DE60125847T3 - Packaging for detergent - Google Patents

Abstract

A water-soluble pouch suitable for use in machine dishwashing and which comprises a plurality of compartments in generally superposed or superposable relationship, each containing one or more detergent active or auxiliary components, wherein at least one of the plurality of compartments of the water-soluble pouch comprises a liquid composition and wherein the preferred pouch has a volume of from about 5 to about 70 ml and a longitudinal/transverse aspect ratio in the range from about 2:1 to about 1:8, more preferably from about 1:1 to about 1:4. The water-soluble pouch allows for optimum delivery of dishwashing detergent.

Description

Field of the invention

The present invention is in the field of dishwashing, more particularly relates to a package for the storage, distribution and display of a water-soluble multi-compartment bag, which has been designed to fit into the dispenser of dishwashers and a product in to deliver the pre-wash, main wash and / or rinse cycles of the dishwasher. The pouch contains a cleaning composition which is released upon disintegration of the pouch.

Background of the invention

It has been found that dishwashing detergents provided in dosage units are more attractive and convenient for some consumers because the consumer no longer has to measure the product, thus a more precise dosage is possible and unprofitable overdosing or underdosing is avoided. For this reason, machine dishwashing detergent products in tablet form have become very popular. Detergent products in pouch form are also known in the art, having the advantage over tablets of avoiding contact of the consumer's fingers with the dishwashing composition which may contain bleaching agents and / or other irritants.

The machine dishwashing process typically includes an initial pre-wash cycle, a main wash cycle, and multiple hot rinse cycles. If the detergent is added at the beginning of the main wash cycle, better performance is achieved than adding the detergent in the pre-wash cycle as it can be lost with the first water. For laundry washing machines, the detergent can be added to the drum or dispenser, but for dishwashers, the detergent is generally added to the main wash cycle via a dispenser to avoid premature prewash dissolution. The amount of detergent is therefore limited by the volume of the dispenser. Dispensers vary from manufacturer to manufacturer in volume and shape. In the case of bulk detergents (i.e., powder, paste, and liquids), the volume of the dispenser is a critical factor. In the case of unitized dosage forms, such as tablets, the geometry and shape of the dispenser also play a major role.

The tablets can be designed so that their size and shape fits all machines. One of the disadvantages of detergent tablets is that in their manufacturing process the additional step of powder compaction is required. This lowers the enzymatic activity and slows the rate of dissolution of the ingredients that make up the tablet, or requires the use of complex and expensive disintegration systems, or complicates the differential resolution of the active detergent ingredients.

Some detergent ingredients used in dishwashing detergent compositions are liquids. The inclusion of these liquid ingredients in a solid detergent composition can be difficult or expensive. In addition, certain ingredients are preferably transported in liquid form and supplied to detergent manufacturers and require additional and sometimes expensive process steps to be incorporated into a solid detergent composition. An example of these detergent ingredients are surfactants, especially nonionic surfactants, which are typically liquid at room temperature or are typically shipped in liquid form and supplied to detergent manufacturers. Another example is organic solvents.

Current methods of incorporating liquid ingredients into solid detergent compositions involve absorbing the liquid ingredient onto a solid carrier, for example by mixing, agglomeration or spray-on methods. Typically, because of the difficulty and cost of incorporating these liquid ingredients into a solid detergent, solid detergent compositions comprise only minor amounts of these liquid detergent ingredients. In addition, the incorporation of liquid ingredients into solid detergent compositions can affect the dissolution properties of the composition (for example, as a result of the formation of surfactant gel phases), increase the moisture absorption of water-sensitive ingredients and also lead to fluidity problems. It would be advantageous to have a detergent composition in which the various ingredients can be in their natural state, ie, liquid or solid. This would simplify the manufacturing process, increase the stability of the ingredients, and also allow the dispensing of liquid ingredients before or after dispensing solid ingredients. For example, the differential resolution would be of active ingredients in the case of enzyme / bleach compositions, to prevent the oxidation of enzymes by the bleach in the dishwashing liquor. It would also be advantageous to separate bleach from perfumes.

Another factor which may contribute to the inefficient delivery of active ingredients to the rinse liquid is, in the case of tablets, the need to add carriers such as porous materials having the ability to bind liquid active ingredients, binders and disintegrators. In particular, the incorporation of liquid surfactants into powdered detergent composition can cause considerable processing difficulties and also the problem of poor dissolution by the formation of surfactant gel phases.

There is still a need for a unitized multi-chamber dosage form that fits into the dispensers of different types of dishwashers and allows the simultaneous dispensing of incompatible ingredients and ingredients in various physical forms. There is also a need for a simplified manufacturing process for the production of multi-compartment pouches and multi-compartment pouches having improved strength, handling, and dissolution properties as well as superior aesthetic properties.

WO97 / 26315 describes a tinted or uncolored translucent container, such as a bottle containing a tinted cleaning liquid. In particular, it discloses a filled package of a blue or violet tinted clear liquid cleaning composition which is in a transparent, blue or violet tint or tinted container such that the appearance of the filled package is substantially transparent or neutral in color or slightly blue / green or slightly yellow-green in appearance.

GB2235206 describes a detergent system comprising two or more components, each individually packaged and dosed, and wherein each of the components has a distinctive color to distinguish them from one another.

EP0414462 discloses a laundry treatment product in the form of a single chamber or multi-compartment bag which is capable of delivering its contents to the wash liquor during the laundry process. D4 also discloses a multi-compartment bag; as EP0414462 However, it is completely silent regarding transparent packaging for storing the bags.

Summary of the invention

The present invention provides a display package according to claim 1 of the accompanying claims and claim 5 of the appended claims.

