US3544258A - Self-propelled liquid dispenser containing an antiperspirant aluminum salt - Google Patents
Self-propelled liquid dispenser containing an antiperspirant aluminum salt Download PDFInfo
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- US3544258A US3544258A US303185A US3544258DA US3544258A US 3544258 A US3544258 A US 3544258A US 303185 A US303185 A US 303185A US 3544258D A US3544258D A US 3544258DA US 3544258 A US3544258 A US 3544258A
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- dimethyl ether
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- alcohol
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
- B65D83/75—Aerosol containers not provided for in groups B65D83/16 - B65D83/74
- B65D83/752—Aerosol containers not provided for in groups B65D83/16 - B65D83/74 characterised by the use of specific products or propellants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/87—Application Devices; Containers; Packaging
Definitions
- This invention relates to the dispensing, from a pressurized container by means of vaporization of a propellant therein, of a deodorant composition containing an aluminum salt as the active antiperspirant agent.
- Our invention relates to the dispensing of liquids from a container under pressure by means of vaporization of a propellent within the container. More particularly, our invention relates to such dispensing of a personal deodorant composition containing an antiperspirant,
- the more effective personal deodorant compositions contain an antiperspirant.
- the most effective antiperspirants are aluminum salts, e.g., aluminum chlorodydrol.
- the aluminum salts present such difficult problems in use in aerosol systems, however, that aerosol deodorants containing such antiperspirant aluminum salts have met with very limited market success.
- the most persistent and most serious problem presented by the aluminum salts is their tendency to precipitate out of the system and clog various parts of the dispenser, for example, the valve and the actuating button, resulting in erratic and ineffective dispensing, e.g., spitting, streaming and interference with the spray.
- This problem has been the main cause of lack of success of aerosol antiperspirants.
- One attempt to solve the problem has been the use of a complex mechanical device comprising a valve with a complex cap. The cap acts as a seal for the valve actuator opening between uses by the consumer to reduce evaporation of water, which is alleged to reduce crystallization of the aluminum salt.
- any eifectiveness of the device is contingent on the consumer replacing the cap securely after each use to make a proper seal. Also, with formulations containing a high concentration of aluminum salts the device does not function effectively. Moreover, the problem of clogging is so complex that it may arise before the aerosol package is used by the consumer, e.g., it can arise by mere actuation of the valve during manufacturing procedures resulting in clogging before the package is used.
- the dispenser of our invention comprises a container containing therein under pressure a fluid system comprising a propellent vapor phase and an essentially continuous liquid aqueous phase containing the antiperspirant aluminum compound, water, alcohol and a propellant comprising dimethyl ether, and in which a particular type of valve is used with a particular type of actuating button for the valve for dispensing the contents of the container.
- the particular hydroalcoholic, dimethyl ether system in combination with the particular valve and actuator provides effective dispensing of the deodorant formulation containing the antiperspirant aluice minum compound without clogging and in the form of a nonflammable spray with a minimum of dripping and cooling eifect, a characteristic which is desirable for a personal deodorant product.
- proportions of water, alcohol and dimethyl ether in the liquid hydroalcoholic phase of from about 20 to about weight percent water, about 12 to about 50 weight percent alcohol and about 12 to about 48 weight percent dimethyl ether, based on the total amount of water, alcohol and dimethyl ether, used in combination with a vapor tap valve provides a nonfiammable spray ranging from a finely atomized to a semicoarse spray.
- the proportions are within the range of about 20 to about 40 weight percent Water, about 25 to about 50 weight percent alcohol and about 25 to about 40 Weight percent dimethyl ether.
- the aluminum salt is employed in an amount of between about 3 to 25 weight percent based on the total amount of water, alcohol, aluminum salt, and dimethyl ether.
- the salt is used in an amount of at least about 6, preferably, about 6 to about 15, weight percent for more effective antiperspirant action.
- the quantities of aluminum salt, water, alcohol and dimethyl ether are adjusted to provide a solubilized system, i.e., a single liquid phase containing the aluminum salt in solution.
- the proportions can range between about 3 to about 25% aluminum salt, about .20 to about 63% water, about 10 to about 48% alcohol and about 10 to about 45% dimethyl ether, and preferably about 6 to about 15% aluminum salt, about 20 to about 35% water, about 22 to about 45% alcohol and about 22 to about 35 dimethyl ether.
- the spray rate is controlled to provide a nonfiammable spray, e.g., between about 15 to about 65 grams per minute at 70 F.
- a nonfiammable spray we mean a spray possessing nonflammable characteristics as defined in I.C.C. Tariff 13.
- the spray rate can be controlled by the size of the orifice diameters of the valve and by the use of a capillary dip tube.
- the useful antiperspirant aluminum salts are those which are compatible with the aqueous phase of water, alcohol and dimethyl ether, i.e., which do not react with any of the materials of the aqueous phase to form precipitates which would cause clogging and interfere with operation of the dispenser.
- the useful aluminum salts include aluminum chlorohydrol, aluminum sulfocarbolate and aluminum chloride. Aluminum chlorohydrol is preferred.
- One salt or a mixture of salts can be employed. Our system is particularly advantageous in that more effective amounts of aluminum salt can be used.
- the formulation preferably also contains a bacteriostatic agent, soluble in the hydroalcoholic-dimethyl ether system, for a more effective deodorant product.
- bacteriostatic agents include hexachlorophene, diaphene, trichlorocarbonilide and actamer (bithionol).
- the bacteriostatic agent is used in conventional amounts, e.g., in an amount of about 0.05 to 0.5 weight percent on a propellent-free basis.
- Other ingredients which can be included are perfumes, alkalizing chelating agents, and emollients conventionally employed in deodorant formulations, in proper amounts, and soluble in the hydroalcoholic-dimethyl ether system.
- an emollient such as ethyl phthallyl ethyl glycollate, aids the nonclogging properties over a prolonged length of time.
- emollients can be used in amounts of about 1 to 7 weight percent on a propellent-free basis.
- valve member employed with the dispenser of our invention is adapted for continuous delivery of the contents of the container, as distinguished from metering valves which are adapted to deliver a discrete quantity of product each time the valve is actuated, and is a vertically actuated valve of the type known as a vapor tap valve.
