EP0755300B1 - Procede et dispositif pour la confluence d'au moins deux substances fluides - Google Patents

Procede et dispositif pour la confluence d'au moins deux substances fluides Download PDF

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Publication number
EP0755300B1
EP0755300B1 EP95915747A EP95915747A EP0755300B1 EP 0755300 B1 EP0755300 B1 EP 0755300B1 EP 95915747 A EP95915747 A EP 95915747A EP 95915747 A EP95915747 A EP 95915747A EP 0755300 B1 EP0755300 B1 EP 0755300B1
Authority
EP
European Patent Office
Prior art keywords
chamber
accordance
fluid medium
opening
flow
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95915747A
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German (de)
English (en)
Other versions
EP0755300A1 (fr
Inventor
Konrad H. Jonas
Hansjörg Maier
Klaus Langendorf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Teroson GmbH
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Henkel Teroson GmbH
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Publication date
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Publication of EP0755300A1 publication Critical patent/EP0755300A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/316—Injector mixers in conduits or tubes through which the main component flows with containers for additional components fixed to the conduit

Definitions

  • the present invention relates at least to a device for merging two flow media with at least one fillable with a first flow medium first chamber and at least one in the area of an opening of the first Chamber attachable and connected to this flow area, which holds the first flow medium emerging from the first chamber and for its delivery up to to an outlet opening of the flow area and a method for Generation of a product strand by merging at least two Flow media that are kept separate before merging.
  • This problem can be summarized in general in that it applies to a first Flow medium to supply at least a second to the properties of the flow media to change, for example their viscosity, mechanical and / or chemical Properties, visual appearances or physical states.
  • Such 2K systems are coaxial cartridges with a static mixer, such as they are offered by Liquid Control under the name "Supermix”.
  • 2K systems with two parallel cartridges and a dynamic one Mixing head known, e.g. in EP-B-313519 or EP-B-351358 are.
  • DE-A-4202591 describes a method for premixing at least two pasty masses when introduced into a mixer, in which the mixer supplied mass strands form thin, adjacent layers.
  • They have in common that special application devices for their application required are.
  • a suitable mixing device for example a static mixer
  • To merge these two Media are extracted from the cylindrical by means of pistons under pressure Cavities of the device are pressed and then emerge as a common strand from the Exit opening from, which is partly formed by the merged media becomes. The strand then enters the downstream mixing device and becomes mixed there to a homogeneous final medium before it is used emerges from the discharge opening of the mixing device.
  • containers containing dental care products are known, into which at least two different, flowable and optically different dental care components are filled.
  • the constructive design of the container leads in the container stacked dental care components in one strand from the discharge opening in which the mutually contacting dental care components are strip-like lie side by side.
  • the technical problem underlying the invention is a device or to propose a method for merging at least two flow media, so that it is possible to have at least two mutually influencing flowable Components or flow media separated until immediately before use from each other, to bring them together immediately before use and if necessary to mix, the proportions of the various components can be specified and influenced.
  • this technical problem is solved in that with a generic Device at least a second, with a second fluid medium Fillable chamber is provided, which has at least a first opening element that it is connected to the flow area and / or to the first opening, and at least has a second opening element, via which it communicates with the flow area and / or is connected to the exit opening and by a generic Process in which the energy with which a fluid flows from its reserve volume is conveyed out, causes at least a second fluid medium from its Reserved volume conveyed out and merged with the first fluid becomes.
  • Device and method according to the invention have the advantage that the from Disadvantages known in the art can be avoided. They allow that at least one fluid medium for the respective application freely selected by the user can be, so that the product consisting of at least two flow media from Users at the place of work can be influenced in its composition. Therefor can at least partially auxiliary devices available on the market such as cartridges, Spray guns and static mixers are used. The device allows merging the media immediately before use, the media being continuous are promoted and only relatively small amounts of already merged or mixed media in the system.
  • the first opening element is adjacent to the front part of the flow area in the flow direction and the second opening element arranged adjacent to the rear part of the flow area in the flow direction the delivery paths for the second fluid medium are advantageously short.
  • the second fluid medium via a channel from the second The opening element is already in the front area of the flow area Flow area is advantageously available for mixing the media.
  • the boundary between the upper part and lower part of the housing provided such that exclusive parts of the upper part with mixed mixed media in contact. This ensures that at least a fluid medium that has not been used up completely or if it is interrupted the upper part of the housing can be removed from the lower part of the application and the media remaining in the lower part are unmixed. Subsequently, after short interruptions put the top back on or a new one at all Top part can be put on the application using the still existing Continuous flow media.
  • Separating elements can expediently be provided on the upper part that protrude into the lower part and mixed media when loosening take away with.
  • the flow cross sections are expedient taking into account the flow properties of the media dimensioned so that the fluid media in the desired Mix out the appropriate quantities.
  • Examples of elements with which the flow cross sections can be set are interchangeable inserts with different cross sections, preferably from externally operable rotary screens or telescoping channels that either through conical design or slots different cross sections form.
  • the double-walled design of the housing provides an effective thermal Isolation represents an isolating effect, also against other influences like diffusing gases or radiation, but can also by other means, can be achieved for example by coating.
  • the placement of desiccants in the housing such that they are in contact with at least one fluid medium effective protection against moisture-related influences on the flow media
  • the at least partially transparent formation of the outer wall in the area of Chamber advantageously enables the fill level of the second fluid medium to be optically closed check.
  • the closability of the outlets of unmixed flow media allows the filled in the device Fluid before application or when application is interrupted and Separate lower and upper part to protect against environmental influences.
  • the arrangement of a spiral static mixer in the mixing area of the upper part of the Housing advantageously creates the conditions for effective mixing of the merged flow media. If the available area in the mixing area channel is used to the greatest possible extent, this results in a Mixing section possible for a long time.
  • a Method for merging at least two flow media which before the Merging separately, is proposed, in which the energy, is conveyed out of its reserve volume with a flow medium, causes conveyed at least a second fluid medium out of its reserve volume and is merged with the first fluid.
  • the energy is conveyed out of its reserve volume with a flow medium, causes conveyed at least a second fluid medium out of its reserve volume and is merged with the first fluid.
  • the energy can also be used to promote of the at least second fluid medium that the strand of the first Flow medium through a nozzle-like device part, for example a venturi-like formation of the flow area is directed, in the area of the nozzle a suction is formed by the negative pressure on the second fluid medium acts that this is promoted out of its reserve volume.
