GB2368570A - Water soluble inflated containers - Google Patents

Water soluble inflated containers Download PDF

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Publication number
GB2368570A
GB2368570A GB0120483A GB0120483A GB2368570A GB 2368570 A GB2368570 A GB 2368570A GB 0120483 A GB0120483 A GB 0120483A GB 0120483 A GB0120483 A GB 0120483A GB 2368570 A GB2368570 A GB 2368570A
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United Kingdom
Prior art keywords
container
composition
water
gas
process according
Prior art date
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Granted
Application number
GB0120483A
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GB0120483D0 (en
GB2368570B (en
Inventor
Geoffrey Robert Hammond
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reckitt Benckiser UK Ltd
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Reckitt Benckiser UK Ltd
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Publication date
Application filed by Reckitt Benckiser UK Ltd filed Critical Reckitt Benckiser UK Ltd
Priority to GB0303107A priority Critical patent/GB2383320B/en
Publication of GB0120483D0 publication Critical patent/GB0120483D0/en
Publication of GB2368570A publication Critical patent/GB2368570A/en
Application granted granted Critical
Publication of GB2368570B publication Critical patent/GB2368570B/en
Anticipated expiration legal-status Critical
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043Liquid or thixotropic (gel) compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B31/00Packaging articles or materials under special atmospheric or gaseous conditions; Adding propellants to aerosol containers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B9/00Enclosing successive articles, or quantities of material, e.g. liquids or semiliquids, in flat, folded, or tubular webs of flexible sheet material; Subdividing filled flexible tubes to form packages
    • B65B9/02Enclosing successive articles, or quantities of material between opposed webs
    • B65B9/04Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B9/00Enclosing successive articles, or quantities of material, e.g. liquids or semiliquids, in flat, folded, or tubular webs of flexible sheet material; Subdividing filled flexible tubes to form packages
    • B65B9/02Enclosing successive articles, or quantities of material between opposed webs
    • B65B9/04Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material
    • B65B9/042Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material for fluent material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/46Applications of disintegrable, dissolvable or edible materials
    • B65D65/466Bio- or photodegradable packaging materials
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
  • Packages (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Toys (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
  • Wrappers (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • External Artificial Organs (AREA)

Abstract

A process for producing an inflated, water-soluble container which comprises: <SL> <LI>a) forming an open container from a water-soluble film; <LI>b) at least partially filling the container with a composition which comprises a component which releases a gas; <LI>c) sealing the container; and <LI>d) allowing the container to inflate. </SL> Preferably the container is made from thermoformed PVA. Also disclosed is an inflated water-soluble container enclosing a composition and a gas, said gas being enriched with a gaseous component.