- a vapor tap valve can be described as including a mixing chamber provided with separate openings for the vapor phase and the liquid phase to be dispensed into the chamber and valve means for releasing the mixture of liquid and vapor in the'chamber into a valve passageway communicating With the exterior of the container.
- the tailpiece orifice of the valve must be of substantially uniform dimension or bore to avoid clogging.
- the valve actuator or button is of the type known as the mechanical break-up type.
- Such buttons provide a particularly desirable spray characteristic, i.e., a soft spray, for personal deodorants.
- Such buttons provide finer spray particles developed by mechanical forces and not solely by expansion and evaporation of thepropellent.
- Such buttons must be of a type known as onepiece buttons to provide nonclogging.
- Such one-piece buttons are described, for example, in U.S. Pats. 3,083,917 and 3,083,918.
- 3,083,917 and 3,083,918 contain essentially one orifice and essentially comprise a one-piece integral button with a chamber to receive a hollow valve stem and a passage leading from the valve stem-oif-center into a circular discharge chamber to produce a swirling discharge of material through a single exit orifice.
- buttons known as two-piece buttons result in clogging of the dispenser by aluminum salts. Such two-piece buttons are described in U.S. Pat. 2,767,023.
- They contain essentially two-orifices and comprise a chamber to receive a valve stem, a chamber above the stem leading to an orifice leading to a socket in the face of the button, slots in the socket leading to a central depression and a separate cup member set within the socket with an exit orifice in the center of the cup over the central depression of the socket.
- the cup member forms with the socket portion containing the slots and central depression a confined chamber in which the material being discharged is imparted a swirling motion. All the useful valves and buttons described above are commercially available.
- FIG. 1 is a vertical cross-sectional view of a pressure container in which the two phases, i.e., propellent vapor phase and the liquid phase, are illustrated as well as a vertically actuated vapor tap dispensing valve, in closed position, and the actuating button of the dispenser of our invention.
- FIG. 2 is a view similar to FIG. 1 showing the valve in open or dispensing position.
- FIG. 3 illustrates a useful modification of the valve of FIGS. 1 and 2.
- FIG. 4 illustrates another useful modification of the valve of FIGS. 1 and 2.
- FIG. 5 illustrates a valve of a type not useful.
- FIG. 6 is a sectional view of the actuating button of FIG. 1 taken along 6-6.
- FIGS. 7-10 illustrate another useful actuating button.
- FIG. 7 is a vertical cross-sectional view of the button.
- FIG. 8 is a top view of the button.
- FIG. 9 is a sectional view of the button of FIG. 8 taken along 99.
- FIG. 10 is a sectional view of the button of FIG. 9 taken along 1010.
- the dispenser comprises a closed container 1 in which is contained atop vapor phase 2 comprising vaporized propellent and a continuous aqueous phase 3 alcohol and liquefied dimethyl'etherpropellent.
- the container 1 can be made of glass, plastic coated glass, plastic materials, aluminum, tin plated steel, and stainless steel. Corrosion inhibitors can be included in the liquid aqueous phase to inhibit corrosion of metal containers.
- the container 1 is provided with a cup member 4 for holding a valve member 5 in the top of the container for dispensing the contents of the container.
- the valve member 5 comprises a hollow stem 6 with the valve 7 normally seated against gasket surface 8 by means of spring 9 (in FIG. 1 the valve is shown in closed or nondispensing position).
- a housing 10 Surrounding the valve 7 is a housing 10 (also known as the spring cup or valve body) with a tailpiece 11, with opening or orifice 12.
- the orifice 12 is of uniform bore, so that there is a straight flow of liquid into the housing 10.
- Attached to the tail-piece 11 is dip tube 13 extending into the liquid aqueous phase.
- the valve housing 10 has an opening or orifice 18 for the separate entry of vapor from the top vapor phase 2.
- an actuator or button 14 On the valve stem 6 is mounted an actuator or button 14 containing a passageway in communication with the hollow stem 6 and containing an orifice 15.
- valve 7 When the valve member is actuated by pressing down the button 14, as shown in FIG. 2, the valve 7 is unseated and the pressure of the propellent vapor extrudes the liquid aqueous phase up the dip tube 13 and through the tailpiece orifice 12 into the chamber 16 formed by housing 10. Vapor fromthe top vapor phase 2 enters the chamber 16 through the vapor tap opening 18 at the same time that the liquid aqueous phase is introduced into the chamber 16 and the vapor and liquid aqueous phase are intermixed in the chamber 16. This mixture then passes into the hollow valve stem 6, where further mixing occurs, through stern orifice 17 (communicating with the hollow stem passageway) and is discharged out through button orifice 15 as a spray.
- FIG. 3 a useful modification of the valve of FIGS. 1 and 2 is illustrated by a partial sectional view.
- the tailpiece 11a contains an orifice 12a of uniform bore and in the lower section an enlarged bore to receive a dip tube 13a.
- This dip tube is of the capillary type and its inner diameter or bore 19 is substantially equal to the bore 12a, thus providing a tailpiece orifice of uniform of FIGS. 1 and 2 is illustrated by a partial sectional view.
- the tailpiece 11b has a large bore to receive a capillary dip tube 13b, i.e., there is no restricted orifice in the tailpiece as in FIGS. 1 or 3.
- FIG. 5 a valve which is not useful, i.e., in which clogging by aluminum salts occurs, is illustrated by a partial sectional view.
- the tailpiece has a restricted orifice 12a in its lower section so that a .well 20 is formed from the change in dimension.
- This type of valve results in clogging.
- Aluminum salts collect in the Well on the shoulders above the orifice and at the vapor tap orifice 18c destroying the effectiveness of the spray.
- the button 14 comprises a chamber 21 adapted to receive the hollow valve stem 6, a channel 22 above the valve stem leading to a circular chamber 23 and to exit orifice 15.
- the particular orifice 15 illustrated is a reverse taper type.
- the circular chamber 23 is preferably coaxial with the exit orifice.
- the channel 22 leads oif-center into chamber 23 and is preferably substantially tangent to the chamber 23.
- the contents of the container exit from the valve stem 6 into the channel 22 from which it is directed tangentially into the chamber 23 to provide a swirling motion in the chamber and out the orifice, as shown more clearly in FIG. 6.
