EP0000062A1 - Valve pour récipient aérosol à agent de propulsion inflammable et récipient muni d'une telle valve - Google Patents

Valve pour récipient aérosol à agent de propulsion inflammable et récipient muni d'une telle valve Download PDF

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Publication number
EP0000062A1
EP0000062A1 EP78100109A EP78100109A EP0000062A1 EP 0000062 A1 EP0000062 A1 EP 0000062A1 EP 78100109 A EP78100109 A EP 78100109A EP 78100109 A EP78100109 A EP 78100109A EP 0000062 A1 EP0000062 A1 EP 0000062A1
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EP
European Patent Office
Prior art keywords
valve
delivery
orifice
vapor tap
container
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.)
Withdrawn
Application number
EP78100109A
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German (de)
English (en)
Inventor
Joseph George Spitzer
Marvin Small
Lloyd I. Osipow
Dorothea C. Marra
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Individual
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Individual
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Publication date
Priority claimed from US05/804,423 external-priority patent/US4116370A/en
Application filed by Individual filed Critical Individual
Publication of EP0000062A1 publication Critical patent/EP0000062A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D83/00—Containers or packages with special means for dispensing contents
    • B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
    • B65D83/44—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
    • B65D83/56—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 with means for preventing delivery, e.g. shut-off when inverted
    • B65D83/565—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 with means for preventing delivery, e.g. shut-off when inverted the delivery-preventing means being responsive to the orientation of the container

Definitions

  • Aerosol sprays are now widely used, particularly in the cosmetic, topical pharmaceutical 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, deodorants, and hair sprays to direct the products to the skin or hair in the form of a finely-divided spray.
  • valves and valve delivery ports, nozzles or orifices which are capable of delivering finely-divided sprays
  • 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 patent describes a type of valve which is now rather common, giving a finely atomized spray, and having a vapor tap, which includes a mixing chamber provided with separate openings for the vapor phase and the liquid phase to be dispensed into the chamber, in combination with a valve actuator or button of the mechanical breakup type.
  • valves provide a soft spray with a swirling motion.
  • Another design of valve 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.
  • Marsh U.S. patent No. 3,148,127 patented September 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 Q f valve is used having a 0.030 inch vapor tap orifice, a 0..30 inch liquid tap orifice, and a 0.018 inch valve stem orifice, with a mechanical breakup button. There is no disclosure of the relative proportions of propellant gas to liquid phase being dispensed.
  • Rabussier U.S. patent No. 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.
  • the capillary dip: tube is provided with a plurality of perforations 0.01 to 1. 2 mm in diameter over its entire length, so that the two phases are admitted together in the valve chamber from the capillary dip tube, instead of the gas being admitted only through 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.
  • the button orifice diameter is 0.016 inch.
  • the composition dispensed is an aluminum antiperspirant comprising aluminum chlorhydroxide, water, alcohol and dimethyl ether.
  • the aluminum chlorhydroxide 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 antiperspirant composition containing dispersed astringent salt particles.
  • the vapor tap type of valve is effective in providing fine sprays.
  • it requires a high proportion of propellant, relative to the amount of active ingredients dispensed per unit time.
  • a vapor tap requires a large amount of propellant gas, because the tap introduces a volume of propellant gas into each squirt of liquid.
  • Such valves therefore require aercsol compositions having a rather high proportion of propellant.
  • a high propellant proportion is dangerous and undesirable, however, when the propellant is flammable. For this reason, the art has preferred nonflammable propellants, such as the fluorocarbons.
  • Vapor tap valves normally have a rather large valve chamber, in the walls of which are placed the vapor tap and liquid tap orifices.
  • the valve chamber houses the bias means tending to hold the valve in a closed position, and at the same time furnishes blending space for the liquid and gaseous components of the aerosol compositions before delivery when the delivery valve is opened.
  • the liquid tap and vapor tap orifices in the valve chamber are normally open to free entry of both liquid aerosol composition and liquefied propellant or propellant gas at all times, even when the delivery valve is closed.
  • the valve chamber can and usually does fill with liquid propellant via at least the vapor tap orifice.
  • the volume of liquefied propellant in the valve chamber is dispensed first, within the first few seconds, This initial delivery of liquefied propellant when the propellant is flammable poses a considerable flame hazard, if the container is used in the vicinity of a flame.
  • a further problem peculiar to vapor tap valves arises when the container is inclined from the normally upright position to below the horizontal, or even inverted. If the container is inclined or tipped below the horizontal, or inverted, the gas propellant phase can pass through the liquid tap orifice, and the liquefied propellant and liquid aerosol composition can pass through the vapor tap orifice. Since the liquid tap orifice and the vapor tap orifice normally differ in restriction to flow, the ratio of gas to liquid is likely to be completely changed, and the proportion of flammable liquid propellant may be greatly increased, with a resulting increase in flammability of the spray that is dispensed. In this case, an extremely flammable spray can be obtained.
  • Aerosol containers are commonly filled so that the liquid phase occupies about 60% of the total container capacity at 21°C.
  • a container with minimum doming, a straight dip tube, and a vapor tap or if ice about 0.6 mm in diameter, off-center and positioned downward when the container is horizontal both vapor and liquid tap orifices will be covered by liquid when the container is positioned so that the valve is in the range of about -5 0 (below horizontal) to +5° (above horizontal).
  • the range in valve position in which both taps are covered by liquid may extend to about -30° (below the horizontal) to about + 5 (above the horizontal).
