• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a container (1) comprising a glass wall (2) delimiting a receiving cavity (3) for a fluid substance, said container (1) comprising a cover (5) for protection and retention which covers the outside. said glass wall (2), said container (1) being characterized in that said protective and retaining coating (5) is a transparent multilayer coating which comprises a lower layer (5A) covering the glass wall (2) and an upper layer (5B) covering said lower layer (5A), said lower layer (5A) being formed of a polyurethane material while said top layer (5B) is formed of a polyurethane material functionalized by a compound based on a fluoropolymer. Hollow body.
    公开号:FR3031740A1
    申请号:FR1550325
    申请日:2015-01-15
    公开日:2016-07-22
    发明作者:Carine Perrot
    申请人:SGD SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the general field of hollow bodies, and more specifically to containers of the type referred to above. vials, provided with a glass surface and usable in various industrial sectors, in particular in the sector of packaging and packaging of liquid, pasty, or powdery substances, such as for example pharmaceutical, cosmetic or food substances. The invention also relates to the technical field of the treatment of glass containers, for a functional and / or decorative purpose, in particular in the pharmaceutical, cosmetic and food sectors. The invention more specifically relates to a container comprising a glass wall delimiting a receiving cavity for a fluid substance, said container further comprising a protective and retaining coating which externally covers at least a fraction of said glass wall. The invention also relates to a kit for producing a protective and retaining coating intended to cover externally at least a fraction of a glass wall of a container. The invention finally relates to a method of manufacturing a container, in which a glass wall delimiting a receiving cavity for a fluid substance is produced or provided, said method comprising a step of external covering of at least one fraction of said glass wall by a protective and retaining coating. It is known to use glass containers to contain liquid products, in particular in the pharmaceutical sector, but also in other sectors (cosmetics sector and in particular perfumery, food sector ...). Glass turns out to be a particularly suitable material for the storage of products for pharmaceutical or veterinary use, because of its relatively neutral nature which avoids or limits interactions with the product contained in the invention. container, its robustness, its transparency (which allows a visual control of the contents) and its mechanical and chemical stability. These different qualities are also sought in sectors other than the pharmaceutical sector, for example in the cosmetics field, where the use of glass for the production of perfume bottles is particularly valued, given the noble nature generally lent to glass by consumers and the aforementioned qualities of transparency, robustness and stability of this material, or in the food field. The glass nevertheless presents certain disadvantages which can lead to particularly damaging consequences. Thus, one of the major drawbacks of glass is its fragile nature. In case of shock, for example due to a fall of the container (which may for example consist of a bottle containing a medicament to infuse or inject), the glass can easily break into multiple pieces of different sizes projected into all meaning, which can be sharp and pointed, with all the risks that this presents for the personnel in charge of handling the bottle concerned (hospital staff for example) and the people who are close to the container when it breaks ( patient for example). Thus, in case of breakage of a glass container, it is necessary to carry out a particularly thorough and tedious cleaning to be certain to eliminate any breakage of glass, even small, which could hurt a person walking on it or ingesting it inadvertently. In addition, when the glass container breaks, the liquid product that it contains spreads brutally outside with generally projections and splashing in a wide perimeter. This not only entails the need for cleaning, but may also and above all pose a risk to the health and safety of the people nearby (hospital staff, patient) when the product contained in the glass bottle is a dangerous product, such as a cytotoxic drug. In order to remedy this problem, it has been proposed to equip glass pharmaceutical bottles containing a cytotoxic product with a protective overwrap of rigid plastic (polypropylene). Such over-packing is intended to prevent the shocks to which the bottles can be subjected, during transport in particular, and also allows users to avoid contact during the handling of the bottles with the glass surface of the latter which could have been polluted by the cytotoxic substance contained in the bottle at the time of filling thereof. Attaching the overpack to the bottle can be achieved by various means, such as for example through small plastic bars or through a finned ring fixed under the neck of the bottle. The use of such over-packs certainly improves the safety of use, but it is nevertheless far from optimal. Thus, the plastic overpack, because of its relatively rigid