WO2005058710A1

WO2005058710A1 - Foam dispenser

Info

Publication number: WO2005058710A1
Application number: PCT/EP2004/013415
Authority: WO
Inventors: Diego Sebastian Briozzo Fernandez
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 2003-12-16
Filing date: 2004-11-24
Publication date: 2005-06-30
Also published as: AR048211A1; EP1699703B1; EP1694567A1; ES2313107T3; ATE390362T1; BRPI0417661B1; ZA200604305B; ES2302056T3; DE602004012775T2; BRPI0417661A; EP1699703A1; WO2005058712A1; DE602004012775D1; EP1694567B1; DE602004016039D1; ATE405495T1

Abstract

A laundry pretreatment or hand washing device, for dispensing a mixture of two or more fluids, e.g. liquid and gas (preferably air) as a foam and/or mist, the dispenser comprising a flexible container for a liquid including a conduit having first and second end portions, the first end portion terminating in an opening in the container through which the mixture 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.

Description

FOAM DISPENSER

The present invention concerns method of pretreating a laundry fabric and a dispenser for use in such a method.

Devices for the pretreatment and hand washing of laundry are known and include e.g. solid detergent bars, detergent liquids, some of which have trigger spray devices.

Pretreatment of fabrics prior to a main washing operation is often carried out by consumers in or to remove tough stains and soils. However, pretreatment / handwashing with solid bars or abrasive tools can be too harsh for delicate fabrics.

Further, pretreatment with such devices often requires a generally flat working surface to support fabrics. Many modern consumers do not have suffic±ent space to pretreat fabrics on a flat surface and so often resort to resting the garment on a knee or tummy, in which case there is a risk of applying the laundry composition to themselves or their clothing, which is undesirable to say the least.

A further problem is that some fabric items may not be easily flattened for pretreatment / washing on a flat surface. 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 pretreatment or hand washing device, for dispensing a mixture of two or more fluids, e.g. liquid and gas (preferably air) as a foam and/or mist, the dispenser comprising a flexible container for a liquid including a conduit having first and second end portions, the first end portion terminating in an opening in the container through which the mixture 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.

With this arrangement and in particular due to the provision of openings at the top and bottom, a pretreatment and/or handwashing device is provided which can be used independently of a work surface and which can function in any orientation, whether it is orientated upright (top above base) or inverted. Further, as the second and third conduit openings are mutually laterally inclined or opposed the device also operate when it is tilted sideways. The user can simply suspend the item and spray the foam/mist solution to difficult to reach parts from below or above or a side as necessary, without having to maintain the dispenser upright.

The invention also provides a highly cost effective foam dispenser which does not require complicated foaming elements in the flow path of the liquid. This greatly simplifies the device and reduces cost. No aerosol propellant is required reducing the environmental impact of the device. A mixture of fluids e.g liquid and air can be ejected from the container simply by squeezing the container.

The conduit may be branched, curved or kinked or a combination thereof to effect the relative orientation of the second and third conduit end portions.

The conduit may be curved or kinked in a section e.g. mid or upper section, so as to incline the second open end portion between 10 - 60 degrees to the longitudinal axis of the container, preferably 15 - 45 degrees, more preferably 15 - 30 degrees, even more preferably 20 degrees.

The third open end portion 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 dispensers according to the invention may be used with any laundry liquid composition. Such cleaning liquids generally contain a foaming surfactant, preferably in completely dissolved form. They may also contain other components known in the art as components of cleaning liquids. They may even contain solid particulate matter provided it is in stable suspension in the liquid. To retain the simplified structure, it is preferred, however, are cleaning liquids that do not contain any undissolved solid matter.

In a second aspect the invention provides a method of pretreating or handwashing a fabric, by applying a foam or mist laundry composition to the fabric using a device according to the first aspect.

In a third aspect the invention provides a kit for pretreating or handwashing a fabric, the kit comprising a device according to the first aspect in combination with a liquid laundry composition. The device may also be used with a powder-solvent mixture, however, in this case, it may be desirable to include filters preferably on the first and second free ends of the conduit to prevent undissolved powder being dispensed.

