High alcohol content foaming compositions comprising an anionic phosphate fluorosurfactant

Information

  • Patent Grant
  • 8569219
  • Patent Number
    8,569,219
  • Date Filed
    Thursday, May 24, 2012
    12 years ago
  • Date Issued
    Tuesday, October 29, 2013
    11 years ago
Abstract
A “high lower alcohol content” (>40% v/v of a C1-4 alcohol) liquid composition is able to be dispensed as a stable foam with the use of non-propellant foam dispensing devices from non-pressurized containers. The liquid compositions comprise an alcohol, C1-4 (>40% v/v), a fluorosurfactant of at least 0.001% by weight to prepare a foamable composition, 0-10% w/w of additional minor components added to obtain the desired performance (a foamable composition with a viscosity less than 4,000 cps), and the balance being purified water. The compositions may include emulsifier-emollients and moisturizers, secondary surfactants, foam stabilizers, fragrances, antimicrobial agents, other type of medicinal ingredients, and the like ingredients or additives or combinations thereof commonly added to alcohol gels or foams, aerosol compositions or to toiletries, cosmetics, pharmaceuticals and the like.
Description
FIELD OF THE INVENTION

The present invention relates to compositions with high contents of lower alcohol (C1-4) that could be a gel-like composition or a solution able to be dispensed as a foam. The compositions to be dispensed as foams contain a fluorosurfactant and when mixed with air provide a stable alcohol foam which can be used for personal cleaning or for disinfecting purposes. The gel-like compositions may or may not contain a fluorosurfactant.


BACKGROUND ART

Ethanol and/or Isopropyl alcohol compositions with at least 60% percent v/v (approximately 52% by weight) are well known to be antibacterial, therefore widely accepted for disinfecting purposes. Nonetheless due to the inherent characteristics of alcohol, it is perceived that the higher the content the better the product and a higher than 60% by volume alcohol content solution is more desirable.


Alcohol disinfectant solutions are generally thickened in order to eliminate the waste and facilitate spreading the composition throughout the desired area. It is also known that other than gelling agents one can use paraffin or waxes to achieve thickening of a solution with high alcohol concentration. Such a composition added with lanolin to reduce the melting point closer to body temperature is described in U.S. Pat. No. 2,054,989. One of the disadvantages of gels and such type thick alcohol containing compositions is that if they do not leave a tacky feeling on the hands after one use (although some do), the effect builds up after repetitive use during the day, making it necessary to eventually wash off the thickeners before continuing the usage of an alcohol antiseptic solution. The present invention if formulated for such type of product does not leave such a feel, and does not need to be washed off after having been used repeatedly.


Another way of thickening high alcohol content solutions has also been taught in U.S. Pat. Nos. 6,090,395 and 6,623,744 where they use emulsifiers and surfactants as the thickening system to produce a hydroalcoholic lotion with a viscosity of at least 4,000 cps. Also, U.S. Pat. No. 4,956,170 discloses polyethoxylated non-ionic surfactants/emulsifiers to stabilize the added emollient oils in addition to a fatty alcohol although with the addition of a polymeric thickening agent to prepare a hydroalcoholic skin moisturizing/conditioning antimicrobial gel. The disinfecting compositions of the present invention that are gel-like have a viscosity lower than 4,000 cps and no polymeric thickening agent is added.


Generally speaking a high alcohol content disinfectant solution disinfects but does not clean. In order to make them disinfect and clean, so much soap would be needed that the skin would feel soapy and disagreeable, unacceptable for rubbing alcohol purposes. Nonetheless, a non-irritant skin disinfecting high lower alcohol content formulation for use as a skin-washing agent is successfully attained by combining emulsifiers, surfactants and skin emollients to be used as a gel or ointment as described in U.S. Pat. No. 5,629,006.


Surfactants other than for cleaning purposes are also used for spreading an aqueous composition containing one or more active substances rapidly and evenly over a surface due to their wetting properties. The use of good wetting agents definitely improves the efficient use of active substances in different compositions as described in U.S. Pat. No. 5,928,993. Hence, the composition described in the present invention includes the addition of surfactants, specifically fluorosurfactants which are well known for their unparalleled wetting power and which are also surface-active in the lower alcohols used as disinfectant and solvent system in levels which make it acceptable even for rubbing alcohol purposes, providing cleaning, wetting and foaming properties to the composition.


Although a high alcohol content disinfectant solution has good disinfectant characteristics, it has a sharp smell and is generally perceived to cause drying of the skin, characteristics which can also be diminished to a desirable level in the present invention.


A greater than 40% v/v alcohol foam product, easy and safe to use, is desirable over conventional gel or ointment type composition products. The concentration of alcohol already poses a hazard in itself, and there are many applications in which the perceived risk may be diminished if it could be dispensed as a foam without the use of pressurized aerosol containers. A foam intended to be useful as a skin disinfecting agent must have a uniform consistency, spreadability, cleansing ability, and have a pleasant feel, i.e. have rapid breaking power when pressure is applied; all of which present a challenge for a high lower alcohol content composition.


The description of an aqueous foaming skin disinfecting composition using 15% w/w alcohol as a co-solvent, which requires no pressurized container or added propellant to produce the foam, is described in U.S. Pat. No. 3,962,150.


The foam-forming agents utilized heretofore, have been incapable of forming stable foams when the liquid phase has high alcohol content without using other ingredients. Furthermore, lower alcohols have been considered to be defoamers rather than foam-promoting chemicals. According to Klausner, in U.S. Pat. No. 3,131,153, if more than 64% alcohol is used non-homogeneous compositions are obtained. The compositions in the patent required propellant to foam and the foams produced were of limited stability.


Prior to this invention, when a greater than 40% v/v alcohol concentration is required in a product, it is generally accepted that the product will be either liquid or gel, and that if a foam is desired then the concentration of alcohol would need to be reduced or the use of a propellant and a pressurized system would be required.


Surprisingly, in the few “foamable” high alcohol content products disclosed, the types of foam obtained were not similar to those expected from aqueous solutions. The foams obtained are described as fast or aerated foam, quick breaking, with low or limited stability, which would not last for more than one minute, being generally gone within seconds.


It has been disclosed that fluorosurfactants and alcohol can be combined to produce a “stable” foam by a process using high-pressurized means to generate the foam. Highly stable pressurized foams containing high lower alcohol contents and methods of forming and using such pressurized foams in the oil industry using a non-ionic surfactant or mixture of non-ionic surfactants of a specific group of fluorosurfactants are provided in U.S. Pat. No. 4,440,653. The compositions in this patent require the use of a pressurized gas system to generate the foam.


Various examples of compositions with a high lower alcohol content that are dispensed as a foam have been described, although for the purpose of the present invention the characteristics of the foam are not of the desired outcome, since they are fast breaking, of low stability and the foam is produced by means of propellants and aerosol containers only, as the one described in U.S. Pat. No. 5,906,808, which discloses a product that uses an emulsifying wax NF, and a combination of stearyl and cetyl alcohol, or other wax combinations, which improve the foaming performance of the composition, in combination with cetyl lactate, to produce a 0.8% chlorhexidine gluconate alcohol product.


U.S. Pat. No. 5,167,950 issued to Lins discloses a foam product which requires a propellant and no surfactant is added as a cleaning agent. The composition disclosed in this patent is based upon using an emulsifier system (fatty alcohol ROH 16-22 carbons) in combination with the use of a thickening agent (carbomer, klucel, etc.).


U.S. Pat. No. 5,167,950 to Lins discloses an antimicrobial aerosol mousse having a high alcohol content. The mousse comprises alcohol, water, a polymeric gelling agent and a surfactant system comprising a C16-C22 alcohol, aerosol propellant and a non-ionic polyethoxylated surfactant. Despite the work done to date it has been shown that there is little specific knowledge on how foams react and are formed, and surprisingly formulations that might seem not foamable result in the best foam producing ones while other formulations which seemed to have been producing foam even while being prepared did not perform well at all in some non-aerosol foam dispensers. The behaviour of aqueous foams is not the same of that of an alcohol foam.


The traditional ways of forming a gel using polymeric thickeners presents undesirable characteristics and similarly little has been done in forming emulsion-like thickened gels.


It would be very advantageous to have alcohol based disinfecting formulations which may be dispensed as either a gel or a foam. Further, it would be very advantageous and desirable to find a foaming agent that could be used in concentrations that would allow it to be used in products that can remain in the area on which they have been applied and do not need to be rinsed or wiped off due to small amounts of residue remaining after evaporation. Thus it would also be very advantageous to provide foams or gels that do not leave an unpleasant sticky after-feel as most commercial alcohol gel products are known to, or which clog up the dispensing equipment used to dispense the foams and gels.


SUMMARY OF THE INVENTION

It is an object of this invention to provide high alcohol content liquid compositions, which contain a surfactant/cleaning agent as well as a disinfectant/cleaning/solvent/carrier and that causes very little drying to the skin or the hands of the user and is able to be dispensed either as a gel or as a foam from both pressurized and non-pressurized systems.


The present invention provides high alcohol content compositions that are either gels or able to be dispensed as a foam, which are readily spread over the desired surface. Amongst the different applications where such compositions might be of use, it is another object to also provide an antimicrobial alcohol foam and an antimicrobial alcohol gel. The foamable compositions when dispensed from a suitable dispenser are stable and do not require the use of propellants and pressurized containers. The gels disclosed herein with a viscosity of less than 4,000 cps do not use the gelling or thickening agents typically used in commercial gels and therefore after single or multiple applications of the gel there is not the usual tacky or sticky after-feel and the gel does not clog the dispensers from which the gels are dispensed.


These and other objects and advantages will be apparent from the following description of the invention. All percentages provided herein are based on the total weight unless otherwise indicated.


Accordingly, the present invention provides compositions for personal hygiene, as follows.


Foamable Compositions


The present invention provides a foamable alcohol composition, comprising:


a) an alcohol C1-4, or mixtures thereof, present in an amount greater than about 40% percent v/v of the total composition;


b) an effective fluorinated surface active agent for foaming, which is physiologically acceptable for skin disinfecting, present in an amount of at least 0.001% weight percent of the total composition such that the composition foams under low pressure conditions; and


c) water present in an amount to balance the total composition to 100% by weight.


In this aspect of the invention the effective fluorinated surface active agent is present in an amount from about 0.001% to about 10.0% weight percent of the total composition which is physiologically acceptable so it can be used in personal care type products.


In a preferred embodiment of the invention the fluorosurfactant may be an amphoteric polytetrafluoroethylene acetoxypropyl betaine of the following formula, (CF3CF2(CF2CF2)nCH2CH2(OAc)CH2N+(CH3)2CH2COO−) where n=2 to 4, an ethoxylated nonionic fluorosurfactant of the following structure: RfCH2CH2O(CH2CH2O)xH where Rf=F(CF2CF2)y, x=0 to about 15 and y=1 to about 7; or an anionic phosphate fluorosurfactant of the following structure: (RfCH2CH2O)xP(O)(ONH4)y where Rf=F(CF2CF2)z, x=1 or 2, y=2 or 1 and z=1 to about 7, or mixtures thereof.


The present invention also provides a foamable, alcohol disinfecting composition, comprising:


a) an alcohol C1-4 or mixtures thereof, present in an amount between about 60% to above 80% v/v of the total composition;


b) a physiologically acceptable fluorosurfactant present in an amount from about 0.01% to about 2.0% by weight of the total composition such that the foamable alcohol disinfecting composition foams under low pressure conditions when dispensed from an unpressurized container;


c) a foam stabilizing agent present in an amount from about 0.01 to about 12.0% by weight;


d) any one of moisturizers, emollients and combinations thereof present in an amount from about 0.05 to about 5.0% by weight; and


e) water in an amount to balance the total compositions to 100% by weight.


In another aspect of the invention there is provided an alcohol disinfecting composition, comprising;


a) ethanol present in an amount between about 60% to 70% percent v/v of the total composition;


b) a physiologically acceptable fluorosurfactant in an amount from about 0.01% to about 2.0% weight percent of the total composition;


c) at least one nonionic surfactant selected from the group consisting of polyethoxylated fatty alcohols present in an amount from about 0.01 to about 10.0% weight percent;


d) a foam stabilizing agent;


e) water in an amount to balance the total composition to 100% weight percent.


The present invention also provides an alcohol disinfecting composition comprising:


a) ethanol present in an amount between about 60% to 70% percent v/v of the total composition;


b) a physiologically acceptable anionic phosphate fluorosurfactant in an amount from about 0.01% to about 2.0% weight percent of the total composition;


c) at least 1% n-propanol;


d) foam stabilizing agents that at least include 1,3-Butyleneglycol % 2, Butoxyethanol in 0.001-3% ea;


e) a lipid layer enhancer such as a mixture of alkylglucoside and glyceryl oleate; and


f) water in an amount to balance the total composition to 100% weight percent.


