WO1997012687A1 - Device of miniaturised construction for producing high pressure in a fluid to be atomised - Google Patents
Device of miniaturised construction for producing high pressure in a fluid to be atomised Download PDFInfo
- Publication number
- WO1997012687A1 WO1997012687A1 PCT/EP1996/004351 EP9604351W WO9712687A1 WO 1997012687 A1 WO1997012687 A1 WO 1997012687A1 EP 9604351 W EP9604351 W EP 9604351W WO 9712687 A1 WO9712687 A1 WO 9712687A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hollow piston
- valve member
- piston
- atomiser
- outlet end
- Prior art date
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M15/00—Inhalators
- A61M15/0065—Inhalators with dosage or measuring devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M15/00—Inhalators
- A61M15/0065—Inhalators with dosage or measuring devices
- A61M15/0068—Indicating or counting the number of dispensed doses or of remaining doses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M15/00—Inhalators
- A61M15/0065—Inhalators with dosage or measuring devices
- A61M15/0068—Indicating or counting the number of dispensed doses or of remaining doses
- A61M15/0081—Locking means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/1001—Piston pumps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/1042—Components or details
- B05B11/1066—Pump inlet valves
- B05B11/1067—Pump inlet valves actuated by pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/1042—Components or details
- B05B11/108—Means for counting the number of dispensing strokes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/109—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle the dispensing stroke being affected by the stored energy of a spring
- B05B11/1091—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle the dispensing stroke being affected by the stored energy of a spring being first hold in a loaded state by locking means or the like, then released
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B53/00—Component parts, details or accessories not provided for in, or of interest apart from, groups F04B1/00 - F04B23/00 or F04B39/00 - F04B47/00
- F04B53/10—Valves; Arrangement of valves
- F04B53/12—Valves; Arrangement of valves arranged in or on pistons
- F04B53/125—Reciprocating valves
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M15/00—Inhalators
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M15/00—Inhalators
- A61M15/0065—Inhalators with dosage or measuring devices
- A61M15/0068—Indicating or counting the number of dispensed doses or of remaining doses
- A61M15/007—Mechanical counters
- A61M15/0071—Mechanical counters having a display or indicator
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M2205/00—General characteristics of the apparatus
- A61M2205/75—General characteristics of the apparatus with filters
- A61M2205/7545—General characteristics of the apparatus with filters for solid matter, e.g. microaggregates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/02—Membranes or pistons acting on the contents inside the container, e.g. follower pistons
- B05B11/026—Membranes separating the content remaining in the container from the atmospheric air to compensate underpressure inside the container
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/109—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle the dispensing stroke being affected by the stored energy of a spring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/7722—Line condition change responsive valves
- Y10T137/7837—Direct response valves [i.e., check valve type]
- Y10T137/7904—Reciprocating valves
- Y10T137/7908—Weight biased
- Y10T137/7909—Valve body is the weight
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/7722—Line condition change responsive valves
- Y10T137/7837—Direct response valves [i.e., check valve type]
- Y10T137/7904—Reciprocating valves
- Y10T137/7908—Weight biased
- Y10T137/7909—Valve body is the weight
- Y10T137/7913—Guided head
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T137/00—Fluid handling
- Y10T137/7722—Line condition change responsive valves
- Y10T137/7837—Direct response valves [i.e., check valve type]
- Y10T137/7904—Reciprocating valves
- Y10T137/7908—Weight biased
- Y10T137/7909—Valve body is the weight
- Y10T137/7913—Guided head
- Y10T137/7915—Guide stem
- Y10T137/7916—With closing stop
Definitions
- the invention relates to a device for producing high pressure in a fluid. It comprises a piston which is movable in a cylinder, and a valve, both preferably of miniaturised construction.
- the invention further relates to a high pressure atomiser which contains this device, and the use thereof, preferably for medicinal purposes.
- One aim of the invention is to enable a device of this kind and the atomiser containing the device to be made simpler in design and cheaper to produce and suited to its function.
- liquid chromatography for example, generally relatively small quantities of liquid are conveyed at high pressure through the separating column.
- aerosols are obtained, by atomising or nebulising liquid drugs for treating diseases of the respiratory tract in humans or for treating asthmatic conditions.
- a high pressure is required in a, generally relatively small, quantity of fluid in order to produce the small droplet size needed for the aerosol.
- a predetermined volume of a fluid is sprayed through a nozzle with a small aperture under a pressure of between 5 and 40 MPa (about 50 to 400 bar) to produce an aerosol.
- the present invention is particularly applicable to such metered dose inhalers and similar devices.
- a device for producing high pressure in a fluid, comp ⁇ sing a piston which is movable in a cylinder, a high pressure chamber which is located in front of the piston inside the cylinder, and a valve, which device includes a cylindrical hollow piston, a valve member which is guided by the hollow piston and is mounted so as to be axially movable against the hollow piston. a stop means on the hollow piston which holds the valve member to the hollow piston and a defined (predetermined) sealing surface at the inlet end of the valve member, the valve member generally being restrained from rotation about any axis transverse to the piston axis.