- This type of button is described in U.S. Pat. 3,083,917, herein incorporated by reference.
- FIGS. 7 to 10 illustrate another useful type of button.
- this button there is a chamber 24 adapted to receive the hollow valve stem 6 and a channel 25 formed between a circular extension 26 which fits into the hollow valve stem.
- Channel 25 leads into a circular chamber 27 and to exit orifice 28.
- the circular chamber 27 is preferably coaxial with the exit orifice.
- the channel 25 leads olfcenter into chamber 27 and is preferably substantially tangent to the chamber 27.
- the contents of the container exit from the valve stem 6 into the channel 25 from which it is directed tangentially into chamber 27 to provide a swirling motion in the chamber and out the orifice 28.
- This type of button is described in U.S. Pat. 3,083,918, herein incorporated by reference.
- the one-piece buttons of FIGS. 1 and 6-10 contain relatively large chambers 23 and 27 for producing a swirling motion as compared to the relatively small and confined chamber of the two-piece button described in U.S. Pat. 2,767,023. It is believed that the confined nature of the chamber of the two-piece button leads to crystallization of the aluminum salt.
- compositions of our invention can be prepared and dispensers filled with them by means known to the art, e.g., pressure filling a suitable container.
- the antiperspirant and other ingredients in proper amounts can be dissolved in the water and alcohol components of the liquid phase and the resulting solution added to an open container, or water and alcohol can be first introduced into an open container and the active ingredients added, and the container then sealed with a closure having a dispensing valve.
- a large cylinder or another aerosol container containing the dimethyl ether under pressure is'then connected to the container to be charged. The dimethyl ether is charged to the dispensing container through the container valve and dissolved in the liquid aqueous phase.
- the quantity of propellent charged to the container can be regulated, for example, by separating a discrete measured quantity of propellent and charging merely this quantity to the container.
- any ingredient is not soluble in any one or two of the water, alcohol and dimethyl ether components, it may be desirable to dissolve the ingredient in the one or two components in which it is soluble and then add the resulting solution to the remaining component or components.
- the finished product containing all three components is a compatible solution with the antiperspirant and other ingredients.
- the alcohol employed in the dispenser of our invention can be ethyl alcohol or isopropyl alcohol with ethyl alcohol being preferred.
- the presence of the alcohol in the system serves the two-fold function of operating as a cosolvent in the liquid aqueous phase and providing a quick drying spray when the product is released from the container.
- a quick drying spray is very desirable for a deodorant spray.
- the dimethyl ether is not only present in the dispensed spray, where it assists in the atomization of the product, but due to its presence in the liquid aqueous phase also serves as a cosolvent for the active ingredients along with the water and alcohol.
- dimethyl ether is also noncorrosive to metals, nontoxic, stable in the presence of heat and moisture, and relatively inert chemically.
- the proportions of aluminum salt, Water, alcohol and dimethyl ether are adjusted to provide a solubilized system, i.e., a single liquid phase containing the aluminum salt in solution.
- Sufllcient water must be used to provide solubility of the aluminum salt.
- the water content must also be adjusted to avoid formation of a three phase system, i.e., two liquid phases, which can occur when the amount of water exceeds the solubility of water in dimethyl ether (7.0% weight percent in dimethyl ether at 24 C. and about 5 atmospheres). This can also be overcome by the use of a larger amount of alcohol.
- EXAMPLE 1 The following formulations were prepared in coated glass bottles with a vapor-tap valve and a capillary dip tube.
- the valve employed was a precision valve (of the type illustrated in FIG. 4 using a capillary dip tube), with the following orifice diameters: 0.050" capillary dip tube, 0.018 stem, 0.023" vapor tap.
- the button was a onepiece mechanical breakup reverse taper button, as illustrated in FIGS. 7 to 10, with an orifice diameter of 0.016".
- the amount of water, alcohol and dimethyl ether based on the total water, alcohol and dimethyl ether was for formulations A and B, respectively, 25 and 22 weight percent water, 44 and 46 weight percent alcohol and 30 and 32 weight percent dimethyl ether.
- the amount of antiperspirant aluminum salt (anhydrous basis) was amout 7.5, based on the total amount of water, alcohol and aluminum salt and dimethyl ether.
- the systems were two phase systems of a propellent vapor phase and a continuous liquid aqueous phase containing water, alcohol, dimethyl ether and aluminum chlorhydrol.
- the systems had a pressure of about 26+3 p.s.i.g. at 70 F. with air evacuated.
- the systems provided a nonfiammable spray, passing the open and closed drum tests and having a flame extension of about 9 inches (the drum and flame extension tests were performed as described in I.C.C. Tariff 13, Sept. 25, 1960).
- the spray was a finely atomized, quick drying spray with a minimum of dripping and cooling effect.
- Tests were run over a period of five months to determine clogging properties by preparing thirty six of the dispensers described above and actuating them daily, weekly and monthly.
- the dispensers using formulation A exhibited no clogging for two months whether actuated daily, weekly or monthly, for three months when actuated weekly and for five months when actuated monthly. When actuated daily, some clogging was observed in the third, fourth and fifth months and when actuated weekly in the fourth and fifth months.
- Tests were also made on identical dispensers except a two-piece button (as described above and in U.S. Pat. 2,767,023) was employed. These dispensers clogged as much as half the times actuated within the first month when actuated daily and within the second month when actuated daily or weekly.
- Tests were also performed on dispensers using formulation B containing the emollient, using the one-piece button and two-piece button.
- the dispensers exhibited no clogging during the six month period whether actuated daily, weekly or monthly.
- the dispensers With the'two-piece button, the dispensers clogged as much as two-thirds of the times actuated within the first month when actuated daily and weekly and within two months when actuated monthly.
- the emollient adds to the length of time clogging is avoided. If the emollient is to be used, however, precaution should be taken to avoid storage at elevated temperatures in the range of about 100 F. since an irreversible gelation can occur.
- EXAMPLE 2 An example of another formulation which can be used in the dispenser system of Example 1 and which provides a nonflammable, finely atomized, quick drying, nonclogging spray with a minimum of dripping and cooling effect is as follows:
- the amount of water, alcohol and dimethyl ether based on the total water, alcohol and dimethyl ether was about 22 weight percent water, about 46 weight percent alcohol and about 32 weight percent dimethyl ether.
