US3211349A - Aerosol dispenser with flexible dip tube - Google Patents

Aerosol dispenser with flexible dip tube Download PDF

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US3211349A
US3211349A US280603A US28060363A US3211349A US 3211349 A US3211349 A US 3211349A US 280603 A US280603 A US 280603A US 28060363 A US28060363 A US 28060363A US 3211349 A US3211349 A US 3211349A
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phase
liquid
float
dip tube
propellent
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US280603A
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Samuel B Prussin
Presant Fred
Herman R Shepherd
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Aerosol Techniques Inc
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Aerosol Techniques Inc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D83/00Containers or packages with special means for dispensing contents
    • B65D83/14Containers 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
    • B65D83/32Dip-tubes

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  • FIG.9 AEROSOL DISPENSER WITH FLEXIBLE DIP TUBE 2 Sheets-Sheet 2 Filed May 15, 1963 FIG] FIG.9
  • Our invention relates to aerosol dispensers. More particularly, our invention relates to a flexible dip tube and float for use with a three phase aerosol system.
  • an aerosol system designed to yield a finely atomized mist consists of a two phase system, one phase of which is a liquid phase to be dispensed comprising a homogeneous solution or an emulsion of the active ingredient concentrate and liquefied propellent, and the second phase of which consists of propellent vapor.
  • the mixture of active ingredient concentrate and liquefied propellent is expended, resulting in a decrease in the vapor pressure.
  • the resultant decrease in vapor pressure permits an additional portion of the liquefied propellent in solution to be converted into gaseous state propellent in the head space above the liquid phase. It is evident that the spray pattern of such an aerosol will be a function of the pressure within the system, the valve mechanism and the concentration of propellent.
  • Aerosol systems such as that described above are well known in the art. However, such systems possess certain disadvantages.
  • One of the major disadvantages of such systems is the high cost of obtaining a suitable spray due to the extremely large quantity of propellent that is required.
  • a quantity of propellent in excess of that required to expel a given quantity of active ingredient must be charged to the system since a substantial quantity of propellent, in solution or emulsion with the active ingre-
  • Another aerosol system termed a three phase aerosol,
  • Such a system consists of a liquid phase to be dispensed, e.g., an aqueous concentrate phase containing the active ingredient, which is sufficiently immiscible with a second liquid propellent phase so that two distinct liquid phases or layers are present, rather than a single liquid phase comprising a solution or emulsion of liquid to be dispensed and liquefied propellent as in the two phase system.
  • the third phase is a gaseous propellent phase or vapor phase.
  • the vapor phase will always be uppermost within the container while the liquid active ingredient and liquid propellent phases will be lower-most within the container.
  • the two liquid phases can be disposed in relatively different positions within the container depending on their relative densities or specific gravities.
  • propellents of greater density than the active ingredient concentrate will pool at the bottom of the container.
  • Propellents of this nature consist of halogenated hydrocarbon propellents, for example, those sold under the trade names Freon, Genetron, Ucon or Isotron.
  • the propellent is less dense than the liquid concentrate it will float on the surface of the concentrate phase.
  • Propellents of this nature include saturated hydrocarbons, e.g., propane or butane, and certain halogenated hydrocarbons such as difluoroethane sold under the trade name Freon 152a.
  • the dip tube employed with such system is cut short of the bottom of the container so that the opening at the bottom of the dip tube extends into the upper liquid active ingredient phase but does not extend into the lower liquid propellent phase. It is evident that as the active ingredient is expelled from the container and more of the liquid propellent is vaporized to maintain the vapor pressure in the head space above the liquid phases, the level of the liquid phase propellent in the container drops. Obviously, as the level of the liquid propellent phase drops, it is replaced by the active ingredient concentrate. Due to this replacement of the propellent by the active ingredient concentrate it can be seen that there is a substantial loss of concentrate material which can never be removed from the container because of the shortness of the dip tube.
  • Our invention provides a novel dip tube apparatus for use in an aerosol dispenser containing a three phase systern which permits substantially complete removal of the liquid active ingredient concentrate from the container.
  • the three phase systems with which our apparatus is useful comprise, as described above, a vapor phase, a liquid phase to be dispensed and a liquid propellent phase of a different specific gravity or density than the liquid phase to be dispensed and sufficiently immiscible with the liquid phase to be dispensed so that two liquid phases or layers are present.
  • the mechanical components of the aerosol dispenser with which our invention is to be used include any of the standard containers and valve members known in the art.
  • the novel apparatus of our invention comprises a flexible dip tube with a float or bob connected at one end of the dip tube.
  • the float employed has an inlet port and an outlet interconnected by an opening through the float.
  • One end of the dip tube is connected with the outlet port of the float while the other end of the dip tube is connected to the valve member.
  • the float employed in our invention is composed of a material having specific gravity or density greater than one of the two liquid phases and less than the other of the liquid phases whereby it is suspended at the interface between the two liquid phases. While the shape of our float can vary considerably, it must be of such configuration that its inlet port is always exposed to the liquid active ingredient phase to be dispensed as the float is suspended at the interface of the two liquid phases.
  • the dip tube is of suflicient length to allow the float or bob to be suspended, i.e.
  • dip tube can vary considerably in length it should be of a length at least substantially equal to, and preferably slightly greater than, distance between the tailpiece of the valve member and the most remote portion of the container.
  • the float of our invention When employing a propellent of greater density than the active ingredient concentrate, so that the liquid propellent layer is at the bottom of the container, the float of our invention is of such a shape that the center of gravity of the float is located within the liquid propellent phase and the inlet port is located within the liquid active ingredient phase.
  • the float of our invention when a propellent is employed which is less dense than the liquid active ingredient phase, so that the liquid active ingredient layer is lowermost in the container, the float of our invention is of such a shape that both the inlet port and the center of gravity of the float are located in the liquid active ingredient phase.
  • the flexible dip tube and float provide for the substantially complete removal of the liquid active ingredient phase from the container since the slack in the tube permits the float to recede as the propellent is expended with the inlet port always exposed to the active ingredient phase and away from the liquid propellent phase regardless of position of usage.
  • FIGURE 1 is a sectional view of a standard aerosol dispenser containing a three phase system having a liquid propellent phase of greater specific gravity than the liquid active ingredient phase in which an embodiment of our invention is incorporated.
  • FIGURE 2 is the device of FIGURE 1 shown in a partially inverted position.
  • FIGURE 3 is an enlarged view of a float of the same shape illustrated in FIGURES 1 and 2 showing an alternate embodiment thereof.
  • FIGURE 4 is an enlarged sectional view of the float of FIGURE 3 taken along the line 4-4 of FIGURE 3.
