# Patent

## Title
Multiuse, solid cleaning device and composition

## Abstract

A multiuse laundry cleaning device in a solid state containing a homogeneous quantity of cleaning agent configured to dissolve and release a substantially consistent quantity of cleaning agent over a plurality of laundry wash and rinse cycles. The cleaning agent includes a gas-releasing component, potassium silicate as a solubility control component to limit the solubility of the cleaning agent, an alkalinity agent as a pH regulator, and a water softener to solvate metal ions in a solution of water. Controlled dissolution of the cleaning agent composition releases a desired quantity of cleaning agent in each cleaning cycle over a plurality of cycles. A porous covering of bag may be disposed around the solid cleaning agent.

## Background
CROSS-REFERENCED RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 10/775,264, filed Feb. 10, 2004, now U.S. Pat. No. 7,053,040, entitled “Autonomous Cleaning Composition And Method.” This application is also a continuation-in-part of U.S. patent application Ser. No. 10/925,331, filed Aug. 24, 2004, now abandoned, entitled “Multiuse, Solid Cleaning Device And Composition.” Both of these applications are incorporated herein by reference.


BACKGROUND OF THE INVENTION
The present invention relates to a multiuse, solid cleaning composition. More specifically, the present invention is drawn to compositions for cleaning with water, including slow release compositions which provide consistent concentrations of cleaning agents delivered into water over multiple wash cycles.
Chemical cleaning agents, in one form or another, have long been used to remove dirt, oil, and particulate matter from a wide variety of articles. Cleaning improves the visual and tactile impression of an article, kills potentially harmful microbes, removes particles that interfere with breathing and vision, and may even extend the life of the article being cleaned. Things such as cookware, homes, automobiles, clothing, and the human body itself stand to benefit from the development of enhanced cleaning agents. Although the present invention contemplates cleaning systems useful for cleaning a wide variety of articles, it is particularly well-adapted for cleaning clothes, as in a washing machine.
Soaps and detergents are two of the most common cleaning agents presently used. While they are often used interchangeably, the words “soap” and “detergent” actually denote different classes of compounds.
Soaps are made by a process of saponification wherein a fatty acid reacts with a base to yield the salt of the fatty acid, i.e., a soap. Soap probably has its origin in reacting animal fats, or lard, with alkaline salts, such as wood ash. Today, they are largely synthesized from animal fats and plant oils. Molecules of soap owe their cleaning capacity to their amphiphilic structure, which includes a hydrophobic portion consisting of a long hydrocarbon chain, and a hydrophilic portion composed of an ionic group at one end of the hydrocarbon chain. Because of the hydrocarbon chain, a molecule of soap is not truly soluble in water. Numerous molecules of soap will suspend in water as micelles, or clusters of molecules with long hydrocarbon chains in the inner portions of the cluster, and ionic, water soluble ends facing the polar water.
Because these micelles form hydrophobic centers, they are able to dissolve other non-polar substances, like oils. Once the non-polar, oily dirt is dissolved within the micelles of soap, the ionic surfaces of the micelle repel each other, suspending the oil droplets and preventing them from coalescing. In this fashion, dirt and oil become trapped within the water soluble micelles, and wash away with the water.
A primary disadvantage of soaps is that they form insoluble salts (precipitates) with ions found in hard water. These salts, usually formed when Ca++ and Mg++ ions react with the carboxylate ends of soap molecules, precipitate out of solution as bathtub rings, grits, and other deposits. Water softeners that exchange Ca++ and Mg++ ions for more soluble Na+ ions can alleviate most of this problem.
Most laundry products and many household cleansers actually contain detergents, not soaps. A detergent is a compound with a hydrophobic hydrocarbon chain plus a sulfonate or sulfate ionic end (whereas soaps have carboxylic ends). Because detergents also have an amphiphilic structure, they also form micelles and clean in the same fashion as soaps. However, detergents have the advantage that most metal alkylsulfonates and sulfates are water-soluble. Therefore, detergents do not precipitate out of solution with metal ions found in water. As a result, detergents are not inhibited by hard water. In addition, detergents can be synthesized with continuous chain alkyl groups, which are more easily broken down, or biodegraded, into smaller organic molecules by the microorganisms in septic tanks and sewage treatment plants.
A drawback of most detergents is that they contain additives that take much longer to biodegrade. Some components containing phosphates must be treated in plants. Phosphates promote algae growth, chocking bodies of water and streams. Another disadvantage of detergents is that they can leave behind an undesirable residue even after thorough rinsing.
Detergents are currently used in many household appliances, such as dishwashers and washing machines. Presently, a user must measure out a dose of detergent to add to the cleaning appliance before every cleaning cycle. Conventional packaging and use of detergents creates messy clutter, consumes time, and typically results in a waste of detergent from overdosing. In addition, most washing machines for clothing use a separate rinsing cycle in order to remove the residue. Thus, additional time, water, and heat energy are required to complete the washing process.
It would be a great advancement in the art to provide a novel cleaning system that uses a novel non-detergent composition of cleaner that leaves no residue and therefore, requires no rinsing cycle. Another improvement in the art would be to provide a cleaning agent that is biodegradable. Still another improvement would be if this cleaning agent were made from natural materials. It would also be a great advancement in the art to provide a new method for making a non-detergent cleaning agent. It would be another advancement in the art to provide a cleaning agent that cleans as good as or better than the detergents presently on the market.
Furthermore, it would be an improvement in the art to simplify the cleaning process and ameliorate the resultant mess with improved, preferably measurement-free or automatic, dosing over many cleaning cycles.
BRIEF SUMMARY OF THE INVENTION
In accordance with the invention as embodied and broadly described herein, a multiuse, solid cleaning device and cleaning method are disclosed in suitable detail to enable one of ordinary skill in the art to make and use the invention.
The multiuse cleaning device contains a homogeneous quantity of cleaning agent in solid form configured to slowly dissolve and release a substantially consistent quantity of cleaning agent over a plurality of wash and rinse cycles. The device may be used in various cleaning applications such as laundry and dish washing applications.
The cleaning agent includes a gas-releasing component, a solubility control component to limit the solubility of the cleaning agent, an alkalinity agent as a pH regulator, a water softener to solvate metal ions in a solution of water, and an optical brightener for increased color clarity and brightness. Gas-releasing component clean by reacting with acids (soils) and by mechanical microscrubbing as they yield gases, such as carbon dioxide. The gas-releasing component is preferably selected from carbonates, bicarbonates, perborates, percarbonates, and mixtures thereof. Sodium perborate monohydrate, sodium percarbonate, sodium bicarbonate, sodium carbonate, and mixtures thereof are presently preferred gas-releasing agents.
