EP1319707B1 - Poche contenant une composition pour le lavage du linge - Google Patents
Poche contenant une composition pour le lavage du linge Download PDFInfo
- Publication number
- EP1319707B1 EP1319707B1 EP02258562A EP02258562A EP1319707B1 EP 1319707 B1 EP1319707 B1 EP 1319707B1 EP 02258562 A EP02258562 A EP 02258562A EP 02258562 A EP02258562 A EP 02258562A EP 1319707 B1 EP1319707 B1 EP 1319707B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pouch
- solid phase
- phases
- composition
- phase
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
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- 159000000001 potassium salts Chemical class 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ASDOMANMPRPBHC-UHFFFAOYSA-M sodium hydrogen sulfate octadecanoic acid Chemical compound S(=O)(=O)([O-])O.[Na+].C(CCCCCCCCCCCCCCCCC)(=O)O ASDOMANMPRPBHC-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- ODNOQSYKKAFMIK-UHFFFAOYSA-N sodium;2-(2-undecylimidazol-1-yl)acetic acid Chemical compound [Na].CCCCCCCCCCCC1=NC=CN1CC(O)=O ODNOQSYKKAFMIK-UHFFFAOYSA-N 0.000 description 1
- ACSMPKOCARMFDD-UHFFFAOYSA-M sodium;2-(dimethylamino)octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCC(N(C)C)C([O-])=O ACSMPKOCARMFDD-UHFFFAOYSA-M 0.000 description 1
- AOVQVJXCILXRRU-UHFFFAOYSA-M sodium;2-(dodecylamino)ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCNCCOS([O-])(=O)=O AOVQVJXCILXRRU-UHFFFAOYSA-M 0.000 description 1
- HWCHICTXVOMIIF-UHFFFAOYSA-M sodium;3-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNCCC([O-])=O HWCHICTXVOMIIF-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical class CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS 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
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/008—Standing pouches, i.e. "Standbeutel"
-
- 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
- C11D17/046—Insoluble free body dispenser
Definitions
- a laundry pouch made of a flexible material comprising a laundry composition with at least two phases, such that one of the phases forms a base upon which the pouch can stand without additional support and a process of its manufacture.
- One convenient form for dispensing laundry products is that of a pouch.
- Using pouches during the washing process is an attractive alternative to conventional laundry powders and liquids since the laundry product contained in the pouch (powder, or liquid) can be deposited in the wash without possibility of contact with the users hands or clothes or with the outer aspects of the washing machine, or the floor, etc.
- the product typically is contained within a pouch formed from a water soluble film and tossed, still in the pouch, into the washer.
- pouches containing detergent products do not have a single predetermined shape, but form their shape based on the distribution of product within the pouch. Moreover, unless extra effort and expense is incurred to provide the pouch with a defined structural bottom, the pouch has no base upon which it will necessarily rest and will often lie on its side. Where such pouches are packaged in a tray, removal of one or more of the pouches may cause others to fall over and disturb the order of the package.
- U.S. Patent No. 6,040,286 discloses a "through the washer dryer" pouch type detergent bag containing granular detergent particulate.
- the pouch type detergent bag is preferably made from a material that is air- and water-permeable such as non-woven polyester.
- the detergent bag has a front panel and a rear panel and they are sealed together around their perimeters to form an inner chamber in which detergent particulate is deposited.
- An alternative embodiment illustrated in, e.g., Figs. 5 and 6 of Huff includes a web of material 44 connecting the bottom edge of two chambers containing detergent particulate.
- Buchanan, U.S. Patent No. 5,273,362 is directed to containers produced from a sheet of flexible material having a thermally bonded inside surface.
- the container includes a reinforced bottom wall and is capable of standing vertically on its own.
- Patent 3,618,758 Guerry et al., U.S. Patent 4,176,079; Davies et al., U.S. Patent 4,410,441; Ginn, U.S. Patent 4,588,080; Ginn, U.S. Patent 4,680,916; Leigh et al., U.S. Patent 4,706,802; Gouge et al., U.S. Patent 5,224,601; Saam, U.S. Patent 5,927,498.
- the present invention includes a laundry composition contained within a pouch wherein the pouch can stand on its own without the need for a reinforced base.
- the pouch is formed from a flexible material, preferably a film, wherein a laundry composition in at least two phases is contained within the pouch.
- One of the phases forms a base upon which the pouch can stand without additional support.
- the phase that assists in forming the pouch base is a solid.
- the solid phase may be introduced into the pouch as a solid or it may be formed after the composition is introduced into the pouch (i.e., it sets upon standing).
- the solid phase is insoluble in the other phases of the composition within the pouch.
- the solid phase separation from the other phases of the composition is attained by either ensuring that the density of the solid phase is higher than the density of the other phases; or by filling the pouch first with a liquid or a slurry that solidifies upon standing, thus forming the solid phase (which regardless of its density stays on the bottom due to the shape restriction of the pouch), and then filling the other phases of the composition.
- the laundry compositions are heavy duty laundry detergents.
- various other laundry products can be contained in the pouches, such as other laundry detergents, fabric softeners, bleaches, bleach precursors, perfumes, anti-bacterial agents, anti-static agents, whitening or bluing agents, enzymes or builders.