Description

WATER- SOLUBLE CONTAINERS
The present invention relates to inflated, water-soluble containers and to a process for their preparation.
It is known to package chemical compositions which may be of a hazardous or irritant nature in water-soluble or water-dispersible materials such as films. The package can simply be added to water in order to dissolve or 10 disperse the contents of the package into the water.
For example, WO 89/12587 discloses a package which comprises an envelope of a water-soluble or water dispersible material which comprises a flexible wall and 15 a water-soluble or water-dispersible heat seal. The package may contain an organic liquid comprising, for example, a pesticide, fungicide, insecticide or herbicide. 20 It is also known to package detergents in water-soluble or water-dispersible containers. For example, WO 94/14941 discloses a water-soluble or water-dispersible capsule containing an aqueous dishwasher detergent. The capsule is made of gelatin.
CA-A-1,112,534 discloses a packet made of a water-
soluble material in film form enclosing within it a paste-form, automatic dishwasher-compatible detergent composition. The water-soluble material may be, for 30 example, poly(vinyl alcohol), polyethylene oxide or methyl cellulose. Example 1 illustrates an embodiment
- 2 wherein a poly(vinyl alcohol)(PVOH) film is made into a 5cm square packet by heat sealing its edges, and the packet is filled with a composition which contains 8.5 wt.% water.
It is also known to form water-soluble containers by thermoforming a water-soluble material. For example, WO 92/17382 discloses a package containing an agrochemical such as a pesticide comprising a first 10 sheet of non-planar water-soluble or water-dispersible material and a second sheet of water-soluble or water-
dispersible material superposed on the first sheet and sealed to it by a continuous closed water-soluble or water-dispersible seal along a continuous region of the 15 superposed sheets. It is stated to be advantageous to ensure that the package produced is evacuated of air or the contents are under reduced pressure to provide increased resistance to shock.
20 In order to improve the strength of packages containing liquids, it is also known to provide the package with residual inflatability. Thus, for example, EP-A-524, 721 describes a water-soluble package which contains a liquid, wherein the package is inflatable to a volume 25 which is greater than the initial volume of the package.
Thus the package is filled to less than its complete capacity, and the unused capacity may be partially, but not totally, filled with a gas such as air. The unused capacity which does not contain gas provides the 30 residual inflatability.
In fields such as detergents for domestic use, an
attractive appearance for an article is extremely desirable. However, in the prior art such as that
described above, the packages do not have an attractive 5 appearance. For example, the packages disclosed in WO 92/17382 are likely to have a nonuniform appearance because they are packaged under reduced pressure. When a bag is formed from a single sheet of water-soluble film by folding the film and heat-sealing the edges to 10 form the bag, which is then filled, such as described in CA-A-1,112,534, the product obtained can be a rather flat, limp envelope containing the product. Again there may also be lack of uniformity between different bags because of their flexible nature.
15. We have discovered that this type of product is not deemed to be attractive by an average consumer.
The present invention seeks to provide a water-soluble 20 container containing a composition, which container has a more attractive appearance. In particular the container should be relatively selfsupporting and look full. Ideally the container should have an attractive, rounded three-dimensional appearance.
EP-A-654,418 describes self-standing flexible pouches which may contain, for example, liquid detergent compositions for refilling other containers. The pouches are cut open and the contents poured into the 30 containers to be refilled. Thus they are not water-
soluble. In order to avoid folding of the pouches,
- 4 which can lead to cracking and leakage, the pouches are inflated by pumping in air before they are sealed.
We have now surprisingly discovered a water-soluble 5 container which contains a composition having an attractive three-dimensional appearance by ensuring that the container is inflated after it has been sealed.
The present invention accordingly provides a process for 10 producing an inflated, water-soluble container which comprises: a) forming an open container from a water-soluble film; b) at least partially filling the container with a 15 composition which comprises a component which releases a gas; c) sealing the container; and d) allowing the container to inflate.
20 The present invention also provides an inflated water-
soluble container comprising a water-soluble film enclosing a liquid or solid composition and a gas, wherein the gas is enriched with at least one gaseous component as compared with air or comprises at least one 25 gaseous component not normally present in air.
The initial step (a) of the process of the invention comprises forming an open container from a water-soluble film. A suitable water-soluble film is a poly(vinyl 30 alcohol) (PVOH) film.
- 5 The PVOH film may be partially or fully alcoholized or hydrolyzed, for example, it may be from 40 to 100%, preferably 70 to 92%, more preferably about 88% or about 92%, alcoholized or hydrolyzed, polyvinyl acetate film.
5 The degree of hydrolysis is known to influence the temperature at which the PVOH starts to dissolve in water. 88% hydrolysis corresponds to a film soluble in cold (i.e. room temperature) water whereas 92% hydrolysis corresponds to a film soluble in warm water.
10 An example of a preferred PVOH is ethoxylated PVOH. The film may be cast, blown or extruded. It may also be unorientated, mono-axially oriented or bi-axially oriented. 15 The film may also comprise a cellulose derivative such as hydroxy propyl methyl cellulose (HPMC). A suitable HPMC is, for example, M900 obtained from Enak Ltd. It is possible for suitable additives such as 20 plasticizers, lubricants and colouring agents to be added to the film. Components which modify the properties of the polymer may also be added.
Plasticisers are generally used in an amount of up to 35 wt%, for example from 5 to 35 wt%, preferably from 7 to 25 20 wt%, more preferably from 10 to 15 wt%. Lubricants are generally used in an amount of 0.5 to 5 wt%. The polymer is therefore generally used in an amount of from 60 to 94.5 wt%, based on the total amount of the composition used to form the film. Suitable 30 plasticizers are, for example, pentaerythritols such as depentaerythritol, sorbitol, mannitol, glycerine and
- 6 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 also be used.