  • Pressure or Negative pressure can be controlled so that the second fluid in one with respect to the volume of the first fluid medium predetermined ratio supplied becomes.
  • first flow media are adhesives and / or sealants as the base component.
  • second or more than second flow media are catalysts, Color components and crosslinkers, with more than one of these substances being used for this Application can come.
  • the device according to the invention of an adapter which is adapted to a commercial cartridge is preferably placed.
  • This adapter can be used with a minor amount of a catalyst and / or crosslinker and / or Color components are filled and is shaped so that the volume flow of the the base component of the adhesive / sealant pushed out continuously with the catalyst and / or crosslinker and / or color component mixed, and this mixture evenly through a possibly in front of the adapter pre-screwed nozzle is discharged. If necessary, the mixing of the both components through a static mixer placed on the adapter to be completed.
  • any form of two-component adhesives / sealants is suitable, in which the second component can be used in a minor amount, is in the particularly preferred embodiments as a one-component base component moisture-curing system used.
  • This basic system can e.g. on the base built up of reactive isocyanate group-containing polyurethane adhesives / sealants the base adhesive / sealant can also be based on Polydimethylsiloxanes, alkoxysilane-terminated polyethers or based on Polymers with reactive epoxy groups.
  • An example of special Suitable polyurethane adhesives / sealants are e.g. in Example 3 of WO 95/00572 described.
  • Adhesives / sealants Suitable adhesives / sealants based on alkoxysilane-terminated Polyethers are described in detail in DE-C-4119484, the ones there Fluorosurfactants described are not necessarily part of the invention Adhesives / sealants to be used.
  • the catalyst component depends on the basic adhesive used - / Sealant, for polyurethanes can be those known in polyurethane chemistry organometallic compounds such as Iron or tin compounds used will. 1,3-dicarbonyl compounds of iron or of the tetravalent or tetravalent tin, but in particular the Sn (II) carboxylates or the Dialkyl-Sn- (IV) dicarboxylates or the corresponding dialkoxylates, e.g. Dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dibutylate, dioctyltin diacetate, Dibutyltin maleate, stannous octoate.
  • organometallic compounds such as Iron or tin compounds used will. 1,3-dicarbonyl compounds of iron or of the tetravalent or tetravalent tin, but in particular the Sn (II) carboxylates or the Dial
  • the highly effective tertiary Amines or amidines can be used as catalysts, possibly in combination with the tin compounds mentioned above.
  • the amines are both acyclic as in particular cyclic compounds in question. May be mentioned as an example Tetramethylbutane diamine, bis (dimethylaminoethyl) ether, 1,4-diaza-dicyclooctane (DABCO), 1,8-diaza-bicyclo- (5.4.0) -undecene, 2,2'-dimorpholinodiethyl ether or Dimethylpiperazine or mixtures of the aforementioned amines.
  • DABCO 1,4-diaza-dicyclooctane
  • 5.4.0 1,8-diaza-bicyclo- (5.4.0) -undecene
  • 2,2'-dimorpholinodiethyl ether Dimethylpiperazine or mixtures of the aforementioned amines.
  • Organic di- or triamines such as e.g. Ethylene diamine, propylene diamine, 1,4-diarainobutane, diethylene triamine or piperazine and optionally also low molecular weight amino-terminated polyethers of the "Jeffamins".
  • polyol crosslinkers Polyols known in polyurethane chemistry, in particular low molecular weight polyether diols or -triols, polyester-polyols, polyols based on -caprolactone, too Called "polycaprolactones".
  • polyester polyols are also particularly preferred oleochemical origin.
  • polyester polyols can, for example, by complete ring opening of epoxidized triglycerides at least partially Fat mixture containing olefinically unsaturated fatty acid with one or more Alcohols with 1 to 12 carbon atoms and subsequent partial transesterification of the Triglyceride derivatives to alkyl ester polyols with 1 to 12 carbon atoms in the alkyl radical can be produced (see e.g. DE-A-3626223).
  • Other suitable polyols are Polycarbonate polyols and dimer diols (from Henkel) and in particular castor oil and its derivatives.
  • crosslinking component for alkoxysilane-terminated polyether systems and for Adhesives / sealants based on polydimethylsiloxanes can be used in the Known low molecular weight silane crosslinking agents are used.
  • liquid crosslinkers or catalysts can be used directly, it may be appropriate to use inert solvents and / or plasticizers relocate and, if necessary, the viscosity of these solutions to the Adjust the viscosity of the basic adhesive / sealant.
  • a color component can be applied via the Adapters are added. This simplifies the process for the user Warehousing, as it only uses a single adhesive / sealant in one basic color (e.g. colorless or white pigmented) and must be the color component Can adapt to needs, e.g. in vehicle construction the one for the vehicle used paint.
  • one basic color e.g. colorless or white pigmented
  • catalyst and / or crosslinking agents and color components can also be used combine in a single paste.
  • the catalyst, crosslinker and / or color component be used in a minor amount with respect to the base component, so that there is a small-volume adapter.
  • This component is preferably in a Amount of 0.5 to 8 wt.%, Based on the base component.
  • the adapter according to the invention was screwed onto the cartridge of a commercially available, one-component, moisture-curing 1-component polyurethane adhesive / sealant (Terostat 8597, Teroson) and two percent by weight of castor oil were added to this adapter.
  • the adhesive / sealant / crosslinker mixture was discharged with a commercially available cartridge gun and applied to aluminum angles. These aluminum angles were previously coated with a polyurethane primer (Terostat 8510 from Teroson) and 15 min. vented.
  • the aluminum brackets were put together so that an adhesive joint 5 mm thick was formed.
  • a tensile strength test of the bond was carried out 45 minutes after the assembly. The tensile strength was 0.6 N / mm 2 . Detachment of the primer from the substrate was observed since the primer had not yet fully achieved its strength. It can be assumed that a higher tensile strength would otherwise have been found.
  • the adhesive / sealant was applied in the same way to the aluminum angles without the use of crosslinking agent and adapter, and its tensile strength was checked. After 45 minutes, the tensile strength was 0.15 N / mm 2 .
  • the first medium is thus received from the first chamber 2 in the flow area 1 designed for this purpose and passed on through this to the outlet opening 3.