  • the extent or span of this range will depend on the dimensions of the container. The larger the ratio of diameter: height, the wider the span of the range.
  • the fire hazard posed when aerosol containers equipped with conventional vapor tap valves are tipped from the upright position to the horizontal or even inverted position is overcome by including, in combination with the delivery valve, an overriding shut-off valve which, although normally open when the container is upright, automatically closes off flow of liquid through the delivery valve from the container to the delivery port at some limiting angle at or below the horizontal as the top of the container is brought below the horizontal, towards the fully inverted position.
  • the shut-off valve will normally have closed fully before the container is fully inverted.
  • the angle to the horizontal at which the valve must close is of course the angle at which liquid can flow to the delivery port and escape as liquid from the container, without benefit of a high gas ratio. This can be within the range from 0° (i.e. hortzontal) to -90°, and preferably is from -5° to -45°, below the horizontal.
  • the aerosol container in accordance with the invention of Serial No. 754,471 comprises', in combination, a pressurizable container having at least one storage compartment for an aerosol composition and a liquefied propellant in which compartment propellant can assume an orientation according to orientation of the container between a horizontal and an upright position, and a horizontal and inverted position; a delivery valve movable manually between open and closed positions, and including a valve stem and a delivery port; an aerosol-conveying passage in flow connection at one end with the storage compartment and at the other end with the delivery port, manipulation of the delivery valve opening and closing the passage to flow of aerosol composition and propellant from the storage compartment to the delivery port; and a shut-off valve responsive to orientation of the container to move automatically between positions opening and closing off flow of liquefied propellant to the delivery port, the shut-off valve moving into an open position in an orientation of the container between ' a horizontal and an upright position, and moving into a closed position in an orientation of the container between the horizontal and an inverted. position.
  • a preferred embodiment of delivery valve Is of the vapor tap type comprising a valve movable manually 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; bias means for holding the delivery 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 a 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; at least one vapor tap orifice through the wall means; and a shut-off valve means movable between a closed position closing off the valve stem passage and an open position allowing aerosol composition to pass through the valve stem passage, the shut-off valve being in the open position at least when the container is fully upright, and being in the closed
  • the containers of Serial No. 754,471 do not however overcome the problem of delivery even when the container is upright, or inclined but above the horizontal, of a highly flammable spray composed predominantly of liquefied flammable propellant when the container is shaken just before the delivery valve is opened, arising from the filling of the valve chamber during shaking with liquefied propellant just before delivery. This is a problem similar to that arising when the container is inverted or held at an angle to the vertical below the horizontal, even though the container may be held fully upright, because the shaking at least partially fills the valve chamber with the liquid phase.
  • a vapor tap valve for aerosol containers comprising, in combination, a delivery valve movable manually between open and closed positions and including a valve stem, a delivery port, and a valve chamber; bias means in the valve chamber biasing the delivery valve towards a closed position; a liquid tap orifice in flow communication with the valve chamber; a vapor tap orifice in flow communication with the valve chamber; and a shut-off valve linked to and movable with the delivery valve, closing off the vapor tap orifice against entry of liquefied propellant therethrough into the valve chamber when the delivery valve is closed, and opening the vapor tap orifice when the delivery valve is manually moved to the open position, against the biasing force of the bias means.
  • the vapor tap valve is combined with a second shut-off valve responsive to orientation of the aerosol container to move automatically between positions opening and closing off flow of propellant to the delivery port via the valve chamber, the shut-off valve moving into an open position in an orientation of the container between a horizontal and an upright position, and moving into a closed position in an orientation of the chamber between the horizontal and an inverted position.
  • This preferred embodiment of vapor tap valve Including first and second shut-off valves inhibits delivery of liquefied propellant under all conditions to which the container may be subjected.
  • the vapor tap valve has a valve housing which may also include or is in flow connection with wall means defining the valve chamber or blending space.
  • the valve chamber is of limited volume, ipsufficient to constitute a foam chamber, and only as large as required for thorough blending of gas and liquid therein before reaching the valve.
  • a delivery valve is movably disposed 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 valve chamber is in flow connection when the delivery valve is open...
  • the valve chamber can be small in volume, and no larger than the volume needed for full movement of a delivery valve therein. It can also be a narrow passage, large enough at one end for the delivery valve, and merging indistinguishably with the dip tube or tail piece passage. Any conventional mixing chamber in a vapor tap valve will serve.
  • the volume of the valve chamber does not usually exceed 1 cc, and can be as small as 0.01 cc, but it is preferably from 0.05 to 0.2 cc.
  • the liquid tap orifice communicates the valve chamber directly or indirectly with a capillary dip tube or a standard dip tube.
  • a standard or capillary dip tube normally extends into the liquid composition or phase in the aerosol container, and may reach to the bottom of the container.
  • a tail piece may be provided (but is not essential) at the valve housing as a coupling for linking the dip tube to the valve chamber 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 thence into the valve chamber.
  • 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.
  • the dip tube communicates directly with the liquid tap orifice, the liquid tap orifice can be at the end opening of the dip tube.
  • capillary 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.
  • the size 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.
  • the vapor tap orifice is in fluid flow connection with the propellant or gas phase of the aerosol container, and admits gas into the valve chamber before the valve stem delivery passage. Normally, therefore, it is in the wall defining the valve chamber, and above the liquid tap orifice, although this is not essential.
  • the vapor tap orifice can be in a wall beside or above the shut-off valve, but it is of course upstream of the shut-off valve.
