ES2580131T3 - Sensitive tissue washing system - Google Patents

Abstract

A washing system for washing multiple textile articles including one or more sensitive textile articles in a washing machine (26) with a detergent composition comprising 5-99.9% of surfactant characterized in that the washing system comprises a system ( 4) hydrogen peroxide generation in situ; a pH regulation device (2); a tag communication device that reads a washing instruction contained in an electronic tag (22) attached to any sensitive textile article; a controller (32) in communication with the communication device (38) with labels for controlling the washing machine (26) to adjust the hydrogen peroxide generation system according to the sensitivity to the bleach and / or the pH of the textile article.

Description

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DESCRIPTION

Sensitive tissue washing system

The present invention relates to a system for the protection of sensitive textile articles in an automatic washing process.

Automatic control of the configuration of a washing machine to properly wash various items is known. US Patent No. 5,388,299 to Lee discloses a wash control system that has an information detection part for reading the wash information. The items are placed manually in front of the detection part, one by one, before putting the clothes in the washing machine.

Document US 5715555 discloses a procedure and a washing system in which the instructions contained in the electronic labels are attached to the material articles. All instructions are read while the material items are inside a washing machine.

An object of the present invention is to provide an improved washing procedure for pH-sensitive textile articles / bleach.

Accordingly, in one aspect, the invention provides a washing system for washing multiple textile articles that include one or more sensitive textile articles in a washing machine with a detergent composition comprising 5-99.9% surfactant, in which the washing system comprises:

an in situ hydrogen peroxide generation system;

a pH regulation device, a communication device with labels that reads a washing instruction contained in an electronic label attached to any sensitive textile article;

a controller in communication with the communication device with labels to control the washing machine to adjust the hydrogen peroxide generation system according to the sensitivity to the bleach and / or the pH of the textile article.

An advantage of the invention is the provision of an in situ hydrogen peroxide generation system that can be controlled by the presence of labeled sensitive textile articles. This means that the washing system can offer all the advantages of a bleaching system without adding this to the composition, while at the same time the labeled sensitive articles automatically modify the system to take into account said sensitivities. The mere presence of at least one labeled article activates the system to modify the pH / bleach levels. The user does not need to classify the wash load before each wash to identify such sensitive items, they identify themselves automatically.

A significant advantage of the invention is that it is only necessary to label a limited number of clothing items. In this way, the penetration speed will be greater. In addition, the producer can add the labels without alerting the consumer that this is a particular sensitive garment. That information is now hidden on the label. Another possible advantage is that it would also be possible to provide / sell labels to consumers, who can label themselves whether or not there are garments that are very sensitive (in their opinion) thereby retaining full control of the procedure.

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

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

The label can be removable for temporary attachment to the fabric, for example, it can be fixed before the washing procedure and then it can be detached after the washing procedure. Advantageously, the label can be attached to the sensitive textile article and remains in place during washing, drying and use (when used, if it is a garment). The label can even be attached to sensitive textile items during their manufacture, packaging. With a more permanent fixation, the modification of the previous washing procedure occurs automatically each time the item is included in a wash load.

The electronic tag can be programmed to store identification information for the textile article identifying it as sensitive to bleach and / or high pH.

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Preferably, the sensitive textile articles having programmed electronic labels attached thereto and these articles are placed in a washing machine inside the washing system.

Each washing machine has a controller that controls its operation. A communication device with labels is included inside the washing machine and reads the washing instructions contained in the electronic labels, while the textile articles are inside the washing machine. Once the label is read, the controller modifies the hydrogen peroxide generation system to reduce the pH and / or bleach levels.

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

The modification of the H2O2 generation system may be preceded by an audible and / or visual alarm to notify the user / consumer. There may be a cancellation option in case the consumer does not want the washing procedure to be modified.

The in situ generation of hydrogen peroxide in a washing procedure combined with a pH regulation device allows the generation in situ of hydrogen peroxide in the washing machine and the formation of a bleaching component from hydrogen peroxide and, for example, a bleaching precursor at a high pH, while allowing the cloth to be washed at a reduced pH, without the need for added chemicals and allows automatic modification by the label system.

The hydrogen peroxide generation device may comprise an electrochemical cell for the production of hydrogen peroxide from tap water and air, and is 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, so that no added chemicals are needed when the device is in operation.

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

In current tissue washing procedures, bleach is usually obtained by forming a peraid from bleach precursor and hydrogen peroxide in the detergent product.

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

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

ROOH (1)

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

C

I

E C-OOH (2)

Another preferred group of peracides is the type of general formula 3.

Kh

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 bond; or a substituted phenylene or phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an aromatic or non-aromatic imido group, a COOH or C = C (OOH) group or a quaternary ammonium group.

The corresponding perars of the peraids of formulas 1, 2 and 3 are also included within the scope of the invention, in particular the alkaline and alkaline earth metal perches, preferably the sodium and potassium persales. Also within the scope of the present patent is the presence of the peraids in the deprotonated form in alkaline solutions.

In order to be effective the washing procedures, the water containing hydrogen peroxide preferably has a hydrogen peroxide concentration of 0.1 to 15 mmol / l, more preferably 2 to 12 mmol / l, even more preferably of 3 to 10 mmol / l when diluted to the final wash solution. Water containing hydrogen peroxide can be used directly in the washing process, or it can be produced in a more concentrated form, stored inside the washing machine and diluted to the intended concentration when necessary. When produced in a more concentrated form, the concentration is preferably between 1 and 500 mmol / l, more preferably between 50 and 200 mmol / l. When the hydrogen peroxide solution is stored inside the washing machine for a longer period of time, a pH of 7 or less is preferred, more preferably 6 or less, still more preferably 5 or less, for the sake of Storage stability

10 Without wishing to be bound by any particular theory, hydrogen peroxide is formed in the cell by reacting water with oxygen. The oxygen is converted into hydrogen peroxide or hydrogen peroxide ions in the cathode, generally as follows:

O2 + 2H + + 2e- ^ H2O2 in acidic conditions or

15 O2 + H2O + 2e- ^ HO2 + OH-

in alkaline conditions.

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

2H2O ^ O2 + 4H + + 4e-

20 The hydrogen peroxide generation reaction does not require added chemicals, only water and air. Preferably, the formation of hydrogen (H2) is avoided for safety reasons. When chlorine is present in the feedwater, the hydrogen peroxide generating device can also produce a smaller amount of chlorine dioxide. Chlorine dioxide is also a suitable bleach.

