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Title:
SIGNAL-BASED ELECTROCHEMICAL METHODS FOR AUTOMATIC DISHWASHING
Document Type and Number:
WIPO Patent Application WO/2003/097782
Kind Code:
A1
Abstract:
Methods of improving tableware cleaning, sanitizing and stain removal using an automatic dishwashing appliance containing an electrochemical cell and/or electrolytic device. The methods comprise steps for generating electrolyzed water by intermittently activating and/or intermittently deactivating the cell so as to sequentially provide a bleaching species at specific times during the wash and/or rinse cycle. Said methods include a signal-sensing system capable of detecting a composition comprising a signal-providing agent, methods of using said compositions, and articles of manufacture. The bleaching liqour comprises the electrolysis products of halide anions and mixture thereof.

Inventors:
Price, Kenneth Nathan (265 Compton Road, Cincinnati, OH, 45215, US)
Scheper, William Michael (2393 Picnic Woods Drive, Lawrenceburg, IN, 47025, US)
Tremblay, Mario Elmen (7897 Woodglen Drive, West Chester, OH, 45069, US)
Drzewiecki, Paul Joseph (3049 Socialville-Foter Road, Maineville, OH, 45039, US)
Application Number:
PCT/US2003/015233
Publication Date:
November 27, 2003
Filing Date:
May 15, 2003
Export Citation:
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Assignee:
THE PROCTER & GAMBLE COMPANY (One Procter & Gamble Plaza, Cincinnati, OH, 45202, US)
International Classes:
A47L15/44; A47L15/00; A47L15/42; A61L2/03; C11D3/02; C11D3/386; C11D3/395; C11D11/00; C11D17/00; C11D17/08; D06F35/00; (IPC1-7): C11D3/395; A47L15/44; C11D3/02; C11D3/386
Attorney, Agent or Firm:
Reed, David T. (The Procter & Gamble Company, 6110 Center Hill Road Cincinnati, OH, 45224, US)
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Claims:
What is Claimed is:
1. A method for cleaning tableware, is characterized in that it comprises the steps of sequentially contacting said tableware with an aqueous cleaning liquor comprising a bleach unstable ingredient and an aqueous bleaching liquor comprising the electrolysis products of electrolytes selected from the group consisting of halide anions, halite anions, and mixtures thereof.
2. A method according to Claim 1 which is conducted in an automatic dishwashing appliance, said appliance comprising an electrochemical cell and means for delivering said aqueous cleaning liquor and said aqueous bleaching liquor to said tableware in a predetermined sequence.
3. A method according to Claims 1 or 2, wherein said bleach unstable ingredient in said cleaning liquor comprises a detersive enzyme selected from the group consisting of protease, amylase, and mixtures thereof, and wherein said tableware is contacted with said cleaning liquor prior to contact with said bleaching liquor.
4. A method according to Claim 2 wherein said automatic dishwashing appliance comprises at least one attached, integrated, signalsensing electrochemical cell and/or at least one attached, integrated electrolytic device comprising said signalsensing cell for producing electrolyzed water, said method comprising the steps of : (a) placing tableware in need of treatment into said appliance; (b) providing said signalsensing cell comprising at least one inlet opening and one outlet opening, and at least one pair of electrodes defining at least one cell gap comprising at least one cell passage formed therebetween through which an aqueous electrolytic solution can flow; (c) providing said aqueous electrolytic solution in said appliance in fluid communication with said signalsensing cell and/or device; (d) providing at least one activator and/or deactivator selected from the group consisting of timer, sensor, signalproviding chemical, signalproviding detergent composition and combinations thereof. (e) intermittently activating said signalsensing cell and/or device via said activator at least one specific time in the wash and/or rinse cycle; (f) electrolyzing said aqueous electrolytic solution in said signalsensing cell to produce at least some electrolyzed water; (g) discharging said electrolyzed water into the wash and/or rinse liquor via a washing basin in said appliance during at least one specific time in the wash and/or rinse cycle (s); (h) interrupting electrolyzation of said aqueous electrolytic solution and/or not releasing said electrolyzed water at other times in the wash and/or rinse cycle (s); (i) contacting said tableware in need of treatment with said wash and/or rinse liquor comprising said electrolyzed water; (j) intermittently deactivating said signalsensing cell via said deactivator during at least one specific time in the wash and/or rinse cycle (s); (k) optionally contacting said tableware with a wash and/or rinse liquor comprising a bleachscavenging agent and/or metalprotecting agent; and (1) optionally repeating steps (c) through (k).
5. A method according to Claim 2 wherein said automatic dishwashing appliance comprises a signalsensing electrochemical cell and/or a signalsensing an electrolytic device comprising said signalsensing cell, said method using a signal system comprising a signal sensor, a signal providing detergent composition in conjunction with said signalsensing cell and/or device, said method comprising the steps of : (a) placing tableware in need of treatment in said appliance (b) providing a signalsensing system; wherein said signalsensing cell comprises at least one inlet opening and one outlet opening, and at least one pair of electrodes defining at least one cell gap comprising at least one cell passage formed therebetween through which an aqueous electrolytic solution can flow, wherein said signal sensor can be activated and/or deactivated by said signalproviding composition, wherein said sensor is located within said appliance, said signalsensing cell, said signal sensing device, and combinations thereof; (c) providing said aqueous electrolytic solution in fluid communication with said signal sensing cell via tap water, wash and/or rinse liquor, and/or mixtures thereof ; (d) providing at least one activator and/or deactivator in the form of said signalproviding composition comprising a signalproviding agent in said wash and/or rinse liquor; (e) optionally contacting said signal sensor with said signalproviding composition in order to activate and/or deactivate said least one signalsensing cell, wherein said signalsensing cell activation and/or deactivation starts or stops electrolyzed water production in said signalsensing cell; (f) optionally contacting said signal sensor of said signalsensing electrolytic device with said at least one signalproviding composition in order to activate a timer to delay said electrolyzed water production in said signalsensing signalsensing cell for a specific time period, wherein after said timed delay said at least one signalsensing cell is activated; (g) passing said aqueous electrolytic solution through at least one activated signal sensing cell to generate at least some electrolyzed water in the wash and/or rinse liquor of said appliance; (h) contacting said tableware with said electrolyzed water in the wash and/or rinse cycle of said appliance; (i) optionally contacting said signal sensor of said electrolytic device with said signal providing composition comprising said signalproviding agent to deactivate said at least one signalsensing cell in order to stop production of said electrolyzed water; (j) optionally contacting said tableware with a wash and/or rinse liquor comprising a chlorinebleachscavenging agent or metalprotecting agent; and (k) optionally repeating steps (c) through (j) until the tableware needing treatment are treated.
6. A method according to Claims 4 or 5, wherein said signalsensing cell and/or device comprises a characteristic selected from the group consisting of attached, integrated, unattached, selfpowered, selfcontained, partitioned, nonpartitioned, recirculating, nonrecirculating, energy saving, disposable, nondisposable, and combinations thereof.
7. A method according to any one of Claims 4 through 6, wherein said signalsensing cell and/or device comprises a sensor which is capable of analyzing the composition and/or properties of the liquid or gaseous environment within said signalsensing cell, said device and/or said appliance, and wherein said sensor can electrically and/or electronically control the production and/or discharge of said electrolyzed water at said specific time during said wash and/or rinse cycle by turning on said activator and/or said deactivator.
8. A method according to any one of Claims 4 through 7, wherein said sensor is one selected from the group consisting of turbidity sensor, water hardness sensor, pH sensor, conductivity sensor, a sensor capable of detecting the presence of a volatile gaseous compound, and combinations thereof.
9. A method according to any one of Claims 4 through 8, wherein said activator and/or deactivator is chemicalbased, wherein said activator and/or deactivator has the ability to detect the presence and/or absence of a signalproviding chemical in said wash and/or rinse liquors and/or their corresponding gaseous vapors via said sensor in order to activate and/or deactivate said signalsensing cell and/or device;.
10. A method according to any one of Claims 4 through 9, wherein said activator and/or deactivator is mechanicalbased, wherein said activator and/or deactivator has the ability to turn on and off said signalsensing cell and/or device via a variety of cyclelinked appliance performance options on said appliance which offer the consumer a combination of cleaning performance and/or sanitization.
11. A method according to any one of Claims 4 through 10, wherein said activator and/or deactivator is electronicbased, wherein said activator and/or deactivator comprises a computer device that communicates with said appliance, signalsensing cell and/or device, and combinations thereof ; wherein said computer device is preprogrammed to offer consumers a means to allow said signalsensing cell and/or device to be turned on or off during specific wash and/or rinse cycles and settings of said appliance, and wherein said computer device is selected from among the group consisting of programmable, nonprogrammable, and combinations thereof.
12. A method according to any one of Claims 4 through 11, wherein said activator and/or said deactivator is electronicbased comprising a radiotransmitting device allowing communication with said appliance, signalsensing cell, and/or device; wherein said radiotransmitting device offers consumers a means to allow said signalsensing cell and/or device to be turned on and/or off at least one specific time during said wash and/or rinse cycle for most major brands of automatic dishwashing appliances available to the consumer.
13. A method according to any one of Claims 4 through 12, wherein said appliance comprises a universal remote control device allowing communication with said signalsensing cell and/or device; wherein said universal remote device is preprogrammed to offer consumers a means to allow said signalsensing cell and/or device to be turned on and/or off at least one specific time during said wash and/or rinse cycle for most major brands of automatic dishwashing appliances available to the consumer.
14. A method according to any one of Claims 4 through 13, wherein said appliance and/or device further comprising a timer to control production of said electrolyzed water, wherein said timer is selected from the group consisting of mechanical timer, electric timer, electronic timer, and combinations thereof ; and wherein when said sensor detects the presence and/or absence of said signalproviding chemical in said wash and/or rinse liquor, said sensor initiates the activation of a timer such that from a certain period of time after activation of said timer, said signalsensing cell and/or device is activated and/or deactivated thereby controlling production and/or discharge of said electrolyzed water.
15. A method according to any one of Claims 4 through 14, wherein said appliance comprises a universal remote control device allowing communication with said electronicbased activator and/or deactivator within said appliance, signalsensing cell and/or device; wherein said universal remote device is preprogrammed to offer consumers a means to allow said signalsensing cell and/or device to be turned on and/or off at least one specific time during said wash and/or rinse cycle for most major brands of automatic dishwashing appliances available to the consumer.
16. A method according to any one of Claims 4 through 15, wherein said signalsensing cell and/or device comprises a signal sensor which is activated and/or deactivated by sensing a signal providing composition via the gaseous phase, the aqueous phase, or combinations thereof.
17. A method according to Claim 16, wherein prior to the step of providing an activator and/or deactivator, said method further comprises the steps of providing a detergent composition, rinse aid composition, and mixtures thereof, and delivering said composition to said wash and/or rinse liquor; wherein said composition comprises at least one signalproviding agent, chemical or composition.
18. A method according to Claim 17, wherein said signalproviding agent is selected from the group consisting of nanoparticles, colloidal particles, functionalized surface molecules, polymers, salts, surfactants, metal ions, proteins, dyes, UVactive materials, fluorescent materials, organic acids, organic bases, inorganic acids, inorganic bases, organic solvents, builders, bleaches, bleach activators, bleach catalysts, enzymes, nonactivated enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release polymers, wetting agents, dispersants, suds suppressors, gases, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, hydrolyzable cosurfactants, antioxidants, germicides, fungicides, halide ions, color speckles, silvercare, anti tarnish and/or anticorrosion agents, alkalinity sources, solubilizing agents, carriers, perfumes, processing aids, pigments, and pH control agents, and mixtures thereof.
19. A method according any one of the preceding claims, wherein said aqueous electrolytic solution or aqueous cleaning liquor comprises salts having the formula (M) x (X02) y and/or (M) x (X) y, wherein X is Cl, Br, or I, wherein M is a metal ion or cationic entity, and wherein x and y are chosen such that said salt is charge balanced.
20. A composition of matter consisting essentially of the in the wash and/or rinse liquor of an automatic dishwashing appliance comprising a signalsensing system comprising a sensor, a signalsensing electrochemical cell and/or electrolytic device comprising said signalsensing cell, for improved tableware cleaning, sanitizing, and/or stain removal, said composition of matter comprising: (a) at least some electrolyzed water comprising halogencontaining mixedoxidant species ; (b) a composition comprising a compound selected from the group consisting of an electrolytic composition comprising halogen ions, an electrolytic composition comprising halogencontaining salts having the formula (M) X (XO2) y and/or (M) X (X) y wherein X is Cl, Br, or I and wherein M is a metal ion or cationic entity and wherein x and y are chosen such that the salt is charge balanced, an electrolysis precursor compound, a halogencontaining salt with low water solubility, an electrolysis precursor compound contained within a medium for controlled release, and mixtures thereof ; (c) a signalproviding detergent composition comprising a signalproviding agent selected from the group consisting of nanoparticles, colloidal particles, functionalized surface molecules, polymers, salts, surfactants, metal ions, proteins, dyes, UVactive materials, fluorescent materials, organic acids, organic bases, inorganic acids, inorganic bases, organic solvents, builders, bleaches, bleach activators, bleach catalysts, enzymes, nonactivated enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release polymers, wetting agents, dispersants, suds suppressors, gases, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, hydrolyzable cosurfactants, antioxidants, germicides, fungicides, halide ions, color speckles, silvercare, antitamish and/or anticorrosion agents, alkalinity sources, solubilizing agents, carriers, perfumes, processing aids, pigments, and pH control agents, and mixtures thereof; and (d) optionally, adjunct ingredient.
Description:
SIGNAL-BASED ELECTROCHEMICAL METHODS FOR AUTOMATIC DISHWASHING FIELD OF THE INVENTION The present invention relates to methods of improving tableware cleaning, sanitizing and stain removal using an automatic dishwashing appliance containing an electrochemical cell and/or electrolytic device. The methods comprise steps for generating electrolyzed water by intermittently activating and/or intermittently deactivating the cell so as to sequentially provide a bleaching species at specific times during the wash and/or rinse cycle. The methods include a signal-sensing system capable of detecting a composition comprising a signal-providing agent, methods of using the compositions, and articles of manufacture.

