WO2009022110A1 - Emballage - Google Patents

Emballage Download PDF

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Publication number
WO2009022110A1
WO2009022110A1 PCT/GB2008/002701 GB2008002701W WO2009022110A1 WO 2009022110 A1 WO2009022110 A1 WO 2009022110A1 GB 2008002701 W GB2008002701 W GB 2008002701W WO 2009022110 A1 WO2009022110 A1 WO 2009022110A1
Authority
WO
WIPO (PCT)
Prior art keywords
compartments
compartment
package according
unit dose
package
Prior art date
Application number
PCT/GB2008/002701
Other languages
English (en)
Inventor
Pawel Jaworski
Charlotta Larrson
David Prinselaar
Original Assignee
Reckitt Benckiser N.V.
Reckitt Benckiser (Uk) Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reckitt Benckiser N.V., Reckitt Benckiser (Uk) Limited filed Critical Reckitt Benckiser N.V.
Priority to US12/672,424 priority Critical patent/US20110127271A1/en
Priority to EP08788273A priority patent/EP2176131A1/fr
Priority to CA2695346A priority patent/CA2695346A1/fr
Publication of WO2009022110A1 publication Critical patent/WO2009022110A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets

Definitions

  • the present invention relates to a package comprising a plurality of unit dose detergent portions.
  • the present invention relates to such packaging comprising two or more separate compartments each containing a plurality of unit dose detergent portions.
  • Unit dose portions are well known in detergent applications as they provide ease of dosing and easy handling for consumers.
  • Typical unit dose forms include tablets and sachets or pouches.
  • the sachets and pouches may be filled with solid detergent (including in granular or powdered form), pastes, liquids or a mixture thereof.
  • Tablets are well known for use in dish-washing machines or laundry washing machines. Such tablets, sachets and pouches are added to the washing machine and are fully consumed by the end of the washing operation. Examples of such tablets are dishwashing tablets such as those sold under the trademark Finish, water-softening tablets such as those sold under the trademark Calgon and laundry detergent tablets such as those sold under the trademark Persil. Such detergent tablets are already known to be wrapped in water-soluble wrappers. This has the advantage that a consumer can take the wrapped tablet and handle it while placing it in a washing machine without having to touch the tablet components.
  • the wrapper is suitably of a water-soluble material such as a polyvinyl alcohol.
  • a wrapped detergent tablet is that sold under the trademark Sun.
  • the present invention provides a primary package comprising two or more compartments which can be opened individually, each compartment comprising a plurality of unit dose detergent portions and wherein at least one compartment is substantially air-tight before it is opened for the first time.
  • the package comprises three or more compartments which are opened individually. It is also preferred that all compartments in the package are substantially air-tight before they are opened for the first time.
  • the compartments preferably comprise a substantially airtight closure means adhered to the compartment before they are opened for the first time, this closure means preferably comprising a flexible web of material.
  • At least a part of at least one compartment is transparent.
  • the compartments of the package are either stacked, arranged adjacent to each other or both.
  • the compartments are reversibly bound to each other, preferably by the compartments being reversibly bound to each other by a wrapper placed around at least a part of the package.
  • the package preferably additionally further comprise a further individual closure means.
  • the further individual closure means preferably connects to the compartment by a tongue-and-groove arrangement.
  • the unit dose detergent portion in the package preferably comprises a compressed particulate material.
  • the unit dose detergent portion comprises an outer wrapper, in particular a water soluble or water dispersible wrapper preferably comprising polyvinyl alcohol .
  • the unit dose detergent portion preferably comprises fabric care, surface care or dishwashing composition (s) .
  • the present invention enables at least some of the unit dose detergent portions in the primary package to be shielded from damaging environmental factors such as moisture and air by virtue of being kept in substantially airtight compartments prior to being opened. It is known that contact with moisture can damage/soften detergent tablets and can adversely affect the integrity of sachets and pouches made of water soluble material. Moreover some of the ingredients conventionally used in detergent compositions exhibit at least some degree of instability over time when in contact with the air. Thus it is desirable to limit the exposure of such tablets to the open air and this is achieved by the substantially airtight compartments which are accessed by the consumer by opening at least a portion of the compartment and closing it when the detergent portion has been removed.
  • these compositions are contained within two or more compartments. This has the advantage that the unit dose detergent portions in a given compartment are only exposed to the aforementioned environmental factors when that compartment is opened thus limiting exposure thereto. Also by placing the unit dose detergent portions into two or more compartments there is a reduced tendency for the portions rub or knock together so reducing attrition between them which otherwise can damage the surfaces of the portions.
  • unit dose detergent portions as used herein is meant a individual portion of a detergent composition sufficient for a single cleaning operation. However, if desired two or more such portions can be used together in a single cleaning operation.
  • substantially all as used herein is meant 80% or more, preferably 90% or more, more preferably 95% or more.
  • the primary package of the invention comprises two or more compartments which are opened and closed individually.
  • the primary package preferably comprises three or more of the aforementioned compartments, such as four or more. In some cases it is desirable for the package to comprise five or more compartments.
  • the compartments may be arranged in any suitable spatial arrangement relative to each other to produce the primary- package. For example the compartments may be arranged side-by-side as shown in figure 1. Alternatively the compartments may be arranged so that they are stacked on top of each other as shown in figure 2. In a further embodiment it is provided for a mixture of stacking and adjacent compartments to be used e.g. 2 or 3 compartments may be placed adjacent to each other and additional compartments placed thereon. For example an additional compartment may be stacked on top of each of two adjacent compartments so that there are four compartments placed two wide and stacked two high. The same arrangement could be used for any desired number of compartments.
  • the two or more compartments which form the primary package of the invention may either permanently, or reversibly, be bound to each other. If the compartments are permanently bound to each other they may be formed from a single piece of material e.g. plastics material. If the compartments are reversibly bound to each other they may be adhered to each other by an adhesive bond which is broken to separate the compartments or they may be reversibly bound in some other way such as by the use of an outer wrapper or by a frangible connection between the compartments .
