Method and device for marking a container containing a medicinal substance

Abstract

The invention relates to a method for marking a container (10) comprising a bottle (12) containing a medicinal substance and closed by a stopper (14) secured to the bottle (12) by a ring (16), the container (10) being at least partially covered with frost, the method comprising a step of laser-marking the ring (16) through the frost. The invention also relates to a device for marking a container.

Description

[0001] Method and device for marking a container containing a medicinal substance

[0002] Technical field

[0003] The present invention relates to a method and a device for marking a container containing a medicinal substance.

[0004] Prior art

[0005] Sometimes medicinal substances (such as vaccines) or other biological substances (such as cells) are stored in containers (such as vials) at very low temperatures. Certain information must be displayed on these containers, but the problem of marking the information arises when these containers are covered with frost. When the containers are removed from the storage enclosure at very low temperatures, frost appears on the containers.

[0006] To this end, document WO2016069984 proposes applying a label to the container before storage at low temperature. The label is then laser marked in an enclosure at storage conditions so that there is no formation of frost. Document US20080178988 proposes applying a marked and preheated label to the frozen container.

[0007] The disadvantage of the processes in these documents is that the glue used to attach the label may migrate into the containers and thus risk damaging the substance contained in the container. In addition, if the label is applied to the bottle before storage at low temperatures, the glue must have cold-resistant qualities. This can generate high costs. Finally, these processes require complex devices for marking the containers, for marking in an enclosure under storage conditions or for preheating the label. These processes are therefore complex.

[0008] Generally, there is therefore a need for a simpler method and device for marking pharmaceutical containers intended to be extracted from a very low temperature storage enclosure. There is therefore a need for a simpler method and device for marking pharmaceutical containers covered with frost.

[0009] Statement of the invention

[0010] To this end, the invention proposes a method for marking a container comprising a bottle containing a medicinal substance and closed by a stopper secured to the bottle by a ring, the container being at least partially covered with frost. The method comprises a step of laser marking the ring through the frost.

[0011] Alternatively, the medicinal substance consists of cells.

[0012] According to one variant, at least one operating parameter of the laser is chosen from the group comprising:

[0013] • A wavelength between 510 nm and 1200 nm, preferably between 1000 nm and 1100 nm, preferably 1064 nm;

[0014] • A power of less than 20W, preferably less than 10W, preferably less than 4W, preferably less than 3W, preferably less than 2W;

[0015] • A marking speed between 4 and 100 mm 2 per second, preferably between 20 and 80 mm 2 per second;

[0016] • A laser pulse duration between 1 and 350 ns nanoseconds, preferably between 4 and 100 ns;

[0017] • A repetition rate between 2 and 4000 kHz and preferably between 50 and 200 kHz;

[0018] • An intensity of 1 mJ per pulse, preferably between 10 and 10OpJ.

[0019] Alternatively, the laser is a fiber laser.

[0020] According to one variant, the marking of the ring is carried out in at least two passes of the laser on the ring, preferably three passes, preferably four passes.

[0021] According to one variant, the ring surrounds the cap and comprises a collar on which the laser marking step is carried out. According to one variant, the ring surrounds the cap leaving an uncovered portion of the upper face of the cap for access to the interior of the container by a needle through the cap, the container further comprising a partially or totally removable capsule which covers the uncovered portion of the upper face of the cap and which is outside the marking area of ​​the ring.

[0022] According to one variant, the cap is made of thermoplastic material.

[0023] Alternatively, the bottle is made of polymer, preferably cyclic olefin copolymer or cyclic olefin polymer.

[0024] Alternatively, prior to the marking step, the container was stored at -80°C or below.

[0025] Alternatively, the marking is chosen from the group of data comprising an expiry date, an individual code, a batch number, an anti-fraud code, a normative code, or a combination of these data.

[0026] Alternatively, the marking is included in a decorative element of the container.

[0027] According to a variant, the marking includes container identification data, part of the bits of the identification data define the position of an invisible anti-fraud code produced by the same process.

