EP1699703B1 - Schaumspender - Google Patents

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Publication number
EP1699703B1
EP1699703B1 EP04803287A EP04803287A EP1699703B1 EP 1699703 B1 EP1699703 B1 EP 1699703B1 EP 04803287 A EP04803287 A EP 04803287A EP 04803287 A EP04803287 A EP 04803287A EP 1699703 B1 EP1699703 B1 EP 1699703B1
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EP
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Prior art keywords
conduit
container
laundry
composition
fabric
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EP04803287A
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English (en)
French (fr)
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EP1699703A1 (de
Inventor
Diego Sebastian Briozzo Fernandez
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GB0329492A external-priority patent/GB0329492D0/en
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    • 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
    • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
    • B65D1/32—Containers adapted to be temporarily deformed by external pressure to expel contents
    • B65D1/323—Containers adapted to be temporarily deformed by external pressure to expel contents the container comprising internally a dip tube through which the contents pass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B15/00—Details of spraying plant or spraying apparatus not otherwise provided for; Accessories
    • B05B15/30—Dip tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
    • B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
    • B05B11/04—Deformable containers producing the flow, e.g. squeeze bottles
    • B05B11/042—Deformable containers producing the flow, e.g. squeeze bottles the spray being effected by a gas or vapour flow in the nozzle, spray head, outlet or dip tube
    • B05B11/043—Deformable containers producing the flow, e.g. squeeze bottles the spray being effected by a gas or vapour flow in the nozzle, spray head, outlet or dip tube designed for spraying a liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/0018—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with devices for making foam
    • B05B7/0025—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with devices for making foam with a compressed gas supply

Definitions

  • the present invention concerns method of pretreating a laundry fabric and a dispenser for use in such a method.
  • Devices for the pretreatment and hand washing of laundry include e.g. solid detergent bars, detergent liquids, some of which have trigger spray devices see for example JP 10 08 1 895 and US-A-4091966 .
  • Pretreatment of fabrics prior to a main washing operation is often carried out by consumers in or to remove tough stains and soils.
  • pretreatment / handwashing with solid bars or abrasive tools can be too harsh for delicate fabrics.
  • pretreatment with such devices often requires a generally flat working surface to support fabrics.
  • Many modern consumers do not have sufficient space to pretreat fabrics on a flat surface and so often resort to resting the garment on a knee or tummy, in which case there is a risk of applying the laundry composition to themselves or their clothing, which is undesirable to say the least.
  • a further problem is that some fabric items may not be easily flattened for pretreatment / washing on a flat surface.
  • the invention provides a laundry pretreatment or hand washing device, for dispensing a mixture of two or more fluids, e.g. liquid and gas (preferably air) as a foam and/or mist, the dispenser comprising all the features of claim 1
  • a laundry pretreatment or hand washing device for dispensing a mixture of two or more fluids, e.g. liquid and gas (preferably air) as a foam and/or mist, the dispenser comprising all the features of claim 1
  • a pretreatment and/or handwashing device which can be used independently of a work surface and which can function in any orientation, whether it is orientated upright (top above base) or inverted. Further, as the second and third conduit openings are mutually laterally inclined or opposed the device also operate when it is tilted sideways. The user can simply suspend the item and spray the foam/mist solution to difficult to reach parts from below or above or a side as necessary, without having to maintain the dispenser upright.
  • the invention also provides a highly cost effective foam dispenser which does not require complicated foaming elements in the flow path of the liquid. This greatly simplifies the device and reduces cost. No aerosol propellant is required reducing the environmental impact of the device. A mixture of fluids e.g liquid and air can be ejected from the container simply by squeezing the container.
  • the conduit may be branched, curved or kinked or a combination thereof to effect the relative orientation of the second and third conduit end portions.
  • the conduit may be curved or kinked in a section e.g. mid or upper section, so as to incline the second open end portion between 10 - 60 degrees to the longitudinal axis of the container, preferably 15 - 45 degrees, more preferably 15 - 30 degrees, even more preferably 20 degrees.
  • the third open end portion extends from an upper section (ie. Toward the top of the container when it is orientated upright) of the conduit, e.g at right angles.
  • the conduit has a T-shaped configuration at the top, wherein the third open end portion branches off orthogonally from a main section of the conduit, preferably generally longitudinally aligned.
  • the top of the conduit may be offset from the central longitudinal axis.
  • the conduit may be in the form of or include a dip tube which may co-operate with a container closure or cap also provided.
  • the container may be flexible by means of one or more flexible portions, and the invention is not restricted to an entirely flexible container. Rigid sections eg. Base, corners etc may be included e.g.for increasing strength.
  • a dispenser of this invention can have any shape suitable to portability and handling, without excluding any shape.
  • the cap of the dispenser of the invention can be of any shape, aimed at the function of closing the container after it has been filled with the liquid and allowing same to be dispensed.