  • the two or more compartments are reversibly bound to each other to form the primary package. It is especially preferred that three or more compartments are reversibly bound to each other to form the primary package .
  • a wrapper placed around at least a part of the package is used to reversibly bind the two or more compartments together.
  • This wrapper is preferably placed around two or more compartments either stacked on top of each other or placed in a side-by-side arrangement.
  • the wrapper may cover all, or substantially all of the exposed face(s) of the compartments, or it may cover the whole or a part of only some of those faces. It is especially preferred that at least one of the faces of each of the compartments is not covered by the wrapper to allow the contents of the compartments to be viewed by the consumer. It is especially preferred that at least two faces of each of the compartments are not covered by the wrapper to provide very good visibility to the consumer of the unit dose detergent portions contained within the compartment. If the wrapper covers substantially all of the faces of the compartments in the primary package, it is then preferred that the contents of at least one of the compartments can be viewed through the wrapper by the consumer .
  • the wrapper is preferably arranged around the perimeter of the primary package formed by the two or more compartments of the primary package. It is of any suitable dimensions and material so as to provide additional dimensional stability to the primary package compared to the package in the absence of the outer wrapper where this is necessary by virtue of the spatial arrangement of the two or more compartments in relation to each other.
  • the wrapper may be applied to the primary package by any suitable conventional method. For the reversibly bound compartments, the primary package is typically formed by bringing together the two or more compartments in the chosen arrangement and then the outer wrapper is applied thereto. When the primary package is formed from permanently bound compartments, the package is formed and the wrapper is applied thereto. In both cases the wrapper may be applied as loosely or tightly fitting as desired.
  • the wrapper is preferably applied in a manner such that it is relatively close fitting and provides additional dimensional stability to the stack.
  • the wrapper may be formed of paper (especially waxed or re-inforced paper) , cardboard or sheets of plastic material such as polyethylene or polypropylene based polymers. It may provide printed information on the product as desired, or, it may be blank and it may be transparent, semi-transparent or opaque as desired.
  • compartments are reversibly connected to each other by the use of one or more adhesive bonds and also by an wrapper as hereinabove described.
  • At least one compartment of the primary package is substantially air-tight before it is opened, preferably two or more compartments are substantially air-tight before they are opened and most preferably three or more are substantially air-tight before they are opened for the first time. It is most preferred that regardless of how many compartments make up the primary package that they are all substantially air-tight before they are opened for the first time.
  • the substantially air-tight seal may be formed in any suitable way using any suitable material.
  • the at least one compartment which is substantially air-tight before it is opened for the first time preferably comprises a substantially air-tight closure means adhered to the compartment. This may take the form of a seal arranged such that it can easily be removed by the consumer when opening the compartment for the first time.
  • Suitable substantially air-tight seals include closure means comprising a flexible web of material, such as a foil, bonded to the compartment e.g. around the edges of the closure means and which are removed by simply peeling it away from the compartment, often aided by a tab placed on one edge or corner of the closure means.
  • Such substantially air-tight seals are known in the art and do not require further description here.
  • the two or more compartments of the primary package are opened individually. Preferably they are also closed individually. This means that when one compartment is opened by removing a part of that compartment thus breaking the substantially air tight seal, the seals of the other compartments remain intact until it is decided by the consumer to break the seal and open the compartment. Accordingly the consumer has the choice of which compartment to open first and when there are three or more compartments also the choice of in which order to open those compartments. Thus the consumer may choose to open the compartments sequentially; as each compartment becomes empty of tablets he/she will choose which compartment to open next. It is of course possible that the consumer may choose to open all compartments at about the same time but this is less preferred as the advantages of the invention are less likely to be achieved.
  • the compartment When a compartment has been opened by breaking its substantially airtight seal in order to remove one or more unit dose detergent portions, the compartment may be closed by any suitable closure means. This closure of the compartment with the closure means may or may not result in a substantially air-tight seal for the compartment being reformed. It is thus preferred that the package comprises a further individual closure means for one or more compartments.
  • Suitable closure means may comprise tongue-and-groove means or faster means such as zip fastener means to connect to the compartment. According to a preferred aspect of the invention tongue-and-grove means are preferred.
  • the closure means comprises a lid which covers the open part of the compartment formed by the removal of the substantially airtight seal.
  • the lid engages with the perimeter of the open part of the compartment and preferably positively engages therewith.
  • the lid is then removed each time it is desired to take a unit dose detergent portion from the compartment.
  • the lid preferably sits above this seal (relative to the compartment) and is also in contact with the compartment.
  • the lid may be designed so that it has an vertically protruding lip on at least a portion of its upper surface (the upper surface being that surface which faces outwards when affixed to the compartment) to provide an additional means for aiding the stability of the primary package when it comprises two or more compartments in a stacked arrangement.
  • This protruding lip aids dimensional stability of stacked compartments as it provides a physical barrier to prevent the compartments moving relative to each other during transport and handling etc and thus reduces the likelihood of one of the compartments in the stack falling off the compartment below.
  • the protruding lip of the lid may be of any suitable height and width but it will not typically be more than 30% of the height of the compartment to which the lid is attached, preferably not more than 20%.
  • the lip will be in the region of 5-10% of the height of said compartment.
  • two or more compartments of the primary package have a protruding lip on the lid (used as a closure means once the airtight seal has been removed) and furthermore are reversibly bound together by an wrapper as described hereinabove.
  • the lid has the aforementioned protruding lip around the perimeter of its upper surface (the upper surface being relative to when it is placed on the compartment) and this lip is shaped so as to allow for an wrapper to engage with the lip across only a proportion thereof without the wrapper protruding above the highest part of the protruding lip.
  • This shaped portion of the protruding lip can take the form of a cut-away section which substantially corresponds to the shape of the wrapper which contacts the lip.