  • the vapor tap valve delivery system of an aerosol container downstream of the vapor tap delivery valve normally includes an actuator which . operates the delivery valve, and movable between open and closed positions against the biasing force at a bias means, with a valve stem and an aerosol composition-conveying valve passage therethrough, in flow connection with a delivery port.
  • valve chamber has a small capacity, e.g., less than about 0.2 cc, it is advantageous that when the first shut-off valve, which is linked with the delivery valve, is in an open position it is in flow communica- tion with both the vapor tap orifice and the liquid tap orifice.
  • This facilitates mixing of the gas and liquid phases which occurs in the valve chamber, before these pass to the delivery valve, and the diameters of the vapor tap and liquid tap orifices as well as the valve passages and orifices with which they are in communication are selected within the stated ranges to provide, in the valve chamber, a gas: liquid volume ratio within the range from about 8: 1 to about 40: 1, and preferably from about 15:1 to about 30: 1.
  • the gas: liquid ratio obtained from gas and liquid fed therethrough from the supply in the container will vary with the particular propellant or propellants and the composition of the liquid phase.
  • the viscosity of the liquid is a factor in determining the proportion that can flow through the liquid tap orifice per unit time, when the valve is open.
  • the valve stem orifice has a diameter within the range from about 0. 3 to about 0.35 mm, at least one liquid tap orifice having a cross-sectional open area within the range from about 0.1 to about 0.8 mm 2 , and at least one vapor tap orifice having a cross-sectional open area within the range from about 0.1 to about 0.8 mm 2 , the ratio of liquid tap orifice to vapor tap orifice cross-sectional open area being within the range from about 0.5 to about 2.5; 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 8:1 to about 40:1, limiting the delivery rate of liquid aerosol composition from the container when the valve is open.
  • the valve stem orifice has a diameter within the range from about 0.5 to about 0. 65 mm, at least one liquid tap orifice having a cross-sectional open area within the range from about 0.4 to about 0.8 mm 2 , and at least one vapor tap orifice having a cross-sectional open area within the range from about 0.3 to about 0.8 mm 2 , the ratio of liquid tap'orifice to vapor tap orifice cross-sectional open area being within the range from about 0.
  • 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 8: 1 to about 40:1, limiting the delivery rate of liquid aerosol composition from the container when the valve is open.
  • the cross-sectional open area thereof is within the range from about 0.1 to about 1.8 mm 2 , for flow of liquid aerosol composition into the valve chamber, and at least one vapor tap orifice through the wall has a cross-sectional open area within the range from about 0.1 to about 0.8 mm 2 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 3.2.
  • the cross-sectional open area thereof is within the range from about 0.6 to about 1. 8 mm 2 , for flow of liquid aerosol composition into the valve chamber, and at least one vapor tap orifice through the wall has a cross-sectional open area within the range from about 0.3 to about 0.8 mm 2 for flow of propellant gas into the valve chamber; and the ratio of capillary dip tube to vapor tap orifice cross-sectional open area is within the range from about 1 to about 3.2.
  • the controlling orifices to achieve the desired proportion of gas and liquid in the blend dispensed from the container are the vapor tap orifice, the liquid tap orifice (or in the case of a capillarly dip tube, the capillary dip tube), and the valve stem orifice.
  • the open areas of these orifices and the ratio of liquid tap orifice to vapor tap orifice open area should be controlled within the stated ranges. However, these dimensions are in no way critical to the operation of the shut-off valve, which can be used advantageously with delivery valves having other dimensions.
  • the valve delivery system normally includes, in addition to the valve stem orifice, an actuator orifice at the end of the passage through the actuator of the valve.
  • the valve delivery system from the valve 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, and the actuator orifice.
  • the controlling orifice in this sequence is the valve stem orifice, and the actuator orifice will normally have a diameter the same as or greater than the valve stem orifice, but not necessarily.
  • the actuator orifice 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 the controlling orifice, downstream of the blending chamber, and its diameter may in that event be within the range from about 0.3 to about 0.65 mm when solids are not present, and from about 0.45 to about 0. 65 mm when solids are present in sufficient amount or size to clog small orifices.
  • the orifice ranges given are applicable to dispersion-type antiperspirant aerosol compositions. Other orifice ranges may be used with other types of aerosol compositions.
  • the invention is also applicable to aerosol containers which have at least two compartments, a first aerosol composition compartment and a second liquefied propellant gas compartment, the propellant compartment and the valve and chamber being communicated by at least one vapor tap orifice, which is across the line of flow through the valve chamber to the valve delivery port from the propellant compartment.
  • a liquid aerosol composition to be foamed and then expelled from the container is placed in the first compartment of the container, which is in flow communication via a liquid tap orifice with the valve chamber, so as to admit liquid aerosol composition into the valve chamber across the line of propellant gas flow via the gas orifice or orifices to the delivery valve.
  • the propellant passes in gaseous form through the vapor tap orifice(s) and propels the liquid aerosol composition to and through the open delivery valve passage out from the container.
  • the overall dimensions of the vapor tap and the liquid tap orifice(s) are selected according to the required product delivery rate (including propellant expelled).
  • Both the vapor tap and liquid tap orifices are in a wall or walls defining the valve chamber or housing
  • the liquid tap orifice is placed so that liquid aerosol composition entering the valve chamber is disposed across the line of flow from the vapor tap orifice into the valve chamber and out from the container.
  • the liquid tap orifice can be below, above, or on a line with the vapor tap orifice.
  • the function of the shut-off valve of the invention is to prevent liquid aerosol composition containing flammable liquefied propellarit.irorri entering the valve chamber when the container is shaken.
