Package having a venting system

Abstract

 The present invention provides a packaging system comprising a sheet of flexible material, the sheet of flexible material comprising a plait, the plait being held flat against a part of the sheet which is thereby covered by the plait, the sheet of flexible material comprising a micro-hole, characterised in that the micro-hole is located in the covered part of the sheet.

Description

Technical Field

[0001] The present invention relates to a packaging system of the venting packaging system type.

Background of the Invention

[0002] Venting packaging systems are widely used in consumer products industry. Such packaging systems often take the form of a wrapper, sometimes a shrinkable wrapper, because such packaging systems are relatively easy to process at high speed and in large quantities. Depending on the consumer product which should be packed, the transfer properties of the packaging system should be adapted so as to provide storage stability. In some cases, the packaging system is preferably made completely gas tight, while in other cases, venting is necessary to allow egress of gases which may be produced for example by a chemical evolution of the product.

[0003] The present invention concerns a packaging system comprising a sheet of flexible material, the sheet of flexible material allowing venting by comprising a micro-hole. Such a packaging system is known from WO 94/07766 published on the 14^th of April 1994.

[0004] Among the advantages of such packaging systems is the fact that they allow egress or ingress of gas between the inside of the packaging system and the outside of the packaging system, which is particularly convenient for the packaging of moisture containing product, for example, which can thereby "breathe" through the micro-holes provided, while preventing ingress of liquids such as water.

[0005] However, in various cases, although it is preferred that gas egress is possible, gas ingress may put the stability of the product at risk. This problem is for example solved in WO 94/07766 by including in the packaging system a moisture absorbing member which allows to stabilise the level of moisture comprised inside of the packaging system, thus preventing possible damage due to the ingress of moisture within the packaging system through the micro-holes. However, the insertion of such a moisture absorbing member introduces extra costs as well as one or more additional steps in the production process of the packaged product. Further, although this solution is effective for moisture, the ingress of other gases is not controlled.

[0006] The invention seeks to provide a packaging system of the above mentioned kind which can be produced at lower costs, allow egress of gas, and controls the ingress of gas.

Summary of the Invention

[0007] In accordance with the invention, this object is accomplished with a packaging system comprising a sheet of flexible material, the sheet of flexible material comprising a plait, the plait being held flat against a part of the sheet which is thereby covered by the plait, the sheet of flexible material comprising a micro-hole, characterised in that the micro-hole is located in the covered part of the sheet.

Detailed Description of the Invention

[0008] A packaging system formed in accordance with the invention has a number of advantages. Since the sheet comprises a micro-hole, egress of gas from the inside to the outside of the package is allowed. Further, as the micro-hole is situated under a plait, ingress of gas from the outside is prevented by the plait which lies on the micro-hole, thus acting as a valve.

[0009] The invention relates to a packaging system comprising a sheet of flexible material. By sheet should be understood a three dimensional structure whereby two of its three dimensions are significantly larger than the third dimension. The third dimension is the thickness of the sheet. This sheet is flexible, which means that it can be folded or bent easily without damage to its structure. Typically, it can handle curvature with a radius of curvature of the order of its thickness. The sheet of material according to the invention comprises a plait. A plait should be understood as a fold, crease or wrinkle, especially a plait is formed by a flattened fold of material made by doubling the material upon itself. Indeed, the plait is held flat against a part of the sheet which is thereby covered by the plait, according to the invention. Furthermore, the sheet of flexible material comprises a micro-hole, a necessary feature of the invention being that the micro-hole is located in the part of the sheet covered by the plait.

[0010] In a preferred embodiment of the invention, the micro-hole has a diameter of at least 0.1 mm and of less than 1 mm, more preferably of at least 0.15 mm and up to 0.8 mm, even more preferably of at least 0.2 and up to 0.6 mm and most preferably of at least 0.3 and up to 0.4 mm. There may also be more than 1 micro-hole. Preferably, there is between 1 and 10 micro-holes per packaging system, more preferably between 2 and 8 micro-holes, even more preferably between 2 and 5 micro-holes and most preferably 3 micro-holes place in the covered part of the sheet. Other micro-holes placed in another part of the sheet may also be provided, depending on the transfer characteristics desired for the packaging system. It should be noted that typically, a micro-hole according to the invention placed in the covered part of the sheet is larger than a micro-hole which is in another non-covered part of the sheet. Normally, micro-holes can be made using a pin, the pin used having a 1mm diameter, the head having a diameter of the order of 0.1 mm for making a 0.1 mm diameter micro-hole, the dimension of the pin varying with the dimension of the micro-hole which is provided. The packaging system may be pinned prior to wrapping, for example using pins fixed onto a cylinder which rotates while the film roll passes to apply the micro-holes. Such micro-holes have a size of typically between 100 and 1000 µm, preferably between 250 and 900 µm, more preferably between 350 and 700 µm and most preferably between 400 and 500 µm. An advantage of using a micro-hole in combination with a material having a given Moisture Vapour Transfer Rate, or MVTR, is that the problem of the ingress of moisture and the problem of evacuation of gas is de-coupled. Indeed, ingress of moisture is readily controlled by choosing the appropriate MVTR, whereas a micro-hole has only a negligible influence on ingress of moisture because it is present only at some points on the packaging system without modifying the characteristics of the remaining surface of the packaging system and a micro-hole will not have a significant influence if there is no pressure gradient and if it is placed under a plait according to the invention. Indeed, if a relatively large micro-hole is provided, for example with a diameter of more than 0.3 mm, the mocro-hole can have a significant influence if it is not covered by a plait. As a pressure gradient will appear precisely when gas needs to be evacuated to prevent deformation of the packaging system, the micro-hole will fulfil its function without significant influence on the ingress of moisture. Indeed, as the sheet has a micro-hole, gas is evacuated out of the packaging system if pressure builds up within the packaging system, whereas gas transfer is very limited when the pressure inside the packaging system is in equilibrium with the external pressure. Indeed, a micro-hole is such that it will give way significantly only in case of a pressure gradient between the two sides of the hole. This is due to the resilience of the packing material. This "one-way" functioning of a micro-hole allowing only egress is particularly effective for micro-holes having a smaller size. Indeed, for micro-holes having a bigger size, the resiliency of the material forming the sheet will not be sufficient to close the micro-hole in the absence of pressure gradient. Therefore, the invention allows to minimise ingress of gas further by use of the plait lying on the micro-hole, so that the plait acts as a valve. This means that better and faster venting with larger micro-holes can be obtained according to the invention, without jeopardising the transfer characteristics of the packaging system.

