CA1048453A - Aerosol containers for delivering high active concentration aerosol compositions at a low delivery rate - Google Patents
Aerosol containers for delivering high active concentration aerosol compositions at a low delivery rateInfo
- Publication number
- CA1048453A CA1048453A CA77281798A CA281798A CA1048453A CA 1048453 A CA1048453 A CA 1048453A CA 77281798 A CA77281798 A CA 77281798A CA 281798 A CA281798 A CA 281798A CA 1048453 A CA1048453 A CA 1048453A
- Authority
- CA
- Canada
- Prior art keywords
- liquid
- orifice
- aerosol
- valve
- propellant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- B65D83/44—Valves specially adapted therefor; Regulating devices
- B65D83/48—Lift valves, e.g. operated by push action
-
- 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
- B65D83/44—Valves specially adapted therefor; Regulating devices
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
Abstract
AEROSOL CONTAINERS FOR DELIVERING HIGH ACTIVE
CONCENTRATION AEROSOL COMPOSITIONS AT A LOW DELIVERY RATE
ABSTRACT OF THE DISCLOSURE
An aerosol container is provided for delivering liquid aerosol compositions highly concentrated with respect to the active ingredient at a low delivery rate, thereby conserving propellant, since less propellant is required to deliver an equivalent amount of active component per unit time, and comprising, in combination, a pressurizable container having a valve movable between open and closed positions, a valve stem, and a delivery port; a valve stem orifice in the valve stem in flow connection at one end with a blending space and at the other end with an aerosol-conveying valve stem passage leading to the delivery port; the valve stem orifice having a diameter within the range from about 0.50 to about 0.65 mm; bias means for holding the valve in a closed position; means for manipulating the valve against the bias means to an open position for expulsion of aerosol composition via the valve stem orifice to the delivery port; wall means defining the blending space and separating the blending space from liquid aerosol composition and propellant within the container; at least one liquid tap orifice through the wall means, having a cross-sectional open area within the range from about 0.4 and 0.6 mm2 for flow of liquid aerosol composition into the blending space;
at least one vapor tap orifice through the wall means, having a cross-sectional open area within the range from about 0.4 to about 0.8 mm2 for flow of propellant into the blending space; the ratio of liquid tap orifice to vapor tap orifice cross-sectional open area being within the range from about 0.5 to about 0.9; the open areas of the liquid tap orifice and vapor tap orifice being selected within the stated ranges to provide a volume ratio of propellant gas:liquid aerosol composition within the range from about 10:1 to about 40:1, thereby limiting the delivery rate of liquid aerosol composition from the container when the valve is opened.
In the special case where the liquid tap orifice is a capillary dip tube, the cross-sectional open area thereof is within the range from about 0.6 to about 1.3 mm2, for flow of liquid aerosol composition into the blending space, and at least one vapor tap orifice through the wall means has a cross-sectional open area within the range from about 0.4 to about 0.8 mm2 for flow of propellant gas into the blending space; and the ratio of capillary dip tube to vapor tap cross-sectional open area is within the range from about 1.0 to about 2Ø
CONCENTRATION AEROSOL COMPOSITIONS AT A LOW DELIVERY RATE
ABSTRACT OF THE DISCLOSURE
An aerosol container is provided for delivering liquid aerosol compositions highly concentrated with respect to the active ingredient at a low delivery rate, thereby conserving propellant, since less propellant is required to deliver an equivalent amount of active component per unit time, and comprising, in combination, a pressurizable container having a valve movable between open and closed positions, a valve stem, and a delivery port; a valve stem orifice in the valve stem in flow connection at one end with a blending space and at the other end with an aerosol-conveying valve stem passage leading to the delivery port; the valve stem orifice having a diameter within the range from about 0.50 to about 0.65 mm; bias means for holding the valve in a closed position; means for manipulating the valve against the bias means to an open position for expulsion of aerosol composition via the valve stem orifice to the delivery port; wall means defining the blending space and separating the blending space from liquid aerosol composition and propellant within the container; at least one liquid tap orifice through the wall means, having a cross-sectional open area within the range from about 0.4 and 0.6 mm2 for flow of liquid aerosol composition into the blending space;
at least one vapor tap orifice through the wall means, having a cross-sectional open area within the range from about 0.4 to about 0.8 mm2 for flow of propellant into the blending space; the ratio of liquid tap orifice to vapor tap orifice cross-sectional open area being within the range from about 0.5 to about 0.9; the open areas of the liquid tap orifice and vapor tap orifice being selected within the stated ranges to provide a volume ratio of propellant gas:liquid aerosol composition within the range from about 10:1 to about 40:1, thereby limiting the delivery rate of liquid aerosol composition from the container when the valve is opened.
In the special case where the liquid tap orifice is a capillary dip tube, the cross-sectional open area thereof is within the range from about 0.6 to about 1.3 mm2, for flow of liquid aerosol composition into the blending space, and at least one vapor tap orifice through the wall means has a cross-sectional open area within the range from about 0.4 to about 0.8 mm2 for flow of propellant gas into the blending space; and the ratio of capillary dip tube to vapor tap cross-sectional open area is within the range from about 1.0 to about 2Ø
Description
~048453 SPECIFICATION
Aerosol sprays are now widely used, particularly in the cosmetic, topical pllarmaceutical and detergent fields for delivery of an additive such as a cosmetic, pharmaceutical, or cleaning composition to a substrate such as the skin or other surface to be treated. Aerosol compositions are widely used as antiperspirants to direct the antiperspirant to the skin in the form of a finely divided spray.
The delivery of antiperspirants to the skin in a fine spray poses a difficult aerosol packagin~ problem. Aerosol antiperspirant compositions based on anhydrous propellant systems normally include ant~?erspirant, filler and other solid particles dispersed in a liquid vehicle, and the solid particlesreadily clog small valve orifices~ On the other hand, if the orifices are large enough to avoid clogging, a coarse liquid spray with large droplets is formed, and there may be excessive drip at the nozzle. The material can even be squirted out in the form of a liquid stream, which rapidly- runs off the surface on which it is deposited.
Much effort has accordingly been directed to the design of valves and valve delivery ports, nozzles or orifices which are capable of delivering finely-divided sprays, of which U.S. patents Nos. 3,083,917 and 3,083,918 patented April 2,1963, to Abplanalp et al, and No. 3,544,258 dated December 1,1970, to Presant et al, are exemplary. The latter 1048gS3 pat ent describes a type of valve ~vhich is now rather common, giving a finely atomized spray, and having a vapor tal~, which includes a mixillg chamber provicled with separate openings for the vapor phase and the liquid pl~ase to be dispensed into the chamber, in combination with a valve actuator or button of the mechanical breakup type. Such valves provide a soft spray with a swirling motion. Another design of valves of this type is described in U. S . patent No. 2, 767, 023 . Valves with vapor taps are generally used where the spray is to be applied directly to the skin, since the spray is less cold.
M~rshU.S. patentNo. 3,148,127patentedSeptember 8, 1964 describes a pressurized self-dispensing package of ingredients for use as a hair spray and comprising; isobutane or similar propellant in one phase and an aqueous phase including the hair setting ingredient. The _ isobutane is in a relatively high proportion to the aqueous phase, and is exhausted slightly before the water phase has been entirely dispensed.
A vapor tap type oiE valve is used having a 0. 030 inch vapor tap orifice, a 0. 030 inch liquid tap orifice, and a 0. 018 inch valve stem orifice~
with a mechanical breakup button. There is no disclosure of the rel~-tive proportions of propellant gas to liquid phase being dispensed.
Rabussier U.S. patentNo. 3,260,421 patented July 12, 1966 describes an aerosol container for expelling an aqueous phase and a propellant phase, fitted with a vapor tap valve, and capilLary dip tube.
To achieve better blending of the phases before expulsion, the capilLary dip tube is provided with a plurality of perforations 0. 01 to 1. 2 mm in diameter over its ~ntire length, so that the two phases are admittecl together in the valve chamber from the capillary dip ~ube, instead of the gas being admitted only througll a vapor tap orifice, and the liquid through a dip tube as is normal. The propellant is blended in the liquid phase in an indeterminate volume in proportion to the aqueous phase in the capillary dip tube.
Presant et al in pat~n t No. 3, 544, 258, referred to above, dis-closes a vapor tap valve having a stem orifice 0. 018 inch in diameter, a vapor tap 0. 023 inch in diameter with a capillary dip tube 0. 050 inch in diameter. The button orifice diameter was 0.016 inch. The composition dispensed is an aluminum antiperspirant comprising aluminum chlor-hydroxide, water, alcoholand dimethyl ether. The aluminum chlorhy-droxi~!e is in solution in the water, and there is therefore only one liquid phase. The dimensions of the orifices provided for this composition are too small to avoid clogging, in dispensing an aluminum antiper-spirant composition containing dispersed astringent salt particles.
- The vapDr tap type of valve is effective in providing fine sprays.
However, it requires a high proportion of propellant, relative to the amount of active ingredients dispensed per unit time. A vapor tap requires a L~rge amount of propellant gas, because the tap introduces more propellant gas into each squirt of liquid. Such valves therefore require aerosol compositions having a rather high proportion of propelL~nt.
A high propellant proportion is undesirable, however. ~he fluorocarbon propellants are thought to be deleterious, in that they are believed to accumulate in the stratosphere, where they may possibly interfere with the protective o~one Layer there~ The hydrocarbon propelL~nts are flam~l~ble, and their proportion must be restricted to avoid a flame hazard. Moreover, both these types o propelL~nts, and especially the fluorocarbons, have become rather expensiveO
Another problem with such valves is that since they deliver a liquid propellant-aerosol composition mixture, and have valve passages in which a residue of liquid remains following the squirt, evaporation of the liquid in the valve passages after the squirt may lead to deposition of solid materials upon evaporation of liquids, and valve clogging. This problem has given rise to a number of expedients, to prevent the depo-sition of solid materials in a form which can result in clogging.
Consequently, it has long been the practice to employ large amounts of liquefied propellant, say 50~C by weight or more,to obtain fine droplets of liquid sprays or fine powder sprays, and ~ r~ther small solids content, certainly less than 10~G, and normally less than 5~. The fine sprays result from the violent boiling of the liquefied propellant after it has left the containerO A case in point is exemplified by the dispersion-type aerosol antiperspirants, which contain 5~7c or less of astringent powder dispersed in liquefied propelLant. It has not been possible to use sub-stantially higher concentrations of astringents without encountering severe clogging problems.
There is considerable current interest inthe substitution of com-pressed gases for fluorocarbons and hydrocarbons as propelLants to obtain fine aerosol sprays. The reasons include the low cost of com-pressed gases, the flammability of liquefied hydrocarbon propellants, and the theorized hazard to the ozone layer of liquefied fluorocarbon propellants. Reasonably fine sprays of alcoholic solutions have been obtained USillg carbon dioxide at 90 psig and valving systems with very fine orifices~ These orifices are so small that dispersed solids cannot be tolerated, and even inadvertent contamination with dust will cause clogging. Thus, a typical system will e mploy a 0O 014 inch capillary dip tube, a 0.010 inch valve stem orifice, and a 0.008 inch orifice in a mechanical break-up actuator button. Only limited variations in delivery rates are possible, since the use of significantly larger orifices will coarsen the spray droplets.
Thus far, the art has not succeeded in obtaining f~ne aerosol sprays using aqueous solutions with compressed gases. The reasons for this are that water has a higher surface tension and a higher viscosity than -~ alcohol (ethanol or isopropanol) and is also a poorer solvent for the compressed gases, particularly carbon dioxide, which is preferred.
All of these factors adversely affect the break-up of droplets to form a fine spray.
Special designs of the delivery port and valve passages have been proposed, to prevent the deposit of solid materials in a manner such that clogging can result . UO S. patent No. 3, 544, 258 provides a structure which is especially designed to avoid this difficulty, for example. Such designs result however in a container and valve system which is rather expensive to produce, complicated to assemble because of the numerous parts, and more prone to failure because of its complexity.
In accordance with Canadian patent No. 1, 030, 497, patented May 2, 1978, aerosol containers are provided that are capable of delivering a foamed aerosol composition. The aerosol composition is foamed inside the aerosol container, and delivered through the valve of the aerosol 5 container, as a foam or collapsed foam. Fine droplets are formed from the foamed aerosol compositions, due at least in part to collapse of thin foam cell walls into fine droplets. The propellant serves to foam the liquid within the container, forming a foamed aerosol composition, and propels from the container through the valve and delivery port both any 10 foam and any droplets that form when the foam collapses.
