BRPI0819794B1 - WASHING SYSTEM - Google Patents

Abstract

sensitive fabric wash system a wash system for washing multiple fabric items including one or more sensitive fabric items in a washing machine having a detergent composition comprising from 5 to 99.9% surfactant, the washing comprising: an in situ hydrogen peroxide generation system (4); a ph regulating device (2); a tag communication device, which reads a wash instruction contained in an electronic tag attached to any sensitive tissue item; a controller communicating with the tag communicating device for controlling the washer (9) in order to adjust the hydrogen peroxide generation system according to the sensitivity of the fabric item to bleach and / or ph.

Description

WASHING SYSTEM

Field of the Invention [0001] This invention relates to a system for protecting items from sensitive fabrics in an automated washing process.

Background of the Invention [0002] It is already known how to automatically control the settings of a washing machine to correctly wash various items. Lee's US 5,388,299 discloses a wash control system with an information sensor for reading wash information. The items are placed manually on the front of the sensor, one by one, before placing the clothes in the washing machine.

[0003] US 5715555 describes a washing method and system in which instructions contained in electronic tags are linked to the materials of the items. The instructions are read, while the materials of the items are inside a washing machine.

Summary of the Invention [0004] It is an object of the present invention to provide an improved washing process for pH sensitive / bleach fabric items.

[0005] Thus, in one aspect, the invention provides a washing system for washing multiple items of fabric (s), including one or more items on sensitive fabrics in a washing machine with a detergent composition comprising from 5 to 99 , 9% surfactant, the washing system including: a hydrogen peroxide generation system in situ;

a pH regulating device;

a communication device with the tag, which reads a washing instruction contained in an electronic tag attached to any

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2/43 sensitive tissue;

a controller in communication with the communication device with the label to control the washing machine, in order to adjust the hydrogen peroxide generation system according to the sensitivity of the fabric item to the bleach and / or pH.

[0006] An advantage of the present invention is the creation of a hydrogen peroxide generator system in situ, which can be controlled by the presence of labeled items from sensitive fabrics. This means that the washing system can offer all the benefits of a bleaching system without adding it to the composition, while at the same time, sensitive items automatically labeled modify the system to take into account such sensitivities. The mere presence of at least one labeled item triggers the system to modify the pH / bleach levels. The user does not need to look at the wash load before each wash to identify such sensitive items - they identify themselves automatically.

[0007] A major advantage of the invention is that only a limited number of garments need to be labeled. Thus, the penetration rate will be higher. In addition, the producer can add the labels without alerting the consumer that it is a particularly sensitive garment. This information is hidden on the label. Another advantage is that it also makes it possible to supply / sell the tags / labels to consumers, who will be able to label the parts that are very sensitive (in your opinion), and thus, maintain total control of the process.

Brief Description of the Figures [0008] Figure 1 shows a flow diagram of a preferred embodiment of an electrolysis cell as an H2O2 generating device;

[0009] Figures 2a-2b show views of the hydrogen peroxide generating cell and figure 2c shows a pH regulating device;

[0010] Figure 3 is a block diagram of a modality of a system

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3/43 smart wash, according to the present invention;

[0011] Figure 4 is a schematic representation of an item in pH sensitive fabric / bleach (coating) that incorporates a label on a button;

[0012] Figure 5 is a block diagram of an example of an electronic tag for use in the mode of the present invention;

[0013] Figure 6 is a block diagram of a configuration of a communication device with the label for use in embodiments of the present invention;

[0014] Figure 7 is a flow chart of a communication method with a plurality of electronic tags;

[0015] Figure 8 is a flow chart of a method of an electronic tag to communicate with a communication device with the tag; and [0016] Figure 9 is a block diagram of an embodiment of a label programming device for use in configurations of the present invention.

Detailed Description of the Invention [0017] All percentages are weight by weight percentages, unless otherwise stated. Numerical scales expressed in the format of X to Y are understood to include X and Y. When for a specific characteristic, multiple preferential ranges are described in the format “from X to Y, it is understood that all ranges combining the different ends are also included .

[0018] The electronic tag can be incorporated within an element of the fabric item, such as inside a button, sewing, lining, etc. of an article of clothing. Alternatively, the label can be of a generic shape that can be attached to any fabric item.

[0019] The label can be detachable for temporary attachment to the fabric, for example, it can be attached before the washing process and then detached after the washing process. Advantageously, the label

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4/43 can be attached to the sensitive fabric item and remain in place during washing, drying and use (when dressed, if it is a garment). The label can even be attached to sensitive fabric items during manufacture, packaging. With a more permanent connection, changes to the above washing process occur automatically each time the item is included in the washing load.

[0020] The electronic tag can be programmed to store identification information for the fabric item identifying it as sensitive to bleaches and / or high pH.

[0021] Preferably, items of sensitive fabric have programmed electronic tags attached to them and these items are then placed in a washing machine within the washing system.

[0022] Each washing machine has a controller that controls its operation. A communication device with the label is fitted inside the washing machine and reads the washing instructions contained in the electronic labels, while the items are inside the washing machine. Once the label has been read, the controller modifies the hydrogen peroxide generation system to reduce the pH and / or bleach levels.

[0023] The invention is advantageous in that by changing the pH, the bleach used in many known detergents will be inactivated. At low pH (7-8), there will be no peracid release and H2O2 will not be activated.

[0024] The modification of the H2O2 generation system can be preceded by an audible and / or visual alarm to notify the user / consumer. There may be a substitution mechanism in case the consumer does not want the washing process modified.

[0025] The in situ generation of hydrogen peroxide in a washing process combined with a pH adjustment device allows the in situ generation of hydrogen peroxide in the washing machine and the formation of a bleaching component of hydrogen peroxide, for example, a bleach precursor at high pH, while allowing tissue washing

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5/43 at reduced pH, without the need to add chemicals and allows automatic change by the label system.

[0026] The hydrogen peroxide generating device may include an electrochemical cell for the production of hydrogen peroxide from water and air, being suitable for use on the machines mentioned when such machines are in operation. The pH regulation device may include an electrochemical cell that includes one or more anodes and cathodes for the production of acidic and alkaline water, in which no addition of chemicals is required when the device is in operation.

[0027] The detergent composition may include a bleach / bleach precursor. This can be added to the washing machine when it is in operation.

[0028] In current tissue cleaning methods, the bleach is usually obtained by forming a peracid from the bleach and hydrogen peroxide precursor in the detergent product.

[0029] Alternatively or additionally, bleaching can be achieved by combining hydrogen peroxide and a bleach catalyst, both present in the detergent product.

[0030] The term peracid or peracid bleach is defined herein as any peroxide acid, as defined by general formula 1.

ROOH (1)

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

O

I

RC-OOH _(2>

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

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ΝΗ

I

RC-OOH ₍₃ ) [0031] R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally with an internal amide bond; or a substituted phenylene or phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH group or a C = O (OOH) or a quaternary ammonium group.

[0032] The corresponding persoles of the peracids of formulas 1,2 and 3 are also included in the scope of the invention, in particular alkali metal and alkaline earth persals, preferably sodium and potassium persals. Also within the scope of this invention is the presence of peracids in the deprotonated form in alkaline solutions.

[0033] In order to be effective for washing processes, hydrogen peroxide containing water preferably has a hydrogen peroxide concentration of 0.1 to 15 mmol / L, preferably 2 to 12 mmol / L, preferably of 3 to 10 mmol / L when diluted in any washing liquid. Hydrogen peroxide containing water 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 expected concentration, when necessary. When produced in a more concentrated form the concentration is preferably between 1 and 500 mmol / L, preferably between 50 and 200 mmol / L. When the hydrogen peroxide solution is stored in the washing machine for a long period of time, a pH equal to or less than 7 is preferred, preferably equal to or less than 6, preferably equal to or less than 5, with the objective storage stability.

[0034] Without wanting to be linked 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 peroxide ions.