It is also possible to include one or more particulate solids in the films in order to accelerate the rate of dissolution of the container. This solid may also be present in the contents of the container. Dissolution 10 of the solid in water is sufficient to cause an acceleration in the break-up of the container, particularly if a gas is generated, when the physical agitation caused may, for example, result in the virtually immediate release of the contents from the 15 container. Examples of such solids are alkali or alkaline earth metal, such as sodium, potassium, magnesium or calcium, bicarbonate or carbonate, in conjunction with an acid. Suitable acids are, for example, acidic substances having carboxylic or sulfonic 20 acid groups or salts thereof. Examples are cinnamic, barbaric, mandelic, fumaric, maleic, malic, palmoic, citric and naphthalene disulfonic acids.
The film is generally cold water (20 C) soluble, but may 25 be insoluble in cold water at 20 C and only become soluble in warm water or hot water having a temperature of, for example, 30 C, 40 C, 50 C or even 60 C. This parameter is determined in the case of PVOH by its degree of hydrolysis.
It is particularly important to avoid pinholes in the film through which leakage of the contained composition may occur. It may therefore be appropriate to use a laminate of two or more layers of a different or the 5 same film, as pinholes are unlikely to coincide in two layers of material.
The open container may be formed by any means. For example, it may be formed by thermoforming a PVOH film 10 to produce a non-planar sheet containing a pocket, such as a recess, which is able to retain the composition.
The pocket is generally bounded by a flange, which is preferably substantially planar. The pocket may have internal barrier layers as described in, for example, WO 15 93/08095. Thus the container may be formed, for example, by a process which is similar to that disclosed in WO 92/17382.
Alternatively the container may be prepared by producing 20 an open-top bag by forming a film around a shoulder and then heat-sealing simultaneously the bottom and sides of the bag. Other methods of sealing may be used, for example infra-red, radio frequency, ultrasonic, laser, solvent, vibration, electromagnetic, hot gas, hot plate, 25 insert bonding, friction sealing or spin welding. An adhesive such as water or an aqueous solution of PVOH may also be used. The adhesive can be applied to the film by spraying, transfer coating, roller coating, or the film can be passed through a mist of the adhesive.
30 The seal desirably is also water-soluble. Such a process is described for example in EP-A-728,673.
- 8 Another method for forming the open container is to seal two films together on three sides of the pocket by superimposing the films on each other and sealing them 5 together as described in WO 95/23099.
When a single water-soluble film is used, or if two films are used which are not thermoformed, the films generally have a thickness of 20 to 500 m, especially 10 30 to 160 m, preferably from 40 to 120 m, more preferably from 50 to 100 m.
When a first and second water-soluble film are used to form the containers of the present invention, the first 15 film will generally have a thickness before thermoforming of 20 to 500 m, especially 70 to 400 m, for example 70 to 300 m, most preferably 70 to 160 m, especially 75 to 100 Em or 90 to 110 to 150 m. The thickness of the second film may be less than that of 20 the first film as the second film will not generally be thermoformed so localized thinning of the sheet will not occur. The thickness of the second film will generally be from 20 to 150 Am or 160 m, preferably from 40 or 50 to 90 or 100 m, more preferably from 50 to 80 m.
25 The films may be chosen, if desired, such that they have the same thickness before the first film is thermoformed, or have the same thickness after the first sheet has been thermoformed in order to provide a composition which is encapsulated by a substantially 30 constant thickness of film.
9 - In step (b) the container is at least partially filled with a composition. The container may be completely filled, or only partially filled, for example to leave 5 an air space from 2 to 20 %, especially from 5 to 10%, of the volume of the container immediately after it is formed. The nature of the composition is not limited. It may, 10 for example, be a solid or a liquid. If it is in the form of a solid it may, for example, be in the form of a powder, granules, an extruded tablet, a compressed tablet or a solidified gel. If it is in the form of a liquid it may be optionally thickened or gelled with a 15 thickener or a gelling agent. One or more than one phase may be present. For example the container may be filled with a liquid composition and a separate solid composition, for example in the form of a ball, pill or speckles. Alternatively two or more solid phases, or two 20 or more immiscible liquid phases, may be present.
Thus the composition need not be uniform. For example, during manufacture the container could first be filled with a gettable composition, for example a gel and then 25 with a different composition. Each of the compositions is independently aqueous. The first composition could dissolve slowly, for example in a washing process, so as to deliver it over a long period. This might be useful, for example, to provide an immediate, delayed or 30 sustained delivery of a component such as a softening agent.
- 10 If the water-soluble container is soluble in cold water at room temperature (20 C) or slightly above, it is important to ensure that the composition itself does not 5 dissolve the container. In general solid compositions will not attack the container, and neither will liquid organic compositions which contain less than around 5% of water as described, for example, in WO 92/17382. If the composition is in the form of a liquid containing 10 more than about 5 wt% water, action must be taken to ensure that the composition does not attack the walls of the container. Steps may be taken to treat the inside surface of the film, for example by coating it with an agent such as PVdC (poly(vinylidene dichloride)) or PTFE 15 (polytetrafluoroethylene). A semi-permeable or partial water barrier such as polyethylene or polypropylene or a hydrogel such as a polyacrylate may also be provided as a coating. The coating will simply fall apart or dissolve or disperse into microscopic particles when the 20 container is dissolved in water. Steps may also be taken to adapt the composition to ensure that it does not dissolve the film. For example, it has been found that ensuring the composition has a high ionic strength or contains an agent which minimises water loss through 25 the walls of the container will prevent the composition from dissolving a PVOH film from the inside. This is described in more detail in EP-A-518, 689 and WO 97/27743.
30 A component which releases a gas is added to the composition. This component may be added separately or
with the remaining components. Thus, for example, the component, or one of the components of a multi-component gas releasing system, may be added first and the remainder of the composition added afterwards., Another 5 possibility is that the components, or one of the components of a multicomponent gas releasing system, may be added after the remainder of the composition. It is also possible for all of the components to be added together in a single composition.
