WO2005058711A1 - Distributeur de mousse et/ou de brouillard - Google Patents

Distributeur de mousse et/ou de brouillard Download PDF

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Publication number
WO2005058711A1
WO2005058711A1 PCT/EP2004/013960 EP2004013960W WO2005058711A1 WO 2005058711 A1 WO2005058711 A1 WO 2005058711A1 EP 2004013960 W EP2004013960 W EP 2004013960W WO 2005058711 A1 WO2005058711 A1 WO 2005058711A1
Authority
WO
WIPO (PCT)
Prior art keywords
conduit
container
foam
end portion
laundry
Prior art date
Application number
PCT/EP2004/013960
Other languages
English (en)
Inventor
Marcio Henrique Perissinotto Bonfa
Diego Sebastian Briozzo Fernandez
Andrew Paul Chapple
Dawn Rigby
Original Assignee
Unilever Plc
Unilever Nv
Hindustan Lever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0329496A external-priority patent/GB0329496D0/en
Application filed by Unilever Plc, Unilever Nv, Hindustan Lever Limited filed Critical Unilever Plc
Priority to EP04820423A priority Critical patent/EP1697219B1/fr
Priority to DE602004006778T priority patent/DE602004006778T2/de
Publication of WO2005058711A1 publication Critical patent/WO2005058711A1/fr