  • Second chamber 9 and flow area 1 of the channel element 6 are connected via at least one discharge opening 11, preferably arranged on the first chamber side, for branching off part of the first medium into the second chamber 9, which at least one second opening 12 is provided for the outlet of the second medium.
  • the second opening 12 is located here in the area next to the outlet opening 3 of the channel element 6 or the flow area 1. It can either extend around the entire circumference of the channel element wall 8 or can be arranged only in a partial area next to the same.
  • first chamber 2 and channel element 6 takes place here, for example in the area of the channel element entrance 7 and the first chamber opening 4 by means of suitable fastening areas 13 (not shown) such as e.g. a screw connection.
  • suitable fastening areas 13 such as e.g. a screw connection.
  • the attachment is not limited to this type of attachment. Rather, other suitable fastening elements, in particular clamping, Snap-in, plug-in connections or in the manner of a bayonet lock or one Combination of at least two of these elements / connections or parts thereof selected will.
  • the connections can be designed to be detachable or non-detachable from one another be.
  • part of the first medium is branched off into the second chamber 9 and displaces the second medium located therein, which leaves the second chamber 9 through the second opening 12 located next to the outlet opening 3, so that the first and second medium are brought together at this point.
  • the second chamber 9 is filled with a second medium here through the second opening 12.
  • the channel element 6 and the second chamber 9 can be composed of several molded parts.
  • the channel element 6 can consist of a possibly flexible tubular or hose-like part and the second chamber 9 can consist of a plastic or metal part, for example.
  • the first chamber 2 and the channel element 6 are preferably connected to one another by means of suitable fastening measures 13.
  • the discharge opening or the first opening element 11 can be designed in the form of a tube or another type of permeable shaped piece.
  • the first chamber, first chamber opening, flow area or channel element, second chamber, discharge opening (s) and second opening (s) accordingly form a functional unit.
  • the user can use existing auxiliary devices available on the market, such as piston-functional pressure and pressing devices etc.
  • the first medium can be manually pressed out or pressed out of plastic tube-like first chambers.
  • the device can have a plurality of second chambers be provided, each with at least one branch element / discharge opening the flow area or the channel element are connected. According to the invention by the above and to the embodiments of the device described further mentioned measures achieved that through the promotion of the first medium by the Flow area automatically a second medium is fed to the first medium, the appropriate drive energy for the second medium from a derived or branched Part of the first medium is delivered itself.
  • Fig. 2 shows a simplified embodiment of the device for merging at least two fluid media with a housing in which the channel element 6 as Flow area 1 in the housing and the second chamber 9 are integrated.
  • the case points a housing inlet opening 15 for the first medium, which is also the inlet opening 7 of the flow area 1 on the housing side or of the channel element 6.
  • the exit opening 16 of the housing 14 here is analogous to FIG. 1, the outlet opening 3 of the Flow area or the channel element 6.
  • a partition 17 which is in the for the second medium provided second chamber 9 and the flow area 1 provided for the first medium divides and in one function channel element wall 8 and second chamber wall 10 takes over. It extends in a protruding manner into the flow area on the housing entrance 1 of the first medium and branches part of the first medium when the device is actuated through the discharge opening 11 into the second chamber 9.
  • the second opening 12 opens here in front of the opening 3 in the flow area 1, so that at this point First medium and second medium are merged.
  • the second opening 12 opens here in front of the outlet opening 3 into the flow area 1, so that the first medium and the second medium are brought together at this point.
  • the housing 14 is provided with a separate filling area 18 for the second medium, which is sealed as tightly as possible after filling the second medium into the second chamber 9 by means of a closure part 19, so that no second medium is actuated from the second chamber 9 through the filling area 18 of the housing when the device is actuated 14 can emerge.
  • the second chamber 9 contains a movable separating element 20 separating the first medium from the second medium, which is driven in the direction of the second opening 12 by the first medium entering the second chamber 9 and presses the second medium out of the second chamber 9 again through the second opening 12.
  • the separating element 20 is designed here as a rigid part and is guided by the second chamber wall 10 and the dividing wall 17 during propulsion. However, it is preferably provided with guide section (s) 21 in the region of the chamber wall 10 and / or partition 17. It also preferably has, on its side facing the first medium, pressure distribution segment (s) 22 which distributes the pressure exerted by the first medium on the separating element 20 in order to build up a driving force which is as uniform as possible.
  • This additional measure is intended to prevent the separating element 20 from tilting on the separating wall 17 and / or the second chamber wall 10.
  • the flow media brought together in the area of the housing outlet 16 or the channel element outlet 3 emerge, for example in the case of two highly viscous flow media or at least one highly viscous flow medium, side by side in the form of a strand from the exit opening.
  • Such an embodiment of the device, which is equipped with a separating element is therefore particularly suitable for those cases in which direct contact between the first and time medium is avoided prior to the intended combination and, for example, premature mixing and / or undesired chemical reaction is to be excluded
  • Fig. 3 also shows in section a further embodiment of the invention Contraption.
  • First chamber 2 and second chamber 9 are attached to one another here in one piece, so that first chamber opening 4 and channel element input 7 and input of Flow area 1 on the housing side merge into one another.
  • Partition 17, which is also part of the channel element 8 and second chamber wall 10 is directed in the direction of the flow area 1 provided for the first medium and narrowed it.
  • the second opening 12 is located next to the housing outlet opening 16, so that until then the first medium does not coincide with the second medium Touch comes.
  • the separating element 20 located in the second chamber 9 is folded here like a film and is formed by the discharge opening 11 into the second chamber 9 penetrating first medium unfolded or expanded and displaced in this way the second medium, which then from the second opening 12 again from the second chamber 9 comes out.
  • a film-like material Separating element can also rubber, latex-like or other stretchable Parts / materials for the separating element or parts thereof are used.
  • tubular or film-like packaging filled with the second medium conceivable, which are given in the second chamber. This type of packaging forms then the foldable or stretchable separating element.
  • a retrofit by means of suitable fastening areas 13 such as e.g. a screw, clamp, snap-in, plug-in connection or in the manner of a Bayonet catch or a combination of at least two of these Elements / connections or parts thereof is an additional one on the housing 14
  • the mixing region 23 connected in this way extends the flow region 1, the outlet opening 3 of which is also the discharge opening of the mixing region 23.