Accordingly, in a fourth aspect, the invention provides a method of pretreating or handwashing a fabric, by applying a foam or mist laundry composition to the fabric using a device according to the first aspect, the method comprising an initial step of mixing a laundry powder composition with a solvent such as water in the device to form a laundry solution.

In a fifth aspect, the invention provides a kit for pretreating or handwashing a fabric, the kit comprising a device according to the first aspect in combination with a particulate e.g. powder, granules etc. laundry e.g. detergent composition.

Preferably the powder comprises a high foaming formulation.

The laundry composition can optionally include one or more detergent materials or other materials for assisting or enhancing cleaning performance, treatment of the fabric to be cleaned, or to modify the aesthetics of the composition (e.g. perfumes, colourants, dyes, etc.). Compositions according to the invention may contain any one or more surface-active compounds (surfactant) which may be chosen from soap and non-soap anionic, cationic, non-ionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof. Many suitable surface-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

The preferred additional detergent-active compounds that can be used are soaps and synthetic non-soap anionic, nonionic and cationic surfactants. Some examples of each of these will now be described.

Anionic Surfactant

At least one anionic co-surfactant is preferably present. It may for example be selected from one or more of alkylbenzene sulphonates, alkyl sulphonates, primary and secondary alkyl sulphates (in free acid and/or salt forms) . The composition may, for example contain from 0.1% to 70%, preferably from 1% to 40%, more preferably from 2% to 30%, especially from 3% to 20% of alkylbenzene sulphonic surfactant (in free acid and/or salt form) .

When it is desired further to enhance calcium intolerance, then any anionic surfactant in the composition may comprise (preferably at a level of 70 wt% or more of the total anionic surfactant) or consist only of one or more calcium- tolerant non-soap anionic surfactants. As referred to herein, a ^'"calcium tolerant" anionic surfactant is one that does not precipitate at a surfactant concentration of 0.4 g/1 (and at an ionic strength of a 0.040 M 1:1 salt solution) with a calcium concentration up to 20° FH (French hardness degrees), i.e. 200 ppm calcium carbonate.

A preferred additional class of non-soap calcium tolerant anionic surfactants for use in the compositions of the present invention comprises the alpha-olefin sulphonate.

Another preferred class on calcium tolerant anionic surfactants comprise the mid-chain branched materials disclosed in WO-A-97/39087, WO-A-97/39088, WO-A-97/39089, WO-A-97/39090, WO-A-98/23712, WO-A-99/19428, WO-A-99/19430, WO-A-99/19436, WO-A-99/19437, WO-A-99/19455, WO-A-99/20722, WO-A-99/05082, WO-A-99/05084, WO-A-99/05241, WO-A-99/05242, WO-A-99/05243, WO-A-99/05244 and WO-A-99/07656.

Yet another suitable class of calcium tolerant anionic surfactants comprises the alkyl ether sulphates (ie the (poly) alkoxylated alkyl sulphates).

Another suitable calcium tolerant anionic surfactants to be used in combination comprises alpha-olefin sulphonate and alkyl ether sulphate in a weight ratio of from 5:1 to 1:15.

Other calcium-tolerant anionic surfactants that may be used are alkyl ethoxy carboxylate surfactants (for example, Neodox (Trade Mark) ex Shell) , fatty acid ester sulphonates (for example, FAES MC-48 and ML-40 ex Stepan) , alkyl xylene or toluene sulphonates, dialkyl sulphosuccinates, alkyl amide sulphates, sorpholipids, alkyl glycoside sulphates and alkali metal (e.g. sodium ) salts of saturated or unsaturated fatty acids.

Yet other suitable anionic surfactants in addition to the calcium tolerant anionics are well-known to those skilled in the art. Examples include primary and secondary alkyl sulphates, particularly C₈-Cι₅ primary alkyl sulphates; and dialkyl sulphosuccinates.

Sodium salts are generally preferred.

Soaps

Optionally, a soap may also be present. Suitable soaps include those having a chain length ranging from Cι₂ to C₂o, mainly saturated, and optionally containing limited levels of 1 or 2 unsaturated bonds, and derived from natural oils and fats such as for example: (hardened or non-hardened) Tallow, Coconut, or Palm Kernel.