[0011] In a further preferred embodiment of the packaging system according to the invention, the sheet of material forms a pocket. Forming of the pocket may be obtained by folding, gluing or sealing, by use of one or more sheets. It should be understood that a pocket is a package element which defines an internal space, whereby the pocket is made from a flexible sheet. In the preferred embodiment, the pocket is sealed with a first end seal, a second end seal and a longitudinal seal. For example, if the pocket is formed from a single rectangular sheet of material, the sheet of material may be folded on itself, sealed so as to form a sleeve, each end of the sleeve being thereafter sealed, whereby the seal forming the sleeve is the longitudinal seal, the end seals being the first end and second end seals. Indeed, it is preferred that the first and second end seals are both in a direction intersecting the direction of the longitudinal seal, most preferably the first and second end seals being both in a direction perpendicular to the direction of the longitudinal seal, each seal being formed by sealing together two opposing parts of the sheet of flexible material, the longitudinal seal forming the plait and being held flat onto the part of the covered part of the sheet by the first and second seals. It should be noted that such an embodiment is particularly suited to use for packing large numbers of consumer products in a flow wrapping process for example, whereby the package takes the shape of a rectangular sachet or pouch. In this case, the packaging system may be filled with product prior to forming the longitudinal seal, typically if the product is a solid product, or after forming the longitudinal seal and a first end seal, typically if the product is a flowing material such as a powder. The packaging system according to the invention may also be used in various other kinds of packages, such as bottles or boxes having a closure made of the sheet of flexible material. Other examples of packages for which the application applies are pouches made of flexible films, optionally of the "stand-up" type, which comprise a plait covering part of the sheet.

[0012] In another aspect, the invention relates to a packaged product comprising the combination of a product and of a packaging system containing the product, the packaging system being according to the invention, whereby the product comprises a component reacting with moisture. The product may be of different forms including liquid, paste, powder, granules, tablets or pellets for example. The product comprises a component reacting with moisture, but other components may also be included, and in particular a plurality of components may react with moisture. By a component reacting with moisture, it should be understood that the component is submitted to a physical or chemical evolution depending on the level of moisture to which it is being exposed, or depending on moisture gradient.

[0013] In a preferred embodiment, the reaction of the component reacting with moisture produces gas. Indeed, in such a situation, a packaging system according to the invention is particularly suited as it allows egress of gas without compromising moisture protection. The component reacting with moisture may also evolve chemically through this reaction, with or without egress of gas, so that it requires effective moisture protection.

[0014] In another preferred embodiment, the product has been submitted to a temperature of more than 30°C prior to being packaged. Indeed, in such a situation, given that the product has a calorific capacity, there will normally be a gradient of temperature between the product and the ambient temperature, so that any gas comprised with the product in the package will tend to be submitted to dilatation, such that the package tends to be put out of shape by the pressure difference induced by the temperature difference between the inside and the outside of the packaging system. In this case, the presence of the micro-hole allows rapid equalisation of the pressure between the inside and the outside of the packaging system, without compromising protection of the content as the plait will act as a valve once the pressure equilibrium is reached. This means that pressure equilibrium can be reached fast after packing even if the product has been submitted to a temperature of more than 30°C prior to being packaged. This is particularly useful when a plurality of such packages should be packed or piled together in one container, whereby piling or packing would take more time and be more difficult if the packages are out of shape. In a preferred embodiment, the product has been submitted to a temperature of more than 35°C, more preferably more than 40°C, even more preferably more than 50°C and most preferably more than 60°C prior to being packaged, whereby the time between submission to such temperature and the complete sealing of the packaging system is of less than 5 minutes, preferably less than 1 minutes, more preferably less than 30 seconds and most preferably less than 5 seconds. It should be noted that submission to high temperature can be obtained by various means including immersion in a heated liquid, spraying of a heated liquid, or passage in a heated gaseous medium for example.