  • Attachable mixing areas are known as additional mixing elements in the form of so-called static mixers and as such do not form part of the invention. They are designed, for example, in the form of a tube in which a swirling element is arranged. However, if known mixing areas / elements are connected to the device according to the innovation, they are part of the device according to the invention. Such a housing design is particularly indicated in such cases when, for example, a chemical reaction of the two flow media is to be avoided when the mixing area is not connected downstream.
  • the device or its housing 14 can thus advantageously be separated from the mixing area after partial use by means of releasable fastening elements 13, then set aside and, if necessary, further used with a new mixing area.
  • the housing-side flow area 1 is here in the form of a channel element 6 which is centrally aligned with the first chamber opening 4 and preferably also has a round channel element wall 8 designed, which extends in the area to the housing entrance preferably only in partial section (s) in the flow area 1 of the first medium and thus narrows it.
  • two discharge openings 11 are arranged here, through which 11 a part of the first medium reaches the separating element 20, which is ring-shaped around the channel element wall 8 or partition wall 17, and drives this and so on Second medium displaced out of the second chamber 9 through the second opening 12.
  • the channel element or its wall (s) extends into the first chamber opening.
  • the discharge opening (s) can also be arranged in or on the first chamber opening itself.
  • the first medium passes through the channel element 6 to the outlet opening 3, the Second opening (s) 12 open into the flow area in front of the outlet opening 3, so that the two flow media are previously brought together 3 and at least one highly viscous flow medium as a common strand then the housing 14 through the Exit exit 3.16 again.
  • Second openings in the channel element wall 8 or chamber wall 10 arise when merging the flow media with, for example, at least one highly viscous or viscous first medium one or more areas that from Second medium to be filled out.
  • the strand of First medium with at least in the area of the confluence of the two flow media provide two diametrically opposite segments of the second medium, the size of which depends on the size of the secondary openings.
  • the separating element can be arranged in a ring around an angled or round-shaped channel element or dividing wall.
  • the regions of a rigid separating element facing the second chamber wall are accordingly also designed to be angular.
  • the housing can have several second chambers, each containing the different second media or being filled with them.
  • the second chamber can be divided into a plurality of sector-shaped subchambers by corresponding radially arranged partition walls, in which, for example, one separating element each with corresponding sector-like sections is arranged. It goes without saying that a filling area for the second medium and at least one discharge opening for the entering first medium and at least one second opening for the outlet of the second medium are assigned to each second chamber.
  • the housing 14 here consists of an upper part 25 and a lower part 26, which are (not) by means of suitable fastening element (s) 13 shown) can be attached to one another, for example by means of a screw, clamp, snap-in, plug-in connection or in the manner of a bayonet catch or a combination of at least two of these elements / connections or parts thereof.
  • the flow region extends from the first chamber 2 to the outlet opening 16 located on the upper housing part 25, which is preceded by a mixing region 23, which here is provided with a swirling element 24 located in the flow region and is designed as a fixed component of the upper housing part 26.
  • the flow area 1 on the housing side with the channel element wall 8 has one or more wall projections 27 directed into the flow area 1 of the first medium in the area in front of the second opening 12.
  • the user places the second medium in the open annular second chamber 9, the filling area 18 of which lies between the channel element wall 8 or the partition wall 17 and the outer housing wall 28, and then closes it with the upper housing part 25, which is at the same time sealing closure part 19 for the second chamber 9.
  • the housing outer wall 28 thus also fulfills the function of part of the second chamber wall 8.
  • the housing is to have a plurality of second chambers, these and their filling regions are formed by the outer wall 28 of the housing, by intermediate walls directed radially to the channel element wall 8 or to the partition 17 and by the channel element wall 8.
  • Each individual second chamber is preferably also sealed with the upper housing part.
  • the second chambers can also be closed with a separate or for all second chambers with an integrally formed additional closure part, the upper housing part is then attached with its outlet opening to the lower housing part.
  • the strand of a preferably viscous or pasty first medium conveyed through the flow area reaches the projections 27 of the channel element wall 8 directed into the flow area 1 of the first medium before the second opening and is provided there with corresponding recesses which are aligned centrally in the flow area 1. These recesses provide space for the supply of the second medium, which does not have to displace part of it when it reaches the first medium through the second opening 12.
  • the second opening (s) 12 are formed here by corresponding structural measures between the upper housing part 25 and the lower housing part 26. However, they can also be arranged in parts of the upper housing part 25.
  • the second medium propelled in the second chamber 9 by means of separating element 20 is fed through the second opening (s) 12 to the first medium provided with the recesses and is brought together with it in the downstream mixing area 23 in a more closely and networked manner. It can then be fed to the application from the outlet opening 3, 16 on the upper housing part 25.
  • the housing of the device is preferably designed here in such a way that its width or its outer diameter is equal to or smaller than the outer cross-section or outer diameter of the first chamber or its outer wall, so that the housing does not obstruct the view when the fluid media are placed cleanly.
  • Fig. 6a illustrates in the sectional view of the channel element 7 in the area in front of the Second opening 12, the projections 27, which are aligned centrally in the flow region 1 Channel element wall 8.
  • Fig. 6b illustrates the part of the flow area 1, which the projections 27 of the Channel element wall 8 connected downstream and configured with the second opening (s) 12 is.
  • Fig. 7 further shows in section a device for merging at least two fluids.
  • the lower housing part 26 is here by means of its outer wall 28 located, extending over the outer wall 30 of the first chamber 2 Attachment sections 31 thereon via corresponding fastening elements 13 (Not shown) attached, the housing input, which is also input 7 of the Channel element 6 or the housing-side flow area 1 is to the First chamber opening 4 is attached.
  • the discharge opening (s) 11 attached distribution element 32 which is preferably designed like a plate and is provided with openings / perforation (s) 33 through which one possible even application of the first medium to the second medium facing side of the distribution element 32 is to be effected.
  • Number and Design of the perforation (s) 33 and the shape of, for example, concave or convex distribution element 32 can thus be different.
  • the Distribution element 32 can additionally on its side facing the second medium a separator if there is premature contact between the two Flow media avoided and / or the even displacement of the second medium from the second chamber should be improved.
  • the discharge openings 11 are arranged here in a flow region 1 which runs parallel to the first chamber opening wall 5 and the channel element wall 8, the housing inlet wall 29 being attached via the first chamber opening wall 5.