In a solid formulation, the amount of optional soap is preferably from 0.1% to 10%, more preferably from 0.1% to 5% by weight of the composition. In liquid compositions, the level of optional soap is preferably from 0.1% to 20%, more preferably from 5% to 15% by weight of the composition. Optional other surfactants

Optional other surfactants include nonionic surfactants, cationic surfactants (for detergency enhancement and/or fabric softening), amphoteric and zwitterionic surfactants.

If desired, nonionic surfactant may also be included. The amount of these materials, in total, is preferably from 0.01% to 50%, preferably from 0.1% to 35%, more preferably from 0.5% to 25%, still more preferably from 0.7% to 20%, even more preferably from 0.8% to 15%, especially from 1% to 10% and even more especially from 1% to 7% by weight of the composition.

Preferred nonionic surfactants are aliphatic alcohols having an average degree of ethoxylation of from 2 to 12, more preferably from 3 to 10. Preferably, the aliphatic alcohols are Cs-Cι₆, more preferably Cι₀-Cι₅.

The mid-chain branched hydrophobe nonionics disclosed in WO- A-98/23712 are another class of suitable nonionic surfactants .

Suitable other non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide) .

Optionally, a composition according to the present invention may comprise from 0.05% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 2.5%, especially from 0.5% to 1% by weight of cationic surfactant. Suitable cationic fabric softening compounds are substantially water-insoluble quaternary ammonium materials comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to C20 ^or _r more preferably, compounds comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C 4- Preferably the fabric softening compounds have two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to Oχg. Most preferably at least 50% of the long chain alkyl or alkenyl groups have a chain length of C]_g ^or above. It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.

Quaternary ammonium compounds having two long-chain aliphatic groups, for example, distearyldimethyl ammonium chloride and di (hardened tallow alkyl) dimethyl ammonium chloride, are widely used in commercially available rinse conditioner compositions. Other examples of these cationic compounds are to be found in "Surfactants Science Series" volume 34 ed. Richmond 1990, volume 37 ed. Rubingh 1991 and volume 53 eds . Cross and Singer 1994, Marcel Dekker Inc.

New York".

It is also possible to include certain mono-alkyl cationic surfactants which can be used for their detergency.

Cationic surfactants that may be used for this purpose include quaternary ammonium salts of the general formula RιR₂R₃R₄N⁺ X^" wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which R_x is a C₈-C₂₂ alkyl group, preferably a C₈-Cι₀ or Cι₂-Cι alkyl group, R₂ is a methyl group, and R₃ and R₄, which may be the same or different, are methyl or hydroxyethyl groups) ; and cationic esters (for example, choline esters) .

Detergency Builders

The compositions used in the invention, will quite often also contain one or more detergency builders. The total amount of detergency builder in the compositions will typically range from 1% to 80 wt%, preferably from 2% to 60 wt%, more preferably from 4% to 30% by weight of the total composition.

Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in

GB-A-1 437 950; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB-A-1 473 201, amorphous aluminosilicates as disclosed in GB-A-1 473 202 and mixed crystalline/amorphous aluminosilicates as disclosed in

GB-A-1 470 250; and layered silicates as disclosed in EP-A- 164 514. Inorganic phosphate builders, for example, sodium orthophosphate, sodium pyrophosphate and sodium tripolyphosphate (STP) are also suitable for use with this invention. 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 20 to 50 wt%.

When the aluminosilicate is zeolite, preferably the maximum amount is 30% by weight.

The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na₂0. A1₂0₃. 0.8-6 Si0₂.

These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg Ca/g. The preferred sodium aluminosilicates contain 1.5-3.5 Si0₂ units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB-A-1 429 143. The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.

The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. 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-A-384 070. Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.

Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally equivalent to at least 150 mg CaO per g of anhydrous material.

Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxy succinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.

Especially preferred organic builders are citrates, suitably used in amounts of from 2 to 30 wt%, preferably from 5 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.

Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form. Bleaches

Laundry wash compositions according to the invention may also suitably contain a bleach system. Fabric washing compositions may desirably contain peroxygen bleaching agents and precursors thereof, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.

