EP3823759A1 - Dispositif de thermorégulation pour récipients de laboratoire - Google Patents

Dispositif de thermorégulation pour récipients de laboratoire

Info

Publication number
EP3823759A1
EP3823759A1 EP19742177.9A EP19742177A EP3823759A1 EP 3823759 A1 EP3823759 A1 EP 3823759A1 EP 19742177 A EP19742177 A EP 19742177A EP 3823759 A1 EP3823759 A1 EP 3823759A1
Authority
EP
European Patent Office
Prior art keywords
temperature control
receiving area
absorber element
housing
laboratory vessels
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.)
Granted
Application number
EP19742177.9A
Other languages
German (de)
English (en)
Other versions
EP3823759B1 (fr
Inventor
Steffen Gehrig
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.)
Brand GmbH and Co KG
Original Assignee
Brand GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE102018005582.6A external-priority patent/DE102018005582A1/de
Priority claimed from DE102018008152.5A external-priority patent/DE102018008152A1/de
Application filed by Brand GmbH and Co KG filed Critical Brand GmbH and Co KG
Publication of EP3823759A1 publication Critical patent/EP3823759A1/fr
Application granted granted Critical
Publication of EP3823759B1 publication Critical patent/EP3823759B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L7/00—Heating or cooling apparatus; Heat insulating devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L9/00—Supporting devices; Holding devices
    • B01L9/06—Test-tube stands; Test-tube holders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/14—Details; Accessories therefor
    • A61J1/16—Holders for containers
    • A61J1/165—Cooled holders, e.g. for medications, insulin, blood, plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00—Additional constructional details
    • B01L2300/12—Specific details about materials
    • B01L2300/123—Flexible; Elastomeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00—Additional constructional details
    • B01L2300/18—Means for temperature control
    • B01L2300/1855—Means for temperature control using phase changes in a medium