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7/43 hydrogen at the cathode, usually as follows:

O2 + 2H ⁺ + 2e ^- ® H2O2 under acidic conditions or

O2 + H2O + 2e ^- ® HO2 ^- + OH ^- in alkaline conditions.

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

2H2O ® O2 + 4H ⁺ + 4e ^- [0035] 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 water, the hydrogen peroxide generating device can also produce less chlorine dioxide. Chlorine dioxide is also a suitable bleaching agent.

[0036] The hydrogen peroxide generating cell is preferably an electrochemical cell that includes one or more anodes and cathodes that are chargeable 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 attached to the cathode surface. The cathode can include conductive materials, such as carbon (for example, graphite, carbon nanotubes and other forms of carbon), metals, 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 spinel. Preferred transition metal macrocycles include: cobalt CoTsPc (tetra phthalocyanine sulfonate) and CoTMPP (tetramethoxyphenyl porphyrin). O

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8/43 anode is preferably a dimensionally stable anode, which is preferably constructed from conductive materials such as metals, carbon, conductive polymers or combinations thereof.

[0037] Some transition metals are not preferred, in particular platinum, platinum alloys, metals of the platinum family, palladium and silver. Also not preferred are perovskites and pyrochlorines, such as transition metal oxides, lead rutenate, and macrocyclic FeTsPc (iron phthalocyanine tetrasulfonate).

[0038] The dimensions and characteristics of the hydrogen peroxide generating cell are dependent on the intended use. If hydrogen peroxide is stored in a reserve tank inside the washing machine, a slow system for producing hydrogen peroxide, for example, during the night is suitable. However, when hydrogen peroxide is produced during the washing process, a rapid production system is required. The hydrogen peroxide generating cell of the present invention preferably comprises a total cathode area of at least 10 cm2, preferably of at least 50 cm2, preferably of at least 100 cm2 and a maximum of 1000 cm2, preferably a maximum of 500 cm2, preferably at most 400 cm2, preferably at most 300 cm2; the area being dependent on the required production rate. The surface is preferably divided between 1 and 25, preferably between 1 and 10 cathode electrodes. The hydrogen peroxide production rate is normally between 0.1 and 2,000 mmol / h. The actual rate is dependent, among others, on the cathode surface area 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 hydrogen peroxide is produced immediately during feeding with water , the preferred production rate is between 200 and 2,000 mmol / h. The efficiency of this type of hydrogen peroxide generating cell is preferably 50 to 100% or right after the start of the production of hydrogen peroxide.

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9/43 hydrogen, usually 60 to 95%.

[0039] The total surface of the anodes is between 10 and 100% of the total surface of the cathode.

[0040] The electrodes are optionally separated by a semipermeable membrane.

[0041] As an alternative to buffers, acids and bases, the pH of the washing liquid of a fabric is adjusted by means of a pH regulating device, which can be electrochemical and can be as described in EP1841697.

[0042] As indicated above, the peracid bleach formation reaction from hydrogen peroxide and bleach precursor is preferably carried out at a high pH, while the bleaching reaction is more efficient at a lower pH. Normally, the pH for the peracid formation reaction is greater than 9, preferably above 9.5. The pH is preferably less than or equal to 13, preferably less than or equal to 12, preferably less than or equal to 11, preferably less than or equal to 10.5. The bleaching reaction using peracid, on the other hand, is preferably carried out at a pH equal to or less than 9.5, preferably more or less than 9, preferably equal to or less than 8.5. The pH of the bleaching reaction is generally above 7, preferably above 7.5, preferably above 8.

[0043] Buffers, salts, acids and bases to adjust the pH of the washing liquid form other bulky ingredients in today's detergent products. However, the application of a pH regulator allows adjustment of the pH in the washing liquid without added chemicals, which is of great convenience to the consumer.

[0044] The pH regulator of the invention is a device that divides a flow of water into an acidic and an alkaline flow, for example, using an electrolysis cell. The pH regulator can be supplied with tap water or softened water. Part of the alkaline flux can be used in the reaction of

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10/43 formation of the whitener. In addition, part of the acid and alkaline flux can 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 alkaline pH of the flow is generally between 9 and 13, preferably between 10 and 12. The ratio between the volume of alkaline water and acidic water produced for the application in the device of the invention is preferably between 1:20 and 20:01, preferably between 1:10 and 10: 1.

[0045] The acidic water from the pH regulator can also be used to regenerate the electrochemical cells of the hydrogen peroxide generating device.

[0046] In short, the pH regulator can be used for the production of acidic water and alkaline water. Acid water can be used for the regeneration of electrochemical cells and for use in the washing process. Alkaline water can be used in the bleaching reaction and in the washing process. This improves the bleaching performance and the robustness of the electrochemical cells, reduces the amount of water needed for the regeneration of electrochemical cells and did not require the addition of chemicals.

[0047] The pH regulator is an electrochemical cell that includes one or more anodes and cathodes. The electrodes can be, for example, in the form of plates or rods, preferably plates. The plates and the conductive surface of the plates can be constructed from conductive materials such as metals, carbon, conductive polymers or combinations thereof.

[0048] The pH regulator preferably has a total production rate between 1 and 500 l / hr, preferably between 2 and 300 l / hr of combined alkaline and acidic water.

[0049] In order to be effective for the fabric washing process, for example, those where no anti-lime agent is applied, the water hardness in the water that is added to the washing process should preferably be less than 5 ° FH, preferably less than 2 ° FH and preferably less than 1 ° FH.

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The reduction of water hardness is desirable, in order to avoid the deposition of calcium soap in the dirt, to avoid the precipitation of surfactants / anionic surfactants, to maximize the colloidal stability and to reduce the substrate - calcium - dirt and dirt interaction - dirt and consequently to improve dirt removal.

[0050] Another advantage of soft water produced using the water softening device of the invention is that hydrogen peroxide is more stable in soft water than, for example, in tap water.

[0051] Most common detergents include an anti-lime agent to sequester hard water ions in tap water. Anti-lime agents are usually present in the composition of a detergent at a concentration of 15-80%. Commonly known anti-lime agents are water-soluble phosphate salts, such as sodium tripolyphosphate (STPP) or zeolites. Phosphates are assumed to cause eutrophication of the water surface, and zeolites cause insoluble matter in the flow of domestic sewage. Due to the nature of the anti-lime agent and the amount in which it is present, it has become increasingly avoided in detergents, especially laundry detergent products.

[0052] As an alternative to the use of anti-lime agent, different water softening devices are known in the art. All of these devices produce soft water by sequestering hard ions, such as Ca2 + and Mg2 + from water, for example, by ion exchange. In WO-01/30229, a system is described, which uses an integrated ion exchange system to remove calcium and magnesium ions from water. However, the ion exchange material requires regular regeneration. For application in a common type of automatic washing machine, for example, large amounts of salt solution would be necessary for the regeneration of the ion exchanger, thus undoing the effect of reducing the detergent's chemical anti-lime agent. Other disadvantages of ion exchange are the limited lifetime of the ion exchange resin and / or the required volume of resin to produce the amount of

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12/43 soft water needed in a washing machine.

[0053] Another method of softening water is electronic deionization (EDI), which combines ion exchange and electrodialysis, as described in document EP 04076353.4. Although this method does not require regeneration chemicals, the other disadvantages related to the use of ion exchange resin remain, as indicated above. In addition, EDI is a complex technology that is difficult to operate robustly over a long period of time, as required in domestic appliances.

[0054] Yet another method of water softening is capacitive deionization, using a flow through a capacitor (FTC), as, among others, disclosed in EP 05075218.7. This method includes the use of an electrically regenerated electrochemical cell for capacitive deionization and electrochemical purification and electrode regeneration, including two plates, one at each end of the cell. By polarizing the cell, the ions are removed from the electrolyte and are retained in the double electrical layers on the electrodes. The cell can be (partially) regenerated electrically to desorb such previously removed ions. Regeneration can be carried out without the addition of chemicals.