  • This liquid composition readily enters the valve chamber through the vapor tap orifice as well as through a liquid tap orifice communicating with a standard dip tube.
  • the liquid tap orifice is a capillary dip tube of narrow bore, very little liquid will enter the valve chamber through the capillary, but it can enter through the vapor tap orifice.
  • shut-off valve close off the vapor tap orifice. While it may also be necessary that it close off the liquid tap orifice to entry of liquefied propellant into the valve chamber if that orifice is large, it is usually unnecessary, and therefore optional to do so.
  • the shut-off valve of the invention can be placed at any convenient location across the line of flow of propellant liquid or gas through the vapor tap orifice into the valve chamber of the vapor tap valve. Thus, it can be placed directly across or beside the vapor tap orifice. It can also be placed in the valve chamber downstream of the liquid tap orifice in the valve chamber. If it is downstream of the liquid tap orifice, it of course closes off the valve chamber to filling with liquid propellant from both liquid tap and vapor tap orifices, while if it is across only the vapor tap orifice, it prevents entry of liquefied propellant into the valve chamber, but only through the vapor tap orifice. If the liquid propellant can readily enter the valve chamber through both the vapor tap and the liquid tap orifices by shaking, it is of course desirable to put the shut-off valve downstream of both the liquid tap and vapor tap orifices in the valve chamber.
  • shut-off valve be linked to the delivery valve, so that when the delivery valve is opened, the shut-off valve is opened as well, thus making possible the passage of both liquid and gas into the valve chamber and through the delivery system to the delivery port.
  • shut-off valve has both shut-off valve and delivery valve means attached to a valve stem, and movable therewith between open and closed positions, opening and closing together at least both the vapor tap orifice and the delivery valve.
  • both the delivery valve and the shut-off valve are slide valves, movable together into the open position against the biasing force of the bias means by manual manipulation of the valve actuator.
  • the shut-off valve is in the form of a reciprocable shaft or cylinder, with at least one flow passage therethrough movable therewith between an open position in which at least both the valve chamber and the vapor tap orifice are linked in fluid flow communication via the passage, and a closed position in which the passage is not in registration with the valve chamber and the vapor tap orifice; and bias means holding the shut-off valve in the closed position.
  • the valve accordingly prevents entry of liquefied propellant through the vapor tap orifice when the container is shaken, because when the container is shaken the delivery valve is closed, and with it the vapor tap orifice.
  • the vapor tap orifice is normally closed, and is opened only when the delivery valve is also opened, for delivery of aerosol composition from the container.
  • the vapor tap valve of the invention and aerosol containers including the same can also include a second shut-off valve, of the type described in Serial No. 754,471.
  • This second shut-off valve can be placed in any convenient location across the line of flow of liquid to the delivery port.
  • it can be at or in the passage leading directly to the delivery port, downstream or upstream of the delivery valve, in the valve chamber, or at or in the vapor tap orifice.
  • shut-off valve can also. be arranged to close off the valve stem orifice, or the valve chamber, or the valve stem passage. In all such cases, all flow is cut off, even if the manipulatable valve be open.
  • the second shut-off valve in accordance with the invention can take any of several forms.
  • a preferred emboutment of shut-off valve has a valve means which is free to roll with gravity, such as a cylinder or ball, which can roll freely along an inclined guide, chute or support, into a position at the valve seat closing off the valve passage when the container is in any position between a few degrees less than horizontal to fully inverted, i. e. , from -2 ° to -90° below the horizontal, but which normally is drawn by gravity into an at-rest position in which the shut-off valve is open when the top of the container is in any position between a few degrees below the .horizontal to fully upright, i. e., +90°.
  • gravity such as a cylinder or ball
  • the ball or cylinder can roll down towards the valve seat, and at some angle near the horizontal will roll into position on the valve seat, closing off flow to the valve passage.
  • the flammability hazard is eliminated when the container is in any position.
  • This embodiment is especially suitable for disposition in a valve chamber, or across a delivery valve stem passage or orifice, including a vapor tap valve in the ball housing.
  • shut-off valve of the invention is a slide valve, slidable along a guide between open and closed positions. In the. open position, the slide valve is away from the valve seat and the valve passage is open. As the container is brought into a fully inverted position at an angle at about 10° or so beyond the horizontal, the slide valve slides along the guide into contact with the valve seat, closing off the valve passage.
  • the slide valve can for example be tubular and arranged to slide along a concentric tubular guide, the guide constituting a dip tube, or a wall enclosing the valve chamber.
  • the vapor tap or valve stem orifice extends radially through the tubular guide, or is disposed axially at one end of the tubular guide.
  • the side of the tubular slide valve can be arranged to close off the orifice through the tubular guide.
  • the end of the slide valve can be arranged to close off the orifice, when brought into abutting relation therewith.
  • slide valve has a disc with a flanged outer periphery, movable along the concentric tubular guide.
  • the orifice or passage to be closed off is axially disposed, in a wall of a valve chamber. It can for example be a vapor tap orifice through the bottom wall of the valve chamber. The vapor tap orifice is accordingly closed off when the disc comes into abutment with the bottom wall, guided in this position by the tubular guide.
  • the preferred 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 vapor tap orifice and at least one liquid tap orifice to a valve chamber of a vapor tap valve which is across the line of flow to the valve delivery port.
