STABLE COMPOSITIONS COMPRISING BENZOYL PEROXIDE, A LOW VISCOSITY LIPOPHILIC SOLVENT, A HIGH VISCOSITY GELLING AGENT, WATER AND A BINDING AGENT, AND DEVICES, SYSTEMS AND METHODS

RELATING THERETO

BACKGROUND

[0001] This application relates, in part, to the "pink-stain" that plagues marine vinyl in seats, benches and such on boats. More particularly, S. reticulum and other members of the order of Actinomycetales, typically in the family of Streptomycetaceae, produce organic stains comprising organic pigments or organic dyes, typically a pink-colored stain comprising an organic pigment, as a byproduct of metabolic processes of the organism. This stain/organic pigment is soluble in polyvinylchloride (PVC) and other synthetic or natural materials. The S. reticulum stain appears, for example, on white marine vinyl and has been a serious problem in the pleasure and commercial boating industry for decades. Accordingly, this is a long standing issue of great concern to vinyl manufacturers and boaters. Other stains, such as those caused by other pigment- producing bacteria, are also discussed herein.

[0002] The bacterium S. Reticulum can grow in the inside and on the back of boat upholstery. Once a colony reaches a certain point of maturity it turns pink, and the pink pigment/stain slowly dissolves into the vinyl. Given enough time, the pink discoloration migrates all the way through the vinyl and shows up as a pink stain on the exterior-side of the vinyl (i.e., the side visible when the vinyl is on an intact cushion, which is the side a user would sit on or against). Perhaps because such stains are inside the vinyl they cannot be removed by mere washing.

[0003] Thus, there has gone unmet a need for improved compositions, methods, devices, systems, etc., that remove such stains. The present systems and methods, etc., provide these and/or other advantages.

SUMMARY

[0004] The compositions, methods, etc., herein are directed to compositions for reduction or elimination of undesired "pink-stain" and other stains or pigments in a substrate such as the seats and benches on a boat. Such compositions, methods, etc., comprise an oxidizing agent carried in an organic solvent, and a gelling agent, water and a binder. Typically, a coating of the organic solvent applied using a fine brush to a marine vinyl fabric without the gelling agent (or as otherwise configured herein) will fully evaporate at the surface within at least about 10 seconds at a temperature of 20°C. The oxidizing agent comprises peroxide, benzoyl peroxide, ozone, percarbonate, perphosophate or hydrogen peroxide.

[0005] In some embodiments, the current compositions, methods, etc., provide for stable delivery of low-evaporation-rate solutions of benzoyl peroxide (BPO) to substrates having stains as discussed herein, and to reducing or eliminating such stains in/from the substrate. Such solutions comprise the BPO dissolved in low viscosity, lipophilic solvents, gelling agent, binders and water, and can be advantageous for purposes such as stain removal or modification of a substrate. For example, the compositions, methods, etc., can be used to remove pink stains caused by Streptoverticillium reticulum in marine vinyl.

[0006] One aspect of the compositions, methods, etc., herein is to provide improved compositions comprising effective solvents such as xylene to deliver strong oxidizing agents such as BPO with additional agents compared to current, known commercial compositions to deliver active ingredients at predictable rate for a given volume of the active agent or agents. Such compositions can be used to reduce and/or render invisible such stains in marine vinyl upholstery and other substrates, including the removal of pink colored stains in marine vinyl fabric caused by S. reticulum bacteria, delivered at a predictable rate of titration and strength of the active agents delivered to provide more optimal methods of stain removal.

[0007] The stains discussed herein can be reduced or eliminated using strong oxidizing agents such as peroxides, or organic or oxygen radicals such as BPO, ozone, percarbonates, perphosophates or hydrogen peroxide. Certain stain removal compositions, systems, methods, etc., are discussed, for example, in U.S. Patent Application Publication 20160281037, now US patent no. 9,816,055, filed on March 24, 2016 and entitled "Compositions, Devices, Systems And Methods Relating To Photo- And Thermal- Oxidative Bleaching Of Pink-Stains"; and U.S. Patent Application Publication 20160281036 filed on March 24, 2016 and entitled "Stable Compositions Comprising Benzoyl Peroxide And Low Viscosity, Lipophilic Solvents And Methods And Systems Related Thereto". These and any other references set forth herein discuss certain systems, apparatus, methods and other information; all such references are incorporated herein by reference in their entirety and for all their teachings and disclosures, regardless of where the references may appear in this application. Citation to a reference herein is not an admission that such reference constitutes prior art to the current application. The compositions, devices, etc., set forth in such references can be used as a source of elements for the compositions herein, but modified or altered in accordance with the discussion herein to provide the compositions, methods, etc., herein.

