Manual Spray Cleaner

Abstract
A cleaning solution package comprising a dispensing container having a body with a closed bottom and an open upper end forming a neck and a dispensing valve mounted in the neck. A flexible pouch is mounted within the container and has an open upper end that is sealed to the dispensing valve. A cleaning composition containing an oxidizing agent is stored in the flexible pouch. A pressurized gas is between the container body and the flexible pouch to pressurize the cleaning solution within the flexible pouch.
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention


This invention relates to a packaged pressurized spray cleaner with an oxidizing composition to clean soft surfaces such as carpets, rugs, upholstery and fabric. In one of its aspects, the invention relates to a manual spray cleaner composition. In another of its aspects, the invention relates to a system for cleaning and protecting carpets and rugs. In yet another of its aspects, the invention relates to a method for cleaning rugs and carpets. In still another of its aspects, the invention relates to a method for cleaning and protecting rugs and carpets.


2. Description of the Related Art


Soft household surfaces such as carpets, rugs, upholstery and fabric are often subject to contact with compositions, such as spills, which can cause a stain on the surface. Such stains are conventionally removed through the use of cleaning compositions, either through manual application or using a cleaning appliance. Many users prefer manually applicable cleaning compositions since they can be quickly applied to a stain without needing a cleaning appliance, many of which are expensive and cumbersome to use.


Numerous cleaning compositions are available for removing soil and stains from carpet. A stain on carpet can penetrate through the nap and into the backing, and even the padding beneath the carpet. Some cleaning compositions only treat the stain formed on the fibers or nap of the carpet. Other cleaning compositions merely “push” the stain from the carpet surface through to the carpet backing. While the stain appears to be gone to the user, over time the stain can be pulled back into the fibers from the backing or padding and reappear on the nap of the carpet.


The addition of hydrogen peroxide to cleaning compositions offers improved cleaning performance. Hydrogen peroxide can penetrate all the way to the backing and padding to treat and remove certain types of stains. However, the use of hydrogen peroxide creates challenges with respect to maximizing the shelf life of such cleaning compositions, while minimizing the effects of the inherent reactive nature of the chemical. The ability to formulate an “all-in-one” cleaning composition, i.e. a cleaning composition that includes both cleaning agents and hydrogen peroxide in a single formulation, that can be packaged within a single container presents many technical challenges, primarily related to: (1) the chemical resistance of the container to the hydrogen peroxide containing formula; (2) the chemical compatibility of the various ingredients present in the cleaning composition; (3) the shelf life of the active ingredients present in the cleaning composition; and (4) the potential premature activation of hydrogen peroxide present in the cleaning composition. This is especially true when the single container is in an aerosol form.


SUMMARY OF THE INVENTION

According to the invention, the invention relates to a cleaning solution package comprising a dispensing container having a body with a closed bottom and an open upper end forming a neck and a dispensing valve mounted in the neck. A flexible pouch is mounted within the container and has an open upper end that is sealed to the dispensing valve. A cleaning composition containing an oxidizing agent is in the flexible pouch. A pressurized gas is located between the container body and the flexible pouch to pressurize the cleaning solution within the flexible pouch.


According to one embodiment of the invention, the flexible pouch is chemically inert to and essentially free from interaction with the oxidizing agent. The flexible pouch can comprise multiple laminated layers, one of which can be a metallic layer. The flexible pouch can further include at least one polyamide layer, at least one polyethylene terephthalate layer and at least one polypropylene layer. The flexible pouch can further comprise an adhesive between at least two of the layers.


According to yet another embodiment of the invention, the oxidizing agent is hydrogen peroxide.


According to another embodiment, the cleaning solution package can comprise an aqueous carrier and at least one surfactant. The aqueous carrier can be deionized water and the at least one surfactant can be biodegradable.


According to another embodiment, the cleaning solution package can comprise at least one organic solvent. The organic solvent can be selected from the group consisting of glycol ethers including propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, and diethylene glycol n-butyl ether.


According to yet another embodiment, the cleaning solution package can contain at least one of an anti-soil and anti-stain agent selected from the group consisting of polymers and copolymers based on acrylic monomers, polyhedral oligomeric silsesquioxane monomers and derivatives thereof.


According to another embodiment, the cleaning solution package can be free of volatile organic compounds. The cleaning solution package can further comprise citric acid in an effective amount to act as a chelating agent and an oxidizing agent stabilizer.


According to another embodiment of the invention, the pressurized gas can be free of volatile organic compounds. The pressurized gas can be air or nitrogen.


As a result, the cleaning composition package meets the United States Environmental Protection Agency's “Design for the Environment” standards.


According to another embodiment of the invention, a method for making a cleaning solution package comprises sealing a flexible pouch having an open end to a dispensing valve and positioning the flexible pouch within an open top container with the dispensing valve in registry with the open top of the container to provide a space between the flexible pouch and an inside surface of the container. The dispensing valve is sealed to the open top of the container. A gas is injected into the space between the flexible pouch and an inside surface of the container to pressurize the space. The flexible pouch is then filled with a cleaning solution containing an oxidizing agent.


According to another embodiment of the invention, the cleaning solution package can further comprise a nestable cap that can be attached to the filled container.





BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings:



FIG. 1 is a perspective view of a pressurized dispenser assembly according to the invention.



FIG. 2 is an exploded view of the pressurized dispenser assembly as shown in FIG. 1.



FIG. 3 is a cut-away perspective view of a cap of the dispenser assembly shown in FIG. 1.



FIG. 4 is a partial section view taken along line 6-6 of FIG. 1.



FIG. 5 is a perspective view of a pouch-on-valve assembly of the dispenser assembly shown in FIG. 2.



FIG. 6 is an exploded view of a valve assembly of the dispenser assembly shown in FIG. 2.



FIG. 7 is a partial section view taken along line 8-8 of FIG. 2



FIG. 8 is a section view taken along line 9-9 of FIG. 2



FIG. 9 is a schematic flow diagram of a method of making a cleaning solution package according to the invention.



FIG. 10 is a view like FIG. 4 of a partial section view of the pressurized dispenser of FIG. 1 illustrating the operation of the dispenser.