With conventional aerosol containers, a substantial proportion of the propellant is in liquid form as the aerosol composition passes through the valve and delivery port. Propellant evaporates as the spray ~ravels through the air, and it continues to evaporate after the 15 spray has landed on a surface. The heat of vaporization is taken from the surface, and the spray consequently feels cold. This is wasteful of propellant, as is readily evidenced by the coldness of sprays from conventional aerosol containers. In contrast, in the invention of No. 1, 030, 497, the propellant is in gaseous form when expelled with 20 the liquid. The propellant is not wasted, therefore, and since there is substantially no liquid propellant to take up heat upon vaporization, the spray is not cold.
The aerosol containers in accordance with the invention of No. 1, 030, 497 accordingly foam an aerosol composition therein prior 1~48453 to expulsion from the container, and then expel the resulting foamed aerosol composition. These aerosol containers comprise, in combination, a pressurizable container having a valve movable between open and closed positions, with a valve stem, and a foam-conveying 5 passage therethrough, in flow connection with a delivery port; bias means for holding the valve in a closed position; and means for manipulating the valve against the bias means to an open position, for expulsion of aerosol composition foamed within the container via the valve passage and delivery port; means defining at least two separate 10 compartments in the container, of which a first compartment is in direct flow connection with the valve passage, and a second compartment is in flow connection with the valve passage only via the first compartment;
and porous bubbler means having through pores interposed between the first and second compartments with the through pores communicating the 15 compartments, the pores being of sufflciently small dimensions to restrict flow of propellant gas from the second compartment therethrough and form bubbles of such gas in liquid aerosol composition across the line of flow from the bubbler to the valve, thereby to foam the aerosol composition upon opening of the valve to atmospheric pressure, and to expel foamed 20 aerosol composition through the open valve.
Canadianpatent application Serial No. 249, 554, filed April 5, 1976 provides another form of foam-type aerosol container, in which the aerosol composition therein is foamed prior to expulsion from the container, and then the resulting foamed aerosol composition is expelled~
25 These aerosol containers comprise, in combination, a pressurizable ,~
. ,~
c ontailler having a valve movable between open and closed positions, with a valve stem, and a foam-conveying passage therethrough, in flow colmection with a delivery port; bias means for holding the valve in a closed position; and means for manipulating the valve against the bias means to an open position or expulsion via the valve passage and delivery port of aerosol composition foamed within the container;
means defining at least two separate compartments in the container, of which a first compartment has a volume of at least 0O 5 cc and is in direct flow connection with the valve passage, and a second compa~tment is in flow connection with the valve passage only via the first compartment;
at least one first liquid tap orifice having a diameter within the range from about 0. 012 to about 0. 2 cm and communicating the first and another compartment for flow of liquid aerosol composition into the first com-partment, and of sufficiently small dimensions to restrict flow of liquid aerosol composition therethrough; the ratio of first compartment volu~.ne/first orifice dLameter being from about 10 and preferably from about 20 to about 400, and preferably about x ~ where x is 1 when the orifice length is less than 1 cm, and 2 when the orifice length is 1 cm or m~e; at least one second gas tap orifice having a total cross-sectional open area within the range from about 7 x 10 to about 20 x 10 in2 (4 x 10-5 to 1. 3 x 1~2 cm2), a single orifice having a diameter within the range from about 0.003 to about 0O05 inch (0.007 to 0.13 cm) and communicating the first and second compartments for flow of propellant gas into the first compartment from the second compartment therethrough, and of suffi-ciently small dimensions to restrict flow of propellant gas and form -bubbles of such g~s in liquid aerosol composition across the line of flow thereof to the valve, thereby to foam the aerosol composition upon o~en~ng of the valve to atmospheric pressure, and to expel the foamed aerosol composition through the open valve.
The advantages of foaming the aerosol composition within the container are twofold. Because the propellant is in gaseous form (having been converted to gas in the foaming) there is no liquid propellant to expel, so all propelL~nt is usefully converted into gas, for propulsion and foaming, before being expelled Because the foamed liquid aerosol composition has a higher volume than the liquid composition, and the expulsion rate is in terms of volume per unit time, less liquid is expelled per unit time. Thus, in effect, the liquid is expelled at a lower delivery rate, which conserves propellant per unit squirt, and means a higher active concentration must be used, to obtain an equivalent delivery rate of active ingredient. Also, since there is less liquid, there is a negligible clogging problem, even at a two or three times higher active concentrationO
The disadvantage of foaming however is the need to provide space for the foaming to take place, which requires either a larger container or a smaller unit volume of composition per container.
In accordance with the instant invention, it has been determined that a low delivery rate can be achieved without the necessity of providing a foam chamber or space within the aerosol container, if the volume proportion of gas to liquid in the blend dispensed from the container is within the range from about 10: 1 to about 40: 1, and preferably within the range from about 15: 1 to about 30:1. This is a sufficient proportion of gas to liquid to form a foam, such as is formed and dispensed from the foam type aerosol containers of Canadian patent No. 1, 030, 497 and Canadian Serial No. 249, 554, referred to above, and a very much higher proportion of gas to liquid than has previously been blended with the liquid for expulsion purposes in conventional aerosol containers, such as the vapor tap containers of the Presant patent No. 3, 544, 258 referred to above. At such high proportions of gas to liquid, the formation of foam is possible, and even probable, despite the small volume of the blending space provided, but foam formation, if it occurs, is so fleeting, having a life of at most a fraction of a second, that a foam cannot be detected by ordinary means, due to the small dimensions of the open spaces in which it may exist, i. e., the blending space and valve passages, and the shortness of the delivery time from blending of gas and liquid to expulsion. However, the proportion of gas to liquid in the blend that is expelled can be deter-mined, and when the proportion is in excess of 10:1, the delivery rate of liquid from the aerosol container is very low, and thus, the objective of the invention is achieved. Whether or not a foam is formed is therefore of no significance, except as a possible theoretical explanation of the - phenomenon.
Accordingly, the invention provides a process for dispensing a spray containing a low proportion of liquid, with a high proportion of -propellant in gaseous form, by blending gas and liquid within the aerosol container prior to expulsion at a ratio of gas:liquid within the range from about 10:1 to about 40:1, and preferably from about 15:1 to about 30:1, with the result that a blend containing this low proportion of liquid and ~- .
1~4~4S3 high proportion o gas is expellecl from the container, and the proportion of liquid composition e~pelled per unit time correspondingly roduced.
The aerosol container in accordance with the invention comprises, ~n combination, a pressurizable container having a valve movable between open and closed positions, a valve stem, and a delivery port;
a valve stem orifice in the valve stem in flow connection at one end with a blending space and at the other end with an aerosol-conveying valve stem passage leading to the delivery port; the valve stem orifice having a diameter within the range from about 0. 50 to about 0. 65 mm; bias means for holding the valve in a closed position; means for manipulating the valve against the bias means to an open position for expulsion of aerosol composition via the valve stem orifice to the delivery port;
wall means defining the blending space and separating the blending space from liq!lid aerosol composition and propellant within the container; at least one liquid tap orifice through the wall means, having a cross-sectional open area within the range from about 0. 4 and 0. 6 mm for flow of liquid aerosol composition into the blending space; at least one vapor tap orifice through the wall means, having a cross-sectional open area within the range from about 0. 4 to about 0. 8 mm for flow of propellant into the blending space; the ratio of liquid tap orifice to vapor tap orifice cross-sectional open area being within the range from about 0. 5 to about 0. 9; the open areas of the liquid tap orifice and vapor. tap orifice being selected within the stated ranges to provide a volume ratio of propellant gas: liquid aerosol composition within the range from about 10:1 to about 40:1, thereby limiting 11)48453 the delivery rate of liquid aerosol composition ~rom the co!ltainer when the valve is opened.
In the special case where the liquid tap orifice is a capillary dip tube the cross-sectional open area thereof is within the range from about 0. 6 to a~out 1. 3 mm2, for flow of liquid aerosol composition into the blending space, and at least one vapor tap orifice through the wall means has a cross-sectional open area within the range from about 0. 4 to about 0 8 mm2 for flow of propellant gas into the blending space;
and the ratio of capillary dip tube to vapor tap orifice cross-sectional open area is within the range from about 1.0 to about 2. 0.
The controlling orifices for the purposes of the invention to achieve the desired proportion of gas and liquid in the blend dispensed from the container àre the vapor tap orifice, the liquid tap orifice (or in the case of a capillary dip tube, the capillary dip tube)7 and the valve stem orifice. The open areas of these orifices and ~he ratio of liquid tap orifice to vapor tap orifice open area should be cont~olled within the stated ranges.
The valve delivery systemnormally includes, in addition tothe valve stem orifice, an actuator orifice at the end of the passage through the actuator of the valve. The valve delivery system from the blending chamber through the valve stem and actuator to the delivery port thus includes, in flow sequence towards the delivery end, the valve stem orifice, the valve stem passage, the actuator passage, and the actuator orifice. The controlling orifice in this sequence is the valve stem orifice, and the actuator orifice willnormally have a diameter the same as or greater than the valve stem orifice.
~048*~3 In the unlikely event that the actuator orifice has an open area that is less than the valve stem orifice, then the actuator orifice becomes tl~e controllillg orifice, downstream of the blending chamber, and diameter must in that event be within the range from about 0. 5 to about 0.65 mm.
The valve is disposed in a valve housing, which may also include or is in flow connection with the wall means defining the blending space.
The blending space is of limited volume~ insufficient to constitute a foam chamber, and only as large as required for thorough blending of gas and liquid t~e rein before reaching the valveO A valve member may be movably disposed in the blending space, for movement between open and closed positions, away from and towards a valve seat at the inner end of the valve stem passage, with which the blending space is in flow connection when the valve is open.
The blending space can be small in volume, and no l~rger than the volume needed for full movement of a valve member thereinO It can also be a narrow passage, large enough at one end for the valve member, and merging indistinguishably with the dip tube or tail piece passageO Any conventional mixing chamber in a vapor tap valve assembly will serve.
The volume of the blending SE~ce does not usually exceed 1 cc, and can be as small as 0.1 cc, but it is preferably from 0~ 5 to 1 cc.
The liquid tap orifice communicates the blending space directly or indirectly with a capillary dip tube or a standard dip tube. A
Aerosol sprays are now widely used, particularly in the cosmetic, topical pllarmaceutical and detergent fields for delivery of an additive such as a cosmetic, pharmaceutical, or cleaning composition to a substrate such as the skin or other surface to be treated. Aerosol compositions are widely used as antiperspirants to direct the antiperspirant to the skin in the form of a finely divided spray.
The delivery of antiperspirants to the skin in a fine spray poses a difficult aerosol packagin~ problem. Aerosol antiperspirant compositions based on anhydrous propellant systems normally include ant~?erspirant, filler and other solid particles dispersed in a liquid vehicle, and the solid particlesreadily clog small valve orifices~ On the other hand, if the orifices are large enough to avoid clogging, a coarse liquid spray with large droplets is formed, and there may be excessive drip at the nozzle. The material can even be squirted out in the form of a liquid stream, which rapidly- runs off the surface on which it is deposited.
Much effort has accordingly been directed to the design of valves and valve delivery ports, nozzles or orifices which are capable of delivering finely-divided sprays, of which U.S. patents Nos. 3,083,917 and 3,083,918 patented April 2,1963, to Abplanalp et al, and No. 3,544,258 dated December 1,1970, to Presant et al, are exemplary. The latter 1048gS3 pat ent describes a type of valve ~vhich is now rather common, giving a finely atomized spray, and having a vapor tal~, which includes a mixillg chamber provicled with separate openings for the vapor phase and the liquid pl~ase to be dispensed into the chamber, in combination with a valve actuator or button of the mechanical breakup type. Such valves provide a soft spray with a swirling motion. Another design of valves of this type is described in U. S . patent No. 2, 767, 023 . Valves with vapor taps are generally used where the spray is to be applied directly to the skin, since the spray is less cold.
M~rshU.S. patentNo. 3,148,127patentedSeptember 8, 1964 describes a pressurized self-dispensing package of ingredients for use as a hair spray and comprising; isobutane or similar propellant in one phase and an aqueous phase including the hair setting ingredient. The _ isobutane is in a relatively high proportion to the aqueous phase, and is exhausted slightly before the water phase has been entirely dispensed.
A vapor tap type oiE valve is used having a 0. 030 inch vapor tap orifice, a 0. 030 inch liquid tap orifice, and a 0. 018 inch valve stem orifice~
with a mechanical breakup button. There is no disclosure of the rel~-tive proportions of propellant gas to liquid phase being dispensed.
Rabussier U.S. patentNo. 3,260,421 patented July 12, 1966 describes an aerosol container for expelling an aqueous phase and a propellant phase, fitted with a vapor tap valve, and capilLary dip tube.