  • a counterpressure in the flow area 1 of the first medium is created in the channel element 6 due to the mixing area 23 arranged on the housing outlet side, which causes part of the first medium to escape through the discharge opening (s) 11 into the second chamber 9.
  • the build-up of back pressure does not depend on a mixing area downstream of the discharge opening (s).
  • the upper housing part 25 is provided with a connecting piece 34, which comprises the channel element wall 8 located in the lower housing part 26 and in partial areas has one or more recesses 35 which form the second opening (s) 12.
  • the second openings 12 can also or additionally be caused by recesses in the channel element wall 8.
  • discharge and / or secondary opening can be designed in a variety of ways.
  • the proportions of the first and second medium are defined.
  • At least partially radially designed opening (s) are preferably provided in order to bring about a uniform flow behavior of the respective flow medium.
  • the opening (s) for example in the wall of the channel element or the flow area, can be accompanied by narrowing (s) and / or widening (s) of the cross section.
  • the invention can be designed in a step-like and / or protruding manner as a diversion or discharge area (s) and / or as inclined bushings for the respective flow medium in order to effect or facilitate the entry of the media into the areas intended for them.
  • a constructive configuration can also bring about the second opening (s) by taking appropriate measures between components of the upper housing part and the channel element located in the lower housing part or the walls thereof.
  • the flow area with the channel element walls can be formed as part of the upper housing part and / or the lower housing part or as a separate molded part inserted into the housing.
  • the opening area of the first chamber - as shown in FIGS. 8 and 9 - can also form at least part of the flow area or the channel element on the housing side.
  • the invention encompasses all possible configurations of the flow area, the discharge and second opening (s) if the desired discharge of the first medium into the at least one second chamber and the exit of the at least one second medium from the at least one second chamber is given.
  • the lower housing part 26 and the first chamber 2 are integrally formed with one another, the outer wall 30 of the first chamber 2 extending beyond the first chamber 2 and forming the outer wall 28 of the lower housing part 26 or part of the second chamber wall 8 there.
  • the discharge opening (s) 11 are arranged here in the intermediate wall 36 connecting the first chamber opening wall 5 with the first chamber outer wall 30, so that the first medium passes directly from the first chamber 2 into the second chamber 9 and the second medium there directly or indirectly via a separating element (s). 20 advances.
  • the first chamber opening 4 extends here with its wall 5 into the housing 14 and there at least partially forms the flow area 1.
  • the second opening (s) 12 for the exit of the second medium from the second chamber 9 are here made by structural measures between components of the upper housing part 26 and the first chamber opening wall 5 , which is at the same time channel element wall 8, part of the second chamber wall 10 and partition 17. However, they can also be arranged in the first chamber opening wall 5 or exclusively in parts of the upper housing part.
  • the outlet opening 3 of the flow area 1 is located at the housing outlet or, in the case of a downstream mixing area 23, at its discharge opening.
  • FIG. 9 shows a further alternative embodiment of the device for Merging at least two flow media.
  • the lower housing part 26 and the first chamber 2 are integrally formed with one another.
  • the partition member 20 the Function of a movable partition 36 takes over.
  • the position of the Discharge opening 11 for the first medium is thus variable and is the respective position of the movable partition 36 or the movable Partition formed partition 20 corresponding to the Side facing the first medium between the first chamber opening wall 5 and the outer wall 30 of the first chamber.
  • FIG. 9 looks at the boundary between First chamber and second chamber support sections, by means of which the movable Partition wall or the separating element before filling the first and / or two chamber is defined defined so that the volume of the first chamber and the second chamber is precisely specified. Designs of the device can also be used arrive at the discharge openings both in the intended for the first medium Flow area as well as in the area between the first chamber opening and the outer wall the first chamber are arranged.
  • a further possible embodiment of the device provides a cascade-like advancement of a plurality of housings, the flow medium consisting of at least two flow media emerging from the first flow area forming the first medium for the downstream flow area.
  • the outlet opening of the first flow area thus opens into the downstream flow area, to which the second medium emerging from a correspondingly downstream at least one second chamber is then fed.
  • This type of device for merging at least two flow media is indicated for the cases in which a connection / reaction of the at least first two merged flow media is to take place before the supply of a further flow medium.
  • the device designed according to the invention can be operated until the second chamber receiving the second medium is filled with the first medium, the second medium having been displaced in whole or in part from the second chamber, or that which has been conveyed from the first chamber through the flow area and partly into the at least one a second chamber derived first medium was pressed or pressed out of the first chamber.
  • the housing can then be cleaned of the first medium and any remaining stocks of the second medium and refilled with the second medium and reused.
  • the device according to the innovation is designed as a disposable article, preferably made of plastic materials, and is disposed of after use. In the technical area, this avoids expensive, possibly environmentally harmful chemicals / solvents etc. cleaning.
  • a plastic housing can be used as often as required after cleaning.
  • the designs of the device with housing for FIGS. 2 to 7 are particularly suitable.
  • paste-like flow media can optionally be combined in a strip-like manner with second flow media, such as cream with flowable chocolate.
  • second flow media such as cream with flowable chocolate.
  • the two components of a two-component adhesive can optionally also be combined with a third coloring component. Sealants or adhesives can also be provided with color so that the seal or adhesive connection of two objects can be matched to the color of the objects.
  • Another advantage of the device is that complex, for example laminate-like packaging for flow media would react with the packaging with itself and / or the natural environment, and its structure or composition can be reduced. This may result in a cost saving in the packaging area and / or a conservation of the natural raw material resources, since the at least one second component of the first component is only supplied before the application and thus does not result in the application medium until this point in time.
  • Fig. 10 shows schematically the side view of an embodiment of the device according to the invention, which acts on a first chamber 2, here as the head of a commercial cartridge shown, is attached.
  • the device consists of Lower part 26 and upper part 25.
  • the stream of the first emerging from the cartridge 2 Flow medium is divided into two sub-streams, one of which is shown to the left in the direction of flow area 1 and the second to the right in the first Opening 11 of the second chambers 9 is directed. That in the second chamber 9 flowing medium flows against the separating element 20 and moves it further flowing up first medium. It expresses another flexible separating element 20 together, in which the second fluid medium is stored.
  • An opening of the flexible partition member 20 is with the second opening 12 second chamber 9 tightly connected, so that when compressing the flexible Separating element 20, the second fluid medium emerges from the second opening 12.