- a device for producing high pressure in a fluid comprising a cylinder, a hollow cylindrical piston which is movable in the cylinder and provides a path for fluid therethrough, a high pressure chamber which is located in front of the piston inside the cylinder and which is supplied with fluid through said path, and an inlet valve in said fluid path which moves with the piston but is also capable of limited guided movement along the piston axis between a closed position in contact with a valve seat provided by the piston and an open position spaced from the valve seat, the valve member being so shaped and guided that it cannot rotate about any axis transverse to the piston axis such that a predetermined surface thereof engages the seat.
- valve member In the preferred arrangement according to the invention, at least a major part of the valve member is cylindrical and is guided in a chamber (which may, for example, be the pump chamber itself or may be part of the interior of the piston) and the valve member cylinder has an end surface which co-operates with the valve seal provided by the piston.
- a ball valve which can be avoided using the invention is that that transverse area of the valve is necessarily considerably smaller than the diameter of the ball and thus the guide cylinder in which it moves; this leads to a reduction in the force applied by the valve member to the valve seat arising from fluid pressure generated during the pressure stroke (forward movement) of the piston.
- a high application force of the valve member is desirable to slightly elastically deform the valve member and and/or the valve seat to close any slight gaps between them.
- inlet and outlet side or inlet and outlet end are used in relation to the main direction of flow of the fluid within the device.
- fluid includes both gases and liquids but the present invention is mainly concerned with liquids.
- the valve member is somewhat displaceable against the hollow piston but it moves substantially with the hollow piston.
- the valve member is preferably uniaxially rotationally symmetrical in shape, e.g. it is a circular cylinder or a frustum. Its cross-section is somewhat smaller than the cross-section of the chamber in which the valve member is movably mounted. This is achieved by means of one or more channels preferably extending in the outer surface of the cylindrical valve member, or by a somewhat smaller diameter of the valve member in relation to the diameter of the chamber in which the valve member is movably mounted.
- valve member is guided in the chamber in which it is movably mounted: a cylindrical valve member can rotate about its axis as required, but its axis always remains parallel to the axis of the hollow piston. This produces a defined sealing surface at the inlet end of the valve member.
- valve member can travel relative to the hollow piston.
- a stop or stop means which holds the movable valve member together with the hollow piston.
- each recess is located either in the valve member at the outlet end thereof or in the stop in the hollow piston.
- valve In the position where the valve member abuts on the stop of the hollow piston, the valve is opened. In the position where the valve member abuts on the defined sealing surface, the valve is closed.
- a valve member arranged inside the hollow piston has virtually no friction against the inner wall of the hollow piston.
- a valve member arranged directly in front of the end of the hollow piston may possibly rub against the wall of the main pump cylinder of the device. In this case, the valve is actively closed and opened as the hollow piston moves, on account of the friction between the valve member and the cylinder wall.
- the cylinder preferably consists of plastics and the hollow piston of metal or plastics.
- the material for the valve member is selected, in terms of its hardness, to complement the hardness of the material for the hollow piston and may be metal, ceramics, glass, gemstone, plastics or elastomer.
- valve member is preferably manufactured in one piece.
- the high pressure chamber When the fluid is sucked in, the high pressure chamber is connected to the fluid supply by means of the hollow piston.
- the fluid flows through the hollow piston and past the valve member into the high pressure chamber of the cylinder.
- the valve seat is sealed in high pressure tight manner against the defined sealing surface of the valve member.
- the device according to the invention for producing high pressure in a fluid is connected to the fluid supply at its inlet end.
- the high pressure chamber is connected to another device into which or through which the fluid is conveyed under high pressure.
- the hollow piston or the cylinder is attached to a drive which brings about relative movement between the hollow piston and cylinder and which applies the force required to generate the high pressure.
- the cylindrical valve member may be guided and mounted in axially movable manner directly in front of the end of the hollow piston, the diameter of the valve member being substantially equal to the internal diameter of the cylinder.
- the hollow piston On the outside, near its outlet end. the hollow piston has an encircling, preferably turned or shaped groove as a stop member, into which a plurality of snap hooks on the valve member engage.
- the hollow piston may have at its outlet end a shaped taper with an encircling, outwardly funnel-shaped edge. The outer diameter of the hollow piston at its outlet end is greater than the base diameter of the groove and less than the diameter of the cylinder.
- the outlet end of the hollow piston may be provided on the outside, at several, preferably 2 diametrically opposed points, with flattened areas which form a step to act as a stop means.
- the flat end of the hollow piston provides a valve seat cooperating with a defined flat sealing surface on the inlet side of the valve member.
- the outer edge at the end of the hollow piston may be chamfered.
- the cylindrical valve member may be guided and movably mounted directly in front of the end of the hollow piston, the diameter of the valve member being substantially equal to the internal diameter of the cylinder.
- the end of the hollow piston is shaped inwardly to provide an inturned lip and acts as a stop means.
- On the valve member is mounted a coaxial, undercut, mushroom-shaped peg the snap hooks of which engage behind the shaped edge of the hollow piston.
- the defined sealing surface which extends around the peg rests on the outlet end of the piston on the edge of the lip.
- the preferably cylindrical valve member may be mounted so as to be fully movable inside the hollow piston.
- the outlet end of the hollow piston has an internal diameter greater than the internal diameter of the remainder of the hollow piston.
- the length of this widened portion of the hollow piston is somewhat greater than the length of the valve membei .
- the diameter of the valve member is substantially equal to the inner diameter at the widened end of the hollow piston.