- Laundry detergents generally comprise surfactants such as anionic and/or nonionic surfactants. Fabric softeners often include cationic surfactants.
- Laundry products which may be considered for use in the present invention include those described in U.S. Patent Nos. 5,132,036 and 4,420,441, the disclosures of which are hereby incorporated by reference.
- the pouch of the invention is preferably made of a water soluble film so that upon use in the wash, the body of the pouch fully dissolves and leaves no remnant.
- various other pouch materials disclosed for use with laundry products such as water permeable pouches or water insoluble pouches with water soluble or permeable seals, may be used.
- the pouch of the invention When the pouch of the invention is used, multiple pouches can be stood upright and packed tightly in a tray or carton to keep the pouches in a vertical position. It is unnecessary in the present invention to employ a reinforced base in order to have the pouch stand upright.
- any particular upper concentration can be associated with any particular lower concentration.
- Water-soluble as used herein means soluble in cold water, i.e. soluble at 5°C and above.
- Liquid phase as used herein includes gels and means that a continuous phase or predominant part of the phase is liquid and that a phase is fluid at 20°C (some solids (suspended or other) may be included).
- Solid phase as used herein includes both hard and soft solids (the latter may yield or deform under pressure) and means that the phase is not fluid at 20°C.
- Transparent as used herein includes both transparent and translucent and means that an ingredient, or a mixture, or a phase, or a composition, or a package according to the invention preferably has a transmittance of more than 25%, more preferably more than 30%, most preferably more than 40%, optimally more than 50% in the visible part of the spectrum (approx. 410-800 nm).
- absorbency may be measured as less than 0.6 (approximately equivalent to 25% transmitting) or by having transmittance greater than 25% wherein % transmittance equals: 1/10absorbancy x 100%.
- % transmittance equals: 1/10absorbancy x 100%.
- composition means the final composition (i.e., the composition itself, but not the pouch body), including at least two phases.
- a pouch may be formed using a flexible material, e.g. film, in any suitable way, but preferably using one of the four ways as herein described.
- the first way involves taking a web of film off of a roll and folding it in half with the top open. This can be done using a Bartlet form/fill/seal machine where the folded web travels in a horizontal direction. Leading and trailing vertical heat-seals are made and individual pouches are cut and supported in an upright position. Product is filled through the top opening, and then a horizontal top heat-seal completes the filled/sealed pouch.
- a front view of the pouch ( Figure 1) shows top and side flange seals, but there is no bottom seal.
- the second way relates to vertical form/fill/seal equipment such as made by Hayssen or Proto-Pak Corporation.
- the web is formed into a tube with a continuous overlap heat-seal of the edges.
- the tube travels vertically downward and a bottom seal is formed.
- a nozzle which is below the top seal area, fills the pouch, and with intermittent motion the pouch is indexed downward.
- a top - seal completes the finished pouch.
- a third way involves the use of horizontal (Hoflinger machine) or rotary (Cloud Corp.) form/fill/seal equipment which can employ either heat or water seals.
- a bottom web is vacuum-formed into a cavity, product is filled and a top web is either slightly wetted and compressed sealed, or heat sealed.
- Different pouch shapes can be achieved such as round with about 40% trim, or rectangular with virtually no trim.
- a top view will show a peripheral seal around the perimeter of the pouch. This third process is preferred due to the optimum production rates.
- the fourth way to produce a pouch is with a continuous, extruded tube of flexible film. This would be similar to the second process described above using vertical form/fill/seal equipment. The difference is that there would be no seal in the longitudinal middle of the pouch, but there would be top/bottom flange heat-seals.
- pouch 10 is comprised of flexible material (e.g. sheet or film) 12 which has been folded upon itself at 14 to form a folded side, using the first process described above.
- Flexible material e.g. sheet or film
- Two halves 16, 18 of sheet 12 which are formed by folding at 14, are sealed to each other to form three walls 20, 22 and 24.
- Folding at line 14 may be assisted, if desired, by an optional line of weakness extending along the projected fold. There is no need for any reinforcing structure and, in fact, the line of weakness may be absent. Indeed, the preferred structure is a simple fold with no reinforcing structure or lines of weakness.
- a preformed tube of the film may be used and then a segment cut-off and sealed at the two ends.
- Other alternative processes for forming a pouch, as described above, may be employed.
- seal side 22 is formed last, after insertion of the laundry composition into the pouch.
- Pouch 10 contains a bottom, base-forming component 30 which is a solid phase of the laundry composition.
- Pouch 10 also includes at least one other phase of a laundry composition such as liquid phase comprising for example a surfactant.
- the solid phase 30 combines with a side of the pouch (e.g. fold 14) to provide a base 36 for the package, which permits the pouch to stand upright unassisted, as seen in Fig. 2.
- the solid phase combines with a side seal (e.g. 20 or 24) to form the bottom base 36.
- Solid phase 30 may be a substance or composition which, although liquid when added to the pouch, eventually solidifies.
- Pouches 10 can be disposed in tight columns and rows in tray 40, as seen in Fig. 3.
- Pouches 10 are disposed vertically with base 36 at the bottom.