[0055] The flow through the capacitor (FTC) is composed of plates with 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 can be constructed from conductive materials such as metals, carbon, conductive polymers or combinations thereof, as also described in WO 01/66217 or WO 02/86195, by Andelman.

[0056] Another important ingredient in conventional granular detergent products is pH modifying substances. For the purposes of the present invention the term pH-modifying substances is used to describe ingredients that affect pH, either by increasing, decreasing or

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13/43 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.

[0057] In conventional detergent products, anti-lime agents and pH modifiers can be up to 70% w / w of the composition. It should be noted that for the purposes of the present invention, surfactants - although some surfactants may have an effect on pH - are not considered to be pH modifying substances.

[0058] The LEIP (Low Environmental Impact Product) according to a preferred embodiment of the invention is substantially free of pH modifying substances. Substantially free of pH-modifying substances is used to describe products that include a maximum of 5% w / w of pH-modifying substances. Preferably LEIP comprises from 0 to 3% w / w, preferably from 0 to 1% w / w, preferably 0% w / w of pH modifying substances, in total weight of the LEIP composition.

[0059] Conventional liquid detergent products often contain acidic components, for example, anionic surfactants such as LAS (linear alkylbenzene sulfonates). To neutralize these acids, the composition can optionally include neutralizers. These neutralizers are preferably organic or inorganic bases. The bases are preferably selected from the group consisting of NaOH, KOH, monoethanol 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.

[0060] It is desirable to equip washing machines with one or more containers for detergent products so that detergent product can be dosed automatically. LEIP can be administered from a single container. Alternatively, the ingredients that make up LEIP can be administered from separate containers, as described in

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14/43 document EP-A-0419036. Thus, in a preferred modality, at least one LEIP ingredient is dosed automatically. An advantage of a LEIP can be that the reduced number and / or the quantity of the ingredients allows a much smaller volume of the detergent product. In practice, this means that the consumer does not need to always fill the containers or that the containers may be smaller, therefore, making an automatic dosing system more viable when using the device of the invention. When an automatic dosing system is applied, it is preferable that the bleach or activator precursor (catalyst) is stored separately from the other detergent components.

[0061] Although hydrogen peroxide (H2O2) is a good bleach / bleach, it only gives a slow oxidation process due to slow kinetics and thus a slow bleaching process. For certain fabrics it is preferable to have a strong oxidizer that is activated at low temperatures and concentration.

[0062] Commonly known methods for improving bleaching are the use of a bleaching catalyst to improve peroxide activity and / or the use of a peracid instead of peroxide; such a peracid is preferably formed in situ from hydrogen peroxide and a bleach precursor.

[0063] The bleaching process can take place in the washing machine drum or in an in-line or offline mixing device. When a mixing device is used, the mixing device is selected from the group consisting of a static mixer, dynamic mixer, agitator tank, storage tank or a combination thereof.

[0064] Peracid can be formed by the perhydration of an acidic bleach precursor by the following reaction:

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15/43

Ο Ο

II ΌΟΗ II R — CX ------ ►R — C — 00 ”+ ΗΧ [0065] Different types of precursors, such as cationic nitriles, have different reaction equations, but are also included in the scope of the present invention.

[0066] The composition of the Low Environmental Impact Product (LEIP) used in the process of the present invention can include one or more bleach precursors.

[0067] Organic peroxyacid precursors may be suitable as the peroxy bleaching compound. After perhydrolysis, these materials usually have the general formula:

O

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

or a group of quaternary ammonium.

[0068] Typical precursors of monoperoxy acids useful in the invention include, for example:

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

(II) aliphatics, substituted aliphatics and arylalkyl monoperoxyacids, for example, peroxilauric acid, peroxysteic acid and capric acid

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N, N-phthaloylaminoperoxy; and (III) 6-octylamino-6-oxo-peroxyhexanoic acid.

[0069] Typical diperoxyacid precursors useful in the invention include, for example:

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

(v) 1,9-diperoxiazelaic acid;

(vi) diperoxibrassilic acid, diperoxysebasic acid and diperoxyisophthalic acid;

(vii) 2-decyldiperoxybutane-1,4-diotic acid; and (viii) 4,4'-sulfonylbisperoxybenzoic acid.

[0070] Precursors of peroxyacid bleach are known and widely described in the literature, as in GB 836988; GB 864,798; GB 907,355; GB 1,003,310 and GB 1,519,351; DE 3,337,921; EP-A0185522; EP-A-0174132; EP-A-0120591, and US 1,246,339; US 3,332,882; US 4,128,494, US 4,412,934 and US 4,675,393.

[0071] Another very useful class of peroxyacid bleach precursors is cationic, for example, substituted quaternary ammonium peroxyacid precursors as disclosed in US 4,751,015 and US 4,397,757, in EP-A02B4292 and EP-A-331,229. Examples of precursors of peroxyacid bleach of this class are:

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

N-octyl-N, Ndimethyl-N10-carbophenoxy decyl ammonium chlorine (CDC);

3- (N, N, N-trimethyl ammonium) propyl sodium-4-sulfonphenyl sulfophenyl; and N, N, N-trimethyl ammonium toluyloxy benzene sulfonate.

[0072] Another special class of bleach / bleach precursors is formed by cationic nitriles, as indicated in document EP-A-303,520 and in document EP 458,396 and EP 464,880.

[0073] Any of these peroxyacid bleach precursors can be used in the present invention, although some may be more

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17/43 preferred than others.

[0074] Of the classes above the bleach precursors, the preferred classes are esters, including acyl phenol sulfonates and acyl alkyl phenol sulfonates; acyl-amides, and precursors of substituted quaternary ammonium peroxyacid including cationic nitriles.

[0075] Examples of such precursors of peroxyacid bleach or preferred activators are sodium-4-benzoyloxy benzene sulfonate (SBOBS); N, N, N'N'tetraacetyl ethylene diamine (TAED); sodium-1-methyl-2-benzoyloxy benzene-4 sulfonate; sodium-4-methyl-3-benzoyloxy benzoate; SPCC; trimethyl ammonium toluyloxybenzene sulfonate; nonanoyloxybenzene sulfonate sodium (SNOBS); 3,5,5-trimethylhexanoyloxybenzene sulfonate sodium (STHOBS); and the substituted cationic nitriles.

[0076] Other classes of bleach precursors for use with the present invention are found in WO 0015750, for example, 6 (nonanamidocaproyl) oxybenzene sulfonate.

[0077] The precursors can be used in an amount of up to 12%, preferably 2 to 10% by weight, of the composition.

[0078] The peroxide-forming reaction of the peroxide and precursor to the detergent bleach can be obtained in the washing liquid inside the drum of the washing machine, or in an offline mixing container. An advantage of the latter is that the peracid can be formed in a concentrated form at the desired pH and can be diluted with acidic water in the machine drum, reducing the pH for the washing process, resulting in better bleaching activity.

[0079] The low environmental impact detergent (LEIP) of the present invention preferably comprises bleach / bleach precursor in a peroxide: precursor ratio between 1: 2 and 25: 1, preferably between 2: 1 and 10: 1, on a molar basis .

[0080] Another way to improve the bleaching performance of hydrogen peroxide, to allow the use of lower temperatures and / or

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18/43 using less peroxide is using a bleach catalyst.

[0081] A bleach catalyst is defined here as any substance to improve the peroxide activity by reducing the activation energy for the bleaching reaction, despite not taking part (that is, being consumed) in the reaction. The use of bleach catalysts for stain removal has been developed in recent years and can be used in the present invention. Examples of transition metal catalysts that can be used are found, for example, in documents: WO01 / 48298, WO-00/60045, WO-02/48301, WO-00/29537 and WO-00/12667. The catalyst can alternatively be supplied as the free binder that forms a complex in situ with transition metals present in the water. In general, the catalyst contains at least one transition metal partially covalently bonded, and bound to the respective at least one binder.