  • FIGURE 5 is another alternate embodiment of a float to be used with the type of three phase system shown in FIGURES 1 and 2.
  • FIGURE 6 is a partial, sectional view of an aerosol dispenser containing a three phase system in which the liquid propellent phase has a lesser specific gravity than the liquid active ingredient phase in which is incorporated another embodiment of our invention.
  • FIGURE 7 is an enlarged sectional view showing an alternate embodiment of a float that can be used with the type of aerosol system shown in FIGURE 6.
  • FIGURE 8 illustrates the same embodiment shown in FIGURE 7 in which the aerosol container is slightly tipped.
  • FIGURE 9 illustrates a particular type of valve for use with the dispensers of the preceding drawings.
  • FIGURE 1 shows a standard aerosol container 10 with a valve cap member 12 and a valve member 14 which interconnects the interior and exterior of aerosol container 10 through passageway 15.
  • the liquid propellent phase 16 is lowermost within the container 10.
  • the liquid active ingredient phase 18 to be dispensed above which is vapor phase 20.
  • the interface between liquid propellent phase 16 and liquid active ingredient phase 18 is designated by the reference numeral 22.
  • the aerosol container and system just described are known in the art.
  • a float 24 having a specific gravity less than that of liquid propellent phase 16 and greater than that of liquid active ingredient phase 18 is shown suspended at the interface 22 between the two liquid phases 16 and 18.
  • 14 and float 24 is a flexible dip tube 26 of a length greater than the distance between the tailpiece of the valve 14 and the bottom of the container 10.
  • an inlet port 28 located at the upper end of float 24 and exposed to active ingredient phase 18.
  • dip tube 26 and inlet port 28 are interconnected by a passageway through float 24, not shown in this figure.
  • FIGURE 2 shows the container 10 of FIGURE 1 in a partially inverted position. It will be noted that while liquid propellent phase 16 is still lowermost in the container, liquid active ingredient phase 18 next and vapor phase 20 uppermost, the liquid phases are now located in what would normally be considered the top of the container. It will also be noticed that float 24 is still suspended at the interface 22 between liquid propellent phase 16 and liquid active ingredient phase 18 and that the inlet port 28 is exposed to the active ingredient phase 18.
  • FIGURES 3 and 4 show an alternate embodiment of a float 24a of the same general shape as that shown in FIGURES 1 and 2. Also shown are one end of the dip tube 26 and inlet port 28a. Referring now to FIGURE 4, the passageway 30 interconnecting the interior of dip tube 26 and inlet port 28a can be seen. Also shown in Interconnecting the tailpiece of valve FIGURE 4 are metal weights 32 embedded in the lower portion of float 24a.
  • ballast in the form of metal weights 32 near the bottom of float 24a increases the total weight of float 24a causing a greater portion of the float 24a to be in propellent phase 16.
  • the presence of weights 32 also lowers the center of gravity of float 24a which changes the relative distance between the center of gravity and the center of buoyancy thereby increasing the metacentric distance and increasing the stability of float 2411.
  • FIGURE 5 illustrates another alternate embodiment of a float.
  • float 24b In this figure can be seen float 24b, inlet port 28b and passageway 3%.
  • Located near the upper portion of float 24b is an air pocket or void 34 and located near the lower portion of float 24b is a metal slug 36.
  • the construction of float 24b is such that the lower portion has a much higher concentration of the weight distribution than the upper portion. It will be understood that the center of gravity of the float 24b is lowered even more than in the embodiments shown in FIGURES 1 through 4 thereby further increasing the stability of float 24b.
  • FIGURE 6 a standard aerosol container 10 and a portion of valve member 14 which interconnects the interior and exterior of aerosol container 10.
  • the liquid active ingredient phase 18 is lowermost in the container 10. Floating on the surface of liquid active ingredient phase 18 is the less dense liquid propellent phase 16 above which is vapor phase 20. Again, the interface between liquid propellent phase 16 and liquid active ingredient phase 18 is designated by the reference numeral 22.
  • This aerosol container and system as just described is also known in the art.
  • a float 38 having a specific gravity greater than that of liquid propellent phase 16 and less than that of liquid active ingredient phase 18 is shown suspended at interface 22 between the two liquid phases 16 and 18.
  • a flexible dip tube 26 Interconnecting the tailpiece of valve 14 and float 38 is a flexible dip tube 26 of a length greater than the distance between the tailpiece of the valve 14 and the bottom of the container 10.
  • an inlet port 40 located at the lower end of float 38 and exposed to active ingredient phase 18. The interior of dip tube 26 and inlet port 40 are interconnected by a passageway through float 38, not shown in this figure.
  • inlet port 40 is located at the lower end of float 38 and that dip tube 26 is connected to the lower end of float 38 in this embodiment of our invent-ion rather than having such port and connection at the upper end of the float as illustrated in FIGURES 1 and 2.
  • FIGURE 7 illustrates an alternate embodiment of a float for employment in a three phase aerosol system similar to that of FIGURE 6. Shown in FIGURE 7 are aerosol container 10, liquid propellent phase 16, liquid active ingredient phase 18, vapor phase 20, interface 22 and dip tube 26. Also shown in FIGURE 7 is float 42 having an annular air pocket or void 44 located near its upper end and an annular metal slug 46 located near its lower end. The purpose of the air pocket or void 44 and the metal slug 46 are the same as the air pocket or void 34 and the metal slug 36 shown in FIGURE 5, i.e., to lower the center of gravity and thereby increase the stability of the float. It will also be noticed in FIGURE 7 that the dip tube 26 extends vertically through float 42 and terminates at a point 48 below the lower end of float 42 providing inlet port 40 in active ingredient phase 18.
  • FIGURE 8 are shown aerosol container 10, liquid propellent phase 16, liquid active ingredient phase 18, vapor phase 20, interface 22, dip tube 26 and float 42. It will be noticed that the aerosol container is tipped slightly to one side and the quantity of propellent phase 16 and active ingredient phase 18 have been substantially reduced. It will also be noticed that float 42 is still suspended at the interface 22 between the two liquid phases 16 and 18 and that the terminal point 48 of dip tube 26 is still exposed to the active ingredient phase 18.
  • the several embodiments of our invention illustrated in the figures of the drawings eifect the same results.
  • the float 24 is suspended at the interface 22 between the two liquid phases 16 and 18 such that the inlet port 28 is always exposed to the active ingredient phase 18.
  • the dip tube 26 is of such construction that it is sufficiently flexible to be oriented by the forces exerted on and by the float 24.