The hydrogen peroxide generation cell is preferably an electrochemical cell comprising one or more 25 cathode and anode electrodes that can be charged by a DC potential. The electrodes can be, for example, in the form of plates or rods, preferably plates. The cathode is preferably a gas diffusion electrode. The cathode preferably comprises a catalyst bonded to the cathode surface. The cathode may comprise conductive materials such as carbon (for example graphite, carbon nanotubes and other forms of carbon), metals or conductive polnrieros or combinations thereof. Preferred metal catalysts are transition metals, 30 transition metal oxides or transition metal macrocycles. Preferred transition metals include gold, mercury and oxide coated metals such as nickel and cobalt. Preferred metal oxides include nickel oxide, cobalt oxide and spinels. Preferred transition metal macrocycles include: CoTsPc (cobalt phthalocyanine tetrasulfonate) and CoTMPP (tetramethoxyphenyl porphyrin). The anode is preferably a dimensionally stable anode, which is preferably constructed from conductive materials such as metals, carbon or conductive polnrieros or combinations thereof.

Some transition metals are not preferred, in particular platinum, platinum alloys, platinum family metals, palladium and silver. Nor are perovskites and pyrochlorides preferred, such as transition metal oxides of lead ruthenate, and macrocyclic FeTsPc (iron phthalocyanine tetrasulfonate).

The dimensions and specification of the hydrogen peroxide generation cell depend on the intended use. If hydrogen peroxide is stored in an intermediate tank inside the washing machine, a slow system of hydrogen peroxide production, for example, overnight, is suitable. However, when hydrogen peroxide must be produced during the washing procedure, a rapid production system is required. The hydrogen peroxide generation 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 a maximum of 1,000 cm2, more preferably at most 500 cm2, even more preferably at most 400 cm2, still more preferably at most 300 cm2; depending on the area of the production speed demanded. The surface area is preferably divided between 1 and 25, more preferably between 1 and 10 cathode electrodes. The production rate of hydrogen peroxide is typically between 0.1 and 2,000 mmol / h. Actual speed depends, among other things, on the surface area of the cathode and the type of operation. In a system with a storage tank 50 of hydrogen peroxide, a slow production regime is preferred, typically 0.1 to 200 mmol / h, while in a system in which hydrogen peroxide is produced immediately during introduction of water, the production speed is preferably between 200 and 2,000 mmol / h. The efficiency of this type of hydrogen peroxide generation cell is preferably 50 to 100% at the beginning or just after the start of the

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production of hydrogen peroxide, typically 60 to 95%.

The total surface area of the anodes is between 10 and 100% of the total surface area of the cathodes.

Optionally, the electrodes are separated by a semi-permeable membrane.

As an alternative to buffers, acids and bases, the pH of a tissue washing solution is adjusted by using a pH regulating device that can be electrochemical and can be as described in EP1841697.

As indicated above, the reaction of bleaching peracide formation from hydrogen peroxide and bleaching precursor is preferably carried out at a high pH, while the bleaching reaction is more efficient at lower pH. Typically, the pH for the peracid formation reaction is greater than 9, preferably greater than 9.5. Preferably, the pH is 13 or less, more preferably it is 12 or less, even more preferably it is 11 or less, ideally it is 10.5 or less. On the other hand, the bleaching reaction using the peraid is preferably carried out at a pH of 9.5 or less, more preferably 9 or less, still more preferably 8.5 or less. The pH of the bleaching reaction is generally greater than 7, preferably greater than 7.5, ideally greater than 8.

Buffers, salts, acids and bases to adjust the pH of the wash solution form other bulky ingredients in current detergent products. However, the application of a pH regulator allows the adjustment of the pH in the washing solution added chemicals, which is a great comfort for the consumer.

The pH regulator of the invention is a device that divides a feedwater stream into an acid stream and an alkaline stream, for example, using an electrolysis cell. The pH regulator can be fed with tap water or softened water. Part of the alkaline stream can be used in the bleach formation reaction. In addition, part of the acid and alkaline stream can be used in the washing procedure. The pH of the acidic water is preferably between 1 and 6, more preferably between 1 and 3. Typically, the pH of the alkaline stream is between 9 and 13, preferably between 10 and 12. The volume ratio between the alkaline water and The acidic water produced for 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 can also be used to regenerate the electrochemical cells of the hydrogen peroxide generation device.

In short, the pH regulator can be used for the production of acid water and alkaline water. Acidic water can be used for the regeneration of electrochemical cells and for use in the washing procedure. Alkaline water can be used in the bleach formation reaction and the washing procedure. This improves the performance of the bleach and the robustness of the electrochemical cells, reduces the amount of water necessary for the regeneration of the electrochemical cells and does not require the addition of chemical products.

The pH regulator is an electrochemical cell comprising one or more cathode and anode electrodes. The electrodes may, for example, be in the form of plates or rods, preferably plates. The plates and the conductive surface on the plates can 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 l / h, more preferably between 2 and 300 l / h of alkaline water and combined acid.

In order to be effective for tissue washing procedures, for example those in which no detergent improver is applied, the hardness of the water in the water added to the washing procedure is preferably less than 5 ° FH, preferably less than 2 ° FH and more preferably less than 1 ° FH. Reduction of water hardness is desirable in order to prevent the deposition of calcium soaps in the dirt, to prevent the precipitation of anionic surfactants, to maximize colloidal stability and to reduce the calcium-dirt-substrate interaction and interaction dirt - dirt and, therefore, to improve the elimination of dirt.

An additional 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, for example, in running water.

The majority of common detergent products comprise detergent improver material for sequestering hardness ions from running water. The detergent builder material is normally present in the detergent composition in a concentration of 15 to 80%. Commonly known detergent builders are water soluble phosphate salts, such as sodium tripolyphosphate (tpfs) or zeolites. Phosphates are supposed to cause eutrophication of surface water, and zeolites cause insoluble matter in household waste. Due to the

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The nature of the detergent-enhancing material and the amount in which it is present has found more and more opposition in detergent products, especially laundry detergent products.

As an alternative to the use of detergent builder material, different water softening devices are known in the art. All these devices produce soft water by sequestering hardness ions such as Ca2 + and Mg2 + from running water, for example by ion exchange. In WO-01/30229, a system is described that uses 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 its application in a common type of automatic washing machine, large quantities of, for example, salt solution for the regeneration of ion exchanger would be required, thus canceling the effect of the reduction of chemical products for the improvement of detergent. in the detergent. Other disadvantages of ion exchange are the limited lifetime of the ion exchange resin and / or the necessary volume of resin for the production of the amount of soft water needed in a washing machine.

Another water softening process is electronic deionization (DE), which combines ionic exchange and electrodialysis, as described in application EP 04076353.4 in process together with this. Although this procedure does not require chemical regeneration products, the other drawbacks related to the use of the ion exchange resin are maintained as indicated above. In addition, ED is a complicated technology, which is difficult to operate in a robust manner for a long period of time, as required in domestic appliances.