- the amount of antiperspirant aluminum salt (anhydrous) was about 8 weight percent.
- EXAMPLE 3 An example of another formulation which can be used in the dispenser system of Example 1 and which provides a nonflammable finely atomized, quick-drying, nonclogging spray with a minimum of dripping and cooling effect is as follows:
- the amount of water, alcohol and dimethyl ether was 19 weight percent water, 49 weight percent alcohol and 33 weight percent dimethyl ether.
- the amount of antiperspirant aluminum salt (anhydrous) was about 12 weight percent.
- the aluminum salt content ranged from 3.0 (Ex. 10) to 25.0 (Ex. 6 and 9) weight percent.
- the water, alcohol and dimethyl ether content (on the basis of the total amount of water, alcohol and dimethyl ether) ranged from 29.9 (Ex. 7) to 75 (Ex. 5) weight percent water, from 10.6 (Ex. 10) to 34.3 (Ex. 8) weight percent alcohol, and 12.5 (Ex. 5) to 48 (Ex. 10) weight percent dimethyl ether.
- a self-propelled liquid dispenser comprising a container containing therein under pressure a fluid system comprising a propellent vapor phase and a continuous liquid aqueous phase containing water, alcohol, and a propellent comprising dimethyl ether; an antiperspirant aluminum salt compatible with the aqueous phase, selected from the group consisting of aluminum chlorohydrol, aluminum sulfocarbolate and aluminum chloride; the water, alcohol and dimethyl ether being in proportions of from about 20 to about 75% by weight water, about 12 to about 50% by weight alcohol and about 12 to about 48% by weight dimethyl ether based on the total of water, alcohol and dimethyl ether ;the aluminum salt being in an amount of about 3 to about 25 weight percent; a vertically actuated vapor-tap valve member associated with the container adaptable for continuous dispensing of the contents of the container at a spray rate providing a nonflammable spray, said valve member including a tailpiece orifice of susbtantially uniform dimension; and a mechanical breakup actuator for the valve
- aqueous phase contains a bacteriostatic agent soluble in the hydroalcoholic-dimethyl ether system.
- a self-propelled liquid dispenser comprising a container containing therein under pressure a fluid system comprising a propellent vapor phase and a continuous liquid aqueous phase containing water, alcohol, a propellant comprising dimethyl ether and aluminum chlorhydrol; the water, alcohol and dimethyl ether being in proportions of from about 20 to about 40% by weight water, about 25 to about 50% by weight alcohol and about 25 to about 40% by weight dimethyl ether based on the total of water, alcohol and dimethyl ether; the aluminum chlorhydrol being in an amount of about 3 to about 25 weight percent, and a vertically actuated vapor-tap valve member associated with the container adaptable for continuous dispensing of the contents of the container at a spray rate providing a non-flammable spray, said valve member including a tailpiece orifice of substantially uniform dimension; and a mechanical breakup actuator for the valve member containing essentially one orifice.
- aqueous phase contains a bacteriostatic agent soluble in the hydroalcoholic-dimethyl ether system.
- said emollient is ethyl phthallyl ethyl glycollate.
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Description
Dec. 1,1970 F. PRESANT EI'AL 3,544,253
SELF-PROPELLED LIQUID DISPENSER CONTAINING AN ANTIPERSPIRANT ALUMINUM SALT Filed Aug. 19 1963 2 Sheets-Sheet 1' 47 I30 0 m S he 3 v,
i lOb l8b 3b 0 V i I 3, no I I FRED PRESANT CARMELO CARRION JR.
. INVENTOR'S.
v n I I n I a i i ATTORNEYS Filed Aug. 19, 1963 SELF- PELLED LIQUID DISPENSER CQNTAININ ANTIPERSPIRANT ALUMINUM SALT 2 Sheet S-Sheet 2 FIG.8
N TORS.
ATTORNEYS FR-E 0 PR ESANT CARMELO CARRION,JR.
INVE
United States Patent 3,544,258 SELF-PROPELLED LIQUID DISPENSER CONTAIN- ING AN ANTIPERSPIRANT ALUMINUM SALT Fred Presant and Carmelo Carrion, Jr., Bridgeport, Conn., assignors to Aerosol Techniques Incorporated, a corporation of New York Filed Aug. 19, 1963, Ser. No. 303,185 The portion of the term of the patent subsequent to Sept. 21, 1982, has been disclaimed Int. Cl. A61k 7/00; B67d /06 US. Cl. 222-192 '12 Claims ABSTRACT OF THE DISCLOSURE This invention relates to the dispensing, from a pressurized container by means of vaporization of a propellant therein, of a deodorant composition containing an aluminum salt as the active antiperspirant agent.
Our invention relates to the dispensing of liquids from a container under pressure by means of vaporization of a propellent within the container. More particularly, our invention relates to such dispensing of a personal deodorant composition containing an antiperspirant,
The more effective personal deodorant compositions contain an antiperspirant. The most effective antiperspirants are aluminum salts, e.g., aluminum chlorodydrol. The aluminum salts present such difficult problems in use in aerosol systems, however, that aerosol deodorants containing such antiperspirant aluminum salts have met with very limited market success.
The most persistent and most serious problem presented by the aluminum salts is their tendency to precipitate out of the system and clog various parts of the dispenser, for example, the valve and the actuating button, resulting in erratic and ineffective dispensing, e.g., spitting, streaming and interference with the spray. This problem has been the main cause of lack of success of aerosol antiperspirants. One attempt to solve the problem has been the use of a complex mechanical device comprising a valve with a complex cap. The cap acts as a seal for the valve actuator opening between uses by the consumer to reduce evaporation of water, which is alleged to reduce crystallization of the aluminum salt. Any eifectiveness of the device, however, is contingent on the consumer replacing the cap securely after each use to make a proper seal. Also, with formulations containing a high concentration of aluminum salts the device does not function effectively. Moreover, the problem of clogging is so complex that it may arise before the aerosol package is used by the consumer, e.g., it can arise by mere actuation of the valve during manufacturing procedures resulting in clogging before the package is used.