- Pouches 10 are self-supporting and removal of one or more of the pouches from tray 40 will not affect the remaining pouches.
- pouch 10 is dropped into the washing machine at an appropriate time during the washing process, for example at the beginning of the wash cycle, and by an appropriate predetermined mechanism the product contained therein is dispersed at an appropriate time.
- the mechanism may involve the water solubility of the pouch 10, or pouch 10 may be water permeable. Or, pouch 10 may have one or more seals which are permeable to water.
- pouches which are of a shape other than the illustrated rectangular shape could be used.
- two sealed walls could extend from the fold line to a point where they intersect to form a triangular-shaped pouch.
- pyramid and tetrahedral shape pouches Any unneeded film could be trimmed.
- a number of pouches may be vertically positioned into a multipack tray or carton.
- the packing operation presses down and flattens the pouch bottom.
- Generally direct pouch contact and the confines of the pack walls will keep the pouches in an upright position.
- the flat-bottom shape will be set either when the higher density solid separates to the bottom, or if the phases are introduced separately, when the bottom phase solidifies.
- the pouch 10 is preferably made of a clear, sealable, cold water soluble film such as polyvinyl alcohol. Thickness could range from 25 to 100 ⁇ m, more preferably from 35 to 80 ⁇ m, most preferably from 45 to 75 ⁇ m. Other materials from which the package can be made include but are not limited to methyl hydroxy propyl cellulose and polyethylene oxide. Polyvinyl alcohol is preferred due to its ready availability and low cost.
- One supplier of polyvinyl alcohol film is Monosol LLC. European suppliers of suitable films include but are not limited to Monosol supplied by Monosol LLC. or PT supplied by Aicello or K-series supplied by Kurary or Hydrafilm supplied by Rainier Specialty Polymers Ltd, or QSA series by Polymer Films, Inc.
- the laundry composition included in the inventive pouch contains at least two phases.
- the phase that assists in forming the pouch base is a solid.
- the solid phase may be introduced into the pouch as a solid or it may be formed after being filled into the pouch (i.e., it sets upon standing).
- the solid phase is insoluble in the other phases of the composition within the pouch.
- the solid phase separation from the other phases of the composition is attained by:
- the density of the product or ingredient that forms a solid phase is higher than the densities of other phases by at least 0.2 g/ml or preferably by at least 0.5 g/ml.
- the density of the lighter product is preferably from 0.8 to 1.5 g/ml; the density of the heavier products is preferably 1.0 to 3.5 g/ml.
- Suitable higher density ingredients are water-soluble solutes and water-insoluble particulates, including but not limited to inorganic or organic salts of carbonate, bicarbonate, phosphate, sulfate, silicate, sugar, sorbitol, silica, zeolite, pigment.
- carbonate is used in order to form a solid base.
- These ingredients are suitable as long as the density of the other phases is in the range of from 0.8 to 1.5 g/ml.
- the solid phase ingredient is typically included in an amount of from 1 to 75%, preferably from 5 to 60%, most preferably from 10 to 50%.
- the pouch It is preferred to fill the pouch with the heavier phase together with the other phases of the laundry composition, in the form of a slurry, for ease of manufacture.
- the heavier phase then separates and sets upon standing, preferably within at least a few days, e.g. in a time span of within 10 days after filling the pouch, preferably within 3 days, more preferably within 24 hours, most preferably within 3 hours, and optimally within 1 hour.
- the phases may be filled individually, in which case again the heavier phase may be added as a solid or as a slurry (e.g. aqueous slurry) and may solidify upon standing.
- the densities of the at least two phases are irrelevant.
- the lower phase is filled into the pouch first, as a liquid or a slurry and is allowed to solidify. Once solidified, the other phases are filled. Even if the other phases are heavier than the solid phase, the solid phase will generally stay on the bottom, constrained by the walls of the pouch from moving upward.
- This option is particularly suitable for those pouches, which have the walls inclined toward the top, to provide for optimum constrain on the movement of the solid phase, e.g. pyramidal, tetrahedral and triangular shapes.
- any ingredient may be employed for the solid phase, as long as it can be first filled as a liquid or slurry and, subsequently, solidified.
- aqueous solution for example containing a surfactant or a builder
- soap e.g. sodium stearate
- Other structurants include, but are not limited to polysaccharides, cross-linked polyacrylates, etc.
- the amount of the structurant is generally in the range of from 0.1 to 10%, preferably from 0.1 to 5%, by weight of the phase.
- the second phase included into the inventive pouches is liquid, which may be hydrophilic or hydrophobic.
- the hydrophilic phase employs water, typically in an amount of from 0 to 60%, preferably from 5 to 50%, most preferably from 10 to 40%, by weight of the hydrophilic phase.
- the amount of water in any event is such as to preserve sufficient solid base phase on the bottom: if a solid is employed which is water-soluble, too high a water amount may dissolve the solid.
- the hydrophobic phase employs a hydrophobic fluid, typically in an amount of from 20 to 100%, preferably from 40 to 80%, most preferably from 50 to 70%, by weight of the hydrophobic phase.