Gel-Like Compositions


In this aspect of the invention there is provided an alcohol gel-like composition, comprising;


a) an alcohol C1-4, or mixtures thereof, present in an amount greater than about 40% percent v/v of the total composition;


b) at least one nonionic surfactant selected from the group consisting of a poly(ethoxylated and/or propoxylated)alcohol, a poly(ethoxylated and/or propoxylated)ester, a derivative of a poly(ethoxylated and/or propoxylated)alcohol, a derivative of a poly(ethoxylated and/or propoxylated)ester, an alkyl alcohol, an alkenyl alcohol, an ester of a polyhydric alcohol, an ether of a polyhydric alcohol, an ester of a polyalkoxylated derivative of a polyhydric alcohol, an ether of a polyalkoxylated derivative of a polyhydric alcohol, a sorbitan fatty acid ester, a polyalkoxylated derivative of a sorbitan fatty acid ester, and mixtures thereof, present in an amount between about 0.10% to about 5% weight percent;


c) an emulsifier present in an amount between about 0.10% to about 3.0% weight percent; and


d) water in an amount sufficient to form a stable gel-like disinfecting composition


The compositions disclosed herein provide a wide variety and range of high alcohol content disinfecting products. According to the percentage of alcohol used in the compositions and by varying the proportions of the other constituents in the formulation, foams with differing properties can be achieved thereby allowing the production of foams that are either coarse or wet which quickly flatten, or foams that are soft which contain fine bubbles and which are relatively dry having long foam stability, or creamy thick foams that are gel-like. Also, the compositions may or may not be disinfecting according to the percentage of alcohol.


It was surprisingly found that by varying the percentages of the ingredients an alcohol gel-like composition was obtained which did not dry the hands or leave a sticky after-feel and that did not clog the gel dispensers, having the desired consistency and showing a viscosity of less than 4,000 cps.


Some of the compositions can conveniently be manufactured in a two step process such that most of the alcohol can be added at a later time and/or location making it the first part a desirable concentrate suitable for shipping less hazardous goods and weight. Warming the first part from 30 to 80 degrees Celsius, (depending on the particular composition) before adding the major portion of alcohol improves the long term stability of the compositions. This warming can either take place the same day in the same location where the finished composition is prepared or the concentrate first part can be stored or shipped elsewhere and the warming can take place either when the first part is mixing or right before adding the major portion of alcohol.


It should be evident that the described embodiment can be subjected to adjustment and/or improvement for specific applications either as a gel or a foam or to contain a desired active ingredient, without departing from the scope of the present invention. Different materials and/or ingredients will be then needed to compensate for the composition and/or foam stability disruption that might be generated by the change (i.e. introducing a more compatible secondary or even primary surfactant, adjusting the compatible foam stabilizer percentage and/or varying the relative amount of emulsifier and/or alcohol or water) or to compensate for shifts in desired viscosity and foam characteristics to obtained the desired gel (i.e. reduce the amount of fluorosurfactant or increase the polyethoxylated surfactants, or add an emulsifier and/or increase or decrease alcohol and/or water). These and other changes may be made in the details within the spirit of the invention, which is to be broadly construed and not to be limited except by the character of the claims appended hereto.


For example, the alcohol based compositions may contain up to 10% by weight of other active ingredients or additives or combinations thereof commonly added to aerosol compositions or to toiletries, cosmetics, pharmaceuticals, etc. Materials that may be added may include organic gums and colloids, lower alkanolamides of higher fatty acids, short chain diols and/or triols, alkylglucosides, fragrance, coloring matter, additional emollients, ultraviolet absorbers, solvents, emulsifiers, foam stabilizers or mixture of such stabilizers, suspending agents, buffers, conditioning agents, antioxidants, bactericides, medicinal active ingredient, and the like.


The present invention provides a composition, comprising;


a) an alcohol C1-4, or mixtures thereof, present in an amount greater than about 40% v/v of the total composition;


b) at least one nonionic surfactant selected from the group consisting of a poly(ethoxylated and/or propoxylated)alcohol, a poly(ethoxylated and/or propoxylated)ester, a derivative of a poly(ethoxylated and/or propoxylated)alcohol, a derivative of a poly(ethoxylated and/or propoxylated)ester, an alkyl alcohol, an alkenyl alcohol, an ester of a polyhydric alcohol, an ether of a polyhydric alcohol, an ester of a polyalkoxylated derivative of a polyhydric alcohol, an ether of a polyalkoxylated derivative of a polyhydric alcohol, a sorbitan fatty acid ester, a polyalkoxylated derivative of a sorbitan fatty acid ester, and mixtures thereof, present in an amount between about 0.10% to about 5% weight percent


c) an emulsifier present in an amount between about 0.10% to about 3.0% weight percent; and


d) water in an amount sufficient to form a stable gel-like composition with a viscosity less than 4,000 cps.


The present invention also provides a method of forming a skin-disinfecting foam containing alcohol, comprising the steps of:


combining an alcohol C1-4, or mixtures thereof, present in an amount greater than about 60% v/v of the total composition with a physiologically acceptable effective fluorinated surface active agent for foaming present in an amount of at least 0.001% by weight percent of the total composition, and water present in an amount to balance the total composition to 100% by weight to form an alcohol-fluorosurfactant mixture and storing said composition in an unpressurized dispenser having a dispenser pump; and


activating the dispenser pump to combine the alcohol-fluorosurfactant mixture with air to form and dispense a skin disinfecting foam containing alcohol.


In another aspect of the invention there is provided a high-alcohol, foamable, skin-disinfecting composition, comprising:


a) an alcohol C1-4, or mixtures thereof, present in an amount greater than about 60% v/v of the total composition;


b) water present in an amount to balance the total composition to 100% by weight; and


c) a physiologically acceptable fluorinated surface active agent for foaming present in an amount of at least 0.001% by weight of the total composition such that the composition has a surface tension less than 20 dynes/cm.


The present invention also provides a high-alcohol, foamable, skin-disinfecting composition, comprising:


a) an alcohol C1-4, or mixtures thereof, present in an amount greater than about 60% v/v of the total composition;


b) water present in an amount to balance the total composition to 100% by weight; and


c) a physiologically acceptable fluorinated surface active agent for foaming present in an amount of at least 0.001% by weight of the total composition such that the composition foams without the use of propellants or pressurized containers.


The present invention also provides a method for personal disinfecting comprising:


applying to a person's skin a skin-disinfecting alcohol foam composition which comprises


a) air mixed under low pressure conditions with


b) a liquid comprising

    • i) an alcohol C1-4, or mixtures thereof, present in an amount greater than about 60% v/v of the total composition;
    • ii) water present in an amount to balance the total composition to 100% by weight; and
    • iii) a physiologically acceptable effective fluorinated surface active agent for foaming present in an amount of at least 0.001% by weight of the total composition.


The present invention also provides a method for producing, and applying to a person's skin, a skin-disinfecting alcohol foam composition, comprising


a) combining an alcohol C1-4, or mixtures thereof, present in an amount greater than about 60% v/v of the total composition with an effective physiologically acceptable fluorinated surface active agent for foaming present in an amount of at least 0.001% by weight of the total composition, and water present in an amount to balance the total composition to 100% by weight to form an alcohol-fluorosurfactant mixture and storing said composition in an unpressurized dispenser having a dispenser pump;


b) activating the dispenser pump to combine the alcohol-fluorosurfactant mixture with air to form and dispense a skin-disinfecting alcohol foam; and


c) applying the skin-disinfecting alcohol foam to the person's skin.


The invention will be described in connection with various specific examples, which are intended to be illustrative rather than limiting. Nevertheless, the present invention lends itself to the preparation of a wide variety of products, and it is to be understood that other embodiments may be utilized and that changes may be made without departing from the scope of the invention.







DETAILED DESCRIPTION OF THE INVENTION

Definitions


The term “emollient” as used herein refers broadly to materials which are capable of maintaining or improving the moisture level, compliance, or appearance of the skin when used repeatedly.


The term “emulsifier” as used herein refers to surfactants or other materials added in small quantities to a mixture of two miscible liquids for the purpose of aiding in the formation and stabilization of an emulsion.


The phrase “emulsifying ingredients” as used herein is synonymous with emulsifier defined above.


The term “emulsion” as used herein refers to a colloidal dispersion of one liquid in another.


The term “surfactant” as used herein is the widely employed contraction for “surface active agents” which is the descriptive generic term for materials that preferentially adsorb at interfaces as a result of the presence of both lyophilic and lyophobic structural units, the adsorption generally resulting in the alteration of the surface or interfacial properties of the system.


The term “fluorosurfactant” as used herein refers to a fluorinated surface active agent which enables the composition in which it is contained to clean, wet and foam.


The phrase “foam stabilizer” as used herein refers to an additive that increases the amount or persistence of foam produced by a surfactant system.


The phrase “gel-like composition” as used herein refers to a hydroalcoholic solution with at least 40% v/v alcohol content, which is thickened by the use of emulsifiers and surfactant to have a viscosity greater than water and less than 4,000 cps.


The term “disinfect” as used herein means to destroy or reduce harmful microorganisms.


The present invention provides compositions with high contents of lower alcohol (C1-4) able to be dispensed as a gel or a foam. The foamable compositions when mixed with air deliver a stable foam to provide an alcoholic liquid solution which can be used for personal cleaning or for disinfecting purposes and which breaks on pressure application such as when a user rubs their hands or when applied over a surface. The gel composition delivers a liquid of the appropriate consistency to be readily spread on the hands, yet without dripping off. This gel composition with at least 60% v/v alcohol provides an effective disinfectant that does not leave a tacky after-feel once the alcohol has evaporated and that is common to such alcohol gels which use thickeners and gelling agents that have been used commonly in the past during single or multiple applications. The gel composition does not easily clog the dispensers as common gel products do.


The alcohol used in the present invention is a lower hydrocarbon chain alcohol such as a C1-4 alcohol. The preferred alcohol is chosen from ethanol, 2-propanol, or n-propanol, most preferably ethanol, well accepted by Health Care personnel as an adequate disinfectant at the right percentages. The invention anticipates that a single alcohol may be used or that a blend of two or more alcohols may comprise the alcohol content of the composition either for a gel-like or foamable product.


Foamable Compositions


One of the main achievements of the present invention is making compositions with a greater than 40% v/v alcohol content able to be dispensed as a cosmetically appealing foam. The other important achievement is to obtain an alcohol gel without using the typical gelling agents know to those skilled in the art which would not clog dispensers or leave a tacky after-feel.


The use of a fluorosurfactant is the key ingredient as the primary foaming agent in the compositions designed to foam disclosed herein. Fluorosurfactants have various interesting properties such as leaving little residue, being able to function in harsh chemical and thermal environments; they have an unparalleled wetting power, etc. Unlike traditional surfactants, they show unusual surface-active properties in organic solvents that are known to those skilled in the art, and that have made them widely used for applications in coatings, oilfield, material finishes, cleaning, paints, etc.


The fluorosurfactants suitable for these types of compositions may include, but are not limited to, ethoxylates, glycerol esters, amine oxides, acetylenic alcohol derivatives, carboxylates, phosphates, carbohydrate derivatives, sulfonates, betaines, esters, polyamides, silicones, and hydrocarbon surfactants that have been fluorinated and are compatible with the other components being used for a particular formulation.


A preferred fluorosurfactant is polytetrafluoroethylene acetoxypropyl betaine CF3CF2(CF2CF2)nCH2CH2(OAc)CH2N+(CH3)2CH2COO—, where n=2-4. However, it is contemplated that other fluorosurfactants may be used including as non-limiting examples for use in the present invention an ethoxylated nonionic fluorosurfactant of the following structure: RfCH2CH2O(CH2CH2O)xH where Rf=F(CF2CF2)y, x=0 to about 15 and y=1 to about 7; an anionic phosphate fluorosurfactant of the following structure: (RfCH2CH2O)xP(O)(ONH4)y where Rf=(CF2CF2)z, x=1 or 2, y=2 or 1, x+y=3, and z=1 to about 7 or mixtures thereof.


It was surprisingly found that despite the characteristics of fluorosurfactants, there was little or no information on their use to produce a foamable product with high alcohol content other than the one using non-ionic fluorosurfactants and pressurized gas as a foamer as taught in U.S. Pat. No. 4,440,653 incorporated herein by reference.


Furthermore, in order to obtain a high alcohol content product able to produce a foam even if no pressurized containers or propellants are used would require surface tension values as low as possible so that the pressure required to produce such foam by hand pumps and mechanical means would be sufficient. Hence, the lower than 20 dynes/cm (0.01% DW 25° C.) surface tension values achievable with these surfactants made them suitable for the application.