- the outlet end of the hollow piston is shaped inwardly to form a lip either over its entire periphery or over a part of its periphery and acts as a stop which holds the valve member inside the hollow piston.
- the base of the widened portion which forms the valve seat may be flat or conical.
- a fluid flow recess in the outlet side the valve member may, for example, take the form of a stepped channel.
- a fluid flow recess in the stop may be constructed, for example, as an indentation in the lip edge.
- valve member may be arranged totally inside the hollow piston at the inlet end thereof.
- the stop will then be Iocated at the outlet end of the widened portion and the defined sealing surface wiil then be on the shaped edge at the inlet end of the hollow piston.
- the hollow piston consists of a thin-walled tube which is shaped at its end projecting into the cylinder and is provided with an encircling constriction at the end of the space allowed for the valve member.
- the cylindrical valve member is guided and movably mounted in the space between the shaped edge and the encircling constriction.
- Another thick-walled tube may be pushed into the inlet end of the hollow piston, its outer diameter being equal to the inner diameter of the hollow piston, and this thick-walled tube further being fixedly connected to the hollow piston and preferably extending approximately up to the encircling constriction in the hollow piston.
- the thick-walled tube acts as a displacement member and makes it easier for the fluid to be sucked into the high pressure chamber virtually without pressure being applied.
- the thick-walled tube is preferably made of plastics.
- valve member may be mounted fully inside the hollow piston at the inlet end thereof.
- the stop is then Iocated at the encircling constriction and the defined sealing surface is located at the shaped edge at the inlet end of the hollow piston.
- the hollow piston comprises a thin-walled tube which contains a thick-walled tube the outer diameter of which is equal to the inner diameter of the hollow piston, and which is fixedly connected to the hollow piston.
- the thick- walled tube functions as a displacement body and makes it easier for the fluid to be sucked in virtually without pressure being applied.
- the inlet end of the hollow piston is widened.
- the hollow piston is fixedly connected to a closure member the outer diameter of which is greater than the outer diameter of the widened inlet end of the hollow piston.
- the closure member contains a depression which is open on its side facing the widened end of the hollow piston. In the base of the depression is an opening acting as an inlet for the fluid.
- the base of the depression may be conical or flat; it forms the defined sealing surface.
- the valve member is arranged in the depression in the closure member; it is guided so as to be axially movable in the depression.
- the external diameter of the valve member is smaller than the internal diameter of the depression, but preferably greater than the internal diameter of the hollow piston in that part of it which projects into the cylinder.
- the valve member may contain, at its outlet end, at least one recess through which the fluid flows into the high pressure chamber during the intake stroke of the hollow piston.
- the stop for the valve member is preferably the end of the displacement body which projects into the widened portion of the hollow piston, or - if the end of the displacement body is located in the unwidened portion of the hollow piston - the transition from the unwidened portion of the hollow piston into the widened inlet end thereof.
- the hollow piston with the widened inlet end preferably consists of metal.
- the displacement body and closure member are preferably made of plastics.
- the valve member may be made of plastics or metal.
- the device according to the invention for producing high pressure in a fluid in an atomiser (nebulizer) for propel lant-free spraying of the fluid.
- an atomiser for spraying a fluid consisting of an upper housing part, a pump housing, a nozzle, a blocking mechanism, a spring housing, a spring and a supply container, characterised by a pump housing fixed in the upper housing part which has at one end a nozzle member with the nozzle. a hollow piston with valve member, a drive flange in which the hollow piston is secured and which is Iocated in the upper housing part, a blocking mechanism located in the upper housing part. a spring housing with the spring located therein, which is rotatably mounted by means of a rotary bearing on the upper housing part, a Iower housing part which is fitted onto the spring housing in the axial direction.
- the atomiser is preferably a metered dose inhaler.
- the hollow piston with valve member preferably corresponds to one of the devices according to the invention mentioned hereinbefore. It projects partially into the cylinder of the pump housing and is mounted in axially movable manner in the cylinder.
- the hollow piston with valve member exerts a pressure of 5 to 60 MPa (about 50 to 600 bar), preferably 10 to 60 MPa (about 100 to 600 bar) on the fluid at its high pressure end at the moment of release of the spring.
- the nozzle in the nozzle member is preferably microstructured, ie. produced by microtechnology.
- Microstructured nozzle members are disclosed, for example, in US Patent 5472143, the entire contents of which are incorporated herein by reference.
- the nozzle member consists, for example, of two plates of glass and/or silicon firmly joined together, of which at least one plate has one or more microstructured channels which connect the nozzle inlet end to the nozzle outlet end.
- At the nozzle outlet end is at least one circular or non-circular opening less than or equal to 10 ⁇ m in size. Size in this connection refers to hydraulic diameter. Hydraulic diameters in this type of apparatus are generally less than 100 micrometres preferably 1-20 micrometres.
- the directions of spraying of the nozzles in the nozzle member may run parallel to one another or may be inclined relative to one another.
- the directions of spray may be inclined relative to one another at an angle from 20 to 160°, preferably at an angle from 60 to 150° .
- the directions of spraying meet in the vicinity of the nozzle openings.
- a non-return valve with or without spring bias may be provided between the nozzle opening and the high pressure chamber of the cylinder.
