WO2009068496A1

WO2009068496A1 - Laundry system for sensitive fabrics

Info

Publication number: WO2009068496A1
Application number: PCT/EP2008/066061
Authority: WO
Inventors: Ronald Hage
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2007-11-27
Filing date: 2008-11-24
Publication date: 2009-06-04
Also published as: EP2220282A1; CN101874133A; EP2220282B1; ES2580131T3; CN101874133B; BRPI0819794A2; ZA201003053B; BRPI0819794B1

Abstract

A washing system for washing multiple fabric items including one or more sensitive fabric items in a washing machine with a detergent composition comprising 5-99.9% surfactant, the washing system comprising: an in situ hydrogen peroxide generating system (4); a pH regulating device (2) a tag communicating device which reads a laundering instruction contained in an electronic tag attached to any sensitive fabric item, - a controller in communication with the tag communicating device to control the laundry machine (9) to adjust the hydrogen peroxide generation system according to bleach and/or pH sensitivity of the fabric item.

Description

LAUNDRY SYSTEM FOR SENSITIVE FABRICS

This invention relates to a system for protecting sensitive fabric items in an automated washing process.

It is known to automatically control the settings of a laundry machine to properly launder various items. U.S. Pat. No. 5,388,299 to Lee discloses a washing control system having an information sensing part for reading the washing information. The items are manually put in front of the sensing part, one by one, before putting the clothes in the washing machine.

US 5715555 discloses a laundering method and system in which instructions contained in electronic tags are attached to material items. The instructions are all read while the material items are within a laundering machine.

An object of the present invention is to provide an improved laundering process for pH/bleach sensitive fabrics items.

Accordingly, in one aspect, the invention provides a washing system for washing multiple fabric items including one or more sensitive fabric items in a washing machine with a detergent composition comprising 5-99.9% surfactant, the washing system comprising:

an in situ hydrogen peroxide generating system;

a pH regulating device a tag communicating device which reads a laundering instruction contained in an electronic tag attached to any sensitive fabric item;

a controller in communication with the tag communicating device to control the laundry machine to adjust the hydrogen peroxide generation system according to bleach and/or pH sensitivity of the fabric item.

An advantage of the invention is the provision of an in-situ hydrogen peroxide generating system which can be controlled by the presence of tagged sensitive fabric items. This means the washing system can offer all the advantages of a bleaching system without adding this to the composition, whilst at the same time tagged sensitive items automatically modify the system to take account of such sensitivities. The mere presence of at least one tagged item triggers the system to modify pH/bleach levels. The user does not need to sort through the washing load before each wash to identify such sensitive items - they identify themselves automatically.

A significant advantage of the invention is that only a limited number of garments need to be tagged. So the rate of penetration will be higher. Further, the producer can add the tags without alerting the consumer that this is a particular sensitive garment. That information is now hidden on the tag. Another possible advantage is that it would also be possible to provide/sell labels to consumers, who can then label themselves if there are garments that are very sensitive (to their opinion) thereby retaining full control of the process.

All percentages are weight/weight percentages unless otherwise indicated. Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.

The electronic tag may be incorporated within an element of the fabric item, such as within a button, seam, lining, etc of an article of clothing. Alternatively the tag may be of a generic form which can be attached to any fabric item.

The tag may be detachable for temporary attachment to the fabric for example it may be attached prior to the washing process and then detached following the wash process. Advantageously, the tag may be attached to the sensitive fabric item and remain in place throughout washing, drying and use (when worn, if it is a garment) . The tag may even be attached to the sensitive fabric items during its manufacture, packaging. With a more permanent attachment, modification of the above washing process occurs automatically every time the item is included in a wash load.

The electronic tag may be programmed to store identification information for the fabric item identifying it as sensitive to the bleach and/or high pH. Preferably the sensitive fabric items having programmed electronic tags attached thereto and these items are then placed into a laundry machine within the laundry system.

Each laundry machine has a controller which controls its operation. A tag communicating device is embedded within the laundry machine and reads laundering instructions contained in the electronic tags while the fabric items are within the laundry machine. Once the tag has been read, the controller modifies the hydrogen peroxide generating system to reduce pH and/or bleach levels.

The invention is advantageous in that by modification of the pH, the bleach used in many known detergents will become inactivated. At low pH (7-8), there will be no peracid release and H2O2 does not be activated.

The H202-generation system modification may be preceded by an audible and/or visual alarm to notify the user/consumer. There may be an override facility in the event that the consumer does not want the washing process modified.

The in situ generation of hydrogen peroxide in a washing process combined with a pH regulating device enables the in situ generation of hydrogen peroxide in the washing machine and the formation of a bleaching component from hydrogen peroxide and e.g. a bleach precursor at high pH, while enabling washing of the fabric at reduced pH, without the need for added chemicals and allows for automatic modification by the tag system. The hydrogen peroxide generating device may comprise an electrochemical cell for the production of hydrogen peroxide from tap water and air, and being suitable for use in said machine when the machine is in operation. The pH regulating device may comprise an electrochemical cell comprising one or more cathode and anode electrodes for the production of acidic and alkaline water, whereby no added chemicals are needed when the device is in operation.

The detergent composition may comprise a bleach precursor. This may be added to the washing machine when in operation.

In today's fabric cleaning methods, bleaching is usually obtained by the formation of a peracid from bleach precursor and hydrogen peroxide in the detergent product.

Alternatively or additionally, bleaching can be obtained by the combination of hydrogen peroxide and a bleach catalyst, both present in the detergent product.

The term peracid or peracid bleach is defined herein as any peroxy acid as defined by general formula 1.

ROOH ₍i₎

A preferred group of peracids is the type of general formula 2.

0 I

R-C-OOH (2) Another preferred group of peracids is the type of general formula 3.