nature, does not allow a good damping of shocks and can itself break. In addition, it does not necessarily allow to retain, if the bottle breaks, not only broken glass but also the liquid in the bottle. Also known are laboratory glass containers covered with a polyurethane film to improve impact resistance. This film, however, has a relatively limited flexibility, so that its effectiveness in impact resistance is not optimal. This film also does not allow to effectively ensure the retention of broken glass and the liquid in the container if it breaks (which is acceptable in this case, being a laboratory container and not a container for containing a pharmaceutical product, and in particular a cytotoxic product). The film in question also has a "hammered" texture, with a slightly rough surface state, which could promote the retention on the surface of any contaminating materials, it being understood further that such a texture is not optimal on the surface. sterilization plan, especially in autoclave. The objects assigned to the invention therefore aim at overcoming the disadvantages set forth in the foregoing and at proposing a new container comprising a glass wall which, while being sterilizable, including by methods inducing high thermomechanical stresses, is also particularly resistant to shocks, makes it possible to effectively retain any breakage of ice as well as the contents of the container in case of breakage of the latter.
    [0002] Another object of the invention is to provide a new container comprising a glass wall provided with a protective coating and retention particularly discreet and effective. Another object of the invention is to provide a novel container having a glass wall which, while having optimum impact and retention properties, is easy, fast and safe to manufacture. Another object of the invention is to propose a new container provided with a glass wall which, while having optimum impact resistance and retention properties, is particularly suitable for sterilization operations, in particular for autoclave. Another object of the invention is to propose a new kit for manufacturing a protection and retention coating of simple and economical design, which is particularly easy, fast and safe to implement. Another object of the invention is to provide a new manufacturing method 15 to obtain in a simple, fast and safe way a container with a glass wall particularly resistant to shocks and having optimal retention properties. Another object of the invention is to propose a novel method of manufacturing a container with a glass wall which requires only simple and standard industrial means for its implementation. The objects assigned to the invention are achieved by means of a container comprising a glass wall delimiting a receiving cavity for a fluid substance, said container further comprising a protective and retaining coating which covers externally at least a fraction of said glass wall, said container being characterized in that said protective and retaining coating is a substantially transparent multilayer coating which comprises a lower layer covering the glass wall and an upper layer covering said lower layer, said layer lower part being formed of a flexible polyurethane material adhered to said glass wall while said top layer is formed of a polyurethane material functionalized with a fluoropolymer compound. The objects assigned to the invention are also achieved by means of a kit for manufacturing a substantially transparent protective and multilayered coating intended to cover externally at least a fraction of a glass wall of a container. said glass wall defining a receiving cavity for a fluid substance, said kit comprising: a first intermediate product to be applied as a first layer to the glass wall, said first intermediate product being a dispersion in the aqueous phase of a non-reactive polyurethane whose molar mass is sufficiently high so that simple evaporation of the aqueous phase results in the formation, from said first layer, of a flexible film adhering to the glass wall; and a second intermediate product in aqueous phase intended to be applied in the form of a second layer covering said first layer, said second intermediate product in aqueous phase including at least one isocyanate and a substance based on a fluoropolymer intended for react together, after application to said first layer of said second intermediate product, to form a polyurethane material functionalized with a fluoropolymer compound. Finally, the objects assigned to the invention are also achieved by means of a method of manufacturing a container, in which a glass wall delimiting a receiving cavity for a fluid substance is produced or supplied, said method comprising a step of externally covering at least a fraction of said glass wall with a protective and retaining coating, said method being characterized in that said protective and retaining coating is a substantially transparent multilayer coating which comprises a a lower layer covering the glass wall and an upper layer covering said lower layer, said lower layer being formed of a polyurethane-based flexible material adhered to said glass wall while said top layer is formed of a polyurethane-based material; polyurethane functionalized with a compound based on a fluoropolymer.