- This non-return valve closes off the high pressure chamber in the resting state of the atomiser, protects the fluid from the entrance of air and may if necessary prevent volatile components of the fluid from evaporating out of the pump housing.
- the non-return valve opens automatically as soon as the pressure of the fluid in the high pressure chamber exceeds a minimum value and the current of fluid is created; it closes automatically as soon as the current of fluid is exhausted.
- the non-return valve may be, for example, a ball valve. It may also consist of a flexible plate which is clamped on one side and rests like a flap on the outlet end of the high pressure chamber.
- it may consist of a disk of preferably flexible material, clamped all the way round, pierced by a pin.
- the pierced hole allows the current of fluid to pass through to the nozzle as soon as the pressure in the fluid exceeds a minimum value. After the current of fluid is exhausted, the pin hole closes up again.
- the valve member is preferably mounted at the end of the cylinder facing the nozzle member.
- the blocking or latching mechanism has a spring, preferably a cylindrical helical compression spring, as a store for mechanical energy.
- the spring acts on the driven flange as a jumping member the movement of which is determined by the position of a blocking member.
- the path of travel of the driven flange is precisely defined by an upper and lower stop.
- the spring is preferably tensioned by an external torque via a force stepping-up device, eg. a helical sawtooth thrust cam, the force being generated as the upper housing part rotates counter to the spring housing in the lower housing part.
- the upper housing part and the driven flange comprise a single or multiple sawtooth wedge arrangement.
- the blocking member with engaging blocking surfaces is arranged in an annular configuration around the driven flange. It consists, for example, of a plastics or metal ring which in one form is inherently radially resiliently deformable. The ring is arranged in a plane at right angles to the atomiser axis. After the biassing of the spring, the blocking surfaces of the blocking member move into the path of the driven flange and prevent the spring from being released.
- the blocking member is actuated by a button. The actuating button is connected or coupled to the blocking member.
- the actuating button is pushed parallel to the plane of the ring, preferably into the atomiser; the deformable ring is thereby deformed in the plane of the ring to release the flange for movement by the spring.
- the preferred blocking member and spring are described and shown in German Patent Application 195452267 and filed by Microparts but assigned to Boehringer Ingelheim International GmbH. The entire contents of this application is incorporated herein by reference.
- the atomiser optionally contains a mechanical counter comprising a screw threaded spindle which is mounted on the spring housing.
- the axis of the spindle extends in the region of the outer surface parallel to the axis of the atomiser.
- the spindle is mounted, in the region of its ends, by means of a rotary bearing on the spring housing.
- the spindle has teeth at the end closest to the upper housing part.
- a slider with rotation prevention means is mounted on the spindle and engages its threads.
- the Iower housing part is pushed axially over the spring housing and covers the mounting, the drive of the spindle and the storage container for the fluid.
- the position of the slider is visible through a recess in the lower housing part and can be read off on a scale, eg. on the Iower housing part.
- the upper housing part When the atomiser is actuated the upper housing part is rotated relative to the lower housing part, the lower housing part carrying the spring housing with it.
- the spring meanwhile is compressed and biassed by means of the helical thrust cam, and the blocking mechanism engages automatically.
- the angle of rotation is preferably a whole-number fraction of 360°, eg. 180°.
- the driven part in the upper housing part is moved a certain distance, the hollow piston is retracted inside the cylinder in the pump housing, as a resuit of which some of the fluid is sucked out of the storage container into the high pressure chamber in front of the nozzle.
- the gears which consist of a piston on one end of the spindle and a rack or racks on the edge of the upper housing part, the relative movement of the two housing parts is picked up and converted into a rotary movement of the spindle and displacement of the slider on the spindle. On each actuation of the atomiser, the slider is moved a certain distance along the spindle.
- the position of the slider indicates what proportion of the fluid to be atomised has already been taken from the storage container and how much is still available.
- the slider on the spindle can be reset if necessary by means of a resetting lug.
- a plurality of (preferably collapsible) replaceable storage containers holding the fluid which is to be atomised can be inserted into the atomiser one after another and used.
- the storage container is not pressurised or substantially not pressurised.
- the pressure of the fluid in the storage container is in any case substantially lower than the pressure generated in the high pressure chamber by the mechanically operated atomiser.
- the storage container contains, for example, a fluid containing a drug.
- the atomising process is started by gently pressing the actuating button.
- the blocking mechanism then opens up a path for the driven part to move.
- the biassed spring pushes the piston into the cylinder of the pump housing.
- the fluid leaves the nozzle of the atomiser in spray form.
- the components of the atomiser are made of a material which is suitable for the function.
- the housing of the atomiser and, insofar as function allows, other parts are preferably made of plastics, eg. by injection moulding.
- physiologically acceptable materials are used for medicinal purposes.
- the atomiser according to the invention is used, for example, for propel lant-free production of medicinal aerosols.
- An inhalable aerosol with a mass average particle (droplet) size of about 5 ⁇ m can be produced thereby. These small particles (average size less than 12 ⁇ m) are necessary for penetration right down into the lungs.
- the amount discharged is preferably about 15 microlitres.
- active substances are mentioned by way of example of pharmaceutical compositions in the form of aqueous or ethanolic solutions, depending on the solubility of the active substance: berotec. berodual, flunisolide, atrovent, saibutamol, budesonide, combivent, tiotropium. oxivent and suitable peptides.