NH I

R-C-OOH ₍₃₎

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 a C=O(OOH) group or a quaternary ammonium group.

The corresponding persalts of the peracids of formulas 1, 2 and 3 are also included in the scope of the invention, in particular alkali and alkaline earth metal persalts, preferably sodium and potassium persalts. Also within the scope of this patent is the presence of the peracids in the deprotonated form in alkaline solutions.

In order to be effective for washing processes, the hydrogen peroxide containing water preferably has a hydrogen peroxide concentration of 0.1 to 15 mmol/1, more preferably 2 to 12 mmol/1, still more preferably 3 to 10 mmol/1 when diluted to the eventual washing liquor. The hydrogen peroxide containing water may be used directly in the washing process, or may be produced in a more concentrated form, stored inside the washing machine and diluted to the intended concentration when required. When produced in a more concentrated form the concentration is preferably between 1 and 500 mmol/1, more preferably between 50 and 200 mmol/1. When the hydrogen peroxide solution is stored inside the washing machine for a longer period of time, a pH of at or below 7 is preferred, more preferably at or below

6, still more preferably at or below 5, for the purpose of storage stability.

Without wishing to be bound to any particular theory, hydrogen peroxide is formed in the cell by the reaction of water with oxygen. Oxygen is converted to hydrogen peroxide or hydrogen peroxide ions at the cathode, generally as follows :

O₂ + 2H⁺ + 2e^~ → H₂O₂

at acidic conditions or

O₂ + H₂O + 2 e^~ → HO₂ ^" + OH^"

at alkaline conditions.

The hydrogen peroxide anions react with protons (H⁺) or water to form hydrogen peroxide. Protons are formed at the anode. The protons are formed by the following reaction:

2H₂O → O₂ + 4H⁺ + 4e^"

The hydrogen peroxide generation reaction does not require added chemicals, only water and air. The formation of hydrogen (H₂) is preferably avoided for safety reasons. When chlorine is present in the feed water, the hydrogen peroxide generating device may also produce a minor amount of chlorine dioxide. Chlorine dioxide is also a suitable bleaching agent.

The hydrogen peroxide generating cell is preferably an electrochemical cell comprising one or more cathode and anode electrodes that are chargeable by a DC potential. The electrodes may for instance be in the form of plates or rods, preferably plates. The cathode is preferably a gas diffusion electrode. The cathode preferably comprises a catalyst bound to the cathode surface. The cathode may comprise conductive materials such as carbon (e.g. graphite, carbon nano-tubes and other forms of carbon) , metals or conductive polymers or combinations thereof. Preferred metal catalysts are transition metals, transition metal oxides or transition metal macrocycles. Preferred transition metals include gold, mercury and oxide covered metals such as nickel and cobalt. Preferred metal oxides include nickel oxide, cobalt oxide and spinels. Preferred transition metal macrocycles include: CoTsPc (phthalocyanine tetra-sulfonate) cobalt) and CoTMPP (tetramethoxyphenyl porphyrine) . The anode is preferably a dimensionally stable anode, which is preferably constructed from conductive materials such as metals, carbon or conductive polymers or combinations thereof.

Some transition metals are not preferred, in particular platinum, platinum alloys, platinum family metals, palladium, and silver. Also not preferred are perovskites and pyrochlores, such as lead ruthenate transition metal oxides, and macrocyclic FeTsPc (iron tetrasulfonato phthalocyanine) . The dimensions and specification of the hydrogen peroxide generating cell are dependent on the intended use. If the hydrogen peroxide is stored in a buffer tank inside the washing machine, a slow system producing hydrogen peroxide e.g. overnight is suitable. However, when the hydrogen peroxide is to be produced during the washing process, a fast producing system is required. The hydrogen peroxide generating cell of the present invention preferably comprises a total cathode area of at least 10 cm², more preferably at least 50 cm², even more preferably at least 100 cm2 and at most 1000 cm², more preferably at most 500 cm², even more preferably at most 400 cm², still more preferably at most 300 cm²; the area being dependent on the demanded production rate. The surface area is preferably divided over between 1 and 25, more preferably between 1 and 10 cathode electrodes. The hydrogen peroxide production rate is typically between 0.1 and 2000 mmol/h. The actual rate is dependent on amongst others the surface area of the cathode and the type of operation. In a system with a hydrogen peroxide storage tank, a slow production rate is preferred, typically from 0.1 to 200 mmol/h, while in a system where the hydrogen peroxide is produced immediately during water intake, the production rate is preferably between 200 and 2000 mmol/h. The efficiency of this type of hydrogen peroxide generating cell is preferably from 50 to 100% at or just after the start of the hydrogen peroxide production, typically from 60 to 95%.

The total surface area of the anodes is between 10 and 100% of the total surface area of the cathodes. The electrodes are optionally separated by a semi-permeable membrane .

As an alternative to buffers, acids and bases, the pH of a fabric washing liquor is adjusted by the use of an pH regulatory device which may be electrochemical and may be as described in EP1841697.

As indicated above, the bleach peracid formation reaction from hydrogen peroxide and bleach precursor is preferably carried out at high pH, whereas the bleach reaction is more efficient at lower pH. Typically, the pH for the peracid formation reaction is above 9, preferably above 9.5. The pH is preferably at or below 13, more preferably at or below 12, still more preferably at or below 11, ideally at or below 10.5. The bleaching reaction using the peracid on the other hand is preferably carried out at a pH at or below 9.5, more preferably at or below 9, still more preferably at or below 8.5. The pH of the bleach reaction is generally above 7, preferably above 7.5, ideally above 8.

Buffers, salts, acids and bases to adjust the pH of the washing liquor form other bulky ingredients in today' s detergent products. However, the application of a pH regulator enables adjustment of the pH in the washing liquor without added chemicals, which is of great convenience to the consumer.