  • the compartments and closure means (lid) may be made of any suitable material, preferably a plastics material.
  • suitable plastics are well known in the packaging art and include materials such as polypropylene, polyethylene (low and high density), polyethylene terephalate, Polystyrene, Expanded Polystyrene, Acrylonitrite Butadiene Styrene, Polyvinyl Chloride, Polyester and mixtures thereof.
  • the actual material, or mixtures of materials used is easily selected by the person skilled in the art on the basis of the degree of transparency desired, the method by which the compartments/closure means will be produced and the required degree of rigidity or flexibility.
  • At least one compartment in the primary package is substantially transparent to the naked eye, preferably transparent to the naked eye, so that the unit dose detergent portions can be seen when placed inside a closed compartment. It is most preferred that two or more compartments are substantially transparent and further preferred that all compartments are substantially transparent. It is especially preferred that two or more compartments are substantially transparent and further preferred that all compartments are substantially transparent.
  • the closure means (lid) may be either transparent or opaque as desired. In one preferred embodiment at least one of the compartments of the primary package is transparent and the closure means (lid) thereof is translucent or opaque, preferably all compartments are transparent and all closure means (lids) are translucent or opaque, more preferably opaque.
  • the compartments and closure means (lid) may be as flexible or as rigid as desired. However, whilst a degree of flexibility is desirable to avoid breakages in transport caused by a very brittle compartment not being able to absorb impacts normally encountered during filling and transport, the compartments and closure means (lid) are preferably sufficiently rigid to allow for at least one more identical compartment with its contents to be stacked on the top of a given compartment without the bottom compartment visibly deforming. It is more preferred that at least two additional identical compartments and their contents may be stacked on the top of a given compartment without it visibly deforming, more preferably at least three.
  • the compartments may be produced by any conventional technical for the manufacture of plastic articles, especially the methods used for the manufacture of plastic packaging items, such as thermoforming or injection or blow moulding. Such techniques are well known in the art and do not need to be described in detail herein.
  • Each compartment of the primary package contains a plurality of unit dose detergent portions. It is preferred that each compartment comprises at least 2 such portions, more preferably at least 5 such portions, most preferably at least 10 such portions, such as 12 or more portions. It is also preferred that each compartment contains up to 50 unit dose detergent compositions, more preferably up to 40, most preferably up to 30, such as up to 20.
  • the total number of unit dose detergent options in the primary package can of course easily be controlled by selecting the appropriate combination of the number of detergent portions per compartment and the number of compartments in the primary package. It is preferred that the primary package contains a total of between 10 and 100 unit dose detergent portions, preferable between 15 and
  • This total number of unit dose detergent portions is divided either equally or unequally over the two or more compartments of the primary package. It is generally preferred that the total number of unit dose detergent portions is divided equally over the two or more compartments of the primary package.
  • unit dose detergent portions included in the compartments may be of any suitable form, for example; tablets of detergent composition (compressed or cast) or pouches, sachets or hollow bodies filled with powder, liquid or gel detergent compositions (and also those filled with discrete mixtures thereof) .
  • the unit dose detergent portion comprises a compressed particulate material.
  • At least one of the compartments in the primary package contains detergent composition in a non-unit dose form e.g. granulated or powdered detergent in a free flowing form.
  • a non-unit dose form e.g. granulated or powdered detergent in a free flowing form.
  • at least half, if not all of the compartments contain unit dose detergent portions.
  • the primary package contains a plurality of unit dose detergent portions which may be of the same or different composition.
  • the unit dose detergent portions in the primary package are of the same composition.
  • the primary package contains two or more different detergent compositions in unit dose form e.g. a machine dishwashing composition and a machine cleaning composition, or, a laundry detergent composition and a fabric softening composition.
  • the tablets may be of either cast or compressed detergent composition although it is preferred that they are of compressed material.
  • the pouches/sachets may be produced by conventional methods such as thermoforming or injection moulding and may be formed from conventional materials. It is preferred that the pouches/sachets are formed from material which comprises water-soluble material and most preferred that they are made from at least 90%wt of such materials, more preferably that they consist of such materials. For the avoidance of doubt the reference here to pouches/sachets is only to the pouch/sachet per se and does not encompass the detergent composition contained within it.
  • the unit dose detergent portions may be of any shape or form including, tablets, sachets and pouches as disclosed herein.
  • the unit dose detergent portion may have a irregular or regular geometrical shape such as a cube, cuboid, pyramid/prism, dodecahedron or cylinder.
  • the cylinder may have any desired cross-section, such as a circular, triangular or square cross-section.
  • the unit dose detergent portion comprises a compressed particulate composition and is most preferably a tablet.
  • the tablet may, for example, be formed by compressing a particulate, for example powder, granulated or agglomerated, composition or may be prepared by setting or gelling a composition into a desired shape.
  • the unit dose detergent portions may comprise a single particulate composition or two, three or even more compositions.
  • the compacted particulate composition may comprise one, two or even three or more layers or visually separate phases.
  • One or more layers may be formed of a gelled composition.
  • the tablet may comprise only compressed particulate composition (s) , only a gelled composition (s ) or both.
  • the portions may contain one or more than one composition, for example compacted particulate compositions. If the packages contain two or more compositions, they can have a particularly attractive appearance since the compositions, which may be identical or different, may be held in a fixed position in relation to each other.
  • the compositions can be easily differentiated to accentuate their difference. For example, the compositions can have a different physical appearance, or can be coloured differently.
  • the individual phases need not necessarily be regular or identical.
  • the individual phases may have different sizes to accommodate different quantities thereof.
  • the phases may have the same or different size and/or shape.
  • the phases have volume ratios of from 1:1 to 20:1, especially from 1:1 to 10:1.
  • the unit dose detergent portion may also, for example, comprise an insert, which may be held in a depression within the portion.
  • the insert may also stand proud of the surface of the portion.