DESCRIPTION OF THE PREFERRED EMBODIMENT

According to the invention, an pressurized dispenser for applying a cleaning composition onto a surface to be cleaned such as carpets, rugs, upholstery and fabric, and the like is provided. In one embodiment, an oxidizing cleaning composition is contained within the pressurized dispenser. The cleaning composition preferably contains hydrogen peroxide due to its superior cleaning performance. The use of hydrogen peroxide as a cleaning composition creates challenges with respect to maximizing shelf life while minimizing the effects of the inherent reactive nature of the chemical and requires specific dispenser design features as will be described fully herein.


Pressurized Dispenser


Referring to FIGS. 1 and 2, an pressurized dispenser 10 comprises a container 22, a pouch-on-valve assembly 38 for storing a cleaning composition and regulating its dispending, an actuator 80 operably coupled to the pouch-on-valve assembly 38 for selectively dispensing the cleaning composition onto the surface to be cleaned, and a removable cap 12 that is selectively placed on the container 22 to cover the actuator 80. The pouch-on-valve assembly 38 comprises a pouch 74 received within the container 22 for storing a supply of cleaning composition and a valve assembly 50 that is hermetically sealed to the pouch 74 and on which the actuator 80 is mounted. The valve assembly further comprises a valve mounting cup 40 that mounts the pouch-on-valve assembly 38 to the container 22.


Referring to FIG. 4, a cleaning composition 96, such as an oxidizing cleaning composition, is contained within the pouch 74, and a quantity of compressed propellant gas 98 is contained within the can assembly 22 surrounding the pouch 74 to provide propellant force necessary to dispense the cleaning composition 96 from the dispenser 10.


The cleaning composition 96 is delivered to the surface to be cleaned via the actuator 80, which is in fluid communication with the push valve assembly 50 that is sealed to the flexible pouch 74 containing the cleaning composition. The flexible pouch 74 containing the cleaning composition 96 resides within the metal can assembly 22. Positive pressure inside the can assembly 22 is generated by the propellant gas 98 that is injected during the can filling process. The propellant gas 98 is filled to a level sufficient for generating the required force to deliver the cleaning composition 96 to the surface to be cleaned with a spray character, i.e. the force of the spray, the diameter of the spray, the type of particle sprayed, etc., that is desirable for the intended application.


With reference to FIG. 3, the cap 12 comprises a circular-shaped bottom edge 14 with a vertical wall 16 extending therefrom that curves inwardly to form a top surface 18. An inner vertical wall 19 spaced from the vertical wall 16 can project from the top surface 18 and define an inner circular-shaped bottom edge 20.


The top surface 18 has a smaller diameter than the diameter of the bottom edge 14 by virtue of the inwardly curved vertical wall 16. The top surface 18 is generally planar but also includes a plurality of concentric circular depressions 13. As can been seen in FIG. 3, a sinusoidal wave pattern 21 is formed in cross-section by the circular depressions 13.


The cap 12 can be manufactured from plastic, such as recyclable polypropylene resin, using injection molding. The cap 12 can be thin-walled, as compared to commonly known aerosol cap wall thicknesses, with a nominal wall thickness of 0.79 mm (0.031 inches) and a range of 0.53 to 1.04 mm (0.021 to 0.041 inches) to minimize plastic material content resulting in a reduced part weight. The depressions 13 can have a nominal depth of 0.91 mm (0.036 inches) and a range of 0.66 to 1.17 mm (0.026 to 0.046 inches).


One benefit offered by the aforementioned cap geometry is that the cap 12 can be stacked with other caps 12 such that a substantial portion of the vertical wall 16 overlaps the cap 12 underneath, thus reducing the overall height of a nested stack of caps 12. The inward curve of the vertical wall 16 can be selected such that a first cap 12 can be nested with a second cap 12 such that the inner bottom edge 20 of the second cap 12 rests on the top surface 18 of the first cap 12. This is particularly beneficial when packing and shipping multiple caps 12, because the bulk container packing density of the caps 12 can be maximized, thereby reducing the shipping volume and overall energy costs associated with bulk shipping to a facility for the final filling and assembly of the dispenser 10.


Referring to FIGS. 2, and 4, the container 22 comprises a body 24 that is generally cylindrical in shape with a closed bottom 26 and an open upper end 28 formed in an inwardly curving neck 29 of the body 24. The neck 29 further comprises a bead 30 defining the periphery of the open upper end 28. The container 22 includes an inner surface 32 and an outer surface 34 on which a polymer coating can be applied. The container 22 may also include an optional lithograph label 36 applied to the outer can surface 32 for decorative purposes such as product use and marketing communications. The container 22 can be manufactured of polymer-coated tin free steel stock T3CA temper with a nominal thickness of about 0.23 mm (0.009 inches). The polymer coating on the inner and outer surfaces 32 and 34 can comprise polyethylene terephthalate (PET) film which offers an improved aesthetic appearance and may also provide corrosion inhibiting properties.


Referring to FIGS. 4 and 5, the valve mounting cup 40 is mounted within the open end 28 of the container 22 to mount the pouch-on-valve assembly 38 within the container 22 and to close the open end 28. The valve mounting cup 40 comprises a central cylindrical protrusion 46 having a dispensing opening 42 therein and an annular lip 44 formed on the periphery of the valve mounting cup 40. The annular lip 44 is sized to receive and seal the open end 28 of the container 22. The annular lip 44 further includes a gasket 72 to insure a leak proof seal to the bead 30 formed on the container 22. The valve mounting cup 40 can be manufactured of a tin steel material. The gasket 72 can be comprised of a butyl rubber material.


Referring to FIGS. 4 and 6, the valve assembly 50 further comprises a valve housing 58 that receives a hollow valve stem 52 having a solid plunger 62 mounted to a lower end thereof. The valve housing 58, which is preferably injection molded polypropylene material, comprises a hollow cylindrical upper portion 59 and a reduced diameter hollow lower valve body portion 61, with a fluid flow channel 60 formed therethough that is in fluid communication with the cleaning composition 96 within the pouch 74. The exterior shape of the lower valve body portion 61 forms an eye-shaped cross-section, as shown in FIG. 7. This shape facilitates improved sealing ability between the valve housing 58 and the flexible pouch 74.


The plunger 62 is received within the protrusion 46 of the valve mounting cup 40, with the valve stem 52 extending through the dispensing opening 42. The plunger 62 comprises a central opening 63 having a closed bottom end and an open top end. Three evenly spaced vertical channels are provided on the central opening 63 and form fluid flow orifices 64 when the plunger 62 is assembled with the valve stem 52 that are in fluid communication with the hollow valve stem 52 via a space 65 formed between the bottom end of the valve stem 52 and the closed bottom of the central opening 63.