[0008] In some aspects, the present compositions, systems, devices and methods, etc., provide compositions comprising an oxidizing agent carried in an organic solvent, a gelling agent, water and a binder, wherein a coating of the organic solvent applied to a marine vinyl fabric with a fine brush will not fully evaporate at the surface within at least about 10 minutes at a temperature of 20°C, wherein the oxidizing agent can comprise peroxide, benzoyl peroxide, ozone, percarbonate, perphosophate or hydrogen peroxide.

[0009] In some respects, the present compositions, systems, devices and methods, etc., provide compositions configured to eliminate pink-stain, the compositions comprising about 2% to 12% w/w oxidizing agent carried in about 30%-40% w/w organic solvent, about 8%-l2% w/w gelling agent, about 40%-60% w/w water, and about 0.5%-l.5% w/w binder. Exemplary binders include soaps, emulsifiers and surfactants, such as BrE, and including nonionic and hydrophilic surfactants, such as Triton-XlOO.

[00010] In further aspects, the present compositions, systems, devices and methods, etc., provide compositions configured to eliminate pink-stain, the compositions comprising, all w/w, about l%-3% oxidizing agent, about 40%-80% organic solvent, about 0.5%-9% gelling agent, about 5%-l0% water, and about l5%-50% nonionic and hydrophilic surfactant. In further embodiments, the compositions can comprise about l.5%-2.5% oxidizing agent, about 50%-70% organic solvent, about l%-7% gelling agent, about 7%- 9% water, and about 20%-30% nonionic and hydrophilic surfactant. In certain embodiments, the oxidizing agent comprises BPO, the organic solvent comprises xylene, the gelling agent comprises carbomer 940, and the nonionic and hydrophilic surfactant comprises triton c-100.

[00011] The organic solvent can have a polarity of about 2 to 3, a viscosity of about 0.3 cP to 1.0 cP, and a vapor pressure of 15 to 250mm Hg. For example, the organic solvent can have a polarity of about 2.5, the organic solvent can have a viscosity of about 0.7 cP to 0.9 cP, or about 0.8 cP. The organic solvent can comprise or consist essentially of a benzene ring and can be xylene, toluene, methyl ethyl ketone (MEK), or methyl tertiary butyl ether (MTBE). The oxidizing agent can comprise or consist essentially of a peroxide such as benzoyl peroxide or hydrogen peroxide, or ozone or sodium hypochlorite.

[00012] In some embodiments, the composition can comprise, by weight, about 4-7% BPO, about 30-40% organic solvent, about 8-12% gelling agent, about 40-60% water, and about 0.5-l.5% binder. The composition can comprise, by weight, about 5% BPO, about 35% organic solvent, about 10% gelling agent, about 49% water, and about 1% binder. The composition can comprise a solvent that can be characterized by having a polarity of about 2.5, a viscosity of about 4,000 cP or more, and a vapor pressure of about 15 to 250mm Hg. The composition can comprise, by weight, about 5% BPO, about 35% Xylene, about 10% Carbomer 940, about 49% water, AND about 1% Bree soap.

[00013] In some embodiments, the systems, etc., herein include methods comprising making the compositions herein, and/or using the compositions to reduce the amount of an undesired pigment or stain in a substrate.

[00014] In further embodiments, the systems, etc., herein include systems comprising the compositions herein in contact with a substrate having stain comprising an organic pigment or organic dye. The substrates can comprise a marine vinyl, which can be part of a seat such as a chair or bench on a boat. The organic pigment or organic dye in the substrate can have been produced by a microorganism living in or otherwise disposed in the substrate, and the stain can be pink-stain.