Yet another water softening process is capacitive deionization, which uses a continuous flow condenser (FTC) as disclosed, among others, in application EP 05075218.7 in process along with this. Said method comprises the use of an electrically regenerable electrochemical cell for capacitive deionization and electrochemical electrode purification and regeneration that includes two end plates, one at each end of the cell. By polarizing the cell, the ions are removed from the electrolyte and retained in the electrical double layers in the electrodes. The cell can be regenerated (partially) electrically to desorb said previously removed ions. Regeneration could be carried out without added chemical substances.

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

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

In conventional detergent products, detergent-enhancing chemicals and pH modifiers may represent up to 70% by weight of the composition. It should be noted that, for the purpose of the present invention, surfactants (although some surfactants may have some effect on pH) are not considered as a pH modifying chemical.

According to a preferred embodiment of the invention, LEIP (product with low environmental impact) is substantially free of pH modifying chemicals. Substantially free of pH modifying chemicals, it is intended to describe products that comprise a maximum of 5% by weight of pH modifying chemicals. Preferably, the LEIP comprises 0 to 3% by weight, more preferably 0 to 1% by weight, more preferably 0% by weight of pH modifying chemical products by weight of the total LEIP composition.

Conventional liquid detergent products often contain acidic components, for example, anionic surfactants such as LAS (linear alkylbenzene sulphonate). To neutralize these acids, the composition may optionally comprise neutralizers. These neutralizers 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 neutralizers are present in a concentration of 50 mol% to 200 mol% of the molar concentration of the components that require neutralization.

It is desirable to equip the washing machines with one or more detergent product containers so that the detergent product can be dosed automatically. The LEIP can be dosed from a single container. By way of

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Alternatively, the ingredients that make up the LEIP can be dosed from separate containers as described in EP-A-0419036. Thus, in a preferred embodiment, at least one ingredient of the LEIP is automatically dosed. One of the advantages of a LEIP may be that the number and / or the reduced amount of ingredients allows a much smaller volume of detergent product. In practice, this means that the consumer does not need to refill the containers so often or that the containers can be smaller, therefore making an automatic dosing system more feasible when the device of the invention is used. When an automatic dosing system is applied, it is preferred that the bleach precursor or activator (catalyst) be stored separately from the other components of the detergent product.

Although hydrogen peroxide (H2O2) is a good bleach, it only provides a slow oxidation process due to the slow kinetics and, therefore, a slow bleaching process. For certain fabrics, it is preferred to have a stronger oxidant that is active at low temperatures and concentrations.

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

A bleach generation process can be carried out in the drum of the washing machine or in a mixing device in line or out of line. When a mixing device is used, the mixing device is selected from the group consisting of a static mixer, a dynamic mixer, a stirred tank or storage tank or a combination thereof.

A peraid can be formed by perhydrolysis of an acid bleach precursor by the following reaction:

0 0 'QOH

R — C — X ►R — C O0 "+ HX

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

The low environmental impact product composition (LEIP) used in the process of the present invention may include one or more bleaching precursors.

Organic peroxyacid precursors may be suitable as the peroxy bleach compound. After perhydrolysis, said materials normally have the general formula:

image 1

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

image2

or a quaternary ammonium group.

Typical monoperoxyacid precursors useful in the present invention include, for example:

(i) peroxybenzoic acid and substituted peroxybenzoic acids in the ring, for example, peroxy-alpha-naphthoic acid;

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, for example peroxylauric acid, peroxystearic acid and caproic N, N-phthaloylaminoperoxy acid; Y

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

Typical diperoxyacid precursors useful herein include, for example:

(iv) 1,12-diperoxidedecanedioic acid (DPDA);

(v) 1,9-diperoxyazelaic acid;

(vi) diperoxybibric acid; diperoxisebacic acid and diperoxyisophthalic acid;

(vii) 2-decyldiperoxybutane-1,4-diotic acid; Y

(viii) 4,4'-sulfonylbisperoxybenzoic acid.

Peroxyacid bleaching precursors are known and widely described in the literature, such as in 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 US Patent Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

Another useful class of peroxyacid bleaching precursors is that of cationic precursors that is quaternary ammonium substituted peroxyacid precursors as disclosed in US Patent Nos. 4,751,015 and 4,397,757, in EP-A0284292 and EP -A-331,229. Examples of peroxyacid bleaching precursors of this class are:

Sodium-4-sulfonphenyl carbonate 2- (N, N, N-trimethyl ammonium) ethyl chloride (SPCC);

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

Sodium-4-sulfophenyl carboxylate 3- (N, N, N-trimethyl ammonium) propyl; Y

Toluyloxy benzene sulfonate of N, N, N-trimethyl ammonium.

An additional special class of bleaching precursors is formed by cationic nitriles as disclosed in EP-A-303,520 and in European patents with specification Nos. 458.396 and 464.880.

Any of these peroxyacid bleaching precursors may be used in the present invention, although some may be more preferred than others.

Of the above classes of bleaching precursors, the preferred classes are esters, including acyl phenol sulphonates and alkyl phenol acyl sulfonates; acyl amides; and peroxyacid precursors substituted with quaternary ammonium, including cationic nitriles.

Examples of such preferred peroxyacid bleach precursors or activators are sodium -4-benzoyloxy benzene sulfonate (SBOBS); N, N, N'-tetraacetyl diamine (TAED); sodium-1-methyl-2-benzoyloxy benzene-4-sulfonate; sodium-4- methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxybenzene sulfonate; sodium nonanoyloxybenzene sulfonate (SNOBS); sodium 3,5,5-trimethyl hexanoyl-oxybenzene sulfonate (STHOBS); and substituted cationic nitriles.

Other classes of bleaching precursors for use with the present invention are found in WO0015750, for example 6- (nonanamidocaproyl) oxybenzene sulfonate.

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

The reaction of peroxide peracide formation and bleaching precursor from the detergent can be obtained in the washing solution inside the drum of the washing machine, or in a mixing vessel outside the line. An advantage of the latter is that the peraid can be formed in a concentrated form at the desired pH and can be diluted with acidic water in the drum of the washing machine, thereby reducing the pH for the washing process resulting in better activity. of bleaching.

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

The reaction of peroxide peracide formation and bleaching precursor from the detergent can be obtained in the washing solution inside the drum of the washing machine, or in a mixing vessel outside the line. An advantage of the latter is that the peraid can be formed in a concentrated form at the desired pH and can be diluted with acidic water in the drum of the washing machine, thereby reducing the pH for the washing process resulting

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in better bleaching activity.