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Classifications

    • 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—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, by deep-drawing operations performed on sheet material
    • B65D1/32—Containers adapted to be temporarily deformed by external pressure to expel contents
    • 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 a device and method of treating a laundry fabric with a foam and/or mist dispenser, in which a colour change is associated with a function of the laundry product.
  • Treatment of fabrics, textiles etc is often carried out by consumers to remove tough stains and soils, and this may precede a main washing process.
  • Devices for the treatment e.g. pretreatment prior to a ⁇ main wash' hand washing of laundry include e.g. solid detergent bars, detergent liquids. Some devices which have trigger or aerosol spray devices for spraying the liquid on fabric.
  • the invention provides a laundry treatment dispenser in combination with a laundry liquid, for dispensing a mixture of the laundry liquid and a gas gas (preferably air) , as a foam and/or mist
  • the dispenser comprising: a flexible container for the fluids including a conduit having first and second end portions, the first end portion terminating in an opening in the container through which the foam and /or mist is expelled from the container and the second open end portion being close to the base of said container, wherein the conduit includes a third open end portion which is located close to the top of the container and laterally inclined or opposed to the second open end portion; and the laundry liquid comprising: (i) a pH dependent chromophore, the pH dependent chromophore having a UV-vis spectrum that changes with pH in the range 1 to 14; and, (ii) a pH changing means.
  • the invention provides a method of treating a fabric, by applying a laundry foam and/or mist to a fabric using the combination of the first aspect of the invention, whereby the treated fabric undergoes a colour change.
  • the foam and/or mist may undergo a colour change following application.
  • the method of treatment of the second aspect of the invention may incorporate the steps of waiting until the originally colour has changed to a second colour followed by rinsing the portion of the fabric to which the foam has been applied with water; and then drying the textile and/or carrying out a further washing process or processes .
  • Such further washing processes main include e.g. a ⁇ main' wash e.g. in an washing machine whereby the method of the second aspect acts as a pretreatment for stain removal on specific areas of the fabric.
  • the invention provides a kit for treating fabric, the kit comprising the combination of device and laundry liquid according to the first aspect, together with instructions for use according to the second aspect of the invention.
  • the invention provides a method of treating a fabric according to the second aspect of the invention, the method comprising an initial step of mixing a concentrated laundry composition comprising: (i) a pH dependent chromophore, the pH dependent chromophore having a UV-vis spectrum that changes with pH in the range 1 to 14; and, (iii) a pH changing means. with a solvent such as water in the device to form a liquid for formation of the foam/mist.
  • the laundry concentrate may be a liquid, gel, paste or solid concentrate.
  • the invention provides a kit for treating fabric, the kit comprising a laundry treatment dispenser and a laundry concentrate, for dispensing a mixture of a laundry liquid and a gas (preferably air) as a foam and/or mist, the dispenser comprising: a flexible container for the mixture including a conduit having first and second end portions, the first end portion terminating in an opening in the container through which the foam and /or mist is expelled from the container and the second open end portion being close to the base of said container, wherein the conduit includes a third open end portion which is located close to the top of the container and laterally inclined or opposed to the second open end portion; and the laundry concentrate comprising: (i) a pH dependent chromophore, the pH dependent chromophore having a UV-vis spectrum that changes with pH in the range 1 to 14; and, (ii)a pH changing means together with instructions for use according to the method according to the fourth aspect of the invention.
  • a pH dependent chromophore the pH dependent chromophore having
  • kit instructions referred to herein may comprise any one or any combination of, visual indicia e.g. text, on the pack, in supplementary / separate materials e.g. leaflets, coupons and which may be sold separately or e.g. in TV commercials.
  • visual indicia e.g. text
  • supplementary / separate materials e.g. leaflets, coupons and which may be sold separately or e.g. in TV commercials.
  • One advantage of the invention is that the colouration effect combined with foam and/or mist dispensing can provide encouragement and interest to the consumer whose participation in the dreary process of fabric pretreating, washing is necessary.
  • a surprising effect of this is that the encouraged consumer pays substantially more attention to the process parameters and therefore is more likely to achieve optimal pretreatment.
  • a solid-solvent mixture is used to form the laundry liquid, it may be desirable to include filters preferably on the first and second free ends of the conduit to prevent undissolved solid matter being dispensed on to the fabric.
  • solid it is intended to include powder, granules, agglomerates, crushed tablets or tablet like objects or the like or any combination thereof.
  • the combination of the device with its arrangement of openings together with a foam and / or mist provides an elegant, inexpensive foam treatment device which can be used to treating a fabric.
  • the device can be used independently of a work surface, because the device can function in any orientation, upright (top above base) or inverted (since the openings are at the top and bottom i.e. opposed ends of the device), or tilted sideways due to the orientation of the the openings (since the second and third conduit openings are mutually laterally inclined or opposed) ; and the coloured foam and/or mist produced to allow targeting in precise registration with a selected area.
  • the user can simply suspend the item (away from their body) 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.