To achieve better blending of the phases before expulsion, the capilLary dip tube is provided with a plurality of perforations 0. 01 to 1. 2 mm in diameter over its ~ntire length, so that the two phases are admittecl together in the valve chamber from the capillary dip ~ube, instead of the gas being admitted only througll a vapor tap orifice, and the liquid through a dip tube as is normal. The propellant is blended in the liquid phase in an indeterminate volume in proportion to the aqueous phase in the capillary dip tube.
Presant et al in pat~n t No. 3, 544, 258, referred to above, dis-closes a vapor tap valve having a stem orifice 0. 018 inch in diameter, a vapor tap 0. 023 inch in diameter with a capillary dip tube 0. 050 inch in diameter. The button orifice diameter was 0.016 inch. The composition dispensed is an aluminum antiperspirant comprising aluminum chlor-hydroxide, water, alcoholand dimethyl ether. The aluminum chlorhy-droxi~!e is in solution in the water, and there is therefore only one liquid phase. The dimensions of the orifices provided for this composition are too small to avoid clogging, in dispensing an aluminum antiper-spirant composition containing dispersed astringent salt particles.
- The vapDr tap type of valve is effective in providing fine sprays.
However, it requires a high proportion of propellant, relative to the amount of active ingredients dispensed per unit time. A vapor tap requires a L~rge amount of propellant gas, because the tap introduces more propellant gas into each squirt of liquid. Such valves therefore require aerosol compositions having a rather high proportion of propelL~nt.
A high propellant proportion is undesirable, however. ~he fluorocarbon propellants are thought to be deleterious, in that they are believed to accumulate in the stratosphere, where they may possibly interfere with the protective o~one Layer there~ The hydrocarbon propelL~nts are flam~l~ble, and their proportion must be restricted to avoid a flame hazard. Moreover, both these types o propelL~nts, and especially the fluorocarbons, have become rather expensiveO
Another problem with such valves is that since they deliver a liquid propellant-aerosol composition mixture, and have valve passages in which a residue of liquid remains following the squirt, evaporation of the liquid in the valve passages after the squirt may lead to deposition of solid materials upon evaporation of liquids, and valve clogging. This problem has given rise to a number of expedients, to prevent the depo-sition of solid materials in a form which can result in clogging.
Consequently, it has long been the practice to employ large amounts of liquefied propellant, say 50~C by weight or more,to obtain fine droplets of liquid sprays or fine powder sprays, and ~ r~ther small solids content, certainly less than 10~G, and normally less than 5~. The fine sprays result from the violent boiling of the liquefied propellant after it has left the containerO A case in point is exemplified by the dispersion-type aerosol antiperspirants, which contain 5~7c or less of astringent powder dispersed in liquefied propelLant. It has not been possible to use sub-stantially higher concentrations of astringents without encountering severe clogging problems.
There is considerable current interest inthe substitution of com-pressed gases for fluorocarbons and hydrocarbons as propelLants to obtain fine aerosol sprays. The reasons include the low cost of com-pressed gases, the flammability of liquefied hydrocarbon propellants, and the theorized hazard to the ozone layer of liquefied fluorocarbon propellants. Reasonably fine sprays of alcoholic solutions have been obtained USillg carbon dioxide at 90 psig and valving systems with very fine orifices~ These orifices are so small that dispersed solids cannot be tolerated, and even inadvertent contamination with dust will cause clogging. Thus, a typical system will e mploy a 0O 014 inch capillary dip tube, a 0.010 inch valve stem orifice, and a 0.008 inch orifice in a mechanical break-up actuator button. Only limited variations in delivery rates are possible, since the use of significantly larger orifices will coarsen the spray droplets.
Thus far, the art has not succeeded in obtaining f~ne aerosol sprays using aqueous solutions with compressed gases. The reasons for this are that water has a higher surface tension and a higher viscosity than -~ alcohol (ethanol or isopropanol) and is also a poorer solvent for the compressed gases, particularly carbon dioxide, which is preferred.
All of these factors adversely affect the break-up of droplets to form a fine spray.
Special designs of the delivery port and valve passages have been proposed, to prevent the deposit of solid materials in a manner such that clogging can result . UO S. patent No. 3, 544, 258 provides a structure which is especially designed to avoid this difficulty, for example. Such designs result however in a container and valve system which is rather expensive to produce, complicated to assemble because of the numerous parts, and more prone to failure because of its complexity.
In accordance with Canadian patent No. 1, 030, 497, patented May 2, 1978, aerosol containers are provided that are capable of delivering a foamed aerosol composition. The aerosol composition is foamed inside the aerosol container, and delivered through the valve of the aerosol 5 container, as a foam or collapsed foam. Fine droplets are formed from the foamed aerosol compositions, due at least in part to collapse of thin foam cell walls into fine droplets. The propellant serves to foam the liquid within the container, forming a foamed aerosol composition, and propels from the container through the valve and delivery port both any 10 foam and any droplets that form when the foam collapses.
With conventional aerosol containers, a substantial proportion of the propellant is in liquid form as the aerosol composition passes through the valve and delivery port. Propellant evaporates as the spray ~ravels through the air, and it continues to evaporate after the 15 spray has landed on a surface. The heat of vaporization is taken from the surface, and the spray consequently feels cold. This is wasteful of propellant, as is readily evidenced by the coldness of sprays from conventional aerosol containers. In contrast, in the invention of No. 1, 030, 497, the propellant is in gaseous form when expelled with 20 the liquid. The propellant is not wasted, therefore, and since there is substantially no liquid propellant to take up heat upon vaporization, the spray is not cold.
The aerosol containers in accordance with the invention of No. 1, 030, 497 accordingly foam an aerosol composition therein prior 1~48453 to expulsion from the container, and then expel the resulting foamed aerosol composition. These aerosol containers comprise, in combination, a pressurizable container having a valve movable between open and closed positions, with a valve stem, and a foam-conveying 5 passage therethrough, in flow connection with a delivery port; bias means for holding the valve in a closed position; and means for manipulating the valve against the bias means to an open position, for expulsion of aerosol composition foamed within the container via the valve passage and delivery port; means defining at least two separate 10 compartments in the container, of which a first compartment is in direct flow connection with the valve passage, and a second compartment is in flow connection with the valve passage only via the first compartment;
and porous bubbler means having through pores interposed between the first and second compartments with the through pores communicating the 15 compartments, the pores being of sufflciently small dimensions to restrict flow of propellant gas from the second compartment therethrough and form bubbles of such gas in liquid aerosol composition across the line of flow from the bubbler to the valve, thereby to foam the aerosol composition upon opening of the valve to atmospheric pressure, and to expel foamed 20 aerosol composition through the open valve.
Canadianpatent application Serial No. 249, 554, filed April 5, 1976 provides another form of foam-type aerosol container, in which the aerosol composition therein is foamed prior to expulsion from the container, and then the resulting foamed aerosol composition is expelled~
25 These aerosol containers comprise, in combination, a pressurizable ,~
. ,~
c ontailler having a valve movable between open and closed positions, with a valve stem, and a foam-conveying passage therethrough, in flow colmection with a delivery port; bias means for holding the valve in a closed position; and means for manipulating the valve against the bias means to an open position or expulsion via the valve passage and delivery port of aerosol composition foamed within the container;
means defining at least two separate compartments in the container, of which a first compartment has a volume of at least 0O 5 cc and is in direct flow connection with the valve passage, and a second compa~tment is in flow connection with the valve passage only via the first compartment;
at least one first liquid tap orifice having a diameter within the range from about 0. 012 to about 0. 2 cm and communicating the first and another compartment for flow of liquid aerosol composition into the first com-partment, and of sufficiently small dimensions to restrict flow of liquid aerosol composition therethrough; the ratio of first compartment volu~.ne/first orifice dLameter being from about 10 and preferably from about 20 to about 400, and preferably about x ~ where x is 1 when the orifice length is less than 1 cm, and 2 when the orifice length is 1 cm or m~e; at least one second gas tap orifice having a total cross-sectional open area within the range from about 7 x 10 to about 20 x 10 in2 (4 x 10-5 to 1. 3 x 1~2 cm2), a single orifice having a diameter within the range from about 0.003 to about 0O05 inch (0.007 to 0.13 cm) and communicating the first and second compartments for flow of propellant gas into the first compartment from the second compartment therethrough, and of suffi-ciently small dimensions to restrict flow of propellant gas and form -bubbles of such g~s in liquid aerosol composition across the line of flow thereof to the valve, thereby to foam the aerosol composition upon o~en~ng of the valve to atmospheric pressure, and to expel the foamed aerosol composition through the open valve.
The advantages of foaming the aerosol composition within the container are twofold. Because the propellant is in gaseous form (having been converted to gas in the foaming) there is no liquid propellant to expel, so all propelL~nt is usefully converted into gas, for propulsion and foaming, before being expelled Because the foamed liquid aerosol composition has a higher volume than the liquid composition, and the expulsion rate is in terms of volume per unit time, less liquid is expelled per unit time. Thus, in effect, the liquid is expelled at a lower delivery rate, which conserves propellant per unit squirt, and means a higher active concentration must be used, to obtain an equivalent delivery rate of active ingredient. Also, since there is less liquid, there is a negligible clogging problem, even at a two or three times higher active concentrationO
The disadvantage of foaming however is the need to provide space for the foaming to take place, which requires either a larger container or a smaller unit volume of composition per container.
In accordance with the instant invention, it has been determined that a low delivery rate can be achieved without the necessity of providing a foam chamber or space within the aerosol container, if the volume proportion of gas to liquid in the blend dispensed from the container is within the range from about 10: 1 to about 40: 1, and preferably within the range from about 15: 1 to about 30:1. This is a sufficient proportion of gas to liquid to form a foam, such as is formed and dispensed from the foam type aerosol containers of Canadian patent No. 1, 030, 497 and Canadian Serial No. 249, 554, referred to above, and a very much higher proportion of gas to liquid than has previously been blended with the liquid for expulsion purposes in conventional aerosol containers, such as the vapor tap containers of the Presant patent No. 3, 544, 258 referred to above. At such high proportions of gas to liquid, the formation of foam is possible, and even probable, despite the small volume of the blending space provided, but foam formation, if it occurs, is so fleeting, having a life of at most a fraction of a second, that a foam cannot be detected by ordinary means, due to the small dimensions of the open spaces in which it may exist, i. e., the blending space and valve passages, and the shortness of the delivery time from blending of gas and liquid to expulsion. However, the proportion of gas to liquid in the blend that is expelled can be deter-mined, and when the proportion is in excess of 10:1, the delivery rate of liquid from the aerosol container is very low, and thus, the objective of the invention is achieved. Whether or not a foam is formed is therefore of no significance, except as a possible theoretical explanation of the - phenomenon.
Accordingly, the invention provides a process for dispensing a spray containing a low proportion of liquid, with a high proportion of -propellant in gaseous form, by blending gas and liquid within the aerosol container prior to expulsion at a ratio of gas:liquid within the range from about 10:1 to about 40:1, and preferably from about 15:1 to about 30:1, with the result that a blend containing this low proportion of liquid and ~- .
1~4~4S3 high proportion o gas is expellecl from the container, and the proportion of liquid composition e~pelled per unit time correspondingly roduced.
The aerosol container in accordance with the invention comprises, ~n combination, a pressurizable container having a valve movable between open and closed positions, a valve stem, and a delivery port;
a valve stem orifice in the valve stem in flow connection at one end with a blending space and at the other end with an aerosol-conveying valve stem passage leading to the delivery port; the valve stem orifice having a diameter within the range from about 0. 50 to about 0. 65 mm; bias means for holding the valve in a closed position; means for manipulating the valve against the bias means to an open position for expulsion of aerosol composition via the valve stem orifice to the delivery port;
wall means defining the blending space and separating the blending space from liq!lid aerosol composition and propellant within the container; at least one liquid tap orifice through the wall means, having a cross-sectional open area within the range from about 0. 4 and 0. 6 mm for flow of liquid aerosol composition into the blending space; at least one vapor tap orifice through the wall means, having a cross-sectional open area within the range from about 0. 4 to about 0. 8 mm for flow of propellant into the blending space; the ratio of liquid tap orifice to vapor tap orifice cross-sectional open area being within the range from about 0. 5 to about 0. 9; the open areas of the liquid tap orifice and vapor. tap orifice being selected within the stated ranges to provide a volume ratio of propellant gas: liquid aerosol composition within the range from about 10:1 to about 40:1, thereby limiting 11)48453 the delivery rate of liquid aerosol composition ~rom the co!ltainer when the valve is opened.