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

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

A bleaching catalyst is defined herein as any substance that improves peroxide activity by reducing the activation energy for the bleaching reaction, while not taking part (i.e., it is consumed) in the reaction.

The use of bleaching catalysts for stain removal has been developed over the past few years and can be used in the present invention. Examples of transition metal catalysts that can be used are found, for example, in WO-01/48298, WO-00/60045, WO-02/48301, WO-00/29537 and WO-00 / 12667. Alternatively, the catalyst can be provided as the free ligand that forms an in situ complex with transition metals present in the water. In general, the catalyst contains a transition metal bonded at least partially covalently, and attached thereto at least one ligand.

In general, the transition metal bleaching 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 present transition metal bleaching 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 fraction capable of direct covalent binding to a metal ion. The ligands can be charged or neutral. The ligands may include simple monovalent donors, such as chloride, or simple amines that form a simple coordinated 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 fractions such as ethylenediamine or aza macrocycles, which form up to the maximum number of bonds simple to one or more metals that are allowed by the available sites in the metal and the number of solitary pairs or alternative binding sites of the free ligand. Numerous ligands can form different links from simple donor links, and can have multiple binding points.

Alternatively, organic bleach catalysts can also be used. In general, organic bleaching catalysts have activated imines that produce an oxaziridine after the reaction with peracide. A preferred non-limiting compound includes 3,4-dihydroisoquinolinium salt, as exemplified in WO / 9513352. Other organic bleaching 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 5,778,886, 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 (LEIP) product of the present invention preferably comprises bleach catalyst in a peroxide: catalyst ratio between 100: 1 and 100,000: 1, more preferably between 500: 1 and 5,000: 1 on a molar basis.

The compositions according to the invention contain one or more surfactant compounds (surfactants) that can be selected from anionic, cationic, non-ionic, amphoteric and zwitterionic, soapy and non-soap surfactant compounds, and mixtures thereof. Many suitable surfactant 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 active detergent compounds that can be used are anionic, non-ionic and cationic, non-soapy, synthetic soaps and surfactants. Next, some examples of each of them will be described.

The anionic surfactant is preferably present. It can be selected, for example, from one or more of alkylbenzene sulfonates, alkyl sulfonates, primary and secondary alkyl sulfates (in the form of free acid and / or salt). The aromatic alkyl sulfonic surfactant preferably constitutes 0.5% to 99.9%, preferably 1% to 80%, more preferably 10% to 60%, especially 15% to 50%, more especially 25% to 45%. % by weight of the total anionic surfactant content of the composition.

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A composition according to the present invention may contain, for example, from 0.1% to 70%, preferably from 1% to 40%, more preferably from 2% to 30%, especially from 3% to 20% of alkylbenzene sulfonic surfactant ( in the form of free acid and / or salt).

When it is desired to further improve calcium intolerance, then any anionic surfactant in the composition that is additional to the aromatic alkyl surfactant, may comprise (preferably at a level of 70% by weight or more of the total anionic surfactant) or consist of only one or more anionic, non-soap, calcium tolerant surfactants.

If a water softening device is incorporated, the Ca sensitivity of the surfactants is less critical.

As referenced herein, an "calcium tolerant" anionic surfactant is one that does not precipitate a surfactant concentration of 0.4 g / l (and an ionic strength of a 0.040 M 1: 1 saline solution) with a calcium concentration of up to 20 ° FH (French degrees of hardness), that is, 200 ppm of calcium carbonate.

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

Another preferred class of calcium-tolerant anionic surfactants comprise the branched medium chain 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 alkyl ether sulfates (ie, alkoxylated (poly) alkyl sulfates).

Other anionic calcium tolerant surfactants suitable for use in combination comprise alpha-olefin sulphonate and alkyl ether sulfate in a weight ratio of 5: 1 to 1:15. Other anionic calcium-tolerant surfactants that can be used are alkyl ethoxy carboxylate surfactants (eg, Shell Neodox (trademark)), fatty acid ester sulphonates (eg, Stees MC-48 and ML-40 Stepan ), alkyl xylene sulfonates

0 toluene, dialkyl sulfosuccinates, alkyl amide sulfates, soforolfpids, alkyl glycoside sulfates and alkali metal salts (eg, sodium) of saturated or unsaturated fatty acids.

In addition to calcium-tolerant anionic components, people with knowledge in the art still know other suitable anionic surfactants. Examples include primary and secondary alkyl sulfates, particularly primary C8-C15 alkyl sulfates and dialkyl sulphosuccinates.

Sodium salts are generally preferred.

Optionally, a soap may also be present. Suitable soaps include those that have a chain length ranging from C12 to C20, mainly saturated, and that optionally contain limited levels of

1 or 2 unsaturated bonds, and derivatives of natural oils and fats such as, for example: tallow (hardened or uncured), coconut or palm kernel.

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

Other optional surfactants include non-ionic surfactants, cationic surfactants (for the improvement of detergency and / or fabric softening), amphoteric and zwitterionic surfactants.

If desired, non-ionic surfactant can also be included. The quantity 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 non-ionic surfactants are aliphatic alcohols having an average degree of ethoxylation of 2 to 12, more preferably 3 to 10. Preferably, the aliphatic alcohols are C8-C16, more preferably C10-C15.

The branched medium-chain hydrophobic non-ionic components disclosed in WO-A98 / 23712 are another class of suitable non-ionic surfactants.

Other suitable non-ionic, non-ethoxylated surfactants include alkyl polyglycosides, glycerolmonoethers and polyhydroxyamides (glucamide).

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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 long chain of alkyl or alkenyl having an average chain length greater than or equal to C20 or, more preferably, compounds comprising a group of polar head and two alkyl or alkenyl chains having an average chain length greater than or equal to C14. Preferably, fabric softening compounds have two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to C16. More preferably, at least 50% of the long chain alkyl or alkenyl groups have a chain length of C18 or greater. It is preferred that 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, distearyl dimethyl ammonium chloride and di (hardened tallow alkyl) -dimethyl ammonium chloride, are widely used in commercially available rinse conditioning compositions. Other examples of these cationic compounds can be found in the publication "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 that can be used for their detergency.

The cationic surfactants that can be used for this purpose include quaternary ammonium salts of the general formula R1R2R3R4N + X- in which the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups and X is a counterion (for example , compounds in which R1 is a C8-C22 alkyl group, preferably a C8-C10 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, hill 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 vary from 1% to 50% by weight, preferably from 2% to 30% by weight, more preferably from 4% to 20% by weight of the total composition.

Inorganic improvers that may be present include sodium carbonate, if desired in combination with a crystallization 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 stratified 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 the present invention. .