  • the invention also provides a highly cost effective foam dispenser which does not require complicated or expensive foaming elements in the flow path of the liquid or pump mechanisms. This greatly simplifies the device and reduces cost. No aerosol propellant is required reducing the environmental impact of the device. A foam can be ejected from the container simply by squeezing the container body.
  • the present invention provides a colour cue, the cue being all the more noticeable by the consumer because the colour appears when the product is added to an aqueous medium or exposed to the atmosphere.
  • the colour cue of the present invention is provided by a pH dependent chromophore; the colour of the pH dependent chromophore is dependent upon the acidity or the alkalinity of its environment.
  • Laundry treatment compositions for stain removal preferably comprise a detergent composition.
  • Detergent compositions are formulated to a high pH and the colour may also serve to indicate that the detergent product is functioning at the optimum pH.
  • the pH dependent chromophore may be maintained at a different pH during storage of the product than when the product is in use.
  • An example of this would be maintaining phenolphthalein, a pH dependent chromophore, at a pH below 8 in a detergent product comprising sodium carbonate so that the phenolphthalein is colourless.
  • the phenolphthalein Upon addition of the detergent product to water the phenolphthalein is released into the aqueous medium whilst the basic sodium carbonate raises, upon dissolution, the pH of the water environment in the range 8.2 to 10.0 causing the water to take a pink hue.
  • a colourless detergent powder containing phenolphthalein could be mixed with water by the user, within the dispenser of the invention to create a coloured solution which is then applied to the fabric as a coloured foam and/or mist for accurate treatment of the fabric so as to focus on specific stains, areas (collars cuffs) .
  • the amount of the basic component in the laundry detergent may be such that the acidity of the cloth dirt (e.g., sebum) serves to shift the pH of the wash liquor during use such that the phenolphthalein loses its pink colour giving an indication of completeness of the treatment process to the consumer.
  • a time release component is added to the laundry such that the colour changes or is removed during treatment or a subsequent wash as the pH changes.
  • the pH dependent chromophore is segregated from the bulk of the material when the commercial product is a solid.
  • the pH dependent chromophore may be encapsulated when the commercial product is a liquid, for example as a coacevated particle.
  • the environment of the pH dependent chromophore may be controlled by the use of a coacevated particle.
  • the internal surface of the coacevated particle may be neutral, acidic or alkaline wherein the pH dependent chromophore is located.
  • the coacevated particle can be ruptured (e.g. by a appropriately sized nozzle on the outlet of the device) bringing the pH dependent chromophore into contact with the remainder of the product resulting in a pH change to the pH dependent chromophore.
  • the pH dependent chromophore is segregated as a particle/granule that is coated with a wax or paraffin.
  • the segregation of the pH dependent chromophore as described above serves to protect the pH dependent chromophore from oxidising materials, if present, and alkaline/acidic conditions .
  • pH jump liquid formulation In contrast to the pH changes discussed above, another way of changing the pH is to use a pH jump liquid formulation. It is preferred that the pH dependent chromophore when used in a pH jump liquid is not encapsulated.
  • the pH dependent composition may absorb carbon dioxide from the atmosphere at dispensing, which results in a pH change which in turn results in the foam changing colour. In this aspect segregation of the pH dependent chromophore is not necessary.
  • the laundry composition comprises a pH dependent chromophore that has a different pH environment to the bulk of the formulation in a solid format.
  • the different pH environment may be provided by a binder or environment thereof.
  • the pH dependent chromophore Upon dissolution of the composition the pH dependent chromophore is subjected to a pH environment different to that prior to use.
  • the bulk may be alkaline and the pH dependent chromophore present in a neutral or acidic environment; this is the preferred format.
  • the bulk may be acidic and the pH dependent chromophore present in an alkaline or neutral environment.
  • pH dependent chromophores are commonly referred to as indicators. However, it is not essential that the pH dependent chromophore is reversible in its colour change. In this regard, pH dependent chromophores other than an indicator may be used. Below is found a Table in which examples of various pH dependent chromophores (indicators) are found. There are many standard texts available that give lists of pH dependent chromophores (indicators) .
  • fluorescent indicators would not be suitable for use in the present invention because of their toxicity and as a result any fluorescent indicator chosen need meet the criteria of being biologically acceptable to the environment and humans.
  • Quinine is a fluorescent indicator changing in the pH range 3.0 to 5.0 from blue to weak violet and further changing in the pH range 9.5 to 10.0 from weak violet non-fluorescent.
  • Salicylaldehyde thiosemicarbazone is a fluorescent indicator changing in the pH range 8.4 from non-fluorescent to fluorescent yellow.
  • Acridine orange is a fluorescent indicator changing in the pH range 8.4 to 10.4 from non-fluorescent to fluorescent yellow/Green.
  • a mixture of pH dependent chromophores and/or fluorescent indicators may be used in the present invention.
  • the amount of the pH dependent chromophores and/or fluorescent indicators present in the composition will vary depending on the extinction coefficient/colour intensity of the indicator required.
  • the amount of pH dependent chromophore having a UV-vis spectrum that changes with pH in the range 1 to 14 required is that sufficient for a discernable change in colour/fluorescence to be observable by the human eye.
  • the pH dependent chromophores and/or fluorescent indicator, or mixtures thereof is present in the composition in the range 0.0001 to 0.5 wt %, preferably 0.001 to 0.4 wt %, most preferably 0.002 to 0.3 wt %.
  • the composition is granulated with a binder.
  • the binder may be neutral, basic or acidic.
  • the acidic binder according to the present invention may be water-soluble acidic polymer.