  • the dispenser parts may be made of any material suitable for the purpose. A majority, if not all, of the parts are suitably made from polymeric material.
  • the dispensers according to the invention may be used with any laundry liquid composition.
  • cleaning liquids generally contain a foaming surfactant, preferably in completely dissolved form. They may also contain other components known in the art as components of cleaning liquids. They may even contain solid particulate matter provided it is in stable suspension in the liquid. To retain the simplified structure, it is preferred, however, are cleaning liquids that do not contain any undissolved solid matter.
  • the invention provides a method of pretreating or handwashing a fabric, by applying a foam or mist laundry composition to the fabric using a device according to the first aspect.
  • the invention provides a kit for pretreating or handwashing a fabric, the kit comprising a device according to the first aspect in combination with a liquid laundry composition.
  • the device may also be used with a powder-solvent mixture, however, in this case, it may be desirable to include filters preferably on the first and second free ends of the conduit to prevent undissolved powder being dispensed.
  • the invention provides a method of pretreating or handwashing a fabric, by applying a foam or mist laundry composition to the fabric using a device according to the first aspect, the method comprising an initial step of mixing a laundry powder composition with a solvent such as water in the device to form a laundry solution.
  • the invention provides a kit for pretreating or handwashing a fabric, the kit comprising a device according to the first aspect in combination with a particulate e.g. powder, granules etc. laundry e.g. detergent composition.
  • a particulate e.g. powder, granules etc. laundry e.g. detergent composition.
  • the powder comprises a high foaming formulation.
  • the laundry composition can optionally include one or more detergent materials or other materials for assisting or enhancing cleaning performance, treatment of the fabric to be cleaned, or to modify the aesthetics of the composition (e.g. perfumes, colourants, dyes, etc.).
  • one or more detergent materials or other materials for assisting or enhancing cleaning performance, treatment of the fabric to be cleaned, or to modify the aesthetics of the composition (e.g. perfumes, colourants, dyes, etc.).
  • compositions according to the invention may contain any one or more surface-active compounds (surfactant) which may be chosen from soap and non-soap anionic, cationic, non-ionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof.
  • surfactant may be chosen from soap and non-soap anionic, cationic, non-ionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof.
  • the preferred additional detergent-active compounds that can be used are soaps and synthetic non-soap anionic, nonionic and cationic surfactants. Some examples of each of these will now be described.
  • At least one anionic co-surfactant is preferably present. It may for example be selected from one or more of alkylbenzene sulphonates, alkyl sulphonates, primary and secondary alkyl sulphates (in free acid and/or salt forms).
  • the composition may, for example contain from 0.1% to 70%, preferably from 1% to 40%, more preferably from 2% to 30%, especially from 3% to 20% of alkylbenzene sulphonic surfactant (in free acid and/or salt form).
  • any anionic surfactant in the composition may comprise (preferably at a level of 70 wt% or more of the total anionic surfactant) or consist only of one or more calcium-tolerant non-soap anionic surfactants.
  • a "calcium tolerant" anionic surfactant is one that does not precipitate at a surfactant concentration of 0.4 g/l (and at an ionic strength of a 0.040 M 1:1 salt solution) with a calcium concentration up to 20° FH (French hardness degrees), i.e. 200 ppm calcium carbonate.
  • a preferred additional class of non-soap calcium tolerant anionic surfactants for use in the compositions of the present invention comprises the alpha-olefin sulphonate.
  • Another preferred class on calcium tolerant anionic surfactants comprise the mid-chain branched materials disclosed in WO-A-97/39087 , WO-A-97/39088 , WO-A-97/39089 , WO-A-97/39090 , WO-A-98/23712 , WO-A-99/19428 , WO-A-99/19430 , WO-A-99/19436 , WO-A-99/19437 , WO-A-99/19455 , WO-A-99/20722 , WO-A-99/05082 , WO-A-99/05084 , WO-A-99/05241 , WO-A-99/05242 , WO-A-99/05243 , WO-A-99/05244 and WO-A-99/07656 .
  • Yet another suitable class of calcium tolerant anionic surfactants comprises the alkyl ether sulphates (ie the (poly)alkoxylated alkyl sulphates).
  • Another suitable calcium tolerant anionic surfactants to be used in combination comprises alpha-olefin sulphonate and alkyl ether sulphate in a weight ratio of from 5:1 to 1:15.
  • alkyl ethoxy carboxylate surfactants for example, Neodox (Trade Mark) ex Shell
  • fatty acid ester sulphonates for example, FAES MC-48 and ML-40 ex Stepan
  • alkyl xylene or toluene sulphonates dialkyl sulphosuccinates
  • alkyl amide sulphates for example, sorpholipids
  • alkyl glycoside sulphates alkali metal (e.g. sodium) salts of saturated or unsaturated fatty acids.
