Anti-Malodour Dispensing Device

The present invention relates to an anti-malodour laundry detergent composition and use thereof.

European Patent 303,520 discloses cationic nitriles.

European patent 382 562 discloses polymeric ammonium triiodides and there use as disinfectants.

United States Patent 6,811,771 discloses an antimicrobial organic polymer material. The organic polymer material has a polymer side chain containing a unit derived from an N- alkyl-N-vinylalkylamide on a backbone of a polymer substrate; a triiodide ion is carried on the organic polymer material .

United States Patent 3,817,860, issued 18 June 1974, discloses an iodine/resin disinfectant and a procedure for the preparation thereof. The iodine/resin is prepared from an anionic exchange resin and an iodine/iodide mixture.

United States Patent 6,899,868 discloses an iodine/resin disinfectant and a procedure for the preparation thereof.

United States Patent 6,680,050 discloses an iodine/resin disinfectant and a procedure for the preparation thereof.

WO 04/029354 discloses a bleaching composition comprising: (a) iodine or a source thereof in the range from 0.0005 wt% to 5.0 wt %; and,

(b) the balance carriers and adjunct ingredients.

In a first aspect the invention provides a dispensing device suitable for use in a fabric washing operation, the device incorporating a anti-malodour component comprising a halide delivery vehicle.

The anti-malodour component reduces bacteria and fungus and thus malodour in clothes that arise as a result of bodily secretions.

In a second aspect, the present invention provides a method of reducing malodour in the wash using a dispensing device of the first aspect of the invention, the method including the step of adding said dispensing device to an aqueous medium and agitating the medium.

In a third aspect, the present invention provides a method of reducing malodour in multiple, successive washes using a dispensing device of the first aspect of the invention, the method including the step of adding said dispensing device to an aqueous medium in a washing receptacle (such as a washing machine drum) and then carrying out an aqueous washing operation therein by agitating the washing medium and retaining the dispensing device therein until and during further washing operations.

In a fourth aspect the invention provides a washing machine comprising a receptacle or drum suitable incorporating a dispensing device according to the first aspect of the

invention, for carrying out an aqueous washing operation according to the second or third aspects of the invention.

The halide delivery vehicle is preferably a cationic species with polyhalide ion. Preferably the cationic species is a polymer .

The halide may be I2 or Br ₂ or CI2, the polyhalide ions having a valence of -1.

As used herein, the terms "polyhalide," "polyhalide ions," and the like refer to or characterise a substance or a complex that has three or more halogen atoms and a valence of -1, and which may be formed if a molecular halogen (e.g. iodine as I ₂ ) combines with a monovalent trihalide ion (e.g. tiiodide ion) or pentahalide ion (e.g., pentaiodide ion). Bromine and chlorine also may be used as a source of molecular halogen. Similarly, the terms "polyiodide, " "polyiodide ions", and the like refer to or characterise a substance or a complex that has three or more iodine atoms and that may be formed if molecular iodine combines with the monovalent triiodine ion. Preferably the polyhalide is a trihalide, and more preferably a triiodine. The terms "triiodide, "triiodide ion," and the like refer to or characterise a substance or a complex that contains three iodine atoms and has a valence of -1. the trihalide ion herein is a complex ion which may be considered as comprising molecular halide (e.g. I2) a halide ion (e.g. I ^~ ) .

The anti-malodour component may comprise an ion exchanger system in which the polyhalide is the counter ion released.

The anti-malodour component is preferably an anion exchange resin. The term ion exchange resin includes resins comprising an organic or inorganic insoluble polymer or polymer network.

The dispensing device may be any suitable shape such as substantially ball/oval shaped.

Preferably dispensing device is water insoluble.

The dispensing device may be fixed to the washing machine so that it stays in place for successive washing operations.

The dispensing device may be comprise a chamber that contains a plurality of delivery members comprising the anti-malodour component.