The pH regulator of the invention is a device that divides a feed water stream in an acidic and an alkaline stream for instance using an electrolysis cell. The pH regulator may be fed with tap water or softened water. Part of the alkaline stream may be used in the bleach formation reaction. Furthermore, part of the acidic and alkaline stream may be used in the washing process. The pH of the acidic water is preferably between 1 and 6, more preferably between 1 and 3. The pH of the alkaline stream is typically between 9 and 13, preferably between 10 and 12. The volume ratio between produced alkaline water and acidic water for the application in the device of the invention is preferably between 1:20 and 20:1, more preferably between 1:10 and 10:1.

The acidic water from the pH regulator may also be used to regenerate the electrochemical cells of the hydrogen peroxide generation device.

In short, the pH regulator may be used for the production of acidic water and alkaline water. The acidic water may be used for the regeneration of electrochemical cells and for use in the washing process. The alkaline water may be used in the bleach formation reaction and the washing process. This improves the bleach performance and the robustness of the electrochemical cells, reduces the required amount of water for regeneration of the electrochemical cells and does not required the addition of chemicals.

The pH regulator is an electrochemical cell comprising one or more cathode and anode electrodes. The electrodes may for instance be in the form of plates or rods, preferably plates. The plates and the conductive surface on the plates may be constructed from conductive materials such as metals, carbon or conductive polymers or combinations thereof.

The pH regulator preferably has a total production rate of between 1 and 500 1/hr, more preferably between 2 and 300 1/hr of combined alkaline and acidic water.

In order to be effective for fabric washing processes, e.g. those where no builder is applied, the water hardness in the water that is added to the washing process is preferably less than 5°FH, preferably less than 2°FH and more preferably less than I⁰FH. The reduction of the water hardness is desirable in order to prevent the deposition of calcium soaps in the soil, to prevent the precipitation of anionic surfactants, to maximise colloid stability and to reduce the calcium - soil - substrate interaction and soil - soil interaction and hence to improve soil removal.

A further advantage of the softened water produced using the water softening device of the invention is that hydrogen peroxide is more stable in softened water than in e.g. tap water .

Most common detergent products comprise builder material to sequester hardness ions from tap water. Builder material is usually present in the detergent composition in a concentration of 15 to 80%. Commonly known builders are water soluble phosphate salts, such as sodium tripolyphosphate (stpp) or zeolites. Phosphates are assumed to cause eutrophication of surface water, and zeolites cause insoluble matter in household waste streams. Due to the nature of builder material and the amount in which it is present, it has become more and more objected to in detergent products, especially laundry detergent products.

As an alternative to the use of builder material, different water softening devices are known in the art. These devices all produce soft water by sequestering hardness-ions like Ca²⁺ and Mg²⁺ from tap water, for instance by ion-exchange. In WO-01/30229, a system is described, which utilises a built-in ion-exchange system to remove calcium and magnesium ions from the water supply. However, the ion-exchange material requires regular regeneration. For application in a common type of automatic washing machine, vast amounts of e.g. salt solution would be required for the regeneration of the ion-exchanger, thereby undoing the effect of the reduction of builder chemicals in the detergent. Further disadvantages of ion-exchange are the limited life-time of the ion-exchange resin and/or the required volume of resin for the production of the amount of soft water required in a washing machine.

Another water softening method is electronic deionisation (EDI), which combines ion exchange and electrodialysis, as described in co-pending application EP 04076353.4. Although this method does not require regeneration chemicals, the other disadvantages relating to the use of the ion-exchange resin remain as indicated above. Furthermore, EDI is a complicated technology, that is difficult to operate in a robust manner over a long time period, as required in house- hold appliances. Yet another water softening method is capacitive deionisation, using a flow through capacitor (FTC) as amongst others disclosed in co-pending application EP 05075218.7. Said method comprises the use of an electrically regenerable electrochemical cell for capacitive deionization and electrochemical purification and regeneration of the electrodes including two end plates, one at each end of the cell. By polarising the cell, ions are removed from the electrolyte and are held in the electric double layers at the electrodes. The cell can be

(partially) regenerated electrically to desorb such previously removed ions. The regeneration could be carried out without added chemical substances.

The flow through capacitor (FTC) comprises plates having a conductive surface. The plates are chargeable in response to an applied DC potential. The plates are separated from each other by non-conductive spacers. The plates and the conductive surface on the plates may be constructed from conductive materials such as metals, carbon or conductive polymers or combinations thereof, as also described in WO01/66217 or WO02/86195, by Andelman.

Another major ingredient in conventional granular detergent products are pH modifying chemicals. For the purpose of the present invention the term pH modifying chemicals is meant to describe ingredients that affect the pH either by increasing, decreasing or maintaining the pH at a certain level. Typical examples include, but are not limited to, salts like acetates, borates, carbonates, (di) silicates, acids like boric acid, phosphoric acid, sulfuric acid, organic acids like citric acid, inorganic bases and organic bases .

In conventional detergent products builder and pH modifying chemicals may account up to 70 wt . % of the composition. It is to be noted that for the purpose of the present invention surfactants - even though some surfactants may have some pH effect - are not considered to be a pH modifying chemical.

The LEIP (Low Environmental product) according to one preferred embodiment of the invention is substantially free of pH modifying chemicals. Substantially free of pH modifying chemicals is meant to describe products comprising at most 5 wt . % of pH modifying chemicals. Preferably the LEIP comprises 0 to 3 wt.%, more preferably 0 to 1 wt.%, most preferably 0 wt.% of pH modifying chemicals by weight f the total LEIP composition.