  • float 24 is such that the metacentric distance is sufficiently great and properly oriented that the couple consisting of the force of gravity acting in a downward direction effective at the center of gravity of float 24 and the buoyant force acting in an upward direction effective at the center of buoyancy of the float 24 is sufiicient to ofiset any force that may be exerted by dip tube 26.
  • float 24 will always remain properly oriented so that inlet port 28 is always exposed to active ingredient phase 18.
  • float 24 still remains suspended at interface 22 with the inlet port 28 exposed to active ingredient phase 18.
  • Our invention thereby constantly provides the proper orientation and disposition of the inlet port 28 permitting the proper operation of the aerosol system in whatever position the container happens to be.
  • the flexible dip tube and float of our invention can also operate in an aerosol system in which the liquid active ingredient phase has a greater specific gravity than that of the liquid propellent phase.
  • the float 24 is of such construction and configuration that the couple consisting of the force of gravity and the buoyant force act through their effective points to maintain constantly the proper orientation of the float 42 such that the inlet port 40 provided by terminal point 48 of dip tube 26 is always exposed to the active ingredient phase 18.
  • valve member 14 comprises a hollow stem 50 with the valve 52 normally seated against surface 54 by means of spring 56.
  • housing 58 Surrounding the valve is a housing 58 with a tail piece 60, with opening 62, to which flexible dip tube 26 is attached.
  • the housing contains opening 64 exposed to the vapor phase 20 in the head space of the dispenser 10.
  • the valve stem has actuator or head 66 mounted thereon with passageway 68 therethrough.
  • actuator or head 66 mounted thereon with passageway 68 therethrough.
  • the valve 52 When actuated by pressing down head 66 the valve 52 is unseated and liquid phase to be dispensed is educted from dip tube 26 and vapor enters through opening 64 and are intermixed in chamber 70 formed by housing 58 and the mixture enters valve stem 50 through opening 72 and out through passage 68.
  • the vapor mixed with the liquid phase to be dispensed atomizes the liquid and a finely atomized spray is obtained.
  • Known mechanical break-up devices can also be used in the head to provide improved atomization, if desired.
  • valve of FIGURE 9 in combination with the flexible dip tube and float and systems of FIGURES 1 to 8 provide substantially complete removal of the liquid phase to be dispensed as well as a finely atomized spray pattern.
  • the liquid active ingredient concentrate replaces that volume of propellent which is expended because of its vaporization into the head space and subsequently out through the vapor tap orifice in the valve housing, and the liquid active ingredient concentrate and propellent are expended uniformly and completely.
  • the container In the use of this valve with a system wherein the liquid propellent is of greater specific gravity than the liquid phase to be dispensed, the container must be used in the upright position to prevent loss of liquid propellent through the vapor tap opening in the valve housing which would occur if the container were inverted.
  • the flexible dip tube of our invention can be made of natural rubber or synthetic rubbers such as neoprene and buna. It can also be made of a wide variety of plastic materials such as modified vinyls (Tyg-on) and flexible polyethylene. As a practical matter, the employment of I neoprene in the dip tube is preferred due to its solvent resistance. While the dimensions of the dip tube may vary considerably, it will be understood that there are practical limitations, the practical limitations being merely to provide a tube of suflicient flexibility to be oriented by the particular float employed and yet provide a dip tube having a sufliciently thick wall and hardness so as to prevent kinking or collapsing of the dip tube. For example, a tube having a bore diameter of about 0.1 inch, a wall thickness of about 0.015 inch and a hardness of 30 (Shore durometer) most nearly meets the flexibility requirements.
  • the float of our invention can be composed of a wide variety of materials including plastics such as polyamide polymers (nylon), polyethylene, polyvinyl chloride, linear acetal resin (Delrin), tetrafluoroethylene polymers (Teflon) and polyvinylidine chloride.
  • plastics such as polyamide polymers (nylon), polyethylene, polyvinyl chloride, linear acetal resin (Delrin), tetrafluoroethylene polymers (Teflon) and polyvinylidine chloride.
  • the two main requirements of the float are mainly that it have a suflicient solvent resistance to withstand contact with the types of ingredients in the propellent and active ingredient phases and that it possess a specific gravity intermediate that of the two liquid phases.
  • the float can be solid or, as illustrated in the drawings, the effective mass or average density of the float can be varied by the inclusion of ballast material or by the provision of an air space within the float.
  • Example I In this example a solid float composed of a polyamide polymer having the shape illustrated in FIGURE 1 of the drawings and having a density of 1.14 was employed. A simulated liquid active ingredient phase consisting of 59 percent alcohol and 41 percent water was employed. This mixture had a specific gravity of 0.92. A liquid propellent phase consisting of 40 percent Freon 12 (CCl F and 60 percent Freon 114 (CClF CClF was employed. This mixture had a specific gravity of 1.41. These two liquid phases Were added to an aerosol container in the same proportion that is normally employed in such aerosol systems. Thus, of the total liquid charged,
  • the float when introduced into the system just described floated at the interface between the upper liquid active ingredient phase and lower liquid propellant phase.
  • the float remains suspended at the interface with the inlet port exposed to the liquid active ingredient phase.
  • Example II In this example the same float as described in Example I was employed. A simulated liquid active ingredient phase consisting of 81 percent alcohol and 19 percent water was employed. This mixture had a specific gravity of 0.85. A propellent phase consisting of 55 percent Freon 12 (CCI F and 50 percent Freon l1 (CCI F) was employed. This mixture had a specific gravity of 1.41. As in Example I, the two liquid phases were charged to an aerosol container such that the active ingredient phase constituted 55 percent by weight of the total liquid and the propellent phase constituted 45 percent by weight of the total liquid. When the float was introduced to this system, it was suspended at the interface between the two liquid phases. When the contents of the container are dispensed using a flexible dip tube, as described above, the float remains suspended at the interface with the inlet port exposed to the liquid active ingredient phase.
  • Liquid active ingredient phases can be formulated for use as hair sprays by the inclusion in the hydroalcoholic liquid phase of proper hydroalcoholic soluble resins such as polyvinylpyrrolidone, certain copolymers of polyvinylpyrrolidone anad vinyl acetate, dimethyl hydantoin formaldehyde, etc., properly plasticized and perfumed; for use as room deodorants by the inclusion of glycols, such as propylene glycol, dipropylene glycol, triethylene glycol, quaternary ammonium compounds, and fragrance; for use as insecticides by the inclusion of either hydroalcoholic soluble or emulsifiable toxicants, including pyrethrins and synergists; for use as colognes by inclusion of suitable fragrances, in proper amounts.