We have now developed a self-propelled liquid dispenser which etfectively dispenses a personal deodorant composition containing antiperspirant aluminum salts without clogging and which does not require the use of protective complex mechanical devices such as described above. The dispenser of our invention comprises a container containing therein under pressure a fluid system comprising a propellent vapor phase and an essentially continuous liquid aqueous phase containing the antiperspirant aluminum compound, water, alcohol and a propellant comprising dimethyl ether, and in which a particular type of valve is used with a particular type of actuating button for the valve for dispensing the contents of the container.
We have found that the particular hydroalcoholic, dimethyl ether system in combination with the particular valve and actuator provides effective dispensing of the deodorant formulation containing the antiperspirant aluice minum compound without clogging and in the form of a nonflammable spray with a minimum of dripping and cooling eifect, a characteristic which is desirable for a personal deodorant product.
We have found that proportions of water, alcohol and dimethyl ether in the liquid hydroalcoholic phase of from about 20 to about weight percent water, about 12 to about 50 weight percent alcohol and about 12 to about 48 weight percent dimethyl ether, based on the total amount of water, alcohol and dimethyl ether, used in combination with a vapor tap valve provides a nonfiammable spray ranging from a finely atomized to a semicoarse spray. Preferably, the proportions are within the range of about 20 to about 40 weight percent Water, about 25 to about 50 weight percent alcohol and about 25 to about 40 Weight percent dimethyl ether. Within these proportions, a quick drying, finely atomized spray is obtained. The aluminum salt is employed in an amount of between about 3 to 25 weight percent based on the total amount of water, alcohol, aluminum salt, and dimethyl ether. Preferably, the salt is used in an amount of at least about 6, preferably, about 6 to about 15, weight percent for more effective antiperspirant action. Within these limits of proportions, the quantities of aluminum salt, water, alcohol and dimethyl ether are adjusted to provide a solubilized system, i.e., a single liquid phase containing the aluminum salt in solution. Expressed on the basis of weight percent of the total amount of aluminum salt, water, alcohol and dimethyl ether, the proportions can range between about 3 to about 25% aluminum salt, about .20 to about 63% water, about 10 to about 48% alcohol and about 10 to about 45% dimethyl ether, and preferably about 6 to about 15% aluminum salt, about 20 to about 35% water, about 22 to about 45% alcohol and about 22 to about 35 dimethyl ether.
In the system, the spray rate is controlled to provide a nonfiammable spray, e.g., between about 15 to about 65 grams per minute at 70 F. By a nonfiammable spray, we mean a spray possessing nonflammable characteristics as defined in I.C.C. Tariff 13. The spray rate can be controlled by the size of the orifice diameters of the valve and by the use of a capillary dip tube.
The useful antiperspirant aluminum salts are those which are compatible with the aqueous phase of water, alcohol and dimethyl ether, i.e., which do not react with any of the materials of the aqueous phase to form precipitates which would cause clogging and interfere with operation of the dispenser. The useful aluminum salts include aluminum chlorohydrol, aluminum sulfocarbolate and aluminum chloride. Aluminum chlorohydrol is preferred. One salt or a mixture of salts can be employed. Our system is particularly advantageous in that more effective amounts of aluminum salt can be used.
The formulation preferably also contains a bacteriostatic agent, soluble in the hydroalcoholic-dimethyl ether system, for a more effective deodorant product. Examples of such bacteriostatic agents include hexachlorophene, diaphene, trichlorocarbonilide and actamer (bithionol). The bacteriostatic agent is used in conventional amounts, e.g., in an amount of about 0.05 to 0.5 weight percent on a propellent-free basis. Other ingredients which can be included are perfumes, alkalizing chelating agents, and emollients conventionally employed in deodorant formulations, in proper amounts, and soluble in the hydroalcoholic-dimethyl ether system. We have found that an emollient, such as ethyl phthallyl ethyl glycollate, aids the nonclogging properties over a prolonged length of time. Such emollients can be used in amounts of about 1 to 7 weight percent on a propellent-free basis.
The valve member employed with the dispenser of our invention is adapted for continuous delivery of the contents of the container, as distinguished from metering valves which are adapted to deliver a discrete quantity of product each time the valve is actuated, and is a vertically actuated valve of the type known as a vapor tap valve. A vapor tap valve can be described as including a mixing chamber provided with separate openings for the vapor phase and the liquid phase to be dispensed into the chamber and valve means for releasing the mixture of liquid and vapor in the'chamber into a valve passageway communicating With the exterior of the container. We have found that the tailpiece orifice of the valve must be of substantially uniform dimension or bore to avoid clogging. We have found that in a valve with a tailpiece orifice in which a well is present, i.eL, in which the orifice varies in size, salt collects in the well on the shoulder and at the vapor tape orifice clogging the internal valve orifices and destroying effectiveness of the spray.
The valve actuator or button is of the type known as the mechanical break-up type. Such buttons provide a particularly desirable spray characteristic, i.e., a soft spray, for personal deodorants. Such buttons provide finer spray particles developed by mechanical forces and not solely by expansion and evaporation of thepropellent. We have found that such buttons must be of a type known as onepiece buttons to provide nonclogging. Such one-piece buttons are described, for example, in U.S. Pats. 3,083,917 and 3,083,918. The buttons of U.S. Pats. 3,083,917 and 3,083,918 contain essentially one orifice and essentially comprise a one-piece integral button with a chamber to receive a hollow valve stem and a passage leading from the valve stem-oif-center into a circular discharge chamber to produce a swirling discharge of material through a single exit orifice. We have found that buttons known as two-piece buttons result in clogging of the dispenser by aluminum salts. Such two-piece buttons are described in U.S. Pat. 2,767,023. They contain essentially two-orifices and comprise a chamber to receive a valve stem, a chamber above the stem leading to an orifice leading to a socket in the face of the button, slots in the socket leading to a central depression and a separate cup member set within the socket with an exit orifice in the center of the cup over the central depression of the socket. The cup member forms with the socket portion containing the slots and central depression a confined chamber in which the material being discharged is imparted a swirling motion. All the useful valves and buttons described above are commercially available.
Our invention and the useful valves and buttons will be further illustrated by reference to the accompanying drawing.
FIG. 1 is a vertical cross-sectional view of a pressure container in which the two phases, i.e., propellent vapor phase and the liquid phase, are illustrated as well as a vertically actuated vapor tap dispensing valve, in closed position, and the actuating button of the dispenser of our invention.