    [0003] Other objects and advantages of the invention will appear better on reading the description which follows, as well as with the aid of the appended figure, given for purely illustrative and non-limiting purposes, and which illustrates, in a schematic view in section, an example of a container according to the invention, constituted in this case by a bottle for receiving a liquid pharmaceutical product, said bottle being in this case closed by a plug. According to a first aspect, the invention relates to a container 1 comprising a glass wall 2 delimiting a receiving cavity 3 for a fluid substance, that is to say a substance capable of flowing, for example a liquid substance. , pasty (such as a liquid with a high degree of viscosity) or pulverulent. Preferably, the container 1 forms a container designed to contain a liquid substance of pharmaceutical nature, such as a drug, and in particular a cytotoxic drug, intended to be optionally injected intravenously or intramuscularly, or to be administered by infusion or still to be ingested by a patient. Although the application to the pharmaceutical field is preferred, the invention is however not limited to containers for pharmaceutical use and also concerns, as an alternative alternative, a container 1 designed to contain a liquid substance for veterinary use, or a liquid substance for food use, or a liquid substance for cosmetic use (body perfume, cream or other). In general, the container 1 is therefore advantageously intended to contain, in its receiving cavity 3, a substance intended to be administered to a human being or an animal. The container 1 may therefore have any form adapted to its function, and may be, for example, as illustrated in FIG. 1, in the form of a bottle, intended for example to contain a liquid product for pharmaceutical use. In this case, the glass wall 2 is advantageously formed by a glass bottom 2A, a glass side wall 2B which rises from and on the periphery of the bottom 2A and a neck 2C which closes the bottle while providing filling / dispensing opening for communicating the cavity 3 with the outside. Said opening is optionally closed by a removable plug 4, as shown in FIG. 1. It is however perfectly conceivable that the container 1 affects any other shape, and in particular a form without a neck such as for example a tube shape, ampoule, syringe, or other, depending on the intended use. Such a glass container, and in particular in the form of a bottle, can be obtained by any conventional glassmaking process (molded glass, drawn glass, Vello process or Danner process, etc.). Preferably, the glass wall 2 of the container 1 delimiting the receiving cavity 3 is in the form of an integral piece which forms at the same time the bottom 2A, the side wall 2B and the neck 2C, so that the receiving cavity 3 is advantageously entirely delimited by a single piece of glass, with the possible exception of the cap 4. It is however perfectly conceivable that only a portion of the container 1 (for example only the side wall 23) is made of glass. More precisely and as illustrated by FIG. 1, the glass wall 2 has an internal face 20 facing the reception cavity 3 and an opposite external face 21. The glass wall 2 thus advantageously forms a hollow and empty body whose inner face 20 delimits directly the cavity 3, which forms a fully enclosed empty interior volume, with the exception of the opening towards the outside formed at the neck 2C whose section is in this case reduced with respect to the average section of the cavity 3 (Figure 1). The term "glass" should be understood here in its conventional sense, and therefore refers to a mineral glass, and preferably a silica glass. For example, the glass constituting the wall 2 is a white, transparent glass, such as a soda-lime glass or a borosilicate glass. The glass used to make the wall 2 is preferably colorless, but may alternatively be colored, for example by metal oxides, to protect the fluid substance contained within the container 1 from the effects of light, particularly in certain length ranges. wave. The container 1 further comprises a protective and retaining coating 5 which externally covers at least a fraction, and preferably substantially all, of the glass wall 2. In the advantageous example illustrated in the figures, the coating 5 thus covers substantially continuously and uniformly the outer face 21 both at the bottom 2A and the side wall 2B and the bottom 2C, so that the bottle illustrated in Figure 1 is in this case fully coated on its outer face 21, which n is therefore more accessible from the outside.