Definitions

  • the invention relates to a temperature control device for holding laboratory vessels around the contents of the laboratory vessels over a longer period of time
  • Patent publication WO92 / 12071A1 shows a storage and transport device for thermally sensitive products.
  • a container carrier of the device has recesses for glass ampoules with the substances contained and to be protected.
  • the container carrier is made of thermoplastic material and forms a closed space around the depressions and around a hollow, circumferential edge region projecting over the depressions. Inside the closed room up to the height of the
  • Temperature control medium which has a large heat of fusion. Water or gel materials can be used as the temperature control medium.
  • the hollow edge area serves to expand the phase change executing
  • a disadvantage of this device is that when this device is thermally conditioned, the temperature control medium on the outside of the hollow space begins the phase change and the volume expansion occurs most strongly in the area in which the phase change takes place last. Since the hollow space filled with air only occupies the edge area, deformation occurs in the center of the container carrier, the depressions no longer being at the same height as the standing surface of the container carrier. Only with the opposite
  • Phase change is the geometric determination again.
  • predetermined temperature over a required period of time is not in everyone
  • EP2428273A1 discloses a temperature control device for sample vessels in a non-self-sufficient design.
  • This temperature control device has two temperature control zones that are insulated from one another and that heats and cools the sample vessels in sections. In the first temperature control zone, a heating element is used and in the second temperature control zone, a flow-through
  • Heat transfer medium set the desired temperature. This temperature control device therefore requires the connection of electrical and thermal energy and is complex in structure and the number of functional elements.
  • the invention has for its object to provide a temperature control device for receiving laboratory vessels of the type mentioned, which keeps the content of the laboratory vessels over the largest possible area of the recording and without supply or withdrawal of thermal energy over a longer period of time at a predetermined temperature and functional is improved by their dimension, which can be influenced thermally, and is less expensive to produce.
  • a temperature control device for receiving laboratory vessels is provided with a hollow one with an inner area and one
  • the temperature control device is thermally conditioned before use without laboratory vessels. During its use, the temperature control device takes the conditioned thermal energy in a finite time course, i.e. Warmth, either from the
  • the housing has a bottom at the bottom and a receiving region on the opposite side, which delimits the hollow inner region of the housing from above. Indentations on the top of the receiving area serve as receptacles for the laboratory vessels to be tempered.
  • the hollow housing preferably has, in addition to the inner region receiving the temperature control medium, a separate air space.
  • the interior can have a separation that the
  • Component such as a partition
  • the interior of the housing is only filled with the temperature control medium and with air, the air contained ultimately forming the air space in the sense of the invention.
  • an interface is formed between the temperature control medium and the air space.
  • An absorber element is arranged in the inner region of the hollow housing, which extends horizontally in the inner region and around which and / or through which the temperature control medium flows.
  • the absorber element is thermally conductively connected to the receiving area. The laboratory vessels inserted into the wells in the receiving area are thus passed through the temperature control medium kept at a constant temperature for a longer period of time.
  • Absorber element is designed in particular as a plate.
  • a material or a component is regarded as "thermally conductive” if its thermal conductivity is at least 5 W / (m K) on average.
  • the heat of fusion of the temperature control medium is absorbed by the absorber element and transported evenly to the receiving area.
  • the absorber element that extends horizontally in the temperature control medium enables the thermal energy of the mass of the temperature control medium to be fully used. Even when the temperature control device is thermally conditioned, the absorber element accelerates the heat transfer from the environment via the
  • a “horizontal” extension relates to the orientation of the temperature control device in the state of use and means that the absorber element is at least essentially transverse to the effect of the
  • Gravity stretches.
  • this also includes such an arrangement in which the absorber element does not run parallel to the floor.
  • the interior of the housing is parallel to the footprint, i.e. to the floor, separated.
  • the air space can advantageously be arranged opposite the receiving area, with the
  • Receiving area adjacent part of the inner area receives or contains the temperature control medium. This enables direct contact and heat exchange of the temperature control medium with the absorber element and the receiving area.
  • a partition is arranged between the inner regions of the housing. The partition seals the two
  • the partition allows the volume of the temperature control medium to be changed in a dimensionally stable manner Casing.
  • the flexibility of the partition is achieved through the use of a resilient material, such as silicone. With the elasticity of the partition, the direct contact of the temperature control medium with the
  • a material or component is "flexible" in the sense of the invention if it has sufficient elasticity to return to its original shape after being deformed by the forces which act on the material or component during the phase change due to a change in volume of the temperature control medium.
  • a particularly suitable flat component such as a partition, can have a spring rate of less than 5 N / mm per mm 2.
  • the area normalization refers to the area of the component on which a corresponding pressure is exerted.
  • the temperature control device can be used for cooling or keeping warm.
  • the housing with the temperature control medium is heated or cooled, preferably the temperature control medium
  • the temperature control medium has a lower or higher density in the solid phase than in its liquid phase. When changing the phase from the outside, this leaves some fluid again
  • Tempering medium float or sink the still solid tempering medium. Due to the different densities, this solid temperature control medium pushes against the absorber element. In a special way, the thermal energy of the receiving area with the laboratory vessels used is caused by the contact of the solid temperature medium with the absorber element, its thermally conductive connection to the receiving area and the
  • Transfer of heat changed The heat is transferred from the Absorber element to the receiving area, then the thermal energy of the receiving area is increased and the laboratory vessels are heated. If the heat is transferred from the receiving area to the absorber element, then the thermal energy of the receiving area is reduced and the laboratory vessels are cooled.