- the hydrophobic fluid is generally selected from the group consisting of paraffin, wax, oil, petrolatum, a hydrophobic polymer and mixtures thereof. Natural or synthetic hydrocarbon oil or mixtures thereof may be employed. Generally, the hydrocarbon oil may be a paraffinic oil, a naphthenic oil, natural mineral oil or the like.
- Examples include but are not limited to mineral oil, castor oil, vegetable oil, corn oil, peanut oil, jojoba oil, 2-ethylhexyl oxystearate (and other alkyl oxystearates), acetylated lanolin alcohol, alkyl palmitates such as isopropyl palmitate, 2-ethylhexyl palmitate, glycerol triacetates, disopropyl adipate, dioctyl adipate (and other alkyl adipates), isopropyl myristate, C 12 to C 15 alcohol benzoates, and the like.
- the oil is mineral oil, because it is both economic and most easily processable.
- the hydrophobic fluid may be employed in combination with a hydrophobic benefit agent and/or colorant (e.g. oil-soluble colorant), or it may form a continuous phase which surrounds a discontinuous phase.
- a hydrophobic benefit agent and/or colorant e.g. oil-soluble colorant
- the discontinuous phase may itself be a benefit agent and/or a colorant or it may contain an additional benefit agent and/or colorant.
- OPTION 1 No. Solid Base Phase Ingredients Range % by weight of phase Liquid Phase Ingredients Range % by weight of phase Volume ratio of solid to liquid phase Water 10-75 Water 0-60 From Sodium 10-90 Propylene Glycol 0-25 10:90 Carbonate 0-80 Surfactant 5-100 to Zeolite 0-15 Miscellaneous 0-10 90:10 Miscellaneous 2 Water 10-75 Water 0-60 From Sodium 0-90 Propylene Glycol 0-25 10:90 Carbonate 0-90 Alcohol 1-95 to Sodium 0-80 ethoxylate 1-75 90:10 Sulfate 0-60 Sodium Zeolite Alkylbenzene 0-10 Sodium sulfonate 0-10 Silicate Soap Miscellaneous 3 Water 10-75 Water 0-60 From Sodium 0-90 Propylene Glycol 0-25 10:90 Carbonate 0-90 Xylene Sulfonate 0-15 to Sodium 0-90 Alcohol 0-95
- Solid Base Phase Ingredients Range % by weight of phase Liquid Phase Ingredients Range % by weight Of phase Volume ratio of solid to liquid phase 1 Water 20-60 Water 0-60 From Zeolite 0-60 Propylene Glycol 0-25 10:90 Sodium 0-30 Xylene Sulfonate 0-15 to borate 0-30 Slcohol ethoxylate 0-95 90:10 Sodium 0.2-10 Sodium 0-75 sulfate Alkylbenzene Sodium sulfonate 0-80 stearate Sodium Alcohol ethoxylate sulfate 0-10 Miscellaneous 2 Water 5-50 Water 0-60 From Xylene 0-15 Monoethanolamine 1-40 10:90 sulfonate 0-15 Monoethanolamine 5-70 to Propylene 1-30 citrate 90:10 glycol 0-30 Alcohol ethoxylate 0-30 Sodium Alkylbenzene 0.2-10 sulfonate 0-10 Sodium Alcohol ethoxylate sulfate Sodium Stearate
- compositions of the resultant phases do not necessarily correspond with the compositions of the phases prior to their being combined into a single composition. This is because of reaction between ingredients, in particular the acidic ingredients and the basic ingredients (e.g., sodium hydroxide) and also, because of possible migration of material between the two phases, or emulsification of some of the phases within each other.
- the volume ratio of the two phases in the final composition is generally in the range of from 10:90 to 90:10, more preferably from 20:80 to 80:20, most preferably from 70:30 to 30:70, and optimally from 40:60 to 60:40, in order to provide the most pleasing appearance and optimum laundry benefits.
- the additional third and further phases may for example be a capsule, dispersion or emulsion layer, as described below under Optional Ingredients.
- a if the second layer is aqueous it may be desirable to include a hydrophilic layer, with a benefit ingredient, such as an enzyme, a bleach, a perfume entrapped therein.
- ingredients may be distributed in either or both phases of the composition.
- compositions of the invention contain one or more surface active agents (surfactants) selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof.
- surfactants selected from the group consisting of anionic, nonionic, cationic, ampholytic and zwitterionic surfactants or mixtures thereof.
- the preferred surfactant detergents for use in the present invention are mixtures of anionic and nonionic surfactants although it is to be understood that any surfactant may be used alone or in combination with any other surfactant or surfactants.
- the surfactant should comprise at least 5%, e.g., 5% to 80%, preferably at least 10% to 80%, more preferably 15% to 40%; even more preferably 15% to 35% of the composition.
- Nonionic synthetic organic detergents which can be used with the invention, alone or in combination with other surfactants, are described below. Nonionic surfactants are typically included.
- Nonionic surfactants are nonionic surfactants which are pourable liquids, gels or pastes at 25°C.
- Nonionic detergent surfactants normally have molecular weights of from about 300 to about 11,000. Mixtures of different nonionic detergent surfactants may also be used, provided the mixture is a liquid gel or paste at 25°C.