Preferably, the chamber has one or more apertures, such as perforations to allow fluid to pass through to contact the contained delivery members. The perforations may be sufficiently large that the container presents a form of cage or a mesh or grid structure. At the same time, it is preferable that the perforations are dimensioned/sized so that the delivery members cannot escape into the wash liquor. This is especially advantageous if the device is to be used repeatedly i.e. without refilling, in multiple successive washes.

Preferably, the delivery members provide a high contact surface area to volume ratio. In the context of this problem

a generally spherical ball or bead is advantageous. However, eliptical or tubular constructions are also possible.

The delivery members are preferably greater than 0.5 cm in diameter, more preferably greater than 0.8 cm and even more preferably greater than 1 cm in diameter. This provides apertures which are sufficiently large to allow the water to pass through to contact the members for anti-malodour treatment .

The dispensing device may be rigid or flexible and may be provide a sealed unit, at least in so far as containment of the anti-malodour component is concerned.

The dispensing device may comprise rigid spacing means such as a rigid member or members which, in use, space the apertures from garment / fabrics in the wash. This helps protect the garment from discolouration due to contact/close proximity with the anti-malodour component.

The rigid spacing means may be restricted to the part of the device containing the apertures.

The rigid spacing means may comprise a rigid structure with apertures or a cage-like structure or mesh structure which surrounds at least the part of the device containing the apertures .

The dispensing device is preferably used in conjunction with a laundry treatment composition. The dispensing device may therefore incorporate, in addition to the anti-malodour

component, a chamber for containment of a unit dose of the laundry treatment agent. In the case of a unit dose such as a tablet or liquid capsule, these may placed into the chamber containing the delivery members. Alternatively to prevent escape of the delivery members, there may be separate chambers for delivery members and laundry treatment composition . The dispensing device may be removable from the washing machine to allow dosing of the laundry treatment composition .

Alternatively, the malodour component may be incorporated in the dispensing device and the laundry treatment composition dosed into the machine/washing receptacle separately e.g. by a further device or directly or via a machine dosing drawer. An anti-malodour component may be also incorporated in the laundry treatment composition. In this case, the cationic species may be present in the composition in an amount from 0.00001 to 20 wt%, preferably 0.0001 to 5 wt%, more preferably 0.001 to 1 wt%.

The present invention extends to method of pretreating a garment with the dispensing device. Preferably armpit areas of a garment are pre-treated.

Accordingly, the dispensing device of the invention may contain an aperture or spout for pretreating a garment or fabric with (i) the incorporated anti-malodour component and/or with (ii) a contained laundry treatment composition containing the anti-malodour component.

In a further aspect the invention provides a method of pretreating a garment or textile, the method comprising the step of contacting the garment/fabric e.g. armpit areas with the dispensing device and particularly with apertured areas of the device, in an aqueous solution such as a pre-wash liquor or simply water.

In a further aspect, the present invention provides a package in combination with (i) a dispensing device of the first aspect and

(ii) a laundry treatment composition comprising the anti- malodour component; and

(iii) instructions for use according to the method of the second or third aspect of the invention.

The cationic species may be an organic polymer material containing a polymer side chain having a unit derived from an N-alkyl-N-vinylalkylamide on a backbone of a polymer substrate, a polyhalide ion being carried on the organic polymer material. United States Patent 6,811,771 and references found therein describe manufacture of such species. The polymeric cationic species should be construed as covering the polymer and proton in column 5 for example, a protonated poly (vinylpyrrolidone) (PVP). Polymer units derived from N-vinylpyrrolidone, l-vinyl-2-piperidone, N- vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl- N-methyl propylamide, N-vinyl-N-ethyl propylamide are preferred but PVP is a preferred polymer. Treatment of (PVP) with I2/KI as essentially described below will yield PVP with a triiodide ion.