  • the heat transfer from or to the receiving area takes place evenly and sufficiently.
  • Temperature control medium can be used over a long period of time and a certain temperature of the laboratory vessels, essentially defined by the physical property of the temperature control medium, can be maintained. In the previous conditioning, the phase change from liquid to solid takes place simultaneously on the almost complete surface of the absorber element in the temperature control medium, and not only in the center of the recording area.
  • the absorber element is arranged at a spatial distance from the receiving area.
  • the absorber element can be designed as a plate and the absorber element can be connected to the receiving area by means of one or more thermally conductive spacer elements.
  • Housing is designed as a separate part. This enables a reduced heat dissipation of the housing or advantageously enables the receiving area to be made of a material with a higher thermal conductivity of at least 100 W / (m K).
  • Aluminum is a dimensionally stable and extremely easy to machine, cost-effective material.
  • the other parts of the hollow housing can consist of a material with a significantly lower thermal conductivity of maximum 1 W / (m K) and can be made of plastic.
  • the air space above the temperature control medium serves to equalize the volume and limits the pressure build-up to the housing and the receiving area.
  • Temperature control device protrudes the absorber element with its underside towards the bottom or as a plate into the temperature control medium.
  • the absorber element can be deformed flexibly or elastically towards the receiving area.
  • the absorber element preferably has an area-related spring rate of less than 1 N / mm per mm 2 area of the underside of the absorber element or is held such that a spring rate of less than 1 N / mm per mm 2 area of the underside of the absorber element results.
  • the absorber element is either designed as a plate or, as an alternative embodiment, a structured, elastic molded body, the plate or the molded body preferably also being provided on the receiving area
  • Temperature control devices are not damaged during a phase change and allow the volume of the temperature control medium to be changed even in the solid state without loss of their function or deformation of the housing. Further preferred configurations of the invention
  • Fig. 1 shows a temperature control device according to the invention in a sectional view.
  • Fig. 2 shows the temperature control device of Fig. 1 in a preferred
  • FIG. 3 shows a detailed view of the temperature control device from FIG. 1 in an alternative preferred embodiment.
  • FIG. 4 shows a detailed view of the temperature control device from FIG. 1 in an alternative preferred embodiment.
  • Fig. 5 shows a diagram of temperature profiles on the
  • the temperature control device 1 shows a temperature control device 1 according to the invention for receiving laboratory vessels 2.
  • the temperature control device 1 is thermally conditioned before use, that is to say without the laboratory vessels 2, and for this purpose in a cooling or
  • Temperature control device 1 in a finite temporal course either the conditioned thermal energy from the laboratory vessels 2 and the environment or releases it.
  • the temperature control device 1 shown in FIGS. 1 and 2 consists of a hollow housing 3 which is at least partially filled with a temperature control medium 4 in the interior of the housing 3.
  • the housing 3 is used in the laboratory as a stand-alone device and, in the state of use, has a receiving area 3.1 at the bottom or at the bottom, a bottom 3.2 and opposite at the top or at the top, which delimits the hollow interior of the housing 3 at the top.
  • On the receiving area 3.1 from above in the direction of the bottom 3.2 and inward-facing depressions 5 are formed which serve as receptacles for the laboratory vessels 2 to be tempered.
  • the floor 3.2 can be in SBS format (Society of Biomolecular Screening) dimensioned and the number of wells 5 arranged in the grid of the SBS standard 12 x 8, 24 x 16, etc.
  • the temperature control device 1 can stand on the floor 3.2 or on the
  • a temperature control device 1 is shown, which represents an embodiment.
  • the receiving area 3.1 can, however, be arranged on the housing 3 in a manner detachable, in particular from above, contrary to the representations.
  • the housing 3 can cover the spaces around the recesses 5 as shown.
  • this part can be made separately from the housing 3.
  • the receiving area 3.1 can be arranged detachably from above on the housing 3, contrary to what is shown.
  • FIG. 2 shows the temperature control device 1 according to the invention with the hollow housing 3, which is one of the temperature medium 4 receiving or
  • the containing the inner region has separated air space 6.
  • the separation of the inner area runs at least essentially parallel to the floor 3.2, which serves in particular as a standing area.
  • the air space 6 is arranged opposite the receiving area 3.1 and represents part of the inner area.
  • the remaining part of the inner area adjacent to the receiving area 3.1 receives the temperature control medium 4.
  • heat transfer between the temperature control medium 4 and the receiving area 3.1 also takes place directly.
  • a partition 3.3 is arranged between the hollow inner regions or the standing surface, ie the floor 3.2, and the housing 3, which seals the two inner regions against one another and is designed to be flexible.
  • the partition 3.3 can also be arranged between other parts of the housing 3. 1 and 2, in which the standing surface or the floor 3.2 has a part of the hollow inner area, is an advantageous embodiment in this regard.
  • the standing surface or the floor 3.2 has a bore 3.4 which aerates and / or vents the air space 6.
  • the air space 6 is sealed and its change in pressure can be used to force the temperature control medium 4 against the receiving area 3.1.
  • the temperature control medium 4 at least substantially completely fills the inner region of the housing 3 adjacent to the receiving region 3.1, which is desirable in practice, but mostly only
  • the temperature control medium 4 direct contact between the temperature control medium 4 and the receiving area 3.1. It is therefore preferable to fill the inner area adjacent to the receiving area 3.1 as much as possible with tempering medium 4.
  • the part of the inner area bordering the receiving area 3.1 is therefore preferably predominantly filled with tempering medium 4.
  • the volume of the temperature control medium contained in the part of the interior area bordering the receiving area 3.1 is greater than the volume of the air contained therein.
  • the temperature control device 1 has an absorber element 7 in the hollow housing 3, which is designed as a plate and extends horizontally in the housing 3.
  • the absorber element 7 is to the receiving area 3.1 and
  • Temperature medium 4 is at least partially flowed around, that is, has contact with the temperature-controlled temperature medium 4 and / or is immersed therein.
  • the absorber element 7 can have one or more openings 7.1, which allow air bubbles to flow through and, depending on the dimensions of the openings 7.1 and the viscosity of the temperature control medium 4, to allow the temperature control medium 4 to flow through the absorber element 7 at least partially.