During the development of the present invention, it was unexpectedly found that a quick breaking aerated foam could even be obtained when using just ethanol and the fluorosurfactant, while using traditional surfactants at even double the percentage bore results that could not be even slightly similar and no foam at all could be obtained.


In order to achieve a commercially suitable formulation, reducing the amount of fluorosurfactant used while using the assistance of other ingredients such as secondary surfactants, emulsifiers, foam stabilizers, fragrances, and the like ingredients employed in cosmetics, aerosols, toiletries, personal care, etc. is one of the approaches followed. One of the commercial products obtained uses emulsifiers and polyethoxylated fatty acid surfactants disclosed in U.S. Pat. Nos. 5,167,950 and 6,090,395, both incorporated herein by reference, while other examples use a combination of different foam stabilizers to achieve a similar result.


Examples of secondary surfactants that may be used in the present compositions include alkylglucosides, a poly(ethoxylated and/or propoxylated)alcohol, a poly(ethoxylated and/or propoxylated)ester, a derivative of a poly(ethoxylated and/or propoxylated)alcohol, a derivative of a poly(ethoxylated and/or propoxylated)ester, an alkyl alcohol, an alkenyl alcohol, an ester of a polyhydric alcohol, an ether of a polyhydric alcohol, an ester of a polyalkoxylated derivative of a polyhydric alcohol, an ether of a polyalkoxylated derivative of a polyhydric alcohol, a sorbitan fatty acid ester, a polyalkoxylated derivative of a sorbitan fatty acid ester, a betaine, a sulfobetaines, imidazoline derivatives, aminoacid derivatives, lecithins, phosphatides, some amine oxides and sulfoxides and mixtures thereof, present in an amount between about 0.10% to about 5% weight percent.


A preferred betaine is cocamidopropyl betaine. A preferred alkylglucoside is cocoglucoside. Preferred polyethoxylated fatty alcohols are polyethoxylated stearyl alcohol (21 moles ethylene oxide) and polyethoxylated stearyl alcohol (2 moles ethylene oxide), and a combination of these two.


The compositions may include an antimicrobial agent. The following antimicrobials are offered as non-limiting examples of suitable antimicrobials for use in the present invention and may include chlorhexidine salt, iodine, a complexed form of iodine, parachlorometaxylenol, triclosan, hexachlorophene, a phenol, a surfactant having a long chain hydrophobic group and a quaternary group, hydrogen peroxide, silver, a silver salt, silver oxide, and mixtures thereof.


A preferred antimicrobial agent in the present compositions is chlorhexidine gluconate (CHG) present in an amount between about 0.50% to about 4.0% weight percent. Another preferred antimicrobial agent is didecyl dimethyl diamonium chloride in an amount between about 0.05% to 5% weight percent.


If the amount of ingredients employed is little enough not to leave a tacky feeling after the composition evaporates after single or multiple uses, and this is achieved while maintaining at least 60% v/v ethanol or n-propanol concentration or 70% v/v isopropanol, then the composition would be ideal for use as an alcohol hand sanitizer/disinfectant foamable composition.


The addition of water to the alcohol produces a more stable foam while allowing to reduce the amount of fluorosurfactant required to foam the product. For instance, using 0.5 to 1.0% fluorosurfactant with a 50 to 60% v/v alcohol water solution produces a stable foam that does not readily collapse and that produces a stable puff that does not fall even when inverted and does not collapse until pressure is applied (such as when rubbed in hands or on over a surface) to provide an alcoholic liquid solution.


The use of a mild non-irritant surfactant widely used in the cosmetic industry such as cocamidopropyl betaine as a secondary surfactant is more suitable to prepare the foamable hydroalcoholic composition of the present invention depending on the fluorosurfactant being used.


In order to stabilize the foam, foam stabilizers, as well as emulsifying ingredients have been tried with good results in allowing the product to be dispensed as a foam even when no propellant and/or pressurized container systems are used.


Examples of compatible foam stabilizers that can optionally be employed include lactic acid esters of monoglycerides, cationic emulsifiers, triquaternized stearic phospholipid complex, hydroxystearamide propyltriamine salts, lactic acid monoglycerides, food emulsifiers such as glyceryl monostearate, propylene glycol monostearate, sodium stearoyl lactylate, silicone wax, an encapsulated oil, Microcapsule Mineral Oil®.


A preferred foam stabilizer used in the present foamable compositions is cetyl betaine. A preferred combination of foam stabilizers is that of butyleneglycol, butoxyethanol and n-propanol.


Examples of moisturizers and/or emollients which may be used in the present formulations include lanolin, vinyl alcohol, polyvinyl pyrrolidone and polyols selected from the group consisting of glycerol, propylene glycol, glyceryl oleate and sorbitol, cocoglucoside or a fatty alcohol selected from the group consisting of cetyl alcohol, stearyl alcohol, lauryl alcohol, myristyl alcohol and palmityl alcohol, cetyl alcohol, ceteareth 20, and combinations thereof, present in an amount up to about 5%.


The compositions may include an acid or a base to adjust a pH of the composition to a pre-selected pH. The acid or base may present in an amount from about 0.05 to about 0.5% by weight of the total composition. Non-limiting examples of the acid used to adjust the pH include hydrochloric acid, citric acid and phosphoric acid, and a non-limiting example of the base used to adjust the pH includes sodium sesquicarbonate.


The compositions may also include a preservative in an amount from about 0.01 to about 5% by weight of the total composition.


The compositions formulated to be dispensed as a foam may be stored in an unpressurized dispenser having a dispenser pump for mixing the composition with air and dispensing foam therefrom. The composition may include an aerosol propellant in an amount from about 3 to about 20 weight percent of the total composition for pressurized discharge of the foam. The aerosol propellant may include propane, carbon dioxide, butane, dichloro difluoro methane, dichloro tetra fluoro ethane, octafluorocyclo butane; 1,1,1,2-tetrafluoroethane; 1,1,1,2,3,3,3 heptafluoropropane, and 1,1,1,3,3,3,-hexafluoropropane. When stored in a metal container with propellant, the formulation may include a corrosion inhibitor such as sorbic acid, benzoic acid, potassium sorbate and sodium benzoate, in an amount from about 0.1 to about 5 weight percent of the total composition.


Gel-Like Compositions


Some of compositions studied had some gel-like properties. This characteristic led to the second most important achievement of the present invention; that is an alcohol gel with viscosities less than 4,000 cps that do not use the conventional polymeric thickeners (i,e, cellulose derivatives, carbomers, etc) that are known to leave a sticky residue on surfaces on single and multiple applications that builds up. This discourages users and tends to clog the dispensers.


In order to prepare a gel-like composition, a fluorosurfactant is not required to form the gel, however, using a small amount improves the after-feel, it also allows one to reduce the usage of other surfactants required, therefore improving the performance of the composition. The use of the fluorosurfactant also noticeably improves the spreadability of the gel disenfecting compositions on the hands or a surface.


The following is a basic formulation of the gel-like compositions. An alcohol C1-4, or mixtures thereof, present in an amount greater than about 40% v/v of the total composition, one or more nonionic surfactants present in an amount between about 0.10% to about 5% weight percent, an emulsifier present in an amount between about 0.10% to about 3.0% weight percent, and water in an amount sufficient to form a stable gel-like composition.


Non-limiting examples of non-ionic surfactants include poly(ethoxylated and/or propoxylated)alcohol, a poly(ethoxylated and/or propoxylated)ester, a derivative of a poly(ethoxylated and/or propoxylated)alcohol, a derivative of a poly(ethoxylated and/or propoxylated)ester, an alkyl alcohol, an alkenyl alcohol, an ester of a polyhydric alcohol, an ether of a polyhydric alcohol, an ester of a polyalkoxylated derivative of a polyhydric alcohol, an ether of a polyalkoxylated derivative of a polyhydric alcohol, a sorbitan fatty acid ester, a polyalkoxylated derivative of a sorbitan fatty acid ester, and mixtures thereof.


A preferred non-ionic surfactant includes polyethoxylated fatty alcohols such as polyethoxylated stearyl alcohol (21 moles ethylene oxide) and polyethoxylated stearyl alcohol (2 moles ethylene oxide), and/or a combination of polyethoxylated fatty alcohols.


To make the gel-like compositions for personal hygiene applications, the compositions may include a physiologically acceptable fluorinated surface active agent up to about 2.5%. A preferred fluorinated surface active agent is that used in the gel-like compositions, namely polytetrafluoroethylene acetoxypropyl betaine CF3CF2(CF2CF2)nCH2CH2(OAc)CH2N+(CH3)2CH2COO—, where n=2-4.


Another fluorinated surface active agent also preferred is an ethoxylated nonionic fluorosurfactant of the following structure: RfCH2CH2O(CH2CH2O)xH where Rf=F(CF2CF2)y, x=0 to about 15 and y=1 to about 7 and yet another one is an anionic phosphate fluorosurfactant of the following structure: (RfCH2CH2O)xP(O)(ONH4)y where Rf=F(CF2CF2)z, x=1 or 2, y=2 or 1, x+y=3, and z=1 to about 7 or mixtures thereof.


The following non-limiting examples are set forth to show for the various preferred embodiments and are not in any way to limit the scope of the present invention.


EXAMPLES

Examples 1 through 12 were prepared to illustrate the ability to produce alcohol-based formulations which can be dispensed as foams using different surfactants and a solution of water and 50% ethanol. Examples 13 through 18 show increasing concentrations of ethanol and fluorosurfactant to produce foam. Examples 19 through 30 illustrate the ability to produce foam using different surfactants and a solution of 70% v/v Isopropanol. All parts and percentages are expressed by weight unless otherwise indicated.






















Amount









Ingredients
Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5
Ex. 6






S.D. Alcohol 3-A
 50.00
 50.00
 50.00
 50.00
 50.00
 50.00



Fluorosurfactant
 0.50








Cocamidopropyl betaine (1)

 8.00







Alkylglucoside (2)


 8.00






Alkylglucoside (3)



 8.00





Glycomul L




 8.00




Sorbitan Sesquioleate





 8.00



Deionized Water
 49.50
 42.00
 42.00
 42.00
 42.00
 42.00



Total %
100.00
100.00
100.00
100.00
100.00
100.00
















Amount








Ingredients
Ex. 7
Ex. 8
Ex. 9
Ex. 10
Ex. 11
Ex. 12





S.D. Alcohol 3-A
 50.00
 50.00
 50.00
 50.00
 50.00
 50.00


Polysorbate 20
 8.00







Polyoxyethylene Sorbitan Monooleate

 8.00






Sorbitan Monooleate


 8.00





Cocamidopropyl betaine & sodium caproyl lactate



 8.00




Cocamidopropyl hydroxysultaine




 8.00



Sodium Cocoamphoacetate





 8.00


Deionized Water
 42.00
 42.00
 42.00
 42.00
 42.00
 42.00


Total %
100.00
100.00
100.00
100.00
100.00
100.00


















Amount









Ingredients
Ex. 13
Ex. 14
Ex. 15
Ex. 16
Ex. 17
Ex. 18






S.D. Alcohol 3-A
 50.00
 60.00
 65.00
 70.00
 80.00
 92.50



Fluorosurfactant
 0.10
 0.75
 0.80
 1.50
 2.00
 7.5



Deionized Water
 49.90
 39.25
 34.20
 28.50
 18.00




Total %
100.00
100.00
100.00
100.00
100.00
100.00


















Amount









Ingredients
Ex. 19
Ex. 20
Ex. 21
Ex. 22
Ex. 23
Ex. 24






70% v/v Isopropanol
 99.90
 92.00
 92.00
 92.00
 92.00
 92.00



Fluorosurfactant
 0.10








Cocamidopropyl betaine (1)

 8.00







Alkylglucoside (2)


 8.00






Alkylglucoside (3)



 8.00





Glycomul L




 8.00




Sorbitan Sesquioleate





 8.00



Total %
100.00
100.00
100.00
100.00
100.00
100.00
















Amount








Ingredients
Ex. 25
Ex. 26
Ex. 27
Ex. 28
Ex. 29
Ex. 30





70% v/v Isopropanol
 92.00
 92.00
 92.00
 92.00
 92.00
 92.00


Polysorbate 20
 8.00







Polyoxyethylene Sorbitan Monooleate

 8.00






Sorbitan Monooleate


 8.00





Cocamidopropylbetaine & sodium caproyl lactate



 8.00




Cocamidopropyl hydroxysultaine




 8.00



Sodium Cocoamphoacetate





 8.00


Total %
100.00
100.00
100.00
100.00
100.00
100.00





(1) Amphoteric,


(2) Nonionic,


(3) Anionic







The solutions prepared, were evaluated as to whether foam was produced or not and if so, then the foam produced was described as follows:















Foam



Example
Produced
Foam Evaluation/Description/Characteristics







Ex. 1
Yes
Very good stable stiff puff creamy and




soft lasts minutes


Ex. 2
No
Just Very Wet Bubbles produced lasting <10




seconds


Ex. 3
No



Ex. 4
No



Ex. 5
No



Ex. 6
No
Just Very Wet Bubbles produced lasting <7




seconds


Ex. 7
No
Just Very Wet Bubbles produced lasting <10




seconds


Ex. 8
No



Ex. 9
No
Just Very Wet Bubbles produced lasting <10




seconds


Ex. 10
No



Ex. 11
No



Ex. 12
No



Ex. 13
Yes
Very good stable stiff puff creamy and




soft lasts minutes


Ex. 14
Yes
Very good creamy and soft lasts more




than a minute


Ex. 15
Yes
Very good creamy and soft lasts more




than a minute


Ex. 16
Yes
Very good creamy and soft lasts more




than a minute


Ex. 17
Yes
Quick fast breaking foam lasts more




than a 15 secs


Ex. 18
Yes
Quick fast breaking foam lasts more




than a 10 secs


Ex. 19
Yes
Quick fast breaking foam lasts more




than a 20 secs


Ex. 20
No



Ex. 21
No



Ex. 22
No



Ex. 23
No



Ex. 24
No



Ex. 25
No



Ex. 26
No



Ex. 27
No



Ex. 28
No



Ex. 29
No



Ex. 30
No










Comparatively, it was also found that for instance, Cocamidopropyl betaine (CAPB) alone even at 40% ethanol and at 3% CAPB, was unable to produce as good results as those with 60% v/v ethanol, and fluorosurfactants using much less percentage (less than 1.0%). Cocamidopropyl betaine does not give any acceptable foam above that percentage of alcohol and the lower than 60% v/v alcohol content makes it inadequate for a sanitizing solution. Also the solution left an unacceptable feeling on the skin after the alcohol evaporated (i.e. a soapy sticky feeling) indicating high levels of surfactant.


Very interestingly fluorosurfactants seemed to be a likely way to achieve a foaming composition that contains more than 40% v/v alcohol. The fact that foam could be achieved even when no added water or ingredients are used other than 95% v/v alcohol and the fluorosurfactant as shown in example 18 makes the present invention suitable for many different applications.


Below are some specific examples for compositions following the above formulation to produce alcohol hand sanitizing solutions; more than one being a foamable composition with alcohol being the only disinfectant ingredient, while other foamable compositions use an added antimicrobial such as Chlorhexidine Digluconate or Didecyl Dimethyl Diammonium Chloride and the third group being alcohol gel-like hand sanitizing solutions.


Example 31

Alcohol hand sanitizing foamable disinfecting composition

  • 0.01-1.0%*amphoteric, anionic or non-ionic fluorosurfactant (primary surfactant)
  • 0.01-1.0% cocoamidopropylbetaine (secondary surfactant)
  • 0.05-1.0% cetyl betaine (foam stabilizing agent)
  • 0.10-1.5% emulsifier fatty alcohol ROH 16-22 carbons or combination that works well in a final formulation containing
  • 60-70% v/v ethanol
  • Q.S. water
    • Preferably Polytetrafluoroethylene Acetoxypropyl Betaine CF3CF2(CF2CF2)nCH2CH2(OAc)CH2N+(CH3)2CH2COO, where n=2-4 or an ethoxylated nonionic fluorosurfactant of the following structure: RfCH2CH2O(CH2CH2O)xH where Rf=F(CF2CF2)y, x=0 to about 15 and y=1 to about 7; or an anionic phosphate fluorosurfactant of the following structure: (RfCH2CH2O)xP(O)(ONH4)y where Rf=F(CF2CF2)z, x=1 or 2, y=2 or 1, x+y=3, and z=1 to about 7, or mixtures thereof.


Example 32

Alcohol Hand Sanitizing Foamable Disinfecting Composition Concentrate




  • 0.01-1.0%*amphoteric, anionic or non-ionic fluorosurfactant (primary surfactant)

  • 0.01-12.0% 1,3 Butyleneglycol, 2-Butoxyethanol, n-propanol (foam stabilizing agents)

  • 0.05-5.0% cocoglucoside, glycerin, glyceryl oleate (moisturizers, emollients and the like)

  • 60-70% v/v ethanol, n-propanol, isopropanol or a combination thereof

  • Q.S. water
    • Preferably an anionic phosphate fluorosurfactant of the following structure: (RfCH2CH2O)xP(O)(ONH4)y where Rf=F(CF2CF2)z, x=1 or 2, y=2 or 1, x+y=3, and z=1 to about 7 or an ethoxylated nonionic fluorosurfactant of the following structure: RfCH2CH2O(CH2CH2O)xH where Rf=F(CF2CF2)y, x=0 to about 15 and y=1 to about 7; or Polytetrafluoroethylene Acetoxypropyl Betaine CF3CF2(CF2CF2)nCH2CH2(OAc)CH2N+(CH3)2CH2COO, where n=2-4, or mixtures thereof



Example 33

Alcohol Hand Sanitizing Foamable Disinfecting Composition


a) ethanol present in an amount between about 60% to 70% percent v/v of the total composition;


b) a physiologically acceptable anionic phosphate fluorosurfactant in an amount from about 0.01% to about 2.0% weight percent of the total composition;


c) at least 1% n-propanol


d) foam stabilizing agents that at least include 1,3-Butyleneglycol % 2, Butoxyethanol in 0.001-3% ea.


e) a lipid layer enhancer such as a mixture of alkylglucoside and glyceryl oleate


f) water in an amount to balance the total composition to 100% weight percent.


Example 34

Chlorhexidine Gluconate (CHG) & Alcohol Hand Sanitizing Foamable Disinfecting Composition




  • Formulations 31 or 32 added with

  • 0.50-4.0% Chlorhexidine Gluconate (CHG)



Example 35



  • Formulations 31 or 32 added with

  • 0.01-5.0% Didecyl Dimethyl Diammonium Chloride



Example 36

Alcohol Hand Sanitizing Gel-Like Disinfecting Composition with a Viscosity Less than 4,000 Cps




  • 0.0-1.0%*amphoteric, anionic or non-ionic fluorosurfactant (primary surfactant)

  • 0.10-2.0% an emulsifier moisturizer and/or emollient preferably a non-ionic surfactant and/or a combination of cetearyl alcohol and ceteareth 20 or a combination thereof to give a composition with a viscosity of less than 4,000 cps;

  • 0.50-4.0% a combination of nonionic surfactants specifically from the group of the polyethoxylated fatty alcohols 60-70% v/v ethanol

  • Q.S. water
    • Preferably Polytetrafluoroethylene Acetoxypropyl Betaine CF3CF2(CF2CF2)nCH2CH2(OAc)CH2N+(CH3)2CH2COO, where n=2-4 or an ethoxylated nonionic fluorosurfactant of the following structure: RfCH2CH2O(CH2CH2O)xH where Rf=F(CF2CF2)y, x=0 to about 15 and y=1 to about 7; or an anionic phosphate fluorosurfactant of the following structure: (RfCH2CH2O)xP(O)(ONH4)y where Rf=F(CF2CF2)z, x=1 or 2, y=2 or 1, x+y=3, and z=1 to about 7, or mixtures thereof.



The process to prepare the compositions of the present invention described herein is straightforward since most of the ingredients are liquid. When wax type ingredients are to be used, they can be incorporated by warming up to 40-45° C. preferably to the alcohol portion while mixing and then allowing it to cool down or they could be added in “cold”, at room temperature to the alcohol before any other ingredient and mixed until completely incorporated before adding the rest of the ingredients according to the composition. Whether all ingredients are liquid or not, warming from 30 to 80 degrees Celsius, (depending on the particular composition) increases the long term stability of the compositions. Active ingredients could be pre-dissolved into the water first. A process that anyone knowledgeable enough of the art would have no problem implementing. If a specific formulation cannot be adjusted for the foamable composition in the percentages of the ingredients, then there is still the option of modifying the characteristics of the foaming pump, such as changing pressures, screen sizes, etc.


The compositions described within the present invention improve over prior similar products commercially available in the high concentrations of alcohol, as well as in the fact of being able to foam even with no propellants or pressurized containers (using propellants would improve considerably the quality of the foam) and being able to produce alcohol gel-like compositions that do not leave a sticky after-feel that builds up and do not clog the dispensers after single or multiple applications.


Depending on the alcohol concentration and the application of the particular composition the foam produced can widely vary, being at the high end of a relatively fast breaking variety stable enough to be thoroughly spread onto the skin without waste in a unique way and the gel-like composition viscosity varies with the alcohol concentration. The gel-like composition obtained is a unique approach that does not follow the traditional ways of making alcohol gels. In summary it could be said that the stated invention has exceeded expectations.


Due to the nature of the base composition with respect to the alcohol concentration and the quality of the ingredients, one of the logical first applications for the present invention would be as an alcohol hand disinfectant composition either for a foamable product or an alcohol gel-like product, examples of which are described above. Nevertheless, the present invention lends itself to the preparation of a wide variety of products, and it is to be understood that other embodiments may be utilized and that changes may be made without departing from the scope of the invention.


Consequently, it is intended that the claims be interpreted to cover such modifications and equivalents. To note a few, the following may be mentioned: medicated foams and gels, sunscreen foams and gels, hand cream foams, brush-less shaving cream foams, shower or bath oil foams, dry hair shampoo foams, make-up remover foams, analgesic foam rubs and gels, hair grooming foams and antiperspirants hair cleaning foam, antiperspirant foam, hair conditioner foams.


As used herein, the terms “comprises”, “comprising”, “includes” and “including” are to be construed as being inclusive and open ended, and not exclusive. Specifically, when used in this specification including claims, the terms “comprises”, “comprising”, “includes” and “including” and variations thereof mean the specified features, steps or components are included. These terms are not to be interpreted to exclude the presence of other features, steps or components.


The foregoing description of the preferred embodiments of the invention has been presented to illustrate the principles of the invention and not to limit the invention to the particular embodiment illustrated. It is intended that the scope of the invention be defined by all of the embodiments encompassed within the following claims and their equivalents.












References Cited


U.S. PATENT DOCUMENTS




















2,054,989
September 1936
Moore
167/58



3,131,153
April 1964
Klausner
252/305



3,962,150
June 1976
Leonard et al.
252/542



4,440,653
April 1984
James et al.
252/8.55



5,167,950
December 1992
Lins
424/47



4,956,170
September 1990
Lee
514/772.1



5,629,006
May 1997
Minh et al.
424/405



5,906,808
May 1999
Osborne, et al.
424/43



5,928,993
July 1999
Ingegärd
504/116



5,951,993
September 1999
Scholz et al.
424/405



6,090,395
July 2000
Asmus et al.
424/401



6,610,315
August 2003
Scholz et al.
424/415



6,623,744
September 2003
Asmus et al.
424/401



6,562,360
May 2003
Scholz et al.
424/405










OTHER PUBLICATIONS



  • Myers, Drew: “Surfactant Science and Technology”,second edition, Drew Myers, VCH Publishers, New York, 1992

  • Reduce Tension Dupont Zonyl® Fluorosurfactants Field Manual published by Dupont Co on May 2001