[0028] Alternatively, during marking, the container is stationary and the laser is mobile.

[0029] Alternatively, the marking includes a 12x12 or 14x14 code on a 2mm x 2mm area or a 10x24 code on a 2mm x 4mm area.

[0030] Alternatively, the marking is repeated over at least part of the circumference of the ring.

[0031] The invention also relates to a device for marking a container comprising a bottle containing a medicinal substance and closed by a stopper secured to the bottle by a ring, the container being at least partially covered with frost, the device comprising a laser capable of marking the ring through the frost. The device is capable of implementing the method.

[0032] According to one variant, at least one operating parameter of the laser is chosen from the group comprising • A wavelength between 510 nm and 1200 nm, preferably between 1000 nm and 1100 nm, preferably 1064 nm;

[0033] • A power of less than 20W, preferably less than 10W, preferably less than 4W, preferably less than 3W, preferably less than 2W;

[0034] • A marking speed between 4 and 100 mm 2 per second, preferably between 20 and 80 mm 2 per second;

[0035] • A laser pulse duration between 1 and 350 ns nanoseconds, preferably between 4 and 100 ns;

[0036] • A repetition rate between 2 and 4000 kHz and preferably between 50 and 200 kHz;

[0037] • An intensity of 1 mJ per pulse, preferably between 10 and 1 OOpJ.

[0038] Alternatively, the laser is a fiber laser.

[0039] Alternatively, during marking, the container is stationary and the laser is mobile.

[0040] The use in this document of the verb "to understand", its variants, as well as its conjugations, cannot in any way exclude the presence of elements other than those mentioned. The use in this document of the indefinite article "un", "une", or of the definite article "le", "la" or "I'", to introduce an element does not exclude the presence of a plurality of these elements.

[0041] The terms "first", "second", "third", etc. are used in this document exclusively to differentiate between different elements, without implying any order between these elements.

[0042] All of the preferred embodiments and all of the advantages of the method according to the invention are transposed mutatis mutandis to the present device and vice versa. The different embodiments can be considered alone or in combination. Brief description of the figures

[0043] Other characteristics and advantages of the present invention will appear on reading the detailed description which follows, for the understanding of which reference will be made to the appended figures which show:

[0044] - figure 1, a schematic view of an embodiment of a container on which the method can be applied;

[0045] - figure 2, a sectional view of a container according to figure 1, in an assembled configuration; figure 3, a view of a container with a marking according to the method.

[0046] The drawings of the figures are not to scale. Like elements are generally denoted by like references in the figures. For the purposes of this document, identical or similar elements may bear the same references. Furthermore, the presence of reference numbers or letters in the drawings cannot be considered as limiting, including when these numbers or letters are indicated in the claims.

[0047] Detailed description of embodiments of the invention

[0048] The invention relates to a method for marking a container comprising a bottle containing a medicinal substance and closed by a cap secured to the bottle by a ring. The container is at least partially covered with frost. The method comprises a step of laser marking the ring through the frost. This allows for simple marking. The method also allows for marking without risk of contamination of the substance contained in the bottle.

[0049] Figure 1 illustrates an embodiment of a container 10 given as an example for carrying out the marking according to the method of the invention. The container 10 may comprise a bottle 12 capable of receiving the medicinal substance. A stopper 14 closes the bottle 12 at the neck 18 of the bottle 12. The container 10 further comprises a ring 16 securing the stopper 14 to the bottle 12.

[0050] The substance may be a medicinal or pharmaceutical substance. The use in this document of the expression "medicinal substance" or "pharmaceutical substance" covers both any type of drug, whether chemical or biological, as well as any other biological substances requiring low-temperature storage, such as cells for example. The substance is preferably fluid, liquid. The substance may be intended to be injected, in particular with a syringe. The substance may be injected into the patient at one time. The container 10 is capable of receiving a predefined quantity of medicinal substance. Preferably, the container 10 can receive a single dose. The quantity of substance then corresponds to what is intended to be administered at one time into the patient.