  • anionic surfactants in addition to the calcium tolerant anionics are well-known to those skilled in the art.
  • examples include primary and secondary alkyl sulphates, particularly C 8 -C 15 primary alkyl sulphates; and dialkyl sulphosuccinates.
  • Sodium salts are generally preferred.
  • a soap may also be present.
  • Suitable soaps include those having a chain length ranging from C 12 to C 20 , mainly saturated, and optionally containing limited levels of 1 or 2 unsaturated bonds, and derived from natural oils and fats such as for example: (hardened or non-hardened) Tallow, coconut, or Palm Kernel.
  • the amount of optional soap is preferably from 0.1% to 10%, more preferably from 0.1% to 5% by weight of the composition.
  • the level of optional soap is preferably from 0.1% to 20%, more preferably from 5% to 15% by weight of the composition.
  • Optional other surfactants include nonionic surfactants, cationic surfactants (for detergency enhancement and/or fabric softening), amphoteric and zwitterionic surfactants.
  • nonionic surfactant may also be included.
  • the amount of these materials, in total, is preferably from 0.01% to 50%, preferably from 0.1% to 35%, more preferably from 0.5% to 25%, still more preferably from 0.7% to 20%, even more preferably from 0.8% to 15%, especially from 1% to 10% and even more especially from 1% to 7% by weight of the composition.
  • Preferred nonionic surfactants are aliphatic alcohols having an average degree of ethoxylation of from 2 to 12, more preferably from 3 to 10.
  • the aliphatic alcohols are C 8 -C 16 , more preferably C 10 -C 15 .
  • mid-chain branched hydrophobe nonionics disclosed in WO-A-98/23712 are another class of suitable nonionic surfactants.
  • Suitable other non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • composition according to the present invention may comprise from 0.05% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 2.5%, especially from 0.5% to 1% by weight of cationic surfactant.
  • Suitable cationic fabric softening compounds are substantially water-insoluble quaternary ammonium materials comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to C 20 or, more preferably, compounds comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C 14 .
  • the fabric softening compounds have two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to C 16 . Most preferably at least 50% of the long chain alkyl or alkenyl groups have a chain length of C 18 or above. It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
  • Quaternary ammonium compounds having two long-chain aliphatic groups for example, distearyldimethyl ammonium chloride and di(hardened tallow alkyl) dimethyl ammonium chloride, are widely used in commercially available rinse conditioner compositions.
  • Other examples of these cationic compounds are to be found in " Surfactants Science Series" volume 34 ed. Richmond 1990, volume 37 ed. Rubingh 1991 and volume 53 eds. Cross and Singer 1994, Marcel Dekker Inc. New York ".
  • Cationic surfactants that can be used for their detergency include quaternary ammonium salts of the general formula R 1 R 2 R 3 R 4 N + X - wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
  • R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 alkyl group
  • R 2 is a methyl group
  • R 3 and R 4 which may be the same or different, are methyl
  • compositions used in the invention will quite often also contain one or more detergency builders.
  • the total amount of detergency builder in the compositions will typically range from 1% to 80 wt%, preferably from 2% to 60 wt%, more preferably from 4% to 30% by weight of the total composition.
  • Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB-A-1 437 950 ; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB-A-1 473 201 , amorphous aluminosilicates as disclosed in GB-A-1 473 202 and mixed crystalline/amorphous aluminosilicates as disclosed in GB-A-1 470 250 ; and layered silicates as disclosed in EP-A-164 514 .
  • Inorganic phosphate builders for example, sodium orthophosphate, sodium pyrophosphate and sodium tripolyphosphate (STP) are also suitable for use with this invention.
  • compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder.
  • Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 20 to 50 wt%.
  • the aluminosilicate is zeolite, preferably the maximum amount is 30% by weight.
  • the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na 2 O. Al 2 O 3 . 0.8-6 SiO 2 .
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB-A-1 429 143 .
  • the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
  • the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
  • the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP-A-384 070 .
  • Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
  • zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • the calcium binding capacity of zeolite MAP is generally equivalent to at least 150 mg CaO per g of anhydrous material.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxy succinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxy succinates, carboxymethyloxymalonates, dipicolinates, hydroxyethy
  • Especially preferred organic builders are citrates, suitably used in amounts of from 2 to 30 wt%, preferably from 5 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • Laundry wash compositions according to the invention may also suitably contain a bleach system.
  • Fabric washing compositions may desirably contain peroxygen bleaching agents and precursors thereof, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • Peroxygen bleaching agents include those peroxygen bleaching compounds which are capable of yielding hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such compounds may also be suitable.
  • Preferred peroxygen bleaching agents include peroxygen bleach selected from the group consisting of perborates, percarbonates, peroxyhydrates, peroxides, persulfates, and mixtures thereof.
  • peroxygen bleach selected from the group consisting of perborates, percarbonates, peroxyhydrates, peroxides, persulfates, and mixtures thereof.