BACKGROUND OF THE INVENTION Electrochemical cells for use in automatic dishwashing appliances are designed to operate by making use of the water electrolysis process. Further, when a halogen-containing water (such as, natural water containing sodium chloride or an aqueous solution of sodium chloride) can be subjected to electrolysis, halogenated mixed oxidants are generated in the electrolyzed water.

The following references disclose use of electrochemical cells: U. S. Patent No.

5,932, 171; U. S. Patent No. 4,481, 086; U. S. Patent No. 4,434, 629; U. S. Patent No. 4,493, 760; U. S.

Patent No. 4,402, 197; U. S. Patent No. 5,250, 160; U. S. Patent No. 5,534, 120; U. S. Patent No.

5,865, 966; U. S. Patent No. 5,947, 135; JP Application No. 10057297A; JP Application No.

10179489A; JP Application No. 10033448A; JP Patent No. 09122060; JP Patent No.

2000116587; JP Patent No. 10178491; and EP Application No. 0983806A1.

The following references are also related to electrolyzed water: U. S. Patent No.

3,616, 355; U. S. Patent No. 4,048, 047; U. S. Patent No. 4,062, 754; U. S. Patent No. 4,100, 052; U. S.

Patent No. 4,328, 084; U. S. Patent No. 4,761, 208; U. S. Patent No. 5,314, 589; U. S. Patent No.

5,395, 492; U. S. Patent No. 5,439, 576; U. S. Patent No. 5,954, 939 (equiv. EP 711,730) ; and WO 00/34184.

A key advantage of electrolyzed water can be that it can provide improved cleaning, stain removal and sterilization benefits in dish care, largely due to the halogenated mixed oxidants generated.

The problem can be that there can be no easy, economical manner to control the production of electrolyzed water in coordination with the cycle times of an automatic dishwasher.

The use of electrolyzed water alone will not achieve satisfactory cleaning, sanitizing and stain removal performance. It is simply not enough to simply provide a source of electrolyzed water for use in an automatic dishwashing appliance comprising an electrochemical cell and/or electrolytic device (hereinafter"cell and/or device"). In order for the electrolyzed water keep from interfering with essential cleaning aspects of the appliance (inter alia, enzyme detergency), it can be necessary for the operation of the cell and/or device to be carefully coordinated with the specific parameters associated with the automatic dishwashing cycle and/or process (e. g. water fills, wash subcycles, rinse subcycles, release of detergents and rinse aid compositions, etc).

Accordingly, there can be a clear need in the art for a method for improving tableware cleaning, sanitizing and stain removal by controlling the production of electrolyzed water at specific times in the wash and/or rinse cycle using an automatic dishwashing appliance. The cell and/or device should be capable of being turned on and off at specific times in the wash and/or rinse cycle by some means of control or coordination.

It has surprisingly been found that a'customized'cell and/or device can provide the control and coordination required to provide electrolyzed water at specific times in the wash and/or rinse cycle in an automatic dishwashing appliance. The key can be providing a form of detection and communication between the appliance and the cell and/or device that allows the cell to be turned off and on at specific times during the wash and/or rinse cycles. One solution to the problem can be using a simple timer. For example, the appliance can turn on the cell and/or device ten minutes after the main wash has begun so that the enzymes present in the formula have had that period of time to render their cleaning action before the enzyme-denaturing halogenated mixed oxidants are released.