- the composition may comprise one or more nonionic surfactants which are solid at 25°C. These dissolved and/or dispersed in either or both liquid layers.
- nonionic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature).
- suitable nonionic surfactants are those disclosed in U.S. Pat. Nos. 4,316,812 and 3,630,929 and applicants' published European specification EP-A-225,654.
- the nonionic detergents are polyalkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic polyalkoxy group to a lipophilic moiety.
- a preferred class of nonionic detergent is the alkoxylated alkanols wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of moles of alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the alkanol is a fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 alkoxy groups per mole.
- Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g. Neodol® 25-7 and Neodol® 23®-6.5, which products are made by Shell Chemical Company, Inc.
- the former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atoms content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5.
- the higher alcohols are primary alkanols.
- Nonionics are represented by the commercially well- known class of nonionics sold under the trademark Plurafac®.
- the Plurafacs® are the reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include C 13 -C 15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, C 13 -C 15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, C 13 -C 15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, or mixtures of any of the above.
- liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol® trademark: Dobanol® 91-5 is an ethoxylated C 9 -C 11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol® 23-7 is an ethoxylated C 12 -C 13 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.
- preferred nonionic surfactants include the C 12 -C 15 primary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, and the C 9 to C 11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.
- R is a monovalent organic radical containing from about 6 to about 30 (preferably from about 8 to about 18) carbon atoms
- R' is a divalent hydrocarbon radical containing from about 2 to 4 carbons atoms
- 0 is an oxygen atom
- y is a number which can have an
- a particularly preferred group of glycoside surfactants for use in the practice of this invention includes those of the formula above in which R is a monovalent organic radical (linear or branched) containing from about 6 to about 18(especially from about 8 to about 18) carbon atoms; y is zero; z is glucose or a moiety derived therefrom; x is a number having an average value of from 1 to about 4 (preferably from about 1 to 4).
- Nonionic surfactants particularly useful for this application include, but are not limited to: alcohol ethoxylates (e.g. Neodol® 25-9 from Shell Chemical Co.), alkyl phenol ethoxylates (e.g. Tergitol® NP-9 from Union Carbide Corp.), alkylpolyglucosides (e.g. Glucapon® 600CS from Henkel Corp.), polyoxyethylenated polyoxypropylene glycols (e.g. Pluronic® L-65 from BASF Corp.), sorbitol esters (e.g. Emsorb® 2515 from Henkel Corp.), polyoxyethylenated sorbitol esters (e.g.
- Emsorb® 6900 from Henkel Corp.
- alkanolamides e.g. Alkamide® DC212/SE from Rhone-Poulenc Co.
- N-alkypyrrolidones e.g. Surfadone® LP-100 from ISP Technologies Inc.
- Mixtures of two or more of the nonionic surfactants can be used.
- Anionic surface active agents which may be used in the present invention are those surface active compounds which contain a long chain hydrocarbon hydrophobic group in their molecular structure and a hydrophilic group, i.e.; water solubilizing group such as sulfonate, sulfate or carboxylate group.
- the anionic surface active agents include the alkali metal (e.g. sodium and potassium) water soluble higher alkyl benzene sulfonates, alkyl sulfonates, alkyl sulfates and the alkyl polyether sulfates. They may also include fatty acid or fatty acid soaps.
- the preferred anionic surface active agents are the alkali metal, ammonium or alkanolamide salts of higher alkyl benzene sulfonates and alkali metal, ammonium or alkanolamide salts of higher alkyl sulfonates.
- Preferred higher alkyl sulfonates are those in which the alkyl groups contain 8 to 26 carbon atoms, preferably 12 to 22 carbon atoms and more preferably 14 to 18 carbon atoms.
- the alkyl group in the alkyl benzene sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms.
- a particularly preferred alkyl benzene sulfonate is the sodium or potassium dodecyl benzene sulfonate, e.g. sodium linear dodecyl benzene sulfonate.
- the primary and secondary alkyl sulfonates can be made by reacting long chain alpha-olefins with sulfites or bisulfites, e.g. sodium bisulfite.
- the alkyl sulfonates can also be made by reacting long chain normal paraffin hydrocarbons with sulfur dioxide and oxygen as described in U.S. Pat. Nos. 2,503,280, 2,507,088, 3,372, 188 and 3,260,741 to obtain normal or secondary higher alkyl sulfonates suitable for use as surfactant detergents.
- the alkyl substituent is preferably linear, i.e. normal alkyl, however, branched chain alkyl sulfonates can be employed, although they are not as good with respect to biodegradability.
- the alkane, i.e. alkyl, substituent may be terminally sulfonated or may be joined, for example, to the carbon atom of the chain, i.e. may be a secondary sulfonate. It is understood in the art that the substituent may be joined to any carbon on the alkyl chain.
- the higher alkyl sulfonates can be used as the alkali metal salts, such as sodium and potassium.
- the preferred salts are the sodium salts.
- the preferred alkyl sulfonates are the C 10 to C 18 primary normal alkyl sodium and potassium sulfonates, with the C 10 to C 15 primary normal alkyl sulfonate salt being more preferred.
- the higher alkyl polyether sulfates used in accordance with the present invention can be normal or branched chain alkyl and contain lower alkoxy groups which can contain two or three carbon atoms.
