US 3832459 A
A three-phase aerosol spray disinfectant-deodorant combining the simultaneous use of a complexing polymer which has a detoxifying effect with respect to a phenolic-type germicidal agent and a surface anesthetic which desensitizes the mucous membrane when the spray composition is either inhaled or deposited on the skin.
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United States Patent [191 Berkeley [451 Aug. 27, 1974 1 SPRAY DISINFECTANT-DEODORANT  Inventor: Bernard Berkeley, Evanston, Ill.
 Assignee: Hysan Corporation, Chicago, Ill.
 Filed: Mar. 18, 1971  Appl. No.: 125,876
 US. Cl. 424/45  Int. Cl A611 9/00  Field of Search 424/45, 76, 47
 References Cited UNITED STATES PATENTS 2,801,201 7/1957 Kipnis 424/45 3,159,535 12/1964 Sesso et a1. 424/76 X 3,287,214 11/1966 Taylor et a1. 424/45 3,303,091 2/1967 Mailander et a1 424/76 X 3,431,208 3/1969 Bailey 424/76 X FOREIGN PATENTS OR APPLICATIONS 648,088 9/1964 Belgium 424/45 Primary Examiner--Albert T. Meyers Assistant Examiner-Dale R. Ore
 ABSTRACT A three-phase aerosol spray disinfectant-deodorant combining the simultaneous use of a complexing polymer which has a detoxifying effect with respect to a phenolic-type germicidal agent and a surface anesthetic which desensitizes the mucous membrane when the spray composition is either inhaled or deposited on the skin.
11 Claims, No Drawings SPRAY DISINFECTANT -DEODORANT The present invention relates to a three-phase aerosol spray disinfectant-deodorant utilizing skin desensitizers to minimize discomfort to nose and throat from the atomized antimicrobial agent.
The application of phenolic-type disinfectants in spray form has become of major importance because of the accepted broad spectrum activity of these disinfectants against a wide variety of pathogenic microorganisms, in combination with the ease of application and convenience of use. Due to the increased use and manner of application of phenolic-type disinfectants as an air spray deodorant, there have been numerous complaints of nose and throat sensitization and discomfort. Furthermore, the discomfort has been directly attributable to the presence in the air of atomized particles of phenolic-type antimicrobial agents which upon inhalation subsequently come into contact with the sensitive membranes of the nose and throat. The degree of discomfort varies with the sensitivity of the individual and the concentration in the air of the spray particles.
Although low concentrations of irritating agents in the spray are more tolerable, overuse of the spray as an air treatment or increased frequency of use can easily raise the concentration of the irritants in the air to an intolerable level.
Numerous methods and formulations have been considered to alleviate the discomfort condition including control of the particle size of the spray, use of nondrying vehicles, restriction of the spray to surface disinfection, control of the quantity of the disinfectant in the air by use of low solution concentrations and directions guarding against misuse. These prior art methods have inherent drawbacks. One method in the prior art is to use a coarse spray which has a drawback in that the product does not remain airborne long enough to be an effective air deodorizer. Another method and formulation is to use non-drying vehicles, such as the glycols, the polyhydric alcohols, the polyglycols and related homologues. The drawback to this composition is that the residual product remains substantially moist or wet when applied as a surface disinfectant. The restrictive use of the disinfectant product as a surface disinfection not only reduces its market acceptability, but technically, this method provides a reasonable probability that dry particles will become airborne by the movement of air currents in a well ventilated area.
Heretofore, various types of disinfectant aerosol compositions have been proposed which fundamentally have been identified as two-phase systems consisting of 1) a homogeneous liquid phase and (2) a vapor phase consisting substantially of propellant.
The prior art alludes to the criterion that a critical property of the gerrnicide depends on maintaining a two-phase system throughout the useful life of the germicide. This interpretation develops from the erroneous conclusion that the two-phase system is the only method for obtaining a desirable balance of spray particle size. The prior art did not anticipate the continuing development of sophisticated diverse valve constructions which would permit one skilled in the art to select Agriculture, wherein a fine mist-like spray may have approximately percent of the particles being less than 30 microns in diameter and all particles being less than 50 microns compared to the macroparticle sizes developed by a surface spray.
In order to achieve various types of two-phase systerns as disclosed in US Pat. No. 2,742,321 to Mina et a1 and US. Pat. No. 3,287,2l4 to Taylor et al, it was necessary to limit the water content of the concentrate and to use liquefied gas propellants such as halocarbon compositions that would be soluble in liquid form with the concentrate.
As a result of the probable alleviation of certain of these restrictions, it becomes feasible to formulate a three-phase low-cost aerosol germicidal-deodorant product with higher concentrations of water and lower cost hydrocarbon propellants.