Claims
  • 1. A method of forming a skin disinfecting foam containing alcohol, comprising the steps of: activating a dispenser pump of an unpressurized dispenser to combine an alcohol-fluorosurfactant mixture with air to form and dispense a skin disinfecting foam containing alcohol, wherein the alcohol-fluorosurfactant mixture comprises an alcohol C1-4, or mixtures thereof, present in an amount greater than or equal to about 60% v/v of the total composition, a physiologically acceptable effective anionic phosphate fluorosurfactant for foaming present in an amount of at least 0.001% by weight of the total composition, and water present in an amount to balance the total composition to 100% by weight.
  • 2. The method of claim 1 wherein the effective physiologically acceptable fluorosurfactant is for wetting.
  • 3. The method according to claim 1 wherein the effective physiologically acceptable fluorosurfactant is present in an amount from about 0.001% to about 10.0% by weight of the total composition.
  • 4. The method according to claim 1 wherein the alcohol C1-4 is an aliphatic alcohol selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, butanol and combinations thereof.
  • 5. The method according to claim 1 wherein the alcohol is present in a range from about 60% to about 90% v/v.
  • 6. The method according to claim 1 further including at least one additional surfactant for adjusting properties of the foam produced from the composition.
  • 7. The method according to claim 6 wherein the additional surfactant is selected from the group consisting of a poly(ethoxylated and/or propoxylated)alcohol, a poly(ethoxylated and/or propoxylated)ester, a derivative of a poly(ethoxylated and/or propoxylated)alcohol, a derivative of a poly(ethoxylated and/or propoxylated)ester, an alkyl alcohol, an alkenyl alcohol, an ester of a polyhydric alcohol, an ether of a polyhydric alcohol, an ester of a polyalkoxylated derivative of a polyhydric alcohol, an ether of a polyalkoxylated derivative of a polyhydric alcohol, a sorbitan fatty acid ester, a polyalkoxylated derivative of a sorbitan fatty acid ester, an alkylglucoside, a betaine, a sulfobetaine, an imidazoline derivative, an aminoacid derivative, a lecithin, a phosphatide, an amine oxide, a sulfoxide and mixtures thereof, present in an amount between about 0.10% to about 5% by weight.
  • 8. The method according to claim 1, wherein the composition does not include a propellant.
  • 9. A method for personal disinfecting comprising: applying to a person's skin a skin-disinfecting alcohol foam composition which comprises a) air mixed under low pressure conditions withb) a liquid comprising i) an alcohol C1-4, or mixtures thereof, present in an amount greater than or equal to about 60% v/v of the total composition;ii) water present in an amount to balance the total composition to 100% by weight; andiii) a physiologically acceptable effective anionic phosphate fluorosurfactant for foaming present in an amount of at least 0.001% by weight of the total composition.
  • 10. The method according to claim 9 wherein the effective physiologically acceptable fluorosurfactant is for wetting.
  • 11. The method according to claim 9 wherein the effective physiologically acceptable fluorosurfactant is present in an amount from about 0.001% to about 10.0% by weight of the total composition.
  • 12. The method according to claim 9 wherein the alcohol C1-4 is an aliphatic alcohol selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, butanol and combinations thereof.
  • 13. The method according to claim 9 wherein the alcohol is present in a range greater than about 60% v/v to about 90% v/v.
  • 14. The method according to claim 9 wherein the alcohol is ethanol present in an amount of at least 60% v/v.
  • 15. The method according to claim 9 wherein the alcohol is a mixture of n-propanol and ethanol present in a combined amount of at least 60% v/v.
  • 16. The method according to claim 9 wherein the alcohol is a mixture of isopropanol and ethanol present in a combined amount of at least 60% v/v.
  • 17. The method according to claim 9 wherein the alcohol is isopropanol present in an amount of at least 70% v/v.
  • 18. The method according to claim 9 wherein the alcohol is n-propanol present in an amount of at least 60% v/v.
  • 19. The method according to claim 9 wherein the alcohol foam composition further includes at least one additional surfactant for adjusting properties of the composition and/or the resulting foam produced from the composition.
  • 20. The method according to claim 19 wherein the additional surfactant is selected from the group consisting of a poly(ethoxylated and/or propoxylated)alcohol, a poly(ethoxylated and/or propoxylated)ester, a derivative of a poly(ethoxylated and/or propoxylated)alcohol, a derivative of a poly(ethoxylated and/or propoxylated)ester, an alkyl alcohol, an alkenyl alcohol, an ester of a polyhydric alcohol, an ether of a polyhydric alcohol, an ester of a polyalkoxylated derivative of a polyhydric alcohol, an ether of a polyalkoxylated derivative of a polyhydric alcohol, a sorbitan fatty acid ester, a polyalkoxylated derivative of a sorbitan fatty acid ester, an alkyglucoside, a betaine, a sulfobetaine, an imidazoline derivative, an aminoacid derivative, a lecithin, a phosphatide, an amine oxide, a sulfoxide and mixtures thereof, present in an amount between about 0.10% to about 5% by weight.
  • 21. The method according to claim 20 wherein the betaine is cocamidopropyl betaine.
  • 22. The method according to claim 20 wherein the alkylglucoside is cocoglucoside.
  • 23. The method according to claim 20 wherein the polyethoxylated fatty alcohol is polyethoxylated stearyl alcohol (21 moles ethylene oxide).
  • 24. The method according to claim 20 wherein the polyethoxylated fatty alcohol is polyethoxylated stearyl alcohol (2 moles ethylene oxide).
  • 25. The method according to claim 20 wherein the polyethoxylated fatty alcohol is a combination of polyethoxylated stearyl alcohol (21 moles ethylene oxide) and polyethoxylated stearyl alcohol (2 moles ethylene oxide).
  • 26. The method according to claim 9 wherein the alcohol foam composition includes a foam stabilizing agent present in an amount up to 5% by weight.
  • 27. The method according to claim 26 wherein the foam stabilizing agent is selected from the group consisting of lactic acid esters of monoglycerides, cationic emulsifiers, triquaternized stearic phospholipid complex, hydroxystearamide propyltriamine salts, lactic acid monoglycerides, food emulsifiers selected from the group consisting of glyceryl monostearate, propylene glycol monostearate, sodium stearoyl lactylate, cetyl betaine, glycolether, n-propanol, butyleneglycol, silicone wax, an encapsulated oil, Microcapsule Mineral Oil®, and combinations thereof.
  • 28. The method according to claim 26 wherein the foam stabilizing agent is selected from the group consisting of glycolether, n-propanol, butyleneglycol, and combinations thereof.
  • 29. The method according to claim 9 wherein the effective physiologically acceptable fluorosurfactant is present in an amount from about 0.1% to about 10.0% by weight of the total composition.
  • 30. A method for producing, and applying to a person's skin, a skin-disinfecting alcohol foam composition, comprising: activating a dispenser pump of an unpressurized dispenser to combine an alcohol-fluorosurfactant mixture with air to form and dispense a skin-disinfecting alcohol foam, the alcohol-fluorosurfactant mixture comprising an alcohol C1-4, or mixtures thereof, present in an amount greater than or equal to about 60% v/v of the total composition, a physiologically acceptable anionic phosphate fluorinated surface active agent present in an amount of at least 0.001% by weight of the total composition, and water present in an amount to balance the total composition to 100% by weight; andapplying the skin-disinfecting alcohol foam to the person's skin.
  • 31. The method according to claim 30 wherein the effective physiologically acceptable fluorinated surface active agent is a fluorosurfactant present in an amount from about 0.1% to about 10.0% by weight of the total composition.
  • 32. An unpressurized dispenser having a dispenser pump for mixing a composition with air and dispensing foam therefrom, said composition comprising: an alcohol C1-4, or mixtures thereof, present in an amount greater than or equal to about 60% v/v of the total composition,a physiologically acceptable effective anionic phosphate fluorosurfactant for foaming present in an amount of at least 0.001% by weight of the total composition, andwater present in an amount to balance the total composition to 100% by weight.
  • 33. The dispenser of claim 32 wherein the effective physiologically acceptable fluorosurfactant is present in an amount from about 0.1% to about 10.0% by weight of the total composition.
  • 34. The method of claim 1 wherein the alcohol-fluorosurfactant mixture further comprises glycerol.
  • 35. The method of claim 9 wherein the liquid further comprises glycerol.
  • 36. The method of claim 30 wherein the alcohol-fluorosurfactant mixture further comprises glycerol.
  • 37. The unpressurized dispenser of claim 32 wherein the composition further comprises glycerol.
CROSS REFERENCE TO RELATED U.S. APPLICATIONS

This patent application is a continuation of U.S. application Ser. No. 12/659,063, filed Feb. 24, 2010, which is a divisional application of U. S. patent application Ser. No. 11/507,626 filed on Aug 22, 2006, which issued as U.S. Pat. No. 7,683,018 on Mar 23, 2010, which was a continuation of U.S. patent application Ser. No. 10/952,474 filed on Sep. 29, 2004, which issued as U.S. Pat. No. 7,199,090 on Apr. 3, 2007, and which relates to, and claims the priority benefit from, U.S. Provisional Patent Application No. 60/506,172 filed on Sep. 29, 2003, and U.S. Provisional Patent Application No. 60/591,601 filed on Jul. 28, 2004, all of which are incorporated herein by reference in their entireties.