The component which releases a gas may, for example, comprise a component or a mixture of two or more components which react in the presence of the contents of the container to release a gas. For example, when 15 water is present in the composition, two components which do not react when in solid form but which will react in the presence of water can be added, such as an acid and a carbonate or bicarbonate. An example of a suitable acid is citric acid. Examples of suitable 20 carbonates and bicarbonates are sodium and potassium carbonate and sodium and potassium bicarbonate.
Another possibility is that a component is added which is able to react with a component already present in the 25 composition contained in the container. For example, an acid may be present within the composition held within the container, and a carbonate or bicarbonate as described above subsequently added. Alternatively a carbonate or bicarbonate may be present in the 30 composition, and an acid subsequently added.
In the above cases, the component which releases a gas may be added in solid form or in a solvent such as water or an organic solvent. The rate of release of the gas may be controlled. For example, a finely divided powder 5 will release the gas quicker than a compressed tablet.
If desired, the component may be encapsulated by a substance which delays the release of the gas.
A further possibility is to add a component to the 10 composition which is a gas at room temperature (20 C) but which, at the time which it is added, is in the form of a solid or liquid because it has been cooled to less than its melting or boiling point. For example, solid carbon dioxide (dry ice) may be added. As the component 15 heats up to room temperature, which may occur naturally or be aided with heating, it will boil or sublime into a gas. Another possibility is to add a compound which is thermally unstable; for example sodium bicarbonate will release carbon dioxide when it is heated to about 60 C.
The component which releases a gas may, for example, be a component which gradually releases a gas such as a bleach, in particular an oxygen bleach or a chlorine bleach. Such bleaches gradually releases a gas such as 25 oxygen or a chlorine containing compound when they contact water. The water may itself be contained in the composition, be contained in another compartment and diffuse through the dividing wall into the compartment holding the bleach, or may diffuse into the composition 30 from outside the container.
Any component or combination of components can be used which will produce a gas. The gas should be non-toxic or produced in small quantities. It is most convenient, however, to produce carbon dioxide gas since this will 5 not cause any environmental concerns.
After the component which releases a gas has been added, for example with or to the composition, the container is sealed in step (c). If the component which releases a 10 gas starts to release a gas immediately, as it generally will, the container should be sealed immediately to ensure that at least some of the gas produced is retained within the container. Sealing can be carried out by any means as described above.
Thus, for example, if the container is in the form of a pocket formed from one or two sheets of film, the container may be sealed by heat- sealing or by any of the remaining sealing methods discussed above. The films 20 may be sealed together, for example by heat sealing, across the flange. A suitable heat sealing temperature is, for example, 120 to 195 C, for example 140 to 150 C.
A suitable sealing pressure is, for example, from 250 to 800 kPa. Examples of sealing pressures are 276 to 552 25 kPa (40 to 80 p. s. i.), especially 345 to 483 kPa (50 to 70 p. s. i.) or 400 to 800 kPa (4 to 8 bar), especially 500 to 700 kPa (5 to 7 bar) depending on the heat sealing machine used. Suitable sealing dwell times are at least 0. 4 seconds, for example 0.4 to 2.5 seconds.
30 Other methods of sealing the films together may be used, for example infra-red, radio frequency, ultrasonic,
- 14 laser, solvent, vibration, electromagnetic, hot gas, hot plate, insert bonding, fraction sealing or spin welding.
An adhesive such as water or an aqueous solution of PVOH may also be used. The adhesive can be applied to the 5 films by spraying, transfer coating, roller coating or otherwise coating, or the films can be passed through a mist of the adhesive. The seal desirably is also water-
soluble. The second film may, for example, comprise PVOH. If more than one container is formed at the same time, the packaged compositions may then be separated from each other. Alternatively, they may be left conjoined and, for example, perforations provided between the 15 individual containers so that they can be easily separated at a later stage, for example by a consumer.
If the containers are separated, the flanges may be left in place. However, desirably the flanges are partially removed in order to provide an even more attractive, 20 three-dimensional appearance. Generally the flange remaining should be as small as possible for aesthetic purposes while bearing in mind that some flange is required to ensure the two films remain adhered to each other. A flange of 1 mm to 10 mm is desirable, 25 preferably 2 mm to 7 mm, more preferably 4 mm to 6 mm, most preferably about 5 mm.
The containers are then allowed to inflate in step (d).
The containers may be allowed to inflate, for example, 30 at rest, or they may be packaged into boxes for retail sale, and left to inflate in the boxes. The containers
- 15 may themselves be packaged in outer containers if desired, for example, non-water-soluble containers which are removed before the watersoluble containers are used. The containers of the present invention generally contain from 5 to 100 g of composition, such as an aqueous composition, especially from 15 to 40 g, depending on their intended use. For example, a 10 dishwashing composition may weigh from 15 to 20 g, a water-softening composition may weigh from 25 to 35 g, and a laundry composition may weigh from 10 to 40 g, especially 20 to 30 g or 30 to 40 g.
15 The containers may have any shape. For example they can take the form of an envelope, sachet, sphere, cylinder, cube or cuboid, i.e. a rectangular parallelepiped whose faces are not all equal. In general, because the containers are not rigid and are inflated, the sides are 20 not planar, but rather are convex. If the container is formed from a thermoformed film and a planar film, the seam between the two films will appear nearer one face of the container rather than the other. Apart from the deformation of the container due to the generation of 25 gas, deformation may also occur at the stage of manufacture if desired. For example, if the pocket is filled with a gelled composition having a height greater than that of the pocket, the second film will be deformed when placed on top of the pocket.
- 16 In general the maximum dimension of the filled part of the container (excluding any flanges) is 5 cm. For example, a rounded cuboid container may have a length of 1 to 5 cm, especially 3.5 to 4.5 cm, a width of 1.5 to 5 3.5 cm, especially 2 to 3 cm, and a height of 1 to 2.5 cm, especially 1 to 2 cm, for example 1.25 to 1.75 cm.