The plunger 62 is biased by a compression spring 68 to the closed position of the valve assembly shown in FIG. 4. The compression spring 68, which can be comprised of INOX AISI 302 stainless steel material, is positioned between a support rib 69 formed within the valve housing 58 and the solid plunger 62. A gasket 70 is located between the valve housing 58 and the valve mounting cup 40 and forms a valve seat for the plunger 62. The gasket 70 can be a butyl rubber. Alternative suitable gasket materials can include: buna-nitrile (buna-n), rubber, or ethylene propylene diene monomer rubber (EPDM).


The valve stem 52 can be manufactured using an injection molded polyethylene material due to its chemical resistivity. The plunger 62 can be manufactured using an injection molded acetal material.


As shown in FIGS. 7 and 8, the pouch 74 comprises multiple layers 76 of flexible material that are laminated together. As shown herein, the pouch comprises seven layers 76A-76G of material. The layers 76 of the pouch 74 can comprise, in order from the outermost layer to the innermost layer, a 12 μm polyethylene terephthalate layer 76A, a first 3 μm adhesive layer 76B, an 8 μm aluminum layer 76C, a second 3 μm adhesive layer 76D, a 15 μm oriented polyamide layer 76E, a third 3 μm adhesive layer 76F, and a 75 μm polypropylene layer 76G, all of which are hermetically sealed to the lower portion 61 of the valve housing 58, as shown in FIGS. 4 and 7. The external dimensions of the pouch 74 are nominally 180 mm tall by 115 mm wide (7.09 inches by 4.53 inches) and, when filled, 70 mm (2.76 inches) deep. The fill volume of the pouch 74 is nominally 400 ml (13.5 fluid oz.). The outer edges of the layers 76 are sealed by a heat seal bonding process that uses heat and pressure to permanently bond the edges of the layers 76 to form a hermetically sealed edge 77 on the pouch 74. The pouch 74 is subsequently sealed to the valve housing 58 by a heat seal bonding process that uses heat and pressure to permanently bond the pouch 74 to the valve housing 58.


Referring to FIG. 4, the actuator 80 comprises a sidewall 81 with a circular base 92 that has a larger diameter than a top surface 94. The top surface 94 further includes a curved depression 88 suitable for mating to a user's fingertip. Extending vertically downward from the top surface 94 is a hollow cylinder 90 having a spray tip orifice 82 that is surrounded by a conically-shaped cut-out 86 formed in the sidewall 81. The hollow cylinder 90 fluidly couples the actuator 80 to the valve stem 52, thereby creating a fluid connection between the spray tip orifice 82 and the flexible pouch 74 containing the cleaning composition 96. The spray tip orifice 82 is surrounded by a conically-shaped cut-out 86 formed in the sidewall 81, which has a terminal aperture 84 defined in the side wall 81.


In one embodiment, the shape of the spray tip orifice 82 comprises a circular through-hole with diameter of 0.51 mm (0.020 inches), which has been found to be effective for application of the cleaning composition 96 in a relatively small diameter for treating small stains and spills on the surface to be cleaned. The spray tip orifice 82 can comprise any number of alternate shapes depending on the desired spray pattern (for example straight line stream, fan shaped, conical patterns, and the like). A combination of the size of the spray tip orifice 82, the size of the terminal aperture 84, and the pressure of the gas propellant 98 can be optimized to achieve the desired spray flow rate and spray pattern of the cleaning composition 96. The spray rate can be 5.5 grams/second (0.19 ounce/second) of cleaning composition, with a range of 5.0 to 6.0 grams/second (0.18 to 0.21 ounce/second) and the preferred spray pattern as measured at roughly 61 cm (24 inches) from the target surface to produce a “forceful stream”.


Since the chemical composition of the invention contains an oxidizing agent, as will be described more fully herein, it should be understood that all surfaces of the dispenser 10 that come into contact with the cleaning composition can be manufactured from materials selected for their known resistance to the components of the cleaning composition, such as hydrogen peroxide. For example, the actuator 80 can comprise an injection molded acetal resin. However, other materials can be used to manufacture the components of the dispenser 10, depending on the cleaning composition 96 used with the dispenser 10.


A suitable valve and pouch system can be purchased from SeaquistPerfect Dispensing, Cary, Ill.



FIG. 9 illustrates a method 100 for assembling and filling the pressurized dispenser 10 in schematic form. Prior to installation in the container 22 and filling with cleaning composition, the pouch 74 can be rolled into tube form and secured in this rolled form near the top and bottom edges with commonly known perforated adhesive tape 78, as shown in FIG. 4. This compact rolled form allows easy installation of the laminated pouch 74 into the open end 28 of the container. The method 100 begins in step 102, with the placement the pouch-on-valve assembly 38 in the container 22. The rolled pouch 74 is inserted through the open end 28 and the valve mounting cup 40 is loosely placed on the bead 30. In step 104, the propellant gas 98 is injected into the container 22 around the rolled pouch 74. Examples of suitable propellant gases are nitrogen and compressed air due to their inert nature and low-impact on the environment as opposed to traditional propellants that are composed of volatile organic compounds (VOCs). The total VOC content for this improved pressurized design is roughly 0-2% by weight versus 15-25 wt % for typical pressurized products within this cleaning category. The pressure level during gas injection in step 104 is controlled to a predetermined level, for example to a preferred pressure level in the range of 35 to 45 psig (pound-force per square inch gauge). This predetermined pressure level is determined experimentally to ensure that the final container pressure is such that it delivers the desired spray characteristics, meets container safety standards, and is in compliance with all government regulations related to the manufacture and shipment of pressurized containers. In step 106, the annular lip 44 on the valve mounting cup 40 is permanently crimped onto the bead 30 while maintaining the propellant gas 98 in a pressurized state. In step 108, the cleaning composition 96 is pressure-filled through the valve assembly 50 and into the pouch 74. The maximum injection pressure can be controlled in order to break the adhesive tape 78 and unroll the pouch, while avoiding rupturing the pouch 74. For example, the maximum injection pressure can be controlled to not exceed 435 psig in order to avoid pouch rupture. The preferred post-fill nominal can pressure at 70° F. should be about 115 psig with a range of 110-120 psig. The filling can be controlled according to the desired net weight of the cleaning composition 96 in the dispenser 10, whereby the pouch 74 is filled with the cleaning composition 96 until the volume of the cleaning composition 96 injected into the dispenser 10 reaches a predetermined net weight. In step 110, the actuator 80 is secured to the valve assembly 50 and the cap 12 is placed on the container 22.