  • a liquid aerosol composition to be blended with propellant gas and then expelled from the container is placed in this compartment of the container, in flow communication via the liquid tap orifice with the valve chamber, so as to admit liquid aerosol composition into the valve chamber, while propellant gas flows into the valve chamber via the vapor tap orifice or orifices to the valve.
  • the aerosol containers in accordance with the invention can be made of metal or plastic, the latter being preferred for corrosion resistance.
  • 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 or Delrin are suitable container materials.
  • the aerosol container 1 shown in Figures 1, 1A and 2 has a vapor tap valve 4 of the invention comprising a valve poppet 8 combining in one member a delivery valve poppet 8a and a shut-off slide valve 8b.
  • the delivery valve poppet 8a seats against the sealing face 19 of a sealing gasket 9.
  • the shut-off slide valve 8b reciprocates through and against the inside wall of the aperture constituting a valve seat 29 of a valve plate 28.
  • the valve plate extends all the way across the valve chamber 5, .separating a lower portion 5b into which open the vapor tap orifice 2 and liquid tap orifice 5a.
  • the poppet 8a is open at the inner end, and defines a socket 8c therein for the reception of a coil spring 18.
  • the passage 13 is separated from the socket 8c within the poppet 8a by the divider wall 8d.
  • valve stem orifice 13a Adjacent the divider wall 8d in a side wall of the stem 11 is a valve stem orifice 13a.
  • the gasket 9 has a central opening 9a therethrough, 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.
  • the slide valve 8b has a solid shaft tip, with a central groove 27 open on one side, and considerably longer than the thickness of the valve plate 28.
  • valve 8b With the valve in the position shown in Figure 1, entry into chamber 5 of both gas and liquid passing through the gas and liquid tap orifices 2 and 5a is prevented by the valve 8b, and thus the valve 8b closes off the valve chamber 5 to outward flow of all of the contents of the container, upstream- . of the valve 8b.
  • the outer end portion 11a 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 socket.
  • the stem is attached to the actuator by a press fit.
  • the axial socket 16 is in flow communication with a lateral passage 17, leading to the actuator (valve delivery) orifice 14 of the button 12.
  • the compression coil spring 18 has one end retained in the socket 8c of the valve poppet 8a, and is based at its other end upon valve plate 28.
  • the spring 18 biases the poppet 8a towards the gasket 9, engaging it in a leak-tight seal at the valve seat 19.
  • the orifice 13a leading into the passage 13 of the valve stem is closed off.
  • the delivery 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 stem 11 and with it poppet 8a against the spring 18.
  • the orifice 13a is brought beneath the valve gasket 9, and a flow passage is therefore open from the valve chamber 5 defined by the valve housing 6 to the delivery port 14.
  • shut-off valve 8b is moved inwardly in aperture 29 so that the groove 27 is brought into registry at one end with valve chamber 5 and at the other. end with the space 5b below the chamber, and a flow passage is therefore opened through the groove 27 from the space 5b into the valve chamber 5 defined by the valve housing 6, and thence to the delivery port 14 via the open valve stem orifice 13a.
  • valve poppet 8a and shut-off valve 8b The limiting open position of the valve poppet 8a and shut-off valve 8b is fixed by the spring 18, which can be compressed at most to the position where the coils of the spring are in contact with each other.
  • valve stem orifice 13a when in the open position communicates the stem passage 13 with the actuator passages 16, 17 and the valve delivery orifice 14, and thus depressing the actuator 12 permits fluid flow past the shut-off valve 8b and the valve stem orifice 13a via the valve chamber 5, to be dispensed from the container at delivery port 14.
  • the spring 18 ensures that the valve poppet 8a and the shut-off valve 8b are normally in a closed position, and that the two valves are open only when the button actuator 12 is moved manually against the force of the spring 18.
  • the valve housing 6 has an expanded portion 6a upon which is the sealing gasket 9, and retained in position at the upper end of the housing.
  • the expanded portion 6a and the sealing gasket 9 are retained by the crimp 23b in the center of the mounting cup 23, with the valve stem 11 extending through an aperture 23a in the cup.
  • the cup 23 is attached to the container dome 24, which in turn is attached to the main container portion 25.
  • a vapor tap orifice 2 Through the bottom wall 7 of the valve housing 6 is a vapor tap orifice 2, which is in flow connection 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 space 5b of the valve housing 6 terminates in a passage 5a, enclosed in the projection 6c of the housing 6.
  • the capillary dip tube 32 In the passage 5a 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. Liquid aerosol composition accordingly enters the space 5b 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 space 5b through the gas tap orifice 2.
  • the diameter of the actuator (valve delivery) orifice 14 is 0.5 mm.
  • the valve stem orifice 13a is 0.6 mm.
  • the diameter of the vapor tap orifice 2 is 0.95 mm, and the inside diameter of the capillary dip tube 32 is 1.0 mm.
  • the valve chamber 5 has a length of 1 cm, . and an inside diameter of 0.78 cm.
  • the stem shaft 11 has a diameter of 0. 3 cm, ard extends almost to the bottom of the space 5b when the valves 8a, 8b are opened.
  • the groove 27 in the valve stem 11 has a rectangular shape, 0.08 cm deep, with a length of 0.4 cm and a width of 0.08 cm, starting 0.1 cm from the bottom of the stem shaft.
  • the shaft 11 fits snugly in a leak-tight fit in the aperture 29 of the valve plate 28.
  • the aperture has an inside diameter of 0.3 cm, the same as the outside diameter of the valve stem.
  • the valve plate 28 is located 0.2 cm above the bottom wall of the valve chamber 5 and is held in position, spaced from the lower wall 6b of the valve chamber 5, by the spring 18 and the lugs 31.