[0015] In a most preferred embodiment of the invention, the product is a detergent tablet. Tablets are portions which may have various cross sections. The cross section is normally circular, but it may be rectangular, square or elliptical for example. It should be noted that the invention applies also to detergent compositions in other forms such as powders for example, whereby the components or compounds forming the composition may be of the same kind as for tablets.

[0016] Preferably, the detergent tablet comprises a bleaching agent. A bleaching agent is very sensitive to humidity, so that it decomposes in a humid environment. Furthermore, a bleaching agent may release gas. Gas release would be accelerated in a high temperature environment. This is particularly adapted when combined with the package for the invention because the pressure gradient is normally such that pressure inside the package is always at least equal to the external pressure, so that water does not have any substantial access to the inside of the package, whereas gas release will be controlled. Consequently, such a packaged product would not induce a risk of explosion while efficiently protecting the tablets from decomposing. Typically, the bleaching agent will be an inorganic per-hydrate bleach. Such bleaching agents comprise sodium per-borate, which may be in the form of the monohydrate or of the tetra-hydrate. Other per-hydrate salts can also be used, such as sodium per-carbonate. Such components are a useful source of carbonate ions for detergency purposes. However, such per-carbonates are particularly unstable in moisture and also release gas, such as oxygen. Therefore, packing needs to be suitable so as to take account of these two features. Because a bleaching agent is decomposing in moisture and consequently loosing its bleaching properties, it is important to protect the tablets from ingress of external moisture. Ideally, this could be achieved by packing each tablet in a separate package to open just prior to use, the package being completely water-impermeable. However, such an option is not environmentally friendly as it is maximising the number of packages used. On the other side of the range, the tablets could be delivered in only one bag, however, first opening of the bag would expose all tablets to the external environment. A compromise is preferable by grouping the tablets in relatively small numbers in a package to reduce the number of packages and to minimise the exposition of tablets remaining in the once opened bag. In order to protect the tablet or tablets remaining in the packaging system after first opening, the packaging system may be re-closed. In order to achieve efficient protection of the tablets, it is preferred that the packaging system has a limited Moisture Vapour Transfer Rate (MVTR). The MVTR of the packaging system is measured at 40°C and 75% eRH, which corresponds to a environment particularly damaging for the tablets. It was found that the MVTR should preferably not exceed 20 g/m²/day, and even more preferably should not exceed 5 g/m²/day, in order to fulfil the requirements of the packaging system, corresponding to a protection effective for a six month period in real conditions. This protection is achieved prior to the first opening of the packaging system, indeed each further opening is potentially introducing moisture within the package, so that protection may not last for as long a time once the packaging system has been opened for the first time.

[0017] The packaging system takes account of the fact that gas is released by its content. This is achieved by the micro-hole which is made in the packaging system. A micro-hole acts as a communication between the inside of the packaging system and the outside of the packaging system. The main characteristics of a micro-hole is that the communication it provided is pressure sensitive. Indeed, if the pressure inside of the packaging system and the pressure outside of the packaging system are in equilibrium, the micro-hole will have an influence on the transmission characteristics of the packaging system which will depend on its size and on the resilience of the material. Indeed, no significant amount of the material is taken away when making a micro-hole. Indeed it will be substantially closed in the absence of a pressure gradient between the inside and the outside of the bag, particularly when covered by the plait according to the invention. However, once a pressure gradient appears, the packaging system will be slightly distorted, so that the micro-hole will open itself and allow significant communication between the outside and the inside of the package in order to minimise the pressure gradient. When a pressure gradient is created, it is usually because the pressure inside the bag increases, as the external pressure is substantially a constant. This means that in case of release of a gas, the inner pressure will increase, thus creating a pressure gradient which will open the micro-hole, through which the excess of gas will be evacuated. The micro-hole is acting as a discharge orifice without letting moisture enter the bag in a significant manner as the external pressure is normally always lower or equal to the inner pressure and as the plait prevents ingress of gas from the outside of the package which would be due to diffusion. This mechanism can be tuned by using various sizes for the micro-holes as well as by choosing the number of micro-holes needed per packaging system, taking account of the composition and of the quantity of the content of the packaging system, and taking also account of the MVTR of the packaging system. Indeed, a non zero MVTR will allow some communication between the inside and the outside of the bag.

[0018] The tablets may also comprise other components such as fragrance, surfactants, enzymes, detergent etc.... Typical tablet compositions for the preferred embodiment of the present invention are disclosed in the pending European applications of the Applicant n° 96203471.6, 96203462.5, 96203473.2 and 96203464.1 for example.

Highly soluble Compounds

[0019] The tablet may comprise 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 follow:
A solution is prepared as follows comprising de-ionised water as well as 20 grams per litre of a specific compound:

1- 20 g of the specific compound is placed in a Sotax Beaker. This beaker is placed in a constant temperature bath set at 10°C. A stirrer with a marine propeller is placed in the beaker so that the bottom of the stirrer is at 5 mm above the bottom of the Sotax beaker. The mixer is set at a rotation speed of 200 turns per minute.

2- 980 g of the de-ionised water is introduced into the Sotax beaker.

