of at least 6, the molar ratio of ζ to y ranges from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be naturally occurring aluminosilicates or synthetically derived. A process for preparing aluminosilicate ion exchange materials is described in U.S. Patent 3,985,669, Krummel et al., issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP, and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na ₁₂ I(AlO ₂ ) ₁₂ (SiO ₂ )i2l' ^x H ₂ O
where &khgr; is about 20 to about 30, especially about 27. This material is

-31-CM 2171 F

known as zeolite A. Dehydrated zeolites (χ = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1 - 10 μηα in diameter.

Organic detergent builders useful for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders generally may be added to the composition in acid form, but may also be added in the form of a neutralized salt. When used in salt form, alkali metals such as sodium, potassium and lithium or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials. An important category of polycarboxylate builders comprises the ether polycarboxylates, including oxydisuccinate, as described in U.S. Patent 3,128,287 to Berg, issued April 7, 1964 and U.S. Patent 3,635,830 to Lamberti et al, issued January 18, 1972. See also "TMS/TDS" builders according to U.S. Patent 4,663,071, issued to Bush et al. on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergent builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

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Citrate builders, for example citric acid and soluble salts thereof (especially sodium salt), are polycarboxylate builders of particular importance for liquid heavy-duty detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, particularly in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

Also useful in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds described in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmitylsuccinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinates are the preferred builders of this group and are described in European Patent Application 86 200 690.5/0,200,263, published January 5, 1986. November 1986.

Other suitable polycarboxylates are described in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979, and U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also U.S. Patent 3,723,322 to Diehl.

Fatty acids, for example C1-C8 monocarboxylic acids, may also be incorporated into the compositions alone or in combination with the aforementioned builders, particularly citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids generally results in a reduction in foaming, which should be taken into account by the formulator.

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In situations where phosphorus-based builders can be used, and particularly in the formulation of bars used in hand washing operations, the numerous alkali metal phosphates such as the well known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

Bleach

The detergent compositions described herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, the levels of bleaching agents are typically from about 1% to about 30%, more typically from about 5% to about 20% of the detergent composition, particularly for fabric washing. When present, the amount of bleach activators is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition containing the bleach plus bleach activator.

The bleaching agents used herein may be any of those known or becoming useful in detergent compositions for fabric cleaning, hard surface cleaning or other cleaning purposes. These include oxygen bleaching agents as well as other bleaching agents. Perborate bleaching agents, for example sodium perborate (for example mono- or tetrahydrate) may be used herein.

Another category of bleaching agents which can be used without limitation includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydode-

ΓΓΓ

-34-CM 2171 F

candiaic acid. Such bleaching agents are described in U.S. Patent 4,483,781, Hartmann, issued November 20, 1984, U.S. Patent Application 740,446, Burn et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid, as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.

Peroxygen bleaches may also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent 'percarbonaf' bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) may also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 μιη to about 100 μιη, with no more than about 10 weight percent of the particles being smaller than about 200 μιη and no more than 10 weight percent of the particles being larger than about 1250 μιη. Optionally, the percarbonate can be coated with silicate, borate or water soluble surfactants. Percarbonate is available from numerous commercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaches can also be used.

Peroxygen bleaches, the perborates, the percarbonates, etc. are preferably combined with bleach activators, resulting in the in situ production in aqueous solution (i.e., during the washing process) of the peroxyacid corresponding to the bleach activator. Numerous non-limiting examples of activators are described in U.S. Patent 4,915,854, issued April 10, 1999 to Mao et al., and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and te-

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traacetylethylenediamine (TAED) activators are typical, and mixtures thereof may also be used. See also US 4,634,551 for other typical bleaching agents and activators useful herein.
5

Highly preferred amido-derived bleach activators are those of the formulas:

R ¹ N(R ⁵ JC(O)R ² C(O)L or R ¹ C(O)N(R ⁵ JR ² C(O)L

wherein R ¹ is an alkyl group having from about 6 to about 12 carbon atoms, R ² is alkylene having from 1 to about 6 carbon atoms, R ⁵ is H or alkyl, aryl or alkaryl having from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group which is removed from the bleach activator as a result of nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.