Referring to FIG. 10, in use, the cleaning composition 96 can be dispensed onto a target surface to be cleaned, such as a carpet, rug, upholstery or fabric, by depressing the actuator 80 and subsequently creating a fluid flow path between the pouch 74 and the spray tip orifice 82. Depression of the actuator 80 forces the plunger 62 downward, compressing the spring 68, and breaking the seal between the plunger 62 and the gasket 70 to create a space between the gasket 70 and the plunger 62, thereby allowing fluid to flow from the fluid flow channel 60 to valve stem through the fluid flow orifices 64. The compressed propellant gas 98 induces a positive pressure inside the container 22 and compresses the pouch 74, thereby forcing the cleaning composition 96 out of the pressurized container 22 to be sprayed out of the spray tip orifice 82. When downward pressure on the actuator 80 is released, the spring 68 forces the plunger 62 and valve stem 52 upward. The plunger 62 seals against the internal gasket 70 and ceases the flow of the cleaning composition 96. A user can hold the dispenser 10 in various orientations during use, such as upright, inverted, sideways, etc., and still achieve the same dispensing action.


Cleaning Composition


The cleaning composition according to the invention comprises one or more oxidizing agents, one or more optional anti-resoil agents, one or more optional solvents, one or more surfactants and a carrier. Additional components such as an anti-stain agent, a preservative, a stabilizer/pH controller, a chelating agent, a peroxide stabilizer, a fragrance, or any combination thereof may also be included. The cleaning composition further has a pH ranging from 5.8 to 6.2, with an average pH of 6.0. The cleaning composition can be filled into the pouch 74 of the pressurized dispenser 10 according to the method 100 given above; however, it is understood that the cleaning composition of the invention can be used with other types of dispensers.


The cleaning composition of the present invention includes from 1.8 to 2.2 wt % of an oxidizing agent, preferably hydrogen peroxide (H2O2). Cosmetic grade 35% hydrogen peroxide such as is available from FMC Industrial Chemicals, trade name “Super D 35”, is the preferred source, due to its good stability characteristics and extended shelf life. The preferred post-fill hydrogen peroxide concentration level for the formulation is 2.0 wt %, however a range of 1.98 to 2.02 wt % is acceptable. Other suitable hydrogen peroxides are known by the trade names Hybrite 32.5%, Durox, Oxypure 35%, Standard 27.5 35%, Technical 35%, Chlorate Grade 20%, Semiconductor Reg, Seg, RGS, RGS 2, RGS 2, 31%. Examples of alternative oxidizing agents include: preformed peracid compounds selected from the group consisting of percarboxylic acid and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof, a persalt such as perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof; or a peroxide compound.


The inventive cleaning composition can also include can also include optional anti-stain/resoil agents such as polymers or copolymers derived from, but not limited to, acrylic or polyhedral oligomeric silsesquioxane (POSS) monomers and derivatives thereof. Examples of suitable acrylic monomers include acrylic acid, methacrylic acid, methacrylate, methylmethacrylate and ethylacrylate. Syntran DX6-125 is an example of a suitable anti-resoil agent that is a copolymer derived from acrylic monomers. If an anti-soil agent is present, the preferred concentration of Syntran DX6-125 can be 3 wt %. PM-1870, manufactured by the 3M Company, is an example of an anti-stain/resoil agent derived from POSS monomers. Another example of an anti-stain/resoil agent is PM-1874, a sulfo-methacrylate resin, manufactured by the 3M Company. If present, the anti-stain/resoil agent is typically present in the cleaning composition from 0.50 to 5 wt %.


The inventive cleaning composition can also include an optional solvent or solvent system (a mixture of one or more solvents), preferably chosen from the family of glycol ethers. Suitable solvents include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, and diethylene glycol n-butyl ether. DOWANOL DPM (dipropylene glycol methyl ether) and DOWANOL PM (propylene glycol methyl ether), both from Dow Chemical Company, are examples of preferred solvents. If present, the preferred concentration range for each solvent used is in the range of 0.9 to 1.1 wt %. Alternatively, the cleaning composition can be formulated without any solvents, thereby eliminating VOCs from the composition. Eliminating VOCs from the cleaning composition can make the composition more environmentally friendly and can also qualify the composition for certification by various environmental stewardship programs such as U.S. EPA's “Design for Environment (DfE)”.


Examples of suitable surfactants include anionic, cationic, nonionic and zwitterionic surfactants. Preferably, the inventive cleaning composition contains a mixture of anionic, nonionic and/or zwitterionic surfactants. Suitable anionic surfactants include alcohol sulfates and sulfonates, alkyl and alkylaryl sulfonates, sulfonated amines and amides and sarcosinates. The surfactants may contain branched or linear components. Nonionic surfactants suitable for use in the inventive cleaning composition include linear or branched alcohol ethoxylates and propoxylates, ethoxylated and propoxylated fatty acids, ethylene oxide/propylene oxide polymers or copolymers, amine oxides and fatty amine oxides.


Preferably, the inventive cleaning composition can comprise a surfactant mixture in the range of 0.75 to 4.5 wt %. For example, if the cleaning composition includes a solvent system comprising VOCs, the surfactant mixture can comprise 0.75 to 2.0 wt % Hamposyl LS-30/Crodasinic LS-30 (sarcosinate), 0.75 to 2.0 wt % Stepanol WAC/Stepanol WA-Extra (lauryl sulfate), 0.25 wt % Tergitol 15-S-9 (alcohol ethoxylate) and 0.25 wt % Surfox LO (amine oxide). These surfactants are readily biodegradable for a reduced environmental impact compared to other commonly known surfactants, although it should be noted that other, non-biodegradable surfactants can be used in the cleaning composition as well. The components of the surfactant mixture can be selected depending on the other components present in the cleaning composition. For example, some surfactants are more suitable than others depending on whether the cleaning composition includes a solvent system comprising VOCs. For example, if the cleaning composition does not contain any VOCs, the surfactant mixture can comprise Hamposyl LS-30/Crodasinic LS-30 (sarcosinate), Stepanol WAC/Stepanol WA-Extra and Tergitol 15-S-9.