  • Specific preferred examples include: sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Particular preferred are sodium perborate tetrahydrate, and especially, sodium perborate monohydrate.
  • Sodium perborate monohydrate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching solution.
  • Sodium percarbonate may also be preferred for environmental reasons.
  • the amount thereof in the composition of the invention usually will be within the range of about 1-35% by weight, preferably from 5-25% by weight.
  • a bleach precursor e.g., N,N,N'N'-tetraacetyl ethylene diamine (TAED).
  • Another suitable hydrogen peroxide generating system is a combination of a C1-C4 alkanol oxidase and a C1-C4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol or glucose oxidase (GOX) and glucose.
  • MOX methanol oxidase
  • GOX glucose oxidase
  • Such combinations are disclosed in International Application PCT/EP 94/03003 and WO9856885 (Unilever ), which is incorporated herein by reference.
  • Alkylhydroperoxides are another class of peroxy bleaching compounds. Examples of these materials include cumene hydroperoxide, t-butylhydroperoxide and hydroperoxides originated from unsaturated compounds, such as unsaturated soaps
  • useful compounds as oxygen bleaches include superoxide salts, such as potassium superoxide, or peroxide salts, such as disodiumperoxide, calcium peroxide or magnesium peroxide.
  • Organic peroxyacids may also be suitable as the peroxy bleaching compound.
  • Such materials normally have the general formula: wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or group (giving di(peroxyacids)) or a quaternary ammonium group.
  • Typical monoperoxy acids useful herein include, for example:
  • Typical diperoxyacids useful herein include, for example:
  • inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-10% by weight, preferably from 4-8% by weight.
  • MPS potassium monopersulphate
  • Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988 ; 864,798 ; 907,356 ; 1,003,310 and 1,519,351 ; German Patent 3,337,921 ; EP-A-0185522 ; EP-A-0174132 ; EP-A-0120591 ; and U.S. Pat. Nos. 1,246,339 ; 3,332,882 ; 4,128,494 ; 4,412,934 and 4,675,393 .
  • peroxyacid bleach precursors are those of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Pat. Nos. 4,751,015 and 4,397,757 , in EP-A0284292 and EP-A-331,229 .
  • peroxyacid bleach precursors of this class are:
  • a further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520 and in European Patent Specification Nos. EP-A-458,396 and EP-A-464,880 .
  • any one of these peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.
  • the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
  • Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoyloxy benzene sulphonate (SBOBS); N,N,N'N'-tetraacetyl ethylene diamine (TAED); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SSPC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyloxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.
  • SBOBS sodium-4-benzoyloxy benzene sulphonate
  • TAED N,N,N'N'-tetraacetyl ethylene diamine
  • TAED sodium-1-methyl-2-benzoyloxy benzene-4-sul
  • aromatic aldehydes and dioxygen as peroxy acid precursor, as disclosed in WO97/38074 .
  • the precursors may be used in an amount of up to 12%, preferably from 2-10% by weight, of the composition.
  • bleach precursors for use with the present invention are found in WO0015750 and WO9428104 , for example 6-(nonanamidocaproyl)oxybenzene sulphonate. See W00002990 for cylic imido bleach activators.
  • the precursors may be used in an amount of up to 12%, preferably from 2-10% by weight, of the composition.
  • the bleaching composition of the present invention has particular application in detergent formulations, especially for laundry cleaning. Accordingly, in another preferred embodiment, the present invention provides a detergent bleach composition comprising a bleaching composition as defined above and additionally a surface-active material, optionally together with detergency builder.
  • bleaching agents in the compositions according to any aspect of the present invention are any of the known organic bleach catalysts, oxygen transfer agents or precursors therefor.
  • EP 446,981 A Preferred examples of such materials include hydrophilic or hydrophobic ketones, used especially in conjunction with monoperoxysulfates to produce dioxiranes in situ, and/or the imines described in U.S. 5,576,282 and references described therein.
  • Oxygen bleaches preferably used in conjunction with such oxygen transfer agents or precursors include percarboxylic acids and salts, percarbonic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. See also U.S. 5,360,568 ; U.S. 5,360,569 ; U.S. 5, 370,826 ; and 5,710,116 .
  • Transition-metal bleach catalysts are well-known in the art. Various classes have been disclosed based on especially cobalt, manganese, iron and copper transition-metal complexes. Most of these bleach catalysts are claimed to yield hydrogen peroxide or peroxyacid activation, certain classes of compounds are also disclosed to give stain bleaching by atmospheric oxygen.
  • manganese-containing bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S.Pat. 5,244,594 .
