WO2005058712A1

WO2005058712A1 - Foam and/or mist dispenser

Info

Publication number: WO2005058712A1
Application number: PCT/EP2004/013961
Authority: WO
Inventors: Marcio Henrique Perissinotto Bonfa; Diego Sebastian Briozzo Fernandez; Andrew Paul Chapple; Dawn Rigby
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 2003-12-16
Filing date: 2004-12-03
Publication date: 2005-06-30
Also published as: BRPI0417661B1; BRPI0417661A; EP1694567B1; EP1699703B1; AR048211A1; EP1694567A1; ES2313107T3; ATE390362T1; ATE405495T1; ES2302056T3; WO2005058710A1; DE602004012775D1; EP1699703A1; ZA200604305B; DE602004016039D1; DE602004012775T2

Abstract

A laundry treatment dispenser in combination with a laundry liquid, for dispensing a mixture of the laundry liquid and a gas (preferably air), as a coloured 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.

Description

FOAM AND/OR MIST DISPENSER

The present invention concerns a device and method of treating a laundry fabric with a foam or mist dispenser, in which a colour change is associated with a function of the treatment product.

Treatment specific areas 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 are known and include e.g. solid detergent bars, detergent liquids. Some devices which have trigger or aerosol spray devices for spraying the liquid on fabric.

However, solid bars and abrasive tools can be too harsh for treatment of delicate fabrics. Further, these types of devices often require a generally flat working surface to support fabrics whilst they are scrubbed. Many consumers have limited space so that treatment of fabrics on a flat surface in not possible. Consumers often therefore resort to resting the garment on a knee or tummy, and with many known devices this carries the risk of applying the laundry composition to there body or their clothing, which is undesirable .

A further problem is that some fabric items, e.g. due to their construction, may not be easily flattened for treatment / washing on a flat surface. A particular problem is that pretreatment products are often difficult to apply precisely and so are common applied indiscriminately. This often leads to more product being applied than is actually necessary to remove a particular stain. Such over dosing is environmentally undesirable (especially as pretreatment products can be highly concentrated) and results in the pretreatment product running out quicker than expected. As a result, the consumer perceives the product to be overly expensive for the amount of usage provided and may not buy the product again. This is, of course, undesirable to the manufacturer.

It is an object of the invention to provide a pretreatment device and method, which overcomes or at least alleviates the above problems.

Accordingly, in a first aspect, 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 coloured 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.

In a second aspect the invention provides a method of treating a fabric, by applying a coloured laundry foam and/or mist to a selected region of a fabric such as a stained or soiled region using the combination of the first aspect of the invention.

The foam and/or mist may undergo a colour change following application.

Accordingly, the method of treatment of the second aspect of the invention may incorporate the steps of waiting until the foam, as applied, has changed colour from its originally applied 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 ^λmain' 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.

In a third aspect 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.

In a fourth aspect, 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 coloured foam/mist.

The laundry concentrate may be a liquid, gel, paste or solid concentrate .

1. In a fifth aspect, 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 coloured 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.

The various 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.

If 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.

By the term "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 coloured foam and / or mist, provides an elegant, inexpensive foam treatment device which can be used to dispense the coloured foam to allow precise treating of a selected region of a fabric, with minimal waste and expense for the consumer and environment. The device can be used independently of a work surface and accurately. This is due to the combination of a device which 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, accurately and without having to maintain the dispenser upright and without having to guess where the spray has been applied due to the colour.

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 coloured foam can be ejected from the container simply by squeezing the container body.

The laundry Fluid / Composition

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. The colour is apparent when the compostion is present in an aqueous medium or exposed to the atmosphere. Therefore the composition may be provided in a coloured state or require dissolution in an aqueous medium preferably water or exposure to the atmosphere.

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. 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. Thus, 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. Alternatively, 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.

It is preferred that the pH dependent chromophore is segregated from the bulk of the material when the commercial product is a solid. However, it is also envisaged that in certain circumstances that 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. During dispensing of the product by the consumer, 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. Alternatively, 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 . 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.

In one embodiment, 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. Upon dissolution of the composition the pH dependent chromophore is subjected to a pH environment different to that prior to use. In this regard, the bulk may be alkaline and the pH dependent chromophore present in a neutral or acidic environment; this is the preferred format. Alternatively, the bulk may be acidic and the pH dependent chromophore present in an alkaline or neutral environment.

The pH dependent Chromophore

Many 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) .

pH Dependent Fluorescent Indicator

Some 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. The following are examples that may be employed for use with the present invention. 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.

There are many standard texts available that give lists of fluorescent indicators.

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. Suitably, 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 %. Environment of the pH dependent chromophore

When the present invention is in a granular format it is preferred that 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. In a preferred embodiment of the present invention, the pH dependent chromophore, with or without cogranulant, is agglomerated, preferably with a water-soluble acidic polymer.

In one embodiment the binder material and the coating material, if present, 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.

In instances an acidic builder may be used with a binder (for example, citric acid with Sokolan— 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.

Another preferred polycarboxylate builder is ethylenediamine-N,N' -disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. 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.