- the normal higher alkyl polyether sulfates are preferred in that they have a higher degree of biodegradability than the branched chain alkyl and the lower poly alkoxy groups are preferably ethoxy groups.
- the preferred higher alkyl poly ethoxy sulfates used in accordance with the present invention are represented by the formula: R'--O(CH 2 CH 2 O) p --SO 3 M, where R' is C 8 to C 20 alkyl, preferably C 10 to C 18 and more preferably C 12 to C 15 ; p is 2 to 8, preferably 2 to 6, and more preferably 2 to 4; and M is an alkali metal, such as sodium and potassium, or an ammonium cation.
- the sodium and potassium salts are preferred.
- a preferred higher alkyl poly ethoxylated sulfate is the sodium salt of a triethoxy C 12 to C 15 alcohol sulfate having the formula: C 12-15 --O--(CH 2 CH 2 O) 3 --SO 3 Na
- alkyl ethoxy sulfates examples include C 12-15 normal or primary alkyl triethoxy sulfate, sodium salt; n-decyl diethoxy sulfate, sodium salt; C 12 primary alkyl diethoxy sulfate, ammonium salt; C 12 primary alkyl triethoxy sulfate, sodium salt: C 15 primary alkyl tetraethoxy sulfate, sodium salt, mixed C 14-15 normal primary alkyl mixed tri- and tetraethoxy sulfate, sodium salt; stearyl pentaethoxy sulfate, sodium salt; and mixed C 10-18 normal primary alkyl triethoxy sulfate, potassium salt.
- the normal alkyl ethoxy sulfates are readily biodegradable and are preferred.
- the alkyl poly-lower alkoxy sulfates can be used in mixtures with each other and/or in mixtures with the above discussed higher alkyl benzene, alkyl sulfonates, or alkyl sulfates.
- the alkali metal higher alkyl poly ethoxy sulfate can be used with the alkylbenzene sulfonate and/or with an alkyl sulfonate or sulfonate, in an amount of 0 to 70%, preferably 10 to 50% and more preferably 10 to 20% by weight of entire composition.
- Anionic surfactants particularly useful for this application include, but are not limited to: linear alkyl benzene sulfonates (e.g. Vista® C-500 from Vista Chemical Co.), alkyl sulfates (e.g. Polystep® B-5 from Stepan Co.), polyoxyethylenated alkyl sulfates (e.g. Standapol® ES-3 from Stepan Co.), alpha olefin sulfonates (e.g. Witconate® AOS from Witco Corp.), alpha sulfo methyl esters (e.g. Alpha-Step® MC-48 from Stepan Co.), alkyl ether sulfates and isethionates (e.g. Jordapon® Cl from PPG Industries Inc.).
- linear alkyl benzene sulfonates e.g. Vista® C-500 from Vista Chemical Co.
- alkyl sulfates e.g. Polystep
- Anionic surfactants may be added pre-neutralized or, preferably, may be formed in situ, by neutralizing a precursor acid (fatty acid in the case of soaps). Further, the anionic precursor or fatty acid should be over-neutralised (i.e. there should be an excess of the alkaline material used to form the counter-ion). Inorganic salt, preferably, sodium or potassium salt of the anionic precursor acid is preferred to improve detergency, but organic salt results in improved transparency.
- cationic surfactants are known in the art, and almost any cationic surfactant having at least one long chain alkyl group of about 10 to 24 carbon atoms is suitable in the present invention. Such compounds are described in "Cationic Surfactants", Jungermann, 1970, incorporated by reference. Specific cationic surfactants which can be used as surfactants in the subject invention are described in detail in U.S. Pat. No. 4,497,718, hereby incorporated by reference.
- compositions of the invention may use cationic surfactants alone or in combination with any of the other surfactants known in the art.
- compositions may contain no cationic surfactants at all.
- Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be a straight chain or a branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g. carboxylate, sulfonate, sulfate.
- an anionic water-solubilizing group e.g. carboxylate, sulfonate, sulfate.
- Examples of compounds falling within this definition are sodium 3(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)propane 1-sulfonate, disodium octadecyl- imminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N, N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.
- Sodium 3-(dodecylamino)propane-1-sulfonate is preferred.
- Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
- the cationic atom in the quaternary compound can be part of a heterocyclic ring.
- zwitterionic surfactants which may be used are set forth in U.S. Pat. No. 4,062,647, hereby incorporated by reference.
- the surfactant in the laundry compositions of the invention is anionic and/or nonionic, especially linear alkylbenzene sulfonate, alkyl ether sulfate, alcohol ethoxylates and mixtures thereof.
- mixtures of anionic and nonionic surfactants are especially preferred, for optimum greasy stain and particulate soil removal.
- the most effective mixtures employ anionic to nonionic ratio of from 10: 1 to 1:10, preferably from 5:1 to 1:5, most preferably from 3:1 to 1:3.
- nonionic surfactants are employed, in the absence of, or lower levels of, anionic surfactants, alone or in combination with cationic surfactants and/or antifoams.