US Referenced Citations (320)
Number Name Date Kind
2054989 Moore Sep 1936 A
2559749 Benning Jul 1951 A
2597702 Benning May 1952 A
2599140 Taub Jun 1952 A
2855367 Buck Oct 1958 A
3131152 Klausner Apr 1964 A
3131153 Klausner Apr 1964 A
3395214 Mummert Jul 1968 A
3708435 Starkman Jan 1973 A
3709437 Wright Jan 1973 A
3770648 Mackles Nov 1973 A
3787566 Gauvreau et al. Jan 1974 A
3824303 Lanzet Jul 1974 A
3928558 Cheesman et al. Dec 1975 A
3962150 Viola Jun 1976 A
3963507 Kuramoto et al. Jun 1976 A
4018364 Wright Apr 1977 A
4086178 Walker Apr 1978 A
4220665 Klein Sep 1980 A
4225456 Schmidt et al. Sep 1980 A
4311695 Starch Jan 1982 A
4313978 Stevens Feb 1982 A
4336151 Like et al. Jun 1982 A
4440652 Hunter Apr 1984 A
4440653 Briscoe et al. Apr 1984 A
4454060 Lai et al. Jun 1984 A
4478853 Chaussee Oct 1984 A
4511486 Shah Apr 1985 A
4559226 Fogel et al. Dec 1985 A
4567038 Ciaudelli et al. Jan 1986 A
4584189 Leipold Apr 1986 A
4613592 Benzoni Sep 1986 A
4714568 Hurnik et al. Dec 1987 A
4772592 Benzoni Sep 1988 A
4826828 Wilmott et al. May 1989 A
4839166 Grollier et al. Jun 1989 A
4839167 Yamamoto et al. Jun 1989 A
4857302 Decker et al. Aug 1989 A
4897262 Nandagiri et al. Jan 1990 A
4906459 Cobb et al. Mar 1990 A
4915934 Tomlinson Apr 1990 A
4919837 Glack Apr 1990 A
4956170 Lee Sep 1990 A
4956173 Le Fur et al. Sep 1990 A
4981678 Tomlinson Jan 1991 A
4983377 Murphy et al. Jan 1991 A
4986922 Snow et al. Jan 1991 A
4988453 Chambers Jan 1991 A
5015228 Columbus et al. May 1991 A
5043088 Falla Aug 1991 A
5047249 Rothman et al. Sep 1991 A
5073371 Turner et al. Dec 1991 A
5100658 Bolich, Jr. et al. Mar 1992 A
5104646 Bolich, Jr. et al. Apr 1992 A
5122541 Eggensperger et al. Jun 1992 A
5128123 Brewster et al. Jul 1992 A
5167950 Lina Dec 1992 A
5180584 Sebag et al. Jan 1993 A
5204099 Barbier et al. Apr 1993 A
D338585 Bell Aug 1993 S
5232691 Lemole Aug 1993 A
5256401 Duckenfield Oct 1993 A
5265772 Bartasevich Nov 1993 A
5266598 Ninomiya et al. Nov 1993 A
D343751 Bell Feb 1994 S
5288486 White Feb 1994 A
5290555 Guthauser et al. Mar 1994 A
D346332 Kanfer Apr 1994 S
5300284 Wiechers et al. Apr 1994 A
5314684 Horoschak et al. May 1994 A
5336497 Guerrero et al. Aug 1994 A
5352437 Nakagawa et al. Oct 1994 A
5362484 Wood et al. Nov 1994 A
5370267 Schroeder Dec 1994 A
5415811 Wile May 1995 A
5441178 Wysocki Aug 1995 A
5443236 Bell Aug 1995 A
5445288 Banks Aug 1995 A
5449137 Bell Sep 1995 A
5462688 Lippman Oct 1995 A
D365509 Bell Dec 1995 S
D365518 Wysocki Dec 1995 S
D365755 Kanfer Jan 1996 S
5484597 Slavtcheff et al. Jan 1996 A
5494533 Woodin, Jr. et al. Feb 1996 A
5523014 Dolan Jun 1996 A
5547662 Khan et al. Aug 1996 A
5549888 Venkateswaran Aug 1996 A
5558453 Bell Sep 1996 A
5567428 Hughes Oct 1996 A
5587358 Sukigara Dec 1996 A
5607980 McAtee et al. Mar 1997 A
5612324 Guang Lin et al. Mar 1997 A
5625659 Sears Apr 1997 A
5626853 Bara et al. May 1997 A
5629006 Hoang May 1997 A
5635462 Fendler Jun 1997 A
5635469 Fowler et al. Jun 1997 A
D383001 Bell Sep 1997 S
5662893 George et al. Sep 1997 A
5665332 Mundschenk et al. Sep 1997 A
D385795 Wysocki Nov 1997 S
5690921 Lang et al. Nov 1997 A
5693255 Okamoto et al. Dec 1997 A
5718353 Kanfer Feb 1998 A
5719113 Fendler Feb 1998 A
D392136 Ross Mar 1998 S
5733535 Hollingshead et al. Mar 1998 A
5756077 Syed et al. May 1998 A
5767054 Sprugel et al. Jun 1998 A
5767161 Stroppolo et al. Jun 1998 A
5776430 Osborne et al. Jul 1998 A
5789371 Tracy et al. Aug 1998 A
5824320 Rouillard et al. Oct 1998 A
D400799 Bell Nov 1998 S
5834516 O'Lenick, Jr. Nov 1998 A
5856347 Hashiguchi et al. Jan 1999 A
5863884 Lafreniere Jan 1999 A
5902778 Hartmann et al. May 1999 A
5906808 Osborne May 1999 A
D411456 Mast Jun 1999 S
5908619 Scholz Jun 1999 A
5919439 Torgerson et al. Jul 1999 A
5922663 Gabriel et al. Jul 1999 A
5928993 Johansson Jul 1999 A
5935587 Cauwet et al. Aug 1999 A
5944227 Schroeder Aug 1999 A
5951993 Scholz et al. Sep 1999 A
5952290 Li et al. Sep 1999 A
5955408 Kaiser Sep 1999 A
5955416 Baillely et al. Sep 1999 A
D415343 Maddox Oct 1999 S
5972356 Peffly et al. Oct 1999 A
D416417 Ross Nov 1999 S
5980876 Peffy Nov 1999 A
5996851 Dolan Dec 1999 A
D418708 Kanfer Jan 2000 S
6019997 Scholz et al. Feb 2000 A
6022551 Jampani et al. Feb 2000 A
6039965 Donian et al. Mar 2000 A
D422828 Kanfer Apr 2000 S
6065639 Maddox May 2000 A
6086856 Saferstein et al. Jul 2000 A
6090395 Asmus Jul 2000 A
6117440 Suh et al. Sep 2000 A
6130253 Franklin et al. Oct 2000 A
6183766 Sine et al. Feb 2001 B1
6217885 Röder et al. Apr 2001 B1
6255265 Van Gunst Jul 2001 B1
6262128 Stern et al. Jul 2001 B1
6264929 Karlen et al. Jul 2001 B1
6265363 Viscovitz Jul 2001 B1
6267976 Barnhart Jul 2001 B1
6274124 Vollhardt Aug 2001 B1
6277359 Raths et al. Aug 2001 B1
6319489 Ashton et al. Nov 2001 B1
6319958 Johnson et al. Nov 2001 B1
6333039 Fendler et al. Dec 2001 B1
6339165 Endo et al. Jan 2002 B1
6342470 Aronson Jan 2002 B1
6352701 Scholz et al. Mar 2002 B1
6358914 Gabriel et al. Mar 2002 B1
6376438 Rosenberger et al. Apr 2002 B1
6383505 Kaiser May 2002 B1
6383997 McManus May 2002 B1
6410005 Galleguillos et al. Jun 2002 B1
6423329 Sine et al. Jul 2002 B1
6462002 Saxena Oct 2002 B2
6471983 Veeger et al. Oct 2002 B1
6472356 Narula et al. Oct 2002 B2
6479442 Berube Nov 2002 B1
6489275 Veeger et al. Dec 2002 B1
6491840 Frankenbach et al. Dec 2002 B1
6497864 Samain et al. Dec 2002 B1
6518228 Jorgensen Feb 2003 B1
6524494 Hart et al. Feb 2003 B2
6524594 Santora Feb 2003 B1
6528544 Stern et al. Mar 2003 B2
6534069 Asmus et al. Mar 2003 B1
6537952 Hayward Mar 2003 B2
6551605 Bondo Apr 2003 B2
6555508 Paul Apr 2003 B1
6562360 Scholz et al. May 2003 B2
6582711 Asmus et al. Jun 2003 B1
6592880 Jager Jul 2003 B1
6610315 Scholz et al. Aug 2003 B2
6617294 Narula et al. Sep 2003 B2
6623744 Asmus Sep 2003 B2
6638527 Gott Oct 2003 B2
6641825 Scholz Nov 2003 B2
6664256 Oohkuchi et al. Dec 2003 B1
6664356 Shih Dec 2003 B1
6666217 Elsner Dec 2003 B2
6685952 Ma et al. Feb 2004 B1
6689593 Millis Feb 2004 B2
6696053 Ma et al. Feb 2004 B1
6696397 Staats Feb 2004 B2
6703007 Glenn, Jr. Mar 2004 B2
6706675 Demson Mar 2004 B1
6709647 Bhakoo Mar 2004 B2
6710022 Kwetkat et al. Mar 2004 B1
6723689 Hoang Apr 2004 B1
6730621 Gott May 2004 B2
6759376 Zhang Jul 2004 B2
6762158 Lukenbach Jul 2004 B2
6777384 Raths et al. Aug 2004 B2
6780826 Zhang Aug 2004 B2
6794345 Elsner et al. Sep 2004 B2
6797687 Kischkel et al. Sep 2004 B2
6805141 Elsner et al. Oct 2004 B2
6815410 Boutique Nov 2004 B2
6818603 Aleles Nov 2004 B2
6846846 Modak et al. Jan 2005 B2
6875539 Ophardt Apr 2005 B2
6884763 Willard Apr 2005 B2
6946120 Wai-Chiu et al. Sep 2005 B2
6977082 Seitz, Jr. et al. Dec 2005 B2
7081246 Asmus et al. Jul 2006 B2
7141237 Abram et al. Nov 2006 B2
7163916 Alief et al. Jan 2007 B2
7164041 Moore et al. Jan 2007 B1
7166435 Rosenbloom Jan 2007 B2
7199090 Koivisto Apr 2007 B2
7241452 Veeger et al. Jul 2007 B2
7297675 Alief et al. Nov 2007 B2
7393817 Kwetket et al. Jul 2008 B2
7530477 Ophardt May 2009 B2
7547732 Moore et al. Jun 2009 B2
7566460 Asmus et al. Jul 2009 B2
7597898 Birkel et al. Oct 2009 B2
7651990 Asmus Jan 2010 B2
7670615 Veeger Mar 2010 B2
7683018 Koivisto et al. Mar 2010 B2
7723279 Lestage et al. May 2010 B2
7790663 Lestage et al. Sep 2010 B2
7803390 Asmus et al. Sep 2010 B2
7842725 Wegner et al. Nov 2010 B2
7850048 Arminak Dec 2010 B2
8058315 Wegner et al. Nov 2011 B2
20020022660 Jampani Feb 2002 A1
20020028187 Nekludoff et al. Mar 2002 A1
20020039562 Kobayashi et al. Apr 2002 A1
20020098159 Wei et al. Jul 2002 A1
20020106399 Durden Aug 2002 A1
20020108640 Barger et al. Aug 2002 A1
20020127253 Scholz et al. Sep 2002 A1
20020142018 Scholz et al. Oct 2002 A1
20020151446 Piterski et al. Oct 2002 A1
20020160029 Asmus et al. Oct 2002 A1
20020160924 Bertrem et al. Oct 2002 A1
20020177535 Piterski et al. Nov 2002 A1
20020187908 Gagilardi et al. Dec 2002 A1
20030134761 Sebillotte-Arnaud et al. Jul 2003 A1
20030203824 Staats Oct 2003 A1
20030211066 Scholz et al. Nov 2003 A1
20030213542 Kobayashi et al. Nov 2003 A1
20030215418 Asmus et al. Nov 2003 A1
20030235550 Pan et al. Dec 2003 A1
20040001797 Saud et al. Jan 2004 A1
20040071748 Asmus et al. Apr 2004 A1
20040072700 Gupta Apr 2004 A1
20040102429 Modak et al. May 2004 A1
20040170592 Veeger et al. Sep 2004 A1
20040191195 Collins et al. Sep 2004 A1
20040191274 Grayson et al. Sep 2004 A1
20040219227 Modak et al. Nov 2004 A1
20040241099 Popp et al. Dec 2004 A1
20040247685 Modak et al. Dec 2004 A1
20040265240 Tamarkin et al. Dec 2004 A1
20050003990 Smith et al. Jan 2005 A1
20050031580 Allef et al. Feb 2005 A1
20050031653 Kwetkat et al. Feb 2005 A1
20050063925 Candau et al. Mar 2005 A1
20050109981 Tucker et al. May 2005 A1
20050129626 Koivisto et al. Jun 2005 A1
20050152931 SaNoguiera et al. Jul 2005 A1
20050222001 Baumeister et al. Oct 2005 A1
20050226838 Krause et al. Oct 2005 A1
20050277574 Niedbala et al. Dec 2005 A1
20060018847 Kroepke et al. Jan 2006 A1
20060104911 Novak May 2006 A1
20060104919 Novak May 2006 A1
20060110416 Ryles et al. May 2006 A1
20060165627 Allef et al. Jul 2006 A1
20060182690 Veeger et al. Aug 2006 A1
20060198859 Allef et al. Sep 2006 A1
20060204468 Allef et al. Sep 2006 A1
20060257334 Dahms et al. Nov 2006 A1
20060263396 Asmus et al. Nov 2006 A1
20060275226 Dahms et al. Dec 2006 A1
20060281663 Asmus et al. Dec 2006 A1
20070027055 Koivisto et al. Feb 2007 A1
20070041927 Blaeser et al. Feb 2007 A1
20070065383 Fernandez de Castro et al. Mar 2007 A1
20070092470 Allef et al. Apr 2007 A1
20070141007 Glynn et al. Jun 2007 A1
20070148101 Snyder et al. Jun 2007 A1
20070179207 Fernandez de Castro et al. Aug 2007 A1
20070258911 Fernandez de Castro et al. Nov 2007 A1
20080051312 Lestage et al. Feb 2008 A1
20080108704 Asmus et al. May 2008 A1
20080145320 Wenk et al. Jun 2008 A1
20080178899 Moenks et al. Jul 2008 A1
20080207767 Dobos Aug 2008 A1
20080293825 Littau et al. Nov 2008 A1
20080305056 Jenni et al. Dec 2008 A1
20090054521 Henwerth et al. Feb 2009 A1
20090098067 Seidling et al. Apr 2009 A1
20090326076 Asmus Dec 2009 A1
20100022660 Wegner et al. Jan 2010 A1
20100069505 Veeger et al. Mar 2010 A1
20100160415 Koivisto et al. Jun 2010 A1
20100187263 Lestage et al. Jul 2010 A1
20100234475 Wegner et al. Sep 2010 A1
20100327013 Asmus Dec 2010 A1
20100331411 Asmus Dec 2010 A1
20110104079 Snyder et al. May 2011 A1
20110110869 Scholtz et al. May 2011 A1
20110201693 Littau Aug 2011 A1
20110319364 Wegner et al. Dec 2011 A1
Foreign Referenced Citations (52)
Number Date Country
2003203452 Oct 2004 AU
2 323 780 Apr 2001 CA
2587086 Apr 2006 CA
2852583 Jun 1979 DE
3306593 Feb 1983 DE
3306593 Sep 1983 DE
19523320 Jan 1997 DE
69512841 May 2000 DE
69630221 Jul 2004 DE
10 2004 050 211 Apr 2006 DE
0160051 Nov 1985 EP
0213527 Mar 1987 EP
0117889 Nov 1987 EP
0260641 Mar 1988 EP