  • Preferred examples of theses catalysts include [Mn IV 2 ( ⁇ -O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 ](PF 6 ) 2 , [Mn III 2 ( ⁇ -O)( ⁇ -OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 ](ClO 4 ) 2 , [Mn IV 4 ( ⁇ -O) 6 (1,4,7-triazacyclononane) 4 ](ClO 4 ) 2 , Mn III Mn IV ( ⁇ -O)( ⁇ -OAc) 2 (1,4,7- trimethyl-1,4,7-triazacyclononane) 2 ](ClO 4 ) 3 , and mixtures thereof.
  • Patent applications EP0549271 ; DE19738273 teach the use of free ligand 1,4,7-trimethyl-1,4,7-triazacyclononane in detergent formulations.
  • a dinuclear manganese compound, [LMn III Mn IV ( ⁇ -O) ( ⁇ -OAc) 2 ](ClO 4 ) 2 with L being an ethylene-bridged-bis(1,4-dimethyl-1,4,7-triazacyclononane) ligands has been disclosed in WO 9606154 .
  • Still another type of bleach catalyst is a water-soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 diclsoses another useful bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
  • said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • Particularly preferred is the ligand 2,2'- bispyridylamine.
  • Preferred bleach catalysts include Co-, Cu-, Mn-, or Fe- bispyridylmethane and bispyridylamine complexes.
  • Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl 2 , Di(isothiocyanato)bispyridylamine-cobalt(II), trisdipyridylamine-cobalt(II) perchlorate, [Co(2,2-bispyridylamine) 2 O 2 ]ClO 4 , Bis-(2,2'-bispyridylamine)copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
  • Preferred ligands include bis(CH 2 COOH) (pyridin-2-ylmethyl)amine, tris(pyridin-2ylmethyl)amine, bis(pyridin-2-ylmethylamine), N,N,N',N'-tetrakis(pyridin-2ylmethyl)-ethylenediamine, N,N,N',N'-tetrakis(benzimidazol-2ylmethyl)-propan-2-ol, N-methyl-N,N',N'-tris(3-methyl-pyridin-2ylmethyl)-ethylenediamine, N-methyl-N,N',N'-tris(5-methylpyridin-2ylmethyl)-ethylenediamine, N-methyl-N,N',N'-tris(3-ethyl-pyridin-2ylmethyl)-ethylenediamine, N-methyl-N,N',N'-tris(3-methyl-pyridin-2ylmethyl)-ethylenediamine.
  • Manganese complexes containing 1,10-phenanthroline and 2,2'-bipyridine as bleaching catalysts have been disclosed in WO9615136 and WO9964554 .
  • Another preferred class of manganese complexes include mononuclear manganese complexes containing cross-bridged macrocyclic ligands. These complexes have been claimed with peroxy compounds and without peroxy compounds present in the formulation ( WO-A-98/39098 , WO-A-98/39405 and WO-A-00/29537 ).
  • the most preferred complexes include dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese (II) and dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II).
  • bleach catalysts are described, for example, in European patent application, publication no. EP-A-0 408,131 (dinuclear cobalt Schiff-base complex catalysts), European patent applications, publication nos. EP-A-384,503 , and EP-A-306,089 (metallo-porphyrin catalysts), U.S.-A-4,711,748 and European patent application, publication EP-A-224,952 , (absorbed manganese on aluminosilicate catalyst), U.S.-A-4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S.-A-4,626,373 (manganese/ligand catalyst), U.S.-A-4,119,557 (ferric complex catalyst), German Pat.
  • cobalt catalysts having the formula [Co(NH 3 ) 5 Cl]Cl 2 has been disclosed in EP-A-0 272 030 .
  • cobalt (III) catalysts [Co(NH 3 ) 5 (carboxylate)]X 2 (with X a non-coordinating anion) is disclosed in US-A-580 001 and US-A-508 198 .
  • Inorganic polyoxometallates as bleaching/oxidation catalysts with peroxy bleaches and air have been claimed in various patent applications, i.e. WO-A-97/07886 , WO-A-99/28426 , DE-A-1 953 0786 , and WO-A-00/39264 .
  • the bleach catalysts may be used in an amount of up to 5%, preferably from 0.001-1% by weight, of the composition.
  • compositions used in the present invention may also optionally contain one or more heavy metal chelating agents.
  • chelating agents suitable for use herein can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove heavy metal ions from washing solutions by formation of soluble chelates; other benefits include inorganic film or scale prevention.
  • Other suitable chelating agents for use herein are the commercial DEQUESTO series, and chelants from Monsanto, DuPont, and Nalco, Inc.
  • Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, is ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044 .
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • a chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially (but not limited to) the [S,S] isomer as described in U.S. Patent 4,704,233 .
  • EDDS ethylenediamine disuccinate
  • the trisodium salt is preferred though other forms, such as magnesium salts, may also be useful.
  • these chelating agents or transition- metal-selective sequestrants will preferably comprise from about 0.001% to about 10%, more preferably from about 0.05% to about 1% by weight of the bleaching compositions herein.
  • Laundry wash compositions according to the invention may also contain one or more enzyme(s).
  • Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
  • Preferred proteolytic enzymes are, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
  • proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention.
  • suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B . Subtilis, B . licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark).
  • Esperase Trade Mark
  • Savinase Trade-Mark
  • the preparation of these and analogous enzymes is described in GB-A- 1 243 785 .
  • Other commercial proteases are Kazusase (Trade Mark obtainable from Showa-Denko of Japan), Optimase (Trade Mark from Miles Kali-Chemie, Hannover, West Germany), and Superase (Trade Mark obtainable from Pfizer of U.S.A.).
  • Detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used.
  • compositions of the invention may contain alkali metal, preferably sodium carbonate, in order to increase detergency and ease processing.
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
  • compositions containing little or no sodium carbonate are also within the scope of the invention.
  • Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.
  • fatty acid soap suitably present in an amount of from 1 to 5 wt%.
  • detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; dyes; coloured speckles; perfumes; foam controllers; fluorescers and decoupling polymers. This list is not intended to be exhaustive.
  • compositions used in present invention may for example be solid compositions such as powders or tablets, or non-solid compositions such as substantially aqueous or substantially non-aqueous liquids, gels or pastes.
  • liquid compositions may be provided in water soluble sachets.
  • Non-solid, e.g. liquid, compositions may have different compositions from solid compositions and may for example comprise from 5% to 60%, preferably from 10% to 40% by weight of anionic surfactant (at least some of which will, of course, be aromaticalkyl sulphonic surfactant) from 2.5% to 60%, preferably from 5% to 35% by weight of nonionic surfactant and from 2% to 99% by weight of water.
  • liquid compositions may for example contain from 0.1% to 20%, preferably from 5% to 15% by weight of soap.
  • Non-solid, e.g. liquid, compositions may also (subject to any exclusions or other provisos expressed herein in the context of any aspect of the invention), comprise one or more hydrotropes, especially when an isotropic composition is required.
  • Such hydrotropes may, for example, be selected from arylsulphonates, e.g. benzene sulphonate, any of which is optionally independently substituted on the aryl ring or ring system by one or more C 1-6 e.g. C 1-4 alkyl groups, benzoic acid, salicylic acid, naphthoic acid, C 1-6 , preferably C 1-4 polyglucosides, mono-, di- and triethanolamine. Where any of these compounds may exist in acid or salt (whether organic or inorganic, such as sodium), either may be used provided compatible with the remainder of the formulation.
  • Figure 1 shows a schematic diagram of one embodiment of the invention.
  • a dispenser 1 for dispensing a mixture of two or more fluids 2,4,e.g. liquid 2 and gas i.e. air 4 as a foam and/or mist.
  • the dispenser 1 comprises a flexible container 6 for containing the liquid and includes a conduit 8 comprising a dip tube 8a having first and second end portions 11,12 the first end portion 11 terminating in an opening in the container 6 through which the mixture 2,4 is expelled from the container and the second open end portion 12 being close to the base 14 of said container 6, wherein the conduit 8 includes a third open end portion 13 which is located close to the top 16 of the container 6 and laterally inclined or opposed to the second open end portion 12.
  • a cost effective foam dispenser is provided which does not require complicated foaming elements in the flow path of the liquid.
  • a mixture of fluids e.g liquid and air can be ejected from the container simply by squeezing the container.
  • the provision of openings at the top and bottom of the container allow the device to function whether it is orientated upright (with central longitudinal axis upright, and top above base) or inverted (base above top).
  • the dispenser 1 also operates when it is tilted sideways.
  • the conduit is kinked or bent (at Y) generally in its upper section 18, so as to incline the second open end portion 12 approximately 20 degrees to the longitudinal axis of the container 6.
  • the third open end portion 13 extend from an upper section 18(ie. Toward the top of the container when it is orientated upright) of the conduit 8, e.g at right angles.
  • the conduit may have tee (T-shaped) configuration at the top, wherein the third open end portion branches off orthogonally from a main section of the conduit, preferably generally longitudinally aligned.
  • the conduit comprises a dip tube in co-operation with the screw-on container closure 20 having dispensing opening 22.
  • the container is flexible by means of a generally flexible body portion 24.
  • certain sections e.g. the base 26 and optionally corner portions may have increased rigidity e.g. for increasing strength.
  • the dispenser parts may be made of any material suitable for the purpose. A majority, if not all, of the parts are suitably made from polymeric material.
  • the dispenser 1 is opened by unscrewing and removing the closure 20 and then filled with laundry detergent liquid 2 (having formulation C and which may be mixed with water to dilute for improved foaming, depending on liquid viscosity) or laundry detergent powder (having formulation A or B) mixed with water to form a solution 2 to leave a head space of air 4.
  • laundry detergent liquid 2 having formulation C and which may be mixed with water to dilute for improved foaming, depending on liquid viscosity
  • laundry detergent powder having formulation A or B
  • a filter may be used, attached to the first and second ends of the conduit to prevent dispensing of undissolved powder.