  • the polymer may be used in the compositions according to the present invention to coat, bind or act as cogranulent .
  • the pH dependent chromophore, with or without cogranulant is agglomerated, preferably with a water-soluble acidic polymer.
  • the binder material and the coating material are different water-soluble acidic polymers, but in another, preferred embodiment the binder material and the coating material, if present, are the same water-soluble acidic polymer.
  • an acidic builder may be used with a binder (for example, citric acid with SokolanTM CP5) or in some instances the builder serves as a binder.
  • Suitable water- soluble monomeric or oligomeric carboxylate builders include lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates, lactoxysuccinates, and aminosuccinates, and the oxypolycarboxylate materials such is 2-oxa-l, 1, 3-propane tricarboxylates.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates, 1, 1, 2, 2-ethane tetracarboxylates, 1,1,3,3- propane tetracarboxylates and 1, 1, 2, 3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives, and the sulfonated pyrolysed citrates.
  • EDDS ethylenediamine-N,N' -disuccinic acid
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include NaEDDS, Na2EDDS and Na4EDDS.
  • magnesium salts of EDDS examples include MgEDDS and Mg2EDDS.
  • the magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5- tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5- tetrahydrofuran - cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1, 2, 3, 4, 5, 6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems of detergent compositions in accordance with the present invention.
  • Suitable water soluble organic salts are the homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • suitable salts are polyacrylates of MWt 2000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • Such builder polymeric materials may be identical to the polymeric materials as binder materials and coating materials, as described hereinabove. These materials are normally used at levels of from 0.5% to 10% by weight more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Organic phosphonates and amino alkylene poly include alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene 1,12 triamine pentamethylenephosphonates, although these materials are less preferred where the minimisation of phosphorus compounds in the compositions is desired.
  • Suitable polymers for use herein are water-soluble.
  • water-soluble it is meant herein that the polymers have a solubility greater than 5 g/1 at 20 °C.
  • Suitable polymers for use herein are acidic.
  • acidic it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5.
  • Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150,000, preferably, suitable polymers for use herein have a melting point above 30 °C.
  • Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention, include those having the following empirical formula I
  • the proportion of M being H in such polymers must be such as to ensure that the polymer is sufficiently acidic to meet the acidity criteria as hereinbefore defined.
  • Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents.
  • Preferred polycarboxylate polymers fall into several categories.
  • a first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
  • preferred polycarboxylate polymers of this type are those in which X is CHO, R3 is H or Cl-4 alkyl, especially methyl, p is from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula II
  • Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form) and Sokalan® CP45 (acidic form) .
  • a second category belongs to the class of polycarboxylate polymers in which referring to formula I, X is CH2, R3 is OH, p is from 0 to 0.1, preferably 0 and n averages from about 50 to about 1500, preferably from about 100 to 1000.
  • Y if present, can be a polycarboxylic acid such as II above, or an ethylene oxide moiety.
  • a third category belongs to the class of acetal polycarboxylate polymers in which, referring to formula I, X is (OR4)2, where R4 is C1-C4 alkyl, R3 is H, p is from 0 to 0.1, preferably 0 and n averages from 10 to 500. If present, - 1!
  • Y again can be a polycarboxylic acid such as II above or an ethyleneoxide moiety.
  • a fourth category belongs to the class of polycarboxylate polymers in which referring to formula I, X is CH2, R3 is H or Cl-4 alkyl, p is 0 and n averages from about 10 to 1500, preferably from about 500 to 1000.
  • a fifth category of polycarboxylate polymers has the formula I in which X is CH2, R3 is H or Cl-4 alkyl, especially methyl, p is from 0.01 to 0.09, preferably from 0.02 to 0.06, n averages from about 10 to about 1500, preferably from about 15 to about 300 and Y is a polycarboxylic acid formed from maleic acid, citraconic acid, mitaconic acid or mesaconic acid, highly preferred being maleic acid-derived comonomers of formula II above.
  • Suitable polymer end groups in formula I suitably include alkyl groups, oxyalkyl groups and alkyl carboxylic acid groups and salts and esters thereof.
  • M is H or mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium.
  • the proportion of M which is H is such as to ensure that the polymer meets the pH criteria described herein above.
  • n the degree of polymerization of the polymer can be determined from the weight average polymer molecular weight by dividing the latter by the average monomer molecular weight.
  • n 182 (i.e. 15,00/(116 x 0.3 + 72 x 0.7).
  • weight-average polymer molecular weights can be determined herein by gel permeation chromotography using Water [mu] Porasil (RTM) GPC 60 A2 and (mu) Bondagel (RTM) E-125, E-500 and E-1000 in series, temperature- controlled columns at 40 °C against sodium polystyrene sulphonate polymer standards, available from Polymer
  • the polymer standards being 0.15M sodium dihydrogen phosphate and 0.02M tetramethyl ammonium hydroxide at pH 7.0 in 80/20 water/acetonitrile.
  • Mixtures of polycarboxylate polymers are also suitable herein, especially mixtures comprising a high molecular weight component having an n value of at least 100, preferably at least 120, and a low molecular weight component having an n value of less than 100, preferably from 10 to 90, more preferably from 20 to 80.
  • Such mixtures are optimum from the viewpoint of providing excellent bleach stability and anti-incrustation performance in the context of a zerophosphate detergent formula.
  • the weight ratio of high molecular weight component to low molecular weight component is generally at least hi, preferably from about 1:1 to about 20:1, more preferably from about 1.5:1 to about 10.1, especially from about 2:1 to about 8:1.