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

4- Step 3 is repeated after 20, 30, 40, 50, 1min, 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 when the conductivity of the solution reaches 80% of its maximum value in less than 10 seconds, starting from the complete addition of the de-ionised water to the compound. Indeed, when monitoring the conductivity in such a manner, the conductivity reaches a plateau after a certain period of time, this plateau being considered as the maximum value. Such a compound is preferably in the form of a flowable material constituted of solid particles at temperatures comprised between 10 and 80°Celsius for ease of handling, but other forms may be used such as a paste or a liquid.
Example of highly soluble compounds include Sodium di isoalkylbenzene sulphonate or Sodium toluene sulphonate.

Cohesive Effect

[0020] The tablet may comprise a compound having 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 characterised by the force required to break a tablet or layer based on the examined detergent matrix pressed under controlled compression conditions. For a given compression force, a high tablet or layer strength indicates that the granules stuck highly together when they were compressed, so that a strong cohesive effect is taking place. Means to assess tablet or layer strength (also refer to diametrical 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 compound having a cohesive effect with the tablet or layer strength of a powder mix which comprises 97 parts of the original base powder and 3 parts of the compound having a cohesive effect. The compound having a cohesive effect is preferably added to the matrix in a form in which it is substantially free of water (water content below 10% (pref. below 5%)). The temperature of the addition is between 10 and 80C, more pref. between 10 and 40C.
A compound is defined as having a cohesive effect on the particulate material according to the invention when at a given compacting force of 3000N, tablets with a weight of 50g of detergent particulate material and a diameter of 55mm have their tablet tensile strength increased by over 30% (preferably 60 and more preferably 100%) by means of the presence of 3% of the compound having a cohesive effect in the base particulate material.
An example of a compound having a cohesive effect is Sodium di isoalkylbenzene sulphonate.

[0021] When integrating a highly soluble compound having also a cohesive effect on the particulate material used for a tablet or layer formed by compressing a particulate material comprising a surfactant, the dissolution of the tablet or layer in an aqueous solution is significantly increased. In a preferred embodiment, at least 1% per weight of a tablet or layer is formed from the highly soluble compound, more preferably at least 2%, even more preferably at lest 3% and most preferably at least 5% per weight of the tablet or layer being formed from the highly soluble compound having a cohesive effect on the particulate material.
It should be noted that a composition comprising a highly soluble compound as well as a surfactant is disclosed in EP-A-0 524 075, this composition being a liquid composition.

[0022] A highly soluble compound having a cohesive effect on the particulate material allows to obtain a tablet having a higher tensile strength at constant compacting force or an equal tensile strength at lower compacting force when compared to traditional tablets. Typically, a whole tablet will have a tensile strength of more than 5kPa, preferably of more than 10kPa, more preferably, in particular for use in laundry applications, of more than 15kPa, even more preferably of more than 30 kPa and most preferably of more than 50 kPa, in particular for use in dish washing or auto dish washing applications; and a tensile strength of less than 300 kPa, preferably of less than 200 kPa, more preferably of less than 100 kPa, even more preferably of less than 80 kPa and most preferably of less than 60 kPa. Indeed, in case of laundry application, the tablets should be less compressed than in case of auto dish washing applications for example, whereby the dissolution is more readily achieved, so that in a laundry application, the tensile strength is preferably of less than 30 kPa.
This allows to produce tablets or layers which have a solidity and mechanical resistance comparable to the solidity or mechanical resistance of traditional tablets while having a less compact tablet or layer thus dissolving more readily. Furthermore, as the compound is highly soluble, the dissolution of the tablet or layer is further facilitated, resulting in a synergy leading to facilitated dissolution for a tablet according to the invention.

Tablet Manufacture

[0023] The tablet may comprise several layers. For the purpose of manufacture of a single layer, the layer may be considered as a tablet itself.
Detergent tablets of the present invention can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press as used, for example, in the pharmaceutical industry. Preferably the principal ingredients, in particular gelling surfactants, are used in particulate form. Any liquid ingredients, for example surfactant or suds suppressor, can be incorporated in a conventional manner into the solid particulate ingredients.
In particular for laundry tablets, the ingredients such as builder and surfactant can 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 100000N, more preferably of less than 50000N, even more preferably of less than 5000N and most preferably of less than 3000 N. Indeed, the most preferred embodiment is a tablet suitable for laundry compressed using a force of less than 2500N, but tablets for auto dish washing may also be considered for example, whereby such auto dish washing tablets are usually more compressed than laundry tablets.
The particulate material used for making the tablet of this invention can be made by any particulation 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 600g/l or lower. Particulate materials of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g. using Lodige® CB and/or Lodige® KM mixers). Other suitable processes include fluid bed processes, compaction processes (e.g. roll compaction), extrusion, as well as any particulate material made by any chemical process like flocculation, crystallisation sentering, etc. Individual particles can also be any other particle, granule, sphere or grain.
The components of the particulate material may be mixed together by any conventional means. Batch is suitable in, for example, a concrete mixer, Nauta mixer, ribbon mixer or any other. Alternatively the mixing process may be carried out continuously by metering each component by weight on to a moving belt, and blending them in one or more drum(s) or mixer(s). Non-gelling binder can be sprayed on to the mix of some, or all of, the components of the particulate material. Other liquid ingredients may also be sprayed on to the mix of components either separately or premixed. For example perfume and slurries of optical brighteners may be sprayed. A finely divided flow aid (dusting agent such as zeolites, carbonates, silicas) can be added to the particulate material after spraying the binder, preferably towards the end of the process, to make the mix less sticky.
The tablets may be manufactured by using any compacting 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 Bonals®). The tablets prepared according to this invention preferably have a diameter of between 20mm and 60mm, preferably of at least 35 and up to 55 mm, and a weight between 25 and 100 g. The ratio of height to diameter (or width) of the tablets is preferably greater than 1:3, more preferably greater than 1:2. The compaction pressure used for preparing these tablets need not exceed 100000 kN/m², preferably not exceed 30000 kN/m², more preferably not exceed 5000 kN/m², even more preferably not exceed 3000kN/m² and most preferably not exceed 1000kN/m². In a preferred embodiment according to the invention, the tablet has a density of at least 0.9 g/cc, more preferably of at least 1.0 g/cc, and preferably of less than 2.0 g/cc, more preferably of less than 1.5 g/cc, even more preferably of less than 1.25 g/cc and most preferably of less than 1.1 g/cc.
Multi layered tablets are typically formed in rotating presses by placing the matrices of each layer, one after the other in matrix force feeding flasks. As the process continues, the matrix layers are then pressed together in the precompression and compression stages stations to form the multilayer layer tablet. With some rotating presses it is also possible to compress the first feed layer before compressing the whole tablet.