  • the volume of the valve chamber 5 is about 0.4 cc, and the volume of the space 5b between the valve plate and the capillary dip tube is-about 0.1 cc.
  • button 12 is depressed so that the valve stem 11 and with it valve poppet 8a, orifice 13a, and shut-off valve 8b are manipulated to the open position, away from the valve seats 19 and 29.
  • Liquid aerosol composition is thereupon drawn up via the capillary dip tube 32 and the passage 5a into the space 5b, whence it flows through the aperture 29 into the valve chamber 5, and then up around the poppet 8a towards the valve stem orifice 13a.
  • Propellant gas passes through the vapor tap orifice 2, and is blended with liquid aerosol composition in the spaces 5b and 5, which it enters via the aperture 29 as it flows past the valve plate 28, and then flows around the poppet 8a through the valve stem orifice 13a and the valve stem passage 13 and valve button passages 16, 17, through the delivery orifice 14.
  • the dimensions of the orifices 2, 32 are such that at least 8 volumes of gas enter through the vapor tap orifice 2 for each volume of liquid entering through the liquid tap orifice, which is the capillary dip tube 32.
  • This embodiment of container includes a second shut-off valve, slide valve 3, arranged to close off the vapor tap orifice 2 when the container is inverted, or inclined below the horizontal.
  • the slide valve 3 has a valve body of plastic, for example polyethylene or polypropylene, with an annular rim 3a and a central disc valve 3b.
  • the rim defines twin recesses 3c and 3d, of which recess 3c is wide enough and deep enough to receive the end 6b of the valve housing 6, and all of wall 7.
  • the disc valve 3b eventually abuts and covers over the bottom wall 7 of the valve housing 6, thus effectively closing off the vapor tap orifice 2, when the valve 3 is in the uppermost position. Accordingly, the valve in this position closes off the vapor tap orifice 2.
  • the disc valve 3b has a central aperture 15 through which passes loosely the projection 6c of the valve housing 6. The loose fit prevents binding of the disc against the projection 6c.
  • the annular rim 3a is long enough to engage the housing 6 over the entire travel of the valve along projection 6c between the closed position abutting the bottom wall 7 of the housing 6, and the open position abutting the stops 6d on the projection 6c.
  • the valve disc 3b In the open position, the valve disc 3b is in the lowermost position, and rests against the stop 6d, as shown in Figure 1. In this'position, the container is upright and the valve under the force of gravity remains in this position.
  • the shut-off valve 8b prevents a flame hazard due to the entry of liquefied propellant into the valve chamber 5 when the container is shaken before opening the delivery valve.
  • the valve 8b closing off the aperture 29 in the valve plate 28, both liquid through the liquid tap orifice 5a and gas or liquefied propellant through the vapor tap orifice 2 are prevented from entering the valve chamber 5, so that the valve chamber is kept relatively free of aerosol composition when the container is shaken to distribute or disperse insoluble material more uniformly through the composition, before opening the delivery valve. Since the valve Chamber 5 is empty, or virtually so, liquefied flammable propellant is not delivered from the valve when the delivery valve is opened, during the first few seconds of the delivery. Thus, again, a flame hazard due to the escape of flammable liquid propellant is avoided.
  • 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% of the normal delivery rate of 1 g/second. Accordingly, in order to obtain the same delivery of active ingredients (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 contain less than 5% active antiperspirant, because of clogging problems usin;; 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 g/second of aerosol antiperspirant composition containing from about 8% to about 20% active ingredient as suspended or dispersed solid material without clogging, because of the high proportion of gas to liquid.
  • the vapor tap valve 40 shown in Figures 3 and 4 is generally similar to that of Figures 1, 1A and 2, and consequently like reference numerals are used for like parts.
  • the shut-off valve 45 of the invention reciprocates in aperture 44 in the bottom wall 6b of the valve chamber 5, and the valve plate 28 is eliminated.
  • the shut-off valve 45 is downstream of both the liquid tap orifice 41 and the vapor tap orifice 42, and consequently all flow from either orifice into the valve chamber 5 is prevented when the shut-off valve is in the closed position, closing aperture 44 as shown in Figures 3 and 4.
  • the vapor tap valve 40 of the invention has 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 housing 6 pinched by crimp 23b in the aerosol container cap 23.
  • the valve housing 6 has a valve chamber 5, and an aperture 44 in bottom wall 6b, the walls of which serve as a valve seat for the shut-off valve tip 45 of the valve stem 11.
  • the delivery valve portion of the valve stem 11 is in the form of a valve poppet 8d.
  • the valve stem orifice 13a is closed off by the poppet when the delivery valve is in the closed position, seen in Figure 3.
  • valve poppet 8d is reciprocably mounted on the valve stem 11, as also is the shut-off valve 45, and both are biased by the spring 18 against the valve seat 19 on the inside face of the gasket 9, in the normally closed position.
  • the valve stem orifice 13a is in flow corimunication via the valve chamber with the liquid tap orifice 41 and the vapor tap orifice 42.
  • valve housing 6 in the portion below the shut-off valve 45 is provided with a tapered passage 46 which is shaped to receive the end 32a of the-capillary dip tube 32.
  • the liquid aerosol composition is stored in the lower portion 21 of the container, and the di p tube 32 extends from the lower portion 21 of the container into the passage 5c of the valve housing 6 in which it is press fitted in place.
  • the dip tube puts the liquid phase in the bottom of the container in flow connection with the liquid passage 41.