  • Preferred polycarboxylate polymers of the low molecular weight type are polycarboxylate polymers of the fourth category (homopolyacrylate polymers) listed above.
  • highly preferred polycarboxylate polymers herein are those of the first category in which n averages from 100 to 800, preferably from 120 to 400 and mixtures thereof with polycarboxylate polymers of the fourth category in which n averages from 10 to 90, preferably from 20 to 80.
  • Suitable polymers for use herein include polymers derived from amino acids such as polyglutamine acid, and polyaspartic acid, as disclosed in EP 305 282, and EP 351 629.
  • the dispensed foam or mist may interact with the environment.
  • Foam has a high surface area to volume ratio and rapidly absorbs air from the atmosphere resulting in a pH change of the foam. If the foam is alkaline the pH of the foam decreases as carbon dioxide is absorbed from the atmosphere. When the appropriate pH dependent chromophore is present a colour change is observed providing a visual colour change.
  • the foam dispenser itself provides the pH changing means by dispensing the foam to a carbon dioxide containing environment (the atmosphere) .
  • the foam needs to be coloured as soon as possible, so as to allow application of a coloured foam to a predetermined fabric area, rather than wait for the foam to colour after application.
  • the bulk within the foam dispenser is in contact with atmospheric gases for fast colouring of the fluid.
  • Suitable and preferred pH dependent chromophores are, for example, phenolphthalein and thymol blue.
  • Anionic Surfactant, Non-ionic surfactant and Amphoteric Surfactants or mixtures thereof may be used in this embodiment.
  • suitable surfactants systems that may be used for the foam are as follows: sodium lauryl slkyl sulphate (LAS) , sodium lauryl ether sulphate (SLES) and coco amidopropyl betaine (CAPB) ; sodium lauryl alkyl sulphate (LAS) non-ionic (NI) and coco amidopropyl betaine (CAPB) ; primary alcohol sulphate (PAS) , sodium lauryl ether sulphate (SLES) and coco amidopropyl betaine (CAPB); primary alcohol sulphate (PAS), sodium lauryl ether sulphate (SLES) and non-ionic (NI) ; and sodium lauryl alkyl sulphate (LAS) and non-ionic (NI) .
  • LAS sodium lauryl alkyl sulphate
  • CAPB coco amid
  • the present invention may be used as a liquid format where the pH of the commercial product is substantially different to that in use.
  • Sorbitol/borate compositions are known from EP 381 262. In a concentrated solution the borate is complexed with the vicinal diol of the sorbitol; upon dilution of the sorbitol/borate composition the borate is liberated from its interaction with the sorbitol resulting in a pH jump.
  • Other pH Jump formulations are disclosed in US 6,509,308 and US 5,484,555.
  • the composition preferably comprises a surfactant and optionally other conventional detergent ingredients. It is most preferred that the detergent composition is alkaline. This alkalinity is preferably provided for by sodium carbonate.
  • the invention in its second aspect provides an enzymatic detergent composition which comprises from 0.1 - 50 % by weight, based on the total detergent composition, of one or more surfactants. This surfactant system may in turn comprise 0 - 95 % by weight of one or more anionic surfactants and 5 to 100 % by weight of one or more nonionic surfactants. The surfactant system may additionally contain amphoteric or zwitterionic detergent compounds, but this in not normally desired owing to their relatively high cost.
  • the enzymatic detergent composition according to the invention will generally be used as a dilution in water of about 0.05 to 2%.
  • nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz &
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Nonionic detergent compounds are C6 ⁇ C 22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C - Ci ⁇ primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Ce-Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 -C 2 o benzene sulphonates, particularly sodium linear secondary alkyl C ⁇ 0 -C ⁇ 5 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the preferred anionic detergent compounds are sodium Cn-C ⁇ 5 alkyl benzene sulphonates and sodium C ⁇ 2 -C ⁇ 8 alkyl sulphates.
  • surfactants such as those described in EP-A-328 177 (Unilever) , which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides .
  • Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) .
  • surfactant system that is a mixture of an alkali metal salt of a Ci 6 ⁇ Ci 8 primary alcohol sulphate together with a Ci 2 -Cis primary alcohol 3-7 EO ethoxylate.
  • the nonionic detergent is preferably present in amounts greater than 10%, e.g. 25-90% by weight of the surfactant system.
  • Anionic surfactants can be present for example in amounts in the range from about 5% to about 40% by weight of the surfactant system.
  • the detergent composition for preparing the solution may take any suitable physical form, such as a powder, granular composition, tablets, a paste or an anhydrous gel.
  • composition of the present invention may also comprise a peroxygen bleach or source thereof.
  • a peroxygen bleach or source thereof should be selected for compatability so that he bleach does not impair the colour of the composition at the treatment stage.
  • Phenolphthalein is a robust chromophore and will colour in most bleach environments.
  • the peroxy bleaching species may be a compound, which is capable of yielding hydrogen peroxide in aqueous solution.
  • Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates persilicates and persulphates . Mixtures of two or more such compounds may also be suitable.
  • sodium perborate tetrahydrate and, especially, sodium perborate monohydrate are particularly preferred.
  • Sodium perborate monohydrate is preferred because of its high active oxygen content.
  • Sodium percarbonate may also be preferred for environmental reasons and the fact that it contributes to the alkalinity when dissolved in water.
  • 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) .
  • TAED tetraacetyl ethylene diamine
  • 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 .
  • MOX methanol oxidase
  • Alkylhydroxy peroxides are another class of peroxy bleaching compounds. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide .
  • Organic peroxyacids may also be suitable as the peroxy bleaching compound.
  • Such materials normally have the general formula:
  • 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