In a preferred embodiment, a transparent, preferably transparent dishwashing detergent package is provided, wherein the number of different groups of bags or other unit doses is at least 2, preferably at least 3, more preferably at least 4 and especially at least 6 and wherein the number of unit doses per package is at least 10 is preferably at least 16, and more preferably at least 20. The unit doses are multi-compartment bags, each compartment itself possibly being different visually or otherwise from the remainder of the chambers in an individual bag. In a preferred embodiment, groups of bags are different in color. At least one group of pouches has a chamber which differs visually, for example in terms of color, from the corresponding chambers in one or more other groups of pouches. Preferably, in such embodiments, all bag groups have at least one "common" chamber, i. H. their appearance is the same from group to group. Preferably, the visually distinct chamber contains a liquid, gel or paste; the common chamber contains a powder or a tablet. The pouches may be arranged in the package in any form, either random or in order, for example in suitable arrangements comprising layers wherein each pouch comprises at least one chamber which is in color from the chambers of the remaining pouches therein Layer different. The pack may be made of plastic or any other suitable material, provided that the material is strong enough to protect the bags during transport. This type of packaging is also very useful because the user does not have to open the package to see how many bags are left, the different colored bags are very easy to see from the outside.

Preferably in the invention according to claim 1 and substantially in the invention according to claim 5, the bag has a volume of 5 to 70 ml, preferably 15 to 60 ml, more preferably 18 to 57 ml and the aspect ratio of longitudinal axis to transverse axis is in the range from 2: 1 to 1: 8, preferably from 1: 1 to 1: 4. The longitudinal dimension is determined by the maximum height of the bag when the bag lies on one of its bases having the maximum base area, the bag chambers being superimposed in a longitudinal direction, ie one above the other, and under a static load of about 0, 02 kN (2 kg). The transverse dimension is defined as the maximum width of the bag in a plane that is under the same conditions perpendicular to the longitudinal direction. These dimensions are suitable for the dispensers of most dishwashers. Although the shape of the bag can vary widely, preferred bags have a footprint that is as similar as possible to the footprint of most dispensers, which is generally rectangular, in order to maximize the available volume.

In one embodiment, the plurality of chambers of the water-soluble bag are in a generally stacked relationship, and the bag includes upper and lower, generally opposing outer walls, skirt-like sidewalls forming the sides of the bag, and one or more inner partitions that separate different chambers and each of the upper and lower outer walls and skirt-like sidewalls is formed by thermoforming, vacuum forming, or a combination thereof.

In a preferred embodiment, each inner divider wall of the water-soluble multi-compartment pouch is secured to an outer or side wall of the pouch along a single seal seam or both outer and sidewall of the pouch along a plurality of seal seams that do not at least partially overlap. Preferably, each partition is secured to one or more outer or side walls by hot or solvent seals.

In particularly preferred embodiments, at least one inner dividing wall of the multi-chamber bag is secured along a first continuous sealing seam to an upper or lower outer wall, and the outer wall and / or the dividing wall is secured along a second continuous sealing seam to the peripheral sidewall, wherein the sealing seams in the case of heat seals substantially do not overlap and in the case of solvent seals at least partially do not overlap.

Non-intersecting seal seams are particularly advantageous in the case of multi-compartment pouches made by a process comprising various non-simultaneous steps of heat sealing. Without wishing to be bound by theory, it is believed that the heat-sealing mechanism involves the step of water evaporation from the film, therefore, it is very difficult to achieve a good intersecting seal if the two seal seams are not formed simultaneously. Heat-sealing is preferred in cases where the bags are filled with water-sensitive ingredients. Solvent sealing can lower processing costs, produce stronger seal seams, and speed up the process. Partially non-intersecting sealing seams allow the arrangement of several chambers of different sizes one above the other.

Preferably, at least one inner dividing wall of the multi-chamber bag is secured to the upper outer wall along a first sealing seam defining the waistline of the skirt-like wall, wherein the second non-intersecting or at least partially non-intersecting sealed seam preferably extends below the sealed seam defining the waistline in the direction of lower outer wall is offset. The apron-like sidewall is also preferably lightly gathered or folded in the finished pouch to provide a mattress-like appearance.

In another embodiment, the water-soluble bag comprises a plurality of chambers in a juxtaposed but generally superimposable relationship (the chambers may be folded over one another, for example). The bag includes upper and lower, generally opposing outer walls, one or more skirt-like sidewalls, and one or more outer partitions, each of the upper and lower outer walls and skirt-like sidewalls being formed by thermoforming, vacuum forming, or a combination thereof.

In one embodiment, at least one of the plurality of chambers of the water-soluble bag comprises a powder or compacted powder composition. The powder composition usually comprises conventional solids used in dishwashing detergents, such as builders, alkalinity sources, enzymes, bleaches, etc. The powder composition may be in the form of dry powder, hydrated Powders, agglomerates, encapsulated materials, extrudates, tablets or a mixture thereof. Also useful are water-soluble bags having different chambers comprising different powder compositions, as a rule, compositions in different chambers comprise incompatible active ingredients or active ingredients which must be dispensed at different times during the dishwashing process. It is advantageous to have bleaching agents and enzymes in different chambers.

In a preferred embodiment, at least one of the powder chambers comprises particulate bleach. The bleaching agent is preferably selected from inorganic peroxides including perborates and percarbonates, organic peroxyacids including preformed monoperoxycarboxylic acids such as phthaloylamidoperoxyhexanoic acid, and diacyl peroxides.

In the case of powder compositions, differential resolution can be achieved, for example, by varying the degree of powder compaction and / or the particle size of the powder compositions in the same chamber or in different chambers. Another way to achieve differential resolution is to use water-soluble films of different thickness or degree of solubility or different rate of solubility under use conditions. The film solubility can be controlled by, for example, pH, temperature, ionic strength or any other means. In order to achieve a phased or sequential delivery of detergent actives, it is preferred that each of the chambers of the bag have a different rate of decomposition or different dissolution profile under use conditions.

In another embodiment, at least one of the plurality of chambers of the water-soluble bag comprises a liquid composition. The liquid compositions include conventional liquid materials used in dishwashing detergents, such as nonionic surfactants, or the organic solvents described below. In preferred embodiments, the liquid composition comprises cleansing enzyme. Particularly useful are water-soluble pouches having a chamber comprising a liquid composition and another chamber comprising a solid composition. In the case of liquid compositions, particularly liquid compositions, enclosed in a secondary packaging, it is desirable to have in the composition a water content which is similar to the water content in the film to avoid water transfer from one to another. In cases where the water content in the composition is lower than in the film, water may migrate from the film to the composition and make the water-soluble bag brittle. For similar reasons, it is also desirable to have a similar amount of plasticizer in the composition and in the film.