The compositions of the invention preferably contain an alkali metal aluminosilicate detergent builder, preferably sodium. Sodium aluminosilicates can generally be incorporated in amounts of 10 to 70% by weight (anhydrous base), preferably 20 to 50% by weight.

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

The alkali metal aluminosilicate can be crystalline or amorphous or mixtures thereof, with the general formula: 0.8-1.5 Na2O.AhO3. 0.8-6 SiO2.

These materials contain a certain amount of bound water and must have a calcium ion exchange capacity of at least 50 mg Ca / g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units (in the above formula). Both amorphous and crystalline materials can be easily prepared by a reaction between sodium silicate and sodium aluminate, as described extensively in the literature. The ionic exchange detergency builders of suitable crystalline sodium aluminosilicates are described, for example, in GB-A-1 429 143. Preferred sodium aluminosilicates of this type are well-known, commercially available Ay X zeolites. their mixtures

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

Especially preferred is the zeolite MAP which has a silicon to aluminum ratio that does not exceed 1.07, but

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preferably about 1.00. The calcium binding capacity of the zeolite MAP is generally equivalent to at least 150 mg of CaO per g of anhydrous material.

Organic detergency 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 tri-succinates, carboxymethyloxy succinates, carboxymethyloxy malonates, dipicolinates, hydroxyethyliminodiacetates, alkyl and alkenyl malonates and succinate salts and salts of fatty acids. This list is not intended to be exhaustive.

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

Detergency builders, both inorganic and organic, are preferably present in the form of alkali metal salt, especially sodium salt.

When the compositions contain bleach or generate bleach, they may also advantageously contain one or more heavy metal chelating agents. This reduces the damage produced by the bleach. Generally, chelating agents suitable for use herein may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Without wishing to be bound to any theona, it is believed that the benefit of these materials is due in part to their exceptional ability to remove heavy metal ions from the wash solutions by forming soluble chelates; Other benefits include the prevention of inorganic films or inlays. Other chelating agents suitable for use herein are the DEQUESTO commercial series and the chelants of Monsanto, DuPont, and Nalco, Inc.

Useful aminocarboxylates as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminotriacetates, nitrilotriacetates, ethylenediamino tetrapropionates, triethylenetetrahexaacetates, diethylenetriamine pentaacetates and ethanediglycides, ammonium metal mixtures and alkali metal salts.

Aminophosphonates are also suitable for use as chelating agents in the compositions in the invention, when at least low levels of total phosphorus are allowed in the detergent compositions, and include ethylenediaminetetrakis (methylene phosphonates). 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 document US-A-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 isomer [S, S] described in US-A-4,704,233. The trisodium salt is preferred, although other forms, such as magnesium salts, may also be useful.

If these selective transition metal chelating agents or sequestrants are used, they will preferably comprise from about 0.001% to about 10%, more preferably from about 0.05% to about 1% by weight of the bleach compositions of the present memory

The lavender wash compositions according to the invention may also contain one or more enzymes. Such enzymes can provide cleaning performance, tissue care and / or sanitation benefits. Suitable enzymes include proteases, amylases, cellulases, lipases, oxidases / oxide reductases, transferases, hydrolases, peroxides, isomerases and ligases, usable for incorporation into 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 65-3, Academic Press.

Examples of the hydrolases are carboxylic ester hydrolase, thiolester hydrolase, phosphoric hydrolase monoster and phosphoric hydrolase diester that act on the ester bond; glycosidase acting on O-glycosyl glycosylase compounds that hydrolyzes N-glycosyl compounds; thioether hydrolase that acts on the ether bond; and exopeptidases and endopeptidases that act on the peptide bond. Preferred among these are carboxylic ester hydrolase, glucosidase 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, papama, chymopapama, ficain, thrombin, thrombin , renin, subtilisin, aspergilopepsin, collagenase, clostripama, calicrema, gastricsin, cathepsin D, bromelama, chymotrypsin C,

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urokinase, cucumisin, orizine, proteinase K, thermicomycin, termitase, lactocepin, thermolysin, bacillolysin. Among these, subtilisin are preferred; (2) glycosidases such as a-amylase, Q-amylase, glucoamylase, isoamylase, cellulase, endo- 1,3 (4) -glucanase, xylanase, dextranase, polygalacturonase (pectinase), lysozyme, invertase, hyaluronidase, pululanase, neopulinase chitinase, arabinosidase, exocelobiohydrolase, hexosaminidase, mycodextranase, endo-1,4-mannanase (hemicellulase), xyloglucanase, endo-galactosidase (queratanasa), mannanase and other enzymes that degrade saccharide gums as described in WO-A- 09/99127. Among these, carboxylic ester a-amylase and cellulase hydrolase including carboxylesterase, lipase, phospholipase, pectinesterase, cholesterol esterase, chlorophylase, tanase and wax ester hydrolase are preferred. Among these, lipase is preferred.

Examples of transferases and ligases are glutathione S transferase and thiol acid ligase as described in WO-A-98/59028 and xyloglycan endotransglycosylase as described in WO-A-98/38288.

Examples of liases are hyaluronate lyase, pectate lyase, lipex, chondroitinase, pectin lyase, alginase II. Pectoliase is especially preferred, which is a mixture of pectinase and pectin lyase.

Examples of 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 cytochrome-based enzymatic bleaching systems described in WO-A-99/02641 .

The activity of oxidoreductases, in particular phenol oxidant enzymes in a bleaching process of fabric stains and / or dyes in solution and / or an antimicrobial treatment can be enhanced by the addition of certain organic compounds, called enhancers. Examples of improvers are 2,2'-azo-bis- (3-ethylbenzothiazoline-6-sulfonate (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. The improvers are generally added at a level of 0.01% to 5% by weight of the detergent composition.

Preferred proteolytic enzymes (protease) are catalytically active protein materials that degrade or alter the types of stain proteins when they are present such as in tissue stains in a hydrolysis reaction. They can be of any suitable origin, such as of vegetable, animal, bacterial or yeast origin.

Proteolytic enzymes or proteases of various qualities and origins and having activity at various pH ranges of 4-12 are available and can be used in the present invention. Examples of suitable proteolytic enzymes are subtilisins, which are obtained from particular strains of B. Subtilis B. licheniformis, such as commercially available Maxatase subtilisins (registered trademark), supplied by Gist Brocades NV, Delft, Holland and Alcalase (registered trademark ), supplied by Novo Industri A / S, Copenhagen, Denmark.