A further advantage relating to the utilization of hydrocarbon and related propellants such as isobutane, propane, n-butane and dimethyl ether concerns the non-reactivity of these propellants with water, the inertness of the hydrocarbon and related propellants with respect to influence on pH and possible variance in antibacterial activity.
In the development of a broad spectrum aerosol-type spray disinfectant-deodorant, the use of cationic as well as anionic germicidal agents have been considered. It soon become apparent that the anionic types in the form of alkyl phenols were better suited in the present invention principally because of the ineffectiveness of the substituted quaternary-type compounds against tubercle bacillus. When one does not wish to control the tubercle bacillus, then the use of the quaternary compounds may be considered.
The following anionic-type alkyl phenol antibacterial disinfectants, singularly or in combination, may be used in the present invention, such as: orthophenylphenol; paratertiaryamylphenol; paratertiarybutylphenol; 4- chloro-2-phenylphenol; 6-chloro-2-phenylphenol; 4-chloro-2-cyclopentylphenol; 4-chloro-3,5-xylenol; o-benzyl-p-chlorophenol; and other homologues of the alkyl and chloroalkyl phenols.
Certain cationic antimicrobial compounds have been utilized; and these compounds generally do not yield a broad spectrum activity. These non-preferred cationic compounds may be generally identified as the quaternary ammonium salts, which are types of organic nitrogen compounds, in which the molecular structure includes a central nitrogen atom joined to four organic groups as well as to an acid radical of some sort. Octadecyl dimethyl benzyl ammonium chloride, hexamethonium chloride, substituted derivatives of imidazoline alkanoic quaternary ammonium hydroxide and quaternary hydroxy cycloimidinic acid metal alcoholates are examples of types of quaternary ammonium salts.
Should a broad spectrum quaternary-type compound be developed in the future which is deemed to be tuberculocidal, it is conceivable that the teachings herein disclosed could be applied to such a broad spectrum quatemary-based aerosol disinfectant-deodorant.
The choice of various liquefied, normally gaseous hydrocarbon and related propellants depends upon certain physical chemical parameters and the particular propellant should exhibit the following characteristics:
a. essentially the propellant should be insoluble in the concentrate;
b. the density of the propellant should be less than the concentrate; I
c. the propellant should be capable of generating internal pressure of about 30 p.s.i.g. to about 70 p.s.i.g. in an ambient temperature of about 70F; and
d. the propellant should be substantially non-reactive to the concentrate.
The following are examples of suitable propellants which may be used singularly or in combination: isobutane, n-butane, propane and dimethyl ether.
Various types of phenolic antimicrobial compounds, primarily the alkyl phenols, are known to be effective in surface disinfection and have been evaluated with excellent results in the adaption of three-phase systems which are suitable as aerosol sprays. In general, these systems comprise the following:
a. the gaseous phase consisting essentially of the propellant;
b. the first liquid phase consisting essentially of liquefied, normally gaseous propellant or a combination of propellants having a density of less than approximately 0.8. The total weight of propellant including both gaseous and liquid phases is in the range from about 5-50 percent by weight with a preferred range from about -35 percent by weight of the total composition; and
c. the second liquid, hereafter referred to as the concentrate, consisting essentially of an alcohol-water vehicle having dissolved therein all other ingredients of the composition. The amount of concentrate is defined in the range between 50-95 percent by weight with a preferred range from about 6585 percent by weight of the total composition. The concentration of water varies proportionately with the following characteristics:
1. a minimum of 7.5 percent water of the concentrate is required for germicidal activity; and
2. the maximum amount of water depends on the solution requirement to maintain a homogeneous concentrate. It has been found experimentally that water may be used up to about 60 percent by weight of the concentrate, although dispersion and spray characteristics are impaired at the upper end.
Although there were many acceptable compositions as regards to germicidal activity, these germicidal compounds, when used as space sprays forming finely atomized mists or clouds, caused discomfort of the nose and throat by virtue of their irritating properties. It was found that the irritating effect on the nose and throat could be substantially minimized when the alkyl phenol antibacterial agents, singularly or in combination thereof, are codissolved in the concentrate with a material capable of acting as a surface anesthetic and certain types of specific desensitizers exhibiting a complexing polymeric property in order to form a molecular adduct. The amount of the alkyl phenol agents will be in the range from about 0.01 to 3.0 percent by weight of the concentrate composition with a preferred range from about 0.1 to 3 percent by weight of the concentrate.