In another embodiment, at least one of the chambers of the water-soluble bag comprises a composition in the form of a paste. The multi-compartment bags may also include compositions in the form of a gel or a wax.

In preferred embodiments, at least one of the compositions of the water-soluble pouch comprises an organic solvent system that is compatible with the water-soluble pouch. The organic solvent system may simply function as a liquid carrier, however, in preferred compositions, the solvent may aid in the removal of coked, baked, or burnt-on soil, and thus has a detergent function of its own. The organic solvent system (comprising a single solvent compound or a mixture of solvent compounds) preferably has a volatile organic content of greater than 0.1 kPa (1 mm Hg), and more preferably greater than 0.01 kPa (0.1 mm Hg). of less than 50% by weight, preferably less than 20% by weight and more preferably less than 10% by weight of the solvent system. The content of volatile organic compounds of the solvent system is defined herein as the content of organic components in the solvent system having a vapor pressure above the prescribed limit at 25 ° C and atmospheric pressure.

The organic solvent system for use herein is preferably of organoamine solvents including alkanolamines, alkylamines, alkyleneamines, and mixtures thereof; alcoholic solvents including aromatic, aliphatic (preferably C ₄ -C ₁₀ ) and cycloaliphatic alcohols and mixtures thereof; Glycols and glycol derivatives including C ₂ -C ₃ (poly) alkylene glycols, glycol ethers, glycol esters and mixtures thereof; and mixtures selected from organoamine solvents, alcoholic solvents, glycols and glycol derivatives. In a preferred embodiment, the organic solvent comprises organoamine (especially alkanolamine) solvent and glycol ether solvent, preferably in a weight ratio of about 3: 1 to about 1: 3, wherein the glycol ether solvent is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and mixtures thereof. Preferably, the glycol ether is a mixture of diethylene glycol monobutyl ether and propylene glycol butyl ether, especially in a weight ratio of 1: 2 to 2: 1.

Detailed description of the invention

The invention provides a detergent package with improved visibility that makes it very easy for the consumer to estimate the amount of bags in the package.

The dishwashing composition or ingredients for use herein are contained in the interior volume of the bag and are typically separated from the outside environment by a protective wall of water-soluble material. Typically, various components of the composition contained in different compartments of the bag are separated by a protective wall of water-soluble material.

The chambers of the water-soluble bag may differ in color, for example, a first chamber may be green or blue, and a second chamber may be white or yellow. One compartment of the bag may be opaque or semi-opaque, and a second compartment of the bag may be translucent, transparent or semi-transparent. The chambers of the bag may be the same size and the same internal volume or have different sizes and different internal volumes.

Suitable water-soluble pouches include, for example, dual-chamber pouches comprising loose powder, compacted powder or tablet in a first chamber and a liquid, paste or waxy or translucent gel detergent in a second chamber. The second liquid, paste or gel chamber could also contain a separately packaged powder, for example in the form of microbeads, strips or one or more bead beads, allowing the effect of sustained or sequential release. If the first chamber comprises a tablet, that tablet may have a recess of such a size and geometric shape (eg rectangular, round or oval) that the second chamber can be partially or completely received. In pouches comprising powders in the first chamber, the powder may be arranged in layers which may be of different colors.

Alternatively, dual-chamber bags may comprise powders of the same or different colors in the two chambers, the powders comprising speckles of one or more colors or having a uniform color. One of the two chambers could also contain a separate compacted powder phase, for example in the form of microbeads, noodles or one or more bead balls (allowing for delayed or controlled release). Other dual-chamber bags include a mono- or multi-phase liquid, pasty or waxy or translucent gel detergent in the two chambers, each chamber comprising either multi-phase liquid or gels thereof or different color and / or density. One or both of these chambers may also contain a separate compacted powder phase, for example, in the form of microbeads, noodles or one or more bead beads (allowing for delayed or sequential release). The chambers of all of the two-compartment bags described above may be superimposed or in overlayable (eg, side-by-side) relationship.

Multi-compartment bags with three compartments may have superimposed compartments of any geometrical shape in a sandwiched arrangement, for example with either loose or compacted powder in the two outer compartments and a liquid, paste or waxy or translucent gel in the middle compartment. On the other hand, the liquid, paste or waxy or translucent gel may be in the two outer chambers and may contain solid suspended solids and granules, and the powder may be present in the middle chamber. A multi-chamber bag may also have in the first chamber a tablet with more than one well and a number of other chambers that are wholly or partially in the wells of the tablet.

The bags may be packaged in a string, wherein each bag is individually separable by a perforated line. Thus, each bag can be torn off individually by the consumer of the rest of the strand.

Particularly suitable for use herein are multi-chambered pouches having a first chamber comprising a liquid composition and a second chamber comprising a powdered composition wherein the weight ratio of the liquid to the solid composition is about 1:30 to about 30: 1, preferably about 1 : 1 to about 1:25 and more preferably about 1:15 to about 1:20.

To allow them to be deformed and fitted into a dispenser when pressure is applied thereto, pouches or pouches containing a liquid component typically contain an air bubble having a volume of up to about 50%, preferably up to about 40%. , more preferably up to about 30%, more preferably up to about 20%, more preferably up to about 10% of the volume of the chamber.

The pouch is preferably made of a pouch material which is water soluble or dispersible and has a water solubility of at least 50%, preferably at least 75% or even at least 95% as measured by the method described below using a glass filter having a maximum pore size of 20 microns.

50 grams ± 0.1 grams of bag material are placed in a pre-weighed 400 ml beaker and 245 ml ± 1 ml of distilled water are added. This is stirred vigorously with a magnetic stirrer set at 600 rpm for 30 minutes. The mixture is then filtered through a qualitative sintered glass fluted filter with the pore size defined above (20 microns max.). The water is dried from the collected filtrate by any conventional method and the weight of the remaining material (which is the dissolved or dispersed fraction) is determined. Thereafter, the percent solubility or the percent dispersibility can be calculated.

Preferred bag materials are polymer materials, preferably polymers, which are formed into a film or a sheet. The bag material can be obtained, for example, by casting, blow molding, extruding or extrusion blow molding the polymer material as known in the art.