Conventional liquid detergents products often contain acidic components, e.g. anionic surfactants such as LAS (linear alkylbenzene sulphonate) . To neutralize these acids, the composition may optionally comprise neutralisers . These neutralisers are preferably organic or inorganic bases. The bases are preferably selected from the group consisting of NaOH, KOH, mono-ethanol amine (MEA) and tri-ethanol amine (TEA) . The neutralisers are present in a concentration of 50 %mol to 200 %mol of the molar concentration of the components that require neutralisation.

It is desirable to equip washing machines with one or more detergent product containers so that the detergent product may be dosed automatically. The LEIP may be dosed from a single container. Alternatively, the ingredients making up the LEIP may be dosed from separate containers as described in EP-A-0419036. Thus in one preferred embodiment at least one ingredient from the LEIP is dosed automatically. One advantage of a LEIP may be that the reduced number and/or amount of ingredients enables a much smaller volume of detergent product. In practice this would mean that the consumer does not need to refill the containers as often or that the containers may be smaller, therefore making an automatic dosage system more feasible when using the device of the invention. When an automatic dosage system is applied, it is preferred that the bleach precursor or activator (catalyst) is stored separately from the other components of the detergent product.

Although hydrogen peroxide (H2O2) is a good bleach, it only gives a slow oxidation process due to slow kinetics and thereby a slow bleaching process. For certain fabric it is preferred to have a stronger oxidant that is active at low temperatures and concentration.

Commonly known methods to improve bleaching are the use of a bleaching catalyst to improve the activity of peroxide, and/or the use of a peracid instead of peroxide; said peracid is preferably formed in situ from hydrogen peroxide and a bleach precursor.

A bleach generating process may take place either in the washing machine drum or in an in-line or off-line mixing device. When a mixing device is used, the mixing device is selected from the group consisting of a static mixer, dynamic mixer, stirred tank or storage tank or a combination thereof .

A peracid may be formed by perhydrolysis of an acidic bleach precursor by the following reaction:

0 0

^"0OH R—C—X ->R—C—00^" +HX

Different types of precursors, such as e.g. cationic nitriles, have different reaction equations, but are also included in the scope of the present invention.

The Low Environmental Impact Product (LEIP) composition used in the method of the present invention may include one or more bleach precursors.

Organic peroxyacids precursors may be suitable as the peroxy bleaching compound. After perhydrolysis, 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 - I i

group or a quaternary ammonium group.

Typical monoperoxy acids precursors 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; and

(iii) 6-octylamino-6-oxo-peroxyhexanoic acid.

Typical diperoxyacid precursors 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. 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 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.

The peracid forming reaction of peroxide and bleach precursor from the detergent may be obtained in the washing liquor inside the washing machine drum, or in an off-line mixing vessel. An advantage of the latter is that the peracid may be formed in a concentrated form at the desired pH and may be diluted with acidic water into the washing machine drum, thereby reducing the pH for the washing process resulting in better bleaching activity. The low environmental impact detergent product (LEIP) of the present invention preferably comprises bleach precursor in a peroxide : precursor ratio of between 1:2 and 25:1, more preferably between 2:1 and 10:1 on a molar basis.

The peracid forming reaction of peroxide and bleach precursor from the detergent may be obtained in the washing liquor inside the washing machine drum, or in an off-line mixing vessel. An advantage of the latter is that the peracid may be formed in a concentrated form at the desired pH and may be diluted with acidic water into the washing machine drum, thereby reducing the pH for the washing process resulting in better bleaching activity.

The low environmental impact detergent product (LEIP) of the present invention preferably comprises bleach precursor in a peroxide : precursor ratio of between 1:2 and 25:1, more preferably between 2:1 and 10:1 on a molar basis.

Another way to improve the bleaching performance of hydrogen peroxide, to enable the use of lower temperatures and/or to use less peroxide is the use of a bleach catalyst.

A bleach catalyst is defined herein as any substance improving the activity of peroxide by the reduction of the activation energy for the bleaching reaction, while not taking part (i.e. being consumed) in the reaction. The use of bleaching catalysts for stain removal has been developed over recent years and may be used in the present invention. Examples of transition metal catalysts that may be used are found, for example, in: WO-01/48298, WO-00/60045, WO-02/48301, WO-00/29537 and WO-00/12667. The catalyst may alternatively be provided as the free ligand that forms a complex in situ with transition metals present in the water. In general, the catalyst contains an at least partially covalently bonded transition metal, and bonded thereto at least one ligand.

In general, transition-metal bleach catalysts herein comprise a transition metal selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II),

Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV) . Preferred transition-metals in the instant transition-metal bleach catalyst include manganese, iron and copper, preferably Mn(II) , Mn(III), Mn(IV), Fe(II), Fe(III), Cu(I), Cu (II) , Cu (III) .

In general, as used herein, a "ligand" is any moiety capable of direct covalent bonding to a metal ion. Ligands can be charged or neutral. The ligands may include simple monovalent donors, such as chloride, or simple amines which form a single co-ordinate bond and a single point of attachment to a metal; to oxygen or ethylene, which can form a three-membered ring with a metal and thus can be said to have two potential points of attachment, to larger moieties such as ethylenediamine or aza macrocycles, which form up to the maximum number of single bonds to one or more metals that are allowed by the available sites on the metal and the number of lone pairs or alternate bonding sites of the free ligand. Numerous ligands can form bonds other than simple donor bonds, and can have multiple points of attachment.

Alternatively, also organic bleach catalysts can be employed. In general organic bleach catalysts have activated imines that upon reaction with peracids yield an oxaziridine. A non-limiting, preferred compound includes, 3, 4-dihydroisoquinolinium salt, as exemplified in WO/9513352. Other organic bleach catalysts can be found in EP0728181, EP0728182, EP0728183, EP0775192, US4,678,792, US 5,045,223, US 5,047,163, US 5,360,568, US 5,360,569, US 5,370,826, US 5,442,066, US 5,478,357, US 5,550,256, US 5,653,910, US 5, 710,116, US 5,760,222, US 5,785,886, US 5,952,282, US 6,042,744, US2007173428 , WO95/13351, WO95/13353, WO97/10323, WO98/16614, WO00/42151, WO00/42156, WO01/16110, WO01/16263, WO01/16273, WO01/16274, WO01/16275, WO01/16276, WO01/16277, WO07/087258.