[0051] The container 10 is intended to be stored for an indefinite period in an environment at -80°C or lower. This allows a substance to be preserved for a long time by rendering it inert. The bottle 12 is made of a material compatible with the substance and capable of withstanding low temperatures as indicated above. The material may thus be a polymer, for example cyclic olefin copolymer (or COC) or cyclic olefin polymer which are amorphous polymers. The material used is not glass because it is not suitable for storage at temperatures such that frost may appear upon removal from storage, in particular at the temperatures mentioned above. The volume of the bottle is for example between 0.2 and 100 ml.For small volumes, the container can be provided with a base 36 fixed to the base of the bottle 12; this allows the container to be kept upright, even though the small diameter bottle 12 may tip over under the weight of the stopper and the ring.

[0052] Figure 2 shows the container 10 of Figure 1 in the assembled configuration. The cap 14 allows the bottle 12 to be sealed; the medicinal substance cannot flow out of the bottle 12 when handling the container 10. The cap 14 can be fixed by a screw thread to the bottle 12; preferably, the cap 14 is inserted by translation into the neck 18 of the bottle 12. The outer wall 20 of the cap collaborates with the inner wall 22 of the bottle and the ring 16 to ensure the sealing of the container 10.

[0053] The stopper 14 is a material resistant to the low temperatures mentioned above. Access to the interior of the container can be made by removing the stopper; preferably, access to the interior of the container is made through the stopper 14. For this, the stopper 14 can be pierced by an upper face 24 by a needle in order to introduce the medicinal substance into the bottle 12 and / or remove the medicinal substance from the bottle 12. The material of the stopper 14 can preferably be resealed after being pierced by the needle - in particular after introduction of the medicinal substance by the needle through the stopper. The material chosen can combine elastic properties - useful for sealing the container - and thermoplastic properties - useful for resealing after piercing by a needle. Such a material can be an elastomer, such as thermoplastic elastomer (TPE).

[0054] The ring 16 allows the cap 14 to be secured to the bottle 12 and ensures that the cap 14 is held in place and that the seal between the bottle 12 and the cap 14 is sealed. The ring is a separate element from the bottle and the cap. The ring is an element of the container, which is attached to the bottle and the cap. The ring 16 prevents the cap 14 from being accidentally removed and ensures the integrity of the container. The ring 16 surrounds the cap 14 to hold it in place in the neck of the bottle 12. The ring 16 surrounds the bottle 12 (to ensure that the cap 14 is held in the bottle 12). The ring 16 can be assembled by screwing to the bottle 12; preferably, the ring 16 is assembled by clipping (or by elastic fitting) to the bottle 12. The ring 16 may have an opening 26 so as to surround the stopper 14 while leaving an uncovered part of the upper face 24 of the stopper 14 for access to the interior of the container by a needle through the stopper.The ring 16 therefore allows the closure of the stopper 14 while allowing the substance to be injected into the container or removed using a needle piercing the stopper 14. The material of the ring 16 is able to withstand the temperatures mentioned above. The material is chosen to have good shock resistance, be relatively rigid, light and able to be molded. The material of the ring is for example a thermoplastic polymer such as acrylonitrile butadiene styrene (ABS). Advantageously, the ring 16 is irremovable, in the sense that its removal causes its deterioration. The ring 16 is not reusable. This is a means contributing to ensuring the integrity of the container. The container 10 comprising the medicinal substance in the bottle 12 can be stored for an indefinite period at temperatures of -80°C or less.When the container 10 is placed in storage, certain information useful for the subsequent use of the medicinal substance is not yet known. For example, the expiration date of the substance inside the container 10 may not be known because it depends on the date of removal of the container from low-temperature storage. Thus, when the substance contained in the container 10 is to be used, the problem arises of providing information on the container useful for the subsequent use of the medicinal substance. More generally still, the problem arises of indicating information on a container containing a medicinal substance, the container being removed from a low-temperature storage enclosure, in particular at temperatures of -80°C or less.Label solutions with glue, ink marking (e.g. ink printing) or even marking within the storage enclosure are not suitable for the reasons given elsewhere.