  • Typical monoperoxy acids useful herein include, for example:
  • peroxybenzoic acid and ring-substituted peroxybenzoic acids e.g. peroxy- .alpha. -naphthoic acid
  • aliphatic, substituted aliphatic and arylalkyl monoperoxyacids e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP)
  • PAP N,N-phthaloylaminoperoxy caproic acid
  • 6-octylamino-6-oxo-peroxyhexanoic acid 6-octylamino-6-oxo-peroxyhexanoic acid.
  • diperoxyacids useful herein include, for example: (iv) 1, 12-diperoxydodecanedioic acid (DPDA) ;
  • 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 used in combination with peroxygen bleach sources, 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;
  • 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:
  • ODC N-octyl-N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride
  • 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 No . ' s 458,396 and 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-l-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4- methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3, 5, 5-trimethyl hexanoyl- oxybenzene sulphonate (STHOBS) ; and the substituted cationic nitriles .
  • SBOBS sodium-4-benzoyloxy benzene sulphonate
  • TAED N,N,N'N'-tetraacetyl ethylene diamine
  • TAED sodium-l-methyl-2-benzoy
  • bleach precursors for use with the present invention are found in WO0015750, for example 6- (nonanamidocaproyl) oxybenzene sulphonate.
  • the precursors may be used in an amount of up to 12%, preferably from 2-10% by weight, of the composition.
  • the composition may also comprise a transition metal catalyst or precursor thereof, for example as described in PCT/GB99/02876 and PCT/EP01/13314.
  • a transition metal catalyst or precursor thereof for example as described in PCT/GB99/02876 and PCT/EP01/13314.
  • the present invention is used in an "air bleach" mode is preferred that the composition is substantially devoid of peroxygen bleach or peroxyl-generating bleach system.
  • the term “substantially devoid” of should be construed within spirit of the invention. It is preferred that the composition has as low a content of peroxyl species present as possible.
  • the bleaching formulation contains less that 1 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, preferably the bleaching formulation contains less that 0.3 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, most preferably the bleaching composition is devoid of peracid or hydrogen peroxide or source thereof.
  • the presence of alkyl hydroperoxides is kept to a minimum in such a bleaching composition.
  • the composition comprises a peroxygen bleach or source thereof examples of which are found above. In such a mode it is most preferred that the composition is solid and in particular granular.
  • the detergent compositions of the present invention may additionally comprise one or more enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.
  • Said enzymes include oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases. Suitable members of these enzyme classes are described in Enzyme nomenclature 1992: recommendations of the Nomenclature Committee of the
  • hydrolases examples include carboxylic ester hydrolase, thiolester hydrolase, phosphoric monoester hydrolase, and phosphoric diester hydrolase which act on the ester bond; glycosidase which acts on O-glycosyl compounds; glycosylase hydrolysing N-glycosyl compounds; thioether hydrolase which acts on the ether bond; and exopeptidases and endopeptidases which act on the peptide bond.
  • carboxylic ester hydrolase, glycosidase and exo- and endopeptidases Preferable among them.
  • suitable hydrolases include (1) exopeptidases such as aminopeptidase and carboxypeptidase A and B and endopeptidases such as pepsin, pepsin B, chymosin, trypsin, chymotrypsin, elastase, enteropeptidase, cathepsin B, papain, chymopapain, ficain, thrombin, plasmin, renin, subtilisin, aspergillopepsin, collagenase, clostripain, kallikrein, gastricsin, cathepsin D, bromelain, chymotrypsin C, urokinase, cucumisin, oryzin, proteinase K, thermomycolin, thermitase, lactocepin, thermolysin, bacillolysin.
  • exopeptidases such as aminopeptidase and carboxypeptidase A and B and endopeptida
  • subtilisin (2) glycosidases such as -amylase, ⁇ -amylase, glucoamylase, isoamylase, cellulase, endo-1, 3 (4 ) - ⁇ -glucanase ( ⁇ -glucanase) , xylanase, dextranase, polygalacturonase (pectinase) , lysozyme, invertase, hyaluronidase, pullulanase, neopullulanase, chitinase, arabinosidase, exocellobiohydrolase, hexosaminidase, mycodextranase, endo- 1, 4- ⁇ -mannanase (hemicellulase) , xyloglucanase, endo- ⁇ - galactosidase (keratanase) , mannanas
  • ⁇ -amylase and cellulase are ⁇ -amylase and cellulase; (3) carboxylic ester hydrolase including carboxylesterase, lipase, phospholipase, pectinesterase, cholesterol esterase, chlorophyllase, tannase and wax-ester hydrolase. Preferred among them is lipase.
  • transferases and ligases are glutathione S- transferase and acid-thiol ligase as described in WO-A-98/59028 and xyloglycan endotransglycosylase as described in WO-A-98/38288.
  • lyases are hyaluronate lyase, pectate lyase, chondroitinase, pectin lyase, alginase II.
  • pectolyase which is a mixture of pectinase and pectin lyase.
  • oxidoreductases examples include oxidases such as glucose oxidase, methanol oxidase, bilirubin oxidase, catechol oxidase, laccase, peroxidases such as ligninase and those described in WO-A-97/31090, monooxygenase, dioxygenase such as lipoxygenase and other oxygenases as described in WO-A-99/02632, WO-A-99/02638, WO-A-99/02639 and the cytochrome based enzymatic bleaching systems described in WO-A-99/02641.
  • oxidases such as glucose oxidase, methanol oxidase, bilirubin oxidase, catechol oxidase, laccase, peroxidases such as ligninase and those described in WO-A-97/31090, monooxygenase, dioxygenase such as
  • Enhancers are 2,2'- azo-bis- (3-ethylbenzo-thiazoline-6-sulphonate (ABTS) and Phenothiazine-10-propionate (PTP). More enhancers are described in WO-A-94/12619, WO-A-94/12620 , WO-A-94/12621, WO-A-97/11217, WO-A-99/23887. Enhancers are generally added at a level of 0.01% to 5% by weight of detergent composition.
  • sodium sulphate (9.9g) was mixed with 0.085g of phenolphthalein. This mixture was granulated with 2.01g CP45 solution (40 % aqueous), and the resulting granules dried in an oven at 80 °C for 10 minutes. The resultant granules were sieved between 180 and 1400 microns.
  • sodium sulphate (9.9 g) was mixed with of phenolphthalein (0.085 g) .
  • phenolphthalein 0.085 g