  • hydroalcoholic soluble resins such as polyvinylpyrrolidone, certain copolymers of polyvinylpyrrolidone anad vinyl acetate, dimethyl hydantoin formaldehyde
  • hydroalcoholic phase is preferred, our invention is not limited to use in a system containing hydroalcoholic phase as the liquid phase to be dispensed, nor is it limited to the specific propellents described above as the liquid propellent phase, but includes liquid propellent phases having the described properties of specific gravity and immiscibility.
  • the float employed in an aerosol system such as that illustrated in FIGURES 1 and 2 of the drawing, has the additional advantage that the portion of the float immersed in the propellent phase serves as an equivalent to boiling chips permitting the propellent to boil up through the active ingredient phase and to establish pressure equilibrium within the vapor phase.
  • an aerosol dispenser for use with a three phase system comprising a vapor phase, a liquid phase to be dispensed, a liquid propellent phase of a different specific gravity than the liquid phase to be dispensed and sufiiciently immiscible with the liquid phase to be dispensed so that two liquid layers are present
  • the dispenser includes a container and a valve member having a passageway therethrough providing communication between the interior and exterior of said container, the improvement which comprises a flexible dip tube attached to and communicating with the passageway through the valve member, a float connected to the dip tube, the float having a passageway therethrough communicating at one end only with the dip tube and at the other end only with the liquid phase to be dispensed to form an inlet port for the liquid phase to be dispensed, the dip tube being of a length at least substantially equal to the distance between the valve member and the portion of the container most remote from the valve member, the float having a specific gravity greater than one of the liquid phases and less than the other of the liquid phases
  • the dispenser of claim 1 in which the liquid propellent phase is of a greater specific gravity than the liquid phase to be dispensed, the float is of a specific gravity less than the liquid propellent phase and greater than the liquiilt phase to be dispensed and the float is shaped and the inlet port disposed such that when the float is suspended at the interface between the liquid phases the center of gravity of the float is located in the liquid propellent phase and the inlet port is located in the liquid phase to be dispensed.
  • liquid propellent phase is of less specific gravity than the liquid phase to be dispensed
  • the float is of a specific gravity greater than the liquid propellent phase and less than the liquid phase to be dispensed and the float is shaped and the inlet port is disposed such that when the float is suspended at the interface between the liquid phases and the inlet port and the center of gravity of the float are located in the liquid phase to be dispensed.
  • valve member includes means for admixing liquid phase to be dispensed with vapor from the vapor phase in the container prior to discharge from the container.
  • valve member includes a mixing chamber provided with openings for the separate entry of the vapor phase and the liquid phase to be dispensed into the chamber and valve means for releasing the mixture of liquid and vapor from the chamber into the valve passageway communicating with the exterior of the container.

Description

Oct. 12, 1965 s. B. PRUSSIN ETAL 3,211,349
AEROSOL DISPENSER WITH FLEXIBLE DIP TUBE 2 Sheets-Sheet 1 Filed May 15, 1963 INVENTORS SAMUEL B. PRUSSI N FRED PRESANT HERMAN R. SH PHERD BY 7 M (2 31 ATTOR EYS Oct. 12, 1965 s. B. PRUSSIN ETAL 3,211,349
AEROSOL DISPENSER WITH FLEXIBLE DIP TUBE 2 Sheets-Sheet 2 Filed May 15, 1963 FIG] FIG.9
United States Patent 3,211,349 AEROSOL DISPENSER WITH FLEXIBLE DIP TUBE Samuel B. Prussin, Los Angeles, Calif., and Fred Presant,
Bridgeport, and Herman R. Shepherd, Fair'field, Conn.,
assignors to Aerosol Techniques, Incorporated, a corporation of New York Filed May 15, 1963, Ser. No. 280,603 5 Claims. (Cl. 222394) Our invention relates to aerosol dispensers. More particularly, our invention relates to a flexible dip tube and float for use with a three phase aerosol system.
Normally an aerosol system designed to yield a finely atomized mist consists of a two phase system, one phase of which is a liquid phase to be dispensed comprising a homogeneous solution or an emulsion of the active ingredient concentrate and liquefied propellent, and the second phase of which consists of propellent vapor. In operation, the mixture of active ingredient concentrate and liquefied propellent is expended, resulting in a decrease in the vapor pressure. The resultant decrease in vapor pressure permits an additional portion of the liquefied propellent in solution to be converted into gaseous state propellent in the head space above the liquid phase. It is evident that the spray pattern of such an aerosol will be a function of the pressure within the system, the valve mechanism and the concentration of propellent. Aerosol systems such as that described above are well known in the art. However, such systems possess certain disadvantages. One of the major disadvantages of such systems is the high cost of obtaining a suitable spray due to the extremely large quantity of propellent that is required. A quantity of propellent in excess of that required to expel a given quantity of active ingredient must be charged to the system since a substantial quantity of propellent, in solution or emulsion with the active ingre- Another aerosol system, termed a three phase aerosol,
permits the use of large amounts of water in the active ingredient concentrate. Such a system consists of a liquid phase to be dispensed, e.g., an aqueous concentrate phase containing the active ingredient, which is sufficiently immiscible with a second liquid propellent phase so that two distinct liquid phases or layers are present, rather than a single liquid phase comprising a solution or emulsion of liquid to be dispensed and liquefied propellent as in the two phase system. The third phase is a gaseous propellent phase or vapor phase. In such a system, the vapor phase will always be uppermost within the container while the liquid active ingredient and liquid propellent phases will be lower-most within the container. The two liquid phases, however, can be disposed in relatively different positions within the container depending on their relative densities or specific gravities. Thus propellents of greater density than the active ingredient concentrate will pool at the bottom of the container. Propellents of this nature, for the most part, consist of halogenated hydrocarbon propellents, for example, those sold under the trade names Freon, Genetron, Ucon or Isotron. On the other hand, if the propellent is less dense than the liquid concentrate it will float on the surface of the concentrate phase. Propellents of this nature include saturated hydrocarbons, e.g., propane or butane, and certain halogenated hydrocarbons such as difluoroethane sold under the trade name Freon 152a. In a three phase system where the liquid propellent is pooled at the bottom of the container, the dip tube employed with such system is cut short of the bottom of the container so that the opening at the bottom of the dip tube extends into the upper liquid active ingredient phase but does not extend into the lower liquid propellent phase. It is evident that as the active ingredient is expelled from the container and more of the liquid propellent is vaporized to maintain the vapor pressure in the head space above the liquid phases, the level of the liquid phase propellent in the container drops. Obviously, as the level of the liquid propellent phase drops, it is replaced by the active ingredient concentrate. Due to this replacement of the propellent by the active ingredient concentrate it can be seen that there is a substantial loss of concentrate material which can never be removed from the container because of the shortness of the dip tube.