- the solutions may also contain pharmaceutically acceptable excipients.
- the device contains a valve which operates without any auxiliary force
- the valve is tight against a pressure generally above 3 MPa (30 bar).
- the valve member is made in one piece; it is easy to manufacture and assemble.
- the valve closes very rapidly owing to the short distance travelled by the valve member to reach the defined sealing surface.
- the valve has a high sealing action.
- the atomiser can be operated safely and easily even by untrained persons, both to bias the spring and to actuate the atomising process.
- the atomiser works without propeilant gas and is therefore environmentally friendly.
- the storage container for the fluid is not pressurised or substantially not pressurised.
- the movement of the blocking member is automatically coupled, by a simple method, to the rotary movement for biassing the spring.
- the atomiser consists of low-wear purely mechanical components and operates reliably over long periods.
- the atomiser can be manufactured cheaply and assembled easily.
- the mechanical counter is automatically advanced as the atomiser is actuated; it is uncritical of tolerance, easy to assemble and operates safely and reliably.
- the counter is inaccessible when the atomiser is used properly and cannot be falsified by accident.
- the counter can be adapted to any number of releases of fluid from the storage container and to different overall numbers of storage containers to be used with one atomiser.
- the counter is integrated in the atomiser and does not take up any additional space.
- Figs la, lb and lc are respectively a longitudinal section of a first embodiment of a pump for producing high pressure in a fluid according to the invention, an oblique view of its hollow piston and an oblique view of its valve member;
- Figs 2a, 2b and 2c are similar views of a second embodiment
- Figs 3a, 3b and 3c are similar views of a third embodiment
- Figs 4a, 4b and 4c are similar views of a fourth embodiment
- Figs 4d, 4e and 4f are similar views of a modification of the fourth embodiment
- Fig 5 is a longitudinal section of a fifth embodiment.
- Figs 6a and 6b are longitudinal cross-sections of a metered dose inhaler according to the invention in different operative conditions.
- Figure la shows a longitudinal section, viewed obliquely, through the first embodiment of the device according to the invention for producing high pressure in a fluid.
- the hollow piston (2) with the coaxial bore (7) and the valve member (3) in the partly open position of the valve.
- the high pressure chamber Between the bottom of the valve member (3) and the end of the cylinder is the high pressure chamber (4).
- the high pressure chamber is closed off by another component (not shown).
- Mounted on the hollow piston, outside the cylinder, is a device (not shown) by means of which the hollow piston can be displaced inside the cylinder.
- Figure lb shows the hollow piston (2) viewed obliquely.
- the end of the hollow piston facing the valve member is provided with a groove (5) which is bounded, at its end facing the valve member, by a rectangular section annular land forming a step (8) the diameter of which is less than the external diameter of the hollow piston (2) and greater than the base diameter of the groove.
- the front edge at the end of the hollow piston may be chamfered.
- Figure lc shows the valve member (3) viewed obliquely. It has. for example, three channels (9) on its outer surface to facilitate fluid flow when the valve is open.
- valve member (3) Mounted on the valve member (3), on its side facing the hollow piston, are, for example, three snap hooks (6) the width of which, in the direction of the circumference of the valve member, is less than a third of this circumference.
- the snap hooks (6) are shorter in the axial direction than the length of the, for example, grooved end of the hollow piston.
- valve member (3) is placed on the end of the hollow piston (2), and the hooks (10) slide into the groove.
- the hollow piston together with the valve member is then pushed into the cylinder.
- the hollow piston In order to take in the fluid, the hollow piston is lifted partly out of the cylinder, whereupon the valve automatically opens. The fluid flows through the bore (7) in the hollow piston and past the valve member into the high pressure chamber (4). In order to expel the fluid, the hollow piston (2) is pushed into the cylinder (1), whereupon the valve closes automatically, virtually instantly, and high pressure is generated in the fluid.
- Figure 2a shows the second embodiment of the device according to the invention for producing high pressure in a fluid as a longitudinal section viewed obliquely.
- the cylinder (1 ) is the hollow piston ( 1 1 ) and the valve member ( 13) in the partly open position of the valve.
- Figure 2b shows a longitudinal section through the hollow piston ( 11) with the shaped outlet end (12) of the hollow piston.
- a displacement body (26) may be fixedly Iocated in the hollow piston.
- Figure 2c shows the valve member (13) as a longitudinal section viewed obliquely. Mounted on the valve member is a coaxial, undercut peg
- the projecting end of which engages behind the shaped edge (12) of the hollow piston engages behind the shaped edge (12) of the hollow piston.
- the end ( 15) of the peg facing the hollow piston may be chamfered.
- the peg may have an indentation or bore ( 16) extending in the axial direction and possibly longitudinal slots extending upwards from the end
- Figure 3a shows the third embodiment of the device according to the invention for producing high pressure in a fluid in longitudinal section viewed obliquely.
- the cylinder ( 1) is the hollow piston (17) and the valve member (18) in the closed position of the valve.
- Figure 3b shows a longitudinal section viewed obliquely through the hollow piston (17) with the shaped end (19).
- the widened portion (20) At the outlet end of the hollow piston is the widened portion (20) in which the valve member ( 18) is guided and mounted in axially movable manner.
- the inlet end of the widened portion (20) is chamfered or flat.