The composition filling the containers is not particularly limited. It can be any composition which 10 is to be added to an aqueous system or used in an aqueous environment. Suitable compositions are fabric care, surface care and dishwashing compositions. For example, the composition may comprise a dishwashing, water-softening, laundry or detergent composition or a 15 rinse aid. In this case it is especially suitable for use in a domestic washing machine such as a laundry washing machine or a dishwashing machine. The container may also comprise a disinfectant, antibacterial or antiseptic composition intended to be diluted with water 20 before use, or a concentrated refill composition, for example for a trigger-type spray used in domestic situations. Such a composition can simply be added to water already held in the spray container. Examples of surface care compositions are those used to clean, treat 25 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. 30 Examples of 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 C8-C20 fatty alcohols.
5 Examples of primary alkyl sulfate surfactants are those of formula: ROSO3 -M+
wherein R is a linear C -C20 hydrocarbyl group and M is a watersolubilising cation. Preferably R is C1O-Cl alkyl, 10 for example Cl2-Cl4, and M is alkali metal such as lithium, sodium or potassium.
Examples of secondary alkyl sulfate surfactants are those which have the sulfate moiety on a "backbone" of 15 the molecule, for example those of formula: CH2 ( CH2) n ( CHOSO3 M) ( CH2) mCH3 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 20 or potassium.
Especially preferred secondary alkyl sulfates are the (2,3) alkyl sulfate surfactants of formulae: 25 CH2(CH2)X( CHOSO3 -M+) CH3 and CH3 ( CH2) x ( CHOSO3 -M+) CH2CH3 for the 2-sulfate and 3-sulfate, respectively. In these 30 formulae x is at least 4, for example 6 to 20,
- 18 preferably 10 to 16. M is cation, such as an alkali metal, for example lithium, sodium or potassium.
Examples of alkoxylated alkyl sulfates are ethoxylated 5 alkyl sulfates of the formula: RO(C2H4O)nSO3 M+ wherein R is a C8-C20 alkyl group, preferably Cl0-Cl8 such 10 as a C12-Cl6, 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 15 cleaning performance benefits when used in combination with alkyl sulfates.
The alkyl sulfates and alkyl ether sulfates will generally be used in the form of mixtures comprising 20 varying alkyl chain lengths and, if present, varying degrees of alkoxylation.
Other anionic surfactants which may be employed are salts of fatty acids, for example C8-C18 fatty acids, 25 especially the sodium, potassium or alkanolammonium salts, and alkyl, for example C8-Cl8, benzene sulfonates.
Examples of nonionic surfactants are fatty acid alkoxylates, such as fatty acid ethoxylates, especially 30 those of formula: R(C2H4O)nOH
wherein R is a straight or branched C8-Cl6 alkyl group, preferably a CgCl5, for example Cl0-Cl4 or Cl2-Cl4, alkyl group and n is at least 1, for example from 1 to 16, 5 preferably 2 to 12, more preferably 3 to 10.
The alkoxylated fatty alcohol nonionic surfactant will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17, more preferably from 6 to 15, 10 most preferably from 10 to 15.
Examples of 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 15 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 20 ethoxylated primary Cl2-Cl3 alcohol having about 9 moles of ethylene oxide; and Neodol 91-10, an ethoxylated C,-
Cll primary alcohol having about 10 moles of ethylene oxide. 25 Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol trademark.
Dobanol 91-5 is an ethoxylated C,-Cll fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated Cl2-Cl5 fatty alcohol with an average of 7 30 moles of ethylene oxide per mole of fatty alcohol.
- 20 Other examples of suitable ethoxylated alcohol nonionic 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 5 S-7 is a mixed ethoxylated product of a C11-C15 linear secondary alkanol with 7 moles of ethylene oxide and Tergitol 15-S-9 is the same but with 9 moles of ethylene oxide. 10 Other suitable alcohol ethoxylated nonionic 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 15 from Shell Chemical Company.
Further nonionic surfactants are, for example, C10-Cl8 alkyl polyglycosides, such as C12-Cl6 alkyl polyglycosides, especially the polyglucosides. These 20 are especially useful when high foaming compositions are desired. Further surfactants are polyLydroxy fatty acid amides, such as C10-Cl8 N-(3-methoxypropyl) glycamides and ethylene oxidepropylene oxide block polymers of the Pluronic type.
Examples of cationic surfactants are those of the quaternary ammonium type.
Examples of amphoteric surfactants are C10-Cl8 amine 30 oxides and the C12-Cl8 betaines and sulfobetaines.
- 21 The total content of surfactants in the composition is desirably 0.1to 95 wt%, especially 60 or 75 to 90 wt%.
The total content of surfactants in a laundry or detergent composition is desirably 60 to 95 wt%,, 5 especially 70 to 90 wt%. Desirably, especially in a laundry composition, an anionic surfactant is present in an amount of 50 to 75 wt%, a nonionic surfactant is present in an amount of 5 to 20 wt%, a cationic surfactant is present in an amount of from O to 10 wt% 10 and/or an amphoteric surfactant is present in an amount from O to 10 wt%. Desirably, in a dishwashing composition, the anionic surfactant is present in an amount of from 0.1 to 50 wt%, a non-ionic surfactant is present in an amount of 0.5 to 20 wt% and/or a cationic 15 surfactant is present in an amount of from 1 to 15 wt%.
These amounts are based on the total solids content of the composition, i. e. excluding any water or solvent which may be present.
20 The compositions, particularly when used as laundry washing or dishwashing compositions, may also comprise enzymes, such as protease, lipase, amylase, cellulase and peroxidase enzymes. Such enzymes are commercially available and sold, for example, under the registered 25 trade marks Esperase, Alcalase, Savinase, Termanyl, Lipolase and Celluzyme by Novo Industries A/S and Maxatasc by International Biosynthetics, Inc. Desirably the enzymes are present in the composition in an amount of from 0.5 to 3 wed, especially 1 to 2 wt%.
- 22 The compositions may, if desired, comprise a thickening agent or gelling agent. Suitable thickeners are polyacrylate polymers such as those sold under the trade mark CARBOPOL, or the trade mark ACUSOL by Rohm and Haas 5 Company. Other suitable thickeners are xanthan gums.
The thickener, if present, is generally present in an amount of from 0.2 to 4 wt%, especially 0.5 to 2 wt%.
Dishwasher compositions usually comprise a detergency 10 builder. Suitable builders are alkali metal or ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, bicarbonates, berates, polyhydroxysulfonates, polyacetates, carboxylates and polycarboxylates such as citrates. The builder is 15 desirably present in an amount of up to 90 wt%, preferably 15 to 90 wt%, more preferably 15 to 75 wt%, relative to the total content of the composition.
Further details of suitable components are given in, for example, EP-A694,059, EP-A-518,720 and WO 99/06522.