Hydrotrope compound

[0024] A highly soluble compound having a cohesive effect may be integrated to the detergent tablet, whereby this compound is also a hydrotrope compound. Such hydrotrope compound may be generally used to favour surfactant dissolution by avoiding gelling. A specific compound is defined as being hydrotrope as follows (see S.E. Friberg and M. Chiu, J. Dispersion Science and Technology, 9(5&6), pages 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 thereafter added to the solution in a proportion of 1.6 times the weight of the specific compound in solution, the solution being at a temperature of 20°Celsius. The solution is mixed in a Sotax beaker with a stirrer with a marine propeller, the propeller being situated at about 5mm above the bottom of the beaker, the mixer being set at a rotation speed of 200 rounds per minute.

3. The specific compound is hydrotrope if the the Octanoic Acid is completely solubilised, i.e. if the solution comprises only one phase, the phase being a liquid phase.
It should be noted that in a preferred embodiment of the invention, the hydrotrope compound is a flowable material made of solid particles at operating conditions between 15 and 60° Celsius.

[0025] Hydrotrope compounds include the compounds listed thereafter:

[0026] A list of commercial hydrotropes could be found in McCutcheon's Emulsifiers and Detergents published by the McCutcheon division of Manufacturing Confectioners Company. Compounds of interest also include:

1. Nonionic hydrotrope with the following structure:

where R is a C8-C10 alkyl chain, x ranges from 1 to 15, y from 3 to 10.

2. Anionic hydrotropes such as alkali metal aryl sulfonates. This includes alkali metal salts of benzoic acid, salicylic acid, bezenesulfonic acid and its many derivatives, naphthoic acid and various hydroaromatic acids. Examples of these are sodium, potassium and ammonium benzene sulfonate salts derived from toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, tetralin sulfonic acid, naphtalene sulfonic acid, methyl- naphtalene sulfonic acid, dimethyl naphtalene sulfonic acid, trimethyl naphtalene sulfonic acid= Other examples include salts of dialkyl benzene sulfonic acid such as salts of di-isopropyl benzene sulfonic acid, ethyl methyl benzene sulfonic acid, alkyl benzene sulfonic acid with an alkyl chain length with 3 to 10, (pref. 4 to 9), linear or branched alkyl sulfonates with an alkyl chain with 1 to 18 carbons.

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

where I, m and n are each a number from 0 to about 20, with I+m+n = from about 2 to about 60, preferably from about 10 to about 45 and R represents H, CH₃ or C₂H₅
Preferred alkoxylated glycerides have the following struture

where R1 and R2 are each C_nCOO or -(CH2CHR₃-O)_i-H where R₃ = H, CH₃ or C₂H₅ and I is a number from 1 to about 60, n is a number from about 6 to about 24.

4. Polymeric hydrotropes such as those described in EP636687:

where E is a hydrophilic functional group,

R is H or a C1-C10 alkyl group or is a hydrophilic functional group;

R1 is H a lower alkyl group or an aromatic group,

R2 is H or a cyclic alkyl or aromatic group.

The polymer typically has a molecular weight of between about 1000 and 1000000.

5. Hydrotrope of unusual structure such as 5-carboxy-4-hexyl-2-cyclohexene-1-yl octanoic acid (Diacid®)
Use of such compound in the invention would further increase the dissolution rate of the tablet, as a hydrotrope compound facilitates dissolution of surfactants, for example. Such a compound could be formed from a mixture or from a single compound.