  • the second slide valve 3 has a valve body of metal, for example, stainless steel or aluminum, with an annular rim 3a and a central disc valve 3b.
  • the rim defines a recess 3d which is wide enough to embrace and conform to the cylindrical tail piece 6f of the valve housing 6.
  • the disc valve 3b covers over vapor tap orifice 42 and abuts the bottom wall 6b of the valve housing 6, thus effectively closing off the vapor tap orifice 2a.
  • the valve 3 When the valve 3 is in its lowermost position, it engages the stop 6h on the tail piece 6f.
  • the disc valve 3b has a central aperture 15, which fits. loosely over the tail piece 6f of the valve housing 6. The loose fit prevents binding of the disc against the tail piece 6f.
  • the valve disc 3b In the open position, the valve disc 3b-rests against the stop 6d, as shown in the Figure. In this position, the container is upright, vapor tap orifice 42 is open, and the second shut-off valve under the force of gravity remains in the lowermost position.
  • valve 3 will tend to slide along the tail piece 6f, into the newly lowermost position corresponding to the closed position, with the valve disc 3b closing off the vapor tap orifice 42.
  • the dip tube 32 now taps the gas phase, and thus it is quite impossible for liquid propellant to escape from the container. Accordingly, a flame hazard when the container is inverted due to the escape of flammable liquid is avoided.
  • the vapor tap valve of the invention is employed in a pressure bottle.
  • the delivery valve 60 is the same as that of Figures 3 and 4, and the shut-off valve 55 is similar.
  • Upstream of the shut-off valve 55 and the vapor tap orifice 51 is a capillary dip tube flow passage 53 through the housing 6, in flow communication at one end with the upper end of the capillary dip tube 52 and at the other end with the valve chamber 61.
  • a second shut-off valve 65 Upstream of the vapor tap orifice 51 within the valve housing 6 in a chamber 54 between the two sections of the vapor tap orifice 51 is a second shut-off valve 65, designed to close off the vapor tap orifice 51. when the container is inclined to below the horizontal, or inverted.
  • This shut-off valve comprises a ball 58 of inert noncorrodible metal such as aluminum, stainless steel, or brass, which is free to roll within the valve chamber 54 .
  • the valve seat is defined by the concave recess 59 in the wall of the chamber adjacent the two sections of orifice 61.
  • the recess 59 is tapered sufficiently to guide the ball 58 and permit it to lodge against the orifice 51, closing it off, when the container is inverted or inclined below the horizontal.
  • the ball 58 In the normal upright position of the container, as shown in Figure 5, the ball 58 is at the bottom of the chamber 54. Accordingly, when the actuator button 12 is depressed, the shut-off valve 55 is opened, as well as the delivery valve 60, and liquid aerosol composition can be drawn up through the dip tube 52 into the valve chamber 61, while vapor phase propellant gas from the head space 62 can enter the valve chamber 61 through the vapor tap orifice 51.
  • the container acts normally when it is in this position, and in fact in all positions above the horizontal, since the ball then tends under gravity to remain in the position shown.
  • the ball 58 When however the container is inverted so the delivery valve 60 is below the horizontal, the ball 58 is free to roll along the side walls of the chamber 54, and when it does so, it moves against the gas tap orifice 51, closing it off. It is guided thereby the concave walls of the recess 59. It is held in this position by gravity. This prevents the escape of liquid propellan through the vapor tap orifice 51 into the passage 53 and from there to the valve stem passage and delivery port, thus avoiding a flame hazard.
  • the pressure bottle has a much smaller opening for the valve assembly than an aerosol can; in this case, 1. 2 cm in diameter as compared to a 2.5 cm opening for an aerosol can.
  • the vapor tap valve oi the invention is mounted across this opening in the cap for the pressure bottle, as in the can embodiments illustrated previously.
  • the upper neck of the bottle is provided with a bulge, and the pressure bottle cap is crimped at its lower edge to retain the cap and the valve to the bottle in a leak-tight seal provided by the rubber gasket.
  • the vapor tap valve shown in Figures 7 and 8 utilizes a slide valve as the shut-off valve.
  • the valve housing 70 has a valve chamber 71 at the upper portion, and a blending chamber or space 72 below the valve chamber.
  • a wall 73 with a central opening 74 separates the valve chamber from the blending space.
  • the vapor tap valve 75 has a valve stem 76 with a valve stem orifice 77 therethrough in flow communication with the valve chamber 71 when the delivery valve is in the open position. In the closed position, the valve stem orifice 77 is sealed off by the gasket 9.
  • valve stem 76 extends as a solid rod.
  • the valve stem 76 includes a valve stem passage 78, which is in fluid flow connection with valve button passages 16 and 17 of the valve button 12 and a delivery orifice 14 at the end of the valve button passage 17.
  • the solid portion 79 of the valve stem extends all the way across the valve chamber 71, and through the aperture 74.
  • a slot 80 At the tip end of the stem 79 is a slot 80, which when the valve is in the open position as shown in dashed lines in Figures 7 and 8 registers with and communicates the blending space 72 with the valve chamber 71.
  • the lower portion of the slot 80 is closed off by the wall 73. Consequently, all flow from the blending space 72 into the chamber 71 is closed off when the delivery valve is in the closed position, and the valve chamber cannot therefore be filled with either gas or liquid from the blending space 72.