[0082] In general, transition metal bleach catalysts here comprise a transition metal selected from the group consisting of Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II) , Fe (IIl), Fe (IV), Co (l), 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 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 (II).

[0083] In general, as used here, a ligand is any molecule capable of making a direct covalent bond to a metal ion. The binders can be charged or neutral. The binders can include simple monovalent donors, such as chloride or simple amines that form a single coordination bond and a single point of attachment to a metal; 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, for larger molecules, such as ethylenediamine or aza macrocycles, which make up to the maximum number of single bonds to one or more metals that are allowed by websites

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19/43 available in the metal and the number of solitary pairs or alternate binding sites of the free ligand. Numerous ligands can form connections different from single donor connections, and can have multiple attachment points.

[0084] Alternatively, organic bleach catalysts can also be employed. In general, organic bleach catalysts have activated imines that in reaction with peracids result in oxaziridine. A preferred non-limiting compound includes: 3,4-dihydroisoquinolinium salt, as exemplified in WO / 9513352. Other organic bleach catalysts can be found in the documents: EP 0728181, EP 0728182 EP 0728183, EP 0775192, US 4,678,782, US 5,045,223, US 5,047,163, US 5,360,568, US 5,360,569, US 5,370,826, US 5,442,366, US 5,478,356, US 5,578,256, US 5,578,256, US 5,578,256, US 5,578,356, US 5,578,356, US 5,578,356, US 5,578,356, US 5,578,356, US 5,578,356, US 5,578,356, US 5,578,356, US 5,578 5,653,910, US 5,710,116, US 5,760,222, US 5,785,886, US 5,952,282, US 6,042,744, US 2007/173428, WO 95/13351, WO 95/13353, WO 97/10323, WO 98/16614, WO 00/42151, WO 00 / 42156, WO 01/16110, WO 01/16263, WO 01/16273, WO 01/16274, WO 01/16275, WO 01/16276, WO 01/16277, WO 07/087258.

[0085] The low environmental impact detergent (LEIP) of the present invention preferably comprises a bleach / bleach catalyst in a peroxide: catalyst ratio between 100: 1 and 100,000: 1, preferably between 500: 1 and 5000: 1, based molar.

[0086] Compositions according to the invention contain one or more active surface compounds (surfactants) that can be chosen from anionic, cationic, non-ionic, non-ionic, amphoteric and zwitterionic surface active compounds and their mixtures . Many suitable surface 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.

[0087] The preferred additional surfactant compounds that can be used are anionic, non-ionic and synthetic cationic soaps and non-soapses. Some examples of each of these will be

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20/43 now described.

[0088] Anionic surfactants are preferably present. These can, for example, be selected from one or more alkylbenzene sulfonates, alkyl sulfonates, primary and secondary alkyl sulfates (in acid and / or salt free forms). The preferred aromatic alkyl sulfonic surfactant represents from 0.5% to 99.9%, preferably from 1% to 80%, preferably from 10% to 60%, preferably from 15% to 50%, especially from 25% to 45% by weight of the total anionic surfactant content of the composition.

[0089] The composition according to the present invention can, for example, contain between 0.1% to 70%, preferably from 1% to 40%, preferably from 2% to 30%, preferably between 3% and 20% of alkylbenzene sulfonic surfactant (in acid and / or salt free forms).

[0090] When it is desired to further increase calcium intolerance, then any anionic surfactants in the composition, which is complementary to the aromatic alkyl surfactant, can comprise (preferably at a level of 70% by weight or more of the total anionic surfactant) or consist only of one or more calcium-tolerant non-saponaceous anionic surfactants.

[0091] If a water softening device is incorporated, the Ca sensitivity of the surfactants is less critical.

[0092] As mentioned here, an "calcium-tolerant anionic surfactant is one that does not precipitate at a surfactant concentration of 0.4 g / L (and an ionic strength of 0.040 M in a 1: 1 salt solution) with a calcium concentration of up to 20 ° FH (French degrees of hardness), that is, 200 ppm of calcium carbonate.

[0093] An additional preferred class of calcium-tolerant non-soapy anionic surfactants for use in the compositions of the present invention comprises alpha-olefin sulfonate.

[0094] Another preferred class of calcium-tolerant anionic surfactants comprises the branched medium chain materials disclosed in

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21/43

documents : WO-A-97/39087, WO-A-97/39088, WO-A-97/39089, WO-A- 97/39090, WO-A-98/2371 2, WO-A-99/19428, WO-A-99/19430, WO-A- 99/19436, WO-A-99/1 9437, 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.

[0095] It is yet another suitable class of calcium-tolerant anionic surfactants that comprises the alkyl sulfate ether (for example, the (poly) alkoxylated alkyl sulfates).

[0096] Other calcium-tolerant anionic surfactants suitable for use in combination comprise alpha-olefin sulfonate and alkyl sulfate ether in a weight ratio of 5: 1 to 1:15. Other calcium-tolerant anionic surfactants that may be used are alkyl ethoxy carboxylate surfactants (eg NeodoxTM ex Shell), fatty acid ester sulfonates (eg FAES MC-48 and ML-40 ex Stepan), xylene alkyl or toluene sulfonates , dialkyl sulfosuccinates and alkyl amide sulfates, sorpholipids, alkyl glycoside sulfates and alkali metals (eg sodium) saturated or unsaturated fatty acid salts.

[0097] Still other anionic surfactants suitable for addition to calcium-tolerant anionics are well known to those skilled in the art. Examples include primary and secondary alkyl sulfates, particularly C3-C15 primary alkyl sulfates; and dialkyl sulfosuccinates.

[0098] Sodium salts are generally preferred.

[0099] Optionally, a soap can 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 derivatives of natural oils and fats, such as: tallow, coconut or palm oil (hardened or not hardened).

[0100] In a solid formulation, the amount of optional soap is preferably 0.1% to 10%, preferably 0.1% to 5% by weight.

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22/43 composition. In liquid compositions, the optional soap level is preferably from 0.1% to 20%, preferably from 5% to 15% by weight of the composition.

[0101] Other optional surfactants include non-ionic surfactants, cationic surfactants (for improving detergency and / or fabric softening), amphoteric and zwitterionic surfactants.

[0102] If desired, a nonionic surfactant can also be included. The amount of these materials, in total, is preferably from 0.01% to 50%, preferably from 0.1% to 35%, preferably from 0.5% to 25%, preferably from 0.7% to 20%, particularly from 0.8% to 15%, especially from 1% to 10% and more especially from 1% to 7% by weight of the composition.

[0103] Preferred nonionic surfactants are aliphatic alcohols with an average degree of ethoxylation from 2 to 12, preferably from 3 to 10. Preferably, the aliphatic alcohols are C8-C16, preferably C10-C15.

[0104] The hydrophobic branched medium chain nonionics disclosed in WO-A-98/23712 are another class of suitable nonionic surfactants.

[0105] Other suitable non-ethoxylated nonionic surfactants include: alkyl polyglycosides, glycerol monoethers and polyhydroxyamides (glucamide).

[0106] Optionally, the composition according to the present invention can include from 0.05% to 10%, preferably from 0.1% to 5%, preferably from 0.25% to 2.5%, preferably from 0, 5% to 1% by weight of cationic surfactant.

[0107] Suitable cationic fabric softening compounds are substantially water-insoluble quaternary ammonium materials comprising a single alkyl or long chain alkenyl with an average chain length greater than or equal to C20 or, preferably compounds containing a polar head group and two alkyls or alkenyl chains having an average chain length of C14 or greater.

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23/43

Preferably, the fabric softening compounds have two long chain alkyl or alkenyl chains each having an average chain length of C16 or greater. Preferably at least 50% of the long chain alkyl or alkenyl groups have a C ₁₈ chain length or greater. It is preferred that the long chain alkyl or alkenyl groups of the fabric softener compound are predominantly linear.