Certain topical surface anesthetics have been found to be acceptable in reducing nose and throat discomfort, and these compositions are: ethyl aminobenzoate (known as benzocaine), lidocaine, xylocaine, pramoxine hydrochloride and other similar types of surface anesthetics. While the amount of surface anesthetic will vary depending on the type and concentration of the specific type of alkyl phenol germicidal agent used, we have found that the amount of surface anesthetic will vary and be proportionate within the general range of about 0.0025 to 6.0 percent by weight of concentrate, although the preferred range of the surface anesthetic is from about 0.025 to 2 percent by weight of the concentrate.
The simultaneous use of a complexing polymer capable of forming a molecular adduct with germicidal agents, such as the alkyl phenols, provides a synergistic advantage in reducing nose and throat irritation. Consequently, the amount of surface anesthetic required to overcome nose and throat irritation is considerably less than would be the case if the surface anesthetic were singularly compounded.
Various types and examples of these complexing polymers which form molecular adducts are:
l. polyvinylpyrrolidone having molecular weights in the range from about 'l0,000 to 360,000 and consisting of repetitive vinylpyrrolidone units;
2. alkylated polyvinylpyrrolidones in which the alkyl group ranges from C to C and is attached to the pyrrolidone moiety;
3. copolymers of vinylpyrrolidone and vinyl acetate in which the ratio of vinylpyrrolidone and vinyl acetate varies proportionately from /30 to 30/70; and
4. copolymers of vinylpyrrolidone and maleic anhydride which are partially esterified with alkyl alcohols.
While the amount of the aforesaid complexing polymers may vary depending on the type and concentration of phenolic germicidal agent used, it has been found that the amount of the complexing polymer present in the concentrate will be in the range from about 0.0025 to 5.5 percent by weight with a preferred range composition from about 0.025 to 1.75 percent by weight of the concentrate.
The presence of water in the concentrate may sometimes makes it desirable to incorporate various types of corrosion inhibitors in the end product to increase shelf life. As a further precaution against corrosion, coated or plastic lined aerosol cans may be used and the valve components can be selected for their resistance to corrosion. Examples of corrosion inhibitors are the borates, silicates, benzoates, phosphates and nitrites.
An important commercial application of the products of the present invention relates to its use as an air deodorizer. A deodorant can be one which functions by desensitizing the nasal passages to odors, by masking the odorous material, by reacting with odor-causing material to form non-odorous compounds or by destroying microorganisms that generate malodors. Typical of such selective types of deodorants are the organic hydroperoxides, the acrylic esters and the quaternary morpholinium alkyl sulfates in combination with masking agents, such as perfumes and essential oils. However, these selective types of deodorants do not achieve the required germicidal-deodorant properties.
In order to indicate even more fully the nature of the present invention, the following specific examples are set forth. It will be understood that these examples are presented for illustrative purposes only and they are not intended to limit the scope of the invention in any manner. The percentage amounts are identified by weight unless otherwise indicated.
In accordance with acceptable manufacturing practices, the concentrate is prepared in clean non-reactive 5 kettles equipped with explosion-proof mixers.
In preparing the concentrate, the alkyl phenol, such as Orthophenylphenol; the essential oil-s, the ethyl aminobenzoate and the polyvinylpyrrolidone are dissolved in the ethyl alcohol after which distilled water and cor- 1O rosion inhibitor are added to form the concentrate. The concentrate is subsequently introduced into the aerosol containers through filler bowls which control precisely the quantity of product added. The propellant can be added to the container by any of the currently acceptable filling methods, such as cold filling, pressure filling and under-the-cap filling. In all cases, precautions must be taken to insure an adequate crimping of the valve assembly including the dip tube, removal of overhead air by purging or evacuation and precise control of the quantity of propellant added.