However, to obtain greater precision than using mechanical timers alone, fine-tuned coordination of the introduction of electrolyzed water can be achieved by using a signal-sensing system. With an attached cell and/or device, sensors can be hard-wired into the appliance's own cycle control system to allow for detection and analysis of a host of matrices, including but not limited to, the detergent composition and/or properties of the liquid or gaseous environment of appliance, cell and/or device, and combinations thereof, wherein the signal-sensing system can control the production and/or release of electrolyzed water at a specific time or times during a wash. Thus, unlike timed cycles, the signal-sensing system of the present invention can be capable of generating electrolyzed water in any number of measured responses to changes in the washing and/or rinsing environment according to the properties detected. For example, use an automatic dishwashing composition comprising a chemical trigger, such as a source of alkalinity, could produce a change in pH in the wash and/or rinse water, which then could be immediately detected by the sensor. The sensor would then alert the cell to activate and/or deactivate production of electrolyzed water during the wash and/or rinse cycle. For example, during the rinse cycle, the signal-sensing system could ensure sanitization without the need of the heating element. This system provides real time control and offers distinct advantages over the timer mechanisms of the prior art.

For unattached electrolytic devices comprising electrochemical cells used to generate electrolyzed water in automatic dishwashing appliances, the signal-sensing system of the present invention provides even more surprising and dramatic results. An unattached device does not know when it should start or stop producing electrolyzed water so as to ensure optimal performance and compatibility with the rest of the chemistry happening during the wash and/or cycle of an automatic dishwashing appliance. Like the attached devices, described above, chemical triggers, such as a signal-providing agent, could be used to provide good end-result performance. Nonetheless, the present invention takes this one step further by designing the dishwashing appliance and the unattached electrolytic device as a pair, providing a precise "match"between the appliance's performance cycles and when the device turns on & off to ensure optimum compatibility and performance.

A signal agent and sensing cell can be described in terms of a"lock & key"analogy.

The electrochemical cell and/or the electrolytic device can be the lock and the signal chemical can be the key. Not to be limited by theory, this invention can comprise use of an electrochemical cell that can be (a) unattached or attached; (b) recirculating or non-recirculating; (c) disposable or non-disposable and (d) partitioned or non-partitioned, and wherein all of these further include a means for turning the electrochemical cell on and/or off at specific times during the wash cycle.

In recirculating method, the appliance will continuously pull wash and/or rinse liquor from the washing basin of the dishwashing appliance basin into the electrochemical cell. A recirculating cell and/or device can also treat both incoming fresh tap water and/or wash/rinse liquor fluid from the appliance basin. Either method preferably includes an indicator (either electrically-based or chemically-based) for communicating to the consumer when it can be time to replace the cell cartridge for disposable cells and/or devices. The chemical-based signal-providing agent can be delivered by a signal-providing detergent composition.

The appliance, electrochemical cell and/or electrolytic device can themselves include a timer, signal-sensing system, sensor, controller, CPU, and combinations thereof, for intermittently activating and turning on the cell at specific time (s) during the wash and/or rinse cycles.

Furthermore, there can be also a long-felt need in the commercial dishwashing industry to eliminate the need for liquid chlorine bleach to be supplied into the final step of an automatic dishwashing process, since liquid chlorine bleach can be often susceptible to serious environmental hazards from spills. The present invention offers a solution to this long-felt need.

Methods of using an automatic dishwashing appliance in combination with an electrochemical device which comprises an electrolytic cell capable of being turned on and off at specific times in the wash and/or rinse cycle by a signal-providing agent for treating tableware by providing hypochlorite in situ would allow commercial dishwashers to only need a source of chloride-or chlorite-containing salts to improve tableware cleaning, sanitizing and stain removal.

SUMMARY OF THE INVENTION In one aspect of the present invention, a method for cleaning tableware, is characterized in that it may comprise the steps of placing tableware in need of treatment in an automatic dishwashing appliance, and sequentially contacting the tableware with an aqueous cleaning liquor comprising a bleach unstable ingredient and an aqueous bleaching liquor comprising the electrolysis products of electrolytes selected from the group consisting of halide anions, halite anions, and mixtures thereof. The automatic dishwashing appliance can comprise an electrochemical cell and means for delivering the aqueous cleaning liquor and the aqueous bleaching liquor to the tableware in a predetermined sequence. The bleach unstable ingredient in the cleaning liquor comprises a detersive enzyme selected from the group consisting of protease, amylase, and mixtures thereof. In the method, the tableware is contacted with the cleaning liquor prior to contact with the bleaching liquor. The predetermined sequence can encompass delivery of the aqueous cleaning liquor and/or aqueous bleaching liquor in any amount and at any convenient time or order.

The means for delivering the local source of halogen ions can comprise a salt chamber or a porous basket comprising the halogenated salt, preferably a pill of tablet, through which at least some of the aqueous electrolytic solution will pass, thereby dissolving at least some of the halide salt into the portion of water. The salted portion of water then ultimately passes into the electrochemical cell. The salt chamber or a porous basket can comprise a salt void that can be formed in the body and positioned in fluid communication with the portion of water that will pass through the electrochemical cell.

In one aspect of the present invention, a method of improved cleaning, sanitizing, and/or stain removal of tableware in an automatic dishwashing appliance can comprise an attached electrochemical cell for producing electrolyzed water.

In another aspect of the present invention, a method of improved cleaning, sanitizing, and/or stain removal of tableware in an automatic dishwashing appliance comprising an unattached electrolytic device for producing electrolyzed water.

In another aspect of the present invention, a method of improved cleaning, sanitizing, and/or stain removal of tableware in an automatic dishwashing appliance can comprise an electrolytic device, the method using a signal system comprising a signal-providing detergent in conjunction with a signal-sensing device.

In yet another aspect of the present invention, an article of manufacture can comprise (a) a component selected from the group consisting of an electrochemical cell refill and/or replacement cartridge, product refill and/or replacement cartridge, filter, elastomeric slit valve, or combinations thereof, (b) information and/or instructions in association with the article comprising the steps describing the use of an electrolytic device, electrochemical cell, electrolytic solution, detergent and/or rinse aid signal-providing composition comprising at least one signal- providing agent, replaceable component, or combinations thereof, in an automatic dishwashing appliance comprising an electrolytic device for treating tableware for improved cleaning, sanitizing, and/or stain removal; (c) optionally, a component selected from the group consisting of suds suppressor, perfume, a chlorine-bleach-scavenging agent, a metal-protecting agent, and mixtures thereof, and mixtures thereof ; and (d) optionally, a component selected from the group consisting of an electrolytic composition comprising chloride ions, an electrolytic composition comprising chlorite ions, an electrolytic composition comprising salts having the formula (M) x (XO2) y and/or (M) X (X) y wherein X can be Cl, Br, or I and wherein M can be a metal ion or cationic entity and wherein x and y are chosen such that the salt can be charge balanced, an electrolysis precursor compound, an electrolysis salt with low water solubility, an electrolysis precursor compound contained within a medium for controlled release, and mixtures thereof, wherein the product optionally housed in a porous basket.

The following description can be provided to enable any person skilled in the art to make and use the invention, and can be provided in the context of a particular application and its requirements. Various modifications to the embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of the invention. The present invention can be not intended to be limited to the embodiments shown. Thus, since the following specific embodiments of the present invention are intended only to exemplify, but in no way limit, the operation of the present invention, the present invention can be to be accorded the widest scope consistent with the principles, features and teachings disclosed herein.

It should be understood that every maximum numerical limitation given throughout this specification will include every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

The various advantages of the present invention will become apparent to those skilled in the art after a study of the foregoing specification and following claims. The following specific embodiments of the present invention are intended to exemplify, but in no way limit, the operation of the present invention. All documents cited are, in relevant part, incorporated herein by reference; the citation of any document can be not to be construed as an admission that it can be prior art with respect to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be explained in detail with reference to the accompanying drawing, in which : -Figure 1 shows an automatic dishwashing appliance with two electrochemical cells; one capable of electrolyzing tap water alone and the other a recirculating electrochemical cell capable of electrolyzing wash and/or rinse liquor.

- Figure la shows a recirculating, electrochemical cell.

-Figure 2 shows an automatic dishwashing appliance with an automatic dishwashing appliance containing an attached, electrochemical cell integrated in the door of the appliance.

-Figure 3 shows an attached, integrated electrolytic device.

-Figure 3a shows the contents of an attached, integrated electrolytic device.

-Figure 4 shows a porous basket comprising product for dispensing.

DETAILED DESCRIPTION OF THE INVENTION Automatic dishwashing appliance 200 of FIG. 1 and FIG. la can be covered with a door (not shown) and a main body cover, 227, and has a washing vessel, 213, therein. A rack, 218, for accommodating tableware to be washed, a rotary washing nozzle, 215, located under rack, 218, and protruding approximately at the center of washing vessel, 213, and a heater, 217, for heating washing water stored in a lower portion of washing vessel, 213, are provided in washing vessel, 213, a plurality of washing water injection openings, 216, are provided on washing nozzle, 215, a recirculated wash and/or rinse liquor collection tray, 239, for collecting recirculated wash and/or rinse liquor, 230, an optional filter, 244, for screening solid leavings, and an inlet port, 238, and an outlet port, 237. In addition, automatic dishwashing appliance, 200, includes, within the automatic dishwashing appliance itself but outside washing vessel, 213, a circulating pump, 214, for supplying washing water stored in washing vessel, 213, to nozzle, 215, a drain pump, 220, for discharging washing water in washing vessel, 213, from a drain pipe, 219, into a drain pipe, 221, and a blower, 224, for sucking air in washing vessel, 213, through an air inlet port, 222, and a sucking duct, 223, and blowing the sucked air into washing vessel, 213, through an air duct, 225, and an air outlet port, 226, to dry the washed tableware.