Preferred polymers, copolymers or derivatives thereof suitable for use as pouch materials are selected from polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyamino acids or peptides, polyamides , Polyacrylamide, copolymers of maleic / acrylic acids, polysaccharides, including starch and gelatin, natural gums such as xanthum and carrageenan. More preferred polymers are selected from polyacrylates and water soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinylalcohol copolymers and hydroxypropylmethylcellulose (HPMC) and mixtures thereof , Preferably, the concentration of polymer in the bag material, for example a PVA polymer, is at least 60%.

The polymer may have any weight average molecular weight, preferably about 1000 to 1,000,000, more preferably about 10,000 to 300,000, even more preferably about 20,000 to 150,000.

Blends of polymers can also be used as the bag material. This may be beneficial in controlling the mechanical and / or solution properties of the chambers or bag, depending on the application and the requirements required. Suitable mixtures include, for example, mixtures in which one polymer has higher water solubility than another polymer and / or one polymer has higher mechanical strength than another polymer. Also suitable are polymer blends having different weight average molecular weights, for example a blend of PVA or a copolymer thereof having a weight average molecular weight of about 10,000-40,000, preferably about 20,000, and a PVA or a copolymer thereof having an average molecular weight ( Weight average) of about 100,000 to 300,000, preferably about 150,000.

Also useful herein are polymer blend compositions comprising, for example, hydrolytically degradable and water-soluble polymer blends, such as polylactide and polyvinyl alcohol, obtained by blending polylactide and polyvinyl alcohol, typically containing about 1-35 weight percent polylactide and about 65 weight percent % to 99% by weight of polyvinyl alcohol.

Preferred for use herein are polymers that are hydrolyzed to about 60% to about 98%, preferably about 80% to about 90% hydrolyzed to improve the dissolution properties of the material.

Most preferred pouch materials are PVA films, known under the trade designation Monosol M8630, as sold by Chris-Craft Industrial Products of Gary, Indiana, USA, and PVA films having appropriate solubility and ductility properties. Other films suitable for use herein include films known under the trade designation PT Film or the IC series of films available from Aicello or VF-HP film available from Kuraray.

The bag material herein may also include one or more additional ingredients. It may, for example, be low, plasticizer, z. For example, glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol and mixtures thereof. Other additives include functional detergent additives to be delivered to the wash liquor, for example, organic polymeric dispersants, etc.

The detergent and cleaning compositions herein may comprise conventional detergent-active ingredients and may also include organic solvents having a cleaning function and organic solvents having a carrier or diluent function or other specialized function. The compositions are generally constructed and include one or more active detergent ingredients which may be bleaches, surfactants, sources of alkalinity, enzymes, thickeners (in the case of liquid, paste, cream or gel compositions), corrosion inhibitors (e.g., sodium silicate), and blasting - And binders (in the case of powder, granules or tablets) may be selected. Highly preferred detergent ingredients include a builder compound, an alkalinity source, a surfactant, an enzyme and a bleach.

Unless otherwise specified, the ingredients described below may be included in either the organic solvent compositions and / or the detergent or cleaning compositions.

The organic solvents should be selected so that they are compatible with the tableware / cookware as well as with the various parts of an automatic dishwashing machine. In addition, the solvent system should be effective and safe to use, with a volatile organic content above 0.1 kPa (1 mm Hg) (and preferably above 0.01 kPa (0.1 mm Hg)) of less than about 50 Wt%, preferably less than about 30 wt%, more preferably less than about 10 wt% of the solvent system. They should also have very mild, pleasant odors. The individual organic solvents used herein generally have a boiling point greater than about 150 ° C, a flash point greater than about 100 ° C, and a vapor pressure of less than about 0.1 kPa (1 mm Hg), preferably less than 0.01 kPa (0 , 1 mm Hg) at 25 ° C and atmospheric pressure.

Solvents useful herein include: i) alcohols, such as benzyl alcohol, 1,4-cyclohexanedimethanol, 2-ethyl-1-hexanol, furfuryl alcohol, 1,2-hexanediol, and other similar materials; ii) amines such as alkanolamines (eg primary alkanolamines: monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyldiethanolamine; secondary alkanolamines: diethanolamine, diisopropanolamine, 2- (methylamino) ethanol; ternary alkanolamines: triethanolamine, triisopropanolamine); Alkyleneamines (e.g., primary alkyleneamines: monomethylamine, monoethylamine, monobutylamine, monopentylamine, cyclohexylamine), secondary alkyleneamines: (dimethylamine), alkyleneamines (primary alkyleneamines: ethylenediamine, propylenediamine), and other similar materials; iii) esters such as ethyl lactate, methyl ester, ethyl acetoacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and other similar materials; iv) glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol butyl ether and other similar materials; v) glycols such as propylene glycol, diethylene glycol, hexylene glycol (2-methyl-2,4-pentanediol), triethylene glycol, composition and dipropylene glycol, and other similar materials; and mixtures thereof.