Our invention provides a novel dip tube apparatus for use in an aerosol dispenser containing a three phase systern which permits substantially complete removal of the liquid active ingredient concentrate from the container. The three phase systems with which our apparatus is useful comprise, as described above, a vapor phase, a liquid phase to be dispensed and a liquid propellent phase of a different specific gravity or density than the liquid phase to be dispensed and sufficiently immiscible with the liquid phase to be dispensed so that two liquid phases or layers are present. The mechanical components of the aerosol dispenser with which our invention is to be used include any of the standard containers and valve members known in the art. The novel apparatus of our invention comprises a flexible dip tube with a float or bob connected at one end of the dip tube. The float employed has an inlet port and an outlet interconnected by an opening through the float. One end of the dip tube is connected with the outlet port of the float while the other end of the dip tube is connected to the valve member. The float employed in our invention is composed of a material having specific gravity or density greater than one of the two liquid phases and less than the other of the liquid phases whereby it is suspended at the interface between the two liquid phases. While the shape of our float can vary considerably, it must be of such configuration that its inlet port is always exposed to the liquid active ingredient phase to be dispensed as the float is suspended at the interface of the two liquid phases. The dip tube is of suflicient length to allow the float or bob to be suspended, i.e. to float, at the interface of the two liquid phases in any position of usage. While the dip tube can vary considerably in length it should be of a length at least substantially equal to, and preferably slightly greater than, distance between the tailpiece of the valve member and the most remote portion of the container.
When employing a propellent of greater density than the active ingredient concentrate, so that the liquid propellent layer is at the bottom of the container, the float of our invention is of such a shape that the center of gravity of the float is located within the liquid propellent phase and the inlet port is located within the liquid active ingredient phase. On the other hand, however, when a propellent is employed which is less dense than the liquid active ingredient phase, so that the liquid active ingredient layer is lowermost in the container, the float of our invention is of such a shape that both the inlet port and the center of gravity of the float are located in the liquid active ingredient phase.
The flexible dip tube and float provide for the substantially complete removal of the liquid active ingredient phase from the container since the slack in the tube permits the float to recede as the propellent is expended with the inlet port always exposed to the active ingredient phase and away from the liquid propellent phase regardless of position of usage.
Our invention will be further illustrated by reference to the accompanying drawings in which:
FIGURE 1 is a sectional view of a standard aerosol dispenser containing a three phase system having a liquid propellent phase of greater specific gravity than the liquid active ingredient phase in which an embodiment of our invention is incorporated.
FIGURE 2 is the device of FIGURE 1 shown in a partially inverted position.
FIGURE 3 is an enlarged view of a float of the same shape illustrated in FIGURES 1 and 2 showing an alternate embodiment thereof.
FIGURE 4 is an enlarged sectional view of the float of FIGURE 3 taken along the line 4-4 of FIGURE 3.
FIGURE 5 is another alternate embodiment of a float to be used with the type of three phase system shown in FIGURES 1 and 2.
FIGURE 6 is a partial, sectional view of an aerosol dispenser containing a three phase system in which the liquid propellent phase has a lesser specific gravity than the liquid active ingredient phase in which is incorporated another embodiment of our invention.
FIGURE 7 is an enlarged sectional view showing an alternate embodiment of a float that can be used with the type of aerosol system shown in FIGURE 6.
FIGURE 8 illustrates the same embodiment shown in FIGURE 7 in which the aerosol container is slightly tipped.
FIGURE 9 illustrates a particular type of valve for use with the dispensers of the preceding drawings.
FIGURE 1 shows a standard aerosol container 10 with a valve cap member 12 and a valve member 14 which interconnects the interior and exterior of aerosol container 10 through passageway 15. As can be seen, the liquid propellent phase 16 is lowermost within the container 10. Floating on the surface of liquid propellent phase 16 is the liquid active ingredient phase 18 to be dispensed above which is vapor phase 20. The interface between liquid propellent phase 16 and liquid active ingredient phase 18 is designated by the reference numeral 22. The aerosol container and system just described are known in the art.
In the particular embodiment of our invention illustrated in FIGURE 1, a float 24 having a specific gravity less than that of liquid propellent phase 16 and greater than that of liquid active ingredient phase 18 is shown suspended at the interface 22 between the two liquid phases 16 and 18. 14 and float 24 is a flexible dip tube 26 of a length greater than the distance between the tailpiece of the valve 14 and the bottom of the container 10. Also shown in FIG- URE l is an inlet port 28 located at the upper end of float 24 and exposed to active ingredient phase 18.
The interior of dip tube 26 and inlet port 28 are interconnected by a passageway through float 24, not shown in this figure.
FIGURE 2 shows the container 10 of FIGURE 1 in a partially inverted position. It will be noted that while liquid propellent phase 16 is still lowermost in the container, liquid active ingredient phase 18 next and vapor phase 20 uppermost, the liquid phases are now located in what would normally be considered the top of the container. It will also be noticed that float 24 is still suspended at the interface 22 between liquid propellent phase 16 and liquid active ingredient phase 18 and that the inlet port 28 is exposed to the active ingredient phase 18.
FIGURES 3 and 4 show an alternate embodiment of a float 24a of the same general shape as that shown in FIGURES 1 and 2. Also shown are one end of the dip tube 26 and inlet port 28a. Referring now to FIGURE 4, the passageway 30 interconnecting the interior of dip tube 26 and inlet port 28a can be seen. Also shown in Interconnecting the tailpiece of valve FIGURE 4 are metal weights 32 embedded in the lower portion of float 24a. While a float having the shape of floats 24 and 24a composed of a material having a specific gravity intermediate that of liquid propellent phase 16 and liquid active ingredient phase 18 will be suspended at the interface 22 with the inlet port 28 exposed to active ingredient phase 18, as shown in FIGURES 1 and 2, the addition of ballast in the form of metal weights 32 near the bottom of float 24a increases the total weight of float 24a causing a greater portion of the float 24a to be in propellent phase 16. The presence of weights 32 also lowers the center of gravity of float 24a which changes the relative distance between the center of gravity and the center of buoyancy thereby increasing the metacentric distance and increasing the stability of float 2411.
FIGURE 5 illustrates another alternate embodiment of a float. In this figure can be seen float 24b, inlet port 28b and passageway 3%. Located near the upper portion of float 24b is an air pocket or void 34 and located near the lower portion of float 24b is a metal slug 36. Thus, it can be seen that the construction of float 24b is such that the lower portion has a much higher concentration of the weight distribution than the upper portion. It will be understood that the center of gravity of the float 24b is lowered even more than in the embodiments shown in FIGURES 1 through 4 thereby further increasing the stability of float 24b.