[0055] The invention proposes a simple marking solution. Thus, when the substance contained in the container 10 is to be used, the container is removed from the storage enclosure and the marking of the container 10 can be carried out even though frost at least partially covers the container 10. The method according to the invention allows the marking of the container even though frost appears on the container upon leaving the storage enclosure. The method does not seek to prevent the appearance of frost, but allows marking even when frost appears. For this, the method allows simple marking. The method simplifies the process of removing the containers from the storage enclosure. The method comprises in particular a step of laser marking the ring 16 through the frost.This firstly avoids the use of a label to be stuck beforehand on the bottle, and therefore avoids the use of glue which must withstand the low temperatures mentioned and which risks migrating towards the substance and contaminating it. The laser avoids harming the substance. Laser marking is simple and fast; the container remains cold and there is no waiting period for drying as with ink marking for example. In addition, the marking is very localized. Due to the marking with the use of the laser, contact with the container weakened by low temperatures is avoided. In addition, the advantage of marking on the ring is that there is no contact with the bottle itself which contains the medicinal substance. The ring 12 is a separate element from the bottle. The ring 12 is an element attached to the bottle. Thus, the marking taking place on the ring 12, the marking is at a distance from the bottle itself. The marking is not on the bottle itself.There is no contact between the marking and the bottle. This avoids the risk of heat transfer and / or degradation of the bottle and avoids damaging the substance. Since the ring 12 is around the bottle when it is opened (the ring surrounds the bottle when it is opened), the marking is at a distance from the bottle itself, which avoids heat transfer and contamination of the bottle and the substance. The absence of contact with the bottle (by marking on the ring and by using the laser) is also preferable to avoid any potential contamination of the medicinal substance present in the container being marked; this preserves the integrity of the medicinal substance. Furthermore, marking through the frost simplifies the marking because it avoids a preliminary step of removing the frost and / or planning the marking in the storage enclosure (or at least, in the storage conditions) to avoid the appearance of frost.In this sense, the invention goes against any prejudice of marking despite the presence of frost, and in particular the use of the laser through frost.

[0056] The laser is a nanosecond laser. A nanosecond laser is a pulsed laser, emitting very short pulses of light. Each pulse can have a very short duration, for example of the order of 1 to 350 nanoseconds (1 ns = 10 -9s) and preferably between 4 ns and 100 ns. The advantage of these pulse durations is that there is little thermal effect due to the use of the laser and therefore the container is not damaged and the marking is more precise. This reduces the risk of affecting the substance. In addition, using such a pulse duration for marking through frost allows limited energy to be applied with a significant contrast effect while still allowing the laser beam to diffuse through the frost. Such a laser ensures precise marking. In addition, marking with such a laser on the finish further reduces the risk of heat propagation to the bottle and the substance.

[0057] The laser power is also chosen to limit the energy applied to the container and to apply a high-quality beam. The power can be, for example, a maximum of 20W, or even less than 10W, or even less than 4W, or even less than 3W, or even less than 2W. A power of less than 4W allows for adequate marking in less than a second. Using a laser with a power of up to 20W limits the heat-affected zone of the ring - which makes the marking more precise and reduces the risk of affecting the container and the substance. Indeed, above 30W of power, thermal effects occur, making the marking less precise and the risk of damaging the container greater.