Coating

[0027] Solidity of the tablet according to the invention may be improved by making a coated tablet, the coating covering a non-coated tablet, thereby further improving the mechanical characteristics of the tablet while maintaining or further improving dissolution.
This very advantageously applies to multi-layer tablets, whereby the mechanical characteristics of a more elastic layer can be transmitted via the coating to the rest of the tablet, thus combining the advantage of the coating with the advantage of the more elastic layer. Indeed, mechanical constraints will be transmitted through the coating, thus improving mechanical integrity of the tablet.
In one embodiment of the present invention, the tablets may then be coated so that the tablet does not absorb moisture, or absorbs moisture at only a very slow rate. The coating is also strong so that moderate mechanical shocks to which the tablets are subjected during handling, packing and shipping result in no more than very low levels of breakage or attrition. Finally the coating is preferably brittle so that the tablet breaks up when subjected to stronger mechanical shock. Furthermore it is advantageous if the coating material is dissolved under alkaline conditions, or is readily emulsified by surfactants. This contributes to avoiding the problem of visible residue in the window of a front-loading washing machine during the wash cycle, and also avoids deposition of undissolved particles or lumps of coating material on the laundry load.
Water solubility is measured following the test protocol of ASTM E1148-87 entitled, "Standard Test Method for Measurements of Aqueous Solubility".
Suitable coating materials are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from the group consisting of 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.
The coating material has a melting point preferably of from 40 °C to 200 °C.
The coating can be applied in a number of ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material.
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 to leave a coherent coating. The substantially insoluble material can be applied to the tablet by, for example, spraying or dipping. Normally when the molten material is sprayed on to the tablet, it will rapidly solidify to form a coherent coating. When tablets are dipped into the molten material and then removed, the rapid cooling again causes rapid solidification of the coating material. Clearly substantially insoluble materials having a melting point below 40 °C are not sufficiently solid at ambient temperatures and it has been found that materials having a melting point above about 200 °C are not practicable to use. Preferably, the materials melt in the range from 60 °C to 160 °C, more preferably from 70 °C to 120 °C.
By "melting point" is meant the temperature at which the material when heated slowly in, for example, a capillary tube becomes a clear liquid.

[0028] A coating of any desired thickness can be applied according to the present invention. For most purposes, the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the tablet weight.
The tablet coatings of the present invention are very hard and provide extra strength to the tablet.
In a preferred embodiment of the present invention the fracture of the coating in the wash is improved by adding a disintegrant in the coating. This disintegrant will swell once in contact with water and break the coating in small pieces. This will improve the dissolution of the coating in the wash solution. The disintegrant is suspended in the coating melt at a level of up to 30%, preferably between 5% and 20%, most preferably between 5 and 10% by weight. Possible disintegrants are described in Handbook of Pharmaceutical Excipients (1986). Examples of suitable disintegrants include starch: natural, modified or pregelatinized starch, sodium starch gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose Sodium, crospovidone, cellulose, carboxymethyl cellulose, algenic acid and its salts including sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone, soy polysacharides, ion exchange resins and mixtures thereof.
The invention relates in a preferred embodiment to a detergent tablet having a soft core and a coating. Indeed, as the coating is typically applied at a temperature above ambient temperature, the packaging system according to the invention is particularly suited, for example in the case of a container comprising a plurality of packaged products, whereby each of the packaged product contains gas, the pressure of the gas comprised in the packaged product being of at least 90% and up to 110% of the ambient pressure.

Tensile Strength

[0029] For the purpose of measuring tensile strength of a layer, the layer may be considered as a tablet itself.

[0030] Depending on the composition of the starting material, and the shape of the tablets, the used compacting force may be adjusted to not affect the tensile strength, and the disintegration time in the washing machine. This process may be used to prepare homogenous or layered tablets of any size or shape.
For a cylindrical tablet, the tensile strength corresponds to the diametrical fracture stress (DFS) which is a way to express the strength of a tablet or layer, and is determined by the following equation :

Where F is the maximum force (Newton) to cause tensile failure (fracture) measured by a VK 200 tablet hardness tester supplied by Van Kell industries, Inc. D is the diameter of the tablet or layer, and t the thickness of the tablet or layer. For a non round tablet, πD may simply be replaced by the perimeter of the tablet.
(Method Pharmaceutical Dosage Forms : Tablets Volume 2 Page 213 to 217). A tablet having a diametral fracture stress of less than 20 kPa is considered to be fragile and is likely to result in some broken tablets being delivered to the consumer. A diametral fracture stress of at least 25 kPa is preferred.
This applies similarly to non cylindrical tablets, to define the tensile strength, whereby the cross section normal to the height of the tablet is non round, and whereby the force is applied along a direction perpendicular to the direction of the height of the tablet and normal to the side of the tablet, the side being perpendicular to the non round cross section.

Tablet Dispensing

[0031] The rate of dispensing of a detergent tablet can be determined in the following way:
Two tablets, nominally 50 grams each, are weighed, and then placed in the dispenser of a Baucknecht® WA9850 washing machine. The water supply to the washing machine is set to a temperature of 20 °C and a hardness of 21 grains per gallon, the dispenser water inlet flow-rate being set to 8 l/min. The level of tablet residues left in the dispenser is checked by switching the washing on and the wash cycle set to wash program 4 (white/colors, short cycle). The dispensing percentage residue is determined as follows:

[0032] The level of residues is determined by repeating the procedure 10 times and an average residue level is calculated based on the ten individual measurements. In this stressed test a residue of 40 % of the starting tablet weight is considered to be acceptable. A residue of less than 30% is preferred, and less than 25% is more preferred.
It should be noted that the measure of water hardness is given in the traditional "grain per gallon" unit, whereby 0.001 mole per litre = 7.0 grain per gallon, representing the concentration of Ca²⁺ ions in solution.