EXAMPLE 1 I Weight Percentage Ethyl Alcohol 54.2 Orthophenylphenol 0.2 Essential Oils 0.3 Ethyl Aminobenzoate 0.1 Polyvinylpyrrolidone 0.05 Corrosion lnhibitor 0.3 Distilled Water 24.85 lsobutane 18.0 Propane 2 .0
EXAMPLE 11 Weight Percentage Ethyl Alcohol 68.0 Orthophenylphenol 0.1 O-Benzyl-p-chlorophenol 0. l Polyvinylpyrrolidone 0.2 Essential Oils 0.3 Lidocaine 0.4 Distilled Water 10.6 Corrosion Inhibitor 0.3 lsobutane 18.0 Propane 2 .0
EXAMPLE Ill Weight Percentage Ethyl Alcohol 50.0 Orthophenylphenol 0.08 4-Chloro-3,S-xylenol 0.02 Polyvinylpyrrolidone 0.1 Essential Oils 0.3 Pramoxine Hydrochloride 0.1 Distilled Water 29.1 Corrosion Inhibitor 0.3 lsobutane 1223.0 Pro ane EXAMPLE IV Weight Percentage Ethyl Alcohol 86.37 Orthophenylphenol 0. 1
EXAMPLE IV-Continued Weight Percentage Paratertiaryamylphenol Polyvinylpyrrolidone Ethyl Aminobenzoate Corrosion Inhibitor Essential Oils Distilled Water lsobutanc Propane EXAh [PLE V Weight Percentage Ethyl Alcohol Orthophenylphenol Polyvinylpyrrolidone Ethyl Aminobenzoate Corrosion Inhibitor Essential Oils Distilled Water lsobutane Propane 5 wio QQQ Q PP O ounopcnoww Example Vl Weight Percentage Ethyl Alcohol Paratertiarybutylphenol Polyvinylpyrrolidone Ethyl Aminobenzoate Corrosion Inhibitor Essential Oils Distilled Water lsobutane Propane EXAMPLE VII Weight Percentage With reference to Example IV, it is noted that the total propellant concentration is somewhat low, thus creating a coarse droplet spray which is not desirable. This specific example of ingredients is submitted to illustrate that a low concentration of propellant may be used in a three-phase system; however, a valve assembly utilizing a vapor tap may be used.
The relationship of the concentration of propellant to the water content is an additional consideration. In this regard, it should be noted that the ratio of propellant to water in the composition of the invention can range from about 0.111 to about 1.521, with a prefered ratio of propellant to water of about 1:]. An additional advantageous characteristic relates to the use of moderate pressures that are generated in the containers which are, at about F not in excess of 70 p.s.i.g. and usually in the range from about 30 to 60 p.s.i.g. Preferred pressures may be utilized in the range from about 50 p.s.i.g. to about 60 p.s.i,g. High vapor pressures in containers are not as acceptable for shipping the aerosol products in commerce.
With reference to Example VII, the substituted use of a quaternary-type compound, such as alkyldimethylbenz yl-ammonium chloride, for an alkyl phenol may be noted; however, the composition is deemed not to be effective against the tubercle bacillus.
As indicated in the preceding examples, the addition of various adjuvant materials to aerosol compositions, such as the masking agents and essential oils, will impart further desired qualities to the dodorizing effect, e. g., pine oil, orange oil, lemon oil, peppermint oil, synthetic musks and the like when added to the present compositions in minor proportions.
The testing of the compositions with respect to their respective disinfectant and air deodorizing properties was performed in accordance with accepted laboratory test standards, and the respective compositions were found to be satisfactory without imparting the characteristic mucous membrane irritation or sensitization.
The present three-phase aerosol spray disinfectantdeodorant system compositions utilizing the hydrocarbon and related propellants are far superior in their non-corrosion characteristics as compared to the chlorofluoroalkane propellant single-phase system which tends to hydrolyze in water as characterized in the compositions set forth in the aforementioned Taylor et al patent. The United States patent to Taylor et al, referenced above, suggested that a multiple-phase system lacks uniformity in the dispersion over the entire contents of the container; however, the present invention utilizing the more sophisticated valve configurations achieves acceptable uniformity. Furthermore, the compositions of the present invention utilize the lower cost hydrocarbon and related propellants which is a decided economic advantage; and these compositions reduce the flammability of the end product due to the use of a lesser amount of alcohol and an increased content of water.
The intrinsic chemical concentrate composition of the present invention relates to the simultaneous use of a complexing polymer which has a detoxifying effect with respect to the alkyl phenol germicidal agent and further which, in combination with a synergistic surface anesthetic, desensitizes the mucous membrane. The collateral ingredients, when formulated in the concentrate composition, afford a unique aerosol spray disinfectant-deodorant composition when incorporated in a three-phase system. Furthermore, the use of the complexing polymer reduces the required amount of topical surface anesthetic material. The three-phase system comprises the heavier density alcohol-water vehicle concentrate composition, the liquid hydrocarbon and related propellant layer, and the vapor phase of the aforementioned hydrocarbon propellant. It shall be noted that ethyl alcohol is preferred; however, other related aliphatic alcohols may be used, such as propanol and isopropanol.
While this invention has been described and exemplified in terms of its preferred embodiments, those skilled in the art will appreciate that variations can be made without departing from the spirit and scope of the invention.