In the special case where the liquid tap orifice is a capillary dip tube the cross-sectional open area thereof is within the range from about 0. 6 to a~out 1. 3 mm2, for flow of liquid aerosol composition into the blending space, and at least one vapor tap orifice through the wall means has a cross-sectional open area within the range from about 0. 4 to about 0 8 mm2 for flow of propellant gas into the blending space;
and the ratio of capillary dip tube to vapor tap orifice cross-sectional open area is within the range from about 1.0 to about 2. 0.
The controlling orifices for the purposes of the invention to achieve the desired proportion of gas and liquid in the blend dispensed from the container àre the vapor tap orifice, the liquid tap orifice (or in the case of a capillary dip tube, the capillary dip tube)7 and the valve stem orifice. The open areas of these orifices and ~he ratio of liquid tap orifice to vapor tap orifice open area should be cont~olled within the stated ranges.
The valve delivery systemnormally includes, in addition tothe valve stem orifice, an actuator orifice at the end of the passage through the actuator of the valve. The valve delivery system from the blending chamber through the valve stem and actuator to the delivery port thus includes, in flow sequence towards the delivery end, the valve stem orifice, the valve stem passage, the actuator passage, and the actuator orifice. The controlling orifice in this sequence is the valve stem orifice, and the actuator orifice willnormally have a diameter the same as or greater than the valve stem orifice.
~048*~3 In the unlikely event that the actuator orifice has an open area that is less than the valve stem orifice, then the actuator orifice becomes tl~e controllillg orifice, downstream of the blending chamber, and diameter must in that event be within the range from about 0. 5 to about 0.65 mm.
The valve is disposed in a valve housing, which may also include or is in flow connection with the wall means defining the blending space.
The blending space is of limited volume~ insufficient to constitute a foam chamber, and only as large as required for thorough blending of gas and liquid t~e rein before reaching the valveO A valve member may be movably disposed in the blending space, for movement between open and closed positions, away from and towards a valve seat at the inner end of the valve stem passage, with which the blending space is in flow connection when the valve is open.
The blending space can be small in volume, and no l~rger than the volume needed for full movement of a valve member thereinO It can also be a narrow passage, large enough at one end for the valve member, and merging indistinguishably with the dip tube or tail piece passageO Any conventional mixing chamber in a vapor tap valve assembly will serve.
The volume of the blending SE~ce does not usually exceed 1 cc, and can be as small as 0.1 cc, but it is preferably from 0~ 5 to 1 cc.
The liquid tap orifice communicates the blending space directly or indirectly with a capillary dip tube or a standard dip tube. A
2~ standard or capillary dip tube normally extends into the liquid compo-1~)48453 sition or phase in the aerosol container, and may reach to the bottorn of the container. A tail piece n~ay be provided (but is not essential) as the valve housin as a coupling for linking the dip tube to the blending space within the valve housing. The tail piece when present has a through passage in fluid flow connection with the liquid composition or phase in the container, via the dip tube, and this passage leads directly into the blending space. The liquid tap orifice in this embodiment is an orifice or constriction in the passage, at the blending space end, at the dip tube end, or intermediate the ends. The orifice can also be in direct communication with the dip tube, in the event the tail piece is omitted. When the dip tube communicates directly with the blending space, the liquid tap orifice can be at the blending space end opening of the dip tube.
In the special case when a capillary dip tube is used, no liquid tap orifice as such is required~ The capillary dip tube serves as the liquid tap orifice. However, the si7e parameters for the capillary dip tube and vapor tap orifice in that event are different, because of the unique flow restriction of the capillary dip tube,as noted previouslyO
The vapor tap orifice is in fluid flow connection with the propelLant or gas phase of the aerosol container, and admits gas into the blending space before the valve stem delivery E~ssage. Normally, therefore, it is in the wall means defining the blending space, and above the liquid tap orifice, although this is not essential. The vapor tap orifice can be in a wall beside or above the valve member, but it is of course upstream of the valve seat.
The valve delivery system of an aerosol container downstream of the valve normally includes all actuator which operates a valve movable between open and closed positions, with a valve stem and an aerosol composition-conveying valve passage therethrough, in flow connection with a delivery port~ The narrowest orifice in this delivery system is within the range from about 0. 5 to about 0. 65 mm.
Mixing of the gas and liquid phase occurs in the blending space, before these pass to the valve, and the diameters of the vapor tap and liquid tap orifices as well as the valve passage with which they are in communication are selected within the stated ranges to provide a gas:
liquid volume ratio within the range from about 10: 1 to about 40:1, and preferably from about 15:1 to about 30:1. It will be appreciated that for a given size of these openings, the gas: liq!lid ratio obtained from gas and liquid fed therethrough from the supply in the container will vary with the particular propellallt or propellants ~d the composition of the liquid phaseO The viscosity of the liquid is a factor in determining the proportion that can flowthrough the liquid tap orifice per unit time, when the valve isopened.
The orifice ranges given are applicable to all dispersion-type antiperspirant aerosol compositions, but the particular values chosen-for the sizes of the orifices within the stated ranges will therefore depend upon the particu]ar composition that is selected for packaging in the aerosol container. Those skilled in the art are aware of how to adjust the applicable parameters for a given aerosol composition, since they already do this in selecting the particular delivery orifice, valve steam passage, dip t~lbe and vapor tap orifice for conventional vapor tap aerosol containers mixing the liquid and gas at a much lower gas:
liquid ratio. By application of these known principles, it is possible to scale up the orifice diameters in proportion to obtain delivery of the gas: liquid ratio required in the invention.
If a capillary dip tube is used, its inside diameter should be within the range from about 1.0 to about 1.5 times the diameter of the vapor tap orifice. If a liquid tap orifice in a restricted tail piece, or equivalent, is used, with a standard dip tube, the restricted tail piece orifice diameter should be within the range from about 0. 75 to about 0. 95 times the diameter of the vapor tap orifice.
Preferred embodiments of aerosol containers in accordance with the invention- are illustrated in the drawings, in which:
~ Figure 1 represents a longitudinal sectional view of one embodiment of aerosol container in accordance with the inv~ntion, including a capill~Lry dip tube in fluid flow connection with the vapor tap orifice;
Figure lA represents a detailed view of the val~e stem and poppet, showing the valve stem orifice in open and closed positions;
Figure 2 represents a cross-sectional view taken along the line 2-2 of Figure lj Figure 3 represents a longitudinal sectional v~ew of another .
embodiment of aerosol container in accordance with the invention, with a restricted tail piece and a standard dip tube in fluid flow connection with the vapor tap orifice; and Figure 4 represents a cross-sectional view taken along the e 4-4 o Figure 3.
~l principle, the aerosol containers of the invention utilize a container having at least one compartment for propellant gas and liquid aerosol composition, communicated by at least one gas tap orifice and at least one liquid tap orifice to a blending space, which is across the line of flow to the valve delivery port. A liquid aerosol composition to be blended with proFelLant gas and then ex-pelled from the container is placed in this compartment of the container, in flow communication via the liquid tap orifice with the blending space, so as to admit liquid aerosol composition into the blending space, while propellant gas flows into the blending space via the gas tap orifice or orifices to the valYe.
Tn summary of the above, the orifice open area dimensions are as follows: ~
OPEN AR:~A
(mm~) ~
.. .. _ . _ OVERALL PREFERRED
Valve stem orifice 0.2 to 0.3 0.2 to 0.3 Vapor tap orifice 0. 4 to 0.8 0. 5 to 0. 7 Liquid tap orifice 0. 4 to 0.6 0. 4 to 0. 5 Ratio liquid tap orifice/ o. 5 to 0. 9 0. 6 to 0. 8 vapor taE~ orifice cross-.
sectional open area In the special case where a capillary dip tube is used, open area is as follows:
104~4S3 OPEN AREA
(mm2) OVERALL PREFERRED
Valve stem orifice 0. 2 to 0. 3 Q. 2 to 0. 3 Vapor tap orifice . 0. 4 to 0. 8 0. 5 to 0. 7 Capillary dip tube 0. 6 to 1. 3 0. 7 to 0. 9 Ratio capillary dlp tube 1. 0 to 2. 0 1. 1 to 1. 5 vapor tap oriEice cross- -sectional open area The orifice diameter dimensions are as follows:
DIAMETER
(mm) - OVERALL PREFERRED
Valve stem orifice diameter 0. 50 to 0. 65 0. 50 to 0. 65 Vapor tap orifice diameter 0. 70 to 1. 0 0. 80 to 0. 95 Liquid tap orifice diameter 0. 70 to U. 90 0. 70 to 0. 80 Ratio of liquid tap orifice 0. 75 to 0. 95 0. 8 to 0. 9 diameter: vapor tap orifice diameter In the special case where a capillary dip tube is used, dimensions are as follows: .
DIAMETER
(mm) OVERALL PREFERRED
-Valve stem orifice diameter 0. 50 to 0. 65 0. 50 to ~5 mm Vapor tap orifice diameter 0. 70 to 1. 0 0. 80 to 0. 95 mm Capillary dip tube diameter 0. 90 to 1. 3 0. 95 to 1. 15 mm Ratio of capillary dip tube 1. 0 to 1. 5 1. 1 to 1. 3 diameter:vapor tap orifice diameter The particular form of aerosol liquid is not critical. The aerosol containers of the invention can foam aqueous aerosols, organic solvent solution aerosols, emulsions, both of water-in-oil and oil-in-water type.
The greater the solubility of the propellant in the aerosol compo-sition, the lower the efficiency of propellant utilization, since more of the propellant remains dissolved, and less is available for blending in the gas phase with the aerosol liquid in the blending space. Accordingly, it is generally preferred that the solubility of the propellant be at a minimum, and additions to the aerosol composition can be made to reduce solubility of the propellant therein. For instance, if the aerosol composition is an alcohol formulation, or employs any other water-soluble organic solvent, water may be added or the amount of water can be increased, so as to reduce the solubility of fluorocarbon and hydrocarbon propellants in the resulting solution. ~E the aerosol composition is an aqueous formulation, less soluble propellants, such as nitrogen, fluorocarbon and hydrocarbon propellants, are preferred over the more soluble propellants, such as carbon dioxide, nitrous oxide and dimethyl ether.
The aerosol containers in accordance with the invention can be made of metal or plastic, the latter being preferred for corrosion resistance. However, plastic-coated metal containers can also be used, to reduce corrosion. Aluminum, anodized aluminum, coated aluminum, zinc-plated and cadmium-plated steel, tin, and acetal polymers such as Celcon (trademark) or Delrin (trademark) are suitable container materials.
The gas tap and liquid tap orifices can ~e disposed in any type of porous or foraminous structure. One each of a gas tap and liquid tap .
. r. ~
104~4~3 orifice througll the compartmellt wall separating the propellant and any other compartmellts from the blending space will suffice. A plurality of gas tap and liquid tap orifices can be used, for more rapid blending and composition delivery, but the delivery rate of liquid will still be low, because of the high gas: liquid ratio. The total orifice open area is of course determinative, so that several large orifices can afford a similar delivery rate to many small orifices. However, gas tap orifice size also affects blending, so that a plurality of sma ll gas tap orifices may be preferable to several large orifices~
Orifices may also be provided on a me mber inserted in the wall or at one end of the wall separating the propel~nt and any other compartments from the blending space. One type of such r~ember is a perforated or apertured plastic or metal plate or sheet.
The liquid tap orifice can be rathe r short or rather long, as in a passage through a tail piece member. While a capillary dip tube extending into the bottom of a layer or compartment for liquid aerosol composition is a kind of liquid tap orifice, different dimensions are applicable The term "orifice" as used herein generically encompasses passages narrow enough to behave as orifices, regardless of length, in re~pect to liquid aerosol composition flowed therethrough.
The cross-sectional shape of the orifice is not critical. The orifices can be circular, elliptical, rectangular, polygonal, or any other irregular or regular shape in cross-section~
ln the aerosol container 1 shown in Figures 1 and 2, the aerosol valve 4 is of conventional type, and comprises a va lve poppet 8 seating against the sealing face 19 of a sealing gasket 9 and integral with a valve stem 11. The valve stem is hollow, and has an axial flow passage 13 therethrough. The valve poppet 8 is open at the inner end, defining a socket 8a therein, for the reception of a coil spring 18. The passage 13 is separated from the socket 8a within the poppet 8 by the divider wall 8b.
Adjacent the poppet wall 8b in a side wall of the stem 11 is a valve stem orifice 13a. The gasket 9 has a central opening 9a there-through, which receives the valve stem 11 in a sliding leak-tight fit, permitting the stem to move easily in either direction through the opening, without leakage of propellant gas or liquid from the container.
When the valve stem is in the outwardly extended position shown in Figure 1, the surface of the poppet portion 8 contiguous with wall 8b is in sealing engagement with the inner face of the gasket 9, closing ~~~ 15 off the orifice 13a and the passage 13 to outward flow of the contents of the container.