Effervescent

[0033] In another preferred embodiment of the present invention the tablets further comprises an effervescent.
Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas,

[0034] Further examples of acid and carbonate sources and other effervescent systems may be found in : (Pharmaceutical Dosage Forms : Tablets Volume 1 Page 287 to 291).
An effervescent may be added to the tablet mix in addition to the detergent ingredients. The addition of this effervescent to the detergent tablet improves the disintegration time of the tablet. The amount will preferably be between 5 and 20 % and most preferably between 10 and 20% by weight of the tablet.

[0035] Preferably the effervescent should be added as an agglomerate of the different particles or as a compact, and not as separated particles.
Due to the gas created by the effervescency in the tablet, the tablet can have a higher D.F.S. and still have the same disintegration time as a tablet without effervescency. When the D.F.S. of the tablet with effervescency is kept the same as a tablet without, the disintegration of the tablet with effervescency will be faster.
Further dissolution aid could be provided by using compounds such as sodium acetate or urea. A list of suitable dissolution aid may also be found in Pharmaceutical Dosage Forms: Tablets, Volume 1, Second edition, Edited by H.A. Lieberman et all, ISBN 0-8247-8044-2.

Detersive surfactants

[0036] Surfactant are comprised in the tablet or powder according to the invention. The dissolution of surfactants is favoured by the addition of the highly soluble compound.
Nonlimiting examples of surfactants useful herein typically at levels from about 1 % to about 55%, by weight, include the conventional C₁₁-C₁₈ alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C₁₀-C₂₀ alkyl sulfates ("AS"), the C₁₀-C₁₈ secondary (2,3) alkyl sulfates of the formula CH₃(CH₂)_×(CHOSO_3-M⁺) CH₃ and CH₃ (CH₂)_y(CHOSO_3-M⁺) CH₂CH₃ where x 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 C₁₀-C₁₈ alkyl alkoxy sulfates ("AE_XS"; especially EO 1-7 ethoxy sulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C₁₀-₁₈ glycerol ethers, the C₁₀-C₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C₁₂-C₁₈ alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C₁₂_C₁₈ alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈ betaines and sulfobetaines ("sultaines"), C₁₀-C₁₈ amine oxides, and the like, can also be included in the overall compositions. The C₁₀-C₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C₁₂-C₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈ N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀-C₂₀ conventional soaps may also be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆ soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. In a preferred embodiment, the tablet comprises at least 5% per weight of surfactant, more preferably at least 15% per weight, even more preferably at least 25% per weight, and most preferably between 35% and 45% per weight of surfactant.

Non gelling binders

[0037] Non gelling binders can be integrated to the particles forming the tablet or powder in order to further facilitate dissolution.
If 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 second edition, has the following binders classification: Acacia, Alginic Acid, Carbomer, Carboxymethylcellulose sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil type I, Hydroxyethyl cellulose, Hydroxypropyl methylcellulose, Liquid glucose, Magnesium aluminum silicate, Maltodextrin, Methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein. Most preferable binders also have an active cleaning function in the laundry wash such as cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene triamines, or others such as pentaamines, ethoxylated polyethylene amines, maleic acrylic polymers.
Non-gelling binder materials are preferably sprayed on and hence have an appropriate 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 may be sprayed in molten form. However, they may also be solid binders incorporated into the matrix by dry addition but which have binding properties within the tablet.
Non-gelling binder materials are preferably used in an amount within the range from 0.1 to 15% of the composition, more preferably below 5% and especially if it is a non laundry active material below 2% by weight of the tablet.
It is preferred that gelling binders, such as nonionic surfactants are avoided in their liquid or molten form. Nonionic surfactants and other gelling binders are not excluded from the compositions, but it is preferred that they be processed into the detergent tablets as components of particulate materials, and not as liquids.

Builders

[0038] Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may 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 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na₂SiO₅ morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi_xO_2x+1.yH₂O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na₂SiO₅ (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

        M_z(zAlO₂)_y]·xH₂O

wherein z and y are integers of at least 6, the molar ratio of z to y is in the range 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 can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed 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 an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

        Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O

wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted 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 builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized 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. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of 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 detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed 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 dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various 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

[0039] The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns 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 bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:

        R¹N(R⁵)C(O)R²C(O)L  or  R¹ C(O)N(R⁵)R²C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbon atoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzene-sulfonate, (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 comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazin-type is:

[0040] Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:

wherein R⁶ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized 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 will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include Mn^IV₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂, Mn^III₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)_2-(CIO₄)₂, Mn^IV₄(u-O)₆(1,4,7-triazacyclononane)₄(CIO₄)₄, Mn^IIIMn^IV₄(u-O)₁(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(PF₆), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States 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 not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.

Enzymes

[0041] Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration. The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).

[0042] Amylases include, for example, α-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
The cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein.
Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.

[0043] Other components which are commonly used in detergent compositions and which may be incorporated into the detergent tablets of the present invention include chelating agents, soil release agents, soil antiredeposition agents, dispersing agents, brighteners, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.

[0044] The compounds disclosed above for a product and reacting with moisture are advantageously packed in a packaging system according to the invention.