surfactant

In the methods of the present invention for use in automatic dishwashing, the detersive surfactant, preferably by itself or in combination with other ingredients (ie suds suppressors), is low foaming. Surfactants useful herein include anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and alkenyl sulfonates, alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyl taurates and alkyl succinates and sulfosuccinates wherein the alkyl, alkenyl or acyl moiety C ₅ -C ₂₀ , preferably C ₁₀ -C ₁₈ , linear or branched; cationic surfactants such as chloroesters ( US-A-4228042 . US-A-4239660 and US-A-4260529 ) and C ₆ -C ₁₆ mono-N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups; nonionic surfactants with a low and high cloud point and mixtures thereof including nonionic alkoxylated surfactants (especially ethoxylates derived from primary C ₆ -C ₁₈ alcohols), ethoxylated-propoxylated alcohols (eg. as Poly-Tergent SLF18 ^® from BASF), epoxy-capped poly (oxyalkylated) alcohols (e.g., poly-Tergent SLF18B ^® from BASF -. see WO 94/22800 ), Ether-capped poly (oxyalkylated) alcohol surfactants, and polyoxyethylene-polyoxypropylene block polymeric compounds such as PLURONIC ^®, REVERSED PLURONIC ^® and TETRONIC ^® from BASF-Wyandotte Corp., Wyandotte, Michigan, USA; amphoteric surfactants such as the C ₁₂ -C ₂₀ alkyl amine oxides (preferred amine oxides for use herein include C ₁₂ lauryldimethyl amine oxide, C ₁₄ and C ₁₆ hexadecyldimethyl amine oxide) and alkyl amphocarboxylic surfactants such as Miranol ^™ C2M; and zwitterionic surfactants such as the betaines and sultaines; and mixtures thereof. Suitable surfactants herein are for example in US-A-3,929,678 . US-A-4,259,217 . EP-A-0414549 . WO-A-93/08876 and WO-A-93/08874 disclosed. Surfactants are typically present at a level of from about 0.2 wt% to about 30 wt%, more preferably from about 0.5 wt% to about 10 wt%, most preferably about 1 Wt .-% to about 5 wt .-% of the composition present. Surfactants preferred for use herein are low sudsing and include low cloud point nonionic surfactants and mixtures of higher sudsing surfactants with low cloud point nonionic surfactants which act as suds suppressors for them.

Builder

Suitable builders for use in the washing and cleaning compositions herein include water-soluble builders such as citrates, carbonates and polyphosphates, e.g. Sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and mixed sodium and potassium tripolyphosphate salts; and partially water-soluble or insoluble builders, such as crystalline layered silicates ( EP-A-0164514 and EP-A-0293640 ) and aluminosilicates including zeolites A, B, P, X, HS and MAP. The builder is typically present at a level of from about 1 wt% to about 80 wt%, preferably from about 10 wt% to about 70 wt%, most preferably from about 20 wt% to about 60% by weight of the composition is present.

Amorphous sodium silicates having a SiO ₂ : Na ₂ O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0, may also be used herein, although from a long shelf life standpoint Compositions containing a total of less than about 22%, preferably less than about 15% silicate (amorphous and crystalline) are highly preferred.

enzyme

Enzymes useful herein include bacterial and fungal cellulases such as Carezyme and Celluzyme (Novo Nordisk A / S); peroxidases; Lipases such as Amano-P (Amano Pharmaceutical Co.), M1 Lipase Lipomax ^® and ^® (Gist-Brocades) and Lipolase ^® and Lipolase Ultra ^® (Novo); cutinases; Proteases such as Esperase ^®, Alcalase ^®, Durazym ^® and Savinase ^® (Novo) and Maxatase ^®, Maxacal ^®, Properase ^®, and Maxapem ^® (Gist-Brocades); α- and β-amylases such as Purafect Ox Am ^® (Genencor) and Termamyl ^®, Ban ^®, Fungamyl ^®, Duramyl ^® and Natalase ^® (Novo); pectinases; and mixtures thereof. Enzymes are preferably added herein as prills, granules or cogranulates, typically in concentrations ranging from about 0.0001% to about 2% by weight of the pure enzyme composition.

bleach

Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium perborate mono- and tetrahydrates, and sodium percarbonate, optionally coated to provide a controlled rate of release (see, for example, US Pat. GB-A-1466799 via sulfate / carbonate coatings), preformed organic peroxyacids and mixtures thereof with precursors of organic peroxyacid bleaches and / or transition metal-containing bleach catalysts (especially manganese or cobalt). Inorganic perhydrate salts are normally present in amounts ranging from 1% to 40%, preferably from 2% to 30%, and more preferably from 5% to 25%, by weight Composition included. Preferred precursors of peroxyacid bleaches for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors; Peracetic acid precursors such as TAED, sodium acetoxybenzenesulfonate and pentaacetylglucose; Pernonanic acid precursors such as sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS) and Sodium nonanoyloxybenzenesulfonate (NOBS); amide substituted alkyl peroxyacid precursors ( EP-A-0170386 ) and benzoxazine peroxyacid precursors ( EP-A-0332294 and EP-A-0482807 ). Bleach precursors are typically included in amounts ranging from about 0.5% to about 25%, preferably from about 1% to about 10% by weight of the composition while the preformed organic peroxyacids themselves are generally included in amounts ranging from 0.5% to 25%, more preferably from 1% to 10%, by weight of the composition. Preferred bleach catalysts for use herein include manganese triazacyclononane and related complexes ( US-A-4246612 . US-A-5227084 ); Co, Cu, Mn and Fe bispyridylamine and related complexes ( US-A-5114611 ) and pentamine acetate-cobalt (III) and related complexes ( US-A-4810410 ) one.

Nonionic surfactants and suds suppressors

Suitable suds suppressors for use herein include nonionic surfactants having a low cloud point. "Cloud point" as used herein is a well-known property of nonionic surfactants that results from the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observed is called the "cloud point" (US Pat. cloud point) (see Kirk / Othmer, pp. 360-362). As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system component having a cloud point below 30 ° C, preferably below about 20 ° C, and even more preferably below about 10 ° C, and most preferably 7, 5 ° C. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially primary alcohol derived ethoxylates, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / PE / PO) reverse block polymers. Furthermore, such nonionic surfactants include low cloud point, for example, ethoxylated-propoxylated alcohol (eg. As Poly-Tergent ^® SLF18 from BASF) and epoxy-capped poly (oxyalkylated) alcohols (eg. As the Poly-Tergent ^® SLF18B series of nonionic surfactants of BASF, such as in US-A-5,576,281 described).

worin R¹ ein linearer Alkylkohlenwasserstoff mit durchschnittlich ungefähr 7 bis ungefähr 12 Kohlenstoffatomen ist, R² ein linearer Alkylkohlenwasserstoff mit ungefähr 1 bis ungefähr 4 Kohlenstoffatomen ist, R³ ein linearer Alkylkohlenwasserstoff mit ungefähr 1 bis ungefähr 4 Kohlenstoffatomen ist, x eine ganze Zahl von ungefähr 1 bis ungefähr 6 ist, y eine ganze Zahl von ungefähr 4 bis ungefähr 15 ist und z eine ganze Zahl von ungefähr 4 bis ungefähr 25 ist.Preferred low cloud point surfactants are the ether-capped poly (oxyalkylated) suds suppressors having the formula:

wherein R ^{1 is} a linear alkyl hydrocarbon having an average of about 7 to about 12 carbon atoms, R ^{2 is} a linear alkyl hydrocarbon having from about 1 to about 4 carbon atoms, R ^{3 is} a linear alkyl hydrocarbon having from about 1 to about 4 carbon atoms, x is an integer of about Y is an integer from about 4 to about 15 and z is an integer from about 4 to about 25.