Deionized or Reverse Osmosis (RO) water has several advantages as a suitable carrier for the inventive cleaning composition. The use of deionized water reduces contamination of the cleaning composition by trace metals that could trigger activation of the oxidizing agent inside the container prior to use. Premature activation of the oxidizing agent could reduce the cleaning efficacy of the cleaning composition and create an undesirable increase in internal can pressure due to a reaction between the oxidizing agent and the contaminants. An additional advantage associated with using deionized water as the carrier is that it evaporates with little or no residue after delivering the cleaning composition to the surface to be cleaned. Deionized water preferably comprises approximately 80-94 wt % of the cleaning composition.


An example of a preferred cleaning composition according to the present invention contains from about 1.98 to 2.02 wt % of an oxidizing agent, from about 0.59 to 0.61 wt % anti-resoil agents, from about 1.8 to 2.02 wt % of one or more solvents, from about 0.75 to 4 wt % of one or more surfactants and from 84 to 95 wt % of an environmentally-friendly carrier such as water.


In an alternate embodiment, the cleaning composition can be a foaming or foamable composition. A foamable cleaning composition can be achieved through the addition of a foaming agent or by selecting a suitable surfactant. Additionally, the spray character of the cleaning composition can be optimized for the generation of foam.


In another alternate embodiment, the cleaning composition can be a zero VOC formulation. The zero VOC formulation can be achieved by eliminating the VOC solvent system from the composition and replacing it with deionized water. In this embodiment, the composition can also include an organic acid, such as citric acid, to act as a chelating agent and increase the stability of the oxidizing agent. Citric acid is also an environmentally friendly chemical that meets DfE requirements.


The cleaning composition can be formulated as an “all-in-one” composition, that can be packaged within an pressurized dispenser, such as the dispenser 10 described above. Testing of the formulation described below resulted in unexpected superior performance with respect to the cleaning composition's compatibility with a laminated pouch, such as pouch 74, extended shelf life, and cleaning ability. Alternate formulations were evaluated and the results were not successful. Specifically, a formulation containing 0.53% Baypure CX100, 1.17% Tomadol 23-6.5 surfactant, 2% Hydrogen Peroxide, 0.17% fragrance, and with the balance being RO water was tried. It was experimentally determined that this alternate formula severely delaminated the pouch, resulting in lamination material plugging the valve orifices and premature failure of the package. As organic molecules are interactive permeants, the observed delamination may be attributed to sorption of this alternate formula by the multilayer pouch material.


EXAMPLES

Exemplary cleaning compositions are presented in Tables 1-4, which give the relative concentration of the ingredients in the exemplary carpet cleaning composition. Table 1 presents an exemplary range of ingredient concentrations for an exemplary carpet cleaning composition, while Table 2 gives specific ingredient concentrations. Table 3 presents an exemplary range of ingredient concentrations for an exemplary zero VOC carpet cleaning composition, while Table 4 gives specific ingredient concentrations.









TABLE 1







Exemplary Carpet Cleaning Composition









CONCENTRATION


INGREDIENT
(Weight %)





Deionized Water
84.39-86.09


Stepanol WAC/Stepanol WA-Extra (Surfactant)
1.09-2.02


Hamposyl L-30/Crodasinic LS-30 (Surfactant)
0.74-0.76


Surfox LO (Amine Oxide Surfactant)
0.248-0.253


Tergitol 15-S-9 (Nonionic Surfactant)
0.248-0.253


Glycol Ether DPM (Solvent)
0.99-1.01


Glycol Ether PM (Solvent)
0.99-1.01


Syntran DX6-125 (Aqueous Polymer; anti-resoil
2.97-3.03


agent)


Surcide P (Preservative)
0.099-0.101


Dequest 2010 (Chelating Agent)
0.396-0.404


Hydrogen Peroxide, 35% Super D Cosmetic
5.65-5.77


Grade\ (Oxidizing Agent)


WY-26 Outdoor Fresh (Fragrance)
0.297-0.303
















TABLE 2







Exemplary Carpet Cleaning Composition









CONCENTRATION


INGREDIENT
(Weight %)











Deionized Water (Carrier)
85.24


Stepanol WAC/Stepanol WA-Extra (Surfactant)
2.00


Hamposyl L-30/Crodasinic LS-30 (Surfactant)
0.75


Surfox LO (Amine Oxide Surfactant)
0.25


Tergitol 15-S-9 (Nonionic Surfactant)
0.25


Glycol Ether DPM (Solvent)
1.00


Glycol Ether PM (Solvent)
1.00


Syntran DX6-125 (Aqueous Polymer; anti-resoil
3.00


agent)


Surcide P (Preservative)
0.10


Dequest 2010 (Chelating Agent)
0.40


Hydrogen Peroxide, 35% Super D Cosmetic
5.71


Grade (Oxidizing Agent)


WY-26 Outdoor Fresh (Fragrance)
0.30
















TABLE 3







Exemplary Zero VOC Carpet Cleaning Composition









CONCENTRATION


INGREDIENT
(Weight %)





Deionized Water
87.03-88.63


Stepanol WAC/Stepanol WA-Extra (Surfactant)
1.09-2.02


Hamposyl L-30/Crodasinic LS-30 (Surfactant)
0.74-0.76


Tergitol 15-S-9 (Nonionic Surfactant)
0.248-0.253


Syntran DX6-125 (Aqueous Polymer; anti-resoil
2.97-3.03


agent)


Surcide P (Preservative)
0.099-0.101


Citric Acid (Chelating Agent/Stabilizer)
0.05-0.20


Hydrogen Peroxide, 35% Super D Cosmetic
5.65-5.77


Grade\ (Oxidizing Agent)


WY-26 Outdoor Fresh (Fragrance)
0.197-0.203
















TABLE 4







Exemplary Zero VOC Carpet Cleaning Composition









CONCENTRATION


INGREDIENT
(Weight %)











Deionized Water (Carrier)
87.83


Stepanol WAC/Stepanol WA-Extra (Surfactant)
2.00


Hamposyl L-30/Crodasinic LS-30 (Surfactant)
0.75


Tergitol 15-S-9 (Nonionic Surfactant)
0.25


Syntran DX6-125 (Aqueous Polymer; anti-resoil
3.00


agent)