The compositions can also optionally comprise one or more additional ingredients. These include conventional detergent composition components such as further surfactants, bleaches, bleach enhancing agents, 25 builders, suds boosters or suds suppressors, anti-
tarnish and anti-corrosion agents, organic solvents, co-
solvents, phase stabilizers, emulsifying agents, preservatives, soil suspending agents, soil release agents, germicides, phosphates such as sodium 30 tripolyphosphate or potassium tripolyphosphate, pH adjusting agents or buffers, non-builder alkalinity
- 23 sources, chelating agents, clays such as smectite clays, enzyme stabilizers, anti-limescale agents, colourants, dyes, hydrotropes, dye transfer inhibiting agents, brighteners and perfumes. If used, such optional 5 ingredients will generally constitute no more than 10 we%, for example from 1 to 6 wt%, of the total weight of the compositions.
The builders counteract the effects of calcium, or other ion, water hardness encountered during laundering or 10 bleaching use of the compositions herein. 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 15 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 20 by Monsanto under the trade mark Dequest and alkylhydroxy phosphonates. Citrate salts and Cl2-C fatty acid soaps are preferred.
Other suitable builders are polymers and copolymers 25 known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic and copolymers and their salts, such as those sold by BASE under the trade mark Sokalan.
The builders generally constitute from O to 3 wt%, more preferably from 0. 1 to l wt%, by weight of the compositions. 5 Compositions which comprise an enzyme may optionally contain materials which maintain the stability of the enzyme. Such enzyme stabilizers include, for example, polyols such as propylene glycol, boric acid and borax.
Combinations of these enzyme stabilizers may also be 10 employed. If utilized, the enzyme stabilizers generally constitute from 0.1 to 1 wt% of the compositions.
Examples of bleaches are, for example, listed in WO 99/06522. These include oxygen releasing bleaching agents such as a hydrogen peroxide source and an organic 15 peroxyacid bleach precursor compound or a preformed organic peroxyacid. Examples of hydrogen peroxide sources are inorganic perhydrate bleaches such as the alkali metal salts of perborate, percarbonate, perphosphate, persulfate and persilicates. Examples of 20 organic peroxyacid bleach precursors are listed in WO 99/06522. The bleaches also include chlorine releasing agents such as hydantoins, for example 1,3-dichloro-5,5-
dimethyl hydantoin, hypochlorites such as sodium hypochlorite or dichloroisocyanurates such as sodium 25 dichloroisocyanurate.
The compositions may optionally comprise materials which serve as phase stabilizers and/or co-solvents. Example are C1-C3 alcohols or dials such as methanol, ethanol, 30 propanol, and 1, 2-propanediol. C1-C3 alkanolamines such as mono-, di- and triethanolamines and
monoisopropanolamine 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 1 wt%, preferably 0.1 to 0.5 wt% of the composition.
If the composition is in liquid form, it may be anhydrous, or, for example, contain up to 5 wt% water.
Aqueous compositions generally contain greater than 8 wt% water based on the weight of the aqueous 10 composition. Desirably the aqueous compositions contain more than 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt% water, but desirably less than 80 wt% water, more desirably less than 70 wt%, 60 wt%, 50 wt% or 40 wt% water. They may, for example, contain from 30 to 55 or 15 55 wt% water.
The compositions may optionally comprise components which adjust or maintain the pH of the compositions at optimum levels. Examples of pH adjusting agents are NaOH 20 and citric acid. The pH may be from, for example, 1 to 13, such as 8 to 11 depending on the nature of the composition. For example, a dishwashing composition desirably has a pH of 8 to 11, a laundry composition desirably has a pH of 7 to 9, and a watersoftening 25 composition desirably has a pH of 7 to 9.
The present invention will now be further explained in the following Examples.
- 26 Example 1
A dishwashing composition was prepared by mixing together the following components in the weight 5 proportions indicated: Potassium tripolyphosphate powder 12% Sodium tripolyphosphate powder 30% Isothiazolinone 0.1% 10 Polyacrylate thickener (Carbopol) 1% Nonionic surfactant 0.5% Sodium citrate 10% Citric acid 0.2% Sodium bicarbonate 0. 2% 15 Rehardened water 46% A Multivac thermoforming machine operating at 6 cycles/min and at ambient conditions of 25 C and 35% RH (+5% RH) was used to thermoform a PVOH film. This was Monosol M8534 obtained from Chris Craft Inc. Gary, 20 Indiana, USA, having a degree of hydrolysis of 88% and a thickness of 100 m. The PVOH film was thermoformed into a rectangular mould of 39 mm length, 29 mm width and 16 mm depth, with the bottom edges being rounded to a radius of 10 mm, at 115-118 C. The thus formed pocket 25 was filled with 10 ml of the dishwashing composition, and a 75 Am thick Monosol M8534 PVOH film was placed on top and heat sealed at 144-148 C. The thus produced containers were separated from each other by cutting the flanges. Each container attained a rounded appearance 30 due to the generation of carbon dioxide gas.
- 27 Example 2
The following formulations were prepared by mining 5 together the indicated components in the weight proportions indicated. In all instances the compositions were filled into containers following the procedure described in Example 1, and containers having an attractive, rounded appearance were obtained after 10 the carbon dioxide gas had generated.
A laundry detergent composition: Sodium carbonate 20% 15 Nonylphenol ethoxylate - 10% -
Accusol 820 obtainable from Rohm and Hass Company 3.3% Sodium citrate 5% Citric acid 0.2% 20 Sodium bicarbonate 0.2% Dehardened water 61.3% An automatic dishwasher detergent: 25 Sodium citrate 8% Van Gel ES thickener obtainable from R.T.Vanderbilt Company 4% Tetrapotassium pyrophosphate 10% 30 Sodium tripolyphosphate 30% Anhydrous sodium metasilicate 2%
Sodium xylene sulfonate 2.25 Deceth-4-phosphate 0.75 Citric acid 0.2% Sodium bicarbonate 0.2% 5 Dehardened water 42.6% A slurry type heavy duty laundry liquid: Neodol 25-7 Cl2l5 linear alcohol 18% 10 Biosoft D-62 sodium alkylbenzenesulfonate 5.5% Sodium carbonate 2% Anhydrous sodium metasilicate 5% Tetrasodium pyrophosphate 20% 15 Sodium citrate 7.5% Carbopol ETDZ691 polymer obtainable from Goodrich 0.5% Citric acid 0.2% Sodium bicarbonate 0.2% 20 Dehardened water 41.1% A slurry-type laundry detergent: Sodium carbonate 40% 25 Sodium citrate 4.8% Accusol 820 obtainable from Rohm and Hass 2% Accusol 810 obtainable from Rohm and Hass 5% 30 Sodium tripolyphosphate 10% Accusol 445 obtainable from
Rohm and Hass 2% Nonylphenol ethoxylate 10% Citric acid 0.25% Sodium bicarbonate 0.25% 5 Dehardened water 26.7% A dishwashing composition: Accusol 810 11% 10 Accusol 445N 4% Sodium tripolyphosphate 20% Tetrapotassium pyrophosphate 10% Potassium silicate 29% Triton CF-32 alkylamine ethoxylate 3% 15 Potassium citrate 5% Citric acid 0.25% Sodium bicarbonate 0.25% Dehardened water 17.4%