  • the absorber element 7 is thermally conductively connected to the receiving area 3.1 for the transfer of thermal energy and thus transfers the
  • the temperature control device 1 is exposed to the desired temperature for a sufficiently long time before it is used.
  • the housing with the temperature control medium 4 of the temperature control device 1 is heated or cooled, depending on the required temperature window of the substances in the laboratory vessels 2.
  • the temperature control medium 4 used in the housing 3 changes its physical state when heated or cooled. When it cools down, it freezes
  • Temperature control medium 4 melts when heated.
  • the energy of the phase transition (for example in the case of water: 333.4 KJ / Kg at 0 ° C) is used effectively.
  • a gel material in particular an aqueous carboxymethyl cellulose gel
  • Temperature control medium 4 uses a mixture of cyclodextrin and 4-methylpyridine.
  • a polymer solution consisting of several soluble substances with different phase temperatures and a concentration-dependent mixture gap, such as a phenol / water mixture, can also be used.
  • the temperature control device 1 according to FIGS. 1 and 2 is alternatively used for heating laboratory vessels 2 between 30 ° C. and 45 ° C.
  • the housing 3 is filled with the mixture of cyclodextrin and 4-methylpyridine already mentioned.
  • the temperature control device 1 is conditioned at approximately 50 ° C. or higher.
  • the absorber element 7 extends over a larger extent in the inner region of the housing 3.
  • the temperature control device 1 shown in FIGS. 1 and 2 is specially designed for temperature control medium 4, which has a lower density in its solid phase than its liquid phase.
  • a temperature control medium 4 which is already partially liquid again during melting, floats in the still partially solid state and urges against the absorber element 7.
  • the temperature control medium 4 which is still solid also urges against the receiving area 3.1.
  • the tempering medium 4 melts over a large area. That tempered
  • Absorber element 7 supplies the heat from the receiving area 3.1 with the laboratory vessels 2 used to the tempering medium 4 and increases its thermal energy or vice versa.
  • Laboratory vessels 2 can be cooled or heated over a long period of time.
  • FIG. 1 shows how effective the embodiment according to the invention according to FIG. 1 or 2 is compared to an embodiment without an absorber element 7, with the respective course of a water-cooled housing 3 of both embodiments, measured in the recesses 5 thereof.
  • the temperature curve "A" corresponds to that
  • FIG. 2 shows the temperature control device 1 according to the invention with the housing 3, which has an air space 6 which is separated from the inner region.
  • the separation of the interior is at least essentially parallel to the floor 3.2.
  • the embodiment according to FIG. 2 shows not only design improvements. Advantages are also surprisingly expressed in the effect and in the resulting temperature profile “B”.
  • the flexible partition 3.3 enables the spatial division of the temperature control medium 4 and air space 6 and the compensation of changes in volume of the temperature control medium 4 into or from the air space 6.
  • the partition 3.3 is made of a flexible, i.e. resilient, material,
  • the increase in volume of the solid or frozen tempering medium 4 is made possible by the expansion of the partition 3.3 into the air space 6 by prestressing.
  • the solid temperature control medium 4 is pressed against the absorber element 7.
  • the heat transfer is increased by pressing and the temperature profile “B” is kept below the temperature limit for an even longer time. This effect lasts even longer if the partition 3.3 also has a low thermal conductivity.
  • Fig. 2 shows an embodiment with a plate as the absorber element 7, which is arranged horizontally in the hollow housing 3.
  • the plate is in this
  • the spacer elements 8 also connect the plate 7 with the
  • Temperature of the tempering medium 4 is transferred to the laboratory vessels 2.
  • the materials used are also decisive in the embodiment according to the invention according to FIG. 1 or 2.
  • Spacer elements 8 and / or the receiving area 3.1 consist in particular of a material with a thermal conductivity of at least 10 W / (m K).
  • the receiving area 3.1 of the housing 3 is designed as a separate part. The materially separated from the housing 3
  • Recording area 3.1 consists of a material with a thermal conductivity of at least 100 W / (m K). Aluminum in particular is used as a suitable material.
  • the other parts of the hollow housing 3 can consist of plastic or have a plastic and preferably have one
  • the housing 3 can be constructed even more discretely. 1 and 2, the housing 3 is provided with a separate base 3.2, which represents the standing area in relation to the receiving area 3.1.
  • Receiving area 3.1 are sealed with seals 3.5 against the housing 3. As shown in Fig. 2, projecting feet 3.6 are arranged on the floor.
  • the absorber element 7 is designed to be flexible with its absorber underside directed towards the bottom 3.2 towards the receiving area 3.1.
  • the increase in volume of the temperature control medium 4 is tolerated by the absorber element 7.
  • the absorber element 7 is a structured elastic molded body 7 ', as shown in FIG. 3.
  • This flat shaped body 7 ' preferably has sufficient flexibility with a spring rate of less than 1 N / mm per mm 2 surface of the underside of the shaped body 7' in order to prevent deformation of the housing 3.
  • the molded body 7 'shown in Fig. 3 is a layer of metal mesh or foam.
  • the molded body 7 ' is arranged on the underside of the receiving area 3.1.
  • Such a mesh or foam serves as an absorber for receiving and at the same time for transporting the thermal energy to the receiving area 3.1.
  • the braid or foam is also positioned so that it is below the
  • Receiving area 3.1 extends through the air space 6 and is at least partially surrounded by the temperature control medium 4 and thereby penetrated as completely as possible.
  • the structure itself enables the required flexibility and the choice of the material and the cross-sectional density sufficient heat conduction to the receiving area 3.1.
  • the braid or the foam can also only serve as flexibly resilient spacing elements 8 ′ of the plate.
  • Spacer 8 resiliently resiliently the plate in relation to the receiving area 3.1.
  • the plate is at least partially surrounded by the tempering medium 4.
  • the absorber element 7 is located on the receiving area 3.1
  • the absorber element 7 is connected to the underside of the receiving area 3.1 several times, e.g. welded with ultrasound. 1 or 2, the spacer elements 8 are integrally formed on the receiving area 3.1 and / or on the plate, so that good heat conduction takes place. 4 shows an embodiment of a flexible spacer element 8 '.
  • Spacer 8 ' is part of the plate.
  • spacer 8 not shown expose the spacer 8 'and allow a meandering bend, as shown in Fig. 4.
  • the free end of the spacer element 8 'bent in this way is welded in particular to the receiving area 3.1.
  • the spacer elements 8 can be screwed on releasably be, i.e. non-positively / positively / frictionally held or permanently attached such as welded, soldered, bonded, glued, or otherwise materially connected.