• (i) einem 4- bis 8-gliedrigen, substituierten oder unsubstituierten, heterozyklischen Ring, der 1 bis 3 Heteroatome enthält; und
• (ii) linearen oder verzweigten, gesättigten oder ungesättigten, substituierten und unsubstituierten, cyclischen oder acyclischen, aliphatischen oder aromatischen Kohlenwasserstoffresten mit ungefähr 1 bis ungefähr 30 Kohlenstoffatomen;
• (b) mit der Maßgabe, dass, wenn R² (ii) ist dann ist entweder: (A) mindestens ein R¹ ungleich C₂- bis C₃-Alkylen; oder (B) R² weist 6 bis 30 Kohlenstoffatome auf, und mit der weiteren Maßgabe, dass, wenn R² 8 bis 18 Kohlenstoffatome besitzt, ist R nicht C₁- bis C₅-Alkyl.

Other low cloud point nonionic surfactants are the ether-capped poly (oxyalkylated) having the formula: R _I O (R _II O) _n CH (CH ₃ ) OR _III wherein R _{I is} selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals containing from about 7 to about 12 carbon atoms; R _{II may be the} same or different and is independently selected from the group consisting of branched or linear C ₂ to C ₇ alkylene in any given molecule; n is a number from 1 to about 30; and R _{III is} selected from the group consisting of:

• (i) a 4- to 8-membered, substituted or unsubstituted, heterocyclic ring containing 1 to 3 heteroatoms; and
• (ii) linear or branched, saturated or unsaturated, substituted and unsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms;
• (b) with the proviso that when R ^{2 is} (ii) then either: (A) at least one R ^{1 is} other than C ₂ to C ₃ alkylene; or (B) R ² has 6 to 30 carbon atoms, and with the further proviso that when R ^{2 has} 8 to 18 carbon atoms, R is not C ₁ to C ₅ alkyl.

Other ingredients useful herein include organic polymers having dispersant, anti-redeposition, soil release or other cleaning properties of the invention in concentrations of from about 0.1% to about 30%, preferably from about 0.5% to about 15%, most preferably from about 1% to about 10% by weight. % of the composition. Preferred anti-redeposition polymers herein include acrylic acid-containing polymers such as Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acrylic acid / maleic acid copolymers such as Sokalan CP5 and acrylic / methacrylic Copolymers. Preferred soil release polymers herein include alkyl and hydroxyalkyl celluloses ( US-A-4,000,093 ), Polyoxyethylenes, polyoxypropylenes and copolymers thereof and nonionic and anionic polymers based on terephthalate esters of ethylene glycol, propylene glycol and mixtures thereof.

Heavy metal sequestrants and crystallization retarders for use herein are generally present in concentrations of from about 0.005% to about 20%, preferably about 0.1% to about 10%, more preferably about 0, From 25% to about 7.5%, and most preferably from about 0.5% to about 5%, by weight of the composition, for example, diethylene triamine penta (methylene phosphonate), ethylenediamine tetra (methylene phosphonate), hexamethylene diamine tetra (methylenephosphonate), ethylenediphosphonate, hydroxyethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediaminetetraacetate, ethylenediamine-N, N'-disuccinate in their salt and free acid forms.

The compositions herein may contain a corrosion inhibitor, such as organic silver coating agents, in amounts of from about 0.05% to about 10%, preferably about 0.1% to about 5%, by weight of the composition (especially paraffins such as Winog 70, available from Wintershall, Salzbergen, Germany), nitrogen-containing anticorrosive compounds (for example, benzotriazole and benzimadazole - see GB-A-1137741 ) and Mn (II) compounds, especially Mn (II) salts of organic ligands in amounts of from about 0.005 wt.% to about 5 wt.%, preferably about 0.01 wt.% to about 1 wt. %, more preferably about 0.02 wt.% to about 0.4 wt.% of the composition.

Other ingredients useful herein include colorants, water-soluble bismuth compounds such as bismuth acetate and bismuth citrate in concentrations of from about 0.01% to about 5%, enzyme stabilizers such as calcium ions, boric acid, propylene glycol and chlorine bleach scavenger in amounts from about 0.01% to about 6%, Lime soap dispersant (see WO-A-93/08877 ), Suds suppressor (see WO-93/08876 and EP-A-0705324 ), polymeric dye transfer inhibitors, optical brighteners, fragrances, fillers and clay.

Liquid detergent compositions may contain minor amounts of low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol which may be used in the liquid detergent of the present invention. Other suitable carrier solvents used in minor amounts include glycerin, propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol, and mixtures thereof.

The bag may be of any shape and shape and be of any material suitable for grasping the product prior to use, e.g. Without allowing the release of the compositions from the bag prior to contact with the composition of the bag with water. The exact version depends on z. G., The type and amount of compositions in the bag, the number of chambers in the bag, and the characteristics that the bag must have to hold, protect, and dispense or release the compositions.

Preference is given to water-soluble pouches having a chamber comprising a liquid composition and a further chamber comprising a pulverulent or compressed pulverulent composition. During the manufacture of the liquid-containing chamber, an air bubble is formed as a rule. This bubble can reduce the compressibility of the bag and therefore make it difficult to close the dispenser after the bag has been inserted. It has been found that closure becomes easier when the ratio of air bubble diameter to maximum width dimension of the bag base is about 1: 5 to about 1: 2. Preferably, the air bubble has a diameter of about 9 to about 16 mm. The bubble size can be controlled with process parameters.