The outer end portion lla of the valve stem 11 is received in the axial socket 16 of the button actuator 12, the tip engaging the ledge 16a of the recess. The stem is attached to the actuator by a press fit.
The axial socket 16 is in flow communication with a lateral E~assage 17, leading to the actuator (valve delivery) orifice 14 of the button 12.
A compression coil spring 18 has one end retained in the socket 8a of the valve poppet 8, and is based at its other end upon inner wall 6b of the valve housing 6. The spring 18 biases the poppet 8 towards the gasl~et 9, engaging it in a leak-tight seal at the valve seat 19.
Whell the valve poppet is against the valve seat 19, the orifice 13a leading into the passage 13 of the valve stem is closed off.
The valve is however reciprocably movable towards and away from the valve seat 19 by pressing inwardly on the button actuator 12, thus moving the valve ste~n 11 and with it poppet 8 against the spring 18.
When the valve is moved far enough away from the seat 19, into the position shown in detail in Figure lA, the orifice 13a is brought beneath the valve gasket 9, and a flow passage is tkerefore open from the blending space 5 defined by the valve housing 6 to the delivery port 14.
The limiting open position of the valve poppet 8 is fixed by the wall 6b of housing 6, the valve poppet 8 encountering the housing wall, and stopped. The valve stem orifice 13a when in the open position com-municates the stem passage 13 with the actuator passages 16,17 and valve delivery orifice 14, and thus depressing the actuator 12 permits fluid flow via the space 5 to be dispensed from the container at delivery port 1'~.
Thus, the spring 18 ensures that the valve poppet 8 and the refore valve 4 is normally in a closed position, and that the valve is open only when the button actuator 12 is moved manually against the force of the spring 180 The valve housing 6 has an expanded portion 6a within which is received the sealing gasket 9 and retained in position at the upper end of the housing. The expanded portion 6a is retained by the crimp 23b in the center of the mounting cup 23, with the valve stem 11 extending 10~8453 tlu~ougll an aperture 23a in the cup. The cup 23 is attached to the container dome 24, whicll in turn is attached to the main container portion 25.
Through the wall 7 of the valve housing 6 is a vapor tap orif ice 2, which is in f low conne ction with the upper portion 20 of the space 21 within the container 1, and therefore with the gas phase of propellant, which rises into this portion of the container. The blending space 5 of the valve housing 6 terminates in a passage 5a, in which is inserted one end of the capillary dip tube 32, which extends all the way to the bottom of the container, and thus dips into the liquid phase of the aerosol composition in portion 21 of the container. Liq!lid aerosol composition accordingly enters the space 5 at the passage 5a, via the capillary dip tube 32, so that the dip tube serves as a long liquid tap orifice, while gas enters the s~ce 5 thro~gh the gas tap orifice 2.
In the valve shown, the diameter of the actuator (valve delivery) orifice 14 is 0.5 mm, the valve stem orifice 13a is 0.5 mm, the diameter of the vapor tap orifice 2 is 0. 76 mm and the inside diameter of the capillary dip tube 32 is 1. 0 mm.
In operation, button 12 is depres6ed, so that the valve stem 11 and with it valve poppet 8 and orifice 13a are manipulated to the open position, away from valve seat 19. Liquid aerosol composition is thereupon drawn up via the capillary dip tube 32 and passage 5a into the blending space 5, where it flows up around the poppet 8 towards the valve stem orifice l~a, while propellant gas passes thro~gh the 10484~3 vapor tap orifice 2, and is blended with the liquid aerosol composition in the space 5 entering from dip tube 32, as it flows around the poppet 8.
The dimensions of the orifices 2, 32 are such that 18 volumes of gas enter through the vapor tap orifice 2 for each volume of liquid entering from the capillary dip tube 32.
This container is capable of delivering a dispersion type aerosol antiperspirant composition of conventional formulation at a delivery rate of about 0. 4 g/second, about 40~C of the normal delivery rate of 1 g/secondO Accordingly, in order to obtain the same delivery of active ~ngredients (such as active antiperspirant) per squirt of a unit time, it is necessary to considerably increase the concentration of active antiperspirant composition. Normally, such compositions con-tain less than 5~7c active antiperspirant, because of clogging problems , . .. .
using standardized aerosol container valve systems and dimensions.
In this container, however, it is possible to deliver at a low delivery rate about 0.3 to about 0.7 gtsecond of aerosol antiperspirant composition containing from about 8~c to about 20~ active ingredient as suspended or dispersed solid m~terial without clogging, because of - the high proportion of gas to liquid.
Tn the aerosol container shown in Figures 3 and 4, the capillary dip tube is replaced by a dip tube of normal dimensions and a restricted tail piece is interposed between the valve and the dip tube to obtain the desired restriction of liquid composition flow towards the val~e delivery - system of the container when the valve is opened In other respects, the container is identical to that of Figures 1 and 2, and therefore like reference numerals are used for like parts.
In this container, the aerosol valve is of conventional type, as shown in Figures 1 and 2, with a valve stem 11 having a valve button 12 attached at one end, with valve button passages 16, 17 and a delivery orifice 14 therethrough, and a valve body 6 pinched by crimp 23b in the aerosol container cap 23. The valve body 6 has a blending space 5, which opens at the lower end into the restricted tail piece orifice 5b constituting a liquid tap orifice, and at the other end, beyond the valve poppet 8, when the valve is open, into the valve stem orifice 13a. The valve poppet 8 is reciprocably mounted at one end of the valve stem 11, and is biased by the spring 18 against the valve seat 19 on the inside face of gasket 9 in the normally closed position. The valve is opened by depressing the button actuator 12. When the valve poppet 8 is away from its seat, the valve stem orifice 13a is in fluid flow communication ~- with the blending space 5.
The valve housing 6 is provided with a vapor tap orifice 2, which puts the blending space 5 in flow connection with the gas or propellant phase in the space 20 at the upper portion of the aerosol container. The liquid aerosol composition is stored in the lower portion 21 of the container; and the dip tube 33 extends from the tail piece, over which it is press-fitted in pL~ce, to the bottom of the container through the liquid phase, in flow connection with tail piece orifice 5b.
In this aerosol container, the diameter of actuator (valve delivery) orifice 14 is 0.5 mm; the diameter of the valve stem orifice 13a is 0. 64 mm; the diameter of the vapor tap orifice 2 is 0089 mm;
1C)48453 and the diameter of the tail piece passage 5b is 0. 76 mm.
In operation, the button 12 is depressed, so that the valve poppet 8 and orifice 13a are manipulated to the open position. Liquid aerosol composition is drawn up by the dip tube 33 via the restricted tail piece orifice passage 5b into the blending space 5, where it is blended with propellant gas entering the space via the vapor tap orifice 2 from the propellant space 21 of the container The blend, in a volume ratio gas:liquid of at least 10, is expelled under pro-- pellant gas pressure through the valve stem orifice 13a, leaving the container via the stem passage 13, button passages 16, 17 and orifice 14 of the valve, as a fine spray.
The aerosol containers and the process of the instant invention can be used to deliver any aerosol composition at a low delivery rate of active ingredient in the form of a spray. The design in the parameters of dimensions stated is especially suited for dis-pen~ing organic solvent-type liquid aerosol dispersions and suspensions containing dispersed or suspended finely divided solid materials, such as astringent antiperspirant salts and compounds, without clogging.
The range of products that can be dispensed by t~is aerosol container is diverse, and includes pharmaceuticals for spraying directly into oral, nasal andvaginalpassages; antiperspirants, hair sprays, fragrances and flavors; body oils; insecticides; window cleaners and other cleaners; spray starches; and polishes for autos, furniture, and shoes.
1~8453 The following Examples in the opi~ion of the inventors represent preferred embodiments of the aerosol containers and process of the invention.
~ the dispersion-type antiperspirant aerosol compositions sho~vn in the following Examples, the aluminum chlorhydroxide is present at a hlgher than conventional concentration to compensate for the reduced delivery rate in the aerosol containers of the invention.
Isopropyl myristate is a nonvolatile oil, and colloidal silica is a bulking agent used to prevent tight pQcking of the aluminum chlorhydroxide ~rticles. The conventional fluorocarbon propellants have been re-placed partially or entirely by the fL~mmable hydrocarbon propellants, isobutane and propane.
The silicones, 2 million cts. and 10-20 million cts., are high molecular weight dimethyl polysiloxanes with a viscosity of 2 million cts. and 10-20 million cts. at 25C. Such high viscosity silicone polymers have not previously been used in dispersion-type aerosol antiperspirant compo-sitions. The silicones are soluble in the organic liquid phase 0f the composi-tion, and a~e employed here to increase the viscosity of th~ organic liquid phase, and thereby increase the volume ratio of gas:liquid dispersion. In general, any organic solvent-soluble polymeric material soluble in the liquid phase of the aerosol composition can be used for this purpose.
Preferred polymers are silicones with a viscosity of at least 500, 000 cts., up to about 30 million cts. The amount used may ran~e from about 0. 01 to about 5% by weight of the composition. The higher the viscosity of the silicone polymer, the less need be used.
104t~453 Five dispersion-type aerosol antiperspirant compositions were prepared, in accordance with the following formulations:
PARTS BY WEIGHT
A B C O E
Aluminum chlorhydroxide 80 0 10. 0 14. 0 .12. 5 180 0 Isopropyl myristate 8.0 10.0 1400 1205 8.0 Colloidal silica 1. 0 1. 0 1D 0 10 0 1. 0 Silicone polymer, . - - - 200 200 2 million cts.
Isobutane 53.0 79O0 7100 7200 7100 Trichlorofluoromethane 15. 0 Dichlorodifluoromethane 150 0 The formulations were packaged into aerosol containers of the 15 invention fitted with capillary dip tubes and having the following vapor tap valve and dip tube specifications:
EXAMPLE NO.
Aerosol For mulation A B C D B D D
Actuator orifice diameter,mm0.50 0.50 0.50 0.50 0.64 0.64 0.6 Valve stem orifice diameter, mm 0.50 0.50 0.50 0O50 0O50 0O50 0.6 Vapor tap orifice diameter, mm 0. 64 0. 76 0. 89 0. 89 0. 89 0. 89 0. 8 Capillary dip tube, inside 1.0 loO 1~0 loO loO loO 1~0 diameter, mm 1l)48453 Three dispersion-type aerosol antiperspirant compositions were preparecl, in accordance with the following formulations:
PARTS BY VVEIGHT
F G H
Aluminum chlorhydroxide 10.0 12. 5 12. 5 Isopropyl myristate 8. 8 11. 0 11. 0 Colloidal silica 1. 0 1. 2 1. 2 Silicone polymer, 0. 2 0. 3 0. 3 10-20 million cts.
Isobutane 64. 0 60. 0 75. 0 Propane 16. 0 150 0 Two of the formulations were packaged into aerosol containers of the invention fitted with capillary dip tubes and having the following vapor tap valve and dip tube specifications:
EXAMP~E NO.
_ Aerosol Formulation - G ~I
~ ~ _ .
Actuator orifice diameter, mm. 0. 50 0. 50 Valve stem orifice diameter, mm. 0. 50 0. 50 Vapor tap orifice diameter, mm. 1.0 1.0 Capillary dip tube, inside 1. 0 1. 0 diameter, mm.-1~)48453 Three of the iormulations were packaged into aerosol containers of the invention fitted with restricted tail pieces and standard dip tubes, and having the following actuator orifice, valve stem orifice, vapor tap orifice and tail piece orifice specifications:
EXAMPL~: NO.
Aerosol Formulation F G F
~ctuator orifice diameter, mmØ 500. 50 0. 50 Valve stem orifice diameter, mm. 0.65 0.65 0.65 Vapor tap orifice diameter, mm. 0.89 1.0 1. 0 Restricted tail piece orifice0.76 0.76 0 89 diameter, mm.
The containers of Examples 1 to 12 were tested to determine.the flame projection, and flash-back in cm., when sprayed into the upper portion 15 of a candle flame f~om a distance of 15 cm. The ratio of gas to liquid dis-, pensed was determined using the following standardized test procedure.
The fil~d container being tested was brought to 70 F, and theactuator button fully depressed to spray for 5 seconds, while collecting all of the spray on an absorbent pad. The pad was allowed to reach constant 20 weight at room temperature. From the increase in weight of the pad and the known concentration of non-vol;atiles in the aerosol composition in the container, the weight of the liquid dispersion expelled is calculated.
This was substracted from the loss ~n weight of the filled co~itainer, to give the weight of propellant gas expelled. The volume of gas expelled 25 was calculated from the gas laws, and expressed as the volume at 70F at the internal absolute pressure of the container. The volume of the liquid dispersion was calculated from the density of 70F, and the ratio of the two volumes was then calculated.