  • low foaming formulation B may be desirable, as the remainder of the mixed solution can be put into the wash with the fabric to be washed to avoid waste.
  • the container is then simply compressed by squeezing the body portion 24 to expel the liquid/air mixture from the container.
  • the container can be used in any orientation e.g. inverted, due to the conduit arrangement to e.g. pretreat difficult to reach areas of garments and other laundry items without need for a support surface or having to maintain the device upright.
  • Powder Formulation A hand washing high foaming formulation
  • Anionic surfactant AS or LAS 25 Nonionic 2 STPP 10 Na silicate 7 Na carbonate 7 Na sulfate 30 Ca carbonate 10 Bentonite clay/calcite 5 Enzymes*,FWAs,SCMC,perfume 2 Water balance
  • Anionic surfactant AS or LAS 15 Nonionic 2 Soap 2 Zeolites 24 Na silicate 5 Na carbonate 13 Na sulfate 20 Na perborate (mono or tetrahydrate) 10 TAED or SNOBS 3 Polymers 1 Enzymes*,FWAs, 2 Perfume 2 Water balance
  • Nonionic surfactant 26.6 Monopropylene glycol 5.5 Pigment premix 0.017 Glycerol 21.36 Monoethanolamine 7.56 Oleic fatty acid 13.10 Water Up to 100 Linear alkyl benzene sulfonate 20.1 Perfume 1.6 Protease Enzyme 1.0 %
  • ABS alkylbenzenesulfonate
  • LAS linear alkylbenzenesulfonate
  • STPP sodium tripolyphosphate
  • SCMC sodium carboxymethylcellulose
  • TAED tetraacetylethylenediamine
  • SNOBS sodium nonanoyloxybenzenesulphonates
  • FWAs fluoresent whitening agents * Exemplary Enzmes include Protease, cellulase, amylase lipase and mixtures thereof.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Detergent Compositions (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Nozzles (AREA)

Claims (14)

  1. Wäschevorbehandlungs- oder Handwäschevorrichtung, in Kombination mit einem Gemisch von zwei oder mehreren Fluiden, wobei eines ein Waschfluid ist und das andere ein Gas ist, die Vorrichtung zum Spenden eines Gemisches als ein Schaum und/oder Nebel vorgesehen ist, der Spender einen biegsamen Behälter für das Gemisch umfasst, einschließlich einer Leitung mit ersten und zweiten Endteilen, wobei das erste Endteil in einer Öffnung in dem Behälter endet, durch die das Gemisch aus dem Behälter ausgestoßen wird, und das zweite offene Endteil sich nahe dem Boden des Behälters befindet, wobei die Leitung ein drittes offenes Endteil einschließt, das nahe der Spitze des Behälters und seitlich geneigt oder gegenüber zu dem zweiten offenen Endteil angeordnet ist, und dadurch gekennzeichnet, dass das dritte offene Endteil sich von dem oberen Abschnitt der Leitung, zum Beispiel im rechten Winkel, erstreckt, wobei die Leitung oben einen "T-förmigen" Aufbau aufweist, wobei das dritte offene Endteil sich im rechten Winkel von dem Hauptabschnitt der Leitung abzweigt.
  2. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, dass sie ein Mittel zum manuellen Unter-Druck-Setzen des Behälters umfasst.
  3. Vorrichtung nach einem vorangehenden Anspruch, wobei die Leitung verzweigt, gekrümmt oder geknickt ist oder eine Kombination davon, um relative Orientierung der zweiten und dritten Leitungsendteile zu bewirken.
  4. Vorrichtung nach einem vorangehenden Anspruch, wobei die Leitung in einem Abschnitt, zum Beispiel mittlerer oder oberer Abschnitt, gekrümmt oder geknickt ist, sodass sich das zweite offene Endteil zwischen 10 - 60 Grad zu der Längsachse des Behälters, vorzugsweise 15 - 45 Grad, bevorzugter 15 - 30 Grad, insbesondere 20 Grad, neigt.
  5. Vorrichtung nach Anspruch 4, wobei die Leitung in einem oberen Abschnitt um 20 Grad geknickt ist.
  6. Vorrichtung nach einem vorangehenden Anspruch, wobei das Obere der Leitung mit der zentralen Längsachse ausgerichtet ist.
  7. Vorrichtung nach einem der Ansprüche 1 - 7, wobei das Obere der Leitung von der mittleren Längsachse versetzt ist.
  8. Vorrichtung nach einem vorangehenden Anspruch, wobei die Leitung in Form von einem Tauchrohr, das mit dem Behälterverschluss oder Becher zusammenwirkt, vorliegt oder ein solches einschließt.
  9. Vorrichtung nach einem vorangehenden Anspruch, die einen oder mehrere Filter einschließt, die in oder an den ersten und/oder zweiten Enden der Leitung angeordnet sind.