The solubility control agent is a material resistant to dissolving in water, i.e., water insoluble or slightly water-soluble. It controls solubility by dissolving only an equilibrium concentration of composition in solution. The amount of solubility control component in the composition determines the equilibrium concentration of the composition in a solution, e.g., water. Therefore, the amount of solubility control component should be sufficient to yield a predetermined equilibrium concentration of the cleaning agent. Similarly, the amount of cleaning agent should be sufficient to provide a predetermined amount of gas in solution. The amount of alkalinity agent should be sufficient to provide a predetermined pH in solution. The amount of water softener should be sufficient to soften household water in solution.
U.S. Pat. Nos. 6,178,987, 6,262,004, and 6,403,551 disclose a solid cleaning composition containing amorphous silica as the solubility control agent. Amorphous silica (H2SiO3) is a preferred solubility control agent because it occurs in nature and is completely biodegradable. In the cleaning compositions containing amorphous silica disclosed in the above-identified patents, careful heating and pressurizing are needed to prepare the cleaning compositions. It has been found that commercially available potassium silicate (K2O.nSiO2.mH2O), in liquid form, may be used to prepare the cleaning agent compositions at room temperature without special heating or pressure. Other silicates, such as sodium silicate, tend to dissolve quickly and may not provide desired solubility control. However, in some cases sodium silicate may be usable within the scope of the present invention. The other ingredients may be used at approximately the same concentration reported in the foregoing patents. Completion of the process may include casting or molding the composition in a shape selected to control surface area, and curing the composition. The composition cures independently at room temperature as water becomes depleted through evaporation and/or as a result of the anhydrous compounds absorbing water.
The water softener is preferably a naturally occurring and biodegradable material capable of solvating hard water ions, such as a zeolite. Naturally occurring zeolites are presently preferred; however, the invention may be used with synthetic zeolites which function in a manner equivalent to natural zeolites and which biodegrade. The water softener solvates hard ions and inhibits them from reacting with other components to form insoluble salts.
The cleaning agent preferably include an optical brightener present in an amount from about 0.5 to 8% by weight, more preferably from about 0.5 to 5% by weight, and optimally from about 0.5 to 3% by weight. The cleaning agent may optionally include a fragrance component present in an amount from about 0.5 to 12% by weight, more preferably from about 1 to 12% by weight, and optimally from about 1 to 5% by weight. The cleaning agent may optionally include an anti-redeposition component present in an amount from about 0.5 to 10% by weight, more preferably from about 0.5 to 5% by weight, and optimally, from about 0.5 to 3% by weight.
The alkalinity agent is present in an amount sufficient to give a solution of the composition a pH greater than 7, and preferably a pH from about 7 to about 10.5, more preferably from 7.8 to about 8.8. Examples of alkalinity agents include, but are not limited to, an alkali hydroxide, alkali hydride, alkali oxide, alkali sesquicarbonate, alkali carbonate, alkali phosphate, alkali borate, alkali salt of mineral acid, alkali amine, alkaloid, alkali cyanide, and mixtures thereof. Sodium hydroxide is one presently preferred alkalinity agent.
In certain embodiments within the scope of the present invention, the method of preparing the solid cleaning agent may include providing a solvent, such as water; providing a gas-releasing agent, such as sodium bicarbonate, sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate, and mixtures thereof; providing a water softener, such as a zeolite; providing a solubility control agent, such as potassium silicate; mixing the ingredients; pouring the mixture into a curing vessel; and allowing the composition to cure to a solid form.
A porous covering or bag may be disposed around the solid cleaning agent to hold it during use. The porous covering or bag may optionally be elastic and conform to the size of the solid cleaning agent as the cleaning agent shrinks in size due to dissolution of cleaning agent. The covering or bag helps reduce or eliminate direct transfer of cleaning agent residue onto fabric surfaces after a final rinse cycle when the cleaning device and fabric surfaces are in contact for an extended time period. The porous covering or bag may be an elastic net-like material or a woven fabric material. It may be a porous fabric bag with a covering of ruffle-like material.
The bag houses or surrounds the cleaning agent may also be used in conjunction with the present invention. The bag may also be configured to retain fragrance with the cleaning agent, to create more sudsing (lathering) during agitation of the washing machine, to create drag in the water to quiet any contact with the agitator/cleaning agent and the tub of the washing machine, and/or to create a barrier between the cleaning agent and the clothes (which prevents or reduces discoloration of the clothes).
In some embodiments, the bag is a multilayered structure. In further embodiments, the bag is made of three layers: an outer layer, a middle layer, and an inner layer. The outer and inner layers may be both made of a porous material through which water may pass. In some embodiments, this porous material is a mesh material that is smooth and non-abrasive. The middle layer may be constructed to provide spacing and/or padding between the outer layer and the inner layer. In some embodiments, the middle layer is made of a material such as ruffled netting and porous foam.
The cleaning device may include a indicator structure disposed within the quantity of cleaning agent to signal when to replace the cleaning device. It may optionally include an internal skeleton within the quantity of cleaning agent to provide structural strength to the cleaning device.
The ball may be spherical, aspherical, oval, oblate, rounded, or irregular shaped. The cleaning device is preferably in the form of a ball. The size of the cleaning device may vary depending upon the concentration of the cleaning agent and its dissolution rate and the desired quantity of cleaning agent to be released in each wash or rinse cycle. For example, a more concentrated cleaning agent, with a slower dissolution rate, may have a smaller size than a device having a lower concentration cleaning agent with a higher dissolution rate. For convenience, the cleaning device may have a diameter in the range from about 2 to about 6 inches in residential applications and 4 to 12 inches in commercial/industrial applications. A device having a size approximately the same as a softball may be used.
The cleaning agent in solid form dissolves and releases a substantially consistent quantity of cleaning agent over from about 5 to 50 (or more) laundry wash or rinse cycles. In other embodiments, the cleaning agent in solid form dissolves and releases a substantially consistent quantity of cleaning agent over from about 10 to 40 laundry wash or rinse cycles. As would be expected, the choice to use hot, warm, or cold water in the wash/rinse cycle will affect the dissolution of the cleaning agent—i.e., the cleaning agent will more readily dissolve in hot water than in cold water. Thus, the exact number of wash/rinse cycles that the cleaning agent will be operable will depend in part on the temperature of the water in the washing machine.
Similarly, the weight of the solid cleaning agent will affect the number of wash or rinse cycles. For example, a 600 gram device is expected to provide more cleaning cycles that a 300 gram device.
As noted above, the cleaning agent 10 is designated such that a substantially consistent quantity of cleaning agent 10 will dissolve during each laundry cycle. “Substantially consistent quantity” means that the amount of cleaning agent that dissolves per wash cycle generally will fall within a predictable range. For example, the range may be defined as follows:

 X10±about50%

where X10 is the average amount of cleaning agent that dissolves during the first 10 wash cycles and “50%” means 50% of the X10 value. However, embodiments in which the amount of cleaning agent 10 that dissolves per wash cycle may range as high as X10± about 65%. Some of the presently preferred embodiments will be designed such that the amount of cleaning agent 10 that dissolves per wash cycle is within the range X10± about 40% and even X10± about 25%.