The results were as follows:
Example Delivery Rate Volume Ratio Flame Projection Flash-Back No. (Gram/second) Gas:liquid (cm. ) (cm. ) 0.50 10 0 0 2 0. 40 18 20 0
In the special case when a capillary dip tube is used, no liquid tap orifice as such is required~ The capillary dip tube serves as the liquid tap orifice. However, the si7e parameters for the capillary dip tube and vapor tap orifice in that event are different, because of the unique flow restriction of the capillary dip tube,as noted previouslyO
The vapor tap orifice is in fluid flow connection with the propelLant or gas phase of the aerosol container, and admits gas into the blending space before the valve stem delivery E~ssage. Normally, therefore, it is in the wall means defining the blending space, and above the liquid tap orifice, although this is not essential. The vapor tap orifice can be in a wall beside or above the valve member, but it is of course upstream of the valve seat.
The valve delivery system of an aerosol container downstream of the valve normally includes all actuator which operates a valve movable between open and closed positions, with a valve stem and an aerosol composition-conveying valve passage therethrough, in flow connection with a delivery port~ The narrowest orifice in this delivery system is within the range from about 0. 5 to about 0. 65 mm.
Mixing of the gas and liquid phase occurs in the blending space, before these pass to the valve, and the diameters of the vapor tap and liquid tap orifices as well as the valve passage with which they are in communication are selected within the stated ranges to provide a gas:
liquid volume ratio within the range from about 10: 1 to about 40:1, and preferably from about 15:1 to about 30:1. It will be appreciated that for a given size of these openings, the gas: liq!lid ratio obtained from gas and liquid fed therethrough from the supply in the container will vary with the particular propellallt or propellants ~d the composition of the liquid phaseO The viscosity of the liquid is a factor in determining the proportion that can flowthrough the liquid tap orifice per unit time, when the valve isopened.
The orifice ranges given are applicable to all dispersion-type antiperspirant aerosol compositions, but the particular values chosen-for the sizes of the orifices within the stated ranges will therefore depend upon the particu]ar composition that is selected for packaging in the aerosol container. Those skilled in the art are aware of how to adjust the applicable parameters for a given aerosol composition, since they already do this in selecting the particular delivery orifice, valve steam passage, dip t~lbe and vapor tap orifice for conventional vapor tap aerosol containers mixing the liquid and gas at a much lower gas:
liquid ratio. By application of these known principles, it is possible to scale up the orifice diameters in proportion to obtain delivery of the gas: liquid ratio required in the invention.
If a capillary dip tube is used, its inside diameter should be within the range from about 1.0 to about 1.5 times the diameter of the vapor tap orifice. If a liquid tap orifice in a restricted tail piece, or equivalent, is used, with a standard dip tube, the restricted tail piece orifice diameter should be within the range from about 0. 75 to about 0. 95 times the diameter of the vapor tap orifice.
Preferred embodiments of aerosol containers in accordance with the invention- are illustrated in the drawings, in which:
~ Figure 1 represents a longitudinal sectional view of one embodiment of aerosol container in accordance with the inv~ntion, including a capill~Lry dip tube in fluid flow connection with the vapor tap orifice;
Figure lA represents a detailed view of the val~e stem and poppet, showing the valve stem orifice in open and closed positions;
Figure 2 represents a cross-sectional view taken along the line 2-2 of Figure lj Figure 3 represents a longitudinal sectional v~ew of another .
embodiment of aerosol container in accordance with the invention, with a restricted tail piece and a standard dip tube in fluid flow connection with the vapor tap orifice; and Figure 4 represents a cross-sectional view taken along the e 4-4 o Figure 3.
~l principle, the aerosol containers of the invention utilize a container having at least one compartment for propellant gas and liquid aerosol composition, communicated by at least one gas tap orifice and at least one liquid tap orifice to a blending space, which is across the line of flow to the valve delivery port. A liquid aerosol composition to be blended with proFelLant gas and then ex-pelled from the container is placed in this compartment of the container, in flow communication via the liquid tap orifice with the blending space, so as to admit liquid aerosol composition into the blending space, while propellant gas flows into the blending space via the gas tap orifice or orifices to the valYe.
Tn summary of the above, the orifice open area dimensions are as follows: ~
OPEN AR:~A
(mm~) ~
.. .. _ . _ OVERALL PREFERRED
Valve stem orifice 0.2 to 0.3 0.2 to 0.3 Vapor tap orifice 0. 4 to 0.8 0. 5 to 0. 7 Liquid tap orifice 0. 4 to 0.6 0. 4 to 0. 5 Ratio liquid tap orifice/ o. 5 to 0. 9 0. 6 to 0. 8 vapor taE~ orifice cross-.
sectional open area In the special case where a capillary dip tube is used, open area is as follows:
104~4S3 OPEN AREA
(mm2) OVERALL PREFERRED
Valve stem orifice 0. 2 to 0. 3 Q. 2 to 0. 3 Vapor tap orifice . 0. 4 to 0. 8 0. 5 to 0. 7 Capillary dip tube 0. 6 to 1. 3 0. 7 to 0. 9 Ratio capillary dlp tube 1. 0 to 2. 0 1. 1 to 1. 5 vapor tap oriEice cross- -sectional open area The orifice diameter dimensions are as follows:
DIAMETER
(mm) - OVERALL PREFERRED
Valve stem orifice diameter 0. 50 to 0. 65 0. 50 to 0. 65 Vapor tap orifice diameter 0. 70 to 1. 0 0. 80 to 0. 95 Liquid tap orifice diameter 0. 70 to U. 90 0. 70 to 0. 80 Ratio of liquid tap orifice 0. 75 to 0. 95 0. 8 to 0. 9 diameter: vapor tap orifice diameter In the special case where a capillary dip tube is used, dimensions are as follows: .
DIAMETER
(mm) OVERALL PREFERRED
-Valve stem orifice diameter 0. 50 to 0. 65 0. 50 to ~5 mm Vapor tap orifice diameter 0. 70 to 1. 0 0. 80 to 0. 95 mm Capillary dip tube diameter 0. 90 to 1. 3 0. 95 to 1. 15 mm Ratio of capillary dip tube 1. 0 to 1. 5 1. 1 to 1. 3 diameter:vapor tap orifice diameter The particular form of aerosol liquid is not critical. The aerosol containers of the invention can foam aqueous aerosols, organic solvent solution aerosols, emulsions, both of water-in-oil and oil-in-water type.
The greater the solubility of the propellant in the aerosol compo-sition, the lower the efficiency of propellant utilization, since more of the propellant remains dissolved, and less is available for blending in the gas phase with the aerosol liquid in the blending space. Accordingly, it is generally preferred that the solubility of the propellant be at a minimum, and additions to the aerosol composition can be made to reduce solubility of the propellant therein. For instance, if the aerosol composition is an alcohol formulation, or employs any other water-soluble organic solvent, water may be added or the amount of water can be increased, so as to reduce the solubility of fluorocarbon and hydrocarbon propellants in the resulting solution. ~E the aerosol composition is an aqueous formulation, less soluble propellants, such as nitrogen, fluorocarbon and hydrocarbon propellants, are preferred over the more soluble propellants, such as carbon dioxide, nitrous oxide and dimethyl ether.
The aerosol containers in accordance with the invention can be made of metal or plastic, the latter being preferred for corrosion resistance. However, plastic-coated metal containers can also be used, to reduce corrosion. Aluminum, anodized aluminum, coated aluminum, zinc-plated and cadmium-plated steel, tin, and acetal polymers such as Celcon (trademark) or Delrin (trademark) are suitable container materials.
The gas tap and liquid tap orifices can ~e disposed in any type of porous or foraminous structure. One each of a gas tap and liquid tap .
. r. ~
104~4~3 orifice througll the compartmellt wall separating the propellant and any other compartmellts from the blending space will suffice. A plurality of gas tap and liquid tap orifices can be used, for more rapid blending and composition delivery, but the delivery rate of liquid will still be low, because of the high gas: liquid ratio. The total orifice open area is of course determinative, so that several large orifices can afford a similar delivery rate to many small orifices. However, gas tap orifice size also affects blending, so that a plurality of sma ll gas tap orifices may be preferable to several large orifices~
Orifices may also be provided on a me mber inserted in the wall or at one end of the wall separating the propel~nt and any other compartments from the blending space. One type of such r~ember is a perforated or apertured plastic or metal plate or sheet.
The liquid tap orifice can be rathe r short or rather long, as in a passage through a tail piece member. While a capillary dip tube extending into the bottom of a layer or compartment for liquid aerosol composition is a kind of liquid tap orifice, different dimensions are applicable The term "orifice" as used herein generically encompasses passages narrow enough to behave as orifices, regardless of length, in re~pect to liquid aerosol composition flowed therethrough.
The cross-sectional shape of the orifice is not critical. The orifices can be circular, elliptical, rectangular, polygonal, or any other irregular or regular shape in cross-section~
ln the aerosol container 1 shown in Figures 1 and 2, the aerosol valve 4 is of conventional type, and comprises a va lve poppet 8 seating against the sealing face 19 of a sealing gasket 9 and integral with a valve stem 11. The valve stem is hollow, and has an axial flow passage 13 therethrough. The valve poppet 8 is open at the inner end, defining a socket 8a therein, for the reception of a coil spring 18. The passage 13 is separated from the socket 8a within the poppet 8 by the divider wall 8b.
Adjacent the poppet wall 8b in a side wall of the stem 11 is a valve stem orifice 13a. The gasket 9 has a central opening 9a there-through, which receives the valve stem 11 in a sliding leak-tight fit, permitting the stem to move easily in either direction through the opening, without leakage of propellant gas or liquid from the container.
When the valve stem is in the outwardly extended position shown in Figure 1, the surface of the poppet portion 8 contiguous with wall 8b is in sealing engagement with the inner face of the gasket 9, closing ~~~ 15 off the orifice 13a and the passage 13 to outward flow of the contents of the container.
The outer end portion lla of the valve stem 11 is received in the axial socket 16 of the button actuator 12, the tip engaging the ledge 16a of the recess. The stem is attached to the actuator by a press fit.
The axial socket 16 is in flow communication with a lateral E~assage 17, leading to the actuator (valve delivery) orifice 14 of the button 12.
A compression coil spring 18 has one end retained in the socket 8a of the valve poppet 8, and is based at its other end upon inner wall 6b of the valve housing 6. The spring 18 biases the poppet 8 towards the gasl~et 9, engaging it in a leak-tight seal at the valve seat 19.
Whell the valve poppet is against the valve seat 19, the orifice 13a leading into the passage 13 of the valve stem is closed off.
The valve is however reciprocably movable towards and away from the valve seat 19 by pressing inwardly on the button actuator 12, thus moving the valve ste~n 11 and with it poppet 8 against the spring 18.
When the valve is moved far enough away from the seat 19, into the position shown in detail in Figure lA, the orifice 13a is brought beneath the valve gasket 9, and a flow passage is tkerefore open from the blending space 5 defined by the valve housing 6 to the delivery port 14.
The limiting open position of the valve poppet 8 is fixed by the wall 6b of housing 6, the valve poppet 8 encountering the housing wall, and stopped. The valve stem orifice 13a when in the open position com-municates the stem passage 13 with the actuator passages 16,17 and valve delivery orifice 14, and thus depressing the actuator 12 permits fluid flow via the space 5 to be dispensed from the container at delivery port 1'~.
Thus, the spring 18 ensures that the valve poppet 8 and the refore valve 4 is normally in a closed position, and that the valve is open only when the button actuator 12 is moved manually against the force of the spring 180 The valve housing 6 has an expanded portion 6a within which is received the sealing gasket 9 and retained in position at the upper end of the housing. The expanded portion 6a is retained by the crimp 23b in the center of the mounting cup 23, with the valve stem 11 extending 10~8453 tlu~ougll an aperture 23a in the cup. The cup 23 is attached to the container dome 24, whicll in turn is attached to the main container portion 25.
Through the wall 7 of the valve housing 6 is a vapor tap orif ice 2, which is in f low conne ction with the upper portion 20 of the space 21 within the container 1, and therefore with the gas phase of propellant, which rises into this portion of the container. The blending space 5 of the valve housing 6 terminates in a passage 5a, in which is inserted one end of the capillary dip tube 32, which extends all the way to the bottom of the container, and thus dips into the liquid phase of the aerosol composition in portion 21 of the container. Liq!lid aerosol composition accordingly enters the space 5 at the passage 5a, via the capillary dip tube 32, so that the dip tube serves as a long liquid tap orifice, while gas enters the s~ce 5 thro~gh the gas tap orifice 2.