- Suitable dyes include but are not limited to:
- the inventive compositions generally include from 0.0001 to 1%, more preferably from 0.0005 to 0.1%, most preferably from 0.0001 to 0.1% of the dye, in order to provide a pleasing appearance (% by weight of the composition).
- compositions may include encapsulated ingredients, preferably in the form of transparent or colored capsules or an emulsion, or a dispersion. These capsules, emulsion, or dispersion, may be distributed in one or more layers of the inventive compositions, or may be present as an additional layer.
- Preferred ingredients to be encapsulated are enzymes, bleaches, colorants, perfumes, and mixtures thereof to minimize the damage to these ingredients from water or surfactant, or alkaline ingredients, and/or to enhance the appearance of the product.
- Preferred inventive compositions comprise from 0.5 to 20%, more preferably from 0.1 to 10%, most preferably from 0.3 to 6%, and optimally from 0.5 to 5%, in order to attain optimum performance and/or appearance (% by weight of the composition).
- the preferred laundry composition may further include one or more well-known laundry ingredients, such as builders (from 0.1 to 20%), anti-redeposition agents, fluorescent dyes, perfumes, soil-release polymers, colorant, enzymes, buffering agents, antifoam agents, UV-absorber, a bleach, a bleach precursor, a whitening agent, a fabric softener, an anti-wrinkle compound, a dye fixative, dye transfer inhibitors, a perfume, a silicone oil, and mixtures thereof.
- laundry ingredients such as builders (from 0.1 to 20%), anti-redeposition agents, fluorescent dyes, perfumes, soil-release polymers, colorant, enzymes, buffering agents, antifoam agents, UV-absorber, a bleach, a bleach precursor, a whitening agent, a fabric softener, an anti-wrinkle compound, a dye fixative, dye transfer inhibitors, a perfume, a silicone oil, and mixtures thereof.
- laundry ingredients such as builders (from 0.1 to 20%), anti-redeposition agents
- the packages of the invention may be prepared from polyvinyl alcohol film, or other suitable material, which is filled, then sealed, preferably heat-sealed or water-sealed.
- the formulation was prepared in two parts and the order of addition was followed by the order of listed ingredients.
- the bottom layer was prepared and agitated at about 46°C.
- a polyvinyl alcohol pouch was prepared by heat-sealing three sides. The bottom layer was filled first and followed by the top liquid layer component. Subsequently, the top opening was also heat-sealed. The pouch was standing due to the lower center of mass contributed by the higher density of bottom layer.
- the bottom layer of this formulation was setup into a piece of solid block between 30 minutes to three hours. Once the block was formed, the pouch was standing up by itself, having the appearance substantially as depicted in Figures 1 and 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Detergent Compositions (AREA)
- Packages (AREA)
Claims (22)
- Poche contenant :(a) un corps fabriqué en un matériau souple,(b) une composition pour le lavage du linge, la composition comprenant au moins deux phases, l'une des phases de la composition étant solide et formant une base sur laquelle ladite poche peut tenir droite sans support supplémentaire.
- Poche selon la revendication 1, dans laquelle la poche est fabriquée, au moins en partie, avec un film soluble dans l'eau.
- Poche selon la revendication 1 ou la revendication 2, dans laquelle le corps de la poche comprend un pli fabriqué en le matériau souple replié sur lui-même, pour former un côté plié de la poche, le matériau souple étant scellé sur lui-même pour former au moins deux autres côtés de la poche.
- Poche selon la revendication 3, dans laquelle la phase solide repose sur le côté plié de la poche.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle les côtés de la poche sont inclinés l'un vers l'autre.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle la poche comprend au moins deux bords scellés.
- Poche selon la revendication 6, dans laquelle la phase solide repose sur le côté de la poche ayant un bord scellé.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle la phase solide repose sur le côté de la poche qui n'est pas muni d'un bord scellé.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle la densité de la phase solide est supérieure à la densité de l'autre phase de la composition.
- Poche selon la revendication 9, dans laquelle la différence de densité entre les deux phases est d'au moins environ 0,2 g/l.
- Poche selon l'une quelconque des revendications précédentes, comprenant au moins trois bords scellés.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle la phase solide comprend un ingrédient sélectionné à partir d'un soluté soluble dans l'eau, d'un matériau particulaire soluble dans l'eau et de mélanges de ceux-ci.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle les côtés de la poche sont inclinés en direction du haut de la poche.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle la poche a la forme d'un tétraèdre.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle la poche a une surface plane rectangulaire ou carrée.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle la phase solide est formée à partir d'une solution aqueuse structurée.
- Poche selon la revendication 16, dans laquelle la phase solide est formée à partir d'une solution aqueuse de tensioactif structurée avec un savon.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle les côtés de la poche sont inclinés en direction du haut de la poche.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle l'une des deux phases au moins est un liquide hydrophile ou hydrophobe.
- Poche selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend au moins trois phases.
- Procédé de fabrication d'une poche selon l'une quelconque des revendications 1 - 20, dans lequel le procédé comprend le fait de remplir la poche avec une composition pour le lavage du linge comprenant un ingrédient ayant une forte densité, qui forme la phase solide au repos.