Another class of bleach activators includes the benzoxazine-type activators as described by Hodge et al. in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred benzoxazine-type activator is:

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Yet another class of preferred bleach activators comprises the acyl lactam activators, particularly acyl caprolactams and acryl valerolactams of the formulas:

oO

The

O C-CH ₂ -CH ₂ O C-CH ₂ -CH ₂

r6-CN^ ^CH ₂ R ⁶ -CN^ I

_{CH2CH2CH2CH2 ​ ​ ​}

wherein R^ is H or an alkyl, aryl, alkoxyaryl or alkaryl group having from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoylvalerolactam, and mixtures thereof. See also U.S. Patent 4,545,784, issued October 8, 1985 to Sanderson, incorporated herein by reference, which describes acylcaprolactams including benzoylcaprolactam adsorbed in sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and may be used herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions typically contain from about 0.025 to about 1.25 weight percent of such bleaching agents, particularly sulfonated zinc phthalocyanine.

If desired, the bleach compounds may be catalyzed by a manganese compound. Such compounds are known in the art and include, for example, the manganese-based catalysts described in U.S. Patent 5,246,621; U.S. Patent 5,244,594; U.S. Patent 5,194,416; U.S. Patent 5,114,606; and European Patent Application

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publication numbers 549,271 Al; 549,272 Al; 544,440 A2 and 544,490 Al; preferred examples of these catalysts include Mn ^IV ₂ (uO)3( 1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mn ⁿⁱ 2(u-0) γ (u-0Ac) ₂ ( 1,4,7-trimethyl-1,4,7-triazacyclononane)2-(CIO ₄ J ₂ .
Mn ^IV 4(uO) ₆ (l,4,7-triazacyclononane)4(CIO4) ₄ ,

Mn ^nI Mn ^IV 4(uO)i (U-OAc) ₂ .(1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (CIO4)3,
Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-

(OCH3)3(PFg) and mixtures thereof. Other metal-based bleach catalysts include those described in U.S. Patent 4,430,243 and U.S. Patent 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following U.S. Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161 and 5,227,084.

As a practical matter, and without limitation, the compositions and methods described herein can be adjusted to provide on the order of at least one part per 10 million of the active bleach catalyst species in the aqueous wash liquor, and preferably about 0.1 ppm to about 700 ppm, more preferably about 1 ppm to about 500 ppm, of the catalyst species in the wash liquor.

Enzymes

Suitable enzymes for use in the compositions of the invention include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, mannanases, ß-glucanases, arabinosidases, hyaluronidases, chondroitinase, laccase or mixtures thereof. A preferred combination is a cocktail of conventionally applicable enzymes, such as protease, amylase-

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se, lipase, cutinase and/or cellulase, in conjunction with one or more plant cell wall degrading enzymes.

The cellulases useful in the present invention include both bacterial and fungal cellulases. Preferably they have a pH optimum between 5 and 12 and a specific activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are described in US Patent 4,435,307, Barbesgoard et al, J61078384 and WO 96/02653 which describe fungal cellulases produced from Humicola insolens, Trichoderma, Thielavia and Sporotrichum respectively. EP 739 982 describes cellulases isolated from new Bacillus species. Suitable cellulases are also described in GB-A-2 075 028; GB-A-2 095 275; DE-OS-2 247 832 and WO 95/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), in particular the Humicola strain DSM 1800. Other suitable cellulases are cellulases derived from Humicola insolens having a molecular weight of about 50 KDa, an isoelectric point of 5.5, and containing 415 amino acids; and a 43kD endoglucanase derived from Humicola insolens, DSM 1800, which exhibits CeI-lulase activity; a preferred endoglucanase component has the amino acid sequence described in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO 94/21801, Genencor, published September 29, 1994. Particularly suitable cellulases are the cellulases which have color care benefits. Examples of such cellulases are the cellulases described in European Patent Application No. 91 202 879.2, filed November 6, 1991 (Novo).

Carezyme and Celluzyme (Novo Nordisk A/S) are particularly useful. See also WO 91/17244 and WO 91/21801. Other suitable cellulases for laundry care and/or cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471.

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These cellulases are normally incorporated into the detergent composition in proportions of 0.0001% to 2% of pure enzyme based on the weight of the detergent composition.

Enzymatic systems can be used as bleaching agents: The hydrogen peroxide can also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefor) capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are described in European patent application 91 202 655.6, filed on 9 October 1991.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc., and with a phenolic substrate as a bleach-enhancing molecule. They are used for "solution bleaching", i.e. to prevent the transfer of dyes or pigments removed from substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, such as chloro- and bromoperoxidase. Detergent compositions containing peroxidase are described, for example, in the international PCT application WO 89/099813, WO 89/09813 and the European patent application EP No. 91 202 882.6, filed on November 6, 1991, and EP No. 96 870 013.8, filed on February 20, 1996. The laccase enzyme is also suitable.