In one embodiment of the cleaning agent within the scope of the present invention, the gas-releasing component is present in an amount from about 20% to 60% by weight, the solubility control component is present in an amount from about 20% to 60% by weight, the water softener is present in an amount from about 0.5% to 20% by weight, the alkalinity agent is present in an amount from about 0.5% to 20% by weight, and the optical brightener is present in an amount from about 0.5% to 8% by weight.
In a preferred embodiment within the scope of the present invention, the gas-releasing component is present in an amount from about 40% to 55% by weight, the solubility control component is present in an amount from about 35% to 50% by weight, the water softener is present in an amount from about 1% to 10% by weight, the alkalinity agent is present in an amount from about 1% to 12% by weight, and the optical brightener is present in an amount from about 0.5% to 5% by weight.
In a more preferred embodiment within the scope of the present invention, the gas-releasing component is sodium perborate monohydrate present in an amount from 42% to 52% by weight, the solubility control component is potassium silicate present in an amount from 35% to 45% by weight, the water softener is a zeolite present in an amount from 1% to 5% by weight, the alkalinity agent is sodium hydroxide present in an amount from 1% to 5% by weight, and the optical brightener is present in an amount from about 0.5% to 3% by weight.
A method of providing laundry cleaning agent to a laundry cleaning machine is disclosed. The method includes the step of obtaining a multiuse laundry cleaning device in a solid state containing a homogeneous quantity of cleaning agent in solid form configured to dissolve and release a substantially consistent quantity of cleaning agent over a plurality of laundry wash and rinse cycles. As mentioned above, the cleaning device may have a porous covering or bag disposed around the solid cleaning agent. The porous covering or bag may be elastic and conform to the size of the solid cleaning agent as the cleaning agent shrinks in size due to dissolution of cleaning agent. The porous covering or bag may be pliable and may not necessarily conform to the size of the solid cleaning agent. The method further includes the step of depositing the laundry cleaning device within the laundry cleaning machine tub under conditions such that the laundry cleaning device is exposed to water from the plurality of laundry wash and rinse cycles.
These and other features, and advantages of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a multiuse cleaning device within the scope of the present invention.
FIG. 2 shows a cross-sectional view of a multiuse cleaning device.
FIG. 3 shows a cross-sectional view of another multiuse cleaning device.
FIG. 4 shows a perspective view of a bag that houses the multiuse cleaning device.
FIG. 5 is a cross-sectional view taken along the line A-A of FIG. 4.
FIG. 6 is a graph of cleaning agent released per load for the results reported in Table 2C.
FIGS. 7A-7G are graphs of cleaning agent released per load for the results reported in Tables 7A-7G.