[0058] To further improve the marking accuracy, it is advantageous to use a fiber laser (with short pulses, as mentioned). This improves the resolution of the laser. It also makes it possible to mark a large amount of information on a small surface. For example, it is possible to mark a 12 x 12 code (i.e. a capacity of 10 numeric characters or 6 alphanumeric characters) or a 14 x 14 code (i.e. a capacity of 16 numeric characters or 10 alphanumeric characters), which can easily be marked in less than 1 s on a 2mm x 2mm surface, offering easy decoding - using a camera for example (dedicated reader or mobile phone).It is also possible to mark in the form of a rectangular code of 10 x 24 (i.e. a capacity of 32 numeric characters or 22 alphanumeric characters) which can easily be marked in less than 1.5 seconds on a surface of 2mm x 4mm offering easy decoding - using a camera for example (dedicated reader or mobile phone). This allows the marking to be carried out on the ring rather than on a label covering a significant part of the container wall. Furthermore, the use of a fiber laser allows rapid marking, within the times indicated above.

[0059] The laser wavelength can be visible or infrared, for example between 510 nm and 1200 nm. A good configuration combining cost and efficiency is between 1000 nm and 1100 nm, more specifically at 1064 nm. The repetition rate can be for example between 2 and 4000 KHz and preferably between 50 and 200 kHz. This also helps to limit the thermal effect with the advantages mentioned above.

[0060] The maximum intensity can be for example 1 mJ per pulse and preferably between 10 and 100 pJ. This makes it possible to limit the thermal effect with the advantages mentioned above, and to reduce the cost.

[0061] The laser focal length is chosen so that marking can be carried out on the circumference without rotating the container. Thus, during marking, the container is stationary and the laser is mobile. This facilitates marking and avoids handling the container. A focal length of 160 mm allows for quality marking on the irradiated circumference and covers positioning uncertainties and manufacturing tolerances of the bottle.

[0062] The resolution obtained in the context of the method and device described is less than 75 pm. The resolution can also reach less than 20 pm, which makes it possible to increase the amount of information contained in the code and / or to introduce several levels of information such as anti-counterfeiting data.

[0063] It is also possible to combine the marking with a logo or text. This increases the available information. It is also possible to repeat the marking on at least part of the circumference of the ring 16 - or even on the entire circumference of the ring 16. This allows random reading, particularly on a production line. Thus, it is not necessary to orient the container in a certain way to access the information.

[0064] The marking of the data on the ring 16 can be carried out in at least two passes. During the first pass, the laser carries out an initial marking simultaneously with the removal of the layer of frost - the specificities of the laser indicated above allow these two actions during the first pass. The energy applied by the laser is moderate to initiate the marking and remove the frost while allowing the beam to diffuse through the frost. An additional pass (two passes in total) or several additional passes allow the marking to be accentuated. For example, two additional passes (three in total) or even three additional passes (four in total) allow the energy to be limited to mark the container precisely without thermal effect and to remove the frost from the first marking pass.

[0065] The scanning speed (or linear speed of the passes) by which the passes are executed can be for example between 700 and 3500 mm / s for marking and between 2000 and 10000 mm / s for jumps. This allows the passes to be executed quickly to avoid heating the container.

[0066] The marking speed for the entire marking can be for example between 4 and 100 mm 2 / s, preferably between 20 and 80 mm 2 / s. This allows marking to be carried out quickly to avoid heating the container.

[0067] According to Figure 2, the ring 16 surrounds the cap 14 and includes a collar 27. The laser marking step can be carried out on the collar. This makes it possible to carry out a marking in an available space on the ring 16 rather than on the bottle and thus to reduce the risks of weakening the bottle. In addition, the marking on the collar which is a lateral face of the ring 16 makes it easy to have read access to the marking. The marking on the collar which is around the bottle (at its opening), prevents heat transfer and contamination of the bottle and the substance. According to Figure 2, the bottle 12 has a rim 29 around the neck 18, projecting towards the outside of the wall of the bottle 12. The ring 16 is engaged by clipping (or by elastic interlocking) from below the rim 29.This allows the ring 16 to be held firmly to the bottle 12 - which is advantageous for the integrity of the marking - and therefore to hold the stopper 14 in place - which is advantageous when using a needle through the stopper 14 to access the interior of the container. The ring may further comprise a shoulder 28 bearing against the stopper 14, the combination of the shoulder 28 on the stopper and the ring 16 engaging with the underside of the rim 29 reinforcing the quality of the sealing of the container 10 and the holding in place of the ring 16 - and therefore the integrity of the marking.