  • To this mixture was added 0.2g of the transition metal catalyst, with thorough mixing.
  • This mixture was granulated with 2.01g CP45 solution (40 % aqueous) , and the resulting granules dried in an oven at 80 °C for 10 minutes. The resultant final granules were sieved between 180 and 1400 microns.
  • sodium sulphate (9.9 g) was mixed with 17ml of a 0.5% (w/v) enthanolic solution of phenolphthalein. The ethanol was evaporated to leave a dry solid. This mixture was granulated with 2.01g CP45 (40 % aqueous), and the resulting granules dried in an oven at 80 °C for 10 minutes. The resultant granules were sieved between 180 and 1400 microns.
  • sodium sulphate (9.9 g) was mixed with 17ml of a 0.5% (w/v) solution of phenolphthalein in ethanol. The ethanol was evaporated to leave a dry solid. To this mixture was added 0.2g transition metal catalyst, with thorough mixing. This mixture was granulated with 2.01g CP45 solution, and the resulting granules dried in an oven at 80 °C for 10 minutes. The final granules were sieved between 180 and 1400 microns.
  • sodium sulphate (9.9g) was mixed with 50ml of a 0.5% (w/v) solution of thymolphthalein in ethanol. The ethanol was evaporated to leave a dry solid. To this mixture was added 0.2g transition metal catalyst, with thorough mixing. This mixture was granulated with 2.01g CP45 solution, and the resulting granules dried in an oven at 80 °C for 10 minutes. The final granules were sieved between 180 and 1400 microns.
  • Example (7) The granules (O.lg) from Example (4) were mixed with 4.0 g of the detergent powder.
  • the mixture as prepared had the appearance of a blue powder containing yellow speckles. This mixture was stored in an open topped glass jar at 37 °C/70%RH for 1 week. On removal its visual appearance remained unchanged.
  • Granules (O.lg) from Example (3) were mixed with 4.0 g of detergent powder.
  • the mixture as prepared had the appearance of a blue powder containing white speckles. This mixture was dissolved in 2 litres of tap water at 20 °C . The solution was initially pale blue, but changed to pink/magenta over the period of approximately 30 seconds.
  • Granules (O.lg) from example (4) were mixed with 4.0 g of the detergent powder.
  • the mixture as prepared had the appearance of a blue powder containing yellow speckles. This mixture was dissolved in 2 litres of tap water at 20 °C. The solution was initially pale blue, but changed to pink/magenta over the period of approximately 30 seconds.
  • Granules (O.lg) from Example (5) were mixed with 4.0 g of the detergent powder.
  • the mixture as prepared had the appearance of a blue powder containing yellow speckles. This mixture was dissolved in 2 litres of tap water at 20 °C . The solution was initially pale blue, but changed to deep blue over the period of approximately 30 seconds.
  • Granules (0.05g) from Example (4), plus 0.05g of the granules from example (5) were mixed with 4.0 g of the detergent powder.
  • the mixture as prepared had the appearance of a blue powder containing yellow speckles. This mixture was dissolved in 2 litres of tap water at 20 °C .
  • the solution was initially pale blue, but changed to lilac/purple over the period of approximately 30 seconds.
  • the following are examples of single, binary and ternary active system that may be used to generate high foam qualities for use in the present invention.
  • the percentages given are wt/wt %.
  • a one litre aqueous solution comprising LAS (3.0%), NI (3.0%) and CAPB (0.5%) .
  • a one litre aqueous solution comprising LAS (5.0 %), SLES (2.5%) and CAPB (0.25%) .
  • a one litre aqueous solution comprising NI (5%), CAPB (0.25%) and PAS (2.5%) .
  • a one litre aqueous solution comprising NI (3%), CAPB (0.25%) and PAS (5.0 %) .
  • a one litre aqueous solution comprising: NI (3%), CAPB (0.50%) and PAS (2.5%)
  • a one litre aqueous solution comprising PAS (2.5%), SLES (5.0%) and CAPB (0.25%) .
  • a one litre aqueous solution comprising: PAS (5.0%), SLES (2.5%) and CAPB (0.25%)
  • a one litre aqueous solution comprising: LAS (1.5%) and NI (1.5 %) .
  • a one litre aqueous solution comprising: LAS (10%) .
  • Table 1 gives formulations A to.J that when made up to 100 % with water provide suitable foaming compositions.
  • 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 may extend 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 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 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 laundry composition may be a cleaning liquids which may 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 preferably 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 unless a filter is used.
  • 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. laundry solution 2 (which may be any one of foam examples A to J described above) 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.
  • 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. However 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 between 20 and 70 of laundry detergent powder (as in the Detergent Powder example above but also with the addition of 2.5 g of granules from Example 3) and approximately 150-180 ml water, this is then mixed by shaking the device to form a solution 2 to leave a head space of air 4.
  • laundry detergent powder as in the Detergent Powder example above but also with the addition of 2.5 g of granules from Example 3
  • approximately 150-180 ml water this is then mixed by shaking the device to form a solution 2 to leave a head space of air 4.
  • the device as it is to be used with a powder and water solutions, includes a simple filter comprising a mesh covering attached to the first and second ends of the conduit to prevent passage of any undissolved powder therethrough.
  • the container is then simply compressed by squeezing the body portion 24 to expel a pink coloured foam / mist 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.
  • the foam turns pink so that the pretreated areas become coloured as a cue to the consumer.
  • the main wash detergent composition in this embodiment also includes the same pH dependent chromophore, as used for the pretreater and for additional colour cues.
  • the pink colouration of pretreatment and colouration of the main wash detergent can be removed in the following washing operation either by relying on dilution or by additional components in a laundry detergent used in the main wash which increase acidity.
  • additional components may comprise e.g. citric acid, polycarboxylates which may be present as coacervated or wax coated particles which break up in the wash delaying the colouration effect.