Surcide P (Preservative)
0.10


Citric Acid (Chelating Agent/Stabilizer)
0.16


Hydrogen Peroxide, 35% Super D Cosmetic
5.71


Grade (Oxidizing Agent)


WY-26 Outdoor Fresh (Fragrance)
0.20









Proof of the superior cleaning performance of the chemical composition of the invention is detailed in the following test results. The exemplary cleaning compositions given in Tables 2 and 4 were tested against three other known cleaning compositions, including OxyDeep® 2× Pet or OxyDeep® Power Shot® (Woolite), Spot Shot® Instant Carpet Stain Remover (WD-40 Company), and Resolve® Spot Magic® Carpet Cleaner (Reckitt Benckiser). The material or substrate on which the cleaning compositions were tested was a carpet (Mohawk 814 Viva cut pile carpet) stripped of any manufacturer-applied soil or stain blocking agents, and comprising one of the stain-forming compositions listed in Table 5. Table 5 further lists the amount of each stain-forming composition applied to the carpet.









TABLE 5







Stain-Forming Compositions











AMOUNT



STAIN-FORMING COMPOSITION
(grams)







Coffee
5.0



Welch's 100% Grape Juice
5.0



Livingston Cabernet Sauvignon Wine
5.0



Dirty Motor Oil
0.1



Revlon's Cover Girl, Love That Red Lipstick
0.1



Heinz Beef Au Jus Gravy
1.0



Mud
1.0



Diet Coke
5.0



Artificial Dog Vomit
1.0



Cat Urine
5.0



Tea
5.0



Cow Blood*
5.0



Tomato Sauce*
1.0










The procedure used to compare the cleaning performance of the inventive cleaning compositions to the three other known cleaning compositions is as follows:

    • (1) The L*a*b color space of untreated carpet samples were measured using a Minolta Chroma Meter CR-410 colorimeter.
    • (2) The stain-forming compositions were applied to the untreated carpet samples. All 5 gram stain-forming compositions were applied to untreated carpet using an adjustable trigger sprayer. Each stain-forming composition was applied within a 2-inch ring and allowed to dwell overnight. The dried stains were then vacuumed to remove any loose soil. All remaining stain-forming compositions were applied to untreated carpet using a 2-inch plastic applicator. These stains were allowed to dwell on the carpet for fifteen minutes. Four stained carpet samples were prepared for each stain-forming composition.
    • (3) The L*a*b color space of the stained carpet samples were measured using the calorimeter and recorded.
    • (4) The stained carpet samples were then treated with one of the four cleaning compositions. Twenty-five grams of each cleaning composition was sprayed on one of the stained carpet samples and allowed to dwell for five minutes. Any excess foam and/or liquid was then removed with a sponge (Ace Hardware General Purpose Cellulose Sponge, UPC 0 82901 10418 6 PN 10418). The stain was then blotted 30 times using a manual blotting cloth (3-inch diameter, 2.5 pound) and a bi-folded wipe (Four Star Converting Corp. Item No. 4035 (Bissell PN X0711) 6½×6½Quilted Wipe). A clean and dry portion on the bi-folded wipe was used every 5 blots. The cleaned stains were allowed to dry overnight and then were vacuumed thoroughly to remove any additional loose soil.
    • (5) The L*a*b color space of the cleaned carpet samples were measured using the calorimeter and recorded.


The average percent clean (% clean) that each cleaning composition had on each stain-forming composition is given in Tables 6 and 7 below. Table 6 illustrates the effectiveness of the exemplary cleaning composition from Table 2 compared to existing commercially available cleaning compositions. Table 7 illustrates the effectiveness of the exemplary zero VOC cleaning composition from Table 4 compared to existing commercially available cleaning compositions.


The boldface value for each stain-forming composition shows which cleaning composition had the highest % clean, thereby indicating which cleaning composition was most effective at treating the stain-forming composition on the carpet fibers.


As illustrated in Table 6, for the majority of stain-forming compositions, eight out of eleven, the exemplary cleaning composition from Table 2 had the highest % clean compared to existing commercially available cleaning compositions.









TABLE 6







Average Percent Clean (% Clean)









CLEANING COMPOSITION












Cleaning


Resolve ®


STAIN-FORMING
Composition
OxyDeep ®
Spot
Spot


COMPOSITION
from Table 2
2X Pet
Shot ®
Magic ®














Coffee

30.97

22.05
4.48
−3.04


Welch's 100% Grape

77.65

53.45
74.89
70.76


Juice


Livingston Cabernet
86.68

88.31

81.58
75.81


Sauvignon Wine


Dirty Motor Oil

89.91

80.61
52.91
67.96


Revlon's Cover Girl,
22.46
12.77

44.89

25.07


Love That Red


Lipstick


Heinz Beef Au Jus

91.76

88.35
85.15
83.29


Gravy


Mud
65.12
44.52
68.53

71.27



Diet Coke

78.52

65.92
67.15
63.33


Artificial Dog Vomit

88.02

79.56
77.21
81.06


Cat Urine

24.61

2.84
14.66
−0.31


Tea

84.68

81.72
54.18
40.71









As illustrated in Table 7, for the majority of stain-forming compositions, the zero VOC cleaning composition from Table 4 was just as good or better at removing stains compared to existing commercially available cleaning compositions.









TABLE 7







Average Percent Clean (% Clean) Zero VOC formulation









CLEANING COMPOSITION












Zero VOC






Cleaning
OxyDeep ®

Resolve ®


STAIN-FORMING
Composition
Power
Spot
Spot


COMPOSITION
from Table 4
Shot ®
Shot ®
Magic ®














Coffee
61.83
56.92

62.10

57.25


Welch's 100% Grape
84.02
84.79

91.72

89.32


Juice


Livingston Cabernet
90.09

91.24

85.52
80.01


Sauvignon Wine


Dirty Motor Oil
47.93

57.34

53.00
63.86


Cow Blood

73.31

67.73
24.99
32.65


Heinz Beef Au Jus
66.61

69.82

53.66
64.22


Gravy


Mud

41.49

26.33
32.07
8.91


Diet Coke
78.20
77.12
80.21

84.95



Artificial Dog Vomit
63.46
63.97
52.29

68.94



Cat Urine
63.66
62.35
65.43

73.16



Tea
62.87
69.71

82.56

72.61


Tomato Sauce
66.10

67.36

53.68
56.30









The cleaning performance of each cleaning composition on the carpet backing was visually evaluated after treatment of the stain and the results are tabulated in Tables 8 and 9. “P(+)” indicates that the cleaner penetrated to the backing and removed the stain from the backing. “NP” indicates that the stain did not penetrate to the backing and therefore there was no opportunity for the cleaning composition to remove the stain from the backing. “P(−)” indicates that the stain did not penetrate to the backing, but that application of the cleaner drove the stain to the backing. “DNR” indicates that the stain penetrated the backing, but that the cleaning composition did not remove the stain from the backing.