  • the portion may be in the form of a tablet, especially a cuboid tablet, comprising one, two or more layers, with an insert, for example in the form of a ball contained within a depression on/in a surface of the tablet.
  • the individual unit dose detergent portions generally weigh from 5 to 100 g, especially from 5 to 40 g.
  • a laundry composition may weigh from 15 to 4Og
  • a dishwashing composition may weigh from 5 to 30 g
  • a water-softening composition may weigh from 15 to 40 g.
  • the individual unit dose detergent portions generally have a maximum dimension of 10cm, excluding any flanges.
  • they may have a length of 1 to 5cm, especially 3.5 to 4.5cm, a width of 1.5 to 3.5cm, especially 2 to 3cm, and a height of 1 to 3cm, especially 1.0 to 2.0cm, e.g. 1.8cm.
  • the unit dose detergent portions contained within the compartments may, for example, comprise fabric care, surface care or dishwashing compositions. If more than one composition is present within the unit dose detergent portion, each composition may be chosen depending on the desired use of the article.
  • the desired number of the unit dose detergent portions are removed from their compartment and are simply added to water.
  • they may be added in the usual way to a dishwasher or laundry machine, especially in the dishwashing compartment or a drum. They may also be added to a quantity of water, for example in a bucket or trigger-type spray.
  • the unit dose detergent portion may comprise any type of detergent composition (s) , preferably fabric care, surface care or dishwashing composition (s) .
  • the unit dose detergent portions are for use in fabric care, they may comprise, for example, a detergent, bleach, stain remover, water-softener, enzyme and/or fabric conditioner.
  • the portions may be adapted to release the compositions at different times during the laundry wash. For example, a bleach or fabric conditioner is generally released at the end of a wash, and a water-softener is generally released at the start of a wash.
  • An enzyme may be released at the start or the end of a wash.
  • the composition may comprise a fabric conditioner and/or an enzyme which is released before or after the fabric conditioner in a rinse cycle.
  • the portion may comprise a detergent, water- softener, salt, enzyme, rinse aid, bleach and/or bleach activator.
  • the detergent portion may be adapted to release the compositions at different times during the wash. For example, a rinse aid, bleach or bleach activator is generally released at the end of a wash, and a water-softener, salt or enzyme is generally released at the start of a wash.
  • Examples of surface care unit dose detergent portions are compositions are those used in the field of surface care, for example to clean, treat or polish a surface.
  • Suitable surfaces are, for example, household surfaces such as worktops, as well as surfaces of sanitary ware, such as sinks, basins and lavatories.
  • dish washing formulations are preferred which are adapted to be used in automatic dish washing machines. Due to their specific requirements specialised formulation is required and these are illustrated below.
  • Amounts of the ingredients can vary within wide ranges, however preferred automatic dishwashing detergent compositions herein (which typically have a 1% aqueous solution pH of above 7, more preferably from 8 to 12, most preferably from 8 to 10.5) are those wherein there is present: from 5% to 90%, preferably from 5% to 75%, of builder; from 0.1% to 40%, preferably from 0.5% to 30%, of bleaching agent; from 0.1% to 15%, preferably from 0.2% to 10%, of the surfactant system; from 0.0001% to 1%, preferably from 0.001% to 0.05%, of a metal-containing bleach catalyst; and from 0.1% to 40%, preferably from 0.1% to 20% of a water-soluble silicate.
  • Such fully- formulated embodiments typically further comprise from 0.1% to 15% of a polymeric dispersant, from 0.01% to 10% of a chelant, and from 0.00001% to 10% of a detersive enzyme, though further additional or adjunct ingredients may be present.
  • Detergent compositions herein in granular form typically limit water content, for example to less than 7% free water, for better storage stability. These granular forms of the detergent composition are typically compacted to produce tablets of detergent composition.
  • the unit dose detergent portions comprise one of more surfactants. If the compositions are not for use in automatic dishwashing applications they typically comprise an anionic surfactant. Such surfactants can be used in automatic dishwashing compositions but this is less preferred because anionic surfactants tend to foam too much for use in a dishwashing machine.
  • anionic surfactants are straight-chained or branched alkyl sulfates and alkyl polyalkoxylated sulfates, also known as alkyl ether sulfates. Such surfactants may be produced by the sulfation of higher C 8 - C 2 O fatty alcohols.
  • Examples of primary alkyl sulfate surfactants are those of formula:
  • R is a linear Cs-C 2 O hydrocarbyl group and M is a water-solubilising cation.
  • R is C10-C16 alkyl, for example Ci 2 -Ci 4
  • M is alkali metal such as lithium, sodium or potassium.
  • secondary alkyl sulfate surfactants are those which have the sulfate moiety on a "backbone" of the molecule, for example those of formula: CH 2 (CH 2 ) n (CHOSO 3 -M + ) (CH 2 ) m CH 3 wherein m and n are independently 2 or more, the sum of m+n typically being 6 to 20, for example 9 to 15, and M is a water-solubilising cation such as lithium, sodium or potassium.
  • Especially preferred secondary alkyl sulfates are the (2,3) alkyl sulfate surfactants of formulae: CH 2 (CH 2 )X(CHOSO 3 -M + )CH 3 and
  • x is at least 4, for example 6 to 20, preferably 10 to 16.
  • M is cation, such as an alkali metal, for example lithium, sodium or potassium.
  • alkoxylated alkyl sulfates are ethoxylated alkyl sulfates of the formula: RO(C 2 H 4 O) n SO 3 -M + wherein R is a Cs-C 2O alkyl group, preferably Ci O -Ci 8 such as a Ci 2 -Ci 6 , n is at least 1, for example from 1 to 20, preferably 1 to 15, especially 1 to 6, and M is a salt- forming cation such as lithium, sodium, potassium, ammonium, alkylammonium or alkanolammonium. These compounds can provide especially desirable fabric cleaning performance benefits when used in combination with alkyl sulfates .
  • alkyl sulfates and alkyl ether sulfates will generally be used in the form of mixtures comprising varying alkyl chain lengths and, if present, varying degrees of alkoxylation.