The low environmental impact detergent product (LEIP) of the present invention preferably comprises bleach catalyst in a peroxide : catalyst ratio of between 100:1 and 100.000:1 more preferably between 500:1 and 5000:1 on a molar basis.

Compositions according to the invention contain one or more surface-active compounds (surfactants) 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 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 aromaticalkyl sulphonic surfactant preferably constitutes from 0.5% to 99.9%, preferably from 1% to 80%, more preferably from 10% to 60%, especially from 15% to 50%, more especially from 25% to 45% by weight of the total anionic surfactant content of the composition.

A composition according to the present invention 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 which is additional to the aromaticalkyl surfactant, 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.

If a water softening device is incorporated, the Ca- sensitivity of surfactants is less critical. 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 20⁰FH (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 Cs-Ci₅ primary alkyl sulphates; and dialkyl sulphosuccinates .

Sodium salts are generally preferred.

Optionally, a soap may also be present. Suitable soaps include those having a chain length ranging from C12 to C20, 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 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-Ciε, more preferably C10-C15.

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 ^orr 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 C]_g. 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 RiR₂R₃R₄N⁺ 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 Ri is a C8-C22 alkyl group, preferably a Cs-Cio or C12-C14 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) . The compositions of the invention may also contain one or more detergency builders but, if the water softening device is included, at lower levels than with conventional systems. The total amount of detergency builder in the compositions will typically range from 1% to 50 wt%, preferably from 2% to 30 wt%, more preferably from 4% to 20% 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-I 437 950; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB-A-I 473 201, amorphous aluminosilicates as disclosed in GB-A-I 473 202 and mixed crystalline/amorphous aluminosilicates as disclosed in GB-A-I 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 Na₂O. Al₂O₃. 0.8-6 SiO₂.

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 SiO₂ 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-I 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.

Where compositions are bleach containing or bleach generating, they may advantageously also contain one or more heavy metal chelating agents. This reduces damage by the bleach. 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 ethylenediaminetetrakis (methylenephosphonates) . Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See

U.S. Patent 3,812,044. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2- dihydroxy-3, 5-disulfobenzene .

A chelator for use herein is ethylenediamine disuccinate

("EDDS"), especially (but not limited to) the [S, S] isomer as described in U.S. Patent 4,704,233. 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.

Laundry wash compositions according to the invention may also contain one or more enzyme (s) . Such enzymes may provide cleaning performance, fabric care and/or sanitation benefits. Suitable enzymes include the proteases, amylases, cellulases, lipases, oxidases/oxido reductases, transferases, hydrolases, peroxidases, lyases isomerases and ligases, usable for incorporation in detergent compositions.

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 10 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, 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 a-amylase, Q-amylase, glucoamylase, isoamylase, cellulase, endo-1, 3 (4) -glucanase, xylanase, dextranase, polygalacturonase (pectinase) , lysozyme, invertase, hyaluronidase, pullulanase, neopullulanase, chitinase, arabinosidase, exocellobiohydrolase, hexosaminidase, mycodextranase, endo- 1, 4-mannanase (hemicellulase) , xyloglucanase, endo- galactosidase (keratanase) , mannanase and other saccharide gum degrading enzymes as described in WO-A-99/09127.

Preferred among them are a-amylase and cellulasei 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 endotransqlycosylase as described in WO-A-98/38288. Examples of lyases are hyaluronate lyase, pectate lyase, lipex, 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.

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. Suitable and preferred enzymes applicable can be found in WO 03/ 104378.

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 of the present invention may for example be provided as 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, eg 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, eg 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, eg benzene sulphonate, any of which is optionally independently substituted on the aryl ring or ring system by one or more Ci-6 eg Ci_₄ alkyl groups, benzoic acid, salicylic acid, naphthoic acid, Ci-6, preferably Ci_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.

Preparation of the Compositions

The compositions of the invention may be prepared by any suitable process.

The choice of processing route may be in part dictated by the stability or heat-sensitivity of the surfactants involved, and the form in which they are available.

For granular products, ingredients such as enzymes, bleach ingredients, sequestrants, polymers and perfumes which are traditionally added separately (e.g. enzymes postdosed as granules, perfumes sprayed on) may be added after the processing steps outlined below. Suitable processes include:

(1) drum drying of principal ingredients, optionally followed by granulation or postdosing of additional ingredients;

(2) non-tower granulation of all ingredients in a highspeed mixer/granulator, for example, a Fukae (Trade Mark) FS series mixer, preferably with at least one surfactant in paste form so that the water in the surfactant paste can act as a binder;

(3) non-tower granulation in a high speed/moderate speed granulator combination, thin film flash drier/evaporator or fluid bed granulator.

Description of Non-limiting Embodiments of the Invention

The invention will be more clearly understood from the following description of some of the embodiments thereof, given by way of example only, with reference to the accompanying drawings in which :-

Figure 1 shows a flow diagram of a preferred embodiment of an electrolysis cell as H2O2 generating device;

Figures 2a -2b show views of the hydrogen peroxide generating cell and figure 2c shows a pH regulating device;

Figure 3 is a block diagram of an embodiment of a smart laundry system in accordance with the present invention; Figure 4 is a schematic representation of a pH/bleach sensitive fabric item (coat) incorporating a tag in a button;

Figure 5 is a block diagram of an embodiment of an electronic tag for use in embodiments of the present invention;

Figure 6 is a block diagram of an embodiment of a tag communicating device for use in embodiments of the present invention;

Figure 7 is a flow chart of a method of communicating with a plurality of electronic tags;

Figure 8 is a flow chart of a method for an electronic tag to communicate with a tag communicating device; and

Figure 9 is a block diagram of an embodiment of a tag programming device for use in embodiments of the present invention .