[0068] The container 10 may further comprise a removable or partially removable capsule 32 (by removing the segment 34) covering the upper face 24 of the stopper 14, left uncovered by the ring 16. The capsule 32 makes it possible to protect the exposed upper face 24 of the stopper 14.

[0069] The capsule 32 is outside the marking area of ​​the ring 16. More specifically, the capsule 32 does not cover the collar 27. The collar which is a lateral face of the ring is left uncovered by the capsule 32. Thus, the presence of the capsule 32 in place on the ring 16 does not prevent the reading of the marking on the ring 16.

[0070] Figure 3 shows an example of marking 36. The container 10 is at least partially covered with frost 38. The container 10 comprises the bottle 12 (whose shape is different from that of figures 1 and 2, the method being applicable to any shape of bottle) and the capsule 32 surmounts the ring 16. The marking 36 is produced on the ring 16 and more precisely, on the collar 27. The capsule 32 is outside the marking zone on the ring 16. More specifically, the capsule 32 does not cover the collar 27 of the ring 16, which allows the laser marking 36 on the collar 27 with or without the presence of the capsule 32. The presence of the marking 36 on an available space on a lateral face of the ring 16 allows easy reading of the marking.

[0071] The laser can create a mark that can be at different depths, and be visible or invisible to the naked eye. Multiple markings can be made. This makes the mark(s) accessible to the naked eye or using a reading system, on the surface or at depth, making the possibility of removing them almost impossible. The mark can be visible from a single viewing angle, change color depending on the viewing angle, or be visible only with appropriate lighting. To further increase security, the viewing angle for reading the mark can be distinctly changed. The mark can be visible to the naked eye, allowing the user to access the data quickly.

[0072] The marking can contain different data (or information) for example, the marking can be chosen from the group of data including:

[0073] - data intended for the end user, for example an expiry date; - data intended for the identification of the container and / or for production management, which may be an individual code, a normative code or a batch number linked to a database enabling the various parameters used for the production of the marked container to be controlled;

[0074] - data intended for counterfeiting expertise, such as an anti-fraud code.

[0075] The marking can be a combination of these data.

[0076] The marking may include container identification data, part of the bits of the identification data define the position of an invisible anti-fraud code produced by the same process.

[0077] The marking may be invisible in daylight but visible at a suitable wavelength with a reading system with a camera sensitive to that wavelength, providing an anti-fraud signature.

[0078] The marking may be data comprising a series of numeric, alphabetic, alphanumeric signs, a 2D matrix, a datamatrix code, a barcode, a logo, a decorative element, etc. and / or a combination of these data. The marking may be included or concealed in a decorative or informative element of the ring. For example, the marking may be in a logo or in text. For example, the marking may be a datamatrix code in the dot of an "i", or even in one of the squares of a datamatrix code.

[0079] The invention also relates to a device for marking the container 10. The device has the particularity of marking the container 10 covered at least in part with frost. The device also has the particularity of marking the container 10 without thermal effect, without risk of contamination of the substance contained in the bottle. The device comprises a laser as described previously, for marking the container 10. In particular, the device allows the implementation of the method described. The device may also comprise members for holding a container to be marked in a stationary position, and members for moving the laser for marking the container.

[0080] The present invention has been described in relation to specific embodiments, which are of purely illustrative value and should not be considered as limiting. In general, it will be obvious to a person skilled in the art that the present invention is not limited to the examples illustrated and / or described above. For example, the cap and the ring could be of a single piece, and / or the shape of the cap and the ring could be other, provided that the marking is without risk of contamination of the substance does not harm the integrity of the container and is accessible for reading.

Claims

Demands 1. Method for marking a container (10) comprising a bottle (12) containing a medicinal substance and closed by a cap (14) attached to the bottle (12) by a ring (16), the container (10) being at least partially covered with frost, the method includes a step of laser marking the ring (16) through the frost.