- Figure 3c shows the cylindrical valve member ( 18) in longitudinal section viewed obliquely. Both ends of the valve member are planar and are Iocated pe ⁇ endicularly to the axis of the valve member.
- the valve member ( 18) contains, for example, four stepped channels or flats (21) on its outer surface to facilitate fluid flow past the shaped end (19), i.e. the inturned lip, when the valve is open, the ends of the channels (21) being radially inward of the lip.
- the edge of the valve member (18) which abuts on the inclined base of the hollow chamber (20) may be chamfered.
- the diameter of the valve member ( 18) is less than the diameter of the widened portion (20) so that the valve member ( 18) can move virtually without friction in the widened portion (20).
- valve member (18) is pushed into the widened portion (20) before the outlet end (19) of the hollow piston is shaped.
- Figure 4a shows the fourth embodiment of the device according to the invention for producing high pressure in a fluid in longitudinal section viewed obliquely.
- the cylinder (1) are the hollow piston (22) and the valve member (23) in the closed position of the valve.
- the diameter of the valve member is less than the inner diameter of the hollow piston.
- Figure 4b shows a longitudinal section, viewed obliquely, through the hollow piston (22) with the shaped outlet end (24) forming an inturned lip and the encircling constriction (25).
- the thick-walled tube (26) acting as the displacement body may be pushed into the hollow piston (22) and secured therein.
- Figure 4c shows the valve member (23) in oblique view.
- a radially extending indentation (27) in the form of a transverse slot to facilitate fluid flow when the valve is open.
- Figure 4d shows an alternative to the fourth embodiment in longitudinal section, viewed obliquely.
- the hollow piston (28) In the cylinder (1) is the hollow piston (28), optionally with the displacement body (26), with the valve in the closed position.
- the diameter of the valve member (29) is less than the internal diameter of the hollow piston.
- Figure 4e shows a longitudinal section, viewed obliquely, through the hollow piston (28) with the shaped outlet end (24) and the encircling constriction (25). At least one indentation (30) in the form of a recess or notch is provided on the shaped outlet end (24) to facilitate fluid flow when the valve is open. Instead of the indentation there may be a convexity.
- Figure 4f shows the valve member (29) in oblique view. In this case , the valve member is a straight cylinder with no recesses.
- Figure 5 shows the fifth embodiment of the device according to the i nvention for producing high pressure in a fluid, in longitudinal sec t ion and viewed obliquely.
- the hollow piston (31) which con t ains the displacement body (32).
- the closure member (34) mounted on the cylindrically widened inlet end (33) of the hollow piston is the closure member (34) with the depression (35 ) and bore ( 36).
- the guided, axially movable valve member ( 37 ) which may be provided at its outlet end with a slot (38) as recess.
- Figure 6a shows a longitudinal section through the preferred atomiser described in detail above with the spring biassed and Figures 6b shows a longitudinal section through the atomiser with the spring released.
- the upper housing part (51) contains the pump housing (52) on the end of which is mounted the holder (53) for the atomiser nozzle.
- This holder is preferably as described in German Patent Application P 19536303.3-51 of 4 October 1995 (and a parallel PCT application being filed simultaneously herewith in the joint names of Boehringer Ingelheim International GmbH and the inventors) the entire contents of which are inco ⁇ orated herein by reference.
- the nozzle member (54) In the holder is the nozzle member (54) and a filter (55).
- the hollow piston (57) fixed in the cup-shaped drive flange (56) of the blocking mechanism (57) partly projects into the cylinder of the pump housing. At its end the hollow piston carries the valve member (58).
- the hollow pis t on is sealed off by the seal (59).
- the abutment (61) On the axial end of the cup-shaped driven flange is the abutment (61) by which the driven flange is held when the spring is biased.
- the generally annular blocking member (62) moves between the abutment (61) and a support (63) in the upper housing part, either because of its own elasticity or (when it is more rigid) by virtue of an external spring (not shown).
- the actuating button (64) is connected to the blocking member and can either move it bodily or deform it so that it releases the abutment (61).
- the upper housing part terminates in the mouth piece (65) and is closed off by the protective cap (66) which can be fitted thereon.
- the spring housing (67) with compression spring (68) is rotatably mounted on the upper housing part by means of the snapping lug (69) and rotary bearing.
- the lower housing part (70) is pushed over the spring housing and rotates with it to operate the helical sawtooth cam drive (not shown) for cocking the atomiser (moving it from the Fig 6b position to the Fig 6a condition).
- Inside the spring housing is the replaceable storage container (71) for the fluid (72) which is to be atomised.
- the storage container is fitted with a stopper (73) through which the hollow piston projects into the storage container and dips its end into the fluid.
- the spindle (74) for the mechanical counter.
- the drive pinion (75) At the end of the spindle facing the upper housing part is the drive pinion (75). The slider (76) sits on the spindle.
- the valve area of a medicinal atomiser according to Figure la consists of a cylinder made of polybutylene- terephthalate with an internal diameter of 1.6 mm and an external diameter of 5 mm.
- the high pressure chamber is closed off by a nozzle carrier plate.
- a nozzle carrier plate In this plate is a nozzle 20 ⁇ m in diameter and the nozzle channel is 2 mm long.
- a metal hollow piston with an external diameter of 1.59 mm and a bore 0.35 mm in diameter is pushed into the cylinder.