Particularly suitable is a protease obtained from a Bacillus strain that has maximum activity in the pH range of 8-12, which is commercially available, for example, in Novo Industri A / S under the registered trade names Esperase (trademark) and Savinase (registered trademark). The preparation of these enzymes and analog enzymes is described in GB-A-1 243 785. Other commercial proteases are Kazusase (trade mark obtainable from Showa-Denko of Japan), Optimase (trademark of Miles Kali-Chemie, Hannover , West Germany) and Superase (trade mark obtainable in US Pfizer).

Detergency enzymes are commonly used in granular form in amounts of about 0.1 to about 3.0% by weight. However, any suitable physical form of enzyme can 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 of treatment. Suitably, sodium carbonate may be present in amounts ranging from 1 to 60% by weight, preferably from 2 to 40% by weight. However, compositions that do not contain or contain little sodium carbonate are also included within the scope of the invention.

The powder flow can be improved by incorporating a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate / copolymer of acrylate / maleate or sodium silicate. A preferred powder structurant is a fatty acid soap, suitably present in an amount of 1 to 5% by weight.

Still other materials that may be present in the detergent compositions of the invention include sodium silicate, anti-redeposition agents such as cellulosic poftmeros, inorganic salts such as sodium sulfate; foaming agents or foaming improvers as appropriate; dyes; colored particles; perfumes; foam forming controllers; contrast agents and poftmeros

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decoupling This list is not intended to be exhaustive.

The compositions of the present invention may 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 can be provided in water soluble sachets. The non-solid compositions, for example liquid, can have different compositions from the solid compositions and can comprise for example from 5% to 60%, preferably from 10% to 40% by weight of an anionic surfactant (at least part of which, naturally , it will be an aromatic alkyl sulfonic surfactant, from 2.5% to 60%, preferably from 5% to 35% by weight of a non-ionic surfactant and from 2% to 99% by weight of water.

Optionally, the liquid compositions may contain, for example, from 0.1% to 20%, preferably from 5% to 15% by weight of soap.

Non-solid compositions, for example, liquids, may also comprise (subject to any exclusion from other conditions expressed herein in the context of any aspect of the invention) one or more hydrotropes, especially when an isotropic composition is required. Said hydrotropes can be selected, for example, from arylsulfonates, for example, benzene sulphonate, any of which is optionally substituted independently in the aryl ring or in the ring system by one or more Cia alkyl groups, for example C1 -4, benzoic acid, salidic acid, naphthoic acid, polyglucosides Ci-a, preferably C1-4, mono-, di- and trioethanolamine. When any of these compounds may exist in acid or salt form (regardless of whether it is organic or inorganic, such as sodium) any of them may be used with the condition that it is compatible with the rest of the formulation.

Preparation of the compositions

The compositions of the invention can be prepared by any suitable procedure.

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

For granular products, ingredients such as enzymes, bleaching ingredients, sequestrants, polymers and perfumes that are traditionally added separately (for example, enzymes subsequently dosed in the form of granules, powdered perfumes) can be added after the stages of processing indicated below.

Suitable procedures include:

(1) drum drying the main ingredients, optionally followed by granulation or subsequent dosing of additional ingredients;

(2) non-tower granulation of all ingredients in a high speed mixer / granulator, for example, a Fukae (registered trademark) FS series mixer, preferably with at least one paste-shaped surfactant so that the water in the Surfactant paste can act as a binder;

(3) non-tower granulation in a combination of high speed / moderate speed granulator, fast thin film dryer / evaporator or fluidized bed granulator.

Description of non-limiting embodiments of the invention

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

Figure 1 shows a flow chart of a preferred embodiment of an electrolysis cell as an H2O2 generation device;

Figures 2a 2b show views of the hydrogen peroxide generation cell and Figure 2c shows a pH regulation device;

Figure 3 is a block diagram of an embodiment of an intelligent washing system according to the present invention;

Figure 4 is a schematic representation of a pH-sensitive textile article (coat) / bleach incorporating a label on a button;

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

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Figure 6 is a block diagram of an embodiment of a communication device with labels for use in the embodiments of the present invention;

Figure 7 is a flow chart of a communication procedure with a plurality of electronic tags;

Figure 8 is a flow chart of a procedure for an electronic tag for communicating with a tag communication device; Y

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

In Figure 1, the main water 1 of the main network is fed to the pH modifying cell 2, where the water is separated into acidic and alkaline water. The acidic water is stored in a storage container 6 and the alkaline water in the storage container 5. The alkaline water from the container 5 is fed to the hydrogen peroxide generation cell 4. Water containing high pH hydrogen peroxide is then fed to a bleach generation vessel 7, in which the hydrogen peroxide is reacted with the bleach precursor 8a to form a peraid. The peraid-containing solution is subsequently fed to the washing machine 9 from the bleach generating container 7. Hydrogen peroxide can react with the peraid precursor in the generation vessel. The generation vessel may also contain a bleach catalyst so that a mixture of bleach catalyst + H2O2 is formed. In addition, hydrogen peroxide can be fed directly to the washing machine containing LEIP. This LEIP formulation may contain no peracide bleach precursor or catalyst, or it may contain a peracide bleach precursor, or it may contain a bleach catalyst or it may contain both.

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

Alternatively, the tap water from the main network can be fed to a FTC water softening cell 3. Next, the softened water is fed to the pH modifier cell 2 and processed as explained above. The wastewater from the regeneration (point currents) from all electrochemical cells is drained 10, as well as the wastewater from the washing machine. The cells are regenerated, for example, with acidic water from the container 6; These currents are not shown in the drawings for the sake of clarity.

Figure 2a shows the hydrogen peroxide cell 4 from the outside, and Figure 2b shows the operation 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 reagents, that is, the oxygen in the air, is introduced into the chamber through an inlet 11 and the air can exit the chamber through the outlet 12 when the device is in operation. Catolith, that is, water, is supplied through inlet 13 and water containing hydrogen peroxide 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, the water is fed to the cell and the dissolved protons of the water are removed from the anode.

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

The electronic tags according to the invention are fixed to a plurality of artifact items, some of which are sensitive to bleach, some of which are sensitive to pH, and some of which are sensitive to both pH and bleach. The identification information on the label is read while the items are inside the washing machine. As a result, pH modification / bleaching instructions can be obtained while the items are loaded into the washing machine. Therefore, it is not necessary for the users of the invention to make an additional effort to order clothes to find sensitive items and to wash them separately from other non-sensitive or less sensitive items.

Figure 3 is a block diagram of a preferred embodiment of a washing system according to the present invention. The washing system is used to wash a plurality of both pH sensitive / bleach items 20 and non-sensitive items 21.