0384126 Aug 1990 EP
0689767 Jan 1996 EP
0882446 Dec 1998 EP
0990412 Apr 2000 EP
1 118 655 Jul 2001 EP
1 584323 Oct 2005 EP
1 893 167 Mar 2008 EP
1811013 Aug 2009 EP
2010874 Jul 1979 GB
11349418 Dec 1999 JP
2006279268 Oct 2006 JP
2007285808 Nov 2007 JP
9300089 Jan 1993 WO
9303704 Mar 1993 WO
9307250 Apr 1993 WO
9501384 Jan 1995 WO
9503772 Feb 1995 WO
9700667 Jan 1997 WO
9700667 Jan 1997 WO
9700668 Jan 1997 WO
9920250 Apr 1999 WO
0006107 Feb 2000 WO
0047183 Aug 2000 WO
02062936 Aug 2002 WO
03028671 Apr 2003 WO
03034994 May 2003 WO
03053388 Jul 2003 WO
04000016 Dec 2003 WO
2005030917 Sep 2004 WO
2005-051341 Jun 2005 WO
2005123012 Dec 2005 WO
2006042588 Apr 2006 WO
2006066888 Jun 2006 WO
WO 2006094387 Sep 2006 WO
2006138111 Dec 2006 WO
2007095008 Aug 2007 WO
2008132621 Nov 2008 WO
2010010475 Jan 2010 WO
Non-Patent Literature Citations (208)
Entry
U.S. Appl. No. 12/514,326, filed May 11, 2009 and entitled “Compositions, in Particular Cream to Protect Against Cold”.
Notice of Allowance and Fee(s) Due and Notice of Allowability mailed Nov. 24, 2009 for U.S. Appl. No. 11/151,563, filed Jun. 13, 2005.
Interview Summary with Notification Date of Nov. 24, 2009 for U.S. Appl. No. 11/312,559, filed Dec. 21, 2005.
Office Action for Canadian Patent Application No. 2,540,085 dated Oct. 29, 2008.
Examiner's first report on Australian Patent Application No. 2004 275900 dated May 21, 2009.
Office Action mailed Dec. 4, 2008 in U.S. Appl. No. 11/312,559.
Office Action mailed Feb. 13, 2009 in U.S. Appl. No. 11/312,559.
Office Action mailed Mar. 16, 2009 in U.S. Appl. No. 11/312,559.
Office Action mailed Oct. 21, 2008 in U.S. Appl. No. 11/151,563.
Office Action mailed Jul. 14, 2009 in U.S. Appl. No. 11/312,559.
Notice of Allowance mailed Jun. 2, 2009 in U.S. Appl. No. 11/151,563.
Interview Summary dated Jul. 14, 2009 for U.S. Appl. No. 11/312,559, filed Dec. 21, 2005.
European Patent Specification EP 1 811 01381 published Aug. 12, 2009.
Request for Foreign Priority mailed Aug. 19, 2009 for U.S. Appl. No. 11/312,559, filed Dec. 21, 2005.
Request for RCE dated Sep. 1, 2009 in U.S. Appl. No. 11/151,563, filed Jun. 13, 2005.
Notice of Allowability dated Sep. 21, 2009 in U.S. Appl. No. 11/151,563, filed Jun. 13, 2005.
Non-Final Rejection mailed Sep. 17, 2009 for U.S. Appl. No. 12/032,083, filed Feb. 15, 2008.
Response dated Oct. 12, 2009 to European Patent Application No. 08250626.2.
Canadian Examination Report dated Oct. 13, 2009 in Application Serial No. 2,595,025.
Notice of Allowability mailed Oct. 13, 2009 in U.S. Appl. No. 11/312,559, filed Dec. 21, 2005.
Office Action dated Oct. 15, 2009 in U.S. Appl. No. 11/438,664, filed May 22, 2006.
Examination Report dated Jul. 20, 2009 for New Zealand Patent Application No. 561741.
Defendant BETCO, Corporation's Initial Disclosures Pursuant to Fed. R. Civ. p. 26(a) (1), DEB Worldwide Healthcare, Inc. v. BETCO, Corp., Case No. 3:08-cv-00052-bbc, US District Court for the Western District of Wisconsin, Apr. 2, 2008.
First Amended Complaint, DEB Worldwide Healthcare, Inc. v. BETCO, Corp., Case No. 3:08-cv-00052-bbc, US District Court for the Western District of Wisconsin, document #21, Apr. 21, 2008.
Complaint, DEB Worldwide Healthcare, Inc. v. BETCO, Corp., Case No. 3:08-cv-00052-bbc, US District Court for the Western District of Wisconsin, document #1, Jan. 22, 2008.
Dewar et al., Effectiveness of Septisol Antiseptic Foam as a Surgical Scrub Agent, Applied Microbiology, Oct. 1973, vol. 26, No. 4, p. 544-549.
Beck, W, Alcohol foam for hand disinfection, AORN Journal, Dec. 1980, vol. 32, No. 6, p. 1087-1088.
3M Fluorad Well Stimulation Additive FC-742 Foamer for Aqueous/Alcoholic Fluids, 3M 1987,6 pages.
Sandra J. Pfaff, Letters to the Editor, Alcohol Foam Use Questioned, AORN Journal, Dec. 1989, vol. 50, No. 6, 1 page.
3M Product Information Well Stimulation Additive FC-742, Foamer for Aqueous/Alcoholic Fluids, 1994,4 pages.
Zonyl FSP fluorosurfactant, Technical Information, DuPont, 1998,2 pages.
Rosen et al., Industrial Utilization of Surfactants; Principles and Practice, AOCS Press, 2000, 4 pages.
Pabon et al., Fluorinated surfactants: synthesis, properties effluent treatment, J. Fluorine Chem. 114 (2002), p. 149-156.
Degussa, Creating Essentials, “Goldschmidt Personal Care,” Catalog of Products, May 2003.
Product Information Sheet, Mackanate DC-50, Mcintyre Group Ltd., 1 page.
Product Information Sheet, Dow Corning 2501, Cosmetic Wax, 4 sheets.
Product Description, GE Silicones, SF1202, Dec. 22, 2004,6 sheets.
Product Description, GE Silicones, SF1388, Dec. 22, 2004, 2 sheets.
Product Information, DOW Corning, Sylgard 309 Silicone Surfactant, 3 sheets.
Product Description, GE Advance Materials Silicones, SF1388, Jan. 5, 2005,2 sheets.
Office Action dated Mar. 28, 2012 in U.S. Appl. No. 13/095,698.
Amendment dated Jun. 28, 2012 in U.S. Appl. No. 13/095,696.
US 7,754,762, Jul. 2010, Wegner et al. (withdrawn).
U.S. Office Action mailed Jun. 28, 2010 for U.S. Appl. No. 11/438,664.
Preliminary Amendment dated Jul. 24, 2008 in U.S. Appl. No. 12/179,410 (Publication No. 2008-0293825 published on Nov. 27, 2008).
International Search Report for International Application No. PCT/US2006/021904 mailed Oct. 24, 2006.
Notice of Allowance dated Jul. 20, 2010 for U.S. Appl. No. 12/179,382.
Supplemental Response and Amendment filed on Aug. 13, 2010 for U.S. Appl. No. 12/032,083.
Request for Continued Examination filed on Jul. 6, 2010 for U.S. Appl. No. 12/032,083.
Advisory Action Communication mailed Jun. 29, 2010 for U.S. Appl. No. 12/032,083.
U.S. Office Action mailed Aug. 3, 2010 for U.S. Appl. No. 11/075,287.
U.S. Office Action mailed Aug. 3, 2010 for U.S. Appl. No. 11/369,381.
Response and Amendment after Final Office Action filed on Jun. 2, 2010 for U.S. Appl. No. 12/032,083.
Communication of Notices of Opposition to a European Patent (EP 1 811 013) filed by Ecolab, Inc., 3M Innovative Properties Company and DEB Worldwide Healthcare Inc. against Gojo Industries dated Jun. 16, 2010.
Affidavit of Bruce Michael Koivisto signed and dated on May 17, 2010.
“Dow Corning® 190 Fluid” product information. Dow Corning, Midland, MI Feb. 24, 2010, Ref. No. 22-1616E-01 (3 pages).
Printout of http://www.rexamairspray.com/products-foampump.php Oct. 5, 2010 (2 pages).
Notice of Opposition to a European Patent (EP 1 811 013) filed by 3M Innovative Properties Company against Gojo Industries dated May 12, 2010.
Notice of Opposition to a European Patent (EP 1 811 013) filed by Ecolab, Inc. against Gojo Industries dated May 6, 2010.
Affidavit of Caroline Fellows dated May 10, 2010.
Technical Information for LUVIQUAT® PQ 11, BASF, May 1997 (3 pages).
Response and Amendment dated Apr. 7, 2010 for U.S. Appl. No. 11/438,664.
Declaration of Amanda J. Copeland dated Apr. 7, 2010.
Notice of Opposition to a European Patent (EP 1 811 013) filed by DEB Worldwide Healthcare Inc. against Gojo Industries dated May 12, 2010.
Complaint for Correction of Inventorship of Patent; Case 1:10-CV-00266-GMS, filed Apr. 2, 2010 in the United States District Court for the District of Delaware.
Worldwide Healthcare, Inc., “Material Safety Data Sheet”, Jan. 24, 2007.
U.S. Office Action mailed Apr. 30, 2007 for U.S. Appl. No. 11/799,042.
Office Action from the Chinese Patent Office (translation) dated Aug. 25, 2010 for Application No. 200680015637.1.
Response to Canadian Patent Office dated May 26, 2010 for Application No. 2,540,085.
Amendments submitted to EPO dated May 26, 2010 for Application No. 06705273.8.
Response to the Australian Patent Office dated Mar. 23, 2010 for Application No. 2004275900.
Response to the Canadian Patent Office dated Mar. 18, 2010 for Application No. 2,595,025.
Amendment filed with the New Zealand Patent Office dated Dec. 21, 2009 for Application No. 561741.
Response to the Canadian Patent Office dated Dec. 22, 2009 for Application No. 2,540,085.
Response to the New Zealand Patent Office dated Nov. 19, 2009 for Application No. 561741.
Response to Canadian Patent Office dated Nov. 10, 2009 for Application No. 2,595,025.
Office Action from the Ukranian Patent Office (translation) dated Jul. 30, 2009 for Application No. a 200710192/M.
Office Action dated May 10, 2011 in U.S. Appl. No. 12/878,786.
Office Action dated May 10, 2011 in U.S. Appl. No. 12/878,793.
Office Action dated Apr. 29, 2011 in U.S. Appl. No. 12/552,126.
Office Action dated Mar. 25, 2011 in U.S. Appl. No. 12/624,073.
Communication dated Mar. 9, 2011 in the opposition to European Patent 1 811 013.
Amendment dated Feb. 23, 2011 in U.S. Appl. No. 12/179,410.
Amendment and Response dated Feb. 18, 2011 in U.S. Appl. No. 12/878,786.
Amendment and Response dated Feb. 18, 2011 in U.S. Appl. No. 12/878,793.
Amendment and Response dated Feb. 18, 2011 in U.S. Appl. No. 12/552,126.
Office Action dated May 24, 2011 in U.S. Appl. No. 12/179,410.
Office Action dated Feb. 15, 2011 in U.S. Appl. No. 11/806,767.
Request for Certificate of Correction for US Patent No. 7,651,990 (U.S. Appl. No. 11/151,563) mailed Jun. 20, 2011.
Communication dated Jun. 20, 2011 in European Application No. 06 772 279.3.
Communication dated Apr. 26, 2010 in European Application No. 04786634.8.
Response to Office Action and Amendments dated Oct. 7, 2010 for Canadian Application No. 2,595,025.
Communication dated Jan. 1, 2010 in European Application No. 04786634.8.
Office Action dated Apr. 13, 2011 in U.S. Appl. No. 11/520,819.
Appellant's Brief on Appeal dated Jun. 13, 2011 in U.S. Appl. No. 11/075,287.
Appellant's Brief on Appeal dated Jun. 14, 2011 in U.S. Appl. No. 11/369,381.
Reply from Australian Patent Office dated Jun. 1, 2010 for Application No. 2005318384.
EP 1 233 749 issued Nov. 21, 2000, Biering, Holger (English-language claims).
Brochure, Polyox Water-Soluble Resins, Nordmann, Rassmann GmbH, Hamburg, Germany, Dec. 16, 2004 or earlier.
DE 10 2004 062 775 A1 filed on Dec. 21, 2004 (Certified translation).
The Dow Chemical Company Sales Specification for Specified Material 00029789-S: Ethocel Standard 100 Industrial Ethylcellulose printed Sep. 11, 2001.
The Dow Chemical Company Sales Specification for Specified Material 00116267-S: Ethocel Standard 300 Industrial Ethylcellulose printed Sep. 11, 2001.
The Dow Chemical Company Sales Specification for Specified Material 00129064-S: Polyox™ WSR N10 Amerchol printed Feb. 28, 2003.
The Dow Chemical Company Sales Specification for Specified Material 00129042-S: Polyox™ WSR N3000 Amerchol printed Feb. 18, 2003.
The Dow Chemical Company Sales Specification for Specified Material 00126141-S: Polyox™ WSR N60K printed Feb. 18, 2003.
Toxicological Test Results From Literature, Final Report of the Safety Assigment of Dimethicone Copolyol, Journal of American College of Toxicology, vol. 1, No. 4, 1982 dated Jul. 30, 2001 (Goldschmidt Personal Care—Degussa).