The polymeric ammonium triiodides as described in European patent 382 582 are also preferred anti-malodour active compounds for use in the present invention. Preferred examples of which are: poly [ (dimethyliminio) -2- hydroxypropylene triiodide] , poly [oxyethylene (dimethyliminio) hydroxypropylene (dimethyliminio) ethylene di (triiodide) ] and poly [2- hydroxyethylene (dimethyliminio) ethylene-dimethyliminio) - methylene di (triiodide) ] .

A suitable triiodide counter ion is produced, for example by combining iodine with sodium, potassium or ammonium iodide and some water. The composition will contain monovalent iodide ion that will combine with diatomic iodine (12) to form polyiodide ion. The molar ratio of iodine ion to diatomic iodine will dictate the nature of the polyiodide ion present, i.e. triiodide ion, mixtures of triiodide ion and other higher polyiodides ions, pentaiodide ion, etc. Using about 1 mole of iodine ion per mole of diatomic iodine the formation of triiodide ion will be favoured. If stiochiometric excess of diatomic iodine is used this will favour the formation of higher polyiodides.

The anti-malodour component is preferably a quaternary ammonium compound. The quaternary ammonium compound is most preferably a trimethyl quaternary ammonium compound.

A preferred class of quaternary amonium compounds are quaternary ammonium resins as disclosed in United States Patent 6,592,861. The resin is United States Patent

6,899,868 discloses an iodine/resin disinfectant and a procedure for the preparation thereof. The resins are insoluble in water. Most preferably the resin is a trimethyl quaternary ammonium compound.

The quaternary ammonium resins having a triiodide counter ion are easily produced. For example, if a triiodide-resin is desired the resin may be contacted with an alkali metal iodide/12 mix wherein the iodide and the diatomic iodine are present in more or less stoichiometric amounts (i.e. a mole ratio of 1) . By applying stoichiometric amounts of the iodine ion and iodine molecule (i.e. one mole of 12 per mole of I-) , the iodide sludge will comprise substantially only the triiodide ions. If stoichiometric excess quantities of 12 are used some of the higher polyiodide ions may be formed. Preferably, no more than the stoichiometric proportions of I- and 12 are used in the initial aqueous starting sludge so that substantially only triiodide attaches to the resin. United States Patent 6,592,861, 6,899,868 and references found therein provide enablement as to how such resins are manufactured. The resins are commercially available, for example the Amberlite series as provides by Rohm and Haas; a preferred example is Amberlite 401-S.

The following is the outline of the procedure from United States Patent 6,680,050.

A quaternary ammonium resin having a triiodide counter ion may be obtained by a) bringing a porous, granular, starting resin into contact with an aqueous sludge of iodine and

potassium iodide so as to obtain a paste mixture, iodine being present in the sludge essentially as triiodide ions, said starting resin being a strong base anion exchange resin having strongly basic groups thereof in a salt form the anion of which is exchangeable with triiodide ions, b) subjecting the paste mixture to elevated temperature and pressure conditions in an enclosed container or reactor (e.g., autoclave) for a predetermined impregnating duration of time, a void space being provided in the reactor such that contact occurs under an iodine atmosphere, and c) washing the obtained iodide-resin product with a suitable deionised water to remove water elutable iodine such as KI from the surface of the resin so that on drying no iodine crystals will form on the surface of the resin.

Where the resin is to be included in the laundry composition, the quaternary ammonium resin is preferably ground into a fine powder. The powder is preferably in the range from 1 nanometre to 1000 microns, more preferably from 500 nanometres to 500 microns. The aforementioned sizes are determined by use of appropriately sized sieves or what would pass through or be retained by an appropriately sized sieve. Indeed, this size is preferred when and solid anti- malodour active, i.e., a cationic species with triiodide counter ion.

The level of the quaternary ammonium resins having a triiodide counter ion in a laundry composition is preferably from 0.001 to 2 wt%

Triosyn® ^ep Ji K-, 'vl jewi to "dve ir J ^" K y K ₁ Lh^ p/eserr application .