Peroxygen bleaching agents include those peroxygen bleaching compounds which are capable of yielding hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such compounds may also be suitable.

Preferred peroxygen bleaching agents include peroxygen bleach selected from the group consisting of perborates, percarbonates, peroxyhydrates, peroxides, persulfates, and mixtures thereof. Specific preferred examples include: sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particular preferred are sodium perborate tetrahydrate, and especially, sodium perborate monohydrate. Sodium perborate monohydrate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching solution. Sodium percarbonate may also be preferred for environmental reasons.

The amount thereof in the composition of the invention usually will be within the range of about 1-35% by weight, preferably from 5-25% by weight. 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 or glucose oxidase (GOX) and glucose. Such combinations are disclosed in International Application PCT/EP 94/03003 and W09856885 (Unilever) , which is incorporated herein by reference.

Alkylhydroperoxides are another class of peroxy bleaching compounds. Examples of these materials include cumene hydroperoxide, t-butylhydroperoxide and hydroperoxides originated from unsaturated compounds, such as unsaturated soaps

Further, useful compounds as oxygen bleaches include superoxide salts, such as potassium superoxide, or peroxide salts, such as disodiumperoxide, calcium peroxide or magnesium peroxide. Organic peroxyacids may also be suitable as the peroxy bleaching compound. Such materials normally have the general formula:

wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or

group (giving di (peroxyacids) ) or a quaternary ammonium group .

Typical monoperoxy acids useful herein include, for example :

( i ) peroxybenzoic acid and ring-substituted peroxybenzoic acids , e . g . peroxy- . alpha . -naphthoic acid or m- chloroperoxybenzoic acid

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, peroxystearic acid, 4-nonylamino-4-oxoperoxybutyric acid, and N,N- phthaloylaminoperoxy caproic acid (PAP) ; and

(iii) 6-octylamino-6-oxo-caproic acid. (iv) magnesium monoperoxophtalate hexahydrate, available from Interox. (v) 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) (vi) Phtaloylimidoperoxycaproic acid

Typical diperoxyacids useful herein include, for example:

(vii) 1, 12-diperoxydodecanedioic acid (DPDA) ;

(vii) 1, 9-diperoxyazelaic acid;

(viii) diperoxytetradecanedioc acid (ix) diperoxyhexadecanedioc acid

(x) diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid; (xi) 2-decyldiperoxybutane-l, 4-diotic acid; and

(xii) 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 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 -4-sulphonylcarbonate (CSPC); as disclosed in US-A-4 751 015;

N-octyl-N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride (ODC) ;

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 Nos. EP-A-458,396 and EP-A- 464,880.

Any one of these peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.

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; SSPC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3, 5, 5-trimethyl hexanoyl- oxybenzene sulphonate (STHOBS) ; and the substituted cationic nitriles.

Each of the above precursor may be applied in mixtures, e.g. combination of TAED (hydrophylic precursor) with more hydrophobic precursor, such as sodium nonanoyloxybenzene sulphonate .

Alternatively, one may apply aromatic aldehydes and dioxygen as peroxy acid precursor, as disclosed in WO97/38074.

The precursors may be used in an amount of up to 12%, preferably from 2-10% by weight, of the composition.

Other classes of bleach precursors for use with the present invention are found in WO0015750 and WO9428104, for example 6- (nonanamidocaproyl) oxybenzene sulphonate. See WO0002990 for cylic i ido bleach activators.

The precursors may be used in an amount of up to 12%, preferably from 2-10% by weight, of the composition. The bleaching composition of the present invention has particular application in detergent formulations, especially for laundry cleaning. Accordingly, in another preferred embodiment, the present invention provides a detergent bleach composition comprising a bleaching composition as defined above and additionally a surface-active material, optionally together with detergency builder.