  10. Verfahren zur Vorbehandlung oder Handwäsche eines Textils durch Auftragen einer Waschzusammensetzung in Form von einem Schaum oder Nebel auf das Textil, unter Verwendung einer Vorrichtung nach einem der Ansprüche 1-10.
  11. Kit zur Vorbehandlung oder Handwäsche eines Textils durch Auftragen einer Schaum- oder Nebel-Waschzusammensetzung, wobei das Kit eine Vorrichtung nach einem der Ansprüche 1-10, in Kombination mit einer flüssigen Waschzusammensetzung, vorzugsweise zusammen mit Anweisungen zur Anwendung der Vorrichtung, umfasst.
  12. Verfahren zur Vorbehandlung oder Handwäsche eines Textils durch Auftragen einer Schaum- oder Nebel-Waschzusammensetzung auf das Textil, unter Anwendung einer Vorrichtung nach einem der Ansprüche 1-10, wobei das Verfahren einen Anfangsschritt des Vermischens einer Waschpulverzusammensetzung mit einem Lösungsmittel, wie Wasser, in der Vorrichtung zur Bildung einer Waschlösung umfasst.
  13. Kit zur Vorbehandlung oder Handwäsche eines Textils, wobei das Kit eine Vorrichtung nach einem der Ansprüche 1-10, in Kombination mit einer teilchenförmigen Waschzusammensetzung, umfasst.
  14. Kit nach Anspruch 12 oder 14, dadurch gekennzeichnet, dass die Zusammensetzung eine stark schäumende Zusammensetzung ist.
EP04803287A 2003-12-16 2004-11-24 Schaumspender Expired - Lifetime EP1699703B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04803287A EP1699703B1 (de) 2003-12-16 2004-11-24 Schaumspender

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP03257896 2003-12-16
GB0329492A GB0329492D0 (en) 2003-12-19 2003-12-19 Foam and/or mist dispenser
PCT/EP2004/013415 WO2005058710A1 (en) 2003-12-16 2004-11-24 Foam dispenser
EP04803287A EP1699703B1 (de) 2003-12-16 2004-11-24 Schaumspender

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EP1699703A1 EP1699703A1 (de) 2006-09-13
EP1699703B1 true EP1699703B1 (de) 2008-03-26

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EP04803287A Expired - Lifetime EP1699703B1 (de) 2003-12-16 2004-11-24 Schaumspender
EP04801215A Expired - Lifetime EP1694567B1 (de) 2003-12-16 2004-12-03 Verfahren zum Behandlung von Stoffen

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AR (1) AR048211A1 (de)
AT (2) ATE390362T1 (de)
BR (1) BRPI0417661B1 (de)
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ES (2) ES2302056T3 (de)
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USD841471S1 (en) 2017-02-24 2019-02-26 S. C. Johnson & Son, Inc. Bottle
USD845135S1 (en) 2017-02-24 2019-04-09 S. C. Johnson & Son, Inc. Bottle neck with cap
US20250121281A1 (en) * 2023-10-12 2025-04-17 Alexander B. Patterson Interactive game room with integrated photobooth and auto-refillable ejection device

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Publication number Priority date Publication date Assignee Title
US4091966A (en) * 1976-06-01 1978-05-30 Laauwe Robert H Squeeze bottle containing a powdered product and operative whether upright or inverted
JPH1081895A (ja) * 1996-09-05 1998-03-31 Lion Corp 漂白洗剤製品
IT1307523B1 (it) * 1999-12-02 2001-11-06 Taplast Spa Metodo di erogazione di liquidi sotto forma di schiuma tramitecontenitori deformabili e dispositivo utilizzante tale metodo
BR8102490Y1 (pt) * 2001-11-21 2009-01-13 distribuidor de espuma ou nÉvoa.
ATE381492T1 (de) * 2003-01-30 2008-01-15 Unilever Nv Schaumspender
GB0305010D0 (en) * 2003-03-05 2003-04-09 Unilever Plc Changing colours

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WO2005058710A1 (en) 2005-06-30
WO2005058712A1 (en) 2005-06-30
ES2313107T3 (es) 2009-03-01
EP1694567A1 (de) 2006-08-30
ATE390362T1 (de) 2008-04-15
DE602004012775T2 (de) 2009-04-09
ZA200604305B (en) 2007-10-31
BRPI0417661A (pt) 2007-04-03
ES2302056T3 (es) 2008-07-01
DE602004012775D1 (de) 2008-05-08
EP1694567B1 (de) 2008-08-20
AR048211A1 (es) 2006-04-12
ATE405495T1 (de) 2008-09-15
DE602004016039D1 (de) 2008-10-02
BRPI0417661B1 (pt) 2019-11-05
EP1699703A1 (de) 2006-09-13

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