  • a vapor tap orifice 81 Through the wall of the housing 70 is a vapor tap orifice 81, and a liquid tap orifice 82 in the form of the open capillary passage through a capillary dip tube 83 extending to the bottom of the container. Since the valve stem 79 is downstream of both the vapor tap and the liquid tap orifices, neither gas nor liquid can pass into the valve chamber 71 when the valve is. closed.
  • shut-off valve 85 Slidably retained within the blending space 72 is a shut-off valve 85, in the form of an annular ring, with a central aperture 86 therethrough.
  • the ring is free to slide within the blending space 72.
  • the valve When the valve is in the upright position, as shown in Figures 7 and 8, the ring is at the lower portion of the blending space.
  • the valve When the valve is inverted, the ring falls by gravity to the other end of the blending space, abutting the solid portion 79 of the valve stem.
  • the liquid aerosol composition is stored in the portion 21 of the container, and the dip tube 83 extends through the lower portion 21 of the container into blending space 72, being inserted into one end of this space through the open end of the valve housing 70.
  • the dip tube puts the liquid phase 29 in the bottom of the container in flow connection with the blending space 72.
  • the vapor tap orifice 81 communicates the upper portion 22 of the container with the blending space 72, and thus puts the gas phase in the upper portion of the container in flow connection with the blending space 72.
  • the slide valve 85 has a valve body of metal, for example, stainless steel or aluminum, and the central opening 86 is just wide enough to accommodate the tip end 79 of the valve stem in sealing relationship.
  • the valve 85 is long enough so that when the valve is inverted and the valve stem 79 is pushed inwardly b' the button actuator 12 as far as it can go, the slot 80 is still not in flow communication with the blending space 72, being closed off by the ring 85.
  • the valve 85 effectively closes off the slot 80, and prevents passage of both liquid and gas from the blending space 72 into the valve chamber 71, and thence eventually through the delivery port 14. Accordingiy, a flame hazard when the container is inverted due to escape of flammable liquid is avoided.
  • the vapor tap valve of the invention can be used in any kind of aerosol container to deliver any aerosol composition in the form of a spray.
  • the range of products that can be dispensed is diverse, and includes pharmaceuticals for spraying directly into oral, nasal and vaginal passages, antiperspirants, deodorants, hair sprays, fragrances and flavors, body oils, insecticides, window cleaners and.other cleaners, spray starches and polishes for autos, furniture and shoes.

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  • 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)
EP78100109A 1977-06-07 1978-06-07 Valve pour récipient aérosol à agent de propulsion inflammable et récipient muni d'une telle valve Withdrawn EP0000062A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/804,423 US4116370A (en) 1976-12-27 1977-06-07 Vapor tap valve for aerosol containers used with flammable propellants
US804423 1991-12-10

Publications (1)

Publication Number Publication Date
EP0000062A1 true EP0000062A1 (fr) 1978-12-20

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Application Number Title Priority Date Filing Date
EP78100109A Withdrawn EP0000062A1 (fr) 1977-06-07 1978-06-07 Valve pour récipient aérosol à agent de propulsion inflammable et récipient muni d'une telle valve

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EP (1) EP0000062A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012175513A1 (fr) 2011-06-20 2012-12-27 Bayer Intellectual Property Gmbh Thiénylpyri(mi)dinylpyrazole
US9944902B2 (en) 2011-02-17 2018-04-17 Boehringer Ingelheim Vetmedica Gmbh Commercial scale process for production of PRRSV
US10010601B2 (en) 2013-12-20 2018-07-03 Boehringer Ingelheim Vetmedica Gmbh PRRS virus variant, European PRRS virus cDNA clone, and uses thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2968428A (en) * 1959-02-26 1961-01-17 Gulf Research Development Co Gravity actuated valves for pressurized dispensers
FR1463819A (fr) * 1964-04-10 1966-07-22 Pittsburgh Railways Company Soupape de pulvérisateur
US3372845A (en) * 1966-06-15 1968-03-12 Revlon Valve for upright or inverted use
GB1154822A (en) * 1966-05-16 1969-06-11 Eaton Yale & Towne Apparatus for Dispensing Fluids from a Pressurized Container
FR2025451A1 (fr) * 1968-12-05 1970-09-11 Underhill Russell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2968428A (en) * 1959-02-26 1961-01-17 Gulf Research Development Co Gravity actuated valves for pressurized dispensers
FR1463819A (fr) * 1964-04-10 1966-07-22 Pittsburgh Railways Company Soupape de pulvérisateur
GB1154822A (en) * 1966-05-16 1969-06-11 Eaton Yale & Towne Apparatus for Dispensing Fluids from a Pressurized Container
US3372845A (en) * 1966-06-15 1968-03-12 Revlon Valve for upright or inverted use
FR2025451A1 (fr) * 1968-12-05 1970-09-11 Underhill Russell

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9944902B2 (en) 2011-02-17 2018-04-17 Boehringer Ingelheim Vetmedica Gmbh Commercial scale process for production of PRRSV
WO2012175513A1 (fr) 2011-06-20 2012-12-27 Bayer Intellectual Property Gmbh Thiénylpyri(mi)dinylpyrazole
US10010601B2 (en) 2013-12-20 2018-07-03 Boehringer Ingelheim Vetmedica Gmbh PRRS virus variant, European PRRS virus cDNA clone, and uses thereof
US10639364B2 (en) 2013-12-20 2020-05-05 Boehringer Ingelheim Vetmedica Gmbh PRRS virus variant, european PRRS virus cDNA clone, and uses thereof

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Inventor name: SPITZER, JOSEPH GEORGE