  • the other partial flow of the first flow medium flows into flow area 1, into one tubular extension 47 of the upper part 25 protrudes.
  • this tube 47 has a side opening that is channel-like Continuation of the exit 12 is aligned.
  • the outlet 46 is the merged flow media arranged.
  • the flow from here media brought together by the mixing area 40, in which a static mixer 24 is arranged, and then further to the outlet opening 16 of the device.
  • the Housing wall is made transparent in the area of the second chamber, so that a viewing window 45 results.
  • FIG. 11 and 12 are lower part 26 and upper part 25 of the housing 14, respectively shown separately.
  • a closure element here a stopper 42 shown with which the lower part 26 is such when the upper part 25 is separated closes that the unmixed media before use or at Application interruptions are kept separate and against Leakage or unwanted contact with the environment can be protected.
  • FIG. 13 shows a top view of the cut lower part 26 of the arrangement of the different components to each other.
  • the second chamber 9, the in this case has a round cross section, is arranged next to the flow area 1, which in this case has the cross section of a radially delimited ring segment.
  • a space 41 can be seen in the upper part of the figure, in which, for example, siccatives can be provided; a connection must be made to be effective be provided between this space 41 and the flow media. Clear The viewing window 45 can also be seen.
  • 14 shows the top view of the upper part 25 cut along the line V-V.
  • the merged media from the Exit opening 46 are guided into a channel-like mixing section 43, which through a Partially circular wall is formed, which is immediately adjacent to the outlet 46 Has connection with the outer wall.
  • the channel 43 can also helically over more than one level before entering the outlet 16 flows.
  • FIG. 16 shows the lower part 26 of another embodiment of the invention Device 14.
  • the essential difference to the embodiment according to FIGS. 10 and 12 is that the second opening 12 of the second chamber 9 with a channel 50th is connected, which is the second fluid medium again contrary to the general Flow direction leads back down.
  • This channel 50 shows one in the lower area Exit opening 51, which has a corresponding opening in the wall of the Flow area 1 is aligned.
  • the second fluid medium enters through the outlet opening 51 the flow area 1, it becomes in the front part of the flow area 1 in the flow direction merged with the first flow medium and through the flow area 1 after headed above.
  • Inside the flow area 1 can already Deflection / swirling elements 52 are provided, which lead to premixing lead before the merged media in the area of the exit 46 in the Enter the mixing area 40 of the upper part 25.
  • the The second can also advantageously be arranged on the pipe or separating element 47
  • Flow medium can also be led into the middle of the flow of the first flow medium can, which can be advantageous with certain consistencies of the two flow media.
  • the channel 50 is on the one hand directly radial can be led to the flow area 1 or the other 50 'radially into a room 41 ', from which a connection through the side partitions to the flow area 1 is provided.
  • the tubular extension 47 of the upper part 25 shown in FIGS. 10, 11 and 15 that protrudes into the flow area 1 is a possible formation of a Separating element through which the parts of the lower part 26 are in direct contact with the merged flow media are protected.
  • the upper part 25 can advantageously consist of two parts which are rotatable are inserted into each other and thereby allow that the inner part on the Lower part 26 is fixed in place, while the outer part of the upper part 25 is rotated is and either via a thread or a bayonet-type closure on Lower part 26 is set.
  • a deflection element 53 which consists of hollow webs 54 is formed and the inner channels of which are connected to the elements 12 and 50, 51 in which the second fluid medium is guided.
  • Deflection element (53) advantageous effect that the webs share the flow of the first fluid and the Partial streams are squeezed through the window-like segments to flow in the direction to converge again into a strand behind the deflecting element. At least at a point in the spaces between the partial strands running second fluid spreads evenly over a previous parting surface.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating Apparatus (AREA)
  • Paper (AREA)
  • Prostheses (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Multiple-Way Valves (AREA)
  • Nozzles (AREA)
  • Reciprocating Pumps (AREA)
  • Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)

Claims (36)

  1. Dispositif pour réunir au moins deux substances fluides conservées dans des chambres (2, 9) séparées, avec au moins une première chambre (2) pouvant être remplie par une première substance fluide et au moins une zone d'écoulement (1), pouvant être fixée dans la zone d'une ouverture (4) de la première chambre (2) et reliée à celle-ci, qui est conformée pour recevoir la première substance fluide sortant de la première chambre (2) en raison de l'actionnement de moyens d'extraction et pour la transporter jusqu'à une ouverture de sortie (3) de la zone d'écoulement (1),
    caractérisé en ce qu'est prévue au moins une seconde chambre (9) pouvant être remplie par une seconde substance fluide, qui présente au moins un premier élément d'ouverture (11) qui est disposé adjacent à la partie antérieure, dans la direction d'écoulement, de la zone d'écoulement (1), et par lequel elle est reliée à la zone d'écoulement (1) et/ou à la première ouverture (4) , et présente au moins un second élément d'ouverture (12), qui est disposé adjacent à la partie postérieure, dans la direction d'écoulement, de la zone d'écoulement, et par lequel elle est reliée à la zone d'écoulement (1) et/ou à l'ouverture de sortie (3).
  2. Dispositif selon la revendication 1,
    caractérisé en ce qu'un canal (50) est guidé à partir du second élément d'ouverture (12), dans la zone antérieure de la zone d'écoulement (1) et lui est relié par l'intermédiaire d'une ouverture de sortie (51).
  3. Dispositif selon la revendication 2,
    caractérisé en ce que des éléments de déflexion - de tourbillonnement (52) pour l'ensemble des substances fluides réunies sont disposés dans la zone d'écoulement (1).
  4. Dispositif selon l'une des revendications 1 à 3,
    caractérisé en ce qu'un élément de distribution (32) est disposé dans la seconde chambre (9).
  5. Dispositif selon l'une des revendications 1 à 4,
    caractérisé en ce qu'un élément de séparation (20) est disposé dans la seconde chambre (9) entre les première et seconde substances fluides.
  6. Dispositif selon la revendication 5,
    caractérisé en ce que l'élément de séparation (20) est réalisé relativement rigide, disposé mobile à l'intérieur de la chambre (9) et étanchéifié par rapport à sa paroi intérieure, et l'élément de séparation (20) présente des éléments de guidage (21) qui sont adjacents à la paroi intérieure de la seconde chambre (9) et/ou de préférence des éléments de distribution de pression (22) sur sa face tournée vers la première substance fluide.