[00015] These and other aspects, features and embodiments are set forth within this application, including the following Detailed Description. Unless expressly stated otherwise, all embodiments, aspects, features, etc., can be mixed and matched, combined and permuted in any desired manner. In addition, as noted above, various references are set forth herein that discuss certain systems, apparatus, methods and other information; all such references are incorporated herein by reference in their entirety and for all their teachings and disclosures, regardless of where the references may appear in this application. DETAILED DESCRIPTION

[00016] Turning to a further discussion of the current compositions, methods, etc., herein, in some embodiments such compositions comprise a solvent that is characterized by having a polarity of about 2.0, 2.5 or 3.0; a viscosity of about 2,000 cP, 3,000 cP, 4,000 cP, 5,000 cP or more; a vapor pressure of about 15 to 250mm Hg, such that a coat of the composition applied to marine vinyl with a medium brush will not evaporate in less than a time selected for the solvent to carry the oxidizing agent into the vinyl sufficiently for the oxidizing agent to effectively contact the stain such that the contact can significantly reduce or eliminate the stain from the vinyl. For example, such evaporation times can be at least about 3 minutes, 4 minutes, 5 minutes, 10 minutes or 15 minutes, as desired, at an ambient temperature of 20°C. The composition can comprise a solvent, which can have a benzene ring such as xylene, in combination with BPO, water, a gelling agent such as Carbopol/Carbomer 940/941 and a solution binder such as a BrE “washing-up liquid soap”.

[00017] The compositions, etc., herein in some embodiments comprise a solution of benzoyl peroxide (BPO), the chemically active ingredient, in xylene, the solvent. BPO is stable when dissolved in xylene; a solution of 10% BPO by mass can be achieved at standard conditions, i.e. traditional standard conditions for temperature and pressure, per NIST, which are 20°C and 101,325 Pa (1 atm). This combination of xylene and BPO results in stability of the BPO, absence of significant damage to substrates that may contain S. reticulum stain such as PVC and other vinyls, absence of significant damage to vinyl finish, and low viscosity. Significant damage to vinyl fabric as the result of stain removal treatment to the treated area are discoloration, removal of water proofing, accelerated aging, reduction in shear or tear strength, physical deformation, increased Shore Durometer hardness ( Hardness and Durometer Durometer is one of several measures of the hardness of a material. Hardness is defined as a material's resistance to permanent indentation as defined by Rockwell Corporation Shore Durometer calibrated measuring devices. See ASTM D2240, Standard Test Method for Rubber Property, reduced ASTM D2240 elastic modulus or changing how the treated fabric feels to the touch.

[00018] As a result of the properties of the compositions herein, an effective amount of BPO can be controllably delivered into vinyl boat upholstery in amounts sufficient for the treatment of pink stains without causing damage to a finish on the upholstery's fabric, if any, nor to the vinyl fabric itself.

[00019] The compositions, etc., herein, which can be used in combination with established methods for treating pinking, significantly reducing the duration of the treatment to remove pink stain, for example from several hours such as 12 hours or more down to about 3, 2, or 1 hour, or even less than about 45', 30', 20' or less for complete eradication of surface-visible pink stain. The current solutions, compositions, methods, etc., can also be used to increase the depth of pink-stain removal. For example, in some embodiments, the pink stain can be removed not just from the visible surface but also as much as about 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 07 mm, 0.8 mm, 0.9 mm, 1.0 mm or 1.1 mm deep, or more, in an affected area of vinyl upholstery. Thus, for a 1.1 mm, 1.2 mm, 1.5, mm, etc., thick piece of upholstery, the compositions, methods, etc., herein can remove pink stain all the way through the vinyl fabric.

[00020] Significant economic value can be realized with predictable, complete eradication of pinking on boat vinyl fabric. Eradication of stains via these methods represent a significant reduction in cost and time when compared to replacing stain- damaged vinyl fabric. The compositions, etc., herein improve both efficacy and time needed to complete successful treatment

[00021] The compositions, etc., herein improve upon purely aquatic suspension attempts to remove pink-stain by dissolving a selected oxidizer, e.g., BPO into a selected solvent, e.g., xylene, in combination with a selected gelling agent and, if desired a selected binder, to provide a composition with low polarity and moderate viscosity so that it can enter small cracks and fissures in the surface of fabric easily, and sufficient vapor pressure so that it will evaporate predictably and slowly once it has been applied to a stain under standard conditions (e.g., the composition will penetrate the vinyl and not dry in less than 3, 4, 5 or 10 minutes, at 20°C at 1 atmospheric pressure at sea level).