Automatic dishwashing appliance, 200, further includes, within the automatic dishwashing appliance itself but outside washing vessel, 213, at least one electrochemical cell.

The automatic dishwashing appliance can contain electrochemical cell, 205, for producing electrolyzed water, 240, from tap water, 201, water feed pipes, 202 and 203, for externally supplying incoming tap water, 201, to electrochemical cell, 205, a valve, 204, for controlling supply of tap water, 201, to the washing vessel, 213, itself or to the inlet opening, 241, of the electrochemical cell, 205, for electrolysis. The controller (not shown) can provide for periodic cell self-cleaning of the cell, 205, by opening valve, 204, and allowing water to flush the cell passage, 254, and be discharged into the washing basin without applying power for electrolyzation. This self-cleaning can occur periodically throughout the operation of the appliance as needed.

The automatic dishwashing appliance can also contain a recirculating electrochemical cell, 235, for producing electrolyzed, recirculated wash and/or rinse liquor, 260, from recirculated wash and/or rinse liquor, 230, for internally supplying recirculated wash and/or rinse liquor, 230, to recirculating electrochemical cell, 235, a filter, 244, covering the inlet port, 238, of the recirculated wash and/or rinse liquor collection tray, 239, a duct or tube, 231, for directing recirculated wash and/or rinse liquor, 230, to a valve 232, for controlling supply of recirculated wash and/or rinse liquor, 230, to the inlet opening, 234, of the recirculating electrochemical cell, 235, itself or to the bypass outlet, 233, to the washing vessel, 213. An inlet opening, 234, or the recirculating electrochemical cell, 235, a cell passage, 253, formed therebetween from at least one pair of electrodes defining a cell gap for electrolyzing wash and/or rinse liquor, an outlet opening, 236, for connecting recirculating electrochemical cell, 235, with washing vessel, 213, via a duct or pipe, 252, an outlet port, 237, for supplying electrolyzed recirculated wash and/or rinse liquor, 260, from recirculating electrochemical cell, 235, to washing vessel, 213. Note that the automatic dishwashing appliances described herein can contain any combination of electrochemical cells and/or electrolytic devices described herein. Furthermore, self-cleaning of the recirculating cell, 235, can be accomplished by attaching a tap water supply (not shown) to the recirculating cell, 235, via the inlet opening, 234, or by a separate inlet opening (not shown) to allow for periodic flushing of the recirculating cell, 235, with tap water to remove food debris deposited in the cell passage, 253, by the recirculating wash and/or rinse liquors, 230. Similarly, self-cleaning of the recirculating filter, 244, can be accomplished by directing a tap water supply (not shown), such as in the form of a jet (not shown), above or below the filter, 244, to remove food debris deposited during collection of the recirculating wash and/or rinse liquor, 230, by spraying the tap water (not shown) at the filter, 244.

The tableware washing and/or rinsing operation of automatic dishwashing appliance, 200, can be carried out based on the control of the microcomputer (not shown). Since washing and/or rinsing of tableware by automatic dishwashing appliance, 200, can consist of a plurality of washing and/or rinsing steps, such a function as to coordinate the production of a proscribed amount of electrolyzed water, 240 and/or 260, required for each washing and/or rinsing step can be provided by a controller (not shown) having a microcomputer (not shown) for controlling a series of operations by automatic dishwashing appliance, 200.

Note that valves, 204 and 232, are in a closed state in an initial state. When a power supply switch (not shown) of an operation panel (which can be not shown) can be turned on, valve, 204 and/or 232, can be brought into an open state, tap water, 201, supplied from a tap of a water pipe can be supplied through water feed pipe, 202, valve, 204, and water feed pipe, 203, to electrochemical cell, 205, and voltage can be applied to electrochemical cell, 205, or recirculated wash and/or rinse liquor, 230, supplied from a recirculated wash and/or rinse liquor collection tray, 239, filter, 244, inlet port, 238, and tube or duct, 231, to the inlet opening, 234, of recirculating electrochemical cell, 235, and voltage can be applied to recirculating electrochemical cell, 235. Thus, tap water, 201, supplied can be electrolyzed in electrochemical cell, 205, and electrolyzed water, 240, can be produced as a discharge effluent at specific time intervals throughout the wash and/or rinse cycles of the appliance operation. Similarly, recirculated wash and/or rinse liquor, 230, supplied can be electrolyzed in recirculating electrochemical cell, 235, and electrolyzed recirculated wash and/or rinse liquor, 260, can be produced as a discharge effluent at specific time intervals throughout the wash and/or rinse cycles of the appliance operation.

Depending on the need or desired mode selected, the controller (not shown) can optionally provide for the electrolyzation of both the tap water, 201, and the recirculated wash and/or rinse liquor, 230, simultaneously or in sequential combination to produce electrolyzed tap water, 240 and/or electrolyzed recirculated wash and/or rinse liquor, 260, as a discharge effluent during the wash and/or rinse cycle of the automatic dishwashing appliance, 200. In this case, both valves, 204 and 211, can be opened, simultaneously or in sequential combination, allowing both tap water, 201, and recirculated wash and/or rinse liquor, 230, to be electrolyzed.

Note that if un-electrolyzed tap water, 201, alone can be required during the wash and/or rinse cycle, the controller (not shown) will open valve, 204, to supply tap water, 201, to feed pipe, 243, which directly opens into washing vessel, 213, to provide washing water, 248. In this case, no electrolyzed water can be present in the washing water, 248, since the tap water, 201, bypasses the electrochemical cell, 205. Note that valve, 204, can be opened such as to provide tap water, 201, to both feed pipes, 203 and 243, simultaneously, to allow for partial electrolyzation of at least some the incoming tap water, 201.

Electrolyzed tap water, 240 and/or electrolyzed recirculated wash and/or rinse liquor, 260, produced by application of voltage to electrochemical cell, 205 and/or recirculating electrochemical cell, 235, can be directed from outlet port, 207 and/or 237, into washing vessel, 213, by inflow pressure of tap water, 201, by mass transport, by pump (not shown), and/or by gravity feed. For sanitization purposes heater, 217, can not be required to be turned on during the wash and/or rinse cycle, due to the halogenated mixed oxidants present in the washing water, 248, comprising electrolyzed tap water, 240 and/or electrolyzed recirculated wash and/or rinse liquor, 260. For other purposes such as cleaning and stain removal, the heater, 217, can be optionally turned on to heat the washing water, 248, in response to the controller (not shown), timer (not shown) and/or sensor (not shown) detecting a change in the fluid or gaseous environment within automatic dishwashing appliance, 200, or the electrochemical cell, 205 and/or 235. With the detection of a specified stimulus, such as a proscribed water level or pH level of the washing water, 248, the circulating pump, 214, can be operated while the washing water, 248, optionally comprising electrolyzed tap water, 240 and/or electrolyzed recirculated wash and/or rinse liquor, 260, can be heated to a proscribed temperature. Note that detection of the water level of washing water, 248, in washing vessel, 213, can be carried out by provision of a float switch type water level sensor (not shown), by the controller (not shown) and/or by water supply time measured with a timer (not shown). Note that a turbidity sensor, water hardness sensor, pH sensor, conductivity sensor, and combinations thereof (not shown), can be used to detect a change in the fluid, the gaseous environment within automatic dishwashing appliance, 200, the electrochemical cell, 205 and/or 235, and/or the electrolytic device (not shown).

Tap water, 201, containing electrolyzed water, 240, and/or recirculated wash and/or rinse liquor, 230, containing electrolyzed wash and/or rinse liquor, 260, can be injected with rotation from injection openings, 216, through washing nozzle, 215, whereby tableware placed in rack, 218, can be treated with electrolyzed tap water, 240, and/or electrolyzed recirculated wash and/or rinse liquor, 260, at specific intervals during the wash and/or rinse cycles of the automatic dishwashing appliance, 200. When washing and/or rinsing for proscribed time can be completed, circulating pump, 214, can be stopped. Then, drain pump, 220, can be operated, and wash and/or rinse liquor, 230, containing used electrolyzed tap water, 240, and/or electrolyzed recirculated wash and/or rinse liquor, 260, can be discharged from drain pipe, 221, through drain pipe, 219, and drain pump, 220. When discharging of the wash and/or rinse liquor, 230, can be completed, drain pump, 220, can be deactivated.

During a second and/or subsequent wash and/or rinse cycle, valve, 204, can optionally be brought into an open state, allowing tap water, 201, to flow through feed pipe, 243, to washing vessel, 213, filling washing basin, 212, to a proscribed level. Valve, 204, can then be brought into a closed state. Note that valve, 204, can be opened for a specific amount of time and then closed to induce self-cleaning of the recirculating cell as described above, at any time during the operation of the appliance. The application of power to the cell can be not necessary during the cell self-cleaning process.