Claims (1)

  1. - 30 CLAIMS
    1.A process for producing an inflated, water-soluble container which comprises: 5 a) forming an open container from a water-soluble film; b) at least partially filling the container with a composition which comprises a component which releases a gas; 10 c) sealing the container; and d) allowing the container to inflate.
    2.A process according to claim 1 wherein the container is at least partially filled with a composition and a 15 component which releases a gas is subsequently added.
    3.A process according to claim 1 wherein the container is filled with a composition which comprises a component which releases a gas in a single step.
    4. A process according to any one of the preceding claims wherein step (a) comprises thermoforming the film to produce a pocket.
    25 5. A process according to claim 4 wherein step (c) comprises placing a second water-soluble film on top of the filled pocket and sealing the films together.
    6. A process according to any one of the preceding 30 claims wherein the water-soluble film is a poly(vinyl alcohol) film.
    7. A process according to any one of the preceding claim where the composition in step (b) is an aqueous or non-aqueous liquid.
    8. A process according to claim 7 wherein the aqueous liquid contains greater than 8wt% water based on the total weight of aqueous liquid and component which releases a gas.
    9. A process according to claim 7 or 8 wherein the component which releases a gas comprises a mixture of compounds which react in the presence of water to produce the gas.
    lO.A process according to claim 7 or 8 wherein the component which releases a gas comprises a compound which reacts with a compound in the aqueous liquid to produce the gas.
    ll.A process according to claim 10 wherein the component which releases a gas is a bleach.
    12.A process according to claim 7 or 8 where the 25 component which releases a gas is a component which is a gas at room temperature (20 C) but which is added in step (b) in the form of a cooled solid or liquid. 30 13.A process according to any one of the preceding claims wherein the gas which inflates the container
    is carbon dioxide.
    14.A process according to any one of the preceding claims wherein the container comprises a fabric care, 5 surface care or dishwashing composition.
    15.A process according to any one of the preceding claims wherein the container comprises a dishwashing, water-softening, laundry or detergent 10 composition or a rinse aid.
    16.A process according to claim 15 wherein the container is suitable for use in a domestic washing machine. 17.A process according to any one of claims 1 to 14 wherein the container comprises a disinfectant, antibacterial or antiseptic composition.
    20 18.A process according to any one of claims 1 to 14 wherein the container comprises a refill composition for a trigger-type spray.
    l9.An inflated water-soluble container comprising a water-soluble film enclosing a liquid or solid composition and a gas, wherein the gas is enriched with at least one gaseous component as compared with air or comprises at least one gaseous component not normally present in air.
    20.A container according to claim 19 wherein the
    gaseous component is carbon dioxide.
    21.A container according to claim 19 wherein the gaseous component is oxygen or a chlorine containing 5 component.
    22.A container according to any one of claims 19 to 21 wherein the watersoluble film is a poly(vinyl alcohol) film.
    23.A container according to any one of claims 19 to 22 wherein the watersoluble film has been thermoformed to form a pocket and the pocket has been sealed by placing a second water-soluble film 15 over the pocket and sealing the films together.
    24.A container according to any one of claims 19 to 23 wherein the watersoluble film has been thermoformed.
    20 25.A container according to any one of claims 19 to 24 wherein the composition is a fabric care, surface care or dishwashing composition.
    26.A container according to any one of claims 19 to 25 25 wherein the composition is a dishwashing, water softening, laundry or detergent composition or is a rinse aid.
    27.A container according to claim 26 which is suitable 30 for use in a domestic washing machine.
    - 34 28.A container according to any one of claims 19 to 25 wherein the composition is a disinfectant, antibacterial or antiseptic composition.
    29.A container according to any one of claims 19 to 25 5 wherein the composition is a refill composition for a trigger-type spray.
GB0120483A 2000-08-25 2001-08-23 Water soluble inflated containers Expired - Fee Related GB2368570B (en)