[0108] Quaternary ammonium compounds having two long chain aliphatic groups, for example, distearyldimethyl ammonium chloride and dimethyl ammonium di (hardened tallow alkyl) ammonium chloride, are widely used in commercially available rinse conditioning compositions. Other examples of these cationic compounds can 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.

[0109] It is also possible to include certain mono-alkyl cationic surfactants that can be used for their detergency.

[0110] The cationic surfactants that can be used for this purpose include quaternary ammonium salts of general formula R1R2R3R4N + X-, where the R groups are long or short chain hydrocarbons, usually alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is an counterion (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a C8-C18 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).

[0111] The compositions of the invention may also contain one or more anti-lime detergent, but, if the water softening device is included, at levels lower than conventional systems. The total amount of anti-lime detergent in compositions will normally vary from 1% to 50% by weight, preferably from 2% to 30% by weight,

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24/43 preferably from 4% to 20% by weight of the total composition.

[0112] Inorganic anti-lime agents that may be present include sodium carbonate, if desired in combination with a calcium carbonate crystallization seed, as disclosed in GB-A-1 437 950; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB-A-1 473 201, amorphous aluminosilicates as disclosed in GB-A-1 473 202 and mixed crystalline / amorphous aluminosilicates as disclosed in GB-A-1 470 250; and layered silicates as disclosed in EP-A-164 514. Inorganic phosphate anti-lime agents, for example, sodium orthophosphate, sodium pyrophosphate and sodium tripolyphosphate (STP) are also suitable for use with this invention.

[0113] The compositions of the invention preferably have an alkali metal, preferably sodium, an aluminosilicate anti-lime agent. Sodium aluminosilicates can generally be incorporated in amounts of 1 to 70% by weight (anhydrous base), preferably 20 to 50% by weight.

[0114] When the aluminosilicate is a zeolite, preferably, the maximum amount will be 30% by weight.

[0115] The alkali metal aluminosilicate can be crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na2O. Al2O3. 0.8-6 SiO2.

[0116] These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg Ca / g. Preferred sodium aluminosilicates have 1.5-3.5 SiO2 units (in the formula above). Both amorphous and crystalline materials can be easily prepared by the reaction between sodium silicate and sodium aluminate, as widely described in the literature. Anti-lime ion detergent detergent agents for crystalline sodium aluminosilicates are described, for example, in GB-A-1 429 143. Preferred sodium aluminosilicates of this type are the well-known commercially available ones

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25/43 zeolites A and X, and mixtures thereof.

[0117] Zeolite may be the commercially available zeolite 4A, currently widely used in powdered laundry detergents. However, according to a preferred embodiment of the invention, the zeolite anti-lime agent incorporated in the compositions of the invention is the maximum aluminum zeolite P (zeolite MAP) as described and claimed in EP-A-384 070. The zeolite MAP is defined as an alkaline metal aluminosilicate of the zeolite type P having a silicon to aluminum ratio not exceeding 1.33, preferably within the range of 0.90 to 1.33, preferably within the range of 0.90 to 1, 20.

[0118] Especially preferred is zeolite MAP with a silicon to aluminum ratio of no more than 1.07, preferably around 1.00. The calcium-binding capacity of the MAP zeolite is generally equivalent to at least 150 mg of CaO per g of anhydrous material.

[0119] Organic anti-lime agents that may be present include polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers and acrylic phosphinates; monomeric polycarboxylates, such as citrates, gluconates, oxidisuccinates, glycerol mono-, di- and tri-succinates, carboxymethyloxy succinates, carboxymethyloxylates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulfonated fatty acid salts. This list is not meant to be exhaustive.

[0120] Especially preferred organic anti-lime agents are citrates, properly used in quantities of 2 to 30% by weight, preferably from 5 to 25% by weight; and acrylic polymers, especially in acrylic / male copolymers, duly used in amounts of 0.5 to 15% by weight, preferably 1 to 10% by weight.

[0121] Anti-lime agents, both organic and inorganic, are preferably present in the form of alkali metal salts, especially sodium salt.

[0122] When compositions have bleaching or generator content

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26/43 of bleaching, they may advantageously also contain one or more heavy metal chelating agents. This reduces bleach damage. Generally, chelating agents suitable for use here can be selected from the group consisting of aminocarboxylate, aminophosphonate, polyfunctional-substituted aromatics and their mixtures. Without claiming to be linked to a theory, it is believed that the advantage of these materials is due in part to their exceptional ability to remove heavy metal ions from washing solutions by the formation of soluble chelates; other benefits include inorganic film or prevention of scale. Other chelating agents suitable for use in the present invention are those from the DEQUESTO commercial series and chelators from Monsanto, DuPont and Nalco Inc.

[0123] Aminocarboxylates useful as optional chelators include ethylene diaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminohexacetates, diethylenetriamine-pentacetates and amine alkalines and ethanoldigines.

[0124] 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 ethylene diaminetetrakis (methylene phosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.

[0125] Polyfunctional-substituted aromatic chelators are also useful in the compositions of the present invention. See U.S. 3,812,044. Preferred compounds of this type of acid are: dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

[0126] A chelator for use in the invention is ethylenediamine disuccinate (“EDDS”), especially (but not limited), to the [S, S] isomer as described

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27/43 in U.S. 4,704,233. Trisodium salt is preferred over other forms, such as magnesium salts, can also be useful.

[0127] If such transition metal selective chelating or sequestering agents are used, it will preferably comprise from about 0.001% to about 10%, preferably about 0.05% to about 1% by weight of the bleaching compositions.

[0128] Compositions for washing clothes according to the invention can also contain one or more enzymes. Such enzymes can provide benefits in cleaning performance, tissue care and / or hygiene. Suitable enzymes include proteases, amylases, cellulases, lipases, oxidases / oxide reductases, transferases, hydrolases, peroxidases, isomerases lyases and ligases, useful for incorporation into detergent compositions.

[0129] Appropriate members of these classes of enzymes are described in the 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.

[0130] Examples of hydrolases are carboxylic ester hydrolase, thiolester hydrolase, phosphoric monoester hydrolase and phosphoric diester hydrolase, which act on the ester bond; glycosidase, which act on Oglycosyl compounds, N-glycosyl compounds hydrolysis glycosylase; thioether hydrolase that act on the ether bond; and exopeptidases and endopeptidases that act on the peptide bond. Preferably among them are the carboxylic ester hydrolases, exo- and endopeptidases and glycosidases. 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, phycin, thrombin, plasmin, renin, subtilisin, aspergillopepsin, collagenase, clostripain, kallikrein, gastricsin, cathepsin D,

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28/43 bromelain, chymotrypsin C, urokinase, cucumisine, orizine, proteinase K, termomycin, termitase, lactocepine, thermolysin, bacillolysin. The preferred one among them is subtilisin; (2) glycosidases such as α-amylase, Q-amylase, glucoamylase isoamylase, cellulase, endo-1,3 (4) -glucanase, xylanase, dextranase, polygalacturonase (pectinase), lysozyme, invertase, hyaluronidase, pululanase, chlulanase, arabinosidase, exocelobiohydrolase, hexosaminidase, mycodextranase, endo-1,4-mannanase (hemicellulase), xyloglucanase, endo-galactosidase (keratanase), mannanase and other enzymes that degrade saccharide gums, as described in document WO-A99 / 09127. Preferred among them are α-amylase and cellulase ester carboxylic ester hydrolase including carboxylesterases, lipase, phospholipase, pectinesterase esterase cholesterol, chlorophyllase, tanase and wax-ester hydrolase. Preferred among them is lipase.

[0131] Examples of transferases and ligases are glutathione S transferase and acid-thiols ligase as described in WO-A-98/59028 and xyloglycan endotransglycosylase as described in WO-A98 / 38288.

[0132] Examples of lyases are hyaluronate lyase, pectate lyase, lipex, chondroitinase, pectin lyase, alginase II. Especially preferred is pectolase, which is a mixture of pectinase and pectin lyase.