FIG. 2 is a view similar to FIG. 1 showing the valve in open or dispensing position.
FIG. 3 illustrates a useful modification of the valve of FIGS. 1 and 2.
FIG. 4 illustrates another useful modification of the valve of FIGS. 1 and 2.
FIG. 5 illustrates a valve of a type not useful.
FIG. 6 is a sectional view of the actuating button of FIG. 1 taken along 6-6.
FIGS. 7-10 illustrate another useful actuating button.
FIG. 7 is a vertical cross-sectional view of the button.
FIG. 8 is a top view of the button.
FIG. 9 is a sectional view of the button of FIG. 8 taken along 99.
FIG. 10 is a sectional view of the button of FIG. 9 taken along 1010.
In FIG. 1, the dispenser comprises a closed container 1 in which is contained atop vapor phase 2 comprising vaporized propellent and a continuous aqueous phase 3 alcohol and liquefied dimethyl'etherpropellent. The container 1 can be made of glass, plastic coated glass, plastic materials, aluminum, tin plated steel, and stainless steel. Corrosion inhibitors can be included in the liquid aqueous phase to inhibit corrosion of metal containers. The container 1 is provided with a cup member 4 for holding a valve member 5 in the top of the container for dispensing the contents of the container. The valve member 5 comprises a hollow stem 6 with the valve 7 normally seated against gasket surface 8 by means of spring 9 (in FIG. 1 the valve is shown in closed or nondispensing position). Surrounding the valve 7 is a housing 10 (also known as the spring cup or valve body) with a tailpiece 11, with opening or orifice 12. The orifice 12 is of uniform bore, so that there is a straight flow of liquid into the housing 10. Attached to the tail-piece 11 is dip tube 13 extending into the liquid aqueous phase. The valve housing 10 has an opening or orifice 18 for the separate entry of vapor from the top vapor phase 2. On the valve stem 6 is mounted an actuator or button 14 containing a passageway in communication with the hollow stem 6 and containing an orifice 15.
When the valve member is actuated by pressing down the button 14, as shown in FIG. 2, the valve 7 is unseated and the pressure of the propellent vapor extrudes the liquid aqueous phase up the dip tube 13 and through the tailpiece orifice 12 into the chamber 16 formed by housing 10. Vapor fromthe top vapor phase 2 enters the chamber 16 through the vapor tap opening 18 at the same time that the liquid aqueous phase is introduced into the chamber 16 and the vapor and liquid aqueous phase are intermixed in the chamber 16. This mixture then passes into the hollow valve stem 6, where further mixing occurs, through stern orifice 17 (communicating with the hollow stem passageway) and is discharged out through button orifice 15 as a spray.
In FIG. 3 a useful modification of the valve of FIGS. 1 and 2 is illustrated by a partial sectional view. In this valve the tailpiece 11a contains an orifice 12a of uniform bore and in the lower section an enlarged bore to receive a dip tube 13a. This dip tube is of the capillary type and its inner diameter or bore 19 is substantially equal to the bore 12a, thus providing a tailpiece orifice of uniform of FIGS. 1 and 2 is illustrated by a partial sectional view.
containing an aluminum salt and other ingredients, water,
In this valve, the tailpiece 11b has a large bore to receive a capillary dip tube 13b, i.e., there is no restricted orifice in the tailpiece as in FIGS. 1 or 3. The capillary dip tube bore 19, in effect, provides the restricted orifice, which is of uniform dimension providing straight flow of liquid into housing 10b.
In FIG. 5 a valve which is not useful, i.e., in which clogging by aluminum salts occurs, is illustrated by a partial sectional view. In this valve, the tailpiece has a restricted orifice 12a in its lower section so that a .well 20 is formed from the change in dimension. This type of valve results in clogging. Aluminum salts collect in the Well on the shoulders above the orifice and at the vapor tap orifice 18c destroying the effectiveness of the spray.
In FIG. 1, the button 14 comprises a chamber 21 adapted to receive the hollow valve stem 6, a channel 22 above the valve stem leading to a circular chamber 23 and to exit orifice 15. The particular orifice 15 illustrated is a reverse taper type. The circular chamber 23 is preferably coaxial with the exit orifice. The channel 22 leads oif-center into chamber 23 and is preferably substantially tangent to the chamber 23. The contents of the container exit from the valve stem 6 into the channel 22 from which it is directed tangentially into the chamber 23 to provide a swirling motion in the chamber and out the orifice, as shown more clearly in FIG. 6. This type of button is described in U.S. Pat. 3,083,917, herein incorporated by reference.
FIGS. 7 to 10 illustrate another useful type of button. In this button there is a chamber 24 adapted to receive the hollow valve stem 6 and a channel 25 formed between a circular extension 26 which fits into the hollow valve stem. Channel 25 leads into a circular chamber 27 and to exit orifice 28. The circular chamber 27 is preferably coaxial with the exit orifice. The channel 25 leads olfcenter into chamber 27 and is preferably substantially tangent to the chamber 27. The contents of the container exit from the valve stem 6 into the channel 25 from which it is directed tangentially into chamber 27 to provide a swirling motion in the chamber and out the orifice 28. This type of button is described in U.S. Pat. 3,083,918, herein incorporated by reference.
The one-piece buttons of FIGS. 1 and 6-10 contain relatively large chambers 23 and 27 for producing a swirling motion as compared to the relatively small and confined chamber of the two-piece button described in U.S. Pat. 2,767,023. It is believed that the confined nature of the chamber of the two-piece button leads to crystallization of the aluminum salt.
The compositions of our invention can be prepared and dispensers filled with them by means known to the art, e.g., pressure filling a suitable container. For example, the antiperspirant and other ingredients in proper amounts can be dissolved in the water and alcohol components of the liquid phase and the resulting solution added to an open container, or water and alcohol can be first introduced into an open container and the active ingredients added, and the container then sealed with a closure having a dispensing valve. A large cylinder or another aerosol container containing the dimethyl ether under pressure is'then connected to the container to be charged. The dimethyl ether is charged to the dispensing container through the container valve and dissolved in the liquid aqueous phase. The quantity of propellent charged to the container can be regulated, for example, by separating a discrete measured quantity of propellent and charging merely this quantity to the container. Where any ingredient is not soluble in any one or two of the water, alcohol and dimethyl ether components, it may be desirable to dissolve the ingredient in the one or two components in which it is soluble and then add the resulting solution to the remaining component or components. In any event the finished product containing all three components is a compatible solution with the antiperspirant and other ingredients.