In use, the water-soluble pouch is usually placed in the dispenser of the dishwasher and released during the main cycle of the dishwashing process. However, the dispensers of some dishwashers are not completely watertight, mainly for two reasons, either the dispenser has some openings to allow water ingress, or the dispenser is sealed with a rubber band that may deform over time due to the high temperature of the dishwashing process , Ingress of water into the dispenser can cause the premature discharge of bag contents, which is lost at the end of the pre-wash. This problem is particularly acute in the case of bags comprising low viscosity liquid compositions wherein a substantial amount of the product may be lost prior to the main wash cycle. This problem can be circumvented by making the bag or at least the liquid containing chamber thereof of a film material designed to outlast the pre-wash and release the bag contents at or after the start of the main wash cycle. In European machines, prewashing is usually a cold water cycle (about 20 ° C or less) with no detergent and with a duration of about 10 to 15 minutes.

Preferably, the film material according to the test defined below has a water solubility of less than about 50%, more preferably less than about 20% and most preferably less than about 5% under cold water conditions (20 ° C or lower) when exposed to the water for at least 10 minutes , preferably at least 15 minutes; and a water solubility of at least about 50%, more preferably at least about 75%, and most preferably at least about 95%, under hot water conditions (30 ° C or higher, preferably 40 ° C or higher) when exposed to the water for about 5 minutes, and preferably when exposed to the water for about 3 minutes. Such sheet materials are referred to herein as being substantially insoluble in cold water but soluble in warm water. Sometimes this is simply abbreviated as "warm water soluble".

50 grams ± 0.1 grams of bag material are placed in a pre-weighed 400 ml beaker and 245 ml ± 1 ml of distilled water are added. This is maintained at the desired temperature by use of a water bath and with vigorous stirring with a magnetic stirrer set at 600 rpm for the desired time. The mixture is then filtered through a high quality sintered glass pleated filter with a maximum pore size of 20 microns. The water is dried from the collected filtrate by any conventional method and the weight of the remaining material (which is the dissolved or dispersed fraction) is determined. Thereafter, the percent solubility or the percent dispersibility can be calculated.

Commercially available films which are insoluble in cold water and soluble in hot water include BP26, available from Aicello, L10 and L15, available from Aquafilm, VF-M and VM-S, available from Kuraray, and E-2060 from Monosol, a.

In a preferred embodiment, a multi-chamber bag comprises a first chamber comprising a liquid composition and a second chamber comprising a powder or compacted powder composition. The liquid containing chamber is preferably made of a hot water soluble material as described above, and the chamber with the powder or compacted powder is made of cold water soluble material, i. H. a material which is soluble under cold water conditions (20 ° C or lower) in an amount of at least 50% by weight, preferably at least 75% by weight, more preferably at least 95% by weight when added to the water for 5 minutes exposed, and preferably, when exposed to the water for 3 minutes. Due to the operation of European dishwashers (they are filled with cold water and the cold water is heated by means of a heater), the chamber of hot water soluble material takes longer to dissolve than the chamber of cold water soluble material. This type of bag allows sustained release of the liquid composition, thus providing optimized use of the detergent composition. Preferably, the liquid composition comprises a cleaning enzyme, which is advantageous from the viewpoint of enzyme storage stability, wherein the enzyme is separated from the bleaching agent and highly alkaline materials contained in the powder or compacted powder composition. In addition, the chamber containing the liquid (substantially cold-water-insoluble and warm-water-soluble) takes longer to dissolve or decompose than the solid-containing chamber (cold-water-soluble), indicating the negative interaction between bleaching agents and enzymes and between surfactant and enzymes in the Minimizes wash liquor and provides a better removal of protein dirt and an advantage of reduced staining in the later stages of the dishwashing process.

Bag compartments containing solid compositions, especially compositions containing oxygen bleach, are commonly pierced with needles to permit the escape of any oxygen formed. However, the holes formed by the piercing also allow the escape of perfumes or unpleasant odors. For example, surfactants often adhere to an offensive odor, and when such bags are packaged in a secondary package, the unpleasant surfactant odor may concentrate in the top portion of the package and be released each time the user opens the package. This problem can be overcome by including the surfactant in the liquid composition are avoided, since fluid-containing chambers must be made free of holes. Thus, according to another embodiment, the liquid composition comprises a surfactant. Another advantage, when the surfactant is in the liquid phase, is that problems in applying the surfactant to the solid material are avoided. Another advantage is that the surfactant is released with a certain delay with respect to the solid composition, which allows for better performance of the bleaching agent and enzymes that may be affected by interaction between the surfactant and the dish surfaces.

Preferably, fragrance is incorporated into the solid composition, where the placement of minute holes allows slow release of the fragrance before the product is used in the dishwasher.

Films that are substantially insoluble in cold water and soluble in warm water have a relatively low moisture and plasticizer content, therefore, the film would take a considerable amount of time and temperature to seal by heat sealing. These requirements can lead to damage to the film, such as holes at the point where the film is stretched in the trough, causing leaks that are particularly problematic in the case of bags containing liquid. Therefore, it is preferred that chambers of films that are substantially insoluble in cold water and soluble in warm water and that contain liquids are sealed using solvents that partially hydrate the film prior to sealing, which requires the sealant Lowers time and temperature, creates strong seals and prevents the formation of holes. In the preferred embodiment, differential solubility bags comprising a chamber comprising a liquid composition and another chamber comprising a powdered composition, wherein the liquid containing chamber is made of material substantially insoluble in cold water and in warm water Water is soluble, and the powder-containing chamber is made of material that is soluble in cold water, it is preferred that the liquid-containing chamber is sealed by solvent seals, while the liquid-containing chamber is sealed by heat sealing with the powder-containing chamber.

The bag may also be positioned outside of the dispenser, for example in the cutlery basket, in a net or on the door of the dishwasher. In this case, it is preferable to make the entire bag from a sheet material, such as that described above, which protects the bag contents at least until the beginning of the main wash cycle.

Although the products contained in the pouch are such that they readily dissolve or disperse in water, it may be preferred that disintegrating agents, such as soda, water-swellable polymers or clays, be present in the pouch itself and / or in the product contained therein are, in particular, sources of soda based on an acid and a carbonate source. Suitable acids include the organic carboxylic acids such as fumaric acid, maleic acid, malic acid, citric acid; Suitable carbonate sources include sodium salts of carbonate, bicarbonate, percarbonate. Preferred amounts of the decomposition aids or soda sources or both are from 0.05% to 15% or even from 0.2% to 10% or even 0.3 to 5% by weight. -% of the total composition in the bag.