  • anionic surfactants which may be employed are salts of fatty acids, for example C 8 -Ci 8 fatty acids, especially the sodium or potassium salts, and alkyl, for example C 8 - Ci 8 , benzene sulfonates.
  • Nonionic surfactants are the preferred surfactants for use in dishwashing applications and they may also be used in other applications in addition to, or in place of, anionic surfactants.
  • nonionic surfactants are typically present at levels of up to 15%wt of the composition. Mixtures of nonionic surfactants may be used if desired.
  • bleach- stable surfactants are preferred.
  • Non-ionic surfactants generally are well known, being described in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference herein.
  • non-ionic surfactants are fatty acid alkoxylates, such as fatty acid ethoxylates, especially those of formula: R(C 2 H 4 O) n OH wherein R is a straight or branched C 8 -Ci 6 alkyl group, preferably a Cg-Ci 5 , for example Ci 0 -Ci 4 , alkyl group and n is at least 1, for example from 1 to 16, preferably 2 to 12, more preferably 3 to 10.
  • R is a straight or branched C 8 -Ci 6 alkyl group, preferably a Cg-Ci 5 , for example Ci 0 -Ci 4 , alkyl group and n is at least 1, for example from 1 to 16, preferably 2 to 12, more preferably 3 to 10.
  • non-ionics are ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles particularly preferred at least 16 moles, and still more preferred at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol.
  • Particularly preferred non-ionic surfactants are the non- ionics from a linear chain fatty alcohol with 16-20 carbon atoms and at least 12 moles particularly preferred at least 16 and still more preferred at least 20 moles of ethylene oxide per mole of alcohol.
  • the alkoxylated fatty alcohol non-ionic surfactant will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17, more preferably from 6 to 15, most preferably from 10 to 15.
  • HLB hydrophilic-lipophilic balance
  • fatty alcohol ethoxylates are those made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials are commercially marketed under the trademarks Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.
  • Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12-C1 3 alcohol having about 9 moles of ethylene oxide; and Neodol 91-10, an ethoxylated C 9 -Cn primary alcohol having about 10 moles of ethylene oxide.
  • Dobanol 91-5 is an ethoxylated C 9 -Cn fatty alcohol with an average of 5 moles ethylene oxide
  • Dobanol 25-7 is an ethoxylated Ci 2 -Ci 5 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable ethoxylated alcohol non-ionic surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates available from Union Carbide Corporation.
  • Tergitol 15-S-7 is a mixed ethoxylated product of a C11-C1 5 linear secondary alkanol with 7 moles of ethylene oxide and Tergitol 15-S-9 is the same but with 9 moles of ethylene oxide .
  • Other suitable alcohol ethoxylated non-ionic surfactants are Neodol 45-11, which is a similar ethylene oxide condensation products of a fatty alcohol having 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also available from Shell Chemical Company.
  • Another preferred non-ionic surfactant can be described by the formula:
  • R 1 represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon atoms or mixtures thereof
  • R 2 represents a linear or branched chain aliphatic hydrocarbon rest with 2-26 carbon atoms or mixtures thereof
  • x is a value between 0.5 and 1.5
  • y is a value of at least 15.
  • Another group of preferred nonionic surfactants are the end-capped polyoxyalkylated non-ionics of formula:
  • R 1 and R 2 represent linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1-30 carbon atoms
  • R 3 represents a hydrogen atom or a methyl, ethyl, n-propyl, iso-propyl, n- butyl, 2-butyl or 2-methyl-2-butyl group
  • x is a value between 1 and 30 and
  • k and j are values between 1 and 12, preferably between 1 and 5.
  • R 1 and R 2 are preferably linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 6-22 carbon atoms, where group with 8 to 18 carbon atoms are particularly preferred. H, methyl or ethyl are particularly preferred, for the group R 3 . Particularly preferred values for x are comprised between 1 and 20, preferably between 6 and 15.
  • each R 3 in the formula can be different.
  • the value 3 for x is only an example and bigger values can be chosen whereby a higher number of variations of (EO) or (PO) units would arise .
  • the PO units constitute up to 25% by weight, preferably up to 20% by weight and still more preferably up to 15% by weight of the overall molecular weight of the non-ionic surfactant.
  • Particularly preferred surfactants are ethoxylated mono-hydroxy alkanols or alkylphenols, which additionally comprises polyoxyethylene- polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol portion of such surfactants constitutes more than 30%, preferably more than 50%, more preferably more than 70% by weight of the overall molecular weight of the non-ionic surfactant.
  • Another class of non-ionic surfactants includes reverse block copolymers of polyoxyethylene and polyoxypropylene and block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane .
  • non-ionic surfactants are, for example, C 10 -Ci 8 alkyl polyglycosides, such s Ci 2 -Ci 6 alkyl polyglycosides, especially the polyglucosides . These are especially useful when high foaming compositions are desired.
  • Further surfactants are polyhydroxy fatty acid amides, such as Ci 0 -Ci 8 N- (3-methoxypropyl) glycamides and ethylene oxide-propylene oxide block polymers of the Pluronic type.
  • Cationic surfactants may also be used in the detergent compositions, for example, those of the quaternary ammonium type.
  • compositions particularly when used as laundry washing or dishwashing compositions, may also independently comprise enzymes, such as protease, lipase, amylase, cellulase and peroxidase enzymes.
  • enzymes such as protease, lipase, amylase, cellulase and peroxidase enzymes.
  • enzymes are commercially available and sold, for example, under the registered trade marks Esperase, Alcalase and Savinase by Nova Industries A/S and Maxatase by International
  • the enzymes are independently present in the compositions in an amount of from 0.01 to 3wt%, especially 0.01 to 2wt%, when added as commercial preparations they are not pure and this represents an equivalent amount of 0.005 to 0.5wt% of pure enzyme .