In order to reduce free iodine in the environment it is preferred that the anti-malodour active is insoluble in water, preferably less than 1 mg/L in water at 20 ⁰ C, most preferably insoluble per se.

SURFACTANT The laundry treatment composition preferably comprises between 2 to 70 wt % of a surfactant, most preferably 10 to 45 wt %. 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. Preferably the surfactants used are saturated.

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 Ce to 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 Cs to Cis 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 Cs to Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl Cio to Ci 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 Cu to Ci ₅ alkyl benzene sulphonates and sodium C ₁₂ to Cis 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 C16 to Cis primary alcohol sulphate together with a C12 to Ci ₅ primary alcohol 3 to 7 EO ethoxylate.

The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system.

In another aspect, which is also preferred, the surfactant may be cationic such that the formulation has a fabric conditioning functionality.

FABRIC CONDITIONING COMPOUNDS

Most preferred cationic compounds are quaternary ammonium compounds .

It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one C12 to C22 alkyl chain.

It is preferred if the quaternary ammonium compound has the following formula:

R2

I ₊

R1-N-R3 X I R4

in which R ¹ is a C12 to C22 alkyl or alkenyl chain; R ² , R ³ and R ⁴ are independently selected from Ci to C ₄ alkyl chains and X ^~ is a compatible anion. A preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.

A second class of materials for use with the present invention are the quaternary ammonium of the above structure in which R ¹ and R ² are independently selected from C12 to C22 alkyl or alkenyl chain; R ³ and R ⁴ are independently selected from Ci to C4 alkyl chains and X ^~ is a compatible anion.

Other suitable quaternary ammonium compounds are disclosed in EP 0 239 910 (Proctor and Gamble) .

It is preferred if the ratio of cationic to nonionic surfactant is from 1:100 to 50:50, more preferably 1:50 to 20:50.

The fabric conditioning cationic compound may be present from 1.5 wt % to 50 wt % of the total weight of the composition. Preferably the cationic compound may be present from 2 wt % to 25 wt %, a more preferred composition range is from 5 wt % to 20 wt %.

The softening material is preferably present in an amount of from 2 to 60% by weight of the total composition, more preferably from 2 to 40%, most preferably from 3 to 30% by weight .

The composition optionally comprises a silicone.

BUILDER

The composition of the present invention preferably comprises one or more detergency builders. The total amount of detergency builder in the compositions will preferably range from 5 to 80 wt%, more preferably from 10 to 60 wt%.

Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever) ; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel) , amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble) ; and layered silicates as disclosed in EP 164 514B (Hoechst) . Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.

The compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis) , preferably from 25 to 50 wt%.

The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na ₂ O. Al ₂ O ₃ . 0.8-6 SiO ₂ .

These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO ₂ units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are

described, for example, in GB 1 429 143 (Procter & Gamble) . The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.

The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever) . Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.

Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.

Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form. It is preferred that the composition comprises from 2 to 30 wt% of sodium carbonate.

BLEACHING COMPONENTS

The composition may contain peroxygen bleaches and bleach activators. When a peroxygen bleach is present the preferred format is granular. If the quaternary ammonium

compound is cationic nitrile then it will function as an activator in itself. Preferred peroxygen bleaches are sodium percarbonate and sodium perborate, most preferred is sodium percarbonate. Activators include amongst other things TAED (( (H ₃ C-CO) 2N-CH ₂ -CH ₂ -N(OC-CH ₃ ) ₂ ) ) and transition metal catalysts. A preferred range for a peroxygen bleach is from 2 to 25 wt %, most preferably 5 to 15 wt %, in the composition. Preferably the peroxygen bleach is in a different granule to the anti-malodour component. Preferably a peroxygen bleach is only present when the anti-malodour species is insoluble in water.