The alcohol employed in the dispenser of our invention can be ethyl alcohol or isopropyl alcohol with ethyl alcohol being preferred. The presence of the alcohol in the system serves the two-fold function of operating as a cosolvent in the liquid aqueous phase and providing a quick drying spray when the product is released from the container. A quick drying spray is very desirable for a deodorant spray.
In addition to the obvious economic advantages involved in employing a substantial quantity of water as a carrier together with the use of the inexpensive dimethyl ether propellent there are other significant advantages obtained through the employment of dimethyl ether in the systems. The low boiling point of dimethyl ether (24.9 C. at 760 mm. Hg) provides excellent atomization of the product dispensed and its low density (0.661 g./ ml. at 20 C.) offers a comparatively large volume of propellent per unit weight. Furthermore, the great solubility of dimethyl ether in water (35.3% by weight in water at 24 C. at about 5 atmospheres) affords a compatible system and further assists in the atomization of the water particles upon release. Since the Water, alcohol and dimethyl ether are present in a single, continuous phase in the dispenser of our invention, the dimethyl ether is not only present in the dispensed spray, where it assists in the atomization of the product, but due to its presence in the liquid aqueous phase also serves as a cosolvent for the active ingredients along with the water and alcohol. Besides the advantages mentioned above, dimethyl ether is also noncorrosive to metals, nontoxic, stable in the presence of heat and moisture, and relatively inert chemically.
As described above, the proportions of aluminum salt, Water, alcohol and dimethyl ether are adjusted to provide a solubilized system, i.e., a single liquid phase containing the aluminum salt in solution. Sufllcient water must be used to provide solubility of the aluminum salt. The water content must also be adjusted to avoid formation of a three phase system, i.e., two liquid phases, which can occur when the amount of water exceeds the solubility of water in dimethyl ether (7.0% weight percent in dimethyl ether at 24 C. and about 5 atmospheres). This can also be overcome by the use of a larger amount of alcohol.
Our invention is further illustrated by the following examples.
EXAMPLE 1 The following formulations were prepared in coated glass bottles with a vapor-tap valve and a capillary dip tube. The valve employed was a precision valve (of the type illustrated in FIG. 4 using a capillary dip tube), with the following orifice diameters: 0.050" capillary dip tube, 0.018 stem, 0.023" vapor tap. The button was a onepiece mechanical breakup reverse taper button, as illustrated in FIGS. 7 to 10, with an orifice diameter of 0.016".
Ethyl phthallyl ethyl glycollate (emollient).
In these systems the amount of water, alcohol and dimethyl ether based on the total water, alcohol and dimethyl ether was for formulations A and B, respectively, 25 and 22 weight percent water, 44 and 46 weight percent alcohol and 30 and 32 weight percent dimethyl ether. The amount of antiperspirant aluminum salt (anhydrous basis) was amout 7.5, based on the total amount of water, alcohol and aluminum salt and dimethyl ether. The systems were two phase systems of a propellent vapor phase and a continuous liquid aqueous phase containing water, alcohol, dimethyl ether and aluminum chlorhydrol.
The systems had a pressure of about 26+3 p.s.i.g. at 70 F. with air evacuated. The systems provided a nonfiammable spray, passing the open and closed drum tests and having a flame extension of about 9 inches (the drum and flame extension tests were performed as described in I.C.C. Tariff 13, Sept. 25, 1960). The spray was a finely atomized, quick drying spray with a minimum of dripping and cooling effect.
Tests were run over a period of five months to determine clogging properties by preparing thirty six of the dispensers described above and actuating them daily, weekly and monthly.
The dispensers using formulation A exhibited no clogging for two months whether actuated daily, weekly or monthly, for three months when actuated weekly and for five months when actuated monthly. When actuated daily, some clogging was observed in the third, fourth and fifth months and when actuated weekly in the fourth and fifth months.
Tests were also made on identical dispensers except a two-piece button (as described above and in U.S. Pat. 2,767,023) was employed. These dispensers clogged as much as half the times actuated within the first month when actuated daily and within the second month when actuated daily or weekly.
Tests were also performed on dispensers using formulation B containing the emollient, using the one-piece button and two-piece button. With the one-piece button the dispensers exhibited no clogging during the six month period whether actuated daily, weekly or monthly. With the'two-piece button, the dispensers clogged as much as two-thirds of the times actuated within the first month when actuated daily and weekly and within two months when actuated monthly. Thus, the emollient adds to the length of time clogging is avoided. If the emollient is to be used, however, precaution should be taken to avoid storage at elevated temperatures in the range of about 100 F. since an irreversible gelation can occur.
EXAMPLE 2 An example of another formulation which can be used in the dispenser system of Example 1 and which provides a nonflammable, finely atomized, quick drying, nonclogging spray with a minimum of dripping and cooling effect is as follows:
Aluminum chloride-611 15.00 Hexachlorophene 0.10 SDA-40 39.90 H O, deionized 12.00 Perfume 0.25 Alkalizing agent, q.s. to pH 4.2 5.00 Dimethyl ether 27.50
In this system the amount of water, alcohol and dimethyl ether based on the total water, alcohol and dimethyl ether was about 22 weight percent water, about 46 weight percent alcohol and about 32 weight percent dimethyl ether. The amount of antiperspirant aluminum salt (anhydrous) was about 8 weight percent.
EXAMPLE 3 An example of another formulation which can be used in the dispenser system of Example 1 and which provides a nonflammable finely atomized, quick-drying, nonclogging spray with a minimum of dripping and cooling effect is as follows:
In this system, the amount of water, alcohol and dimethyl ether was 19 weight percent water, 49 weight percent alcohol and 33 weight percent dimethyl ether. The amount of antiperspirant aluminum salt (anhydrous) was about 12 weight percent.