- the hollow piston can be pushed 50 mm into the cylinder and its stroke is 12 mm long.
- the hollow piston has an encircling turned groove 4 mm wide with a base diameter of 0.75 mm.
- the groove is bounded by a 4.0 mm long step with a diameter 1. 15 mm.
- the outer edge of the turned end of the hollow piston is chamfered.
- the valve member made of polybutyleneterephthalate consists of a 2 mm thick disk 1.59 mm in diameter and 3 snap hooks. Three semi-cylindrical channels 0.4 mm in diameter are provided as recesses on the outer surface of the disk. The snap hooks project 6 mm from the disk and the inner edge of the hooks is 4.2 mm away from the disk. The valve member may thus be moved axially 0.2 mm relative to the hollow piston.
- the delivery volume is 23.4 mm 3 .
- the pressure in the fluid is about 32 MPa (320 bar).
- This atomiser is used to atomise or nebulize liquid pharmaceuticals for medicinal aerosol therapy.
- the atomiser delivers the drug in the required dose on each actuation.
- Example 2 Miniaturised device for producing high pressure for a cosmetic atomiser
- the valve area of a cosmetic atomiser corresponding to Figure 3a consists of a cylinder of polyetherether-ketone with an internal diameter of 2.5 mm and an outer diameter of 8 mm.
- the high pressure chamber is closed off by a nozzle carrier plate.
- this plate is a nozzle 25 ⁇ m in diameter with a nozzle channel 2 mm long.
- a hollow piston of reinforced plastics with an external diameter of 2.48 mm and a bore 0.5 mm in diameter is pushed into the cylinder.
- the hollow piston can be pushed 45 mm into the cylinder and its stroke is 24 mm.
- the hollow piston is drilled out to an internal diameter of 1.85 mm over a length of 5.0 mm at its outlet end.
- the base of the drilled-out chamber in the hollow piston is chamfered.
- the outlet end of the hollow piston is thermally deformed.
- the valve member is a cylinder of polypropylene which is 3.0 mm high and 1.6 mm in diameter. Four stepped channels are provided as recesses in the outer surface. The valve member can be displaced axially about 0.5 mm inside the hollow piston.
- the delivery volume is about 116 mm 3 .
- the pressure in the fluid is about 3 MPa (30 bar).
- This atomiser is used to atomise a hair spray.
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Pulmonology (AREA)
- Anesthesiology (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Hematology (AREA)
- General Health & Medical Sciences (AREA)
- Biophysics (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
- Details Of Reciprocating Pumps (AREA)
- Reciprocating Pumps (AREA)
- Nozzles (AREA)
- Catching Or Destruction (AREA)
- Pens And Brushes (AREA)
- Fluid-Pressure Circuits (AREA)
- Spray Control Apparatus (AREA)
Abstract
Description
Claims
Priority Applications (23)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
UA98042211A UA54402C2 (en) | 1995-10-04 | 1996-04-10 | Minituarised design for producing high pressure fluids to be sprayed |
IL12363496A IL123634A (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
SI9630645T SI0853501T1 (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
PL96356022A PL185789B1 (en) | 1995-10-04 | 1996-10-04 | Fluid sprayer, containing miniaturized fluid compression device |
DK96934565T DK0853501T3 (en) | 1995-10-04 | 1996-10-04 | Miniaturized device for producing high pressure in a fluid to be atomized |
JP1997513985A JP3488717B6 (en) | 1995-10-04 | 1996-10-04 | A device with a miniaturized structure for generating high pressure in a fluid to be atomized |
HU9900741A HU221232B1 (en) | 1995-10-04 | 1996-10-04 | Pressure-increasing device for fluid to be atomised, dispenser and puming device with alternating movement |
BR9611140A BR9611140A (en) | 1995-10-04 | 1996-10-04 | Miniaturized construction device to produce high pressure in a fluid to be atomized |
AU72870/96A AU730797B2 (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
PL96325961A PL185631B1 (en) | 1995-10-04 | 1996-10-04 | Apparatus of miniaturised construction for generating hight pressure of a fluid to be atomised |
DE69629708T DE69629708T2 (en) | 1995-10-04 | 1996-10-04 | MINIATURIZED DEVICE FOR PRODUCING HIGH PRESSURE IN FLUIDS TO BE SPRAYED |
EP96934565A EP0853501B1 (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
NZ320179A NZ320179A (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
CN96197411.7A CN1091660C (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
DK02003525T DK1214985T3 (en) | 1995-10-04 | 1996-10-04 | Miniature device for generating high pressure in a fluid for atomization |
CA002232151A CA2232151C (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
SK426-98A SK283515B6 (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
AT96934565T ATE248028T1 (en) | 1995-10-04 | 1996-10-04 | MINIATURIZED DEVICE FOR PRODUCING HIGH PRESSURE IN FLUID TO BE SPRAYED |