In FIGURE 6 is shown a standard aerosol container 10 and a portion of valve member 14 which interconnects the interior and exterior of aerosol container 10. As opposed to the aerosol system illustrated in FIGURES 1 and 2, the liquid active ingredient phase 18 is lowermost in the container 10. Floating on the surface of liquid active ingredient phase 18 is the less dense liquid propellent phase 16 above which is vapor phase 20. Again, the interface between liquid propellent phase 16 and liquid active ingredient phase 18 is designated by the reference numeral 22. This aerosol container and system as just described is also known in the art.
In the particular embodiment of the invention illustrated in FIGURE 6, a float 38 having a specific gravity greater than that of liquid propellent phase 16 and less than that of liquid active ingredient phase 18 is shown suspended at interface 22 between the two liquid phases 16 and 18. Interconnecting the tailpiece of valve 14 and float 38 is a flexible dip tube 26 of a length greater than the distance between the tailpiece of the valve 14 and the bottom of the container 10. Also shown in FIGURE 6 is an inlet port 40 located at the lower end of float 38 and exposed to active ingredient phase 18. The interior of dip tube 26 and inlet port 40 are interconnected by a passageway through float 38, not shown in this figure. It will be not-iced that the inlet port 40 is located at the lower end of float 38 and that dip tube 26 is connected to the lower end of float 38 in this embodiment of our invent-ion rather than having such port and connection at the upper end of the float as illustrated in FIGURES 1 and 2.
FIGURE 7 illustrates an alternate embodiment of a float for employment in a three phase aerosol system similar to that of FIGURE 6. Shown in FIGURE 7 are aerosol container 10, liquid propellent phase 16, liquid active ingredient phase 18, vapor phase 20, interface 22 and dip tube 26. Also shown in FIGURE 7 is float 42 having an annular air pocket or void 44 located near its upper end and an annular metal slug 46 located near its lower end. The purpose of the air pocket or void 44 and the metal slug 46 are the same as the air pocket or void 34 and the metal slug 36 shown in FIGURE 5, i.e., to lower the center of gravity and thereby increase the stability of the float. It will also be noticed in FIGURE 7 that the dip tube 26 extends vertically through float 42 and terminates at a point 48 below the lower end of float 42 providing inlet port 40 in active ingredient phase 18.
In FIGURE 8 are shown aerosol container 10, liquid propellent phase 16, liquid active ingredient phase 18, vapor phase 20, interface 22, dip tube 26 and float 42. It will be noticed that the aerosol container is tipped slightly to one side and the quantity of propellent phase 16 and active ingredient phase 18 have been substantially reduced. It will also be noticed that float 42 is still suspended at the interface 22 between the two liquid phases 16 and 18 and that the terminal point 48 of dip tube 26 is still exposed to the active ingredient phase 18.
Thus, it can be seen that in operation the several embodiments of our invention illustrated in the figures of the drawings eifect the same results. Thus, for example, in a three phase aerosol sysetem in which the liquid propellent phase has a greater specific gravity than that of the liquid active ingredient phase, such as illustrated in FIGURES 1 and 2 of the drawings, the float 24 is suspended at the interface 22 between the two liquid phases 16 and 18 such that the inlet port 28 is always exposed to the active ingredient phase 18. The dip tube 26 is of such construction that it is sufficiently flexible to be oriented by the forces exerted on and by the float 24. Therefore, when the aerosol container is completely filled by the initial charge of liquid active ingredient phase 18 and liquid propellent phase 16 and the aerosol container 10 is maintained in an upright position as shown in FIGURE 1, the buoyant force exerted by liquid propellent phase 16 is suificient to suspend the float 24 at the fliiterface 22. It will be obvious that a greater amount of slack will exist in dip tube 26 under such conditions than is shown in FIGURE 1 and may, therefore, exert some force on the float 24 which may have a tendency to tip the float 24. The configuration of float 24, however, is such that the metacentric distance is sufficiently great and properly oriented that the couple consisting of the force of gravity acting in a downward direction effective at the center of gravity of float 24 and the buoyant force acting in an upward direction effective at the center of buoyancy of the float 24 is sufiicient to ofiset any force that may be exerted by dip tube 26. Thus, whether aerosol container 10 be completely filled or nearly empty, as shown in FIGURE 1, float 24 will always remain properly oriented so that inlet port 28 is always exposed to active ingredient phase 18. Thus, if aerosol container 10 is inverted or partially inverted, as shown in FIGURE 2, float 24 still remains suspended at interface 22 with the inlet port 28 exposed to active ingredient phase 18. Our invention thereby constantly provides the proper orientation and disposition of the inlet port 28 permitting the proper operation of the aerosol system in whatever position the container happens to be.
Referring now to FIGURE 7 one can see that the flexible dip tube and float of our invention can also operate in an aerosol system in which the liquid active ingredient phase has a greater specific gravity than that of the liquid propellent phase. Again, the float 24 is of such construction and configuration that the couple consisting of the force of gravity and the buoyant force act through their effective points to maintain constantly the proper orientation of the float 42 such that the inlet port 40 provided by terminal point 48 of dip tube 26 is always exposed to the active ingredient phase 18.
With dispensers containing three phase systems, the use of valves admitting only the liquid phase to be dispensed into the valve passageway results in a coarse, wet, spray pattern which is desirable for many uses. By the use of a valve provided with means for admixing the liquid phase to be dispensed with vapor from the vapor phase in the dispenser a finely atomized spray pattern is obtained. Such a valve is illustrated in FIGURE 9. In FIGURE 9, valve member 14 comprises a hollow stem 50 with the valve 52 normally seated against surface 54 by means of spring 56. Surrounding the valve is a housing 58 with a tail piece 60, with opening 62, to which flexible dip tube 26 is attached. The housing contains opening 64 exposed to the vapor phase 20 in the head space of the dispenser 10.
The valve stem has actuator or head 66 mounted thereon with passageway 68 therethrough. When actuated by pressing down head 66 the valve 52 is unseated and liquid phase to be dispensed is educted from dip tube 26 and vapor enters through opening 64 and are intermixed in chamber 70 formed by housing 58 and the mixture enters valve stem 50 through opening 72 and out through passage 68. The vapor mixed with the liquid phase to be dispensed atomizes the liquid and a finely atomized spray is obtained. Known mechanical break-up devices can also be used in the head to provide improved atomization, if desired. The use of the valve of FIGURE 9 in combination with the flexible dip tube and float and systems of FIGURES 1 to 8 provide substantially complete removal of the liquid phase to be dispensed as well as a finely atomized spray pattern. The liquid active ingredient concentrate replaces that volume of propellent which is expended because of its vaporization into the head space and subsequently out through the vapor tap orifice in the valve housing, and the liquid active ingredient concentrate and propellent are expended uniformly and completely. In the use of this valve with a system wherein the liquid propellent is of greater specific gravity than the liquid phase to be dispensed, the container must be used in the upright position to prevent loss of liquid propellent through the vapor tap opening in the valve housing which would occur if the container were inverted.