Examples: All examples are given for the purpose of illustration.

Abbreviations used in examples

Carbonat

Wasserfreies Natriumcarbonat

STPP

Natriumtripolyphosphat

Silicat

Amorphes Natriumsilicat (SiO₂:Na₂O = 2:1 bis 4:1)

HEDP

Ethan-1-hydroxy-1,1-diphosphonsäure

Perborat

Natriumperboratmonohydrat

Percarbonat

Natriumpercarbonat der Nominalformel 2Na₂CO₃·3H₂O₂

Carbonat

Wasserfreies Natriumcarbonat

Termamyl

α-Amylase, erhältlich von Novo Nordisk A/S

Savinase

Protease, erhältlich von Novo Nordisk A/S

FN3

Protease, erhältlich von Genencor

SLF18

Poly-Tergent^®, erhältlich von BASF

ACNI

Alkylverkapptes nichtionisches Tensid der Formel C_9/11 H_19/23 EO₈-Cyclohexylacetal

C₁₄AO

Tetradecyldimethylaminoxid

C₁₆AO

Hexadecyldimethylaminoxid

Duramyl

α-Amylase, erhältlich von Novo Nordisk A/S

DPM

Dipropylenglycolmethylether

DPG

Dipropylglycol

Methocel

Celluloseverdickungsmittel, erhältlich von Dow Chemical

In the examples, the abbreviated component identifiers have the following meanings:

carbonate

Anhydrous sodium carbonate

STPP

sodium tripolyphosphate

silicate

Amorphous sodium silicate (SiO ₂ : Na ₂ O = 2: 1 to 4: 1)

HEDP

Ethane-1-hydroxy-1,1-

perborate

sodium perborate

percarbonate

Sodium percarbonate of the nominal formula 2Na ₂ CO ₃ · 3H ₂ O ₂

carbonate

Anhydrous sodium carbonate

Termamyl

α-amylase, available from Novo Nordisk A / S

Savinase

Protease, available from Novo Nordisk A / S

FN3

Protease, available from Genencor

SLF18

Poly-Tergent ^®, available from BASF

ACNI

_Alkyl-capped nonionic surfactant of the formula C _9/11 H _19/23 EO ₈ -cyclohexyl acetal

C ₁₄ AO

tetradecyl

C ₁₆ AO

hexadecyl

Duramyl

α-amylase, available from Novo Nordisk A / S

DPM

dipropylene

DPG

Dipropylglycol

Methocel

Cellulose thickener, available from Dow Chemical

In the following examples, all amounts are given in weight percent (wt%).

Examples 1 to 8

The compositions of Examples 1 to 4 are placed in a layered PVA two-compartment bag with a rectangular base. The dual chamber bag is made from a Monosol M8630 film as available from Chris-Craft Industrial Products. 17.2 g of the particulate composition and 4 g of the liquid composition are added to the two different chambers of the bag. The dimensions of the bag below 0.02 kN (2 kg) load are: length 3.7 cm, width 3.4 cm and height 1.5 cm. The aspect ratio of longitudinal axis to transverse axis is therefore 1.5: 3.2 or 1: 2.47. The pouch is made by a process with two endless surfaces, both surfaces moving in a continuous horizontal rectilinear motion as described herein. According to this method, a first web of bags is formed by forming and filling a first web of open pouches mounted on a first endless surface and closing the first web of open pouches with the second web of filled and sealed pouches moving in synchronism therewith. produced.

The bag is placed in the 25 ml dispenser chamber of a Bosch Siemens 6032 dishwasher, the dispenser is closed and the dishwasher is operated in its normal 55 ° C program. example 1 2 3 4 Particulate composition C ₁₄ AO 5 5 C ₁₆ AO 5 5 ACNI 5 5 SLF18 5 5 STPP 55 55 56 56 HEDP 1 1 1 1 Termamyl 1.5 1.5 FN3 2 2 percarbonate 15 15 15.5 15.5 carbonate 9 9 10 10 silicate 6 6 7 7 perfume 0.5 0.5 0.5 0.5 Liquid composition DPG 99.5 99.5 95 95 FN3 Liquid 2.6 2,4 Duramyl Liquid 2.0 2,4 dye 0.5 0.5 0.4 0.2 example 5 6 7 8th Particulate composition STPP 60 60 61 61 HEDP 1 1 1 1 Termamyl 1.5 1.5 FN3 2 2 percarbonate 17 17 17.5 17.5 carbonate 11 11 12 12 silicate 7 7 8th 8th perfume 0.5 0.5 0.5 0.5 Liquid composition DPG 59.5 59.5 55 55 FN3 Liquid 2.6 2,4 Duramyl Liquid 2.0 2,4 C ₁₄ AO 20 20 C ₁₆ AO 20 20 ACNI 20 20 SLF18 20 20 dye 0.5 0.5 0.4 0.2

Claims (7)

A display case comprising a clear container containing a plurality of unit dosages of a detergent product in a plurality of sensory differentiable groups, and wherein the groups are distinguishable in color, shape, pattern or ornament, the unit dosages being multi-compartment bags. A display case according to claim 1, wherein the number of unit dosages is at least 10 and wherein the number of sensory differentiable groups is at least 2. Display case according to one of claims 1 or 2, wherein at least two groups are visually distinguishable in color. A display case according to any one of claims 1 to 3, wherein at least two groups are distinguishable with respect to the fragrance. A display case comprising a clear container containing a plurality of unit dosages in the form of water-soluble bags in a plurality of sensory differentiable groups, each bag comprising a plurality of chambers in generally stacked or stackable relationship, each containing one or more cleaning agents Each of the pouches has a volume of 5 to 70 ml and an aspect ratio of length to width ranging from 2: 1 to 1: 8, preferably from 1: 1 to 1: 4. The display case of claim 5, wherein at least one of the plurality of ingredients comprises a powder composition. A display case according to claim 5 or 6, wherein at least one of the plurality of chambers comprises a liquid composition.