[0133] Examples of oxidoreductases are oxidases like glucose oxidase, methanol oxidase, bilirubin oxidase, catechol oxidase, laccase, peroxidases like the ligninases described in WO-A-97/31090, monooxygenases, dioxigenase like 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 as described in WO-A-99/02641.

[0134] The activity of oxidoreductases, in particular phenoloxidizing enzymes in a process of bleaching stains on fabrics and / or inks in solution and / or antimicrobial treatment, can be enhanced by

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29/43 addition of certain organic compounds, called enhancers. Examples of enhancers are: 2,2'-azo-bis- (3-ethylbenzo-thiazoline) -6sulfonate (ABTS) and phenothiazine-10-propionate (PTP). Other enhancers are described in WO-A-94/12619, WO-A-94/12620, WO-A94 / 12621, WO-A-97/11217, WO-A-99/23887. Potentiators are generally added at a level of 0.01% to 5% by weight of the detergent composition.

[0135] Preferred proteolytic enzymes (proteases) are catalytically active protein materials that degrade or alter the protein types of stains when present as stains on tissues in a hydrolysis reaction. They can be of any suitable origin, such as vegetable, animal, bacterial or yeast.

[0136] Proteolytic enzymes or proteases of different qualities and origins and having activity in different pH ranges ranging from 4 to 12 are available and can be used in the present invention. Examples of suitable proteolytic enzymes are subtilisins that are obtained from specific B. subtilis and B. licheniformis strains, such as the commercially available subtilisins MaxataseTM, supplied by Gist Brocades N.V., Delft, The Netherlands; and AlcalaseTM, supplied by Novo lndustri A / S, Copenhagen, Dinaetiqueta.

[0137] Especially suitable is a protease obtained from a strain of Bacillus having maximum activity throughout the pH range 8 to 12, being commercially available, for example, by Novo Industri A / S registered under the trade name EsperaseTM and SavinaseTM. The preparation of these and similar enzymes are described in GB-A-1 243 785. Other commercial proteases are KazusaseTM (obtained from Showa-Denko in Japan), OptimaseTM (from Miles Kali-Chemie, Hannover, West Germany), and SuperaseTM ( obtained from Pfizer in the USA).

[0138] Detergent 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 the enzyme can be used. Enzymes

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Suitable and preferred 30/43 can be found in WO 03/104378.

[0139] The compositions of the invention may contain alkali metals, preferably sodium carbonate, to increase detergency and ease of processing. Soda ash can be duly present in amounts ranging from 1 to 60% by weight, preferably from 2 to 40% by weight. However, compositions containing little or no sodium carbonate are also within the scope of the present invention.

[0140] The powder flow can be improved by incorporating a small amount of a powdered structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate / maleate copolymer, or sodium silicate. A preferred structuring powder is fatty acid soap, properly present in an amount of 1 to 5% by weight.

[0141] Still, other materials that may be present in detergent compositions of the invention include: sodium silicate; anti-replenishing agents, such as cellulosic polymers; inorganic salts like sodium sulfate; foam control agents or foam enhancers as appropriate; dyes; colored beads; Perfumes; foam controllers; fluorescent and dissociation polymers. This list is not meant to be exhaustive.

[0142] The compositions of the present invention can, 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, gel or paste. Optionally, liquid compositions can be supplied in water-soluble sachets. Non-solid, e.g. liquid, compositions can have different compositions from solid compositions and can include, for example, from 5% to 60%, preferably from 10% to 40% by weight of anionic surfactants (at least some of which it will, of course, be an aromatic alkyl surfactant

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31/43 sulfonic, from 2.5% to 60%, preferably from 5% to 35% by weight of nonionic surfactant and from 2% to 99% by weight of water.

[0143] Optionally, liquid compositions can, for example, contain from 0.1% to 20%, preferably from 5% to 15% by weight of soap.

[0144] Non-solid, e.g. liquid, compositions may also (subject to any exclusions or other caveats expressed here in the context of any aspect of the invention), include one or more hydrotropes, especially when an isotropic composition is required. Such hydrotropes can, for example, be selected from arylsulfonates, for example benzene sulfonate, one of which is optionally substituted on the aryl ring or ring system by one or more C1-6, for example C1-4 alkyl groups, benzoic acid, salicylic acid, naphthoic acid, C1-6 polyglucosides, preferably C1-4, mono-, di- and tri-ethanolamine. Where any of these compounds can exist in acid or salt (still organic or inorganic, such as sodium), or can be used as long as they are compatible with the rest of the formulation.

Preparation of Compositions [0145] The compositions of the invention can be prepared by any suitable process.

[0146] The choice of the processing route can be partly dictated by the stability or heat sensitivity of the surfactants involved, and in the form in which they are available.

[0147] For granular products, ingredients such as: enzymes, bleaching ingredients, scavengers, polymers and perfumes that are traditionally added separately (for example, post-dosed enzymes such as granules, perfumes sprayed on top), can be added after the described below.

[0148] Suitable processes include:

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

(2) “non-tower” granulation of all ingredients in one

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32/43 high speed mixer / granulator, for example, a Fukae ^TM FS series mixer, preferably with at least one paste surfactant so that the water in the paste surfactant can act as a binder;

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

Description of Non-limiting Examples of the Invention [0149] The invention will be better understood from the following description of some of the examples of the present invention, given by way of example only, with reference to the attached figures.

[0150] In figure 1, water 1 from the main feed is introduced into the pH 2 modifying cell, where the water is separated into acidic and alkaline water. The acidic water is stored in a storage container 6 and alkaline water in storage container 5. The alkaline water in container 5 is fed into the hydrogen peroxide generating cell 4. Water containing high pH hydrogen peroxide is then fed to a bleach generating container 7, where the hydrogen peroxide reacts with the bleach / bleach precursor 8a to form peracid. The peracid-containing solution is subsequently introduced into the washing machine 9 of the bleach generator container 7. The hydrogen peroxide can react with the peracid precursor in the generator container. The generator container can also contain a bleach / bleach catalyst, so a mixture of bleach catalysts + H2O2 is formed. In addition, hydrogen peroxide can be fed directly into the washing machine containing LEIP. This LEIP formulation may contain neither peracid bleach precursor nor catalyst, or may contain peracid bleach precursor, or may contain one bleach catalyst or may contain both.

[0151] Part of the acidic and / or alkaline 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 introduced directly

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33/43 in the washing machine.

[0152] Alternatively, tap water from the main feed can first be fed into a water softening FTC-3 cell. Soft water is then introduced into the pH 2 modifier cell and processed, as explained above. The regeneration of waste water (dotted lines) from all electrochemical cells is drained 10, as well as the waste water from the washing machine. The cells are, for example, regenerated with acidic water from vessel 6; these flows are not shown in the figures to maintain clarity.

[0153] Figure 2 shows the hydrogen peroxide cell 4 from the outside, figure 2b shows the functioning of the components in an exploded view of the cell. 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, oxygen from the air is brought into the chamber through the air inlet 11 and the air can leave the chamber through the outlet 12, when the device is in operation. The catholyte, that is, water, is fed through inlet 13 and the water containing hydrogen peroxide is removed through outlet 14, when the device is in operation, thus producing hydrogen peroxide. Likewise, the anolyte is fed and removed through ports 15 and 16; when the device is in operation the water is fed to the cell and the protons dissolved in water are removed from the anode.

[0154] Figure 2c shows the operation of an electrolysis cell as a pH modifier. In Figure 2c an electrolysis cell, suitable as a pH modifier is shown schematically. 123 water is fed to the cell. Within the cell of figure 2c are two cathodes 125 and anode 124 separated by a non-conductive spacer 126. When in operation, alkaline water 110 is produced at the cathode and acidic water 115 at the anode.