DETAILED DESCRIPTION OF THE INVENTION
The present invention is drawn to a multiuse cleaning device containing a homogeneous quantity of cleaning agent in solid form and to methods of manufacture and use. The cleaning agent in solid form preferably provides controlled dissolution in contact with water such that a sufficient quantity of cleaning agent is dissolved and released for use in multiple wash cycles of a cleaning appliance.
The cleaning agent composition may include a gas-releasing agent that is water soluble, and a solubility control agent that is only slightly water soluble. The gas-releasing agent provides cleaning action. However, if the gas-releasing agent is permitted to freely dissolve, the resulting cleaning solution will have an unknown or uncontrolled concentration of gas-releasing agent. Thus, it is desirable to add a solubility control agent to the cleaning agent to control its equilibrium concentration, and hence, the concentration of gas-releasing agent in the cleaning solution.
The cleaning agent may be further enhanced through the addition of an alkalinity agent and a water softener. The alkalinity agent controls the pH of the cleaning agent, and therefore the pH of the resultant cleaning solution. The pH of the cleaning solution preferably remains within a certain range because the pH controls the rate at which the gas-releasing agent reacts. The gas-releasing agent or the solubility control agent may be configured to control the pH of the cleaning solution, but a separate alkalinity agent is presently preferred. The softener prevents the formation of a residue on the items to be cleaned by solvating hard water ions. The gas-releasing agent, the solubility control agent, or the alkalinity agent may be configured to solvate hard water ions, but a separate softener is preferable.
The gas-releasing agent should not release gas in the solid state cleaning agent, but it should be able to release gas in a cleaning solution of the cleaning agent at ambient temperature. The gas-releasing agent need not react with other agents, but may simply decompose at ambient temperature to release gas. Those gas-releasing compounds that are natural and biodegradable are preferred. In some embodiments, the gas-releasing agent is a carbonate, bicarbonate, percarbonate, or perborate. For example, sodium percarbonate, which is also known as sodium carbonate peroxyhydrate, (2Na2CO3.3H2O2), sodium bicarbonate, (NaHCO3), sodium perborate monohydrate (NaBO3.H2O), sodium perborate tetrahydrate (NaBO3.4H2O), and sodium carbonate (Na2CO3) are effective, low cost gas-releasing agents. Mixtures of gas releasing agents may be used. However, numerous other gas-releasing agents are known to those skilled in the art, and all are within the scope of the present invention. Sodium perborate monohydrate is a presently preferred gas releasing agent.
The solubility control agent should be either water insoluble or only slightly water soluble. Numerous compounds may serve this function, including but not limited to hydrophobic compounds. Those solubility control agents that are both found in nature and biodegradable are preferred. Potassium silicate is presently preferred because it may be used to prepare the solid cleaning agent composition at room temperature.
The alkalinity agent may be selected from, but is not limited to, a group consisting of alkali hydroxide, alkali hydride, alkali oxide, alkali carbonate, alkali bicarbonate, alkali phosphate, alkali borate, alkali salt of mineral acid, alkali amine, alkaloid, alkali cyanide, alkali metal, and alkali earth metal. Sodium hydroxide is an example of one presently preferred alkalinity agent. Other alkalinity agents that tend to increase the pH of a neutral solution are familiar to those in the art, and are within the scope of the present invention. Those alkalinity agents that are both found in nature and biodegradable are preferred. Sodium carbonate provides the dual function of an alkalinity agent and a gas releasing agent. Potassium silicate may provide the dual function of an alkalinity agent and a solubility control agent. Similarly, sodium percarbonate provides alkalinity control in addition to its gas release function. In addition to being an alkalinity agent, sodium hydroxide may provide the dual function of being an a processing aid that facilitates the formation of a potassium silicate slurry and/or provides catalytic action for solidification of the cleaning agent.
The softener should preferably be selected to exchange soluble sodium or other ions for the insoluble calcium and magnesium ions. Those softeners that are both found in nature and biodegradable are preferred. A cleaning agent composition wherein the softener is natural zeolite (Na2O.Al2O3.(SiO2)x(H2O)x) is presently preferred because it occurs in nature and is completely biodegradable. Synthetic zeolites may be used provided that they perform the desired softening function and are biodegradable.
The amount of gas-releasing agent in the cleaning agent determines how much gas is released in a cleaning solution of the cleaning agent formed when the cleaning agent dissolves in a solvent, e.g., water. Therefore, the gas-releasing agent in the cleaning agent should comprise an amount sufficient to release a predetermined amount of gas in a cleaning solution of the cleaning agent. A concentration of gas-releasing agent from 20% to 60% by weight of the cleaning agent may be used, with a concentration from 40% to 55% being more preferred. In one embodiment, the concentration of gas-releasing agent is from 42% to 52% by weight.
The amount of solubility control agent in the cleaning agent determines the equilibrium concentration of the cleaning agent in the cleaning solution. Therefore, the amount of solubility control agent in the cleaning agent should be selected to yield a predetermined equilibrium concentration of cleaning agent in the cleaning solution. A concentration of solubility control agent from 20% to 60% by weight of the cleaning agent may be used, with a concentration from 35% to 50% being more preferred. In one embodiment, the concentration of solubility control agent is about 35% to 45% by weight.
The amount of alkalinity agent in the cleaning agent affects the pH of the cleaning solution. Therefore, the cleaning agent should include an amount of alkalinity agent selected to provide a cleaning solution within a predetermined pH range. A concentration of alkalinity agent from 0.5% to 20% by weight of the cleaning agent may be used, with a concentration from 1% to 12% by weight being more preferred. Because the alkalinity agent may also provide gas releasing finctionality, in the case of sodium carbonate, the actual concentration of the gas releasing agent and alkalinity agent may be outside the foregoing concentration range. In one embodiment, the concentration of alkalinity agent is about 1% to 5% by weight, providing a cleaning solution with a pH of about 8.8 after dilution inside the cleaning appliance.
The softener in the cleaning agent softens the cleaning solution by scavenging residue-forming ions. Therefore, the softener should comprise an amount of cleaning agent sufficient to soften household water. A concentration of softener from 0.5% to 20% by weight of the cleaning agent may be used, with a concentration from 1% to 10% being more preferred. In one embodiment, the concentration of the softener is about 1% to 5% by weight.
The optical brightener is an additive that improves visual appearance in cleaned fabrics. Optical brighteners are known to persons having ordinary skill in the art. An optical brightener may be added to the cleaning agent in an amount from about 0.5% to 8% by weight, and more preferably from about 0.5% to 5% by weight. In one embodiment, the concentration of optical brightener is about 0.5% to 3% by weight. One currently preferred optical brightener is sold under the tradename Tinopal by Ciba Specialty Chemicals, Inc. of Basel, Switzerland.
Water molecules may form complexes with these components and could be bound up within the cleaning agent by virtue of the process of making the cleaning agent. Water may comprise from 1% to 50% of the cleaning agent by weight. Preferably, water comprises approximately 20% by weight of the cleaning agent. It will be appreciated that some components of the cleaning agent may contain water, such as potassium silicate, sodium perborate monohydrate, sodium hydroxide, zeolite, and other ingredients, which may limit the amount of extra water that needs to be mixed with the dry ingredients.
In operation, items to be cleaned are exposed to the cleaning solution, which causes a number of processes occur. The basic cleaning solution attacks the acids in dirt and oil. The gas-releasing agent releases gas that reacts with dirt and oil. In a cleaning appliance for washing clothing, dirt and oil would be dislodged from clothing in a removal step due to reaction with the released gas. The gas-releasing agent provides a sustained release of gas that continues to react with removed soils.
Simultaneously, in a scavenging step, the softener scavenges ions to prevent the buildup of residue on the articles to be cleaned. In addition, the alkalinity agent keeps the pH of the cleaning solution slightly basic. This serves two functions. First of all, it limits the reaction of the gas-releasing agent so that the gas evolves at a controlled rate and the cleaning solution has time to become thoroughly intermixed with the articles to be cleaned. Second, the basic cleaning solution reacts to neutralize acids in the soils.