2. A method according to the preceding claim, wherein the medicinal substance consists of cells.

3. A method according to any one of the preceding claims, wherein at least one laser operating parameter is selected from the group comprising: • A wavelength between 510 nm and 1200 nm, preferably between 1000 nm and 1100 nm, preferably at 1064 nm; • A power of less than 20W, preferably less than 10W, preferably less than 4W, preferably less than 3W, preferably less than 2W; • A marking speed between 4 and 100 mm 2 per second, preferably between 20 and 80 mm 2 per second; • A laser pulse duration of between 1 and 350 ns nanoseconds, preferably between 4 and 100 ns; • A repetition rate between 2 and 4000 kHz and preferably between 50 and 200 kHz; • An intensity of 1 mJ per draw, preferably between 10 and 10OpJ.

4. A method according to any one of the preceding claims, wherein the laser is a fiber laser.

5. The method according to any one of the preceding claims, wherein the marking of the ring is carried out in at least two passes of the laser on the ring, preferably three passes, preferably four passes.

6. A method according to any one of the preceding claims, wherein the ring (16) surrounds the cap (14) and includes a collar (27) on which the laser marking step is carried out.

7. A method according to any one of the preceding claims, wherein the ring (16) surrounds the stopper (14) leaving an uncovered portion of the upper face (24) of the stopper for access to the inside of the container (10) by a needle through the stopper (14), the container (10) further comprising a partially or totally removable cap (32) which covers the uncovered portion of the upper face of the stopper and which is outside the marking area of ​​the ring.

8. A method according to any one of the preceding claims, wherein the stopper (14) is made of thermoplastic material.

9. A method according to any one of the preceding claims, wherein the bottle (12) is made of polymer, preferably cyclic olefin copolymer or cyclic olefin polymer.

10. A method according to any one of the preceding claims, wherein, prior to the marking step, the container was stored at -80°C or less. 1 1. A method according to any one of the preceding claims, wherein the marking (36) is selected from the group of data comprising an expiry date, an individual code, a batch number, an anti-fraud code, a normative code, or a combination of these data.

12. A method according to any one of the preceding claims, wherein the marking is included in a decorative element of the container.

13. A method according to any one of the preceding claims, wherein the marking includes container identification data, a portion of the bits of the identification data define the position of an invisible anti-fraud code produced by the same method.

14. A method according to any one of the preceding claims, wherein, during marking, the container is stationary and the laser is mobile.

15. A method according to any one of the preceding claims, wherein the marking comprises a 12x12 or 14x14 code on a surface of 2 mm x 2 mm or a 10x24 code on a 2 mm x 4 mm surface.

16. A method according to any one of the preceding claims, wherein the marking is repeated over at least a part of the circumference of the ring (16).

17. Device for marking a container (10) comprising a bottle (12) containing a medicinal substance and closed by a cap (14) attached to the bottle (12) by a ring (16), the container (10) being at least partially covered with frost, the device comprising a laser capable of marking the ring (16) through the frost.

18. A device according to the preceding claim, wherein at least one laser operating parameter is selected from the group comprising • A wavelength between 510 nm and 1200 nm, preferably between 1000 nm and 1100 nm, preferably at 1064 nm; • A power of less than 20W, preferably less than 10W, preferably less than 4W, preferably less than 3W, preferably less than 2W; • A marking speed between 4 and 100 mm 2 per second, preferably between 20 and 80 mm 2 per second; • A laser pulse duration of between 1 and 350 ns nanoseconds, preferably between 4 and 100 ns; • A repetition rate between 2 and 4000 kHz and preferably between 50 and 200 kHz; • An intensity of 1 mJ per pulse, preferably between 10 and 1 OOpJ.

19. A device according to any one of the two preceding claims, wherein the laser is a fiber laser.

20. A device according to any one of the three preceding claims, wherein, during marking, the container is stationary and the laser is mobile.

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