[0045] Materials suitable for use as a flexible sheet include mono-layer, co-extruded or laminated films. Such films may comprise various components, such as poly-ethylene, poly-propylene, poly-styrene, poly-ethylene-terephtalate. In a most preferred embodiment of the invention, the packaging system is composed of a poly-ethylene and bi-oriented-poly-propylene co-extruded film with an MVTR of less than 1 g/day/m². The MVTR of the packaging system is preferably of less than 10 g/day/m², more preferably of less than 5 g/day/m², even more preferably of less than 1 g/day/m² and most preferably of less than 0.5 g/day/m². The film (2) may have various thicknesses. The thickness should typically be between 10 and 150 µm, preferably between 15 and 120 µm, more preferably between 20 and 100 µm, even more preferably between 25 and 80 µm and most preferably between 30 and 40 µm.

[0046] The packing method used are typically the wrapping methods disclosed in WO92/20593, including flow wrapping or over wrapping. This document is included as a reference for the present invention. When using such processes, a longitudinal seal is provided, which may be a fin seal or an overlapping 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 re-closing means as described in WO92/20593. In particular, using a twist, a cold seal or an adhesive is particularly suited to the packaging system of the present invention. 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 may provide both the initial seal and re-closure of the packaging system. In such a case the adhesive or cold seal band may correspond to a region having a cohesive surface, i.e. a surface which will adhere only to another cohesive surface. Such re-closing means may also comprise spacers which will prevent unwanted adhesion. Such spacers are described in WO 95/13225, published on the 18^th of May 1995. There may also be a plurality of spacers and a plurality of strips of adhesive material. The main requirement is that the communication between the exterior and the interior of the package should be minimal, even after first opening of the packaging system. In a preferred embodiment of the present invention, a cold seal is used, and in particular a grid of cold seal, whereby the cold seal is adapted so as to facilitate opening of the packaging system.

[0047] Preferably, the tablets of the invention are containing a detergent composition. Protection against moisture is an issue which is more acute for detergent tablets than for usual detergent powders. Indeed, when exposed to moisture, a first effect on detergent compositions is to soften its structure and consistency. This change in consistency of the detergent composition due to moisture does not always have significant consequences on the chemical properties of the detergent. However, a change in structure will be significant for the tablets because they are likely to break, thus making use awkward and unpleasant. However, this applies less to powders in a granular form as dosing is made by scooping the powder.

[0048] The invention is particularly useful in the case of a container comprising a plurality of packaged products. Typically, each of the packaged product contains gas, the pressure of the gas comprised in the packaged product being of at least 90% and up to 110% of the ambient pressure. Indeed, such a container will contain the products preferably placed in an ordered manner, so that filing of such a container would be difficult with packages being bulged or out of shape due to a pressure gradient between the outside and the inside of the packages.

[0049] In a preferred embodiment, the container is stored in a position such that for each or for some of the packaged products, the plait is held flat against the part of the sheet by the weight of the product. In other words, the plait is situated under the product in the storage position. In this manner, the plait is held against the micro-hole by gravity, thus improving the valve closure effect. It should be noted that in case of a large gravity force applying itself onto the plait and closing the micro-hole, release of pressure build-up can be facilitated by integrating evacuation rails consisting for example in having the plait formed so that it has a wavy section, each wave acting as an evacuation rail for gas from the micro-hole. Such a wavy section is typically to be found on the seal of a package, whereby the seal has been made with sealing jaws having a wavy profile so as to reinforce the strength of the seal. This in most useful in combination with the invention when a plurality of packages are piled together in a container, so that the gravity force of each pack is accumulated to be applied on the packages situated towards the bottom of the pile when the container is in the storing position.

Claims

1. A packaging system comprising a sheet of flexible material, the sheet of flexible material comprising a plait, the plait being held flat against a part of the sheet which is thereby covered by the plait, the sheet of flexible material comprising a micro-hole, characterised in that the micro-hole is located in the covered part of the sheet.

2. A packaging system according to claim 1, whereby the micro-hole has a diameter of at least 0.2 mm and of less than 0.4 mm.

3. A packaging system according to claim 1, whereby the sheet of flexible material forms a pocket, the pocket being sealed with a first end seal, a second end seal and a longitudinal seal, the first and second end seals being both in a direction intersecting the direction of the longitudinal seal, each seal being formed by sealing together two opposing parts of the sheet of flexible material, the longitudinal seal forming the plait and being held flat onto the part of the covered part of the sheet by the first and second end seals.

4. A packaged product comprising the combination of a product and of a packaging system according to any of the above claims containing the product, whereby the product comprises a component reacting with moisture.

5. The packaged product according to claim 4, whereby the reaction of the component with moisture produces gas.

6. The packaged product according to claim 4, whereby part of the product has been submitted to a temperature of more than 30°C prior to being packaged.

7. The packaged product according to claim 4, 5 or 6, whereby the product is a detergent tablet.

8. The packaged product according to claim 7, whereby the detergent tablet comprises a soft core and a coating.

9. A container, whereby the container comprises a plurality of packaged product according to any of claims 4 to 8.

10. A container according to claim 9, whereby the container is stored in a position such that for each of the packaged products, the plait is held flat against the part of the sheet by the weight of the product.