Each of the pH-sensitive textile articles 20 / bleach has an electronic tag 22 attached thereto. The electronic tag 22 is permanently incorporated into an element of an article 20, (here, a button

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23) shown in Figure 4. Other pH-sensitive textile / bleach items have a temporary generic electronic tag 22 (not shown). Other textile items sensitive to pH / bleach are included in the wash load, but may not have any labels.

The electronic tags used in this example are pre-programmed with varied information. However, they can also be programmed by a tag programming device 24. The tag programming device 24 is operative to read and / or write information stored in the electronic tag 22, such as identification information, and also additional washing instructions, and a wash count for the item 20 of material. The label programming device 24 can be used to identify the material articles 20 and / or locate each element 20 within the washing system. Labels can identify textile items as pH sensitive and / or bleach sensitive or both. If the fabrics undergo discoloration of the dye / damage due to bleach, then it is not necessary to adjust the pH, but the generation of H2O2 will need adjustment / stopping. Certain wool items can be labeled as pH sensitive (so that the pH is kept low).

Each washing machine has a controller that controls its operation. In the embodiment of Figure 3, the washing machine 26 is controlled by a controller 32 that provides a series of controls that have a number of control positions or parameters including those related to the hydrogen peroxide generation system in situ.

A communication device 38 with labels is included within the washing machine and communicates information with the electronic labels 22, while the washing load including the textile items 20 sensitive to bleaching / pH is inside the washing machine. The presence of a single tag 22 is sufficient to communicate the information to the controller to adjust the hydrogen peroxide generation system. The system is adjusted according to the sensitivity to bleaching and / or pH. The H2O2 generation can be stopped completely and / or the pH can be reduced according to the tag 22 set. If sensitivity to both pH and bleach is identified, then both are adjusted / restricted. In additional embodiments, the tag communication device / controller may include a visual presentation of the information identified to allow the user to control, for example, override this protection system.

Figure 5 is a schematic of an embodiment of an electronic tag 22 contained in button 23 of Figure 4, which can be used in embodiments of the present invention. The electronic tag 22 includes a memory 70 that stores the information for a textile article sensitive to pH / bleaching. The information includes pH sensitivity information and H2O2 sensitivity information. Preferably, the memory 70 is non-volatile so that the stored information is maintained without the application of energy to it.

A processor 72 executes a series of stages programmed to communicate the information between memory 70 and the communication device with labels in the laundry system. The processor 72 may be in the form of a microprocessor, a custom integrated circuit, a programmable logic matrix or a specific integrated circuit of the application, for example. A receiver 74 is included to receive the information transmitted from the tag communication device. A transmitter 76 is provided to transmit information to the communication device with labels. Preferably, receiver 74 and 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 the 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 inside the electronic tag are powered by a receiver 78 of electromagnetic energy. The electromagnetic energy receiver 78 receives electromagnetic energy transmitted thereto, and converts the electromagnetic energy to a DC voltage to the energy circuits within the electronic tag (namely, memory 70, processor 72, receiver 74 and transmitter 76).

The electronic label is hermetically sealed with respect to water vapor, high temperature and washing solutions. The electronic tag is also relatively small and flat so that it is discrete when permanently attached to an item. According to these preferred specifications, the electronic label can be constructed according to a production process of a sealed transponder with respect to the environment described in US5420757.

Figure 6 is a schematic diagram of an embodiment of a communication device with labels for use in the embodiments of the present invention. The tag communication device includes a processor 80 that executes a series of stages programmed to communicate information with the electronic tags 22. As with the processor 72, the processor 80 may be in the form of a microprocessor, a custom integrated circuit, a programmable logic matrix or a specific integrated circuit of the application. The processor 80 communicates with a memory 81 to store the information communicated with the electronic tags 22.

The tag communication device includes an electromagnetic energy transmitter 82 to transmit a

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55

Jan. electromagnetic signal to supply circuits in electronic tags 22. The electromagnetic energy transmitter 82 is activated and deactivated in response to commands provided by the processor 80. A transmitter 84 transmits the information generated by the processor 80 and / or stored in memory 81 for reception by the receiver 74 in the electronic tag . A receiver 86 receives the information transmitted by the transmitter 76 in the electronic tag. The receiver 86 communicates the information received to the processor 80. The processor 80 processes the information received to provide a signal to configure or verify the controls in the controller, or to alert a user of an incorrect configuration.

Figure 7 is a flow chart of a communication procedure with a plurality of electronic tags. This procedure can be used by a communication device with labels to read a plurality of washing instructions stored in a plurality of electronic labels contained within a washing machine. It should be noted that in washing procedures within the scope of the present invention, a plurality of garments containing labels may be present to communicate the presence of garments sensitive to pH and / or bleach, a single garment sensitive to pH, a unique garment sensitive to bleach, a unique garment sensitive to pH and bleach, or there 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 that warns of a pH sensitivity and / or a bleach sensitivity, then the following sequence will be applied. The procedure begins with a step of transmitting a sequence signal 130, to the electronic tags 22 using the transmitter 84 in the tag communication device. The sequence signal is used by each of the electronic tags to determine its position in a sequence for communication with the tag communication device. In a preferred embodiment, the sequence signal includes a representation of a sequence length that is used by each electronic tag to randomly determine its position within the sequence. The sequence length can be selected depending on the capacity of the washing machine. As indicated by block 132, an initialization step of a counter is performed. The counter is used to indicate the current position in the communication sequence. The counter is typically initialized using processor 80 and stored within processor 80 or memory 81. Next, transmitter 84 in the tag communication device transmits an information request signal, as indicated by block 134 The information request signal requests the electronic label that has the current position in the sequence that transmits information to the communication device with labels. As indicated by block 136, the receiver 86 in the tag communication device listens to a tag signal from one or more of the electronic tags. Next, the processor 80 checks whether a tag signal has been received from a single electronic tag, as indicated by block 138.

If a tag signal is received from a single electronic tag, then the information contained within the tag tag is stored in memory 81 of the tag communication device, as indicated by block 140. To confirm receipt of the label signal, the transmitter 84 sends a confirmation signal as indicated by block 142.

It should be noted that a tag signal is not received from a single electronic tag if no tag signal has been transmitted or if two or more tag signals have been transmitted. If two or more tag signals have been transmitted, a collision occurs so that the information cannot not be extracted from each tag signal. After sending the confirmation signal in block 142, or if a label signal is not received from a single electronic label in block 138, a step of determining whether the counter has reached a predetermined threshold is carried out, such as indicated by block 144. The predetermined threshold is indicative of a predetermined sequence length, which is preferably contained within the sequence signal transmitted at the stage indicated by block 130.

If the counter has not reached the predetermined threshold, a step is performed to increase the counter, as indicated by block 146. Next, the process flow is again directed to block 134 to transmit another request signal to communicate with another electronic label.