Priority Applications (1)

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GB0303107A GB2383320B (en) 2000-08-25 2001-08-23 Water-soluble containers

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GBGB0021112.8A GB0021112D0 (en) 2000-08-25 2000-08-25 Improvements in or relating to containers

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GB0120483D0 GB0120483D0 (en) 2001-10-17
GB2368570A true GB2368570A (en) 2002-05-08
GB2368570B GB2368570B (en) 2003-05-28

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GB0303107A Expired - Fee Related GB2383320B (en) 2000-08-25 2001-08-23 Water-soluble containers
GB0120483A Expired - Fee Related GB2368570B (en) 2000-08-25 2001-08-23 Water soluble inflated containers

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GB0303107A Expired - Fee Related GB2383320B (en) 2000-08-25 2001-08-23 Water-soluble containers

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US (1) US20040035739A1 (en)
EP (1) EP1311430B1 (en)
AT (1) ATE281351T1 (en)
AU (2) AU2001282344B2 (en)
CA (1) CA2420380C (en)
DE (3) DE20121785U1 (en)
ES (1) ES2227251T3 (en)
GB (3) GB0021112D0 (en)
WO (1) WO2002016206A1 (en)

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US7125828B2 (en) 2000-11-27 2006-10-24 The Procter & Gamble Company Detergent products, methods and manufacture
ATE340850T1 (en) 2000-11-27 2006-10-15 Procter & Gamble DISHWASHING METHOD
GB2387598A (en) * 2002-04-20 2003-10-22 Reckitt Benckiser Nv Water-soluble container and a process for its preparation
DE10237200A1 (en) 2002-08-14 2004-03-04 Henkel Kgaa Portioned detergent or cleaning agent composition
DE10244803B4 (en) * 2002-09-26 2012-03-22 Henkel Ag & Co. Kgaa Shrunken detergent tablets
DE10244802B4 (en) 2002-09-26 2011-12-22 Henkel Ag & Co. Kgaa Plump detergent tablets
DE10356824A1 (en) * 2003-12-05 2005-07-07 Henkel Kgaa Continuous production of water soluble containers, comprises deep drawing a water soluble film material, filling the chamber formed, and finishing
DE10356769B4 (en) * 2003-12-05 2007-06-14 Henkel Kgaa packing method
EP1678037B1 (en) 2003-10-31 2009-10-28 Henkel AG & Co. KGaA Packaging method
DE10350931B4 (en) * 2003-10-31 2007-06-14 Henkel Kgaa packing method
EP1679362A1 (en) * 2005-01-10 2006-07-12 The Procter & Gamble Company Cleaning composition for washing-up or washing machine
EP1679363B1 (en) * 2005-01-10 2008-07-09 The Procter and Gamble Company Cleaning composition for washing-up or washing machine
US8772220B2 (en) 2007-08-24 2014-07-08 Sekisui Specialty Chemicals America, Llc Chemical delivery product and process for making the same
US20130114917A1 (en) * 2010-07-16 2013-05-09 Du Pont-Mitsui Polychemicals Co., Ltd. Filling method, manufacturing method of liquid sachet package, and liquid sachet package
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GB0303107D0 (en) 2003-03-19
ATE281351T1 (en) 2004-11-15
GB0120483D0 (en) 2001-10-17
CA2420380A1 (en) 2002-02-28
AU2001282344B2 (en) 2006-02-16
EP1311430B1 (en) 2004-11-03
GB2383320B (en) 2004-05-19
GB2383320A (en) 2003-06-25
EP1311430A1 (en) 2003-05-21
GB2368570B (en) 2003-05-28
DE20121785U1 (en) 2003-10-23
CA2420380C (en) 2009-03-31
DE10196553T1 (en) 2003-08-07
US20040035739A1 (en) 2004-02-26
DE60106939T2 (en) 2005-11-10
AU8234401A (en) 2002-03-04
WO2002016206A1 (en) 2002-02-28
DE60106939D1 (en) 2004-12-09
GB0021112D0 (en) 2000-10-11
ES2227251T3 (en) 2005-04-01

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Effective date: 20050823