  • compositions which comprise an enzyme may optionally contain materials which maintain the stability of the enzyme.
  • enzyme stabilizers include, for example, polyols such as propylene glycol, boric acid and borax. Combinations of these enzyme stabilizers may also be employed. If utilized, the enzyme stabilizers generally constitute from 0.01 to 2wt% of the compositions.
  • compositions usually comprise a detergency builder.
  • the builders counteract the effects of calcium, or other ion, water hardness.
  • examples of such materials are citrate, succinate, malonate, carboxymethyl succinate, carboxylate, polycarboxylate and polyacetyl carboxylate salts, for example with alkali metal or alkaline earth metal cations, or the corresponding free acids.
  • Specific examples are sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, C10-C22 fatty acids and citric acid.
  • Other examples are organic phosphonate type sequestering agents such as those sold by Monsanto under the trade mark Dequest and alkylhydroxy phosphonates .
  • Citrate salts and Ci 2 -Ci 8 fatty acid soaps are preferred. Further builders are; phosphates such as sodium, potassium or ammonium salts of mono-, di- or tri-poly or oligo-phosphates; zeolites; silicates, amorphous or structured, such as sodium, potassium or ammonium salts. For laundry compositions, alumino silicates (zeolites) may also be used and these are less preferred in automatic dishwashing applications.
  • phosphates such as sodium, potassium or ammonium salts of mono-, di- or tri-poly or oligo-phosphates
  • zeolites silicates, amorphous or structured, such as sodium, potassium or ammonium salts.
  • silicates alumino silicates (zeolites) may also be used and these are less preferred in automatic dishwashing applications.
  • Suitable builders are polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic and copolymers and their salts, such as those sold by BASF under the trade mark Sokalan.
  • the builder is desirably present in an amount of up to 90wt%, preferably 0.01 to 90wt%, more preferable 0.01 to 75wt%, relative to the total weight of the composition. Further details of suitable components are given in, for example, EP-A-694 , 059, EP-A-518,720 and WO 99/06522.
  • compositions of the present invention may comprise conventional bleaching compounds and bleach activators in conventional amounts. If a bleaching compound is used in the compositions of the invention, then any type of bleaching compound conventionally used in detergent compositions may be used.
  • the bleaching compound is selected from inorganic peroxides or organic peracids, derivatives thereof (including their salts) and mixtures thereof.
  • Especially preferred inorganic peroxides are percarbonates, perborates and persulphates with their sodium and potassium salts being most preferred.
  • Sodium percarbonate and sodium perborate are most preferred, especially sodium percarbonate.
  • Organic peracids include all organic peracids traditionally used as bleaches, including, for example, perbenzoic acid and peroxycarboxylic acids such as mono- or diperoxyphthalic acid, 2-octyldiperoxysuccinic acid, diperoxydodecanedicarboxylic acid, diperoxy-azelaic acid and imidoperoxycarboxylic acid and, optionally, the salts thereof.
  • perbenzoic acid and peroxycarboxylic acids such as mono- or diperoxyphthalic acid, 2-octyldiperoxysuccinic acid, diperoxydodecanedicarboxylic acid, diperoxy-azelaic acid and imidoperoxycarboxylic acid and, optionally, the salts thereof.
  • PAPJ phthalimidoperhexanoic acid
  • a bleaching compound is present in the compositions in an amount of from 1 to 60wt%, especially 5 to 55wt%, most preferably 10 to 50%wt, such as 10 to 20%wt.
  • a bleaching compound it may be used with any suitable bleach activator compound, such as TAED or any multi-valent metal ion compounds or salts as known in the art. Such a compound may be used in any suitable amount.
  • compositions may optionally comprise materials which serve as phase stabilizers and/or co-solvents.
  • materials which serve as phase stabilizers and/or co-solvents are C x -C 3 alcohols such as methanol, ethanol and propanol.
  • C 1 -C 3 alkanolamines such as mono-, di- and triethanolamines can also be used, by themselves or in combination with the alcohols.
  • the phase stabilizers and/or co-solvents can, for example, constitute 0 to lwt%, preferably 0.1 to 0.5wt%, of the composition.
  • the compositions may optionally comprise components which adjust or maintain the pH of the compositions at optimum levels.
  • the pH may be from, for example, 1 to 13, such as 8 to 11 depending on the nature of the composition.
  • a dishwashing composition desirably has a pH of 8 to 11
  • a laundry composition desirable has a pH of 7 to 9
  • a water-softening composition desirably has a pH of 7 to 9.
  • pH adjusting agents are soda ash (Na 2 C ⁇ 3) and citric acid.
  • the compositions can also optionally comprise one or more additional ingredients.
  • detergent composition components such as suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, organic solvents, co-solvents, emulsifying agents, preservatives, soil suspending agents, soil release agents, germicides, non-builder alkalinity sources, chelating agents, clays such as smectite clays, anti- limescale agents, colourants, dyes, hydrotropes, dye transfer inhibiting agents, brighteners, and perfumes. If used, such optional ingredients may constitute up to 60wt%, for example from 1 to 50wt%, the total weight of the compositions.
  • Detergent tablets are fairly fragile, and are liable to break, fracture or chip, particularly when dropped by a consumer, or when a package containing them is dropped or falls. It is possible to improve the strength of tablets by increasing the pressure at which they are compressed, but this can undesirably retard their dissolution properties in water.
  • Most tablets are wrapped in a protective wrapping material prior to packaging, such as blister packs, or individual sachets. Often the wrapping is needed for any one or more of the following reasons: (1) to act as a physical barrier, so as to protect the contents from moisture; (2) to physically protect the contents such that if they fracture, the broken tablet does not contaminate the primary packaging and/or (3) to act as a child resistant closure .
  • the unit dose detergent portions especially of compressed particulate material, and most especially tablets, are wrapped in an outer wrapper, especially a water soluble or water dispersible outer wrapper. For such unit dose detergent portions wrapped in water soluble wrappers there is a real need to protect these products from moisture as this over time can begin degrade the wrapper thus reducing the integrity of the portion.