If the counter has reached the predetermined threshold, then steps are taken to determine if the information has been received and has been successfully stored from all electronic tags. First, the transmitter 84 carries out a step of transmitting an unrecognized tag signal request signal, as indicated by block 148. Next, the receiver 86 listens to the signals produced by any of the non-tagged tags. recognized, as indicated by block 150. As indicated by block 152, processor 80 performs a step of determining whether or not to receive a signal from an unrecognized tag.

If a signal is received from an unrecognized tag, then the process flow is directed back to block 130 in which a new sequence signal is transmitted. Preferably, the new sequence signal includes a representation of a shorter length sequence to communicate with unrecognized tags. If no signals are received from the unrecognized tags, then the communication procedure with the electronic tags is completed.

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It should be noted that in washing procedures within the scope of the present invention, a plurality of garments containing labels may be present to communicate the presence of garments sensitive to pH and / or bleach, a single garment sensitive to pH, a unique garment sensitive to bleach, a unique garment sensitive to pH and bleach, or there may be no sensitive garments present. If there are no sensitive garments 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 procedure for an electronic tag for a tag communication device. As indicated by block 160, the receiver 74 in the electronic tag performs a reception step of the sequence signal transmitted by the tag communication device. Preferably, the sequence signal includes a representation of an integer indicative of the length of the predetermined sequence. 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 is generated based on a predetermined probability distribution (that is, the probability mass function or probability function). Preferably, the probability distribution depends on the representation of the length of the predetermined sequence contained within the sequence signal. In one embodiment, the random number is representative of an integer of one to the length of the sequence. The random number is generated based on a discrete uniform distribution in which each of the whole numbers from one to the length of the sequence has the same probability of being selected. The receiver 74 on the electronic tag listens for any signal transmitted by the tag communication device, as indicated in block 164. As indicated by block 166, the processor 72 determines whether or not a signal is received from request for information for the electronic label based on the random number. If an information request 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 a confirmation signal from the communication device with labels, as indicated by the step of block 170. If a confirmation signal is received in block 172, then the Communication device with labels has correctly received the information signal and the execution of the procedure is completed. If a confirmation signal is not received or, equivalently, if an error signal is received, then the process flow is directed back to block 164. It should be noted that an information request signal for the label is not received. electronic in block 166 if the communication device with tags transmits an information request signal for another electronic tag, or if a request signal is transmitted for unrecognized tags.

If the electronic tag does not receive an information request signal in block 166, then block 174 performs a step of determining whether or not a request signal has been received for unrecognized tags. If a request signal for unrecognized labels is not received, then the process flow is directed back to block 164. If a request signal is received for unrecognized labels, then a sending step of a signal is carried out. indicating an unrecognized tag, as indicated by block 176. Next, the process flow is directed back to block 160 to receive another sequence signal.

Figure 9 is a block diagram of an embodiment of a label programming device for use in the embodiments of the present invention. The tag programming device includes a processor 180 that executes a series of stages programmed to communicate information with the electronic tags 22. The processor 180 may be in the form of a microprocessor, a custom integrated circuit, a programmable logic matrix or a specific integrated circuit of the application. The processor 180 communicates with a memory 182 to store the information communicated with the electronic tags 22.

An electromagnetic energy transmitter 184 is provided to transmit an electromagnetic energy signal to supply power to the circuits in an electronic tag. The electromagnetic energy 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 may take the form of one or more buttons, a keyboard, a touch screen or a touch screen, which allows the introduction of information and / or instructions to the label programming device by a user. The processor 180 processes the information and instructions to form the signals that are applied to a transmitter 188. The transmitter 188 transmits the signals for reception by the receiver 74 on the electronic label. The signals may 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 for the current value of the counter. The signals may also be indicative of the information that should be stored on the electronic label, such as identification information, washing instructions and water processing instructions. A receiver 190 receives information transmitted by the transmitter 76 on the electronic tag. The receiver 190 communicates the information received to the processor 180. The processor 180 processes the information received to provide a signal to drive a visualization device 192. The visualization device 192 provides means to display the information requested by a user, such as identification information and the current counter value. It is preferred that the display device 192 be able to display information

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numeric or alphanumeric. In this way, the display device 192 may be based on light emitting diodes or liquid crystal technologies.

A significant advantage of the invention is that it is only necessary to label a limited number of garments. In this way, the penetration speed will be greater. In addition, the producer can add the labels without alerting the consumer that it is a particular sensitive garment. That information is now hidden on the label. Another possible advantage is that it may also be possible to provide / sell labels to consumers, who can then label themselves if there are garments that are very sensitive (in their opinion) thus retaining full control of the procedure.

It will be apparent to persons with knowledge in the field that the disclosed invention can be modified in many ways and can assume many different embodiments of the preferential form established and described specifically in the foregoing.

Claims (11)

5 10 fifteen twenty 25 30 35 1. A washing system for washing multiple textile articles that include one or more sensitive textile articles in a washing machine (26) with a detergent composition comprising 5-99.9% of surfactant characterized in that the washing system comprises a system (4) for generating hydrogen peroxide in situ; a pH regulation device (2); a communication device with labels that reads a washing instruction contained in an electronic label (22) attached to any sensitive textile article; a controller (32) in communication with the communication device (38) with labels for controlling the washing machine (26) to adjust the hydrogen peroxide generation system according to the sensitivity to the bleach and / or the pH of the textile article. 2. Washing system according to claim 1, wherein the hydrogen peroxide generation system (4) comprises an electrochemical cell (4) for the production of hydrogen peroxide from running water and air. 3. Washing system according to any of the preceding claims, wherein the pH regulating device (2) comprises an electrochemical cell (2) comprising one or more cathode (125) and anode (124) electrodes for the production of acidic and alkaline water, so that no added chemicals are needed when the device (2) is in operation. 4. Washing system according to any of the preceding claims, wherein the detergent composition comprises a bleaching precursor. 5. Washing system according to any one of the preceding claims wherein the detergent composition comprises a bleaching catalyst. 6. Washing system according to any of the preceding claims, wherein the detergent composition comprises a bleach precursor and a bleach catalyst. 7. Washing system according to any of the preceding claims, further comprising a water softener. 8. Washing system according to any of the preceding claims, wherein the water softener (3) comprises an ion exchanger and / or electrodialysis and / or capacitive deionization and / or continuous flow capacitance. 9. Washing system according to any of the preceding claims, wherein the detergent composition is substantially free of pH modifying components. 10. Washing system according to any of the preceding claims, wherein the detergent composition is substantially free of detergent builder. 11. Washing system according to any of the preceding claims, 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.