  7. Dispositif selon la revendication 5,
    caractérisé en ce que l'élément de séparation (20) est un élément de séparation flexible expansible.
  8. Dispositif selon la revendication 7,
    caractérisé en ce que l'élément de séparation (20) flexible expansible est fixé de manière étanche à la paroi intérieure.
  9. Dispositif selon la revendication 5 ou 7,
    caractérisé en ce que l'élément de séparation est réalisé de telle manière que la seconde substance fluide peut être reçue dedans.
  10. Dispositif selon l'une des revendications précédentes,
    caractérisé en ce qu'un élément de déflexion (53), constitué au moins partiellement de traverses (54) munies de canaux internes qui s'étendent orthogonalement à la direction d'écoulement de la première substance fluide et ont au moins une ouverture, de préférence orientée centralement, à l'ubac de l'écoulement, est disposé dans la zone d'écoulement (1), les traverses (54) se croisant de telle manière qu'elles divisent la section transversale de la zone d'écoulement (1) en plusieurs ouvertures d'écoulement, analogues à des fenêtres, pour la première substance fluide et que les canaux internes sont en liaison avec des canaux (12 ; 50, 51) guidant la seconde substance fluide.
  11. Dispositif selon l'une des revendications précédentes,
    caractérisé en ce que la seconde chambre (9) présente une ouverture de remplissage (18) pour la seconde substance fluide et un obturateur (19) pour l'ouverture de remplissage (18).
  12. Dispositif selon l'une des revendications précédentes,
    caractérisé en ce que la seconde chambre (9) et la zone d'écoulement (1) sont disposées dans un boítier (14) commun de préférence à section ronde.
  13. Dispositif selon la revendication 12,
    caractérisé en ce que le boítier (14) est constitué d'une partie inférieure (26) et d'une partie supérieure (25), la partie supérieure (25) pouvant être fixée à la partie inférieure (26) et pouvant économiser l'obturateur (19).
  14. Dispositif selon la revendication 12 ou 14,
    caractérisé en ce que la seconde chambre (9) est disposée annulairement, en particulier centralement, autour de la zone d'écoulement (1) et est constituée d'une chambre ou de plusieurs chambres partielles en forme de secteurs.
  15. Dispositif selon la revendication 12 ou 13,
    caractérisé en ce que, dans le boítier (14), la seconde chambre (9) est disposée à côté de la zone d'écoulement (1).
  16. Dispositif selon la revendication 15,
    caractérisé en ce que, dans le boítier (14), la seconde chambre (9) est entourée au moins partiellement annulairement par la zone d'écoulement (1).
  17. Dispositif selon une ou plusieurs des revendications précédentes,
    caractérisé en ce que, après la réunion des première et seconde substances fluides dans la zone de l'ouverture de sortie (3), est disposée une zone de mélange qui est intégrée ou peut être fixée et qu'un dispositif mélangeur (24) est disposé dans la zone de mélange.
  18. Dispositif selon au moins l'une des revendications précédentes,
    caractérisé en ce que la délimitation entre la partie supérieure (25) et la partie inférieure (26) du boítier (14) est prévue de telle manière qu'exclusivement des parties de la partie supérieure (25) sont en contact avec les substances fluides mélangées.
  19. Dispositif selon au moins l'une des revendications précédentes,
    caractérisé en ce que les sections transversales d'écoulement sont réglables pour au moins l'une des substances fluides non mélangées.
  20. Dispositif selon au moins l'une des revendications précédentes,
    caractérisé en ce qu'un dispositif d'obturation est disposé à au moins l'une des sorties (6, 12) des substances fluides non mélangées et obture, de préférence automatiquement, la sortie (6, 12) dans le cas d'un enlèvement de la partie supérieure (25).
  21. Dispositif selon l'une des revendications précédentes,
    caractérisé en ce qu'un élément à ressort pouvant être écarté par flexion sous pression dans la direction d'écoulement de la seconde substance fluide est disposé à la sortie (12) et obture la sortie (12) à l'état non écarté par flexion.
  22. Dispositif selon au moins l'une des revendications précédentes,
    caractérisé en ce qu'au moins une saillie de paroi (27) est disposée dans la zone d'écoulement (1), avant la seconde ouverture (12) dans la direction d'écoulement, par laquelle la première substance fluide est partiellement écartée.
  23. Dispositif selon au moins l'une des revendications précédentes,
    caractérisé en ce que les parois externes du boítier (14) sont réalisées isolantes, en particulier à double paroi, et la paroi externe est au moins partiellement transparente (45) dans la zone de la chambre (9) et au moins un volume (41) est prévu dans le boítier (14) pour le logement actif de siccatifs.
  24. Dispositif selon l'une des revendications 13 à 23,
    caractérisé en ce qu'au moins une des sorties (6, 12) des substances fluides non mélangées peut être obturée lorsque la partie supérieure (25) est enlevée, en particulier par un bouchon (42).
  25. Dispositif selon l'une des revendications précédentes,
    caractérisé en ce que le dispositif mélangeur (24) est réalisé de telle manière que les substances fluides mélangées sont guidées à travers un canal (43), disposé angulairement, de préférence transversalement, à la direction d'écoulement, dans la section transversale duquel font saillie des éléments de déflexion (44), jusqu'à l'ouverture de sortie (3) et le canal (43) s'étend, depuis une sortie (46) des substances fluides réunies, disposée périphériquement, en forme de spirale et en recouvrant le plus possible au moins la surface d'un plan de la zone de mélange (40), jusqu'à l'ouverture de sortie (3) centrale.
  26. Dispositif selon une ou plusieurs des revendications précédentes,
    caractérisé en ce qu'un autre boítier, avec une zone d'écoulement et une chambre pour une autre substance fluide, est monté en forme de cascade sur l'ouverture de sortie du boítier (14) de telle manière que le mélange des première et deuxième substances fluides peut être amené dans la zone d'écoulement du boítier monté et, par l'intermédiaire d'une ouverture de liaison, également dans la chambre pour l'autre substance fluide.
  27. Procédé pour réunir au moins deux substances fluides qui, avant la réunion, sont maintenues séparées côte à côte, dans lequel l'énergie par laquelle une substance fluide est extraite de son volume de maintien produit qu'au moins une seconde substance fluide est extraite de son volume de maintien et est réunie à la première substance fluide.