Valve, 232, can simultaneously and/or in sequential combination with the operation of valve, 204, be optionally brought into an open state, recirculated wash and/or rinse liquor, 230, collected by the recirculated wash and/or rinse liquor collection tray, 239, passing through the filter, 244, inlet port, 238, duct or tube, 231, feed pipe, 208, into the cell passage, 253, through inlet opening, 234, of recirculating electrochemical cell, 235, and voltage can be applied to electrochemical cell, 205, wherein electrolyzed recirculated wash and/or rinse liquor, 260, can be produced and discharged from the outlet opening, 236, the duct or tube, 260, the outlet port, 237, into the washing vessel, 213, and collected in the washing basin, 212, for additional recirculation.

Subsequent washing and/or rinsing steps can be carried out in a manner similar to that of the first one. Thus, the number of steps required can be carried out, whereby washing and/or rinsing can be completed. To put drying after the completion of washing and/or rinsing step briefly, blower, 224, can be first operated, and air in washing vessel, 213, can be sucked from air inlet port, 222, through sucking duct, 223, and directed through blower, 224, air duct, 225, and air outlet port, 226, into washing vessel, 213, to absorb heat energy of heater, 217, while circulating in washing vessel, 213, for proscribed time, whereby drying of the tableware can be completed.

Thus, in automatic dishwashing appliance, 200, of FIG. 1 and FIG. la, while electrolyzed tap water, 240, can be produced by electrochemical cell, 205, electrolyzed tap water, 240, will not be discarded being unused, and water can be saved. This can be especially true for electrolyzed recirculated wash and/or rinse liquor, 260. The water-saving benefit occurs when recirculated wash and/or rinse liquor, 230, can be used as the aqueous electrolytic solution. In this case, an increase in the activity of halogenated mixed oxidants can be delivered to the recirculating wash and/or rinse liquor during the wash and/or rinse cycle of the automatic dishwashing appliance, 200. Water can be saved by recirculating the existing wash and/or rinse liquor, 230, through the recirculating electrochemical cell, 235, without having to add additional electrolyzed tap water, 240. Recirculation also promotes the benefits of cleaning, sanitizing, and stain removal by preventing excessive dilution of the wash and/or rinse liquor, 230, during operation of the automatic dishwashing appliance, 200. Because the heater, 217, can be not required for sanitization purposes, automatic dishwashing appliance, 200, achieves energy-savings by reducing the total energy consumption less than about 1.8 kWh per operating cycle or about 600 kWh per year, preferably less than about 1.7 kWh per operating cycle or about 555 kWh per year, most preferably can be less than about 1.2 kWh per operating cycle or about 400 kWh per year.

FIG. 2 depicts an automatic dishwashing appliance, 200, having an automatic dishwashing appliance containing a device, 300, located in a sealed or salable compartment, 301, with a salable cover, 302, and cover latch, 303, in the door, 306, of the automatic dishwashing appliance, 200. The electrolytic device, 300, can be electronically connected to a replacement indicator, 304, located on the interior surface of the door, 306, which can alert the consumer to the need to replace the electrolytic device, 300, itself and/or a disposable electrolytic component (not shown) within cell and/or device, 300. For simplicity, the electrochemical cell can be not shown.

The appliance, 200, and/or the electrolytic device, 300, can comprise a sensor (not shown) to detect and/or analyze the composition and/or properties of the liquid or gaseous environment within the signal-sensing cell and/or device, 300, the appliance, 200, and combinations thereof.

FIG. 3 and FIG. 3a depict another embodiment of the present invention. The electrolytic device, 500, can be located on any interior surface of the washing vessel, 213, of the automatic dishwashing appliance (not shown) itself. The electrolytic device, 500, respectively, having a body, 512, with a substantially continuous outer surface, 508. The body, 512, comprising an inlet port, 506, which can be covered by a detachable filter or screen (not shown), to minimize fouling of the electrochemical cell, due to the large debris load during the collection of electrolytic solution in the wash and/or rinse cycle of the automatic dishwashing appliance, an outlet port, 507, for discharge of the electrolyzed water to the washing vessel (not shown). The body, 512, can optionally comprise at least one additional compartment, 509. The compartment, 509, can house a product or local source of halogen ions, 511, which dissolves slowly (e. g. over months) when exposed to the wash and/or rinse liquor (not shown). The compartment, 509, comprising an easily removable and replaceable plastic screen, 510, which helps to contain the product, 511, in the compartment, 509, and also allows for fluid communication between the product, 511, and the wash and/or rinse liquor (not shown) during operation of the appliance (not shown). When the product, 511, can be completely dissolved, the consumer can add a product refill by removing the plastic screen, 510, and inserting a new product, 511, or refill in the compartment, 509, and then closing the screen, 510, to contain the new product, 511.

The electrochemical cell, 520, can be in fluid communication with the aqueous electrolytic solution, comprising the wash and/or rinse liquors from the appliance, via the inlet port, 506, of the body, 512. The inlet port, 506, can be outwardly connected to a funnel or water collection tray (not shown) to allow electrolytic solution comprising wash liquor, rinse liquor, tap water, and mixtures thereof, to be directed to an electrochemical cell, 520. The inlet port, 506, can be inwardly connected to a tube or duct, 550, which can be connected to an electrochemical cell, 520, having an inlet opening, 525, an anode electrode, 521, a cathode electrode, 522, defining a cell gap comprising a cell passage, 523, formed therebetween through which the aqueous electrolytic solution can flow, an outlet opening, 526, connected to a tube or duct, 551, which can be connected to the outlet port, 507, to allow the electrolyzed water (not shown) to discharge into the washing vessel (not shown) of the automatic dishwashing appliance (not shown).

The automatic dishwashing appliance can comprise a source of electrical current supply (not shown), which can be integrated into appliance itself. Besides having a source of electrical current supply (not shown), the attached, integrated electrochemical cell, 520, and/or electrolytic device, 300, can optionally have a supplemental battery, 530, which can provide the current used by the electrochemical cell, 520, to the anode lead, 527, and the cathode lead, 528, of the electrochemical cell, 520, to generate electrolyzed water in the cell passage, 524. The electrochemical cell, 520, can be optionally electrically and/or electronically connected to a controller, 531, which can comprise an on-off switch (not shown), a timer (not shown), a sensor (not shown) to detect and/or analyze the composition and/or properties of the liquid or gaseous environment within the signal-sensing cell and/or device, 500, the appliance (not shown), and combinations thereof, and an indicator lamp, 505, that indicates to the consumer the status of the appliance, the cell and/or the device during operation. The indicator can shown the consumer that the electrolytic device, 500, the cell, 520, and/or the batteries, 530, need to be replaced. The cathode lead, 552, can be connected to the controller, 531, which can be connected to the positive lead of the battery, 530, to the anode lead, 553, connected to the negative lead of the battery, 530.

The water collected by the inlet port, 506, can flow by gravity and/or by pump through the electrochemical cell, 520, and out the outlet port, 507, via a tube or duct, 551. The release or discharge of at least some electrolyzed water (not shown) as a discharge effluent via the outlet opening, 526, of the electrochemical cell, 520, itself and/or the outlet port, 507, of the electrolytic device, 500, into the appliance (not shown) can occur at specific timed intervals or continuously during operation of the wash and/or rinse cycles.

During operation, the electrochemical cell, 520, positioned inside the body, 512, can be placed into fluid communication with the aqueous electrolytic solution (not shown) of the automatic dishwashing appliance (not shown) comprising tap water, wash and/or rinse liquor, and mixtures thereof (not shown), via at least one inlet port, 506. The inlet port, 506, can be connected to a tube or duct, 550, that connects to the inlet opening, 525, of the electrochemical cell, 520. Likewise, the body, 512, can have an outlet port, 507, that can be in fluid communication between the outlet opening, 526, and with the wash and/or rinse liquor (not shown) of the automatic dishwashing appliance (not shown) via a tube or duct, 551.

FIG. 4 depicts a porous basket, 174, for dispensing a product, 175, which can be placed in rack, 218, of any automatic dishwashing appliance of the present invention to deliver the product to the washing water of the appliance over time by slowly dissolving with each wash and/or rinse cycle. The product can comprise a signal-providing detergent composition, signal-providing agent, and combinations thereof.

Although the present invention has been described and illustrated in detail, it can be clearly understood that the same can be by way of illustration and example only and can be not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims.

Sensors A"chemical sensor"can be a device for detecting the presence or concentration of an analyte.

At specific time intervals throughout the wash and/or rinse cycles of an automatic dishwashing appliance comprising an electrochemical cell and/or electrolytic device, the signal- sensing system can activate and/or deactivate the signal-sensing cell and/or device using at least one sensor capable of analyzing or detecting the composition of the fluid or gaseous environment of the electrochemical cell and/or device or within the appliance.

SIGNAL-PROVIDING DETERGENT COMPOSITION The signal-providing detergent composition of the present invention can include, but can comprise, but is not limited to, the following signal-providing chemicals and agents: (a) Halogenated Salt The present invention can comprise one or more halogenated salts selected from the group consisting of halite salt, halide salt, and mixtures thereof.