Examples of such other magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.

The structure of the acid form of EDDS is as follows: H H

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.

Other 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. Examples of such salts are polyacrylates of MWt 2000 to 5000 and their copolymers with aleic 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 (alkylene phosphonates) 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. By 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. By 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

wherein X is 0 or CH2; Y is a comonomer or comonomer mixture; RI and R2 are bleach-stable polymer-end groups; R3 is H, OH or Cl-4 alkyl; M is H, and mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10, and mixtures thereof. 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. Referring to formula I, therefore, 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

C0₂M C0₂M

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, Y again can be a polycarboxylic acid such as II above or an ethyleneoxide moiety. - I I

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.

In formula I above, 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.

In the 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. Thus, for a maleic-acrylic copolymer having a weight average molecular weight of 15,500 and comprising 30 mole % of maleic acid derived units, n is 182 (i.e. 15,00/(116 x 0.3 + 72 x 0.7). In case of doubt, 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 Laboratories Ltd., Shropshire, UK, 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.

In mixtures of this type, 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. Of all the 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.

Other 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.

Air as the pH changing means

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.

In this case the foam dispenser itself provides the pH changing means by dispensing the foam to a carbon dioxide containing environment (the atmosphere) . However, 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. Preferably, 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. Examples of 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) .

pH Jump Compositions

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 Laundry Detergent Composition 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%.

In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch" , H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. 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. Specific nonionic detergent compounds are C₆-C₂₂ 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 C₈- Ciβ 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. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C₈-Cι₈ alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg-C₂₀ benzene sulphonates, particularly sodium linear secondary alkyl C₁0-C₁5 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 C₁₁-C₁₅ alkyl benzene sulphonates and sodium Cι₂-Cιs alkyl sulphates. Also applicable are 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) . Especially preferred is surfactant system that is a mixture of an alkali metal salt of a Ci6~Ci8 primary alcohol sulphate together with a Ci₂-Ci₅ 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.

Peroxygen Bleach or Source Thereof

The composition of the present invention may also comprise a peroxygen bleach or source thereof. However the pH dependent chromophores and bleach 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 enviroments. 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.

Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. 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. One skilled in the art will appreciate that these amounts may be reduced in the presence of 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. Such combinations are disclosed in International Application PCT/EP 94/03003 (Unilever), which is incorporated herein by reference.

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:

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 or a quaternary ammonium group.

Typical monoperoxy acids useful herein include, for example: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy-. alpha. -naphthoic acid;

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, peroxystearic acid and N, N-phthaloylaminoperoxy caproic acid (PAP); and (iii) 6-octylamino-6-oxo-peroxyhexanoic acid.

Typical diperoxyacids useful herein include, for example: (iv) 1, 12-diperoxydodecanedioic acid (DPDA) ;

(v) 1, 9-diperoxyazelaic acid; (vi) diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid;

(vii) 2-decyldiperoxybutane-l, 4-diotic acid; and

(viii) 4, 4 ' -sulphonylbisperoxybenzoic acid.

Also 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.

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; 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.

Another useful class of peroxyacid bleach precursors is that 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. Examples of peroxyacid bleach precursors of this class are:

2- (N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride (SPCC) ; N-octyl-N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride (ODC) ;

3- (N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and

N, N, N-trimethyl ammonium toluyloxy benzene sulphonate.

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.

Of the above classes of bleach precursors, 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 . Other classes of 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.

Peroxyl catalysts and "Air Bleach" Catalysts

The composition may also comprise a transition metal catalyst or precursor thereof, for example as described in PCT/GB99/02876 and PCT/EP01/13314. When 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. In this regard, 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. It is preferred that 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. In addition, it is preferred that the presence of alkyl hydroperoxides is kept to a minimum in such a bleaching composition.

In a "peroxyl mode" 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.

Enzymes

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 International Union of Biochemistry and Molecular Biology on the nomenclature and classification of enzymes, 1992, ISBN 0-12-227165-3, Academic Press.

Examples of the hydrolases are 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. Preferable among them are carboxylic ester hydrolase, glycosidase and exo- and endopeptidases. Specific examples of 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. Preferred among them is subtilisin; (2) glycosidases such as -amylase, β-amylase, glucoamylase, isoamylase, cellulase, endo-1, 3 (4) -β-glucanase (β-glucanase), xylanase, dextranase, polygalacturonase (pectinase) , lysozy e, invertase, hyaluronidase, pullulanase, neopullulanase, chitinase, arabinosidase, exocellobiohydrolase, hexosaminidase, mycodextranase, endo- 1, 4-β-mannanase (hemicellulase) , xyloglucanase, endo-β- galactosidase (keratanase) , mannanase and other saccharide gum degrading enzymes as described in WO-A-99/09127. Preferred among them are α-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.

Examples of 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.

Examples of lyases are hyaluronate lyase, pectate lyase, chondroitinase, pectin lyase, alginase II. Especially preferred is pectolyase, which is a mixture of pectinase and pectin lyase. Examples of the oxidoreductases are 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.