It is claimed:
l. A three-phase pressurized germicidal deodorant composition comprising a gaseous propellant phase, a liquid propellant phase and an alcohol-water concentrate composition phase comprising:
a. an anionic germicidal compound, said anionic ger-.
a co-polymer of vinylpyrrolidone and vinyl acetate wherein the weight ratio of vinylpyrrolidone to vinyl acetate varies from :30 to 30:70 and mixtures thereof;
c. a topical surface anesthetic selected from the group consisting of benzocaine, lidocaine xylocaine, pramoxine hydrochloride and mixtures thereof, and
d. an alcohol and water solution, said alcohol being selected from the group consisting of ethyl alcohol, propanol and isopropanol, said germicidal agent being present in said concentrate at a level of from about 0.01 percent to about 3.0 percent by weight of the concentrate, said complexing polymer being present in said concentrate at a level of from about .0025 percent to about 5.5 percent by weight of the concentrate, said topical anesthetic being present at a level of from about .0025 percent to about 6 percent by weight of the concentrate, said water i being present at a level of from about 7.5 percent to about 60 percent by weight of the concentrate, said alcohol comprising the balance of said concentrate, said concentrate comprising from 50 percent to percent by weight of said deodorant composition, and said propellant comprising from about 5 percent to about 50 percent by weight of said deodorant composition, said liquid propellant being a liquified hydrocarbon which is insoluble in said concentrate.
2. A deodorant composition according to claim 1 wherein the alkyl phenol germicidal agent is orthophenylphenol and said topical surface anesthetic is benzocaine.
3. A deodorant composition according to claim 1 wherein said complexing polymer is polyvinylpyrrolidone.
4. A package of a pressurized aerosol three-phase heterogeneous composition comprising a fluid-tight container having a valve assembly for discharging the contents wherein the contents comprise a liquid concentrate phase which is confined in the container with a liquid propellant which is insoluble in said liquid concentrate phase and under a vapor pressure provided by a gaseous propellant phase to provide a three-phase deodorant composition, said concentrate comprising:
a. an anionic germicidal compound, said anionic germicidal compound being an alkyl phenol selected from the group consisting of oithophenylphenol; paratertiaryamylphenol; paratertiarybutylphenol; 4-chloro-2-phenylphenol; 5-chloro-2- c. a topical surface anesthetic selected from the group consisting of benzocaine, lidocaine, xylocaine, pramoxine hydrochloride and mixtures thereof, and d. an alcohol and water solution, said alcohol being selected from the group consisting of ethyl alcohol, propanol and isopropanol, said germicidal agent being present in said concentrate at a level of from about 0.01 percent to about 3.0 percent by weight of the concentrate, said complexing polymer being present in said concentrate at a level of from about .0025 percent to about 5.5 percent by weight of the concentrate, said topical anesthetic being present at a level of from about .0025 percent to about 6 percent by weight of the concentrate, said water being present at a level of from about 7.5 percent to about 60 percent by weight of the concentrate, said alcohol comprising the balance of said concentrate, said concentrate comprising from 50 percent to 95 percent by weight of said deodorant composition, and said propellant comprising from about percent to about 50 percent by weight of said deodorant composition, said liquid propellant being a liquified hydrocarbon which is insoluble in said concentrate. 5. A package as set forth in claim 4 wherein the relative amounts of said water, alcohol, non-miscible liquid propellant and gaseous propellant are such that said container has an internal vapor pressure of from about 30 to pounds per square inch gauge at about 70 F.
6. A package as set forth in claim 4 wherein said germicidal agent in said concentrate is orthophenylphenol.
7. A package as set forth in claim 4 wherein said germicidal agent in said concentrate is a combination of orthophenylphenol and paratertiaryamylphenol.
8. A package as set forth in claim 4 wherein said complexing polymer in said concentrate is polyvinylpyrrolidone.
9. A package as set forth in claim 4 wherein said topical surface anesthetic in said concentrate is benzocaine.
10. A package as set forth in claim 4 wherein said liquid propellant and said gaseous propellant is a combination of isobutane and propane.
11. A heterogeneous three-phase liquid composition adapted to be discharged from a pressurized container to thereby form a spray disinfectant-deodorant having a detoxifying effect in combination with a topical surface anesthetic which desensitizes the mucous membrane upon contact comprising:
a. about 0.2 percent orthophenylphenol,
b. about 0.04 percent paratertiaryamylphenol,
c. about 0.l percent polyvinylpyrrolidone,
d. about 0.3 percent benzocaine,
e. about 0.3 percent essential oils,
f. about 25 percent water,
g. about 50 percent alcohol, and
h. about 20 percent of a mixture of isobutane and propane; said amounts being based on the weight of the composition and said composition having a vapor pressure of from about 45 to 65 pounds per square inch gauge at 70 F.
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