The signal-providing composition of the present invention can comprise a local source of halogenated salt, and a means for delivering the halogenated salt to the wash and/or rinse liquor.

This embodiment can be advantageously used in those situations when the target water to be treated with the electrochemical cell does not contain a sufficient amount, or any, of the halogenated salt.

The local source of halogen ions can be from a signal-providing detergent and/or rinse aid composition, a concentrated brine solution, a halogenated salt tablet, granule, or pellet in fluid contact with the aqueous electrolytic solution, or in a porous basket hanging on the rack of the automatic dishwashing appliance, or both.

One embodiment of the present invention relates to a signal-providing composition, wherein the halogenated salt can be in a form selected from the group characterized by low water solubility, contained within a medium for controlled release, and combinations thereof.

Another embodiment of the present invention relates to a signal-providing composition, wherein the controlled release form provides a local source of the halogenated salt comprising a form such that once placed inside a dishwashing appliance it provides a controlled release of steady levels of halogen dioxide salts into the wash and/or rinse liquors during operation of an automatic dishwasher over a period of from 1 day to 365 days of regular household and/or commercial use.

(i) Halogen Dioxide Salt-The precursor material from which halogen dioxide can be formed can be referred to as a halogen dioxide salt. The halogen dioxide salt of the present invention having the formula (M) X (XO2) y, wherein X can be Cl, Br, or I and wherein M can be a metal ion or cationic entity, and wherein x and y are chosen such that the salt can be charge balanced. The halogen dioxide salt can comprise two or more salts in various mixtures.

(ii) Other Halogenated Salts-In substitution of and/or addition to halogen dioxide salt, the present invention can comprise one or more halide salts. The halide salt of the present invention having the formula (M) X (X) y, wherein X can be Cl, Br, or I and wherein M can be a metal ion or cationic entity, and wherein x and y are chosen such that the salt can be charge balanced, can be used to enhance the disinfection and bleaching performance of the effluent that can be discharged from the electrochemical cell, or to provide other halogenated mixed oxidants, when preferred, in response to the passing of electrical current through the electrochemical cell.

(b) Builders Detergent builders are included in the compositions herein to assist in controlling mineral hardness and dispersancy. Inorganic as well as organic builders can be used.

(i) Phosphate Builders-Phosphate detergent builders for use in detergent compositions are well known. They include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates). Phosphate builder sources are described in detail in Kirk Othmer, 3rd Edition, Vol. 17, pp. 426-472 and in"Advanced Inorganic Chemistry"by Cotton and Wilkinson, pp. 394-400 (John Wiley and Sons, Inc.; 1972).

Inorganic or non-phosphate P-containing detergent builders include, but are not limited to, phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, citrate, zeolite or layered silicate, and aluminosilicates. See U. S. Pat. 4,605, 509 for examples of preferred aluminosilicates.

(ii) Silicate Builders-The present automatic dishwashing detergent compositions can further comprise water-soluble silicates.

(iii) Carbonate Builders-Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321, 001 published on November 15,1973. Various grades and types of sodium carbonate and sodium sesquicarbonate can be used, certain of which are particularly useful as carriers for other ingredients, especially detersive surfactants.

(iv) Organic Detergent Builders-Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.

(v) Other Useful Builders-Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3, 5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

(c) Suds Suppressor The signal-providing compositions of the present invention can optionally contain an alkyl phosphate ester suds suppressor, a silicone suds suppressor, or combinations thereof. Levels in general are from 0% to about 10%, preferably, from about 0.001% to about 5%. However, generally (for cost and/or deposition considerations) preferred compositions herein do not comprise suds suppressors or comprise suds suppressors only at low levels, e. g. , less than about 0. 1% of active suds suppressing agent.

(d) Perfume (i) Non-Blooming Perfumes-Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like.

(ii) Blooming Perfumes-Blooming perfume compositions, as disclosed herein, can be formulated into automatic dishwashing detergent compositions and provide significantly better noticeability to the consumer than non-blooming perfume compositions not containing a substantial amount of blooming perfume ingredients.

One embodiment of the present invention relates to a signal-providing composition, wherein the perfume can be from about 0.01% to about 5%, by weight, a blooming perfume composition, wherein the blooming perfume composition can comprise from about 50% to about 99% of blooming perfume ingredients having a boiling point of less than about 260°C and a ClogP of at least about 3, and wherein the blooming perfume composition comprising at least about 5 different blooming perfume ingredients, and from about 0.5% to about 10% of base masking perfume ingredients having a boiling point of more than about 260°C and a ClogP of at least about 3.

(e) Bleach-scavenging Agent Additionally, from 0% to about 10%, preferably from about 0. 01% to about 6% by weight, of bleach-scavengers can be added to compositions of the present invention to prevent chlorine and/or oxygen bleach species present in the wash and/or rinse liquor as well as in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.

(f) Metal-Protecting Agent The present signal-providing compositions can contain one or more material care agents which are effective as corrosion inhibitors and/or anti-tarnish aids. Such materials are preferred components of machine dishwashing compositions especially in certain European countries where the use of electroplated nickel silver and sterling silver can be still comparatively common in domestic flatware, or when aluminum protection can be a concern and the composition can be low in silicate.

ADJUNCT INGREDIENTS AS SIGNAL-PROVIDING AGENTS Detersive ingredients or adjuncts optionally included in the instant signal-providing compositions can include one or more materials for assisting or enhancing cleaning, sanitizing and stain removal performance of tableware treated by electrolyzed water in an automatic dishwashing appliance containing an electrochemical cell and/or electrolytic device. They themselves can be the signal-proving agent of the present invention and are further selected based on the form of the composition, i. e. , whether the composition can be to be sold as a liquid, paste (semi-solid), or solid form (including tablets and the preferred granular forms for the present compositions).

Adjuncts which can also be included in signal-providing detergent compositions of the present invention, at their conventional art-established levels for use (generally, adjunct materials comprise, in total, from about 1% to about 90%, preferably from about 5% to about 75%, more preferably from about 10% to about 50%, by weight of the compositions), and can include other active ingredients such as nanoparticles, functionalized surface molecules, polymers, surfactants, co-surfactants, metal ions, proteins, dyes, acids, bases, organic solvents, enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release agents, wetting agents, dispersants, blooming perfumes, colorants, filler salts, hydrotropes, anti-oxidants, germicides, fungicides, color speckles, silvercare, anti-tarnishing agents, alkalinity sources, solubilizing agents, carriers, electrode maintenance and/or descaling agents, processing aids, pigments, and pH control agents, bleaching agent, bleach activators, bleach catalysts and mixtures thereof. These adjuncts are described in detail in U. S. Patent 6,143, 707, Trinh et al. , incorporated herein by reference.

The precise nature of these additional detergent ingredients, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which the composition can be to be used. The selection of the adjunct will depend upon the type and use of the composition. Non-limiting illustrative examples of compositions as well as suitable adjunct (s) for the illustrative compositions are described hereinafter. Particularly preferred adjuncts are surfactants, enzymes, chelants, dispersant polymers, thickeners, and pH adjusting agents as described in detail hereinafter.

(a) Surfactant One embodiment of the present invention relates to a signal-providing composition comprising a surfactant can be selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, ampholytic surfactants, zwitterionic surfactants, and mixtures thereof.

It should be noted that low foaming nonionic surfactants are useful in automatic dishwashing to assist cleaning, help defoam food soil foams, especially from proteins, and to help control spotting/filming and are desirably included in the present detergent compositions at levels of from about 0.1% to about 20%, preferably from about 0.5% to about 5%, by weight of the composition. In general, bleach-stable surfactants are preferred. signal-providing compositions of the present invention preferably comprise low foaming nonionic surfactants (LFNIs).

LFNIs are most typically used in ADDs on account of the improved water-sheeting action (especially from glass) which they confer to the signal-providing composition. They also encompass non-silicone, nonphosphate polymeric materials further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.

(b) Co-Surfactant The composition of the present invention can further contain optional co-surfactants.

These optional surfactants will be preferably bleach stable. Preferred optional co-surfactants are low cloud point nonionic surfactants, high cloud point nonionic surfactants, anionic surfactants and mixtures thereof.

(c) Enzyme "Detergent enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a signal-providing composition. Preferred enzymes are hydrolases such as proteases, amylases and lipases. Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more bleach compatible, have a remaining degree of bleach deactivation susceptibility.

Enzyme-containing compositions, especially liquid compositions, herein can comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which can be compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.

One embodiment of the present invention relates to a liquid and/or gel automatic dishwashing composition for treating tableware in an automatic dishwashing appliance comprising an electrochemical cell for improved tableware cleaning, sanitizing, and/or stain removal, the composition comprising: (a) at least about 0.1%, by weight of the composition, of a halogenated salt having the formula (M) x (X) y, wherein X can be Cl, Br, or I and wherein M can be a metal ion or cationic entity, and wherein x and y are chosen such that the salt can be charge balanced; (b) a component selected from the group consisting of a builder, suds suppressor, perfume, a bleach-scavenging agent, a metal-protecting agent, and mixtures thereof; and (c) an effective amount of an enzyme; and (d) an effective amount of a thickening agent; wherein the liquid and/or gel composition can be optionally free of bleach. Another embodiment of the present invention relates to a signal-providing composition, wherein the composition does not contain chlorine bleach, oxygen bleach, or mixtures thereof.