In figure 1, tap water 1 from the main is fed to the pH-modifier cell 2, where the water is separated into acidic and alkaline water. The acidic water is stored in a storage vessel 6 and the alkaline water in storage vessel 5. The alkaline water from vessel 5 is fed into the hydrogen peroxide generating cell 4. The hydrogen peroxide containing water of high pH is then fed to a bleach generation vessel 7, where the hydrogen peroxide is reacted with the bleach precursor 8a to form peracid. The solution containing peracid is subsequently fed to the washing machine 9 from bleach generation vessel 7. The hydrogen peroxide may react with the peracid precursor in the generation vessel. The generation vessel may also contain a bleach catalyst so a mixture of bleach catalyst + H2O2 is formed. Furthermore, the hydrogen peroxide may be fed directly into the washing machine containing LEIP. This LEIP formulation may contain no peracid bleach precursor nor catalyst, or it may contain a peracid bleach precursor, or it may contain a bleach catalysts or it may contain both.

Part of the alkaline and/or acidic water from respective vessels 5 and 6 may be added directly to the washing machine 9. The remaining detergent components 8b from the detergent product are fed to the washing machine directly.

Alternatively the tap water from the main may first be fed into a water softener FTC-cell 3. The softened water is then fed into the pH modifier cell 2 and processed as explained above. Regeneration waste water (dotted streams) from all electrochemical cells is drained 10 as well as the washing machine waste water. The cells are e.g. regenerated with acidic water from vessel 6; these streams are not shown in the drawings to maintain clarity.

Figure 2a shows the hydrogen peroxide cell 4 from the outside, and figure 2b shows the working of the components in an exploded view of the cell. The cell 4 comprises a gas diffusion cathode 17 and a dimensionally stable anode 19 separated by a membrane 18, which together form a chamber. The reactants, i.e. oxygen from air is brought into the chamber through inlet 11 and the air can leave the chamber from outlet 12 when the device is in operation. Catholyte, i.e. water, is fed through inlet 13 and hydrogen peroxide containing water is removed from outlet 14 when the device is in operation, thereby producing hydrogen peroxide.

Similarly, the anolyte is fed and removed from ports 15 and 16; when the device is in operation water is fed to the cell and water dissolved protons are withdrawn from the anode.

Figure 2c shows the working of an electrolysis cell as pH modifier. In figure 2c an electrolysis cell, suitable as pH modifier is schematically depicted. Water 123 is fed to the cell. Inside the cell of figure 2c are two cathodes 125 and one anode 124 separated by a non-conductive spacer 126. When in operation, alkaline water 110 is produced at the cathodes and acidic water 115 at the anode.

Electronic tags according to the invention are attached to a plurality of items some of which are bleach sensitive, some of which are pH sensitive, and some of which are both pH and bleach sensitive. The identifying information on the tag is read while the items are within the laundry machine. As a result, the pH/bleach modifying instructions can be obtained whilst items are loaded into the laundry machine. Hence, users of the invention are not required to expend additional effort sort through laundry to find sensitive items and wash separately from other non or less sensitive items.

Figure 3 is a block diagram of a preferred embodiment of a laundry system in accordance with the present invention. The laundry system is utilized to launder a plurality of both bleach/pH-sensitive items 20 and non-sensitive items 21.

Each of the bleach/pH-sensitive fabric items 20 has an electronic tag 22 attached thereto. The electronic tag 22 is permanently incorporated within an element of one item 20, (here a button 23 - shown in figure 4. Other bleach/pH- sensitive fabric items carry a temporary generic electronic tag 22 (not shown) . Further bleach/pH-sensitive fabric items are included in the wash load, but may not carry any tag.

The electronic tags used in this example are pre-programmed with the various information. However, they may be also programmed by a tag programming device 24. The tag programming device 24 is operative to read and/or write information stored within the electronic tag 22, such as identification information, and also further laundering instructions, and a laundering count for the material item 20. The tag programming device 24 can be utilized to identify the material items 20 and/or locate each item 20 within the laundry system. The tags may identify the fabric items as pH sensitive and/or bleach sensitive or both. If fabrics suffer dye fading/damage due to bleach, then the pH need not be adjusted but the H2O2 generation will need adjusting/stopping. Certain woollen items may be tagged as pH-sensitive (so that pH is maintained low) .

Each laundry machine has a controller which controls its operation. In the embodiment of Figure 3, the washing machine 26 is controlled by a controller 32 which provides a number of controls having a number of control positions or settings including those relating to the in-situ hydrogen peroxide generating system.

A tag communicating device 38 is embedded within the washing machine and communicates information with the electronic tags 22 while the washing load including the bleach/pH- sensitive fabric items 20 are within the laundry machine. The presence of only one tag 22 is sufficient to communicate information to the controller to adjust the hydrogen peroxide generation system. The system is adjusted according to bleach and/or pH sensitivity. The H2O2 generation may be halted altogether and/or the pH lowered according to the tag 22 attached. If both pH and bleach sensitivity is identified then both are adjusted/restricted. In further embodiments, the tag communicating device/ controller may include a visual display of identified information to allow user control e.g. override of this protection system.