As illustrated in Table 8, the exemplary cleaning composition from Table 2 had the best overall performance, cleaning the stain all the way through to and visually removing it from the backing of the carpet for six of the eleven stain-forming compositions. OxyDeep® only visually removed the stains from the carpet backing for three stain-forming compositions, while Spot Shot® and Resolve® Spot Magic® did not visually remove the stains from the carpet backing for any of the stain-forming compositions.









TABLE 8







Stain Penetration and Cleaner Performance









CLEANER












Cleaning






Composition


Resolve ®


STAIN-FORMING
from
OxyDeep ®
Spot
Spot


COMPOSITION
Table 2
2X Pet
Shot ®
Magic ®





Coffee
P(+)
DNR
DNR
DNR


Welch's 100% Grape
P(+)
DNR
DNR
DNR


Juice


Livingston Cabernet
P(+)
P(+)
DNR
DNR


Sauvignon Wine


Dirty Motor Oil
NP
NP
NP
NP


Revlon's Cover Girl,
P(−)
P(−)
P(−)
P(−)


Love That Red


Lipstick


Heinz Beef Au Jus
NP
NP
NP
NP


Gravy


Mud
DNR
DNR
DNR
DNR


Diet Coke
P(+)
P(+)
DNR
DNR


Artificial Dog Vomit
NP
NP
NP
NP


Cat Urine
P(+)
DNR
DNR
DNR


Tea
P(+)
P(+)
DNR
DNR









As illustrated in Table 9, the exemplary zero VOC cleaning composition from Table 4 was just as good or better than the existing commercially available cleaning compositions, cleaning the stain all the way through to the backing and visually removing it from the backing of the carpet for six of the twelve stain-forming compositions. OxyDeep® Power Shot visually removed the stains from the carpet backing for six of the stain-forming compositions, while Spot Shot® and Resolve® Spot Magic® did not visually remove the stains from the carpet backing for any of the stain-forming compositions.









TABLE 9







Stain Penetration and Cleaner Performance (Zero VOC formulation)









CLEANER












Zero VOC






Cleaning



Composition
OxyDeep ®

Resolve ®


STAIN-FORMING
from
Power
Spot
Spot


COMPOSITION
Table 4
Shot ®
Shot ®
Magic ®





Coffee
P(+)
P(+)
DNR
DNR


Welch's 100% Grape
P(+)
P(+)
DNR
DNR


Juice


Livingston Cabernet
P(+)
P(+)
DNR
DNR


Sauvignon Wine


Dirty Motor Oil
DNR
DNR
P(−)
P(−)


Cow Blood
DNR
DNR
DNR
DNR


Heinz Beef Au Jus
NP
NP
NP
NP


Gravy


Mud
DNR
P(−)
P(−)
P(−)


Diet Coke
P(+)
P(+)
DNR
DNR


Artificial Dog Vomit
DNR
DNR
P(−)
P(−)


Cat Urine
P(+)
P(+)
DNR
DNR


Tea
P(+)
P(+)
DNR
DNR


Tomato Sauce
NP
NP
NP
NP









Tables 10 and 11 illustrate the color difference indicia (Delta E) between the untreated and the cleaned carpet samples for each cleaning composition. Lower Delta E values correlate to better cleaning performance. The data in Table 10 illustrates the overall improved cleaning performance of the exemplary cleaning composition from Table 2 compared to the existing commercially available cleaning compositions.









TABLE 10







Delta E Values









CLEANING COMPOSITION












Cleaning






Composition


Resolve ®


STAIN-FORMING
from
OxyDeep ®
Spot
Spot


COMPOSITION
Table 2
2X Pet
Shot ®
Magic ®














Coffee
6.5
7.98
8.83
9.87


Welch's 100% Grape
4.38
8.84
4.69
5.61


Juice


Livingston Cabernet
2.81
2.4
3.87
4.98


Sauvignon Wine


Dirty Motor Oil
2.66
5.2
12.29
8.56


Revlon's Cover Girl,
59.28
66.33
42.72
58.46


Love That Red


Lipstick


Heinz Beef Au Jus
1.96
2.68
3.46
3.87


Gravy


Mud
13.21
21.33
11.42
10.46


Diet Coke
0.99
1.67
1.64
1.82


Artificial Dog Vomit
3.15
5.48
5.67
4.77


Cat Urine
2.07
2.83
2.31
2.85


Tea
0.84
0.99
2.8
3.58









The data in Table 11 illustrates that the zero VOC cleaning composition from Table 4 performed equally well at removing stains compared to the existing commercially available cleaning compositions.









TABLE 11







Delta E Values (Zero VOC formulation)









CLEANING COMPOSITION












Zero VOC






Cleaning



Composition
OxyDeep ®

Resolve ®


STAIN-FORMING
from
Power
Spot
Spot


COMPOSITION
Table 4
Shot ®
Shot ®
Magic ®














Coffee
8.4
8.11
8.22
7.48


Welch's 100% Grape
17.26
17.90
17.97
17.32


Juice


Livingston Cabernet
27.13
28.12
25.22
24.10


Sauvignon Wine


Dirty Motor Oil
15.61
17.14
14.39
17.64


Cow Blood
31.17
31.53
10.06
11.54


Heinz Beef Au Jus
11.67
12.80
8.93
10.58


Gravy


Mud
13.16
9.88
11.17
3.46


Diet Coke
6.69
6.78
6.25
5.96


Artificial Dog Vomit
13.78
14.31
10.60
14.43


Cat Urine
4.34
4.08
3.76
3.95


Tea
5.26
6.17
6.45
5.59


Tomato Sauce
17.06
16.59
12.86
14.56









The pressurized dispenser and cleaning solution described herein provides several advantages over previous dispensers and cleaning. One such advantage is the ability to provide a pressurized cleaning solution containing hydrogen peroxide in a single dispenser. The specific formulation of the hydrogen peroxide cleaning solution is surprisingly compatible with the flexible pouch and provides a stable, single pressurized package for storing and delivering a cleaning solution containing hydrogen peroxide.