  • WO06/095190 which is incorporated by reference herein, discloses a process for packaging compacted particulate compositions, especially tablets, by which the resistance of the composition to physical damage is surprisingly increased.
  • This allows for a wider range of physical properties of the compacted particulate composition to be tolerated, such as reduced hardness and increased friability, thus allowing a wider window of ingredient selection and manufacturing tolerances.
  • the tablets produced by the process exhibit good dissolution properties in water.
  • the process comprises wrapping a compacted particulate composition (tablet) in a water soluble film by wrapping it with a first film and treating the wrapped compacted particulate composition at an elevated temperature to shrink the film such that it clings to said composition.
  • Flow wrapping is particularly preferred.
  • Generally flow wrapping comprises sealing peripheral regions of a web of film around an object to form a tube with a longitudinal seam.
  • the two ends of the tube are sealed around the product being packaged by transverse seams.
  • the longitudinal seam is brought next to the surface of the packaged product and is normally disposed in the middle of the rear face of the packaging.
  • This method of wrapping compacted particulate compositions with a film of material is straightforward and economical, when compared to, for example, dipping or spray coating.
  • the film is preferably sealed together in a known manner. Sealing can simply occur under the forming conditions used, particularly when heat and/or pressure are used. However, it is also possible for additional sealing techniques to be used. For example, heat sealing or infra-red, radio frequency, ultrasonic, laser, solvent, adhesive, vibration, electromagnetic, hot gas, hot plate or insert bonding friction sealing, cold sealing or spin welding can be used. Heat sealing is preferred.
  • Heat sealing conditions depend on the machine and material used. Generally the sealing temperature is from 100 to 180°C. The pressure is usually from 100 to 500 kPa (1 to 5 bar) . The dwell time is generally from 0.02 to 0.6 seconds .
  • a heat treatment step may optionally be carried out to shrink the film.
  • the heat treatment step is preferably carried out over a short timescale to avoid thermal damage to the film and/or the compacted particulate composition. It will be appreciated that the amount of time required for this step will be dependent on the thickness of the film being used. Generally the heat treatment step is carried out in a time of 0.1 to 5 seconds, more preferably 0.2 to 4 seconds, more preferably 0.5 to 2 seconds, more preferably 1.0 to 2.0 seconds, e.g. about 1.5 seconds.
  • the heat treatment step is carried out in a zone through which the wrapped composition is conveyed.
  • the heat treatment step may form part of a production process for a wrapped compacted particulate composition wherein the process includes other steps, such as the compaction of the composition.
  • Such processes generally operate at around 1500 individual compacted particulate compositions per minute on a single operational line. It has been found that advantageously the process of the present invention is able to work with this rate of throughput.
  • the zone comprises a flow (e.g. in the form of jets) of hot air over the wrapped compacted particulate compositions.
  • a flow e.g. in the form of jets
  • a plurality of jets of hot air are passed over the wrapped composition.
  • a jet of air may be directed at the composition from above
  • a jet of air may be directed at the composition from below
  • a jet of air may be directed at one or more sides of the composition.
  • the composition is carried on an apertured conveyor through the zone.
  • the temperature of the jets of air will depend upon the nature of the wrapped composition (particularly if the composition is thermally sensitive) and the film, material being used. Generally the air is heated to a temperature of between 90 to 950 0 C, more preferably 140 to 800 0 C, more preferably 180 to 650 0 C.
  • the film temperature may be lower than the temperature of the air jet. Most preferably the film temperature is between 80 to 220 0 C and more preferably 120 to 180 0 C.
  • the film has an aperture to allow the release of any trapped air during the heating process.
  • the film when applied to the compacted particulate composition, has a plurality of apertures.
  • the apertures are disposed on the upper surface of the particulate composition.
  • the apertures are applied using a punch.
  • the apertures have a preferred size (before the heat treatment step) of from around 0.1 to 0.3mm.
  • a cooling step has been found to be only optional rather than a requisite.
  • the film used in the process for wrapping the tablet may be any film which is water-soluble or water dispersible.
  • the tablet is preferably wrapped in a outer wrapper which is water soluble or water dispersible.
  • References hereinafter to water soluble also include water dispersible.
  • a water soluble film allows the tablet to be dispersed in an aqueous medium without having to be unwrapped.
  • the film comprises a polymeric material.
  • water-soluble polymers are poly (vinyl alcohol) (PVOH), cellulose derivatives such as hydroxypropyl methyl cellulose (HPMC) , gelatin, poly (vinylpyrrolidone) , poly(acrylic acid) or an ester thereof or poly(maleic acid) or an ester thereof.
  • Copolymers of any of these polymers may also be used.
  • Poly (vinyl alcohol), and copolymers thereof is especially preferred for the outer wrapper.
  • PVOH is an esterified or etherified PVOH.
  • the PVOH may be partially or fully alcoholised or hydrolysed. For example it may be from 40 to 100%, preferably from 70 to 92%, more preferably about 88% or about 92%, alcoholised or hydrolysed.
  • the degree of hydrolysis is known to influence the temperature at which the PVOH starts to dissolve in water. 88% hydrolysis corresponds to a PVOH soluble in cold (i.e. room temperature) water, whereas 92% hydrolysis corresponds to a PVOH soluble in warm water.
  • the film may be cold water (20°C) soluble, but may be insoluble in cold water and only become soluble in warm or hot water having a temperature of, for example, 30 0 C, 40°C, 50 0 C or even 60 0 C.
  • the film consists essentially of, or consists of, the polymer composition.
  • suitable additives such as plasticisers, lubricants and colouring agents to be added.
  • a particularly attractive appearance can be achieved by having the films in different colours, or by having one film uncoloured and the other coloured.
  • Components which modify the properties of the polymer may also be added.
  • Plasticisers are generally used in an amount of up to 20wt%, for example from 5 to 20wt% or 10 to 20wt%.