Also useful as bleaching agents in the compositions according to any aspect of the present invention are any of the known organic bleach catalysts, oxygen transfer agents or precursors therefor. These include the compounds themselves and/or their precursors, for example any suitable ketone for production of dioxiranes and/or any of the heteroatom containing analogs of dioxirane precursors or dioxiranes, such as sulfonimines R1R2C=NS02R3 (EP 446 982 A) and sulfonyloxaziridines, for example:

EP 446,981 A. Preferred examples of such materials include hydrophilic or hydrophobic ketones, used especially in conjunction with monoperoxysulfates to produce dioxiranes in situ, and/or the imines described in U.S. 5,576,282 and references described therein. Oxygen bleaches preferably used in conjunction with such oxygen transfer agents or precursors include percarboxylic acids and salts, percarbonic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. See also U.S. 5,360,568; U.S. 5,360,569; U.S. 5, 370,826; and 5,710,116.

Transition-metal bleach catalysts are well-known in the art. Various classes have been disclosed based on especially cobalt, manganese, iron and copper transition-metal complexes. Most of these bleach catalysts are claimed to yield hydrogen peroxide or peroxyacid activation, certain classes of compounds are also disclosed to give stain bleaching by atmospheric oxygen.

One type of manganese-containing bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S.Pat. 5,244,594. Preferred examples of theses catalysts include [Mn^IV ₂ (μ-O) ₃ (1, 4, 7-trimethyl-l, 4, 7- triazacyclononane)₂] (PF₆)₂, [Mn^πι ₂ (μ-O) (μ -OAc) ₂ (1, 4, 7- trimethyl-1, 4, 7-triazacyclononane) ₂](C10₄)₂, [Mn^IV ₄(μ- 0) ₆ (1,4, 7-triazacyclononane) ₄] (C10₄)₂, n^III n^IV(μ-0) (μ- OAc) ₂ ( 1 , 4, 7- trimethyl-1, 4, 7-triazacyclononane) ₂] (CIO4) 3, and mixtures thereof. See also European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9- trimethyl-1, 5, 9-triazacyclododecane, 2-methyl-l, 4, 7-triazacyclononane, 2- methyl-1, 4, 7-trimethyl- 1,4,7- triazacyclononane, and mixtures thereof. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as [Mn (1, 4, 7-trimethyl-l, 4, 7- triazacyclononane) (OCH₃) ₃] (PFβ) . Patent applications EP0549271; DE19738273 teach the use of free ligand 1,4,7- trimethyl-1, 4, 7-triazacyclononane in detergent formulations. A dinuclear manganese compound, [LMn^IIIMn^IV (μ-O) (μ-

OAc)₂. (C10₄)₂ with L being an ethylene-bridged-bis (1, 4- dimethyl-1, 4, 7-triazacyclononane) ligands has been disclosed in WO 9606154.

Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114, 606, is a water-soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, eso-inositol, lactose, and mixtures thereof.

U.S. Pat. 5,114,611 diclsoses another useful bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non- (macro) -cyclic ligand. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'- bispyridylamine . Preferred bleach catalysts include Co-, Cu-, Mn-, or Fe- bispyridylmethane and bispyridylamine complexes. Highly preferred catalysts include Co (2, 2 ' -bispyridylamine) Cl₂, Di (isothiocyanato) bispyridylamine-cobalt (II) , trisdipyridylamine-cobalt (II) perchlorate, [Co (2,2- bispyridylamine) ₂0₂] C10₄, Bis- (2,2'- bispyridylamine) copper (II) perchlorate, tris (di-2- pyridylamine) iron (II) perchlorate, and mixtures thereof.

Various manganese and iron complexes containing (pyridin- 2ylmethyl) amine moieties as bleach catalyats are disclosed in DE19755493, EP0783035, US5850086, EP0782998, EP0782999, W09748787, WO9730144, WO0027975, WO0027976, WO0012667, and WO0012668. Preferred ligands include bis (CH₂COOH) (pyridin-2- ylmethyl) amine, tris (pyridin-2ylmethyl) amine, bis (pyridin-2- ylmethylamine) , N,N,N' ,N' -tetrakis (pyridin-2ylmethyl) - ethylenediamine, N,N,N' ,N' -tetrakis (benzimidazol-2ylmethyl) - propan-2-ol, N-methyl-N, N' , N' -tris (3-methyl-pyridin- 2ylmethyl) -ethylenediamine, N-methyl-N, N' , N' -tris (5-methyl- pyridin-2ylmethyl) -ethylenediamine, N-methyl-N, N' ,N' -tris (3- ethyl-pyridin-2ylmethyl) -ethylenediamine, N-methyl-N, N' ,N' - tris (3-methyl-pyridin-2ylmethyl) -ethylenediamine.