In the valve shown, the diameter of the actuator (valve delivery) orifice 14 is 0.5 mm, the valve stem orifice 13a is 0.5 mm, the diameter of the vapor tap orifice 2 is 0. 76 mm and the inside diameter of the capillary dip tube 32 is 1. 0 mm.
In operation, button 12 is depres6ed, so that the valve stem 11 and with it valve poppet 8 and orifice 13a are manipulated to the open position, away from valve seat 19. Liquid aerosol composition is thereupon drawn up via the capillary dip tube 32 and passage 5a into the blending space 5, where it flows up around the poppet 8 towards the valve stem orifice l~a, while propellant gas passes thro~gh the 10484~3 vapor tap orifice 2, and is blended with the liquid aerosol composition in the space 5 entering from dip tube 32, as it flows around the poppet 8.
The dimensions of the orifices 2, 32 are such that 18 volumes of gas enter through the vapor tap orifice 2 for each volume of liquid entering from the capillary dip tube 32.
This container is capable of delivering a dispersion type aerosol antiperspirant composition of conventional formulation at a delivery rate of about 0. 4 g/second, about 40~C of the normal delivery rate of 1 g/secondO Accordingly, in order to obtain the same delivery of active ~ngredients (such as active antiperspirant) per squirt of a unit time, it is necessary to considerably increase the concentration of active antiperspirant composition. Normally, such compositions con-tain less than 5~7c active antiperspirant, because of clogging problems , . .. .
using standardized aerosol container valve systems and dimensions.
In this container, however, it is possible to deliver at a low delivery rate about 0.3 to about 0.7 gtsecond of aerosol antiperspirant composition containing from about 8~c to about 20~ active ingredient as suspended or dispersed solid m~terial without clogging, because of - the high proportion of gas to liquid.
Tn the aerosol container shown in Figures 3 and 4, the capillary dip tube is replaced by a dip tube of normal dimensions and a restricted tail piece is interposed between the valve and the dip tube to obtain the desired restriction of liquid composition flow towards the val~e delivery - system of the container when the valve is opened In other respects, the container is identical to that of Figures 1 and 2, and therefore like reference numerals are used for like parts.
In this container, the aerosol valve is of conventional type, as shown in Figures 1 and 2, with a valve stem 11 having a valve button 12 attached at one end, with valve button passages 16, 17 and a delivery orifice 14 therethrough, and a valve body 6 pinched by crimp 23b in the aerosol container cap 23. The valve body 6 has a blending space 5, which opens at the lower end into the restricted tail piece orifice 5b constituting a liquid tap orifice, and at the other end, beyond the valve poppet 8, when the valve is open, into the valve stem orifice 13a. The valve poppet 8 is reciprocably mounted at one end of the valve stem 11, and is biased by the spring 18 against the valve seat 19 on the inside face of gasket 9 in the normally closed position. The valve is opened by depressing the button actuator 12. When the valve poppet 8 is away from its seat, the valve stem orifice 13a is in fluid flow communication ~- with the blending space 5.
The valve housing 6 is provided with a vapor tap orifice 2, which puts the blending space 5 in flow connection with the gas or propellant phase in the space 20 at the upper portion of the aerosol container. The liquid aerosol composition is stored in the lower portion 21 of the container; and the dip tube 33 extends from the tail piece, over which it is press-fitted in pL~ce, to the bottom of the container through the liquid phase, in flow connection with tail piece orifice 5b.
In this aerosol container, the diameter of actuator (valve delivery) orifice 14 is 0.5 mm; the diameter of the valve stem orifice 13a is 0. 64 mm; the diameter of the vapor tap orifice 2 is 0089 mm;
1C)48453 and the diameter of the tail piece passage 5b is 0. 76 mm.
In operation, the button 12 is depressed, so that the valve poppet 8 and orifice 13a are manipulated to the open position. Liquid aerosol composition is drawn up by the dip tube 33 via the restricted tail piece orifice passage 5b into the blending space 5, where it is blended with propellant gas entering the space via the vapor tap orifice 2 from the propellant space 21 of the container The blend, in a volume ratio gas:liquid of at least 10, is expelled under pro-- pellant gas pressure through the valve stem orifice 13a, leaving the container via the stem passage 13, button passages 16, 17 and orifice 14 of the valve, as a fine spray.
The aerosol containers and the process of the instant invention can be used to deliver any aerosol composition at a low delivery rate of active ingredient in the form of a spray. The design in the parameters of dimensions stated is especially suited for dis-pen~ing organic solvent-type liquid aerosol dispersions and suspensions containing dispersed or suspended finely divided solid materials, such as astringent antiperspirant salts and compounds, without clogging.
The range of products that can be dispensed by t~is aerosol container is diverse, and includes pharmaceuticals for spraying directly into oral, nasal andvaginalpassages; antiperspirants, hair sprays, fragrances and flavors; body oils; insecticides; window cleaners and other cleaners; spray starches; and polishes for autos, furniture, and shoes.
1~8453 The following Examples in the opi~ion of the inventors represent preferred embodiments of the aerosol containers and process of the invention.
~ the dispersion-type antiperspirant aerosol compositions sho~vn in the following Examples, the aluminum chlorhydroxide is present at a hlgher than conventional concentration to compensate for the reduced delivery rate in the aerosol containers of the invention.
Isopropyl myristate is a nonvolatile oil, and colloidal silica is a bulking agent used to prevent tight pQcking of the aluminum chlorhydroxide ~rticles. The conventional fluorocarbon propellants have been re-placed partially or entirely by the fL~mmable hydrocarbon propellants, isobutane and propane.
The silicones, 2 million cts. and 10-20 million cts., are high molecular weight dimethyl polysiloxanes with a viscosity of 2 million cts. and 10-20 million cts. at 25C. Such high viscosity silicone polymers have not previously been used in dispersion-type aerosol antiperspirant compo-sitions. The silicones are soluble in the organic liquid phase 0f the composi-tion, and a~e employed here to increase the viscosity of th~ organic liquid phase, and thereby increase the volume ratio of gas:liquid dispersion. In general, any organic solvent-soluble polymeric material soluble in the liquid phase of the aerosol composition can be used for this purpose.
Preferred polymers are silicones with a viscosity of at least 500, 000 cts., up to about 30 million cts. The amount used may ran~e from about 0. 01 to about 5% by weight of the composition. The higher the viscosity of the silicone polymer, the less need be used.
104t~453 Five dispersion-type aerosol antiperspirant compositions were prepared, in accordance with the following formulations:
PARTS BY WEIGHT
A B C O E
Aluminum chlorhydroxide 80 0 10. 0 14. 0 .12. 5 180 0 Isopropyl myristate 8.0 10.0 1400 1205 8.0 Colloidal silica 1. 0 1. 0 1D 0 10 0 1. 0 Silicone polymer, . - - - 200 200 2 million cts.
Isobutane 53.0 79O0 7100 7200 7100 Trichlorofluoromethane 15. 0 Dichlorodifluoromethane 150 0 The formulations were packaged into aerosol containers of the 15 invention fitted with capillary dip tubes and having the following vapor tap valve and dip tube specifications:
EXAMPLE NO.
Aerosol For mulation A B C D B D D
Actuator orifice diameter,mm0.50 0.50 0.50 0.50 0.64 0.64 0.6 Valve stem orifice diameter, mm 0.50 0.50 0.50 0O50 0O50 0O50 0.6 Vapor tap orifice diameter, mm 0. 64 0. 76 0. 89 0. 89 0. 89 0. 89 0. 8 Capillary dip tube, inside 1.0 loO 1~0 loO loO loO 1~0 diameter, mm 1l)48453 Three dispersion-type aerosol antiperspirant compositions were preparecl, in accordance with the following formulations:
PARTS BY VVEIGHT
F G H
Aluminum chlorhydroxide 10.0 12. 5 12. 5 Isopropyl myristate 8. 8 11. 0 11. 0 Colloidal silica 1. 0 1. 2 1. 2 Silicone polymer, 0. 2 0. 3 0. 3 10-20 million cts.
Isobutane 64. 0 60. 0 75. 0 Propane 16. 0 150 0 Two of the formulations were packaged into aerosol containers of the invention fitted with capillary dip tubes and having the following vapor tap valve and dip tube specifications:
EXAMP~E NO.
_ Aerosol Formulation - G ~I
~ ~ _ .
Actuator orifice diameter, mm. 0. 50 0. 50 Valve stem orifice diameter, mm. 0. 50 0. 50 Vapor tap orifice diameter, mm. 1.0 1.0 Capillary dip tube, inside 1. 0 1. 0 diameter, mm.-1~)48453 Three of the iormulations were packaged into aerosol containers of the invention fitted with restricted tail pieces and standard dip tubes, and having the following actuator orifice, valve stem orifice, vapor tap orifice and tail piece orifice specifications:
EXAMPL~: NO.
Aerosol Formulation F G F
~ctuator orifice diameter, mmØ 500. 50 0. 50 Valve stem orifice diameter, mm. 0.65 0.65 0.65 Vapor tap orifice diameter, mm. 0.89 1.0 1. 0 Restricted tail piece orifice0.76 0.76 0 89 diameter, mm.
The containers of Examples 1 to 12 were tested to determine.the flame projection, and flash-back in cm., when sprayed into the upper portion 15 of a candle flame f~om a distance of 15 cm. The ratio of gas to liquid dis-, pensed was determined using the following standardized test procedure.
The fil~d container being tested was brought to 70 F, and theactuator button fully depressed to spray for 5 seconds, while collecting all of the spray on an absorbent pad. The pad was allowed to reach constant 20 weight at room temperature. From the increase in weight of the pad and the known concentration of non-vol;atiles in the aerosol composition in the container, the weight of the liquid dispersion expelled is calculated.
This was substracted from the loss ~n weight of the filled co~itainer, to give the weight of propellant gas expelled. The volume of gas expelled 25 was calculated from the gas laws, and expressed as the volume at 70F at the internal absolute pressure of the container. The volume of the liquid dispersion was calculated from the density of 70F, and the ratio of the two volumes was then calculated.
The results were as follows:
Example Delivery Rate Volume Ratio Flame Projection Flash-Back No. (Gram/second) Gas:liquid (cm. ) (cm. ) 0.50 10 0 0 2 0. 40 18 20 0
3 0. 35 23 15 0
4 0. 28 40 10 0 0. 40 18 20 0 6 0.41 18 20 0 7 0. 44 16 25 0 8 0. 40 26 10 0 9 0.34 15 10 0 0. 37 13 10 0 11 0. 32 26 10 0 12 0. 48 18 15 0 It is apparent that isobutane and propane can be used in this way with perfect safety and especially in Examples 1, 4 and 8 to 12.
At the exceptionally high concentration cf aluminum chlorhydroxide in formulations A through H, the amount of aluminum chlorhydroxide dispensed per squirt of 5 seconds was about 0. 035 gram/second, about the same as that obtained with a conventional aerosol antiperspirant formulation in a conven-tional vapor tap-valve-equipped aerosol container.
There was no clogging of the valve during a normal use period of these containers, i. e., a daily ~-second squirt, until the containers were empty.
These results should be compared with a conventionally packaged dispersion-type aerosol antiperspirant, with the fluorocarbon propellants replaced by isobutane. The following Control is typical.
Composition Parts By We ight _ Aluminum chlorhydroxide3.5 Isopropyl myristate 5.0 Colloidal silica 0 . 5 Isobutane 91 o 0 Container Diameter (mm) Actuator orifice 0.50 Valve stem orifice 0. 64 Vapor tap orifice 0O 50 Tail piece orifice 2. 0 -- Dip tube, inside 3 1 Delivery rate, gram/second 1.0 Volume ratio, gas:llquid 2 Flame projection, cm. ~50 Flash-back, crn. - 15 -Cle;~rly, much more isobutane is expelled per unit time, and isobutane in such an amount is too dangerous to use in such a container.
Substitution of fluorocarbons for isobutane is essential, as is conventional.
Tn this case, the delivery rate is about 1. 2 gram/second, volume ratio gas: liquid is about 2, and both flame projection and flash-back are zero.
11~)48453 The aerosol containers of the instant invention can be used to deliver any aerosol composition in the form of a spray. They are particularly suited for use with dispersion-type antiperspirant compo-sitions, but any liquid aerosol composition can be dispensed, and the
At the exceptionally high concentration cf aluminum chlorhydroxide in formulations A through H, the amount of aluminum chlorhydroxide dispensed per squirt of 5 seconds was about 0. 035 gram/second, about the same as that obtained with a conventional aerosol antiperspirant formulation in a conven-tional vapor tap-valve-equipped aerosol container.
There was no clogging of the valve during a normal use period of these containers, i. e., a daily ~-second squirt, until the containers were empty.