[00022] In some embodiments, the treatment can be repeated. For example, in some embodiments, the treatment period can be 60 minutes, and 6 re-applications can be applied to substantially reduce or even eradicate the pink stains. Thus, the current compositions deliver an effectively greater amount of BPO (or other selected oxidant) to the vinyl or other substrate and can be controllably delivered onto/into the vinyl for any desired time, such as 10 minutes 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes or more using any desired number of applications, for example 1 application every 10 minutes, 15 minutes, 20 minutes or 30 minutes, or perhaps 1 application).

[00023] Significant amounts/concentrations of BPO can be provided, for example about 2% BPO, 3% BPO, 5% BPO, 8% BPO, 10% BPO, 11% BPO, or 12% BPO (w/w). Because of this, for an 11% w/w BPO solution, for example, only about 0.05 milliliters of the solution (containing 730 micrograms of BPO) can be applied per square inch of vinyl fabric yet pink stain still removed. The compositions and methods, etc., herein allow for a deeper and more rapid delivery of BPO into the vinyl for pink stain treatment compared to aqueous suspensions.

[00024] In some embodiments, the composition can comprise the oxidizing agent is about 1%, 1.5%, 1.7%, 2%, 2.5% or 3% w/w benzoyl peroxide; the organic solvent is about 40%, 50%, 60%, 70% or 80% w/w xylene; the water is about 5%, 6%, 7%, 8%, 9%, or 10% w/w; the binder (here, emulsifier) is about 15%, 20%, 25%, 30%, 35%, 40% or 50% w/w triton c-100; and, the gelling agent is about 4%, 5%, 6%, 7%, 8%, or 9% carbomer 940.

[00025] Turning to a discussion of some of the technical features of certain aspects of viscosities, etc., discussed herein, the table below compares a) a known low viscosity composition (Gestalt Scientific PA15), which contains 11% BPO as the active agent and 89% Xylene as the delivery agent and has a viscosity of about 0.8 cP which evaporates under 20 seconds at 20°C, against b) a higher viscosity composition as disclosed herein (henceforth "Comp-B") having an about 4000 cP viscosity and containing about 5% BPO active agent, 35% Xylene delivery agent, 10% Carbomer 940 gelling agent, 49% water, and 1% BrE soap binder agent. Comp-B takes about 10 minutes to evaporate at 20°C at sea level; faster or longer evaporation rates can be configured as desired, provided that the evaporation rate is slow enough for the BPO to substantially, adequately penetrate the selected substrate such as marine vinyl such that a pink-stain therein is significantly reduced or even eliminated. The following represent anticipated results where PA 15 and Comp-B are applied to marine vinyl with a fine (approximate amounts)

[00026] As shown in the table above, Comp-B compared to PA 15 delivers over 5 times the effective amount of BPO into the vinyl in the same timeframe in 75% less volume of coating. Additionally, the Comp-B composition is not flammable and has no special shipping or handling limitations, which provide extra advantages over PA15.

[00027] In one embodiment for use of the compositions herein, the treatment of pink stains, the Comp-B solution is applied with a fine painter's brush or felt pen. The medium viscosity of the solvent allows for the solution to penetrate any cracks and fissures of vinyl fabric and carry amounts of BPO with it that are sufficient for complete pink stain eradication. [00028] In some embodiments, the current compositions, methods, etc., may work as follows: The low vapor pressure of the xylene (or other low viscosity lipophilic solvent), along with the water-based gelling agent, delivers the oxidizing agent (in this example, BPO) into the substrate (in this example, PVC) in a predicable amount and at a predictable rate. As the xylene evaporates, BPO remains in solution with the water, gelling agent and/or binder, typically at a slightly increasing density due to the loss of the xylene, but within acceptable absorption parameters of a PVC target. In other words, the BPO is carried into the substrate/vinyl fabric everywhere the solvent is able to reach, typically with virtually no waste, and is kept there a prolonged amount of time relative to prior solutions thereby surprisingly enhancing the effectiveness of the BPO despite using less quantity of the composition.