  28. Procédé selon la revendication 27,
    caractérisé en ce que l'énergie par laquelle une substance fluide est extraite de son volume de maintien produit qu'une surpression est exercée sur la au moins seconde substance fluide, par laquelle la seconde substance fluide est extraite de son volume de maintien.
  29. Procédé selon la revendication 27,
    caractérisé en ce que l'énergie par laquelle une substance fluide est extraite de son volume de maintien produit qu'une dépression ou une succion est exercée sur la au moins seconde substance fluide, par laquelle la seconde substance fluide est extraite de son volume de maintien.
  30. Procédé selon l'une des revendications 27, 28 ou 29,
    caractérisé en ce que la pression à exercer sur la au moins seconde substance fluide et produite par l'énergie extrayant la première substance fluide est contrôlée de telle manière que la au moins seconde substance fluide est réunie à la première substance fluide dans une proportion prédéterminée.
  31. Procédé selon l'une des revendications 27 à 30,
    caractérisé en ce qu'au moins deux substances fluides, après la réunion et avant l'extraction d'un dispositif de réunion, sont mélangées.
  32. Procédé selon une ou plusieurs des revendications 27 à 31, pour la formation d'un cordon de matériau d'étanchéité et/ou de collage,
    caractérisé en ce que la première substance fluide est une colle/une matière d'étanchéité en tant que composant de base et la deuxième substance fluide ainsi que les plus que deuxième substances fluides sont respectivement un corps du groupe des composants catalyseurs, réticulants et colorants et au moins une deuxième substance fluide est amenée en continu au composant de base en quantité dépendant du composant de base et est mélangée à celui-ci.
  33. Procédé selon la revendication 32,
    caractérisé en ce que le composant de base est une colle/matière d'étanchéité monocomposant durcissant à l'humidité et le composant catalyseur et/ou réticulant et/ou colorant est réuni en quantité de 0,5 à 8% en poids, rapportée au composant de base.
  34. Procédé selon les revendications 32 ou 33,
    caractérisé en ce que le composant de base est choisi dans le groupe des colles/matières d'étanchéité polyuréthannes contenant des groupes isocyanates réactifs, des colles/matières d'étanchéité à base de polydiméthysilonanes, des colles/matières d'étanchéité à base de polyèthers à terminaison alcoxysilane, des colles/matières d'étanchéité contenant des groupes époxy réactifs.
  35. Procédé selon au moins l'une des revendications 32 à 34,
    caractérisé en ce que le composant catalyseur et/ou réticulant est une pâte qui contient des composés organostanniques, des amines tertiaires, de l'eau, des di- ou tri-amines organiques, des alcanolamines et/ou des polyols et que le mélange des composants est effectué par un mélangeur statique.
  36. Procédé selon au moins une des revendications 32 à 35,
    caractérisé en ce que le composant de base est appliqué à partir d'une cartouche du commerce pour colles/matières d'étanchéité avec des appareils de traitement du commerce et que les composants catalyseurs et/ou réticulants et/ou colorants sont mélangés à partir d'un adaptateur monté sur la cartouche.
EP95915747A 1994-04-09 1995-04-07 Procede et dispositif pour la confluence d'au moins deux substances fluides Expired - Lifetime EP0755300B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4412261 1994-04-09
DE4412261A DE4412261C2 (de) 1994-04-09 1994-04-09 Vorrichtung zum Zusammenführen wenigstens zweier Fließmedien
DE19507448A DE19507448A1 (de) 1994-04-09 1995-03-03 Vorrichtung zum Zusammenführen wenigstens zweier Fließmedien
DE19507448 1995-03-03
PCT/DE1995/000462 WO1995027558A1 (fr) 1994-04-09 1995-04-07 Procede et dispositif pour la confluence d'au moins deux substances fluides

Publications (2)

Publication Number Publication Date
EP0755300A1 EP0755300A1 (fr) 1997-01-29
EP0755300B1 true EP0755300B1 (fr) 1998-06-24

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EP95915747A Expired - Lifetime EP0755300B1 (fr) 1994-04-09 1995-04-07 Procede et dispositif pour la confluence d'au moins deux substances fluides

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US (1) US6079871A (fr)
EP (1) EP0755300B1 (fr)
JP (1) JP3625829B2 (fr)
KR (1) KR100297273B1 (fr)
CN (1) CN1050068C (fr)
AT (1) ATE167639T1 (fr)
CA (1) CA2187549C (fr)
CZ (1) CZ294303B6 (fr)
DE (3) DE4412261C2 (fr)
DK (1) DK0755300T3 (fr)
ES (1) ES2118591T3 (fr)
HU (1) HU219006B (fr)
PL (1) PL176626B1 (fr)
SK (1) SK280921B6 (fr)
WO (1) WO1995027558A1 (fr)

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EP2975487A1 (fr) 2014-07-17 2016-01-20 Jürgen Hoffner Dispositif destiné à doser et mélanger deux composants pouvant s'écouler

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DE19507448A1 (de) 1996-09-05
DE4412261A1 (de) 1995-10-26
HU9602761D0 (en) 1996-12-30
JP3625829B2 (ja) 2005-03-02
DE59502653D1 (de) 1998-07-30
CN1147212A (zh) 1997-04-09
SK128196A3 (en) 1997-04-09
HUT76023A (en) 1997-06-30
CN1050068C (zh) 2000-03-08
DE4412261C2 (de) 1996-10-17
MX9604677A (es) 1997-11-29
ES2118591T3 (es) 1998-09-16
DK0755300T3 (da) 1999-04-06
WO1995027558A1 (fr) 1995-10-19
JPH09511442A (ja) 1997-11-18
ATE167639T1 (de) 1998-07-15
CA2187549A1 (fr) 1995-10-19
HU219006B (hu) 2001-01-29
CZ294303B6 (cs) 2004-11-10
SK280921B6 (sk) 2000-09-12
PL176626B1 (pl) 1999-07-30
PL316729A1 (en) 1997-02-03
CZ295196A3 (en) 1997-03-12
KR100297273B1 (ko) 2001-09-03
KR970702098A (ko) 1997-05-13
US6079871A (en) 2000-06-27
EP0755300A1 (fr) 1997-01-29
CA2187549C (fr) 2005-10-11

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