Figure 5 is a schematic of an embodiment of an electronic tag 22 contained in the button 23 of figure 4, which can be used in embodiments of the present invention. The electronic tag 22 includes a memory 70 which stores information for a pH/bleach-sensitive fabric item. The information includes pH-sensitivity and H2O2-sensitivity information. Preferably, the memory 70 is non-volatile so that the stored information is maintained without the application of power thereto. A processor 72 executes a series of programmed steps to communicate information between the memory 70 and the tag communicating device in the laundry system. The processor 72 can be in the form of a microprocessor, a custom integrated circuit, a programmable logic array, or an application-specific integrated circuit, for example. A receiver 74 is included to receive information transmitted from the tag communicating device. A transmitter 76 is provided to transmit information to the tag communicating device. Preferably, the receiver 74 and the transmitter 76 communicate the information using radio frequency signals. Both the receiver 74 and the transmitter 76 are coupled to the processor 72 to communicate information with the memory 70. As a result, the transmitter 76 is operatively associated with the memory 70 to transmit the information for external reading.

The circuits within the electronic tag are powered by an electromagnetic power receiver 78. The electromagnetic power receiver 78 receives electromagnetic power transmitted thereto, and converts the electromagnetic power to a DC voltage to power circuits within the electronic tag (namely, the memory 70, the processor 72, the receiver 74, and the transmitter 76) .

The electronic tag is hermetically sealed relative to water vapour, high temperature, and laundering solutions. The electronic tag is also relatively small and flat so as to be unobtrusive when permanently attached an item. In accordance with these preferred specifications, the electronic tag can be constructed in accordance with a method of producing an environmentally sealed transponder disclosed in US5420757.

Figure 6 is a schematic diagram of an embodiment of a tag communicating device for use in embodiments of the present invention. The tag communicating device includes a processor 80 which executes a series of programmed steps to communicate information with the electronic tags 22. As with the processor 72, the processor 80 can be in the form of a microprocessor, a custom integrated circuit, a programmable logic array, or an application-specific integrated circuit. The processor 80 communicates with a memory 81 for storing information communicated with the electronic tags 22.

The tag communicating device includes an electromagnetic power transmitter 82 for transmitting an electromagnetic power signal to supply power to the circuits in the electronic tags 22. The electromagnetic power transmitter 82 is activated and deactivated in response to commands provided by the processor 80. A transmitter 84 transmits information generated by the processor 80 and/or stored in the memory 81 for reception by the receiver 74 in the electronic tag. A receiver 86 receives information transmitted by the transmitter 76 in the electronic tag.

The receiver 86 communicates the received information to the processor 80. The processor 80 processes the received information to provide a signal either for setting or verifying the controls on the controller, or for alerting a user of an incorrect setting. Figure 7 is a flow chart of a method of communicating with a plurality of electronic tags. This method can be utilized by a tag communicating device for reading a plurality of laundering instructions stored in a plurality of electronic tags contained within a laundry machine. It should be noted that in the washing processes within the scope of this invention, a plurality of garments contain tags to communicate the presence of pH and/or bleach sensitive garments may be present, a single pH sensitive garment, a single bleach sensitive garment, a single pH and bleach sensitive garment, or the may be no sensitive garments present. If no sensitive garment is present, then the following scheme will not be followed. If at least one garment is present with a label alerting for pH sensitivity and/or bleach sensitivity, then the following sequence will apply. The method begins with a step of transmitting a sequence signal 130, to the electronic tags 22 using the transmitter 84 in the tag communicating device. The sequence signal is utilized by each of the electronic tags to determine its position in a sequence for communicating with the tag communicating device. In a preferred embodiment, the sequence signal includes a representation of a sequence length which is utilized by each electronic tag to randomly determine its position within the sequence. The sequence length may be selected in dependence upon the capacity of the laundry machine. As indicated by block 132, a step of initializing a counter is performed. The counter is utilized to indicate the current position in the communication sequence. The counter is typically initialized using the processor 80 and stored within either the processor 80 or the memory 81. Next, the transmitter 84 in the tag communicating device transmits a request-for- information signal, as indicated by block 134. The request- for-information signal requests the electronic tag having the current position in the sequence to transmit information to the tag communicating device. As indicated by block 136, the receiver 86 in the tag communicating device listens for a tag signal from one or more of the electronic tags. The processor 80 then checks if a tag signal is received from a single electronic tag, as indicated by block 138. If a tag signal is received from a single electronic tag, then information contained within the tag signal is stored in the memory 81 of the tag communicating device, as indicated by block 140. To acknowledge the reception of the tag signal, the transmitter 84 sends an acknowledge signal as indicated by block 142.

It is noted that a tag signal is not received from a single electronic tag if no tag signals were transmitted or if two or more tag signals were transmitted. If two or more tag signals were transmitted, a collision occurs whereby information may not be extractable from each tag signal. Upon sending the acknowledge signal in block 142, or if a tag signal is not received from a single electronic tag in block 138, a step of determining if the counter has attained a predetermined threshold is performed, as indicated by block 144. The predetermined threshold is indicative of a predetermined sequence length, which is preferably contained within the sequence signal transmitted in the step indicated by block 130. If the counter has not attained the predetermined threshold, then a step of incrementing the counter is performed, as indicated by block 146. Thereafter, flow of the method is directed back to block 134 to transmit another request signal to communicate with another electronic tag.

If the counter has attained the predetermined threshold, then steps are performed to determine whether information has been successfully received and stored from all of the electronic tags. First, a step of transmitting a request- for-unacknowledged-tags signal is performed by the transmitter 84, as indicated by block 148. The receiver 86 then listens for signals produced by any unacknowledged tags, as indicated by block 150. As indicated by block 152, the processor 80 performs a step of determining if a signal is received from an unacknowledged tag.

If a signal is received from an unacknowledged tag, then flow of the method is directed back to block 130 wherein a new sequence signal is transmitted. Preferably, the new sequence signal includes a representation of a shortened sequence length to communicate with the unacknowledged tags. If no signals are received from unacknowledged tags, then the method of communicating with the electronic tags is completed.