[00029] In some embodiments, the process of pink stain eradication can be accelerated by orders of magnitude when a light source and a heat source are provided, for example as shown in U.S. Patent Application Publication 20160281037, then further accelerated by a factor of 5 to 6 by controlling the evaporation rate and/or rate of titration of the oxidizer using a water-based gelling agent and/or binder.

[00030] In one example, a mixture containing the active agent BPO powder, containing 75% benzoyl peroxide and 25% water, are added to xylene. Once all the BPO powder is dissolved, more BPO powder is added until a saturated solution of benzoyl peroxide in xylene is formed. This can be done using a heated plate with a built-in magnetic stirring device at about l00°F until all BPO crystals are dissolved and the water is separated (about 30 minutes). The resulting approximate concentration is 11% benzoyl peroxide, by weight. The separated water is siphoned off and the remaining turbid mixture is then filtered through a 20 micron paper filter into a receiving vessel.

[00031] The receiving vessel contains an adequate amount of xylene in it to prevent formation of a super saturated solution, e.g., about 20% by volume compared to the xylene-BPO solution being poured into the receiving vessel. The filtration process is stopped when about 70% of the initial mixture has passed through the filter, to avoid water accumulated at the bottom of the vessel. The remainder, comprising suspended water, xylene, and BPO powder and solution, is rejected. This procedure is carried out using closed vessels for mixing, an open to the air filter, at standard conditions. The solution, once extracted, is then held in a closed glass vessel. [00032] A solution of benzoyl peroxide of 11 % by weight is formed. This solution is clear and colorless.

[00033] A gelling agent, in this example Carbomer 940, is mixed with water to achieve viscosity of 40,000 to 100,000 cP at room temperature, to provide a final gel composition that is about 6.3% water, and 93.7% carbomer 940 (by weight). This results in a jell-like consistency.

[00034] The prior mixture of BPO+Xylene is added to the gel composition at 50% BPO + Xylene to 50% of gel composition. About four drops (0.2 ml or 0.14 gm per 100 ml of solution) of BrE washing-up soap is added as a binder to keep the solution from immediately separating. The final composition is mixed using a low speed impeller-type industrial chemical blender for 5 minutes at a speed low enough to not introduce air into the mixture, for example at about 200 rpm (this can be done in an inert gas environment).

[00035] Turning one embodiment for application of the composition to a substrate, a clean artist's oil paint brush of approximate 1/4” width is used to apply the solution to vinyl fabric affected by pink-staining. Once the brushed area is visibly dry, a combination heat and light source are placed directly overhead. The light source can have, for example, a luminous output of about l.8W/in ² of light at a wavelength of 492 nm, and the temperature on the vinyl can be raised to and held at about l45°F for a period of ten minutes. The application of the solution to the stained vinyl and subsequent illumination and heating were repeated three times. Fluoroscopic examination showed complete eradication of pinking at the end of this process.

[00036] In another embodiment a polypropylene“dial up” reservoir brush applicator is used to distribute the solution to vinyl fabric; otherwise the application is the same as above.

[00037] In still a further embodiment, the removal of the pink-stain or other offending pigment/dye is accomplished using only available sunlight, e.g., about 1,000-10,000 ftcd (10,752-107,520 Lux), and/or ambient electric light at least as strong as in a typical office setting, e.g., about 250, 1000, 2000, 3000, 5000 lux. Such pink-stain removal in in such light intensity levels in this paragraph in PVC can be effected in about 4 days, 3 days, 2 days, one day, 300', 200', 120', 90', 60', 45', or 30' as desired. [00038] In some embodiments, the compositions comprise solvents other than xylene able to dissolve benzoyl peroxide or other selected oxidizer. Suitable solvents can exhibit the following properties:

• Dissolves benzoyl peroxide to form a solution of benzoyl peroxide adequate to treat the pink stain, for example about 3%, 4%, 5% 8% to l2% BPO by weight.