EE9800107A EE03519B1 (en) | 1995-10-04 | 1996-10-04 | Device for high pressure fluid |
BG102345A BG64081B1 (en) | 1995-10-04 | 1998-03-24 | Device of a miniaturized structure for exercising high pressure in fluid so that it will not be pulvaerized |
NO981521A NO981521L (en) | 1995-10-04 | 1998-04-03 | Arrangement of miniaturized structure for producing high pressure in a fluid to be atomized |
HK99100301A HK1015304A1 (en) | 1995-10-04 | 1999-01-22 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
NO20074487A NO20074487L (en) | 1995-10-04 | 2007-09-05 | Miniaturized fluid pressure setting device, fluid atomizer atomizer and a reciprocating pump device for producing high pressure in a fluid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19536902A DE19536902A1 (en) | 1995-10-04 | 1995-10-04 | Miniature fluid pressure generating device |
DE19536902.5 | 1995-10-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997012687A1 true WO1997012687A1 (en) | 1997-04-10 |
Family
ID=7773961
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/004351 WO1997012687A1 (en) | 1995-10-04 | 1996-10-04 | Device of miniaturised construction for producing high pressure in a fluid to be atomised |
Country Status (39)
Country | Link |
---|---|
US (7) | US5964416A (en) |
EP (2) | EP0853501B1 (en) |
JP (4) | JP2003056458A (en) |
KR (1) | KR100431011B1 (en) |
CN (1) | CN1091660C (en) |
AR (1) | AR003794A1 (en) |
AT (2) | ATE352379T1 (en) |
AU (1) | AU730797B2 (en) |
BG (1) | BG64081B1 (en) |
BR (1) | BR9611140A (en) |
CA (4) | CA2551891C (en) |
CO (1) | CO4560418A1 (en) |
CZ (1) | CZ295103B6 (en) |
DE (3) | DE19536902A1 (en) |
DK (2) | DK1214985T3 (en) |
EE (1) | EE03519B1 (en) |
EG (1) | EG21374A (en) |
ES (2) | ES2280442T3 (en) |
HK (1) | HK1015304A1 (en) |
HR (1) | HRP960448B1 (en) |
HU (1) | HU221232B1 (en) |
IL (3) | IL123634A (en) |
MY (1) | MY115214A (en) |
NO (2) | NO981521L (en) |
NZ (1) | NZ320179A (en) |
PE (1) | PE29098A1 (en) |
PL (2) | PL185789B1 (en) |
PT (2) | PT1214985E (en) |
RU (1) | RU2179075C2 (en) |
SA (1) | SA97170624B1 (en) |
SI (2) | SI1214985T1 (en) |
SK (1) | SK283515B6 (en) |
TR (1) | TR199800586T1 (en) |
TW (1) | TW364041B (en) |
UA (1) | UA54402C2 (en) |
UY (1) | UY24339A1 (en) |
WO (1) | WO1997012687A1 (en) |
YU (1) | YU49228B (en) |
ZA (1) | ZA968317B (en) |
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- 1996-10-04 CA CA2551891A patent/CA2551891C/en not_active Expired - Lifetime
- 1996-10-04 RU RU98108402/12A patent/RU2179075C2/en active
- 1996-10-04 PE PE1996000705A patent/PE29098A1/en not_active IP Right Cessation
- 1996-10-04 AU AU72870/96A patent/AU730797B2/en not_active Expired
- 1996-10-04 AR ARP960104602A patent/AR003794A1/en unknown
- 1996-10-04 EE EE9800107A patent/EE03519B1/en unknown
- 1996-10-04 CZ CZ19981015A patent/CZ295103B6/en not_active IP Right Cessation
- 1996-10-04 EP EP96934565A patent/EP0853501B1/en not_active Expired - Lifetime
- 1996-10-04 MY MYPI96004102A patent/MY115214A/en unknown
- 1996-10-04 DE DE69629708T patent/DE69629708T2/en not_active Expired - Lifetime
- 1996-10-04 TR TR1998/00586T patent/TR199800586T1/en unknown
- 1996-10-04 DE DE69636875T patent/DE69636875T2/en not_active Expired - Lifetime
- 1996-10-04 NZ NZ320179A patent/NZ320179A/en not_active IP Right Cessation
- 1996-10-04 AT AT02003525T patent/ATE352379T1/en active
- 1996-10-04 IL IL14022196A patent/IL140221A/en not_active IP Right Cessation
- 1996-10-04 DK DK02003525T patent/DK1214985T3/en active
- 1996-10-04 ES ES96934565T patent/ES2201204T3/en not_active Expired - Lifetime
- 1996-10-04 HU HU9900741A patent/HU221232B1/en unknown
- 1996-10-04 CA CA2473681A patent/CA2473681C/en not_active Expired - Lifetime
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- 1996-10-04 DK DK96934565T patent/DK0853501T3/en active
- 1996-10-04 CN CN96197411.7A patent/CN1091660C/en not_active Expired - Lifetime
- 1996-10-04 SK SK426-98A patent/SK283515B6/en not_active IP Right Cessation
- 1996-10-04 AT AT96934565T patent/ATE248028T1/en active
- 1996-10-04 KR KR10-1998-0702174A patent/KR100431011B1/en not_active IP Right Cessation
- 1996-10-04 PT PT02003525T patent/PT1214985E/en unknown
- 1996-10-04 US US08/726,219 patent/US5964416A/en not_active Expired - Lifetime
- 1996-10-04 EP EP02003525A patent/EP1214985B1/en not_active Expired - Lifetime
- 1996-10-04 WO PCT/EP1996/004351 patent/WO1997012687A1/en active IP Right Grant
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1997
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1998
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1999
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2000
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2002
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2004
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