FLUORESCENT AGENT

The composition preferably comprises a fluorescent agent (optical brightener) . Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4-styryl-3- sulfophenyl) -2H-napthol [ 1 , 2-d] trazole, disodium 4,4'- bis { [ (4-anilino-6- (N methyl-N-2 hydroxyethyl) amino 1,3,5- triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, disodium 4 , 4 ' -bis { [ (4-anilino-6-morpholino-l , 3, 5-triazin-2-yl) ] amino }

- I i

stilbene-2-2 ' disulfonate, and disodium 4, 4 '-bis (2- sulfoslyryl) biphenyl .

PERFUME Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.

Enzymes as optional ingredients may also be present as found in WO0060045.

The washing operation of the invention may be carried out in an aqueous medium comprising from of 0.5 g/L to 30 g/1 of the laundry treatment composition incorporated, the aqueous medium may have a pH in the range 4 to 11, and may be followed by a rinsing step wherein the garment/textile is rinsed with water. This may be followed by a drying operation .

It is preferred that the laundry composition is added to water such that it provides from 0.2 g/L to 5 g/L of surfactant in the aqueous medium.

The composition may be liquid or solid. If a solid, a granular format is preferred.

Various non-limiting embodiments of the invention will now be more particularly described with reference to the accompanying drawings :

Figure 1 shows a perspective view of one embodiment according to the invention; and

Figure 2 shows a perspective view of a second embodiment according to the invention.

Figure 1 shows a dispensing device 1 suitable for use in a fabric washing operation in a washing machine, the device 1 incorporating a anti-malodour component comprising delivery members which are in this embodiment insoluble spherical iodised anion exchange resin beads having a triiodide counter ion. This is prepared from Amberlite IR-400, per example 9 of US6,899,868 but beginning with beads of the required mesh size, instead of granules.

The dispensing device 1 comprises a rigid (insoluble) plastic shuttle which has a chamber 5 containing the anion exchange resin beads. The device 1 is opaque and so the bead are not visible, but for the purposes of explaining this embodiment, the position of the beads is generally indicated at 13.

The chamber 5 is closed to retain the beads therein for successive washes. However the chamber has perforations 9 which are dimensioned to allow fluid to enter but to prevent egress of the beads during the wash. Accordingly, the beads 13 are lcm in diameter whereas the perforations 9 are 0.8 cm in diameter.

The dispensing device 1 also has a second chamber 3 for containment of a unit dose of laundry treatment composition 15 (e.g. exemplary composition A below) which may optionally contain the malodour component (ground into a fine powder as exemplified in composition B described below) . This chamber 3 has an filling and dispensing aperture 11. The chamber is refilled before each washing operation and the laundry composition is dispensed from the aperture 11 during the wash.

In an alternative embodiment (not shown) , a dispensing device is as for the above described device but further includes a rigid spacing member or members. These function to space the perforations 9 from the laundry in the event of any discolouration due to contact/close proximity with the anti-malodour component. The rigid spacing means may be restricted to the part of the device containing the perforations. The rigid spacing means may comprise a rigid structure with large apertures or a cage-like structure or mesh having large aperture-size at least surrounding the device or part of the device. The apertures of any rigid structure, cage or mesh are preferably 0.5 - 5 cm in diameter .

A further embodiment is shown in figure 2, comprising a woven fabric sachet 100 which allows fluid (wash liquor) to pass through. The sachet 100 has a chamber 105 containing anion exchange resin beads generally indicated at 113 and is sealed or sewn shut to prevent escape of the beads 113.

The sachet simply remains in the wash for successive washes The laundry treatment composition is added to the wash separately, e.g. via the draw or a dosing shuttle.

Bottle embodiments are used over successive washes, and do not require refilling with malodour component.

Exemplary Detergent A

Exemplary detergent B is as above except that it includes a quaternary ammonium resin having a triiodide counter ion prepared from Amberlite IR-400, per example 9 of

US6,899,868. The resin is ground and sieved to provide a fine powder of less than 200 microns.

This powder is then added to the base detergent at a level of 0.1 wt % to provide an anti-malodour formulation.