Enhancers are generally present in an amount of 0.1 to 5% by weight of the total composition. Preferred enhancers are substituted phenthiazine and phenoxasine, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred water-

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peroxide sources.

These peroxidases are normally incorporated into the detergent composition in proportions of 0.0001 to 2% of pure enzyme based on the weight of the detergent composition.

Other preferred enzymes which may be included in the detergent compositions of the invention include lipases. Suitable lipase enzymes for laundry use include those produced by microorganisms of the Pseudomonas group such as Pseudomonas stutzeri ATCC 19.154 as described in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody to the lipase produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan under the trade name Lipase P "Amano", referred to herein as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases from Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from US Biochemical Corp., USA and Disoynth Co., Netherlands, and lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as Ml Lipase^ and Lipomax^ (Gist-Brocades) and Lipolase ¹ * and Lipolase Ultra ^R (Novo), which have been found to be very effective when used in combination with the compositions of the invention. Also suitable are the lipolytic enzymes as described in EP 258 068, WO 92/05249 and WO 95/22615 from Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 from Unilever.

Also suitable are cutinases [EC 3.1.1.50], which can be considered as a special type of lipase, namely lipases that do not require surface activation. The addition of cutinases to detergent compositions has been described, for example, in WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO

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94/14963 and WO 94/14964 (Unilever).

The lipases and/or cutinases are normally incorporated into the detergent composition in proportions of 0.0001% to 2% of pure enzyme based on the weight of the detergent composition.

Suitable proteases are the subtilisins obtained from special strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). A suitable protease is obtained from a strain of Bacillus with a maximum activity over the entire pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The production of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein-engineered Maxacal) from Gist-Brocades. Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO 91/02792 and its variants described in WO 95/23221. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A from Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 from Novo. If desired, a protease with reduced adsorption and increased hydrolysis is available as described in WO 95/07791 from Procter & Gamble. A recombinant trypsin-like protease for detergents useful herein is described in WO 94/25583 from Novo. Other suitable proteases are described in EP 516 200 by Unilever.

Proteolytic enzymes also include modified bacterial serine proteases such as those described in European Patent Application No. 87 303 761.8, filed on 28 April 1987 (in particular pages 17, 24 and 98), hereinafter referred to as "Protease B", and in European Patent Application 199 404, Venegas, published on 29 October

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1986, which refers to a modified bacterial serine proteolytic enzyme referred to herein as "Protease A". Suitable is what is referred to herein as "Protease C", which is a variant of a Bacillus alkaline serine protease in which lysine at position 27 has replaced arginine, tyrosine at position 104 has replaced valine, serine at position 123 has replaced aparagine and alanine at position 274 has replaced threonine. Protease C is described in EP 90 915 958.4, corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants, in particular Protease C, are also included herein.

A preferred protease, designated "Protease D", is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a plurality of amino acid residues with a different amino acid at a position in the carbonyl hydrolase which is equivalent to position +76, preferably also in combination with one or more amino acid residue positions which are equivalent to those selected from the group consisting of +99, +101, +103, +104, + 107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin as described in WO 95/10591 and in the patent application of C. Ghosh, et al., "Bleaching Compositions Comprising Protease Enzymes" with the US serial number 08/322,677, filed on October 13, 1994. Also suitable is a carbonyl hydrolase variant of the protease described in WO 95/10591 having an amino acid sequence derived by exchanging a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210, in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, + 104, +107,+128, +129,+130, +132, +135, +156,+158,+164,+166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions correspond to the naturally occurring subtilisin of Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin (also pending U.S. patent application Serial No. 60/048,550, filed

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on 4 June 1997).

More preferred proteases are multiply substituted protease variants. These protease variants comprise a substitution of an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution at amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 15 9, 160, 166, 167, 170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209, 210, 211, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amyloliquefaciens subtilisin; wherein, when said protease variant comprises a substitution of amino acid residues at positions corresponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions which are different from amino acid residue positions corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefaciens subtilisin and/or multiply substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amyloliquefaciens subtilisin, as described in PCT applications PCT/US98/22588, PCT/US98/22482 and PCT/US98/22486, all filed October 23, 1998 by The Procter & Gamble Company.

The proteolytic enzymes are incorporated into the detergent compositions according to the invention in a proportion of 0.0001% to 2%, preferably

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0.001% to 0.2%, more preferably 0.005% to 0.1% pure enzyme, based on the weight of the composition.