Abstract

L'invention concerne un distributeur pour le traitement de blanchisserie qui fonctionne en combinaison avec un liquide de blanchisserie, pour la distribution d'un mélange constitué de ce liquide et d'un gaz (de préférence de l'air), sous forme de mousse et/ou de brouillard de couleur. Le distributeur comprend un conduit ayant des première et seconde extrémités qui se terminent par une ouverture dans le contenant, permettant le passage de la mousse et/ou du brouillard, aux fins d'expulsion depuis le contenant. La seconde extrémité est proche de la base du contenant, et le conduit comporte une troisième ouverture qui se trouve près du haut du contenant avec une inclinaison latérale ou opposée à la seconde extrémité. Le liquide comprend : (I) un chromophore qui dépend du pH, avec spectre UV/Vis évoluant avec le pH entre 1 et 14 ; et (ii) un système de modification de pH.
PCT/EP2004/013960 2003-12-16 2004-12-03 Distributeur de mousse et/ou de brouillard WO2005058711A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP04820423A EP1697219B1 (fr) 2003-12-16 2004-12-03 Distributeur de mousse et/ou de brouillard
DE602004006778T DE602004006778T2 (de) 2003-12-16 2004-12-03 Schaum- und/oder sprühspender

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP03257896 2003-12-16
EP03257896.5 2003-12-16
GB0329496A GB0329496D0 (en) 2003-12-19 2003-12-19 Foam and/or mist dispenser
GB0329496.4 2003-12-19

Publications (1)

Publication Number Publication Date
WO2005058711A1 true WO2005058711A1 (fr) 2005-06-30

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EP (1) EP1697219B1 (fr)
AR (2) AR047285A1 (fr)
AT (1) ATE363434T1 (fr)
DE (1) DE602004006778T2 (fr)
ES (1) ES2287810T3 (fr)
WO (1) WO2005058711A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
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
WO2003043743A1 (fr) * 2001-11-21 2003-05-30 Unilever Plc Distributeur de mousse ou de fines gouttelettes
WO2004067392A2 (fr) * 2003-01-30 2004-08-12 Unilever Plc Distributeur de mousse
WO2004078896A1 (fr) * 2003-03-05 2004-09-16 Unilever Plc Procede de traitement d'un produit textile au moyen d'une mousse a changement de couleur

Patent Citations (5)

* Cited by examiner, † Cited by third party
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
WO2003043743A1 (fr) * 2001-11-21 2003-05-30 Unilever Plc Distributeur de mousse ou de fines gouttelettes
WO2004067392A2 (fr) * 2003-01-30 2004-08-12 Unilever Plc Distributeur de mousse
WO2004078896A1 (fr) * 2003-03-05 2004-09-16 Unilever Plc Procede de traitement d'un produit textile au moyen d'une mousse a changement de couleur

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 08 30 June 1998 (1998-06-30) *

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DE602004006778D1 (de) 2007-07-12
EP1697219A1 (fr) 2006-09-06
DE602004006778T2 (de) 2008-02-07
AR047285A1 (es) 2006-01-11
AR048136A1 (es) 2006-04-05
ATE363434T1 (de) 2007-06-15
ES2287810T3 (es) 2007-12-16
EP1697219B1 (fr) 2007-05-30

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