These results should be compared with a conventionally packaged dispersion-type aerosol antiperspirant, with the fluorocarbon propellants replaced by isobutane. The following Control is typical.
Composition Parts By We ight _ Aluminum chlorhydroxide3.5 Isopropyl myristate 5.0 Colloidal silica 0 . 5 Isobutane 91 o 0 Container Diameter (mm) Actuator orifice 0.50 Valve stem orifice 0. 64 Vapor tap orifice 0O 50 Tail piece orifice 2. 0 -- Dip tube, inside 3 1 Delivery rate, gram/second 1.0 Volume ratio, gas:llquid 2 Flame projection, cm. ~50 Flash-back, crn. - 15 -Cle;~rly, much more isobutane is expelled per unit time, and isobutane in such an amount is too dangerous to use in such a container.
Substitution of fluorocarbons for isobutane is essential, as is conventional.
Tn this case, the delivery rate is about 1. 2 gram/second, volume ratio gas: liquid is about 2, and both flame projection and flash-back are zero.
11~)48453 The aerosol containers of the instant invention can be used to deliver any aerosol composition in the form of a spray. They are particularly suited for use with dispersion-type antiperspirant compo-sitions, but any liquid aerosol composition can be dispensed, and the
5 containers can be used for any liquid aerosol composition. The range of products that can be dispensed by these aerosol containers is diverse, and includes pharmaceuticals for spraying directly into oral, nasal and vaginalpassages; antiperspirants; deodorants; hair sprays, fragrances and flavors9 body oils; insecticides; window cleaners and other cleaners;
10 spray starches; and polishes for autos, furniture and shoes.
10 spray starches; and polishes for autos, furniture and shoes.
Claims (23)
1. An aerosol container for delivering liquid aerosol compo-sitions highly concentrated with respect to the active ingredient at a low delivery rate, comprising, in combination, a pressurizable container having a valve movable between open and closed positions, a valve stem, and a delivery port; a valve stem orifice in the valve stem in flow connection at one end with a blending space and at the other end with an aerosol-conveying valve stem passage leading to the delivery port;
the valve stem orifice having a diameter within the range from about 0.50 to about 0.65 mm; bias means for holding the valve in a closed position; means for manipulating the valve against the bias means to an open position for expulsion of aerosol composition via the valve stem orifice to the delivery port; wall means defining the blending space and separating the blending space from liquid aerosol composition and propellant within the container; at least one liquid tap orifice through the wall means, having a cross-sectional open area within the range from about 0.4 and 0.6 mm2 for flow of liquid aerosol composition into the blending space; at least one vapor tap orifice through the wall means, having a cross-sectional open area within the range from about 0.4 to about 0.8 mm2 for flow of propellant into the blending space; the ratio of liquid tap orifice to vapor tap orifice cross-sectional open area being within the range from about 0.5 to about 0.9; the open areas of the liquid tap orifice and vapor tap orifice being selected within the stated ranges to provide a volume ratio of propellant gas: liquid aerosol composition within the range from about 10:1 to about 40:1, thereby limiting the delivery rate of liquid aerosol composition and propellant gas from the container when the valve is opened.
the valve stem orifice having a diameter within the range from about 0.50 to about 0.65 mm; bias means for holding the valve in a closed position; means for manipulating the valve against the bias means to an open position for expulsion of aerosol composition via the valve stem orifice to the delivery port; wall means defining the blending space and separating the blending space from liquid aerosol composition and propellant within the container; at least one liquid tap orifice through the wall means, having a cross-sectional open area within the range from about 0.4 and 0.6 mm2 for flow of liquid aerosol composition into the blending space; at least one vapor tap orifice through the wall means, having a cross-sectional open area within the range from about 0.4 to about 0.8 mm2 for flow of propellant into the blending space; the ratio of liquid tap orifice to vapor tap orifice cross-sectional open area being within the range from about 0.5 to about 0.9; the open areas of the liquid tap orifice and vapor tap orifice being selected within the stated ranges to provide a volume ratio of propellant gas: liquid aerosol composition within the range from about 10:1 to about 40:1, thereby limiting the delivery rate of liquid aerosol composition and propellant gas from the container when the valve is opened.
2. An aerosol container according to claim 1, in which the liquid tap orifice is a capillary dip tube whose cross-sectional open area is within the range from about 0.6 to about 1.3 mm2, for flow of liquid aerosol composition into the blending space; the vapor tap orifice through the wall means has a cross-sectional open area within the range from about 0.4 to about 0.8 mm2 for flow of propellant gas into the blending space; and the ratio of capillary dip tube to vapor tap cross-sectional open area is within the range from about 1.0 to about 2Ø
3. An aerosol container according to claim 1, in which the blending space has a volume of from about 0.1 to about 1 cc.
4. An aerosol container according to claim 1, having a single gas tap orifice and a single liquid tap orifice.
5. An aerosol container according to claim 1, having a tail piece passage as the liquid tap orifice.
6. An aerosol container according to claim 1, in which the container is cylindrical, with the valve at one end, the wall means defining the blending space comprises a concentric inner cylinder spaced from the walls of the container surrounding and housing the valve; the gas tap orifice is through a wall of the inner cylinder; the liquid tap orifice is through a wall of the inner cylinder, and the remainder of the interior of the aerosol container outside the walls and bottom of the inner cylinder comprises an annular compartment for propellant gas and liquid aerosol composition.
7. An aerosol container according to claim 6, having a plurality of gas tap orifices through a side wall of the inner cylinder.
8. An aerosol container according to claim 6, comprising a separate compartment for liquid aerosol composition and for propellant, each in direct flow connection with the blending space via the liquid tap and gas tap orifices, respectively.
9. An aerosol container according to claim 6, in which the liquid tap orifice is a capillary dip tube whose cross-sectional open area is within the range from about 0.6 to about 1.3 mm2, for flow of liquid aerosol composition into the blending space; the vapor tap orifice through the wall means has a cross-sectional open area within the range from about 0.4 to about 0.8 mm2 for flow of propellant gas into the blending space; and the ratio of capillary dip tube to vapor tap cross-sectional open area is within the range from about 1.0 to about 2Ø
10. An aerosol container according to claim 6, in which the liquid tap orifice is disposed in a tail piece passage in flow connection to a dip tube.
11. A process for dispensing from an aerosol container without clogging of valve parts orifices and passages, an antiperspirant spray containing a low proportion of liquid, and having solid particulate antiperspirant astringent dispersed therein, with a propellant in gaseous form, which comprises blending within the aerosol container prior to expulsion propellant gas and liquid aerosol antiperspirant composition containing at least gas by weight solid particulate antiperspirant astrin-gent salt dispersed therein at a ratio of gas: liquid within the range from about 10:1 to about 40:1, and expelling the resulting low liquid blend containing such low proportion of liquid and high proportion of gas from the container, thereby reducing the proportion of liquid composition expelled per unit time, but not the delivered amount of astringent salt, and conserving propellant.
12. A process according to claim 11, in which the propellant gas is stored under pressure in liquefied form in the container, but when the valve is opened and pressure reduced a proportion of liquefied propellant is volatilized to gas form and blended with liquid aerosol composition prior to expulsion.
13. A process according to claim 11, in which the propellant gas is stored under pressure in gaseous form in the container, but when the valve is opened and pressure reduced a proportion of propellant is blended with liquid aerosol composition prior to expulsion.
14. A process according to claim 11, in which at least a proportion of liquid aerosol composition dispensed is in the form of a foam.
15. A process according to claim 11, in which at least a proportion of the liquid aerosol composition dispensed is in the form of mixed foam and liquid droplets.
16. A process according to claim 11, in which at least a proportion of the liquid aerosol composition is dispensed in the form of a liquid spray comprising liquid droplets.
17. A process according to claim 11, in which the aerosol composition is an anhydrous dispersion of astringent salt in propellant liquid and nonvolatile organic liquid.
18. A process according to claim 17, in which the aerosol composition comprises a polymeric material soluble in the organic liquid phase and increasing the viscosity of the organic liquid phase.
19. A process according to claim 17, in which the organic liquid is isopropyl myristate, a lower alkyl ester of an aliphatic fatty acid.
20. A process according to claim 17, in which the composition comprises a bulking agent tending to inhibit agglomeration of solid particulate astringent.
21. A process according to claim 17, in which the astringent is aluminum chlorhydroxide.
22. A process according to claim 17, in which the delivery rate is within the range from about 0.3 to about 0.7 g/second.
23. A process according to claim 17, in which the aerosol composition comprises a silicone polymer having a viscosity of at least 500, 000 cts. at 25°C, soluble in the organic liquid phase and increasing the viscosity of the organic liquid phase.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70685776A | 1976-07-19 | 1976-07-19 | |
| US75741477A | 1977-01-06 | 1977-01-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048453A true CA1048453A (en) | 1979-02-13 |
Family
ID=27107776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA77281798A Expired CA1048453A (en) | 1976-07-19 | 1977-06-30 | Aerosol containers for delivering high active concentration aerosol compositions at a low delivery rate |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2677077A (en) |
| CA (1) | CA1048453A (en) |
| GB (1) | GB1555044A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4940171A (en) * | 1989-05-18 | 1990-07-10 | Gilroy Gordon C | Aerosol package having compressed gas propellant and vapor tap of minute size |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010063754A1 (en) * | 2010-12-21 | 2012-06-21 | Beiersdorf Ag | Aerosol formulations with improved spray properties |
| WO2015137952A1 (en) * | 2014-03-13 | 2015-09-17 | The Procter & Gamble Company | Aerosol antiperspirant compositions, products and methods |
| US10398633B2 (en) | 2014-10-27 | 2019-09-03 | Conopco, Inc. | Anhydrous antiperspirant compositions |
| EA036617B1 (en) * | 2015-11-06 | 2020-11-30 | Юнилевер Н.В. | Antiperspirant aerosol product |
| WO2017076840A1 (en) | 2015-11-06 | 2017-05-11 | Unilever Plc | Aerosol antiperspirant product |
| AU2016349244B2 (en) | 2015-11-06 | 2018-12-20 | Unilever Global Ip Limited | Antiperspirant compositions |
-
1977
- 1977-06-30 CA CA77281798A patent/CA1048453A/en not_active Expired
- 1977-07-05 AU AU26770/77A patent/AU2677077A/en active Pending
- 1977-07-19 GB GB30225/77A patent/GB1555044A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4940171A (en) * | 1989-05-18 | 1990-07-10 | Gilroy Gordon C | Aerosol package having compressed gas propellant and vapor tap of minute size |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2677077A (en) | 1979-01-11 |
| GB1555044A (en) | 1979-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4124149A (en) | Aerosol container with position-sensitive shut-off valve | |
| US4117958A (en) | Vapor tap valve for aerosol containers used with flammable propellants | |
| EP0008109B1 (en) | Aerosol container and valve system for use with liquefied flammable propellants and process for delivery therefrom of a spray of abnormally low flammability | |
| US4019657A (en) | Aerosol containers for foaming and delivering aerosols | |
| US4141472A (en) | Aerosol container with gas-permeable membrane | |
| US4546905A (en) | Aerosol dispensing system | |
| US3137416A (en) | Composition for aerosol dispenser consisting of two immiscible liquid phases | |
| US10427862B2 (en) | Aerosol dispenser assembly having VOC-free propellant and dispensing mechanism therefor | |
| US3207386A (en) | Aerosol dispenser producing non-flammable spray with fluid system having a flammable propellant | |
| US6824079B2 (en) | Aerosol dispenser assembly and method of reducing the particle size of a dispensed product | |
| US3970219A (en) | Aerosol containers for foaming and delivering aerosols and process | |
| US3325056A (en) | Apparatus for codispensing a plurality of liquids | |
| US3544258A (en) | Self-propelled liquid dispenser containing an antiperspirant aluminum salt | |
| US3995778A (en) | Aerosol dispensing device | |
| US4322037A (en) | Aerosol can, having a super-fine atomization valve, with a filling which contains a propellant, process for its manufacture, and its use | |
| US5125546A (en) | Flow discharge valve | |
| US4174386A (en) | Aerosol antiperspirant compositions with good adherence to the skin | |
| US5143288A (en) | Compressed gas aerosol spray system with a dip tube vapor tap hole | |
| AU646943B2 (en) | Multi-fluid mixing and automatic metering dispenser | |
| US6173907B1 (en) | Dispenser for dispensing in the form of fine droplets a liquid product with a film-forming polymer | |
| EP1453611A2 (en) | Apparatus for atomizing a liquid product | |
| JPS6317875B2 (en) | ||
| CA1048453A (en) | Aerosol containers for delivering high active concentration aerosol compositions at a low delivery rate | |
| EP3659943A1 (en) | Aerosol product | |
| GB1597147A (en) | Aerosol dispenser |