An exemplary cleaning process utilizing an exemplary cleaning agent will now be described. First, the sodium percarbonate and sodium carbonate attack acids within the dirt and oils. The acid-base reactions have an emulsifying affect on the dirt and oils. Particularly, sodium percarbonate (which includes sodium carbonate) reacts with acids to generate carbon dioxide in an acid and base reaction: 2H+(aq)+Na2CO3(aq)→2Na+(aq)+H2O+CO2(g). Most oils and dirts found in clothing are slightly acidic, and so the sodium carbonate component of the percarbonate may react with these dirts and oils to produce carbon dioxide. This tiny explosion of gas, as it bubbles out of solution, dislodges the dirt from clothes and other materials, allowing it to be washed away. The reaction yields sodium ions in solution, or the sodium salts of the oils and dirts of the reaction, water and carbon dioxide.
In this embodiment, the byproducts of the cleaning process appear in nature, so there is no need for the extensive treatment of phosphates and other non-biodegradable materials, as required by presently available detergents. However, the alkalinity agent, which may include sodium carbonate, is added primarily to increase the pH of the cleaning solution but also functions as a gas releasing agent, described above. In a similar manner, sodium percarbonate, is added primarily as a gas releasing agent but also increases the pH of the cleaning solution as an alkalinity agent.
The alkalinity agent provides a mildly basic solution to prevent the sodium percarbonate from reacting with excess hydrogen ions (H+) in aqueous solution. Without the alkalinity agent, CO2 would bubble out of solution too quickly as the sodium percarbonate reacts with random hydrogen ions. With a slightly alkaline cleaning solution, in one embodiment approximately 8.5 to 10 pH, the sodium percarbonate reacts at a controlled rate, and preferably with the acids in the dirts and oils.
The softener, which may be natural or synthetic zeolite, exchanges sodium ions (Na+) for magnesium (Mg++) and calcium (Ca++) ions: Mg+++Ca+++zeolite→zeolite+4Na+. Sodium ions and sodium salts are readily water soluble and will not form precipitates. Without the softener, the Mg++ and Ca++ could react to form insoluble salts, precipitating out of solution and leaving a hard film behind, as shown by the following equations: NaHCO3+Mg++→MgCO3, and NaHCO3+Ca++→CaCO3.
One possible method for making the cleaning agent in a solid state will be described. In the described method a solvent, a gas releasing agent, a solubility control agent, an alkalinity agent, and a softener, are combined to form the cleaning agent. It will be appreciated that the cleaning agent may be manufactured with some components performing multiple functions or with additional, unnamed agents.
The solvent may be included with the solubility control agent, if in liquid form. The solvent will typically be water, and may comprise from 1% to 50% by weight of the cleaning agent composition.
Referring to FIG. 1, a multiuse cleaning device 10 is illustrated. The cleaning device 10 is shown in the form of a spherical ball. The ball does not need to be spherical, but it can take any practical, easily manufactured shape such as aspherical, oval, oblate, rounded, or other irregular shaped configuration.
As shown in FIG. 2, the multiuse cleaning device 10 contains a homogeneous quantity of cleaning agent 12 in solid form. The cleaning agent 12 has a composition as described herein. In the embodiment shown in FIG. 2, the cleaning device 10 is a solid mass of cleaning agent. The cleaning device is deposited within the laundry cleaning machine tub under conditions such that the laundry cleaning device is exposed to water from the plurality of laundry wash and rinse cycles. Under typical conditions, the cleaning device is deposited within the tub or wash basin together with the soiled clothing, towels, linens, and similar articles (hereinafter referred to as “laundry articles”), to be laundered. Water from wash and rinse cycles dissolves a portion of the cleaning device and releases a controlled quantity of cleaning agent which is able to clean the laundry articles as described herein. Upon completion of the cleaning cycle, the clean laundry articles are removed, but the cleaning device may remain within the laundry cleaning machine tub for use in multiple cleaning cycles.
Referring to FIG. 3, the cleaning device 10 may have an indicator structure 16 which indicates when it is time to replace a used cleaning device with a fresh cleaning device 10. The structure 16 may take a variety of different forms. For example, it may spherical, disk, rod, spiked, or irregular shaped. The important feature is that the structure be able to indicate, such as by a visible sign, that the cleaning device 10 should be replaced. The cleaning device 12 may include a support structure or internal skeleton disposed within the quantity of cleaning agent 12 to provide structural strength to the cleaning device.
Also shown in FIG. 3 is a porous covering or bag 14 disposed around the solid cleaning agent 12. The porous covering or bag 14 may be elastic and conform to the size of the solid cleaning agent 12 as the cleaning agent shrinks in size due to dissolution of cleaning agent 12. The porous covering or bag 14 may be pliable or flexible and not necessarily conform tightly to the cleaning agent as it dissolves and shrinks in size. The covering 14 helps reduce or eliminate direct transfer of cleaning agent residue onto fabric surfaces after a final rinse cycle when the cleaning device and fabric surfaces are in contact for an extended time period. For example, users do not always remove laundry articles from the laundry cleaning machine as soon as the wash cycle is completed. Under such circumstances, the cleaning device 10 would contact moist fabric surfaces for a period of time. This may result in transfer of cleaning agent onto fabric surfaces. The porous covering or bag 14 provides a barrier which separates the cleaning agent 12 from the fabric surfaces. The covering 14 may be a net-like material or a woven fabric material. The covering 14 may include ruffles on the outer surface to create a greater separation distance between the cleaning agent 12 and clean or moist fabric surfaces.
Referring now to FIG. 4, an embodiment of the bag 14 is illustrated in greater detail. As explained in greater detail above, the bag 14 is designed such that it may surround and/or house the cleaning agent 10. In general, the bag 14 has a top end 80 and a bottom end 82. The bottom end is 82 sealed through sewing, stitching, Velcro, elastic, bonding, or other similar methods. The top end 80 comprises a closeable top 86 such that the bag 14 may surround and house the agent 10. In some embodiments, the closeable top 86 is a drawstring. However, Velcro, elastic, or other items/methods capable of forming a closeable top may also be used.
FIG. 4 also shows a graphical illustration of pores or openings 90 that may be part of the material used to make the bag 14. Such pores 90 are added to all or a portion of the bag 14 and are designed to allow water to pass through the bag 14 but to retain the solid cleaning agent 10. As noted above, the pores 90 may be formed by using a woven fabric material, a net-like material, or other materials. In one presently preferred embodiment, the bag 14 is made from material of the type used to make athletic jerseys, such as football jerseys. This material not only has adequate porosity to freely allow the passage of water, but also this type of material is non-abrasive to the other laundry articles in the washing machine.
FIG. 5 is a cross-sectional view taken along the line A-A of FIG. 4 and illustrates the construction of the bag 14. The bag 14 may comprise multiple layers of material. In general, these multiple layers of material are used so that when the bag 14 surrounds the agent 10, there is about 1⁄2 inch of material between the agent 10 and the laundry articles in the washing machine. In the embodiment shown in FIG. 5, three distinct layers of material have been used. Other embodiments may also be made using more or less than three layers, as desired.
In FIG. 5, the porous bag 14 includes an outer layer 100, a middle layer 102, and an inner layer 104 which have been connected together via stitching 106. Of course, other methods of connecting the layers together such as bonding with adhesive or heat, weaving, etc. may also be used. In some embodiments, it may be important to select materials for the layers 100, 102, 104 that (1) allow the water freely pass in and out of the bag 14 and (2) will not retain more than negligible amounts of water.
The outer layer 100 and the inner layer 104 may be both made of a porous material, such as a mesh material. However, the outer layer 100 and the inner layer 104 need not be made of the same material. They may be made of different materials. The outer layer 100 is preferably smooth and non-abrasive to the clothing or other laundry articles. The inner layer 104 may be smooth and non-abrasive to the cleaning device to minimize unwanted mechanical abrasion of the cleaning agent.
The middle layer 102 is made of a padding material to provide spacing and/or structure between the outer layer 100 and the inner 104. The middle layer may be constructed of materials such as ruffled netting, porous foam, or other similar materials.
In further embodiments, the bag 14 may also be configured such that it performs one or more of the following functions:

    
    
        (1) retains fragrance with the cleaning agent;
        (2) creates more sudsing (lather) during agitation of the washing machine;
        (3) creates drag in the water to quiet any contact with the agitator/cleaning agent and the tub of the washing machine;
        (4) retains fragments of the cleaning agent;
        (5) creates a barrier between the cleaning agent and the clothes (which prevents/reduces discoloration of the clothes); and/or
        (6) provides a more consistent dissolution rate of the cleaning device over multiple wash/rinse cycles.
    
    


Of course, the bag 14 may perform other functions depending on factors such as the construction of the bag, the size of the bag, etc.
EXAMPLES
The following examples are given to illustrate various embodiments within the scope of the present invention. These are given by way of example only, and it is to be understood that the following examples are not comprehensive or exhaustive of the many embodiments within the scope of the present invention.
Example 1
A cleaning agent composition was prepared by mixing the dry ingredients listed in Table 1A with the wet ingredients listed in Table 1B:











TABLE 1A







Dry Ingredients
Weight (g)
Weight Percent





















Sodium perborate monohydrate
230
g
45.5



Optical brightener
5
g
1.0



Antiredeposition agent
5
g
1.0



Zeolite
15
g
3.0



Fragrance
22
g
2.2



Total:
267
g
52.7





















TABLE 1B







Wet Ingredients
Weight (g)
Weight Percent




















Potassium Silicate
201 g
39.8



Sodium hydroxide
 9 g
1.8



Surfactant
 29 g
5.7



Total:
239 g
47.3










After the foregoing ingredients are mixed, the mixture is poured into a mold and allowed to cure and solidify.
Example 2
A multiuse laundry cleaning device in a solid state was prepared by molding cleaning agent having the formula of Example 1 into a spherical ball. The spherical ball was placed inside a washing machine tub and subjected to repeated wash cycles in the washing machine tub. Additional multiuse laundry cleaning devices were prepared and tested in several different types of commercially available washing machines. Wash cycles ranged from delicate to regular to heavy duty, and different water temperature settings were used. The multiuse laundry cleaning device remained in the washing machine tub for both wash and rinse cycles. After the cleaning cycles were complete, the cleaning device was removed from the washing machine and weighed to determine the quantity of cleaning agent that was dissolved during the preceding wash cycle. Representative results from two tests are reported in Tables 2A and 2B.









TABLE 2A






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released

















0
422



1
394
28


2
336
58


3
283
53


4
231
52


5
189
42


6
164
25


7
129
35


8
99
30


9
76
23


10
64
12


11
44
20


12
35
9


13
30
5


14
27
3


15
21
6


















TABLE 2B






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released

















0
435



1
389
46


2
335
54


3
283
52


4
236
47


5
206
30


6
171
35


7
145
26


8
134
11


9
124
10


10
102
22









The average amount of cleaning agent released per wash cycle in Table 2A over 10 wash cycles was 35.8 g. The average amount of cleaning agent released per wash cycle in Table 2B over 10 wash cycles was 33.3.
Results from a test with more wash cycles are reported in Table 2C below:









TABLE 2C






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released

















0
430



1
401
29


2
366
35


3
336
30


4
306
30


5
281
25


6
252
29


7
238
14


8
218
20


9
193
25


10
179
14


11
157
22


12
137
20


13
122
15


14
103
19


15
78
25


16
64
14


17
46
18


18
31
15


19
11
20









The average amount of cleaning agent released per wash cycle in Table 2C over 19 wash cycles was 22.1 g. A graph of the results shown in Table 2C, grams of cleaning agent released per wash cycle load, is shown in FIG. 6.
One cleaning agent composition within the scope of the invention has the following ingredients set forth in Table 3:










TABLE 3







Ingredient
Weight Percent









Water
29%



Sodium Bicarbonate
39%



Natural Zeolite
 8%



Potassium silicate
21%



Sodium Sesquicarbonate
 3%










Another cleaning agent composition within the scope of the present invention has the following ingredients set forth in Table 4:










TABLE 4







Ingredient
Weight Percent









Sodium Perborate
37.0%



Monohydrate



Sodium Carbonate
31.2%



Natural Zeolite
  8%



Optical Brightener
 1.0%



Potassium silicate
22.8%










With the formula of Table 4, ingredients were added as listed. The powders (first four items) were combined and mixed prior to adding liquid potassium silicate. After adding the potassium silicate, the product was mixed briefly and poured into a mold. Set-up and hardening began within twenty minutes after the addition of the potassium silicate at room temperature.
The sodium perborate monohydrate and the sodium carbonate both release gas. The carbonate releases carbon dioxide and the perborate releases oxygen. The potassium silicate provides some solubility control. The sodium carbonate serves a dual role as gas releaser and alkalinity agent.
It has been found that potassium silicate may be used successfully, while sodium silicate is noticeably less-effective to prepare the cleaning agent. While not being bound by theory, it is believed that potassium silicate is operative because it does not raise the pH too high and does not dissolve in water as readily as sodium silicate. Potassium silicate has a pH of about 11, whereas sodium silicate has a pH of about 13. With this information, it may be possible to include a suitable pH modifier with sodium silicate to successfully prepare the cleaning agent.
Yet another cleaning agent composition within the scope of the present invention has the following ingredients set forth in Table 5:










TABLE 5







Ingredient
Weight Percent



















Sodium Percarbonate
38%



Sodium Carbonate
25%



Carboxymethylcellulose
1%



Natural Zeolite
8%



Potassium silicate
28%










With the formula of Table 5, ingredients were added as listed. The powders (first four items) were combined and slowly mixed to minimize dusting, but mixed briskly enough to ensure total dispersion. The liquid potassium silicate was added slowly with the mixer running. As the product thickens, a small amount of base (sodium hydroxide, less than 0.5 weight percent) was added to aid in processing by thinning the material and allowing a longer mix time. After about 5 to 10 minutes, the product started to stiffen, and it was poured into a mold for curing. Set-up and hardening began within ten minutes after the addition of the potassium silicate at room temperature.
The carboxymethylcellulose is a soil anti-redeposition compound. The sodium percarbonate and the sodium carbonate both release gas. The carbonate releases carbon dioxide and the percarbonate releases oxygen. The potassium silicate provides some solubility control. The sodium carbonate serves a dual role as gas releaser and alkalinity agent. The amounts listed in Table 4 can be varied by a few weight percent.
Another cleaning agent composition within the scope of the present invention has the following ingredients set forth in Table 6:









TABLE 6







Weight Percent



















Dry Ingredients




Gas-releasing Agent
43.7%



Antiredeposition Agent
1.0%



Optical brightener
1.0%



Natural Zeolite-40 mesh
3.2%



Fragrance-linen
3.0%



Wet Ingredients



Surfactant
1.9%



Potassium silicate
43.7%



Sodium hydroxide-25%
2.5%










The cleaning agent disclosed in Table 6 is made in accordance with the procedures of Example 1 outlined above. The amounts listed in Table 6 can be varied by a few weight percent.
In Table 6, the anti-redeposition agent was carboxymethylcellulose. The gas-releasing agent was sodium perborate monohydrate. The potassium silicate provides some solubility control. The alkalinity agent was sodium hydroxide. The optical brightener was Tinopal, which is made and available from the Ciba Specialty Chemicals, Inc. The surfactant was Calsoft F-90, which is available from the Pilot Chemical Co.
Additional tests were also done regarding the dissolution of the cleaning agent in the washing machine. In these tests, the laundry cleaning device remained in the washing machine tub for both wash and rinse cycles. After the cleaning cycles were complete, the cleaning device was removed from the washing machine and weighed to determine the quantity of cleaning agent that was dissolved during the preceding wash cycle. Representative results from two tests are reported in Tables 7A-7G.









TABLE 7A






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released (g)

















0
430
0


1
430
35


2
395
30


3
365
30


4
335
25


5
310
29


6
281
14


7
267
20


8
247
25


9
222
14


10
208
22


11
186
20


12
166
15


13
151
19


14
132
25


15
107
14


16
93
18


17
75
15


18
60
20


19
40
40









The average amount of cleaning agent released per wash cycle in Table 7A over 19 wash cycles as 22.6 grams. A graph of the results shown in Table 7A, grams of cleaning agent released per wash cycle load, is shown in FIG. 7A.
Results from another test with more wash cycles are reported in Table 7B below. These tests were done with a warm wash and a cold rinse cycle.









TABLE 7B






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released (g)

















0
680
0


1
680
13


2
667
13


3
654
13


4
641
11


5
630
14


6
616
19


7
587
20


8
567
25


9
542
14


10
528
12


11
516
13


12
503
15


13
488
17


14
471
11


15
460
14


16
446
18


17
428
15


18
413
20


19
393
9


20
384
6


21
378
11


22
367
10


23
357
10


24
347
9


25
338
11


26
327
16


27
311
14


28
297
13


29
284
10


30
274
15


31
259
16


32
243
22


33
221
17


34
204
12


35
192
9


36
183
17


37
166
20


38
146
15


39
131
13


40
118
15


41
103
8


42
95
10


43
85
13


44
72
6


45
66
4


46
62









The average amount of cleaning agent released per wash cycle in Table 7B over 46 wash cycles was 13.2 grams. A graph of the results shown in Table 7B, grams of cleaning agent released per wash cycle load, is shown in FIG. 7B.
Results from yet another test with more wash cycles are reported in Table 7C below. These tests were done with a cold wash and a cold rinse cycle.









TABLE 7C






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released (g)

















0
680
0


1
680
14


2
666
11


3
655
9


4
646
10


5
636
9


6
627
8


7
619
7


8
612
8


9
604
12


10
592
6


11
586
5


12
581
8


13
573
11


14
562
5


15
557
8


16
549
13


17
536
8


18
528
7


19
521
10


20
511
8


21
503
7


22
496
11


23
485
13


24
472
8


25
464
7


26
457
7


27
450
8


28
442
10


29
432
9


30
423
9


31
414
7


32
407
8


33
399
12


34
387
11


35
376
9


36
367
10


37
357
11


38
346
10


39
336
10


40
326
9


41
317
6


42
311
5


43
306
7


44
299
10


45
289
8


46
281
9


47
272
10


48
262
12


49
250
9


50
241
14


51
227
8


52
219
9


53
210
10


54
200
7


55
193
7


56
186
6


57
180
10


58
170
11


59
159
7


60
152
7


61
145
5


62
140
6


63
134
12


64
122
10


65
112
8


66
104
6


67
98
10


68
88
12


69
76
9


70
67
9


71
58
8


72
50
9


73
41
8


74
33
8


75
25









The average amount of cleaning agent released per wash cycle in Table 7C over 75 wash cycles was 8.7 grams. A graph of the results shown in Table 7C, grams of cleaning agent released per wash cycle load, is shown in FIG. 7C.
It is important to note that even though a smaller amount of cleaning agent dissolved in the cold water tests shown in Table 7C, the dissolved cleaning agent in these tests was at least as effective in cleaning the laundry articles as detergents currently available and used in cold water. However, the use of the cleaning agent in exclusively cold water did increase significantly the longevity of the cleaning agent supply. In fact, these results indicate that, in cold water, the cleaning agent may provide adequate results in upwards of 70 wash/rinse cycles.
Results from a further test with multiple wash cycles are reported in Table 7D below. These tests were done with using lower density wash loads using a cold wash and a cold rinse cycle.









TABLE 7D






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released (g)

















0
450
0


1
438
12


2
425
13


3
414
11


4
400
14


5
390
10


6
378
12


7
365
13


8
354
11


9
343
11


10
333
10


11
319
14


12
306
13


13
297
9


14
286
11


15
274
12


16
260
14


17
249
11


18
239
10


19
230
9


20
218
12


21
205
13


22
193
12


23
183
10


24
171
12


25
160
11


26
152
8


27
142
10


28
130
12


29
122
8


30
109
13


31
98
11


32
88
10


33
79
9


34
71
8


35
61
10


36
55
6


37
44
11


38
36
8


39
30
6


40
24
6









The average amount of cleaning agent released per wash cycle in Table 7D in 40 wash cycles was 10.6 grams. A graph of the results shown in Table 7D, grams of cleaning agent released per wash cycle load, is shown in FIG. 7D.
Results from a further test with multiple wash cycle are reported in Table 7E below. These tests were done with using higher density wash loads using a cold wash and a cold rinse cycle.