The signal-providing compositions herein optionally comprise one or more enzymes. If only one enzyme can be used, it can be preferably an amyolytic enzyme. Highly preferred for automatic dishwashing can be a mixture of proteolytic enzymes and amyloytic enzymes. More generally, the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice can be governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders, etc. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

(d) Cheating Agents The compositions herein can also optionally contain one or more transition-metal <BR> <BR> selective sequestrants, "chelants"or"chelating agents", e. g. , iron and/or copper and/or manganese chelating agents. Chelating agents suitable for use herein can be selected from the group consisting of aminocarboxylates, phosphonates (especially the aminophosphonates), polyfunctionally-substituted aromatic chelating agents, and mixtures thereof. Without intending to be bound by theory, it can be believed that the benefit of these materials can be due in part to their exceptional ability to control iron, copper and manganese in washing solutions which are known to decompose hydrogen peroxide and/or bleach activators; other benefits include inorganic film prevention or scale inhibition. Commercial chelating agents for use herein include the DEQUEST series, and chelants from Monsanto, DuPont, and Nalco, Inc.

(e) Dispersant Polymer Preferred signal-providing compositions herein can additionally contain a dispersant polymer. When present, a dispersant polymer in the instant signal-providing compositions can be typically at levels in the range from 0 to about 25%, preferably from about 0.5% to about 20%, more preferably from about 1% to about 8%, by weight of the signal-providing composition.

Dispersant polymers are useful for improved filming performance of the present signal-providing compositions, especially in higher pH embodiments, such as those in which wash pH exceeds about 9.5. Particularly preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on dishware.

(f) Thickeners The physical stability of the liquid or gel product can be improved, and the thickness of the product can be altered, by the addition of a cross-linking thickener to the liquid or gel detergent product as a thixotropic thickener.

(g) Functionalized Surface Molecules The functionalized surface molecule of the present invention can be present in the composition to provide hydrophilic or hydrophobic character to the composition, to anchor and/or enhance surface adsorption of the tableware, and/or to provide water-affinity to treated tableware.

(h) PH adjusting components The above liquid or gel detergent product can be preferably low foaming, readily soluble in the washing medium and most effective at pH values best conducive to improved cleaning performance, such as in a range of desirably from about pH 6.5 to about pH 12.5, and preferably from about pH 7.0 to about pH 12.0, more preferably from about pH 8.0 to about pH 12.0.

Preferably the pH can be less than about 10.0 for better enzyme stability, most preferably less than about 9.0. The pH adjusting components are desirably selected from sodium or potassium hydroxide, sodium or potassium carbonate or sesquicarbonate, sodium or potassium silicate, boric acid, sodium or potassium bicarbonate, sodium or potassium borate, and mixtures thereof. NaOH or KOH are the preferred ingredients for increasing the pH to within the above ranges. Other preferred pH adjusting ingredients are sodium carbonate, potassium carbonate, and mixtures thereof.

(i) Organic Solvent One embodiment of the present invention relates to a signal-providing composition comprising an organic solvent selected from the group consisting of low molecular weight aliphatic or aromatic alcohols, low molecular weight alkylene glycols, low molecular weight alkylene glycol ethers, low molecular weight esters, low molecular weight alkylene amines, low molecular weight alkanolamines, and mixtures thereof.

(j) Bleach, Bleach, Bleach Catalyst And/Or Bleach Activator One embodiment of the present invention relates to a signal-providing composition comprising a bleach, bleach catalyst and/or bleach activator (h) (k) Electrochemically-Activated Pro-Benefit Agent Another embodiment of the present invention relates to a signal-providing composition comprising an electrochemically-activated pro-benefit agent selected from the group consisting of pro-perfume, pro-oxidant, pro-reductant, pro-surface active agent, pro-glass care agent, and mixtures thereof, wherein when the electrochemically-activated pro-benefit agent is exposed to at least one electrochemical cell it undergoes oxidation and/or reduction and can be thereby converted into an active agent which provides a treatment benefit to tableware upon contact with the tableware, and wherein the benefit can be selected from the group consisting of cleaning, aesthetic, disinfecting, stain-removal, dish-care, and combinations thereof.

(1) Moisture Content Since signal-providing compositions herein can contain water-sensitive ingredients or ingredients which can co-react when brought together in an aqueous environment, it can be desirable to keep the free moisture content of the automatic dishwashing detergent (ADD) at a <BR> <BR> minimum, e. g. , 7% or less, preferably 4% or less of the ADD; and to provide packaging which can be substantially impermeable to water and carbon dioxide. Coating measures have been described herein to illustrate a way to protect the ingredients from each other and from air and moisture. Plastic bottles, including refillable or recyclable types, as well as conventional barrier cartons or boxes are another helpful means of assuring maximum shelf-storage stability. As noted, when ingredients are not highly compatible, it can further be desirable to coat at least one such ingredient with a low-foaming nonionic surfactant for protection. There are numerous waxy materials which can readily be used to form suitable coated particles of any such otherwise incompatible components; however, the formulator prefers those materials which do not have a marked tendency to deposit or form films on dishes including those of plastic construction.

One embodiment of the present invention relates to a signal-providing composition, wherein the composition can be present in the form selected from the group consisting of liquid, gel, tablet, powder, and mixtures thereof.

EMBODIMENTS One embodiment of the present invention relates to a method of improved cleaning, sanitizing, and/or stain removal of tableware in an automatic dishwashing appliance comprising at least one attached, integrated, signal-sensing electrochemical cell and/or at least one attached, integrated electrolytic device comprising the signal-sensing cell for producing electrolyzed water, the method comprising the steps of : (a) placing tableware in need of treatment into the appliance; (b) providing the signal-sensing cell comprising at least one inlet opening and one outlet opening, and at least one pair of electrodes defining at least one cell gap comprising at least one cell passage formed therebetween through which an aqueous electrolytic solution can flow, wherein the signal-sensing cell and/or appliance further can comprise a signal sensor that can electrically and/or electronically activate and/or deactivate the production of electrolyzed water in the signal- sensing cell; (c) providing the aqueous electrolytic solution in the appliance in fluid communication with the signal-sensing cell and/or device; (d) providing at least one activator and/or deactivator; (e) intermittently activating the signal-sensing cell and/or device via the activator at least one specific time in the wash and/or rinse cycle; (f) electrolyzing the aqueous electrolytic solution in the signal-sensing cell to produce at least some electrolyzed water; (g) discharging the electrolyzed water into the wash and/or rinse liquor via a washing basin in the appliance during at least one specific time in the wash and/or rinse cycle (s); (h) interrupting electrolyzation of the aqueous electrolytic solution and/or not releasing the electrolyzed water at other times in the wash and/or rinse cycle (s); (i) contacting the tableware in need of treatment with the wash and/or rinse liquor comprising the electrolyzed water; (j) intermittently deactivating the signal-sensing cell via the deactivator during at least one specific time in the wash and/or rinse cycle (s); (k) optionally contacting the tableware with a wash and/or rinse liquor comprising a bleach-scavenging agent and/or metal-protecting agent; and (1) optionally repeating steps (c) through (k).

Another embodiment of the present invention relates to a method, wherein the signal- sensing cell and/or device comprises a characteristic selected from the group consisting of attached, integrated, unattached, self-powered, self-contained, partitioned, non-partitioned, recirculating, non-recirculating, energy-saving, disposable, non-disposable, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein the cell gap having a gap spacing between about 0.1 mm to about 5. 0 mm.

Another embodiment of the present invention relates to a method, wherein the aqueous electrolytic solution can comprise salts having the formula (M) X (XO2) y and/or (M) X (X) y, wherein X can be Cl, Br, or I, wherein M can be a metal ion or cationic entity, and wherein x and y are chosen such that the salt can be charge balanced.

Another embodiment of the present invention relates to a method, wherein the sensor can be capable of analyzing the composition and/or properties of the liquid or gaseous environment within the signal-sensing cell, the device and/or the appliance, and wherein the sensor can electrically and/or electronically control the production and/or discharge of the electrolyzed water at the specific time during the wash and/or rinse cycle by turning on the activator and/or the deactivator.

Another embodiment of the present invention relates to a method, wherein the sensor can be one selected from the group consisting of turbidity sensor, water hardness sensor, pH sensor, conductivity sensor, a sensor capable of detecting the presence of a volatile gaseous compound, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein the sensor can be a pH sensor, which detects the change in pH in the wash, and/or rinse liquor.

Another embodiment of the present invention relates to a method, wherein the volatile gaseous compound can be a perfume.