The activity of oxidoreductases, in particular the phenol oxidising enzymes in a process for bleaching stains on fabrics and/or dyes in solution and/or antimicrobial treatment can be enhanced by adding certain organic compounds, called enhancers. Examples of 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.

Builders, polymers and other enzymes as optional ingredients may also be present as found in WO0060045 and WO0034427.

Examples

1) Preparation of phenolphthalein sodium sulphate/ Sokolan™

CP45 granule

In a pestle and mortar, 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.

2) Preparation of phenolphthalein in sodium sulphate/CP45/and a transition metal catalyst

In a pestle and mortar, sodium sulphate (9.9 g) was mixed with of 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.

3) Preparation of Phenolphthalein in sulphate/CP45 (from ethanol)

In a pestle and mortar, 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.

4) Preparation of Phenolphthalein in sulphate/CP45/ transition metal catalyst (from ethanol)

In a pestle and mortar, 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.

5) Preparation of Thymolphthalein in sulphate/CP45/ transition metal catalyst (from ethanol)

In a pestle and mortar, 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. Stability and Colour Change Experiments

Stability of Granules from Example (3]

6) O.lg of the granules from Example (3) were mixed with 4.0 g of detergent powder (details given below) . The mixture as prepared had the appearance of a blue powder containing white 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. Detergent Powder

Stability of Granules from Example (4)

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.

8) Comparative example: Phenolphthalein powder (0.00085g) (equivalent to the weight of phenolphthalein in O.lg of the granules from examples 3 or 4) were mixed with 4.0 g of the detergent powder. The mixture as prepared had the appearance of a blue powder. This mixture was stored in an open topped glass jar at 37 °C /70%RH for 1 week. On removal its colour had changed to magenta/purple .

Colour Change of Granules from Example (3)

9) 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.

10) 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.

11) 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.

12) 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.

High Foam Examples especially for use where device/air is pH changing means

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 %) .

Foam Examples

Table 1 gives formulations A to J that when made up to 100 % with water provide suitable foaming compositions.

Table 1

A one litre aqueous solution comprising: LAS (10%).

The device

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.

Non-limiting embodiments of the invention are outlined below with reference to the drawings attached hereto.

Figure 1 shows a schematic diagram of one embodiment of the invention. Referring to figure 1, there is shown 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.

As the second and third conduit openings 12,13 are both longitudinally and laterally opposed the dispenser 1 operates when it is inverted and 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. However certain sections e.g. the base 26 and optionally corner portions may have increased rigidity e.g. for increasing strength.

In use, 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.

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.

After a period of at least 30 seconds, and preferably 1-5 minutes so that the foam has had sufficient time to change colour (to pink) . The container is then simply compressed by squeezing the body portion 24 to expel the 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 colour of the expelled foam/mist allows precise targeting in registration with stains and soiled regions and keeps overdosing to a minimum.

The pink colouration 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. Such 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.

It is of course to be understood that the invention is not intended to be restricted to the details of the above embodiments which are described by way of example only.

Claims

Claims .

1. 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 coloured 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, (ϋ)a pH changing means.

2. A combination according to claim 1 characterized in that the device comprises a means for manually pressurising the container to expel foam/mist therefrom.

3. A combination according to any preceding claim wherein the conduit is branched, curved or kinked or a combination thereof to effect the relative orientation of the second and third conduit end portions.

4. A combination according to any preceding claim wherein the conduit is 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.

5. A combination according to claim 4 whereint the conduit is kinked in a upper section by 20 degrees.

6. A combination according to any preceding claim wherein the third open end portion extends from an upper section of the conduit, e.g at right angles.

7. A combination according to any preceding claim wherein the conduit has a tee (T-shaped) configuration at the top, wherein the third open end portion branches off orthogonally from a main section of the conduit.

8. A combination according to any preceding claim wherein the top of the conduit is aligned with the central longitudinal axis.

9. A combination according to any of claims 1 - 8 wherein the top of the conduit is offset from the central longitudinal axis.

10.A combination according to any preceding claim wherein the conduit is in the form of or include a dip tube which co-operates with a container closure or cap.

11.A combination according to any preceding claim in which the device includes one or more filters located in or on the first and/or second ends of the conduit.

12.A method of treating a fabric, by applying a coloured laundry foam and/or mist to a selected area of a fabric such as a stained or soiled region using the combination of any preceding claim.

13. The method according to claim 12, incorporating the steps of waiting until the foam, as applied, has changed colour from its originally applied 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.

14.A kit for treating a fabric, comprising the combination of a device and laundry liquid of claims 1 -11, the kit including instructions for use of the device and laundry fluid according to any of claims 12 - 13.

15.A method of treating a fabric, according to any of claims 12-13, 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, (iv) a pH changing means, with a solvent such as water in the device to form a laundry liquid for formation of the coloured foam and/or mist.

16.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 coloured 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 of claim 15.

17.A kit according to claim 16 in which the device is according any of claims 1-11.

18. A kit according to claims 14, 16 or 17 including a main wash composition.