- Procédé de fabrication de la poche selon l'une quelconque des revendications 1 - 20, dans lequel le procédé comprend le fait de remplir la poche avec un liquide et ensuite, le fait de structurer le liquide pour former une phase solide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US107129 | 1987-10-09 | ||
| US17129 | 2001-12-14 | ||
| US10/017,129 US20030136701A1 (en) | 2001-12-14 | 2001-12-14 | Laundry pouch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1319707A1 EP1319707A1 (fr) | 2003-06-18 |
| EP1319707B1 true EP1319707B1 (fr) | 2005-03-02 |
Family
ID=21780881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02258562A Expired - Lifetime EP1319707B1 (fr) | 2001-12-14 | 2002-12-11 | Poche contenant une composition pour le lavage du linge |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20030136701A1 (fr) |
| EP (1) | EP1319707B1 (fr) |
| AT (1) | ATE290063T1 (fr) |
| DE (1) | DE60203088T2 (fr) |
| ES (1) | ES2236451T3 (fr) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003903116A0 (en) * | 2003-06-20 | 2003-07-03 | Plantic Technologies Ltd | Easy open package |
| DE102004039472A1 (de) † | 2004-08-14 | 2006-03-02 | Henkel Kgaa | Verfahren zur Herstellung portionierter Wasch- oder Reinigungsmittel |
| BRPI0707211A2 (pt) * | 2006-01-23 | 2011-04-26 | Procter & Gamble | composições para tratamento na lavagem de roupas com corante de tiazólio |
| JP5117403B2 (ja) * | 2006-01-23 | 2013-01-16 | ザ プロクター アンド ギャンブル カンパニー | 酵素および光漂白剤を含む組成物 |
| US20080177089A1 (en) * | 2007-01-19 | 2008-07-24 | Eugene Steven Sadlowski | Novel whitening agents for cellulosic substrates |
| US8715368B2 (en) | 2010-11-12 | 2014-05-06 | The Procter & Gamble Company | Thiophene azo dyes and laundry care compositions containing the same |
| US9796952B2 (en) * | 2012-09-25 | 2017-10-24 | The Procter & Gamble Company | Laundry care compositions with thiazolium dye |
| HUE035129T2 (en) | 2014-02-27 | 2018-05-02 | Unilever Nv | Water-soluble detergent capsule with reduced fine fine particles in HEDP |
| HUE042647T2 (hu) * | 2014-08-07 | 2019-07-29 | Procter & Gamble | Mosószerkészítmény |
| USD765335S1 (en) | 2015-03-10 | 2016-08-30 | Polder Products, Llc | Drying rack |
| ES2739662T3 (es) | 2015-12-16 | 2020-02-03 | Procter & Gamble | Artículo de dosis unitaria soluble en agua |
| EP3574069B1 (fr) * | 2017-01-27 | 2024-10-30 | The Procter & Gamble Company | Articles en doses unitaires hydrosolubles comprenant des structures fibreuses hydrosolubles et des particules |
| CN110225966B (zh) * | 2017-01-27 | 2022-04-05 | 宝洁公司 | 包含水溶性纤维结构和颗粒的水溶性单位剂量制品 |
| USD881465S1 (en) * | 2018-04-27 | 2020-04-14 | Guang Dong You Kai Technical Co, Ltd | Laundry capsule |
| EP3914682B1 (fr) * | 2019-01-22 | 2024-10-16 | Unilever IP Holdings B.V. | Détergent pour lessive |
| EP3752589B1 (fr) * | 2019-01-22 | 2023-08-30 | Unilever Global IP Limited | Détergent pour lessive |
| JP6910624B1 (ja) * | 2021-02-02 | 2021-07-28 | スモリホールディングス株式会社 | 難燃剤組成物 |
| EP4053039A1 (fr) * | 2021-03-03 | 2022-09-07 | Henkel AG & Co. KGaA | Présentation de détergent |
| WO2025152061A1 (fr) * | 2024-01-17 | 2025-07-24 | The Procter & Gamble Company | Produit de lessive emballé |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8729221D0 (en) * | 1987-12-15 | 1988-01-27 | Unilever Plc | Casting method |
| DK0626319T3 (da) * | 1993-06-25 | 1997-04-14 | Procter & Gamble | Selvstående pose med udvidet bunddel |
| EP0654418A1 (fr) * | 1993-11-15 | 1995-05-24 | The Procter & Gamble Company | Poche flexible tenant debout gonflée |
-
2001
- 2001-12-14 US US10/017,129 patent/US20030136701A1/en not_active Abandoned
-
2002
- 2002-12-11 AT AT02258562T patent/ATE290063T1/de not_active IP Right Cessation
- 2002-12-11 ES ES02258562T patent/ES2236451T3/es not_active Expired - Lifetime
- 2002-12-11 DE DE60203088T patent/DE60203088T2/de not_active Expired - Lifetime
- 2002-12-11 EP EP02258562A patent/EP1319707B1/fr not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE290063T1 (de) | 2005-03-15 |
| EP1319707A1 (fr) | 2003-06-18 |
| ES2236451T3 (es) | 2005-07-16 |
| DE60203088D1 (de) | 2005-04-07 |
| US20030136701A1 (en) | 2003-07-24 |
| DE60203088T2 (de) | 2006-05-11 |
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