Another embodiment of the present invention relates to a method, wherein the location of the activator and/or deactivator can be selected from the group consisting of the signal-sensing cell, the device, the appliance, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein prior to the step of providing at least one activator and/or deactivator, the method further can comprise the steps of providing a detergent composition, rinse aid composition, and mixtures thereof, and delivering the composition to the wash and/or rinse liquor; wherein the composition can comprise at least one signal-providing chemical.

Another embodiment of the present invention relates to a method, wherein the activator and/or deactivator are selected from the group consisting of chemical-based, mechanical-based, electronic-based, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein the activator and/or the deactivator can be chemical-based having the ability to detect the presence and/or absence of a signal-providing chemical in the wash and/or rinse liquors and/or their corresponding gaseous vapors via the sensor in order to activate and/or deactivate the signal-sensing cell and/or device.

Another embodiment of the present invention relates to a method, wherein the appliance and/or device further comprising a timer to control production of the electrolyzed water, wherein the timer can be selected from the group consisting of mechanical timer, electric timer, electronic timer, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein when the sensor detects the presence and/or absence of the signal-providing chemical in the wash and/or rinse liquor, the sensor initiates the activation of the timer such that from a certain period of time after activation of the timer, the signal-sensing cell and/or device can be activated and/or deactivated thereby controlling production and/or discharge of the electrolyzed water.

Another embodiment of the present invention relates to a method, wherein the activator and/or the deactivator can be mechanical-based having the ability to turn on and off the signal- sensing cell and/or device via a variety of cycle-linked appliance performance options on the appliance which offer the consumer a combination of cleaning performance and/or sanitization.

Another embodiment of the present invention relates to a method, wherein the activator and/or the deactivator can be electronic-based comprising a computer device that communicates with the appliance, signal-sensing cell and/or device, and combinations thereof; wherein the computer device can be pre-programmed to offer consumers a means to allow the signal-sensing cell and/or device to be turned on or off during specific wash and/or rinse cycles and settings of the appliance, and wherein the computer device can be selected from among the group consisting of programmable, non-programmable, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein the appliance can comprise a universal remote control device allowing communication with the electronic- based activator and/or deactivator within the appliance, signal-sensing cell and/or device; wherein the universal remote device can be pre-programmed to offer consumers a means to allow the signal-sensing cell and/or device to be turned on and/or off at least one specific time during the wash and/or rinse cycle for most major brands of automatic dishwashing appliances available to the consumer.

Another embodiment of the present invention relates to a method, wherein the activator and/or the deactivator can be electronic-based comprising a radio-transmitting device allowing communication with the appliance, signal-sensing cell, and/or device; wherein the radio- transmitting device offers consumers a means to allow the signal-sensing cell and/or device to be turned on and/or off at least one specific time during the wash and/or rinse cycle for most major brands of automatic dishwashing appliances available to the consumer.

Another embodiment of the present invention relates to a method, wherein prior to the step of providing at least one activator and/or deactivator, the method further can comprise steps of providing a detergent composition comprising enzyme to the wash liquor, contacting the tableware with the enzymes for an effective period of time during at least one wash cycle; wherein during the cycle no electrolyzed water comes into contact with the enzymes.

Another embodiment of the present invention relates to a method, wherein the method further can comprise step of contacting the tableware with a wash and/or rinse liquor comprising a bleach-scavenging agent and/or metal-protecting agent.

Another embodiment of the present invention relates to a method, wherein after contacting the tableware with a wash and/or rinse liquor comprising the bleach-scavenging agent and/or metal-protecting agent, no further electrolyzed water comes into contact with the dishes.

One embodiment of the present invention relates to a method, of improved cleaning, sanitizing, and/or stain removal of tableware in an automatic dishwashing appliance comprising a signal-sensing electrochemical cell and/or a signal-sensing an electrolytic device comprising the signal-sensing cell.

Another embodiment of the present invention relates to a method, wherein after contacting the tableware with a wash and/or rinse liquor comprising a bleach-scavenging agent and/or metal-protecting agent, no further electrolyzed water comes into contact with the dishes.

Another embodiment of the present invention relates to a method, wherein the signal sensor can be activated and/or deactivated by sensing the signal-providing composition via the gaseous phase.

Another embodiment of the present invention relates to a method, wherein the signal sensor can be activated and/or deactivated by sensing the signal-providing composition via the aqueous phase.

Another embodiment of the present invention relates to a method, wherein the signal- providing composition can be selected from the group consisting of detergent compositions, rinse aid compositions, and mixtures thereof.

Another embodiment of the present invention relates to a method, wherein the signal- providing agent can be selected from the group consisting of nanoparticles, colloidal particles, functionalized surface molecules, polymers, salts, surfactants, metal ions, proteins, dyes, UV- active materials, fluorescent materials, organic acids, organic bases, inorganic acids, inorganic bases, organic solvents, builders, bleaches, bleach activators, bleach catalysts, enzymes, non- activated enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release polymers, wetting agents, dispersants, suds suppressors, gases, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, hydrolyzable cosurfactants, anti-oxidants, germicides, fungicides, halide ions, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity sources, solubilizing agents, carriers, perfumes, processing aids, pigments, and pH control agents, and mixtures thereof.

Another embodiment of the present invention relates to a method, wherein the signal- providing agent can comprise OH-or H30+.

Another embodiment of the present invention relates to a method, wherein the signal- sensing cell and/or device can be selected from the group consisting of attached, integrated, unattached, self-powered, self-contained, partitioned, non-partitioned, recirculating, non- recirculating, energy-saving, disposable, non-disposable, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein the appliance, the signal-sensing cell, and/or device further can comprise a signal-detecting device comprising a sensor capable of analyzing the contents of the liquid and/or gaseous environment of the appliance, signal-sensing cell, and/or device for the presence of the signal-providing agent.

Another embodiment of the present invention relates to a method, wherein the sensor can be one selected from the group consisting of turbidity sensor, water hardness sensor, pH sensor, conductivity sensor, a sensor capable of detecting the presence of a volatile compound, perfume, and/or gas within the gaseous environment of the device, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein the signal sensor can comprise a chemical sensor selected from the group consisting of fiber optic chemical sensor, porous polymer sensor, semiconductor chemical sensor, acoustic wave chemical sensor, optical chemical sensor, organic sensor, porous organic sensor, bio-sensor,'electronic nose' sensor,'electronic tongue'sensor, and combinations thereof.

Another embodiment of the present invention relates to a method, wherein the chemical sensor can comprise component selected from the group consisting of flow-through chamber, selective membrane, dialyzing membrane, ion-selective membrane, gas-permeable membrane, analyte-selective membrane, organic polymer film, metal oxide film, organometallic film, and combinations thereof.

One embodiment of the present invention relates to an article of manufacture comprising: (a) a package; (b) a replacement signal-providing detergent composition comprising a signal- providing agent selected from the group consisting of nanoparticles, colloidal particles, functionalized surface molecules, polymers, salts, surfactants, metal ions, proteins, dyes, UV- active materials, fluorescent materials, organic acids, organic bases, inorganic acids, inorganic bases, organic solvents, builders, bleaches, bleach activators, bleach catalysts, enzymes, non- activated enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release polymers, wetting agents, dispersants, suds suppressors, gases, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, hydrolyzable cosurfactants, anti-oxidants, germicides, fungicides, halide ions, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity sources, solubilizing agents, carriers, perfumes, processing aids, pigments, and pH control agents, and mixtures thereof ; (c) information in association with the package comprising instructions to insert the replacement product, replacement signal-providing detergent composition, and/or the replacement a porous basket in the appliance and/or the electrolytic device.

One embodiment of the present invention relates to a composition of matter consisting essentially of the in the wash and/or rinse liquor of an automatic dishwashing appliance comprising a signal-sensing system comprising a sensor, a signal-sensing electrochemical cell and/or electrolytic device comprising the signal-sensing cell, for improved tableware cleaning, sanitizing, and/or stain removal, the composition of matter comprising: (a) at least some electrolyzed water comprising halogen-containing mixed-oxidant species; (b) a composition comprising a compound selected from the group consisting of an electrolytic composition comprising halogen ions, an electrolytic composition comprising halogen-containing salts having the formula (M) x (XO2) y and/or (M) X (X) y wherein X can be Cl, Br, or I and wherein M can be a metal ion or cationic entity and wherein x and y are chosen such that the salt can be charge balanced, an electrolysis precursor compound, a halogen-containing salt with low water solubility, an electrolysis precursor compound contained within a medium for controlled release, and mixtures thereof; (c) a signal-providing detergent composition comprising a signal-providing agent selected from the group consisting of nanoparticles, colloidal particles, functionalized surface molecules, polymers, salts, surfactants, metal ions, proteins, dyes, UV-active materials, fluorescent materials, organic acids, organic bases, inorganic acids, inorganic bases, organic solvents, builders, bleaches, bleach activators, bleach catalysts, enzymes, non-activated enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release polymers, wetting agents, dispersants, suds suppressors, gases, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, hydrolyzable cosurfactants, anti-oxidants, germicides, fungicides, halide ions, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity sources, solubilizing agents, carriers, perfumes, processing aids, pigments, and pH control agents, and mixtures thereof; and (d) optionally, adjunct ingredient.