The flexible dip tube of our invention can be made of natural rubber or synthetic rubbers such as neoprene and buna. It can also be made of a wide variety of plastic materials such as modified vinyls (Tyg-on) and flexible polyethylene. As a practical matter, the employment of I neoprene in the dip tube is preferred due to its solvent resistance. While the dimensions of the dip tube may vary considerably, it will be understood that there are practical limitations, the practical limitations being merely to provide a tube of suflicient flexibility to be oriented by the particular float employed and yet provide a dip tube having a sufliciently thick wall and hardness so as to prevent kinking or collapsing of the dip tube. For example, a tube having a bore diameter of about 0.1 inch, a wall thickness of about 0.015 inch and a hardness of 30 (Shore durometer) most nearly meets the flexibility requirements.
The float of our invention can be composed of a wide variety of materials including plastics such as polyamide polymers (nylon), polyethylene, polyvinyl chloride, linear acetal resin (Delrin), tetrafluoroethylene polymers (Teflon) and polyvinylidine chloride. The two main requirements of the float are mainly that it have a suflicient solvent resistance to withstand contact with the types of ingredients in the propellent and active ingredient phases and that it possess a specific gravity intermediate that of the two liquid phases. The float can be solid or, as illustrated in the drawings, the effective mass or average density of the float can be varied by the inclusion of ballast material or by the provision of an air space within the float.
The following examples illustrate one type of float that can be employed with a three phase aerosol system of the type shown in FIGURES 1 and 2 of the drawing.
Example I In this example a solid float composed of a polyamide polymer having the shape illustrated in FIGURE 1 of the drawings and having a density of 1.14 was employed. A simulated liquid active ingredient phase consisting of 59 percent alcohol and 41 percent water was employed. This mixture had a specific gravity of 0.92. A liquid propellent phase consisting of 40 percent Freon 12 (CCl F and 60 percent Freon 114 (CClF CClF was employed. This mixture had a specific gravity of 1.41. These two liquid phases Were added to an aerosol container in the same proportion that is normally employed in such aerosol systems. Thus, of the total liquid charged,
-' the simulated active ingredient phase comprised percent by weight and the propellent phase comprised 45 percent by weight. The float when introduced into the system just described floated at the interface between the upper liquid active ingredient phase and lower liquid propellant phase. When the contents of the container are dispensed using flexible dip tube, as described above, the float remains suspended at the interface with the inlet port exposed to the liquid active ingredient phase.
Example II In this example the same float as described in Example I was employed. A simulated liquid active ingredient phase consisting of 81 percent alcohol and 19 percent water was employed. This mixture had a specific gravity of 0.85. A propellent phase consisting of 55 percent Freon 12 (CCI F and 50 percent Freon l1 (CCI F) was employed. This mixture had a specific gravity of 1.41. As in Example I, the two liquid phases were charged to an aerosol container such that the active ingredient phase constituted 55 percent by weight of the total liquid and the propellent phase constituted 45 percent by weight of the total liquid. When the float was introduced to this system, it was suspended at the interface between the two liquid phases. When the contents of the container are dispensed using a flexible dip tube, as described above, the float remains suspended at the interface with the inlet port exposed to the liquid active ingredient phase.
The basic systems of Examples I and II, can be adapted for use to a wide variety of products such as hair sprays, room deodorants, insecticides and colognes by inclusion of active ingredients in proper amounts. Liquid active ingredient phases can be formulated for use as hair sprays by the inclusion in the hydroalcoholic liquid phase of proper hydroalcoholic soluble resins such as polyvinylpyrrolidone, certain copolymers of polyvinylpyrrolidone anad vinyl acetate, dimethyl hydantoin formaldehyde, etc., properly plasticized and perfumed; for use as room deodorants by the inclusion of glycols, such as propylene glycol, dipropylene glycol, triethylene glycol, quaternary ammonium compounds, and fragrance; for use as insecticides by the inclusion of either hydroalcoholic soluble or emulsifiable toxicants, including pyrethrins and synergists; for use as colognes by inclusion of suitable fragrances, in proper amounts. It will be understood that while a hydroalcoholic phase is preferred, our invention is not limited to use in a system containing hydroalcoholic phase as the liquid phase to be dispensed, nor is it limited to the specific propellents described above as the liquid propellent phase, but includes liquid propellent phases having the described properties of specific gravity and immiscibility.
In addition to the other advantages of the dip tube and float of our invention described above, the float employed in an aerosol system such as that illustrated in FIGURES 1 and 2 of the drawing, has the additional advantage that the portion of the float immersed in the propellent phase serves as an equivalent to boiling chips permitting the propellent to boil up through the active ingredient phase and to establish pressure equilibrium within the vapor phase.
We claim:
1. In an aerosol dispenser for use with a three phase system comprising a vapor phase, a liquid phase to be dispensed, a liquid propellent phase of a different specific gravity than the liquid phase to be dispensed and sufiiciently immiscible with the liquid phase to be dispensed so that two liquid layers are present, which dispenser includes a container and a valve member having a passageway therethrough providing communication between the interior and exterior of said container, the improvement which comprises a flexible dip tube attached to and communicating with the passageway through the valve member, a float connected to the dip tube, the float having a passageway therethrough communicating at one end only with the dip tube and at the other end only with the liquid phase to be dispensed to form an inlet port for the liquid phase to be dispensed, the dip tube being of a length at least substantially equal to the distance between the valve member and the portion of the container most remote from the valve member, the float having a specific gravity greater than one of the liquid phases and less than the other of the liquid phases whereby the float is suspended at the interface of the liquid phases, and the inlet port of the float disposed such that it is always and only in communication with the liquid phase to be dispensed.
2. The dispenser of claim 1 in which the liquid propellent phase is of a greater specific gravity than the liquid phase to be dispensed, the float is of a specific gravity less than the liquid propellent phase and greater than the liquiilt phase to be dispensed and the float is shaped and the inlet port disposed such that when the float is suspended at the interface between the liquid phases the center of gravity of the float is located in the liquid propellent phase and the inlet port is located in the liquid phase to be dispensed.
3. The dispeser of claim 1 in which the liquid propellent phase is of less specific gravity than the liquid phase to be dispensed, the float is of a specific gravity greater than the liquid propellent phase and less than the liquid phase to be dispensed and the float is shaped and the inlet port is disposed such that when the float is suspended at the interface between the liquid phases and the inlet port and the center of gravity of the float are located in the liquid phase to be dispensed.