TABLE 7E






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released (g)

















0
450
0


1
442
8


2
433
9


3
425
8


4
418
7


5
408
10


6
400
8


7
392
8


8
385
7


9
379
6


10
372
7


11
363
9


12
355
8


13
345
10


14
338
7


15
332
6


16
324
8


17
319
5


18
312
7


19
304
8


20
296
8


21
287
9


22
280
7


23
275
5


24
266
9


25
259
7


26
251
8


27
245
6


28
235
10


29
226
9


30
218
8


31
211
7


32
204
7


33
193
11


34
184
9


35
176
8


36
166
10


37
160
6


38
155
5


39
147
8


40
137
10


41
128
9


42
121
7


43
115
6


44
106
9


45
99
7


46
91
8


47
83
8


48
77
6


49
72
5


50
67
5


51
61
6









The average amount of cleaning agent released per wash cycle in Table 7E in 51 wash cycles was 7.6 grams. A graph of the results shown in Table 7E, grams of cleaning agent released per wash cycle load, is shown in FIG. 7E.
Results from a further test with multiple wash cycles are reported in Table 7F below. These tests were done with using lower density wash loads using a warm wash and a wash rinse cycle.









TABLE 7F






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released (g)

















0
450
0


1
432
18


2
409
23


3
388
21


4
369
19


5
347
22


6
323
24


7
301
22


8
280
21


9
263
17


10
243
20


11
224
19


12
202
22


13
184
18


14
163
21


15
149
14


16
131
18


17
112
19


18
90
22


19
73
17


20
59
14


21
48
11


22
38
10









The average amount of cleaning agent released per wash cycle in Table 7F in 22 wash cycles was 18.7 grams. A graph of the results shown in Table 7F, grams of cleaning agent released per wash cycle load, is shown in FIG. 7F.
Results from a further test with multiple wash cycles are reported in Table 7G below. These tests were done with using higher density wash loads using a warm wash and a wash rinse cycle.









TABLE 7G






Cleaning
Cleaning


Wash
Device
Agent


Cycle
Weight (g)
Released (g)

















0
450
0


1
434
16


2
419
15


3
401
18


4
389
12


5
375
14


6
364
11


7
352
12


8
337
15


9
325
12


10
315
10


11
297
18


12
284
13


13
274
10


14
262
12


15
248
14


16
230
18


17
211
19


18
197
14


19
175
22


20
163
12


21
146
17


22
134
12


23
124
10


24
113
11


25
103
10


26
90
13


27
82
8


28
73
9


29
63
10


30
56
7


31
48
8


32
39
9









The average amount of cleaning agent released per wash cycle in Table 7G in 32 wash cycles was 18.7 grams. A graph of the results shown in Table 7G, grams of cleaning agent released per wash cycle load, is shown in FIG. 7G.
The present invention may be embodied in other specific forms without departing from its structures, methods, or other essential characteristics as broadly described herein and claimed hereinafter. The described embodiments are to be considered in all respects only as illustrative, and not restrictive. The scope of the invention is, therefore, indicated by the appended claims, rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.

## Claims

1. A method of providing laundry cleaning agent to a laundry cleaning machine comprising:
obtaining a multiuse laundry cleaning device in a solid state comprising a homogeneous quantity of cleaning agent in solid form comprising a gas-releasing component selected from the group consisting of perborates, percarbonates, and mixtures thereof, a potassium silicate solubility control component to limit the solubility of the cleaning agent, wherein the solubility control component is present in an amount sufficient to cause the multiuse laundry cleaning device to dissolve in water and release a substantially consistent quantity of cleaning agent over a plurality of laundry wash and rinse cycles; and
depositing the laundry cleaning device within the laundry cleaning machine tub under conditions such that the cleaning agent in solid form in the laundry cleaning device is exposed to water from the plurality of laundry wash and rinse cycles.

2. The method according to claim 1, further comprising the step of disposing the solid cleaning agent within a porous covering or bag.

3. The method according to claim 2, wherein the porous, covering or bag comprises a pliable fabric material.

4. The method according to claim 2, wherein the porous covering or bag conforms to the size of the solid cleaning agent as the cleaning agent shrinks in size due to dissolution of cleaning agent.

5. The method according to claim 2 wherein the porous covering or bag comprises:
an outer layer made of a mesh material;
an inner layer made of a mesh material; and
a middle layer made from a padding material.

6. The method according to claim 5 wherein the padding material used to make the middle layer is selected from the group consisting of porous foam and ruffled netting.

7. The method according to claim 1, wherein the cleaning agent in solid form further comprises a structure disposed within the quantity of cleaning agent to signal when to replace the cleaning device.

8. The method according to claim 1, wherein the cleaning agent in solid form is in the form of a ball.

9. The method according to claim 1, wherein the gas-releasing component is present in an amount from 20% to 60% by weight, and wherein the solubility control component is present in an amount from 20% to 60% by weight.

10. The method according to claim 9, wherein the cleaning agent further comprises:
a fragrance component present in an amount from about 0.5 to 15% by weight; and
an anti-redeposition component present in an amount from about 0.5% to 10% by weight.

11. The method according to claim 1, wherein the gas-releasing component is sodium perborate monohydrate present in an amount from 42% to 52% by weight, wherein the solubility control component is potassium silicate present in an amount from 35% to 45% by weight.

12. The method according to claim 1,further comprising a water softener present in an amount from 0.5% to 20% by weight; an alkalinity agent present in an amount from 0.5% to 20% by weight, and an optical brightener is present in an amount from 0.5% to 8% by weight.

13. The method according to claim 1, further comprising a zeolite water softener present in an amount from 1% to 5% by weight; an alkalinity agent comprising sodium hydroxide present in an amount from 1% to 5% by weight, and an optical brightener present in an amount from 0.5% to 3% by weight.

14. The method according to claim 1, wherein the cleaning agent in solid form dissolves and releases a substantially consistent quantity of cleaning agent over from about 10 to 40 cleaning wash or rinse cycles.

15. The method according to claim 12, further comprising the step of retaining the laundry cleaning device deposited within the laundry cleaning machine tub from one laundry wash and rinse cycle to another laundry wash and rinse cycle.

16. The method according to claim 9 further comprising the step of disposing the solid cleaning agent within a porous covering or bag.