Landscapes

  • Health & Medical Sciences (AREA)
  • Clinical Laboratory Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Automatic Analysis And Handling Materials Therefor (AREA)
  • Control Of Temperature (AREA)

Abstract

L'invention concerne un dispositif de thermorégulation destiné à recevoir des récipients de laboratoire qui comporte un boîtier creux rempli d'un milieu de thermorégulation. Le dispositif de thermorégulation est conditionné thermiquement avant emploi et, en cours d'utilisation, l'énergie thermique conditionnée est soit absorbée par les récipients de laboratoire soit restituée par lesdits récipients de laboratoire dans un déroulement final dans le temps. Le boîtier présente en bas un fond et une zone de réception située à l'opposé, en haut, ladite zone de réception délimitant la zone intérieure creuse du boîtier. Des évidements dirigés vers l'intérieur sur la zone de réception font office de cavités de réception pour les récipients de laboratoire à thermoréguler. Un espace rempli d'air, séparé de la zone intérieure, se trouve dans le boîtier creux. Un élément absorbant s'étendant horizontalement dans la zone intérieure est entouré et/ou parcouru au moins partiellement par le milieu de thermorégulation et est relié de manière thermoconductrice à la zone de réception. Les récipients de laboratoire insérés dans les évidements de la zone de réception sont ainsi maintenus à une température constante sur une plus longue période par le milieu de thermorégulation.
EP19742177.9A 2018-07-16 2019-07-16 Dispositif de thermorégulation pour récipients de laboratoire Active EP3823759B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102018005582.6A DE102018005582A1 (de) 2018-07-16 2018-07-16 Temperiervorrichtung für Laborgefäße
DE102018008152.5A DE102018008152A1 (de) 2018-10-16 2018-10-16 Temperiervorrichtung für Laborgefäße
PCT/EP2019/069105 WO2020016219A1 (fr) 2018-07-16 2019-07-16 Dispositif de thermorégulation pour récipients de laboratoire

Publications (2)

Publication Number Publication Date
EP3823759A1 true EP3823759A1 (fr) 2021-05-26
EP3823759B1 EP3823759B1 (fr) 2022-03-23

Family

ID=67383761

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19742177.9A Active EP3823759B1 (fr) 2018-07-16 2019-07-16 Dispositif de thermorégulation pour récipients de laboratoire

Country Status (4)

Country Link
US (1) US12005455B2 (fr)
EP (1) EP3823759B1 (fr)
CN (1) CN112368080A (fr)
WO (1) WO2020016219A1 (fr)

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CN112368080A (zh) 2021-02-12
EP3823759B1 (fr) 2022-03-23
US12005455B2 (en) 2024-06-11
WO2020016219A1 (fr) 2020-01-23

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