4. The dispenser of claim 1 in which the valve member includes means for admixing liquid phase to be dispensed with vapor from the vapor phase in the container prior to discharge from the container.
5. The dispenser of claim 4 in which the valve member includes a mixing chamber provided with openings for the separate entry of the vapor phase and the liquid phase to be dispensed into the chamber and valve means for releasing the mixture of liquid and vapor from the chamber into the valve passageway communicating with the exterior of the container.
References Cited by the Examiner UNITED STATES PATENTS 158,326 12/74 Steves et al 22248l.5 275,134 4/83 Burton 210-242 1,181,783 5/16 Lyons 222464 2,932,433 4/60 Abplanalp 222394 2,995,278 8/61 Clapp. 3,113,698 12/63 Abplanalp 222464 X RAPHAEL M. LUPO, Primary Examiner.

Claims (1)

1. IN AN AEROSOL DISPENSER FOR USE WITH A THREE PHASE SYSTEM COMPRISING A VAPOR PHASE, A LIQUID PHASE TO BE DISPENSED, A LIQUID PROPELLENT PHASE OF A DIFFERENT SPECIFIC GRAVITY THAN THE LIQUID PHASE TO BE DISPENSED AND SUFFICIENTLY IMMISCIBLE WITH THE LIQUID PHASE TO BE DISPENSED SO THAT TWO LIQUID LAYERS ARE PRESENT, WHICH DISPENSER INCLUDES A CONTAINER AND A VALVE MEMBER HAVING A PASSAGEWAY THERETHROUGH PROVIDING COMMUNICATION BETWEEN THE INTERIOR AND EXTERIOR OF SAID CONTAINER, THE IMPROVEMENT WHICH COMPRISES A FLEXIBLE DIP TUBE ATTACHED THE VALVE COMMUNICATING WITH THE PASSAGEWAY THROUGH THE VALVE MEMBER, A FLOAT CONNECTED TO THE DIP TUBE, THE FLOAT HAVING A PASSAGEWAY THERETHROUGH COMMUNICATING AT ONE END ONLY WITH THE DIP TUBE AND AT THE OTHER END ONLY WITH THE LIQUID PHASE TO BE DISPENSED TO FORM AN INLET PORT FOR THE LIQUID PHASE TO BE DISPENSED, THE DIP TUBE BEING OF A LENGTH AT LEAST SUBSTANTIALLY EQUAL TO THE DISTANCE BETWEEN THE VALVE MEMBER AND THE PORTION OF THE CONTAINER MOST REMOTE FROM THE VALVE MEMBER, THE FLOAT HAVING A SPECIFIC GRAVITY GREATER THAN ONE OF THE LIQUID PHASES AND LESS THAN THE OTHER OF THE LIQUID PHASES WHEREBY THE FLOAT IS SUSPENDED AT THE INTERFACE OF THE LIQUID PHASES, AND THE INLET PORT OF THE FLOAT DISPOSED SUCH THAT IT IS ALWAYS AND ONLY IN COMMUNICATION WITH THE LIQUID PHASE TO BE DISPENSED.
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US3580430A (en) * 1968-04-25 1971-05-25 Valois Sa Aerosol containers
US3872886A (en) * 1973-09-12 1975-03-25 Albert Shotmeyer Combined water removing and contents indicating device for underground liquid fuel containing tanks
US3885588A (en) * 1973-09-12 1975-05-27 Albert Shotmeyer Device for removing water from the bottom of underground liquid fuel tanks
US3908690A (en) * 1973-09-12 1975-09-30 Albert Shotmeyer Device for removing water from the bottom of existing underground liquid fuel tanks
US4062475A (en) * 1975-04-25 1977-12-13 S. C. Johnson & Son, Inc. Pressurized container for two-phase system
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FR2437246A1 (en) * 1978-09-28 1980-04-25 Inaba Sangyo Co IMPROVED TUBE FOR AEROSOL SPRAY VALVE
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US5195664A (en) * 1992-04-03 1993-03-23 Steven Rhea All directional fluid pick-up
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US5755572A (en) * 1992-08-10 1998-05-26 Novadent Ltd. Oral hygiene irrigator syringe bulb
US5527577A (en) * 1993-06-22 1996-06-18 Aptar Group, Inc. Flexible eduction tube for hand dispenser
FR2707265A1 (en) * 1993-07-05 1995-01-13 Oreal Device for dispensing liquid, in aerosol form in particular
US5655714A (en) * 1994-12-08 1997-08-12 Wagner Spray Tech Corporation Pivotable syphon tube
US5657909A (en) * 1996-01-04 1997-08-19 Calmar Inc. Manual sprayer having multi-directional liquid pickup and container venting
US6517009B2 (en) 1997-12-25 2003-02-11 Gotit Ltd. Automatic spray dispenser
US6540155B1 (en) 1997-12-25 2003-04-01 Gotit Ltd. Automatic spray dispenser
US6394319B1 (en) 2000-11-21 2002-05-28 Robert Pucillo Flexible liquid feeding assembly
US6935542B2 (en) 2002-05-15 2005-08-30 S. C. Johnson & Son, Inc. Device for retaining and for inserting a flexible tube assembly into a fluid container
US20030213816A1 (en) * 2002-05-15 2003-11-20 Kevin Harrity Device for retaining and for inserting a flexible tube assembly into a fluid container
US20040069797A1 (en) * 2002-09-30 2004-04-15 Andrew Tien Gas extraction Apparatus
US20080190838A1 (en) * 2003-08-15 2008-08-14 Angus Reardon Bailing Apparatus
US20080110937A1 (en) * 2006-11-14 2008-05-15 Sidney Guill Spray bottle
US20100243761A1 (en) * 2009-03-31 2010-09-30 Anatoly Gosis Method and device for preventing liquid dispensation from an aerosol spray can
US20110087194A1 (en) * 2009-10-08 2011-04-14 Mark Carpenter High Flow Volume Nasal Irrigation Device and Method for Alternating Pulsatile and Continuous Fluid Flow
US20110087174A1 (en) * 2009-10-08 2011-04-14 Mark Carpenter High Flow Volume Nasal Irrigation Device and Method for Alternating Pulsatile and Continuous Fluid Flow
US7976529B2 (en) * 2009-10-08 2011-07-12 Skylab Developments Inc. High flow volume nasal irrigation device and method for alternating pulsatile and continuous fluid flow
US8657794B2 (en) * 2009-10-08 2014-02-25 Skylab Development, Inc. High flow volume nasal irrigation device and method for alternating pulsatile and continuous fluid flow
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