Amylases (α and/or β) may be included for the removal of carbohydrate-based stains. WO 94/02597, Novo Nordisk A/S, published February 3, 1994, describes detergent compositions containing mutant amylases. See also WO 95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in detergent compositions include both α- and β-amylases. α-Amylases are known in the art and include those described in US Patent No. 5,003,257; EP 252,666; WO 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases as described in WO 94/18314, published August 18, 1994, and WO 96/05295, Genencor, published February 22, 1996, and amylase variants with additional modification of the immediate parent available from Novo Nordisk A/S, described in WO 95/10603, published April 95. Also suitable are the amylases described in EP 277 216, WO 95/26397 and WO 96/23873 (all from Novo Nordisk). Examples of commercial cc-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark. WO 95/26397 describes further suitable amylases: a-amylases which are characterized by a specific activity which is at least 25% higher than the specific activity of Thermamyl® at a temperature range of 25°C to 55°C and at a pH in the range of 8 to 10, measured by the Phadebas® a-amylase activity assay. Preferred are variants of the above enzymes described in WO 96/23873 (Novo Nordisk). Preferably, the variants are those which demonstrate improved thermal stability, more preferably those in which at least one amino acid residue equivalent to F180, R181, G182, T183, G184 or K185 has been deleted from the parent a-amylase. Particularly preferred are those variants with improved thermal stability which

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which comprise the amino acid deletions R181* + G182* or &Tgr;183* + G184*. Other amylolytic enzymes with improved properties in terms of the level of activity and the combination of thermostability and a higher level of activity are described in WO 95/35382. 5

The amylolytic enzymes are incorporated into the detergent compositions of the invention in a proportion of 0.0001 to 2%, preferably 0.00018% to 0.06%, more preferably 0.00024% to 0.048%, pure enzyme, based on the weight of the composition.

The above mentioned enzymes can be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. The origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halogenophilic etc.). Purified or non-purified forms of these enzymes can be used. Also included by definition are mutants of native enzymes. Mutants can be obtained, for example, by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. It is also common practice to express the enzyme via white organisms in which the genetic material responsible for the production of the enzyme has been cloned.

These enzymes are normally incorporated into the washing or cleaning composition in proportions of 0.0001% to 2% pure enzyme by weight of the cleaning composition. The enzymes may be added as separate individual components (prills, granules, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more enzymes (e.g. cogranules).

Other suitable detergent ingredients which may be added are enzyme oxidation scavengers which are described in co-pending European Patent Application No. 92 870 018.6, filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

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A range of enzyme materials and means for incorporating them into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A to Genenocr International, WO 8908694 A to Novo and US 3,553,139, January 5, 1971, to McCarty et al. Enzymes are further described in US 4,101,457, Place et al, July 18, 1978, and in US 4,507,219, Hughes, March 26, 1985. Enzyme materials suitable for liquid detergent formulations and their incorporation into such formulations are described in US 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergent compositions can be stabilized by a variety of techniques. Enzyme stabilization techniques are described and exemplified in US 3,600,319, August 17, 1971, Gedge et al, EP 199 405 and EP 200 586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in US 3,519,570. A useful Bacillus sp.

AC13, which yields proteases, xylanases and cellulases, is described in WO 9401532 A by Novo.

Other components commonly used in detergent compositions and which may be incorporated into detergent tablets include complexing agents, soil release agents, anti-staining agents, dispersants, foam suppressors, fabric softeners, dye transfer inhibiting agents and perfumes.

The above-described compounds for a product are advantageously packaged in a packaging system. A packaging system may be formed from a sheet or flexible material. Materials suitable for use as a flexible sheet include monolayer, coextruded or laminated films. Such films may have numerous

Components such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate. Preferably, the packaging system is composed of a coextruded film of polyethylene and bi-oriented polypropylene with an MVTR of less than 5 g/day/m^. The MVTR of the packaging system is preferably less than 10 g/day/m^, because

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ter preferably less than 5 g/day/m ² . The film (2) can have numerous thicknesses. The thickness should typically be between 10 and 150 μηα, preferably between 15 and 120 μηα, more preferably between 20 and 100 μηα, even more preferably between 25 and 80 μια, and most preferably between 30 and 40 μια.