A series of patent applications deal with iron complexes containing the bis (pyridin-2yl)methyl-amine moiety both for peroxy bleaching activation and atmospheric air bleaching of stains, i.e. W09534628, EP0909809, WO0060044, WO0032731, WO0012667, and WO0012668, wherein the iron complexes containing N, N-bis (pyridin- 2-yl-methyl) -1, 1-bis (pyridin-2- yl) -1-aminoethane are often the most preferred catalysts.

Manganese complexes containing 1, 10-phenanthroline and 2,2'- bipyridine as bleaching catalysts have been disclosed in W09615136 and W09964554.

Manganese complexes with Schiff-base ligands to bleach stains or dyes in solution have been disclosed in various patent applications (GB-A-2 325 001, WO-A-00/ 53708, EP-A- 896 171 WO-A-97/44430, WO-A-97/07191, and WO-A-97/07192 ) .

Another preferred class of manganese complexes include mononuclear manganese complexes containing cross-bridged macrocyclic ligands. These complexes have been claimed with peroxy compounds and without peroxy compounds present in the formulation (WO-A-98/39098, WO-A-98/39405 and WO-A- 00/29537). The most preferred complexes include dichloro- 5, 12-dimethyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) and dichloro-4, 10-dimethyl-l, 4,7, 10- tetraazabicyclo [5.5.2] tetradecane Manganese (II) .

Further a class of manganese complexes containing bispidon as ligand has been disclosed as a family of bleach catalysts in the presence and absence of peroxy compounds (WO0060045) , wherein dimethyl 2, 4-di- (2-pyridyl) -3, 7-dimethyl-3, 7-diaza- bicyclo [3.3.1] nonan-9one-l, 5-dicarboxylate is the preferred ligand.

Other bleach catalysts are described, for example, in European patent application, publication no. EP-A-0 408,131 (dinuclear cobalt Schiff-base complex catalysts) , European patent applications, publication nos. EP-A-384, 503, and EP- A-306,089 (metallo-porphyrin catalysts) , U. S . -A-4, 711, 748 and European patent application, publication EP-A-224, 952, (absorbed manganese on aluminosilicate catalyst), U.S.-A- 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U. S . -A-4, 626, 373 (manganese/ligand catalyst), U. S. -A-4, 119, 557 (ferric complex catalyst), German Pat. specification DE-A-2, 054, 019 (cobalt-1, 10- phenanthroline catalyst), Canadian 866,191 (transition metal-containing salts), U. S . -A-4, 430, 243 (chelants with manganese cations and non-catalytic metal cations), and U.S. -A- 4,728,455 (manganese gluconate catalysts). Another class of preferred cobalt catalysts having the formula [Co (NH₃) ₅C1] Cl₂ has been disclosed in EP-A-0 272 030. Yet another class of preferred of cobalt (III) catalysts [Co (NH₃) ₅ (carboxylate) ]X₂ (with X a non-coordinating anion) , as disclosed in US-A-580 001 and US-A-508 198.

Inorganic polyoxometallates as bleaching/oxidation catalysts with peroxy bleaches and air have been claimed in various patent applications, i.e. WO-A-97/07886, WO-A-99/28426, DE- A-l 953 0786, and WO-A-00/39264.

The bleach catalysts may be used in an amount of up to 5%, preferably from 0.001-1% by weight, of the composition.

Chelating Agents

The compositions used in the present invention may also optionally contain one or more heavy metal chelating agents. Generally, chelating agents suitable for use herein can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove heavy metal ions from washing solutions by formation of soluble chelates; other benefits include inorganic film or scale prevention. Other suitable chelating agents for use herein are the commercial DEQUESTO series, and chelants from Monsanto, DuPont, and Nalco, Inc. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N- hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates , diethylenetriamine- pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenedia inetetrakis (methylenephosphonates) . Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1, 2-dihydroxy-3, 5- disulfobenzene .

A chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially (but not limited to) the [S,S] isomer as described in U.S. Patent 4,704,233. The trisodium salt is preferred though other forms, such as magnesium salts, may also be useful.

If utilized these chelating agents or transition- metal- selective sequestrants will preferably comprise from about 0.001% to about 10%, more preferably from about 0.05% to about 1% by weight of the bleaching compositions herein. Enzymes

Laundry wash compositions according to the invention may also contain one or more enzyme (s). Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and Upases usable for incorporation in detergent compositions. Preferred proteolytic enzymes (proteases) are, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.

Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention.

Examples of suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B. Subtilis B. licheniformis, such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist Brocades N.V.,

Delft, Holland, and Alcalase (Trade Mark) , as supplied by

Novo Industri A/S, Copenhagen, Denmark.

Particularly suitable is a protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark) . The preparation of these and analogous enzymes is described in GB-A- 1 243 785. Other commercial proteases are Kazusase (Trade Mark obtainable from Showa-Denko of Japan) , Optimase (Trade Mark from Miles Kali-Chemie, Hannover, West Germany) , and Superase (Trade Mark obtainable from Pfizer of U.S.A.).

Detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt% . However, any suitable physical form of enzyme may be used.

Other Optional Minor Ingredients

The compositions of the invention may contain alkali metal, preferably sodium carbonate, in order to increase detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%. However, compositions containing little or no sodium carbonate are also within the scope of the invention.

Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap) , a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate. One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.

Yet other materials that may be present in detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; dyes; coloured speckles; perfumes; foam controllers; fluorescers and decoupling polymers. This list is not intended to be exhaustive . Compositions used in present invention may for example be solid compositions such as powders or tablets, or non-solid compositions such as substantially aqueous or substantially non-aqueous liquids, gels or pastes. Optionally, liquid compositions may be provided in water soluble sachets. Non- solid, e.g. liquid, compositions may have different compositions from solid compositions and may for example comprise from 5% to 60%, preferably from 10% to 40% by weight of anionic surfactant (at least some of which will, of course, be aromaticalkyl sulphonic surfactant, from 2.5% to 60%, preferably from 5% to 35% by weight of nonionic surfactant and from 2% to 99% by weight of water. Optionally, liquid compositions may for example contain from 0.1% to 20%, preferably from 5% to 15% by weight of soap.

Non-solid, e.g. liquid, compositions may also (subject to any exclusions or other provisos expressed herein in the context of any aspect of the invention) , comprise one or more hydrotropes, especially when an isotropic composition is required. Such hydrotropes may, for example, be selected from arylsulphonates, e.g. benzene sulphonate, any of which is optionally independently substituted on the aryl ring or ring system by one or more Cι-₆ e.g. Cι_₄ alkyl groups, benzoic acid, salicylic acid, naphthoic acid, Cχ-₆, preferably Cι-₄ polyglucosides, mono-, di- and triethanolamine . Where any of these compounds may exist in acid or salt (whether organic or inorganic, such as sodium) , either may be used provided compatible with the remainder of the formulation. Exemplary laundry powders and liquids are detailed in the described embodiements .

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. liquid 2 and gas i.e. air 4 as a foam and/or mist. The dispenser 1 comprises a flexible container 6 for containing the liquid and includes a conduit 8 comprising a dip tube 8a having first and second end portions 11,12 the first end portion 11 terminating in an opening in the container 6 through which the mixture 2,4 is expelled from the container and the second open end portion 12 being close to the base 14 of said container 6, wherein the conduit 8 includes a third open end portion 13 which is located close to the top 16 of the container 6 and laterally inclined or opposed to the second open end portion 12.

With this arrangement a cost effective foam dispenser is provided which does not require complicated foaming elements in the flow path of the liquid. A mixture of fluids e.g liquid and air can be ejected from the container simply by squeezing the container. The provision of openings at the top and bottom of the container allow the device to function whether it is orientated upright (with central longitudinal axis upright, and top above base) or inverted (base above top) .