Floyd, et al., “Performance-Drive: New Silicone Copolymers,” Global Cosmetics Industry, Sep. 2000.
Degussa Creating Essentials, Product Data Record for ABIL® B 8832 (3 pages) dated Jul. 14, 2004, Mat. No. 202534, Edition 1.
Degussa, Product Specification for ABIL® B 8832 (1 page) dated Aug. 26, 2004 (printed Sep. 6, 2004), Spec. No. ST-980121.
Degussa, Summary of toxicological and ecotoxicological data for ABIL® B 8832 (3 pages) dated May 17, 2002.
Dow PowerPoint Presentation entitled: “METHOCEL Applications in Personal Cleansing, a Superior Sensory Experience”, Dec. 9, 2004 or earlier.
Dow PowerPoint Presentation entitled: ETHOCEL General Properties (15 pages, Dec. 9, 2004 or earlier).
Response to the Chinese Patent Office dated May 18, 2011 in Application No. 200680015637.1.
Office Action dated Apr. 11, 2011 in U.S. Appl. No. 11/806,767.
Office Action dated Apr. 15, 2011 in U.S. Appl. No. 10/591,243.
Office Action dated May 26, 2011 in US Application No. 12/659,063.
Deb Worldwide Healthcare Inc. and Deb Canadian Hygiene Inc., Plaintiffs, and Ecolab Co., Defendant, Court File No. T-379-11, Deb's Statement of Claim dated Mar. 7, 2011.
Deb Worldwide Healthcare Inc. and Deb Canadian Hygiene Inc., Plaintiffs, and Ecolab Co., Defendant, Court File No. T-379-11, Ecolab's Statement of Defense and Counterclaim dated Jun. 3, 2011.
Deb Worldwide Healthcare Inc. and Deb Canadian Hygiene Inc., Plaintiffs, and Ecolab Co., Defendant, Court File No. T-379-11, Deb's Reply and Defence to Counterclaim dated Jul. 11, 2011.
Deb Worldwide Healthcare Inc. and Deb Canadian Hygiene Inc., Plaintiffs, and Ecolab Co., Defendant, Court File No. T-379-11, Ecolab's Reply to Defence to Counter dated Jul. 11, 2011.
Deb Worldwide Healthcare Inc., Applicants and Kimberly-Clark Australia Pty. Ltd., No. VID 295 of 2011, Statement of Cross-Claim dated Aug. 2, 2011 (Federal Court of Australia, District Victoria, General Division).
Deb Worldwide Healthcare Inc., Applicants and Kimberly-Clark Australia Pty. Ltd., No. VID 295 of 2011, Notice of Filing, Statement of Claim and Certificate of Legal Representation dated Apr. 18, 2011 (Federal Court of Australia, District Victoria, General Division).
Amendment in U.S. Appl. No. 12/624,073, filed Jul. 29, 2011.
Amendment in U.S. Appl. No. 12/787,624, filed Jul. 19, 2011.
Notice of Allowance in U.S. Appl. No. 12/787,624 mailed on Aug. 5, 2011.
Communication in European Application No. 06 772 279.3-2108 dated Jun. 20, 2011.
Office Action dated May 13, 2011 in U.S. Appl. No. 12/787,624.
Acknowledgement of documents and Summons to Attend Oral Proceedings dated Sep. 9, 2011 for EP Patent No. 18110130.
Translation of Communication from the European Patent Office in Veeger et al, EP 05 825 981.3 (counterpart to U.S. Appl. No. 12/624,073).
Office Action dated Oct. 26, 2011 in U.S. Appl. No. 11/075,287, filed Mar. 8, 2005.
Appellant's Brief on Appeal dated Oct. 31, 2011 in U.S. Appl. No. 12/179,410, filed Jul. 24, 2008.
Office Communication from the US Patent Office dated Oct. 21, 2011 in U.S. Appl. No. 11/806,767, filed Jun. 4, 2007.
Office Communication from the US Patent Office dated Oct. 21, 2011 in U.S. Appl. No. 11/520,819, filed Sep. 14, 2006.
Translation of International Preliminary Report on Patentability from International Application No. PCT/EP2005/013742 dated Sep. 20, 2007.
Wang, et al., “Direct Force Measurement of Comb Silicone Surfactants in Alcoholic Media by Atomic Force Microscopy”, Journal of Colloid and Interface Science 242, 337-345 (2001).
Prieto et al., “Structure-function relationships of dimethicone copolyol”, j. Cosmet. Sci., 51, 91-101 (Mar./Apr. 2000).
Japanese Patent Application No. 2008-500017, Drafting Date: May 26, 2011, Mailing Date: May 31, 2011 “Notice of Reasons for Rejection”.
Japanese Publication No. 06-327750 published Nov. 29, 1994, “English Abstract of Reference 2”.
Gojo submission of Feb. 15, 2012 in the Opposition to European Patent No. 1 811 013 B1 (including Auxiliary Claim Sets).
Declaration of Evan Hillman and Annexes submitted in the Opposition to European Patent No. 1 811 013 B1.
Declaration of Amanda J. Copeland and Annexes submitted in the Opposition to European Patent No. 1 811 013 B1.
Submission by Deb Worldwide Healthcare, Inc. in the Opposition to European Patent No. 1 811 013 B1 (including Exhibit E).
Reply dated Dec. 30, 2011 to the European Patent Office Communication dated Jun. 20, 2011 by 3M regarding 06 77 2279.3, including an Amended set of claims (marked-up and clean copy) and Acknowledgment of receipt.
Examiner's Answer mailed Feb. 9, 2012 to Appeal Brief filed Jul. 18, 2011 for U.S. Appl. No. 11/369,381.
Request for Oral Hearing filed Feb. 8, 2012 in U.S. Appl. No. 12/179,410.
Amendment and Response dated Feb. 12, 2007 in U.S. Appl. No. 11/340,778.
Amendment and Response dated Sep. 11, 2008 in U.S. Appl. No. 11/340,778.
Preliminary Amendment dated Aug. 22, 2006 for U.S. Appl. No. 11/507,626.
Notice of Reasons for Rejection for Canadian Patent Application No. 2008-500017 mailed Jan. 17, 2012.
Mason Chemical Company, brochure for Masurf FS-115/FS-130 100504.
Decision in the Opposition to European Patent No. 1 811 013 B1 (including Auxiliary Requests) dated Apr. 10, 2012.
Notice of Reasons for Rejection for Canadian Patent Application No. 2008-500017 mailed May 31, 2011.
http://www.ipc.bas.bg/book1.htm (webpage regarding Exerowa et al., Foam and Foam Films; Theory, Experiment, Application, published by Elsevier (Dec. 1997)).
Amendment and Response filed Oct. 31, 2007 in U.S. Appl. No. 10/400,597.
Amendment and Response and Request for Reconsideration filed Jun. 2, 2008 in U.S. Appl. No. 11/312,559.
Interview Summary mailed Apr. 23, 2008 in U.S. Appl. No. 11/312,559.
Non-final rejection mailed Feb. 20, 2008 in U.S. Appl. No. 11/312,559.
Amendment and Response filed Jun. 22, 2007 in U.S. Appl. No. 11/312,559.
Non-final Rej˜ction mailed Feb. 22, 2007 in U.S. Appl. No. 11/312,559.
S.C. Crema et al., “Foaming of Anhydrous Methanol for Well Stimulation”, Society of Petroleum Engineers, SPE 13565, (1985).
Paul A. Sanders, “Aqueous Alcohol Aerosol Foams”, Drug & Cosmetic Industry, XP000960450, vol. 99, No. 2, 1966, pp. 56, 58, 60,142,143,146-154.
Amendment and Response filed Apr. 18, 2008 in U.S. Appl. No. 11/561,563.
Non-final Rejection mailed Jan. 29, 2008 in U.S. Appl. No. 11/561,563.
Amendment and Response and RCE filed Nov. 13, 2007 in U.S. Appl. No. 11/561,563.
Advisory action mailed Oct. 1, 2007 in U.S. Appl. No. 11/561,563.
Amendment and Response filed Sep. 11, 2007 in U.S. Appl. No. 11/561,563.
Final Rejection mailed Jun. 11, 2007 in U.S. Appl. No. 11/561,563.
Amendment and Response filed Mar. 19, 2007 in U.S. Appl. No. 11/561,563.
Non-final rejection mailed Oct. 19, 2006 in U.S. Appl. No. 11/561,563.
Amendment and Response filed Oct. 31, 2007 in U.S. Appl. No. 11/340,778.
Non-Final Rejection mailed Jan. 3, 2006 in U.S. Appl. No. 10/992,494.
Amendment and Response filed Jul. 3, 2006 in U.S. Appl. No. 10/992,494.
Non-final Rejection mailed Sep. 26, 2006 in U.S. Appl. No. 10/992,494.
Amendment and Response and RCE filed Mar. 26, 2007 in U.S. Appl. No. 10/992,494.
Non-final rejection mailed Apr. 9, 2007 in U.S. Appl. No. 10/992,494.
Final Rejection mailed May 7, 2007 in U.S. Appl. No. 11/048,031.
Non-final rejection mailed May 11, 2006 in U.S. Appl. No. 11/048,031.
Amendment and Response filed Aug. 11, 2006 in U.S. Appl. No. 11/048,031.
Final Rejection mailed Feb. 11, 2008 in U.S. Appl. No. 11/048,040.
Amendment and Response filed Nov. 29, 2007 in U.S. Appl. No. 11/048,040.
Notice of Non-Compliant Amendment mailed Oct. 29, 2007 in U.S. Appl. No. 11/048,040.
Amendment and Response filed Oct. 16, 2007 in U.S. Appl. No. 11/048,040.
Non-final Rejection mailed Jul. 16, 2007 in U.S. Appl. No. 11/048,040.
Amendment and Response filed Jun. 11, 2007 in U.S. Appl. No. 11/048,040.
Notice of Non-Compliant Amendment mailed Jun. 1, 2007 in U.S. Appl. No. 11/048,040.
Amendment and Response and RCE filed May 21, 2007 in U.S. Appl. No. 11/048,040.
Final Rejection mailed Nov. 20, 2006 in U.S. Appl. No. 11/048,040.
Amendment and Response filed Sep. 5, 2006 in U.S. Appl. No. 11/048,040.
Non-final Rejection mailed Jul. 18, 2006 in U.S. Appl. No. 11/048,040.
Final Rejection mailed Jul. 9, 2008 in U.S. Appl. No. 11/561,563.
Final rejection mailed Sep. 19, 2008 in U.S. Appl. No. 11/312,559.
Complaint. 3M Company and 3M Innovative Properties Company v. Gojo Industries, Inc. United States District Court for the District of Minnesota. Case No. 0:10cv04065. Filed Sep. 28, 2010.
Response to Opposition (European Patent Application No. 06256249.1/European Patent No. EP 1 811 013) as filed by Ecolab, Inc. by Gojo Industries, Inc. dated Dec. 20, 2010.
U.S. Office Action mailed Jan. 19, 2011 for U.S. Appl. No. 11/075,287, filed Mar. 8, 2005.
U.S. Office Action mailed Jan. 19, 2011 for U.S. Appl. No. 11/369,381, filed Mar. 7, 2006.
Protest Under 37 C.F.R. 1.291 electronically filed on Dec. 20, 2010 for U.S. Appl. No. 12/878,786, filed Sep. 9, 2010.
U.S. Office Action mailed Dec. 13, 2010 for U.S. Appl. No. 12/878,786, filed Sep. 9, 2010.
Protest Under 37 C.F.R. 1.291 electronically filed on Dec. 20, 2010 for U.S. Appl. No. 12/878,793, filed Sep. 9, 2010.
U.S. Office Action mailed Dec. 10, 2010 for U.S. Appl. No. 12/878,793, filed Sep. 9, 2010.
U.S. Office Action mailed Dec. 13, 2010 for U.S. Appl. No. 12/552,126, filed Sep. 1, 2009.
Amendment electronically filed on Nov. 2, 2010 for U.S. Appl. No. 11/075,287, filed Mar. 8, 2005.
Response in European Patent Application No. 08250626.2 in the name of Gojo Industries, Inc. dated Dec. 12, 2009.
Supplemental Response and Amendment electronically filed on Aug. 13, 2010 for U.S. Appl. No. 12/032,083, filed Feb. 15, 2008.
U.S. Office Action mailed Aug. 3, 2010 for U.S. Appl. No. 11/075,287, filed Mar. 8, 2005.
U.S. Office Action mailed Aug. 3, 2010 for U.S. Appl. No. 11/369,381, filed Mar. 7, 2005.
Information Disclosure Statement electronically filed on Nov. 19, 2010 for U.S. Appl. No. 12/624,073, filed Nov. 23, 2009.
U.S. Office Action mailed Nov. 23, 2010 for U.S. Appl. No. 12/179,410, filed Jul. 24, 2008.
Myers, D., “Surfactant Science and Technology”, selected pages, 1992, 2nd ed., VCH Publishers, Inc. New York, NY.
Related Publications (1)
Number Date Country
20120232161 A1 Sep 2012 US
Provisional Applications (2)
Number Date Country
60591601 Jul 2004 US
60506172 Sep 2003 US
Divisions (1)
Number Date Country
Parent 11507626 Aug 2006 US
Child 12659063 US
Continuations (2)
Number Date Country
Parent 12659063 Feb 2010 US
Child 13479630 US
Parent 10952474 Sep 2004 US
Child 11507626 US