EXAMPLES 4 TO 10 Examples of other formulations useful in the dispenser system of Example 1 and providing a solubilized system, i.e., a single liquid phase containing the aluminum salt, water, alcohol and dimethyl ether, and nonflammable, nonclogging suitable sprays are as follows (in weight percent):
Aluminum chlorhydrol, 50% 1 40 50 15 40 50 6. 0 Water, de-ionized 40 40 15 30 15 10 36. 8 SBA-40 10 10 10 30 15 10. 6 Dimethyl ether 35 10 35 15 25 46. 6
Total 100 100 100 100 100 100 100. 0
1 50% water solution.
In these examples, the aluminum salt content (anhydrous) ranged from 3.0 (Ex. 10) to 25.0 (Ex. 6 and 9) weight percent. The water, alcohol and dimethyl ether content (on the basis of the total amount of water, alcohol and dimethyl ether) ranged from 29.9 (Ex. 7) to 75 (Ex. 5) weight percent water, from 10.6 (Ex. 10) to 34.3 (Ex. 8) weight percent alcohol, and 12.5 (Ex. 5) to 48 (Ex. 10) weight percent dimethyl ether.
We claim: I
1. A self-propelled liquid dispenser comprising a container containing therein under pressure a fluid system comprising a propellent vapor phase and a continuous liquid aqueous phase containing water, alcohol, and a propellent comprising dimethyl ether; an antiperspirant aluminum salt compatible with the aqueous phase, selected from the group consisting of aluminum chlorohydrol, aluminum sulfocarbolate and aluminum chloride; the water, alcohol and dimethyl ether being in proportions of from about 20 to about 75% by weight water, about 12 to about 50% by weight alcohol and about 12 to about 48% by weight dimethyl ether based on the total of water, alcohol and dimethyl ether ;the aluminum salt being in an amount of about 3 to about 25 weight percent; a vertically actuated vapor-tap valve member associated with the container adaptable for continuous dispensing of the contents of the container at a spray rate providing a nonflammable spray, said valve member including a tailpiece orifice of susbtantially uniform dimension; and a mechanical breakup actuator for the valve member containing essentially one orifice.
2. The dispenser of claim 1 in which the aluminum compound is aluminum chlorhydrol.
3. The dispenser of claim 1 in which the aluminum salt is in an amount of about 6 to about 15 weight percent.
4. The dispenser of claim 1 in which the aqueous phase contains a bacteriostatic agent soluble in the hydroalcoholic-dimethyl ether system.
5. The dispenser of claim 1 in which the hydroalcoholic phase also contains an emollient which is soluble therein.
6. The dispenser of claim 1 in which the water is about 20 to about 40 weight percent, the alcohol is about 25 to about 50 weight percent and the dimethyl ether is about 25 to about 40 weight percent.
7. A self-propelled liquid dispenser comprising a container containing therein under pressure a fluid system comprising a propellent vapor phase and a continuous liquid aqueous phase containing water, alcohol, a propellant comprising dimethyl ether and aluminum chlorhydrol; the water, alcohol and dimethyl ether being in proportions of from about 20 to about 40% by weight water, about 25 to about 50% by weight alcohol and about 25 to about 40% by weight dimethyl ether based on the total of water, alcohol and dimethyl ether; the aluminum chlorhydrol being in an amount of about 3 to about 25 weight percent, and a vertically actuated vapor-tap valve member associated with the container adaptable for continuous dispensing of the contents of the container at a spray rate providing a non-flammable spray, said valve member including a tailpiece orifice of substantially uniform dimension; and a mechanical breakup actuator for the valve member containing essentially one orifice.
8. The dispenser of claim 7 in which the aluminum chlorhydrol is in an amount of about 6 to about 15 weight percent.
9. The dispenser of claim 7 in which the aqueous phase contains a bacteriostatic agent soluble in the hydroalcoholic-dimethyl ether system.
10. The dispenser of claim 7 in which the hydroalcoholic phase contains an emollient which is soluble therein.
11. The dispenser of claim 5 wherein said emollient is ethyl phthallyl ethyl glycollate.
10 12. The dispenser of claim 10 wherein said emollient De Navarre: International Encyclopedia of Cosmetic is ethyl phthallyl ethyl glycollate. Material Trade Names, a Moore business publication,
N Y 1;, 1957, 237 d 323. References Cited ew or PP an UNITED STATES PATENTS ALBERT T. MEYERS, Primary Examiner 3,207,386 9/ 1965 Presant et a1 167--82 v TURNER, Assistant Examiner OTHER REFERENCES Shepherd: Aerosols: Science and Technology, Interscience Publishers, Inc., New York, 1961, pp. 220-22l, 10 424-47; 222-402.18 350 and 351.
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US303185A Expired - Lifetime US3544258A (en) | 1963-08-19 | 1963-08-19 | Self-propelled liquid dispenser containing an antiperspirant aluminum salt |
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US4045548A (en) * | 1974-02-13 | 1977-08-30 | The Procter & Gamble Company | Aerosol antiperspirant containing emollients |
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Cited By (96)
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US3647119A (en) * | 1970-05-26 | 1972-03-07 | S C John & Son Inc | Pressurized package |
US4045548A (en) * | 1974-02-13 | 1977-08-30 | The Procter & Gamble Company | Aerosol antiperspirant containing emollients |
JPS5274910A (en) * | 1975-12-18 | 1977-06-23 | Toyo Eazooru Kougiyou Kk | Sprayyarrestors for aerosol |
FR2362201A1 (en) * | 1976-08-16 | 1978-03-17 | Grace W R Ltd | USE OF BIS- (DIFLUOROMETHYL) OXIDE AND PERFLUORODIMETHYL OXIDE AS A PROPELLANTS FOR AEROSOLS |
FR2369007A1 (en) * | 1976-10-28 | 1978-05-26 | Unilever Nv | PACKAGING TO CONTAIN AND DISTRIBUTE A POWDER IN THE FORM OF AEROSOL |
US4295581A (en) * | 1976-12-09 | 1981-10-20 | Sumitomo Chemical Company, Limited | Insecticidal aerosol formulation having a liquified petroleum gas propellant |
WO1980002293A1 (en) * | 1979-04-13 | 1980-10-30 | Mclaughlin Gormley King Co | Non-pressurized dispensing system and composition |
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