• Forms a stable solution that does not substantially degrade BPO, is substantially free from secondary reactions such as the formation of explosive peroxides, and maintains those qualities for a minimum of six months when stored at temperatures less than 45 °F.

• The solution has low viscosity to such that it can enter fissures and cracks in vinyl fabric.

• The dried solution's residue does not auto ignite at or below l60°F in air.

• The solution does not alter or otherwise damage the vinyl fabric.

• The solution does not alter or damage any non-vinyl coating on a vinyl fabric, such as acrylic coatings.

• The solution, once applied, will evaporate within seconds.

• The solvent has a polarity of about 2.5; a viscosity of about 4000 cP or more.

• The solvent has a vapor pressure of 15 to 250mm Hg.

• The solvent may have a benzene ring in chemical composition.

[00039] Some exemplary alternate solvents include toluene and methyl tertiary butyl ether (MTBE).

[00040] The process of forming a solution of benzoyl peroxide in a solvent can be altered in a number of ways and still provide desirable results. Some examples of those changes include:

• Use of a different solvent

• Direct formation of desired concentration of benzoyl peroxide in solution using sufficiently pure ingredients to eliminate the filtration step.

• Agents to increase viscosity such as Carbomer copolymers type 940 and Homopolymer type A, B, or C. [00041] The compositions, etc., herein can also comprise other agents, for example to control odor. Another variation is the use of a different oxidizing active ingredients or combination of ingredients.

[00042] A further exemplary protocol comprises:

1. Provide a S. reticulum pink-stained piece of fabric.

2. If desired, perform a fluoroscopic analysis of the stained fabric such as vinyl; take still picture if desired for later comparison.

3. Apply BPO in xylene gelled solution with painter's brush to the stained fabric.

4. Let stand about 15 seconds, drying should not occur.

5. Apply light and heat to illuminate at 492 nm with 2W/in ² at a surface temperature of about l50°F.

6. Apply BPO composition once for 60 minutes, or twice 30 minutes apart in hot dry environments.

7. Repeat steps 2 to 5 one more time if desired (i.e., reapply the BPO-xylene gel solution and light/heat two times). In some embodiments, one 60-minute or two

30-minute treatment sessions are used to substantially or fully eliminate the pink- stain visible to the human eye.

8. If not using a heat+Light device as described above, then one treatment twice a day for three to four days in bright sunlight can eliminate pink stains visible to the human eye.

9. If desired, perform a further analysis capable of determining the presence of the pink stain below the surface of the fabric, for example a fluoroscopic analysis. If desired, take still picture to document the status and/or elimination of the pink stain. [00043] All terms used herein are used in accordance with their ordinary meanings unless the context or definition clearly indicates otherwise. Also unless expressly indicated otherwise, in the specification the use of "or" includes "and" and vice-versa. Non-limiting terms are not to be construed as limiting unless expressly stated, or the context clearly indicates, otherwise (for example, "including," "having," and "comprising" typically indicate "including without limitation"). Singular forms, including in the claims, such as "a," "an," and "the" include the plural reference unless expressly stated, or the context clearly indicates, otherwise.

[00044] Unless otherwise stated, adjectives herein such as“substantially” and“about” that modify a condition or relationship characteristic of a feature or features of an embodiment, indicate that the condition or characteristic is defined to within tolerances that are acceptable for operation of the embodiment for an application for which it is intended.

[00045] The scope of the present devices, systems and methods, etc., includes both means plus function and step plus function concepts. However, the claims are not to be interpreted as indicating a "means plus function" relationship unless the word "means" is specifically recited in a claim, and are to be interpreted as indicating a "means plus function" relationship where the word "means" is specifically recited in a claim. Similarly, the claims are not to be interpreted as indicating a "step plus function" relationship unless the word "step" is specifically recited in a claim, and are to be interpreted as indicating a "step plus function" relationship where the word "step" is specifically recited in a claim.

[00046] From the foregoing, it will be appreciated that, although specific embodiments have been discussed herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the discussion herein. Accordingly, the systems and methods, etc., include such modifications as well as all permutations and combinations of the subject matter set forth herein and are not limited except as by the appended claims or other claim having adequate support in the discussion and figures herein.