Another advantage of the inventive dispenser and hydrogen peroxide cleaning solution package described herein is the impact of the package on the environment and human health. There is currently increasing pressure in society, in both the market place and in the government, to promote development of products that have minimal impact on the environment and human health. Large retailers are increasingly pressuring vendors and suppliers to provide products that reduce waste and have a decreasing impact on the environment and human health. The United States Environmental Protection Agency (EPA) has also initiated a program called “Design for the Environment” (DfE) that certifies products as meeting stringent standards for environmental and health impacts.


The inventive dispenser and cleaning solution described herein provides a dispenser for delivering a hydrogen peroxide cleaning solution to a surface to be cleaned under pressure without the disadvantages of traditional aerosol dispensers. Aerosol dispensers that utilize propellants such as volatile organic carbons and compressed gasses like nitrous oxide can contribute to ground-level ozone levels. Traditional dispensers such as these are believed to be currently not being considered by the EPA for the DfE program.


The inventive pressurized dispenser described herein relies on air or nitrogen gas, which have minimal environmental impact, to pressurize the cleaning solution. In addition, the cleaning solution can also be provided free of volatile organic compounds, resulting in a dispenser and cleaning solution package that is free of volatile organic compounds and has minimal impact on the environmental and human health.


The unique combination of a pressurized dispenser and a hydrogen peroxide cleaning composition that does not contain volatile organic carbons provides a product that is able to meet the DfE standards set by the EPA. A pressurized dispenser and hydrogen peroxide cleaning solution based on the exemplary zero VOC composition described herein recently became the first pressurized product to be granted the DfE label by the EPA. The DfE label is based on an evaluation of all of the components of the product, including all of the components of the cleaning solution. One of the factors in the EPA's approval of the product based on the inventive disclosure above is the use of citric acid to stabilize the hydrogen peroxide and act as a chelating agent.


The hydrogen peroxide cleaning solution described herein provides a cleaning composition that is stable under pressure, can contain little or no VOCs and can be provided in a single, pressurized dispenser for delivery to a surface to be cleaned under pressure. The hydrogen peroxide cleaning solution package described herein has the additional benefit of containing no VOCs and meeting high standards for environmental and human health impacts while performing just as well or better than traditional cleaners that do not have the same environmental and human health benefits.


While this invention has been specifically described in connection with certain specific embodiments thereof, it is to be understood that this is by way of illustration and not of limitation. Reasonable variation and modification are possible within the scope of the foregoing description and drawings without departing from the scope of the invention, which is defined in the appended claims.

Claims
  • 1. A cleaning solution package comprising: a dispensing container having a body with a closed bottom and an open upper end forming a neck and a dispensing valve mounted in the neck;a flexible pouch mounted within the container having an open upper end that is sealed to the dispensing valve;a cleaning composition including an oxidizing agent within the flexible pouch; anda pressurized gas between the container body and the flexible pouch to pressurize the cleaning solution within the flexible pouch.
  • 2. The cleaning solution package according to claim 1 wherein the flexible pouch is essentially free from interacting with the oxidizing agent.
  • 3. The cleaning solution package according to claim 2 wherein the flexible pouch comprises multiple laminated layers, and wherein at least one of the multiple layers is a metallic layer.
  • 4. The cleaning solution package according to claim 3 wherein the flexible pouch includes at least one polyamide layer.
  • 5. The cleaning solution package according to claim 3 wherein the flexible pouch includes at least one polyethylene terephthalate layer.
  • 6. The cleaning solution package according to claim 3 wherein the flexible pouch includes at least one polypropylene layer.
  • 7. The flexible pouch according to claim 3 further comprising an adhesive between at least two of the multiple layers.
  • 8. The cleaning solution package according to claim 1 wherein the oxidizing agent is hydrogen peroxide.
  • 9. The cleaning solution package according to claim 1 and further comprising an aqueous carrier and at least one surfactant.
  • 10. The cleaning solution package according to claim 9 wherein the aqueous carrier is deionized water.
  • 11. The cleaning solution package according to claim 9 wherein the at least one surfactant is biodegradable.
  • 12. The cleaning solution package according to claim 1 and further comprising at least one organic solvent.
  • 13. The cleaning solution package according to claim 12 wherein the at least one organic solvent is selected from the group consisting of glycol ethers including propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, and diethylene glycol n-butyl ether.
  • 14. The cleaning solution package according to claim 13 further comprising at least one of an anti-soil and anti-stain agent selected from the group consisting of polymers and copolymers based on acrylic monomers, polyhedral oligomeric silsesquioxane monomers and derivatives thereof.
  • 15. The cleaning solution package according to claim 1 wherein the cleaning composition is free of volatile organic carbon compounds.
  • 16. The cleaning solution package according to claim 15 further comprising at least one organic acid in an effective amount to act as a chelating agent and an oxidizing agent stabilizer and wherein the solution package meets the United States Environmental Protection Agency's “Design for the Environment” standards.
  • 17. The cleaning solution package according to claim 16 wherein the at least one organic acid is citric acid.
  • 18. The cleaning solution package according to claim 1 wherein the pressurized gas is free of volatile organic carbon compounds.
  • 19. The cleaning solution package according to claim 18 wherein the pressurized gas is selected from at least one of air and nitrogen.
  • 20. A method for making a cleaning solution package comprising: sealing a flexible pouch having an open end to a dispensing valve;positioning the flexible pouch within an open top container with the dispensing valve in registry with the open top of the container, to provide a space between the flexible pouch and an inside surface of the container;sealing the dispensing valve to the open top of the container;injecting a gas into the space between the flexible pouch and an inside surface of the container to pressurize the space;filling the flexible pouch with a cleaning solution containing an oxidizing agent.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application No. 61/036,706, filed Mar. 14, 2008, which is incorporated herein by reference in its entirety.

Provisional Applications (1)
Number Date Country
61036706 Mar 2008 US