Further, as the second and third conduit openings 12,13 are laterally opposed the dispenser 1 also operates when it is tilted sideways.

The conduit is kinked or bent (at Y) generally in its upper section 18, so as to incline the second open end portion 12 approximately 20 degrees to the longitudinal axis of the container 6.

The third open end portion 13 extend from an upper section 18 (ie. Toward the top of the container when it is orientated upright) of the conduit 8, e.g at right angles. The conduit may have tee (T-shaped) configuration at the top, wherein the third open end portion branches off orthogonally from a main section of the conduit, preferably generally longitudinally aligned. The conduit comprises a dip tube in co-operation with the screw-on container closure 20 having dispensing opening 22. The container is flexible by means of a generally flexible body portion 24. 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.

In use, the dispenser 1 is opened by unscrewing and removing the closure 20 and then filled with laundry detergent liquid 2 (having formulation C and which may be mixed with water to dilute for improved foaming, depending on liquid viscosity) or laundry detergent powder (having formulation A or B) mixed with water to form a solution 2 to leave a head space of air 4. In the case of devices to be used with powder and water solutions, a filter may be used, attached to the first and second ends of the conduit to prevent dispensing of undissolved powder.

If used to pretreat an article prior to a main wash cycle in a machine, low foaming formulation B may be desirable, as the remainder of the mixed solution can be put into the wash with the fabric to be washed to avoid waste. The container is then simply compressed by squeezing the body portion 24 to expel the liquid/air mixture from the container. The container can be used in any orientation e.g. inverted, due to the conduit arrangement to e.g. pretreat difficult to reach areas of garments and other laundry items without need for a support surface or having to maintain the device upright.

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.

Powder Formulation A - hand washing high foaming formulation % Anionic surfactant AS or LAS 25

Nonionic 2

STPP 10

Na silicate 7

Na carbonate 7 Na sulfate 30

Ca carbonate 10

Bentonite clay/calcite 5

Enzymes*, FWAs,SCMC, perfume 2

Water balance

Powder Formulation B - (machine) low foaming formulation

Anionic surfactant AS or LAS 15

Nonionic 2 Soap 2

Zeolites 24

Na silicate 5

Na carbonate 13

Na sulfate 20 Na perborate (mono or tetrahydrate) 10 TAED or SNOBS 3 Polymers 1 Enzymes*, FWAs, 2 Perfume 2 Water balance

Laundry Liquid Formulation C

Liquid formulation

Percentages given are percentage by weight. Abbreviations :

ABS alkylbenzenesulfonate LAS linear alkylbenzenesulfonate STPP sodium tripolyphosphate SCMC sodium carboxymethylcellulose TAED : tetraacetylethylenediamine

SNOBS : sodium nonanoyloxybenzenesulphonates FWAs : fluoresent whitening agents

* Exemplary Enzmes include Protease, cellulase, amylase lipase and mixtures thereof.

Claims

Claims .

1. A laundry pretreatment or hand washing device, for dispensing a mixture of two or more fluids, e.g. liquid and gas (preferably air) as a foam and/or mist, the dispenser comprising a flexible container for a liquid including a conduit having first and second end portions, the first end portion terminating in an opening in the container through which the mixture 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.

2. A device according to claim 1 characterized in that it comprises a means for manually pressurising the container.

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

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

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

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

12.A method of pretreating or handwashing a fabric, by applying a laundry composition in the form of a foam or mist to the fabric using a device according to the any of claims 1-10.

13.A kit for pretreating or handwashing a fabric by applying a foam or mist laundry composition, the kit comprising a device according to any of claims 1-10 in combination with a liquid laundry composition, preferably together with instructions for use of the device.

14.A method of pretreating or handwashing a fabric, by applying a foam or mist laundry composition to the fabric using a device according to the first aspect, the method comprising an initial step of mixing a laundry powder composition with a solvent such as water in the device to form a laundry solution.

15.A kit for pretreating or handwashing a fabric, the kit comprising a device according to any of claims 1-10 in combination with a particulate laundry composition.

16.A kit according to claim 14 characterised in that the composition is a high foaming composition.