It should be noted that in the washing processes within the scope of this invention, a plurality of garments contain tags to communicate the presence of pH and/or bleach sensitive garments may be present, a single pH sensitive garment, a single bleach sensitive garment, a single pH and bleach sensitive garment, or the may be no sensitive garments present. If no sensitive garment is present, then the following scheme will not be followed. If at least one garment .

Figure 8 is a flow chart of an embodiment of a method for an electronic tag to communicate with a tag communicating device. As indicated by block 160, a step of receiving the sequence signal transmitted by the tag communicating device is performed by the receiver 74 in the electronic tag. Preferably, the sequence signal includes a representation of an integer indicative of the predetermined sequence length. As indicated by block 162, the processor 72 in the electronic tag generates a random number to determine its position in the communication sequence. The random number is discrete and generated based upon a predetermined probability distribution (i.e. probability mass function or probability function) . Preferably, the probability distribution is dependent upon the representation of the predetermined sequence length contained within the sequence signal. In one embodiment, the random number is representative of an integer from one to the sequence length. The random number is generated based upon a discrete uniform distribution wherein each of the integers from one to the sequence length are equally likely to be selected. The receiver 74 in the electronic tag listens for any signals transmitted by the tag communication device, as indicated by block 164. As indicated by block 166, the processor 72 determines whether a request-for-information signal is received for the electronic tag based on the random number. If a request-for-information signal is received for the electronic tag, then a step of transmitting an information signal is performed as indicated by block 168.

After transmitting the information signal, the receiver 74 listens for an acknowledge signal from the tag communicating device, as indicated by the step of block 170. If an acknowledge signal is received in block 172, then the information signal was successfully received by the tag communicating device, and execution of the method is completed. If an acknowledge signal is not received, or equivalently if an error signal is received, then flow of the method is directed back to block 164. It is noted that a request-for-information signal is not received for the electronic tag in block 166 if a request-for-information signal is transmitted by the tag communicating device for another electronic tag, or if a request-for-unacknowledged- tags signal is transmitted.

If a request-for-information signal is not received for the electronic tag in block 166, then a step of determining whether a request-for-unacknowledged-tags signal is received is performed by block 174. If a request-for-unacknowledged- tags signal is not received, then flow of the method is directed back to block 164. If a request-for- unacknowledged-tags signal is received, then a step of sending a signal indicating an unacknowledged tag is performed, as indicated by block 176. Flow of the method is then directed back to block 160 to receive another sequence signal . Figure 9 is a block diagram of an embodiment of a tag programming device for use in embodiments of the present invention. The tag programming device includes a processor 180 which executes a series of programmed steps to communicate information with the electronic tags 22. The processor 180 can be in the form of a microprocessor, a custom integrated circuit, a programmable logic array, or an application-specific integrated circuit. The processor 180 communicates with a memory 182 for storing information communicated with the electronic tags 22.

An electromagnetic power transmitter 184 is provided to transmit an electromagnetic power signal to supply power to the circuits in an electronic tag. The electromagnetic power transmitter 184 is activated and deactivated in response to commands provided by the processor 180. An input device 186 is provided in communication with the processor 180. The input device 186 can take the form of one or more buttons, a keyboard, a touchpad, or a touchscreen, which allows information and/or instructions to be inputted to the tag programming device by a user. The processor 180 processes the information and instructions to form signals which are applied to a transmitter 188. The transmitter 188 transmits the signals for reception by the receiver 74 in the electronic tag. The signals can be indicative of a request for information stored in the electronic tag, such as a request for identification information for the material item or a request of the current value of the count. The signals can also be indicative of information which is to be stored in the electronic tag, such as identification information, laundering instructions, and water processing instructions. A receiver 190 receives information transmitted by the transmitter 76 in the electronic tag. The receiver 190 communicates the received information to the processor 180. The processor 180 processes the received information to provide a signal for driving a display device 192. The display device 192 provides means for displaying information requested by a user, such as identification information and the current value of the count. It is preferred that the display device 192 be capable of displaying numeric or alphanumeric information. As such, the display device 192 can be based on light-emitting diode or liquid crystal technologies .

It will be apparent to those skilled in the art that the disclosed invention may be modified in numerous ways and may assume many embodiments other than the preferred form specifically set out and described above.

Claims

1. A washing system for washing multiple fabric items including one or more sensitive fabric items in a washing machine with a detergent composition comprising 5-99.9% surfactant, the washing system comprising:

an in situ hydrogen peroxide generating system;

a pH regulating device

a tag communicating device which reads a laundering instruction contained in an electronic tag attached to any sensitive fabric item;

2. A washing system according to claim 1 wherein the hydrogen peroxide generating system comprises an electrochemical cell for the production of hydrogen peroxide from tap water and air.

3. A washing system according to any preceding claim wherein the pH regulating device comprises an electrochemical cell comprising one or more cathode and anode electrodes for the production of acidic and alkaline water, whereby no added chemicals are needed when the device is in operation.

4. A washing system according to any preceding claim wherein the detergent composition comprises a bleach precursor .

5. A washing system according to any preceding claim wherein the detergent composition comprises a bleach catalyst.

6. A washing system according to any preceding claim wherein the detergent composition comprises a bleach precursor and a bleach catalyst.

7. A washing system according to any preceding claim further comprising a water softener.

8. A washing system according to any preceding claim wherein the water softener comprises an ion exchanger and/or electrodialysis and/or capacitive deionisation and /or flow through capacitance.

9. A washing system according to any preceding claim wherein the detergent composition is substantially free of pH modifying components.

10. A washing system according to any preceding claim wherein the detergent composition is substantially free of builder.

11. A washing system according to any preceding claim wherein the detergent composition is substantially free of hydrogen peroxide, sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate, or a hydrogen peroxide generating oxidase enzyme.