[0155] The electronic tags according to the invention are attached to a plurality of items, some of which are sensitive to the bleach; some of which are sensitive to pH; and some of which are sensitive to both, pH

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34/43 and bleach. The identification information on the label is read while the items are inside the washing machine. As a result, pH modifier / bleach instructions can be obtained while items are loaded / placed in the washing machine. Thus, users of the invention are not required to spend any additional effort through washing to find sensitive items and to wash separately from other non-or less sensitive items.

[0156] 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 items 20 sensitive to both pH / bleach and non-sensitive items 21.

[0157] Each item in pH-sensitive fabric / bleach 20 has an electronic tag 22 attached to it. The electronic tag 22 is definitely incorporated within an element of an item 20, here the button 23 - shown in Figure 4. Other pH sensitive / bleach sensitive items carry a temporary generic electronic tag 22 (not shown). Additional pH-sensitive fabric / bleach items are included in the wash charge, but may not carry any label.

[0158] The electronic tags used in this example are pre-programmed with the various 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 on electronic tag 22, such as identification information, as well as other instructions for washes, and the wash count of item 20. The tag scheduling device 24 can be used to identify items 20 and / or the location of each item 20 within the wash system. Labels can identify items on fabric as sensitive to bleach and / or pH or both. If the fabrics suffer damage / fading due to bleach, then the pH should not be corrected, but the generation of H2O2 will need to be adjusted / stopped. Some items

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35/43 of wool can be labeled as pH sensitive (so that the pH is kept low).

[0159] Each washing machine has a controller that controls its operation. In the configuration of figure 3, the washing machine 26 is controlled by a controller 32, which provides a series of controls having a number of control positions or configurations, including those related to the hydrogen peroxide generation system in situ.

[0160] The communication device with the label 38 is fitted inside the washing machine and communicates the information with the electronic labels 22, while the washing load, including the pH / bleach sensitive fabric items 20 are inside the washing machine. to wash. The presence of only one tag 22 is sufficient to transmit information to the controller to adjust the hydrogen peroxide generation system. The system is adjusted according to the bleach / bleach sensitivity and / or pH. The generation of H2O2 can be stopped completely and / or reduced the pH according to the attached label 22. If both, sensitivity to pH and bleach is identified, then both are adjusted / restricted. In other configurations, the communication device with the tag may include a visual display of the identified information to allow user control, for example, in substitution for this protection system.

[0161] Figure 5 is a schematic of a configuration of an electronic label 22 contained in button 23 of figure 4, which can be used in configurations of the present invention. The electronic tag 22 includes a memory 70, which stores information about an item in pH sensitive fabric / bleach. The information includes sensitivity to pH and sensitivity to H2O2. Preferably, memory 70 is non-volatile so that the stored information is maintained without applying energy to it.

[0162] A processor 72 performs a series of programmed steps to transmit information between memory 70 and the communication device with the label on the washing system. Processor 72 can be in the form of

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36/43 a microprocessor, a custom integrated circuit, a programmable logic matrix, or an application-specific integrated circuit, for example. A receiver 74 is included to receive the information transmitted from the communication device with the tag. A transmitter 76 is provided to transmit information to the communication device with the tag. Preferably, receiver 74 and transmitter 76 transmit information by radio frequency signals. Both receiver 74 and transmitter 76 are coupled to processor 72 to transmit / exchange information with memory 70. As a result, transmitter 76 is operatively associated with memory 70 to transmit information for external reading.

[0163] The circuits inside the electronic tag are powered by an electromagnetic energy receiver 78. The electromagnetic energy receiver 78 receives the electromagnetic energy transmitted to it, and converts the electromagnetic energy into a DC voltage to supply the circuits within the tag. electronics (ie memory 70, processor 72, receiver 74 and transmitter 76).

[0164] The electronic tag is hermetically sealed, in relation to water vapor, high temperature, and washing solutions. The electronic tag is also relatively small and flat, in order to be discreet when permanently attached to an item. In accordance with these preferred specifications, the electronic tag can be constructed in accordance with a method of producing an indoor transmitter-transmitter disclosed in US 5,420,757.

[0165] Figure 6 is a schematic diagram of a configuration of a communication device with the label for use in embodiments of the present invention. The tag communication device includes a processor 80, which performs a series of programmed steps to communicate information to electronic tags 22. As with processor 72, processor 80 can be in the form of a microprocessor, an integrated circuit custom, a logical matrix

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37/43 programmable, or an application-specific integrated circuit. Processor 80 communicates with memory 81 to store information transmitted to electronic tags 22.

[0166] The communication device with the tag includes an electromagnetic transmitter 82 for transmitting an electromagnetic energy signal to supply power to the circuits on the 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 information generated by processor 80 and / or stored in memory 81 to be received by receiver 74 of the electronic tag. A receiver 86 receives the information transmitted by the transmitter 76 from the electronic tag. Receiver 86 communicates information received to processor 80. Processor 80 processes information received to provide a signal, either to adjust or verify controls on the controller, or to alert a user of an incorrect setting.

[0167] Figure 7 is a flow chart of a method of communication with a plurality of electronic tags. This method can be used by a communication device with the tag to read a plurality of washing instructions stored in a plurality of electronic tags contained within a washing machine. It should be noted that in the washing processes, within the scope of this invention, a plurality of garments have labels to communicate that the presence of pH-sensitive garments / bleach may be present, a single pH-sensitive garment, a single bleach / bleach sensitive part, a single pH sensitive and bleach part, or there may be no sensitive parts present. If no sensitive parts are present, then the following scheme will not be followed. If at least one garment is present with a warning label / instruction for pH sensitivity and / or bleach sensitivity, then the following sequence will be applied. The method starts with a step of transmitting a signal from

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38/43 sequence 130, electronic tags 22 using transmitter 84 on the communication device with the tag. The sequence signal is used by each of the electronic tags to determine their position in a sequence to communicate with the communication device with the tag. In a preferred embodiment, the sequence signal includes a representation of a length sequence, which is used by each electronic tag to randomly determine its position within the sequence. The length of the sequence can be selected depending on the capacity of the washing machine. As indicated by block 132, a counter initialization step is performed. The counter is used to indicate the current position in the communication sequence. The counter is normally initialized using processor 80 and stored either within processor 80 or memory 81. Then, transmitter 84 on the communication device with the tag transmits an information request signal, as indicated by block 134. The information request signal requests the electronic tag having the current position in the sequence to transmit information to the communication device with the tag. As indicated by block 136, the receiver 86 in the communication device with the tag hears a signal from the tag, from one or more of the electronic tags. Processor 80 then verifies that the tag signal is received from a single electronic tag, as indicated by block 138. If a tag signal is received from a single tag, then the information contained in the tag signal is stored in memory 81 of the communication device with the tag, as indicated by block 140. To confirm receipt of the signal from the tag, transmitter 84 sends an acknowledgment signal, as indicated by block 142.

[0168] Note that a tag signal is not received from a single electronic tag if no tag signal has been transmitted or if signals from two or more tags have been transmitted. If two or more tag signals have been transmitted, a collision occurs where the information cannot

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39/43 be extracted from each tag signal. When sending the signal warning at block 142, or if a tag signal is not received from a single electronic tag at block 138, a step of determining whether the counter has reached a certain limit is performed, as indicated by block 144. The predetermined limit is indicative of a sequence of predetermined length, which is preferably contained in the stepwise transmitted signal indicated by block 130.

[0169] If the counter has not reached the predetermined limit, then a step of incrementing the counter is performed, as indicated by block 146. Subsequently, the flow of the method is directed back to block 134 to transmit another signal order to communicate with another electronic tag. If the meter has reached the predetermined limit, then steps are taken to determine whether the information has been successfully received and stored from all electronic tags. First, a step of transmitting a request signal for unknown tags is performed by transmitter 84, as indicated by block 148. Receiver 86 then listens for signals produced by all unknown tags, as indicated by block 150. As indicated by block 152, processor 80 performs a step to determine whether a signal is received by an unrecognized tag.