  • Lubricants are generally used in an amount of 0.5 to 5wt%.
  • the polymer is therefore generally used in an amount of from 75 to 94.5wt%, based on the total amount of the moulding composition.
  • Suitable plasticisers are, for example, water, pentaerythritols such as depentaerythritol, sorbitol, mannitol, glycerine and glycols such as glycerol, ethylene glycol and polyethylene glycol.
  • Solids such as talc, stearic acid, magnesium stearate, silicon dioxide, zinc stearate or colloidal silica may be used as lubricants.
  • alkali and alkaline earth metal such as sodium, potassium, magnesium and calcium, bicarbonate and carbonate, in conjunction with an acid.
  • Suitable acids are, for example acidic substances having carboxylic or sulfonic acid groups or salts thereof.
  • examples are cinnamic, tartaric, mandelic, fumaric, maleic, malic, palmoic, citric and naphthalene disulfonic acids, as free acids or as their salts, for example with alkali or alkaline earth metals.
  • the film may be a single film, or a laminated film as disclosed in GB-A-2, 244 , 258.
  • the layers in a film laminate may be the same or different. Thus the layers may each comprise the same polymer or a different polymer.
  • the film may be produced by any process, for example by extrusion and blowing or by casting.
  • the film may be unoriented, monoaxially oriented or biaxially oriented. If the layers in the film are oriented, they usually have the same orientation, although their planes of orientation may be different if desired.
  • the thickness of the film is preferably 10 to 2000 ⁇ m, especially 10 to 150 ⁇ m and more especially 15 to 80 ⁇ m. These measurements are before any heat treatment is applied to shrink the film; after heat treatment some of the film may have a different thickness, particularly around the corners of the wrapped composition.
  • the outer wrapper helps provide structural integrity to the wrapped detergent composition, which is typically in a solid form such as a detergent tablet formed by compaction. It is to be understood that extruded and injected moulded compositions are to be classed as compacted compositions herein.
  • the wrapped unit dose detergent portion is softer than conventional compacted particulate compositions.
  • the latter typically have hardness values in the range 230-260 N.
  • the wrapped unit dose detergent portions have a hardness value not exceeding 200 N, preferably not exceeding 150 N.
  • they have a hardness value of at least 80 N, preferably at least 100 N.
  • the hardness testing may be as determined across the width of a standard shaped cuboid 2Og unwrapped detergent portion, tested to destruction, using an ERWEKA tablet hardness tester THB30. In this test the detergent portion is set on a generally L-shaped support, against the upwardly projecting limb thereof. A circular piston of 8 mm diameter is advanced at a rate of 30 mm per minute and pressed onto the central region of the respective side wall, until the tablet is broken.
  • the plastic lid was removed on one of the compartments, the substantially air-tight seal was broken and the tablet (s) removed by hand.
  • the plastic lid was applied thereto and was held in place by the tongue-and-groove arrangement. Each compartment could be opened and closed individually.
  • the tablets in the compartments showed good stability (physical and chemical) for all 42 dishwashing tablets.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention porte sur un emballage primaire comportant deux ou plusieurs compartiments pouvant être ouverts individuellement, chaque compartiment comprenant une pluralité de parties de détergent de dose unitaire, et au moins un compartiment étant sensiblement hermétique à l'air avant d'être ouvert pour la première fois. L'emballage assure une bonne stabilité des parties de détergent.
PCT/GB2008/002701 2007-08-10 2008-08-11 Emballage WO2009022110A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US12/672,424 US20110127271A1 (en) 2007-08-10 2008-08-11 Packaging
EP08788273A EP2176131A1 (fr) 2007-08-10 2008-08-11 Emballage
CA2695346A CA2695346A1 (fr) 2007-08-10 2008-08-11 Emballage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0715606.0 2007-08-10
GBGB0715606.0A GB0715606D0 (en) 2007-08-10 2007-08-10 Packaging

Publications (1)

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WO2009022110A1 true WO2009022110A1 (fr) 2009-02-19

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US (1) US20110127271A1 (fr)
EP (1) EP2176131A1 (fr)
CA (1) CA2695346A1 (fr)
GB (1) GB0715606D0 (fr)
WO (1) WO2009022110A1 (fr)

Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2011094685A3 (fr) * 2010-01-29 2011-10-27 The Procter & Gamble Company Systèmes de contenant ayant couvercles pour des compositions détergentes en doses unitaires
WO2020254406A1 (fr) * 2019-06-18 2020-12-24 Unilever Plc Emballage contenant des capsules hydrosolubles
EP3763806A1 (fr) * 2019-07-11 2021-01-13 The Procter & Gamble Company Produit de consommation contenant une bande adhésive
WO2021013515A1 (fr) * 2019-07-24 2021-01-28 Unilever N.V. Conditionnement pour doses unitaires

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DE102017205050A1 (de) 2017-03-24 2018-09-27 Henkel Ag & Co. Kgaa Behälter mit tiefgezogener Wanne und darin befindlichen Dosiereinheiten
ES2932508T3 (es) * 2020-05-08 2023-01-20 Procter & Gamble Recipiente de producto detergente con cierre

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WO2011094685A3 (fr) * 2010-01-29 2011-10-27 The Procter & Gamble Company Systèmes de contenant ayant couvercles pour des compositions détergentes en doses unitaires
WO2020254406A1 (fr) * 2019-06-18 2020-12-24 Unilever Plc Emballage contenant des capsules hydrosolubles
EP3763806A1 (fr) * 2019-07-11 2021-01-13 The Procter & Gamble Company Produit de consommation contenant une bande adhésive
WO2021013515A1 (fr) * 2019-07-24 2021-01-28 Unilever N.V. Conditionnement pour doses unitaires

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EP2176131A1 (fr) 2010-04-21
US20110127271A1 (en) 2011-06-02
CA2695346A1 (fr) 2009-02-19

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