A packaging material preferably comprises a barrier layer, which is typically found in packaging materials having a low oxygen transmission rate, typically less than 300 cm ³ /m ² /day, preferably less than 150 cm ³ /m ² /day, more preferably less than 100 cm ³ /m ² /day, even more preferably less than 50 cm ³ /m ² /day, and most preferably less than 10 cm ³ /m ² /day. Typical materials with such barrier properties include bioriented polypropylene, polyethylene terephthalate, nylon, poly(ethylene vinyl alcohol) or laminated materials comprising any of these, as well as SiOx (silicon oxides) or metal foils such as aluminum foils. Such a packaging material can have a beneficial influence on the stability of the product, for example during storage. Among the packaging methods used are typically wrapping methods as described in WO 92/20593, including flow-wrapping or over-wrapping. When using such methods, a longitudinal seal is provided, which may be a bead seal or overlap seal, after which a first end of the packaging system is closed with a first end seal, followed by closure of the second end with a second end seal. The packaging system may comprise reclosable means as described in WO 92/20593. In particular, the use of a twist, a cold seal or an adhesive is particularly suitable. Indeed, a band of cold seal or a band of adhesive may be applied to the surface of the packaging system at a position adjacent to the second end of the packaging system, so that this band can provide both the initial sealing and the re-closure of the packaging system. In such a case, the adhesive may

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fabric or cold seal tape to a region of cohesive surface, that is, a surface which adheres only to another cohesive surface. Such reclosure means may also comprise spacers which prevent undesired adhesion. Such spacers are described in WO 95/13225, published on 18 May 1995. A plurality of spacers and a plurality of strips of adhesive material may also be provided. The main requirement is that communication between the outside and the inside of the package should be minimal, even after a first opening of the packaging system. A cold seal may be used, and in particular a network of cold seal, the cold seal being adapted to facilitate opening of the packaging system.

The invention will now be described by way of example and with reference to the accompanying drawings, in which:

Figure 1 illustrates a device according to the invention, the flap of the device being partially raised;
20

Figure 2 illustrates the device of Figure 1 with a tablet inserted into the device;

Figure 3 illustrates the device of Figure 2, wherein the device containing the tablet is inserted into a washing machine.

The device 1 of Figure 1 is made entirely of a mesh material 4 and comprises only one wall. The flap 2 is an extension of the wall of the device which covers another part of the wall of the device, the opening 3 for inserting the tablet being located under the flap 2. The flap 2 remains folded over the opening 3 by threading a lateral side 20 of the flap to the wall. It should be noted that both lateral sides 20 and 21 of the flap can be threaded so that a tablet 5 can still be inserted under the flap 2 and

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can be inserted through the opening 3 of the device 1 due to the flexibility of the mesh material 4. In this example, the device comprises a top 11, a bottom 12 and a left side 13 and a right side 14. However, a simpler version can be formed only from the sides of the top 11 and the bottom 12, the internal volume for the tablet 5 being formed by the flexibility of the mesh material 4.

In Figure 2, the tablet 5 is inserted into the device 1 by lifting the flap 2 and inserting the tablet through the opening 3. Once this has been done, the device 10 containing the tablet can be inserted into the washing machine to carry out a normal wash, as illustrated in Figure 3.

Claims (7)

1. A dispensing device ( 1 ) for a detergent tablet ( 5 ) formed at least partially from a flexible, water-permeable material ( 4 ), the device ( 1 ) comprising at least one wall and the wall comprising an opening ( 3 ) for inserting the tablet ( 5 ), characterized in that the device ( 1 ) further comprises a flap ( 2 ), the flap ( 2 ) being folded over the opening ( 3 ) and the flap ( 2 ) remaining folded over the opening. 2. Dispensing device ( 1 ) according to claim 1, wherein the flexible, water-permeable material ( 4 ) is a mesh material. 3. Dispensing device ( 1 ) according to claim 1 and/or 2, wherein the flap ( 2 ) remains permanently folded over the opening ( 3 ). 4. Dispensing device ( 1 ) according to at least one of the preceding claims, wherein the flap ( 2 ) remains removably folded over the opening ( 3 ). 5. Dispensing device ( 1 ) according to at least one of the preceding claims, wherein the device ( 1 ) is partially formed from a flexible, water-impermeable material. 6. Dispensing device ( 1 ) according to at least one of claims 1 to 4, wherein the device ( 1 ) is formed by folding a single piece of the flexible material ( 4 ). 7. Kit comprising a device ( 1 ) according to at least one of claims 1 to 6 and further comprising a plurality of detergent tablets ( 5 ), wherein the device ( 1 ) and the plurality of detergent tablets ( 5 ) are provided in a pack.