[0170] If a signal is received from an unrecognized tag, then the method flow is directed back to block 130 where a new sequence signal is transmitted. Preferably, the new sequence signal includes a representation of a shortened sequence to communicate with unknown tags. If no signal is received from the unknown tags, then the method of communicating with the electronic tags is complete.

[0171] It should be noted that in the washing processes, within the scope of this invention, a plurality of garments containing labels to communicate the presence of pH sensitive and / or bleach clothing may be

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40/43 present, a single piece sensitive to pH, a single piece sensitive to bleach, a single piece sensitive to pH and bleach / bleach, or the absence of sensitive pieces present. If no sensitive parts are present, then the following scheme will not be followed. If at least one garment.

[0172] Figure 8 is a flow chart of a method configuration for an electronic tag to communicate with a communication device with the tag. As indicated by block 160, a step of receiving the sequence signal transmitted by the communication device with the tag is performed by the receiver 74 on the electronic tag. Preferably, the sequence signal includes a representation of an integer indicative of the length of the predetermined sequence. As indicated by block 162, processor 72 on the electronic tag generates a random number to determine its position in the communication sequence. The random number is discrete and generated based on a predefined probability distribution (that is, the probability mass function or probability function). Preferably, the probability distribution is dependent on the representation of the length of the predetermined sequence contained in the sequence signal. In one embodiment, the random number is representative of an integer from one to the length of the sequence. The random number is generated based on a uniform discrete distribution where each of the integers from one to the length of the sequence is equally likely to be selected. Receiver 74 on the electronic tag responds to all signals transmitted by the communication device with the tag, as indicated by block 164. As indicated by block 166, processor 72 determines whether an information request signal is received for the electronic tag based on the random number. If an information request signal is received by the electronic tag, a step of transmitting an information signal is performed as indicated by block 168.

[0173] After transmitting the information signal, receiver 74 answers a

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41/43 recognition signal from the communication device with the label, as indicated in step 170 of block. If a recognition signal is received in block 172, then the information signal was successfully received by the communication device with the label and the method execution is complete. If an acknowledgment signal is not received, or equivalent, if an error signal is received, then the method flow is directed back to block 164. Note that an information request signal is not received by the electronic tag on the block 166, if an information request signal is transmitted by the communication device with the tag to another electronic tag, or if an unknown tag request signal is transmitted.

[0174] If an information request signal is not received by the electronic tag in block 166, then a step to determine if an unknown label request signal has been received is performed by block 174. If a label request signal unknown is not received, then the flow of the method is directed back to block 164. If an unknown tag request signal is received, then a step of sending a signal indicating an unknown tag is performed, as indicated by block 176. The method flow is then directed back to block 160 to receive another sequence signal.

[0175] Figure 9 is a block diagram of a configuration of a label programming device for use in configurations of the present invention. The tag programming device includes a processor 180 that performs a series of programmed steps to communicate information with electronic tags 22. Processor 180 can be in the form of a microprocessor, a custom integrated circuit, a programmable logic matrix, or a integrated circuit for specific application. Processor 180 communicates with memory 182 to store information communicated with electronic tags 22.

[0176] An electromagnetic energy transmitter 184 is provided for

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42/43 transmit an electromagnetic energy signal to power the circuits of an electronic label. The electromagnetic energy transmitter 184 is activated and deactivated in response to commands provided by processor 180. An input device 186 is provided in communication with the processor 180. Input device 186 may be in the form of one or more buttons, a keyboard, a "touchpad", or "touchscreen", which allows information and / or instructions to be entered into the label programming device by the user. Processor 180 processes information and instructions to form signals that are applied to a transmitter 188. Transmitter 188 transmits the signals for reception by receiver 74 on the electronic tag. The signs can be indicative of a request for information stored on the electronic tag, such as a request for identifying information for the item material or a request for the current count value. The signs can be indicative of information that must be stored on the electronic label, such as identification information, washing instructions and water processing instructions. A receiver 190 receives the information transmitted by transmitter 76 on 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 a means for presenting the information requested by the user, such as information identification number and the current count value. It is preferred that the display device 192 is capable of displaying numerical or alphanumeric information. As such, the display device 192 can be based on light emitting diodes or liquid crystal technologies.

[0177] The great advantage of the invention is that only a limited number of garments need to be labeled. Thus, the penetration rate will be higher. In addition, the producer can add the labels without alerting the consumer that this is an especially sensitive piece. This information

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43/43 is hidden on the label. Another possible advantage is that it would also be possible to supply / sell labels / tags to consumers, who will be able to label parts that are very sensitive (in their opinion), and thus, maintain total control of the process.

[0178] It will be apparent to those skilled in the art, that the present invention can be altered in various ways and may take on many different configurations from those specifically preferred and described above.

Claims (3)

1. Washing system for washing multiple items of fabric (s), including one or more items of sensitive fabric in a washing machine (26) with a detergent composition comprising 3 to 20% by weight of the total fabric composition. alkylbenzene sulfonic surfactant, in its acid and / or salt-free forms, characterized by the washing system comprising: a hydrogen peroxide generation system in situ (4); a pH regulating device (2); a communication device with the tag, which reads a washing instruction contained in an electronic tag (22) connected to any item in sensitive fabric; a controller (32) in communication with the communication device with the label (38) to control the washing machine (26), in order to adjust the hydrogen peroxide generation system according to the sensitivity of the fabric item to the bleach and / or pH. 2/3 sulfonate (SBOBS); Ν, Ν, Ν’Ν’-tetraacetyl ethylene diamine (TAED); sodium-1-methyl2-benzoyloxy benzene-4-sulfonate; sodium-4-methyl-3-benzoyloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulfonate; nonanoyloxybenzene sulfonate sodium (SNOBS); 3,5,5-trimethyl hexanoyloxybenzene sulfonate sodium (STHOBS); substituted cationic nitriles or (nonanamidocaproyl) oxybenzene sulfonate. Washing system according to any one of claims 1 to 4, characterized in that the detergent composition comprises a bleach catalyst, selected from transition metal bleach catalysts, containing at least one transition metal partially covalently bonded, and bonded to at least one binder, or organic bleach catalysts, having activated imines which in reaction with peracids result in oxaziridine; in a peroxide: catalyst ratio between 500: 1 and 5000: 1, on a molar basis. Washing system according to any one of claims 1 to 5, characterized in that the detergent composition comprises a bleach precursor and a bleach catalyst. 7. System in wash, in wake up with any one of claims 1 to 6, featured for understanding a water softener Water. 8. System in wash, in wake up with any one of claims 1 to 7, characterized by the water softener (3) comprising an ion exchanger and / or electrodialysis and / or capacitive deionization and / or flow through capacitance. Washing system according to any one of claims 1 to 8, characterized in that the detergent composition is substantially free of pH-modifying components. Washing system according to any one of claims 1 to 9, characterized in that the detergent composition is substantially free of anti-lime agent. 11. Washing system, according to any of the Petition 870190031026, dated 04/01/2019, p. 54/68 2. Washing system according to claim 1, characterized by the hydrogen peroxide generation system (4) comprising an electrochemical cell (4) for the production of hydrogen peroxide from water and air. Washing system according to any one of claims 1 to 2, characterized in that the pH regulating device (2) comprises an electrochemical cell (2) that includes one or more anodes (124) and cathodes (125) for the production acid and alkaline water, in which no addition of chemicals is required when the device (2) is in operation. Washing system according to any one of claims 1 to 3, characterized in that the detergent composition comprises 2 to 10% by weight of the composition of bleach precursors or activators, selected from the group consisting of: sodium-4-benzoyloxy benzene Petition 870190031026, dated 04/01/2019, p. 53/68 3/3 claims 1 to 10, characterized in that the detergent composition is substantially free of hydrogen peroxide, sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate, or an oxidase enzyme that generates hydrogen peroxide.