    [0004] The protection and retention coating 5 is intended to provide different functions, and in particular the following functions: - Shock protection function, in order to increase the impact resistance of the container 1, the coating 5 playing the role for this purpose; a shock-absorbing protective envelope "anti-breakage"; - Retention function in case of breakage of the glass wall 2, for example following a fall of the container 1, this retention function to ensure that the coating 5 forms an envelope retaining within it both the broken glass and the fluid that was present within the container 1.
    [0005] Preferably, the coating 5 also performs a function of reinforcing the glass wall 2, in particular by filling the microcracks potentially present on the surface of the glass wall 2. The protective protective coating 5 is a multilayer coating, that is, it is formed of at least two superimposed layers. In the preferred embodiment illustrated, the coating 5 consists of two layers. It is however perfectly conceivable that the coating 5 comprises more than two layers, and for example three or four layers, or more. The coating 5 is also preferably substantially transparent, to allow in particular a visual control of the contents of the container 1, especially when it is a product for pharmaceutical use according to the preferred embodiment. This means that the different layers comprising the coating 5 are each individually transparent, so that the resulting multilayer structure forming the coating 5 is itself substantially transparent, or at least sufficiently transparent to allow visual inspection of the contents of the receiving cavity. 3.
    [0006] As illustrated in FIG. 1, the coating 5 comprises a lower layer 5A which covers the glass wall 2. In the preferred embodiment illustrated in FIG. 1, the lower layer 5A directly covers the glass wall 2; that is, it comes into direct contact with the outer face 21 of the glass wall 2, without any intervening layer being interposed between the lower layer 5A and said outer face 21. In this case the lower layer 5A therefore adheres, preferably by itself and directly (without adhesive layer or intermediate primer) to the glass wall 2. The coating 5 also comprises an upper layer 5B which covers the lower layer 5A , that is to say which is superimposed on and against said lower layer 5A so that the latter is interposed between the glass wall 2 on the one hand and the upper layer 5B on the other hand. In the preferred embodiment illustrated in FIG. 1, the coating 5 is a two-layer coating, the lower layer 5A adhering directly to the glass wall 2 while the upper layer 5B forms the surface layer of the coating 5.
    [0007] According to the invention, the lower layer 5 is formed of a flexible material based on polyurethane adhering to the glass wall 2, preferably directly as described above. The flexible material in question is advantageously predominantly formed of a polyurethane> and preferably substantially entirely consisting of a polyurethane chosen for its qualities of adhesion to glass, its flexible nature (which allows a good cushioning effect and protection against shocks), as well as its mechanical strength which makes it possible to ensure the retention of both possible breakage of ice resulting from the breakage of the glass wall 2 and the fluid substance contained in the container 1. Preferably, the material flexible forming said lower layer 5A is obtained by drying a first intermediate product consisting of a dispersion in aqueous phase of a polymerized material (polyurethane) non-reactive (that is to say already fully polymerized) whose molar mass is sufficiently high (for example at least 200 000 g.mo1-1, and still more preferably at least 300 000 g.rnorl) for that the mere evaporation of the aqueous phase resulting from said drying results in the formation of a film forming the lower layer 5A. In other words, the lower layer 5A is preferably obtained exclusively by drying the first intermediate product once it has deposited as a layer on the surface of the glass wall 2, preferably without any reaction, and in particular polymerization or crosslinking, does not intervene after deposition of said first intermediate product on the glass wall 2. Advantageously, the only evaporation of the aqueous phase in which is dispersed the polymerized material is sufficient to form a cohesive film which adheres directly on the outer face 21 of the glass wall 2 and thus forms the lower layer 5A. The first intermediate product therefore contains no reactive products, of the isocyanate type, but directly includes the polymer already completely polymerized and dispersed in the aqueous phase. Preferably, said dispersion forming the first intermediate product is an aqueous emulsion of the polymerized material, i.e. liquid or semi-liquid particles of said PU-based polymer are dispersed in water. In particular, it facilitates the application process, in particular by means of spraying tools. The invention is however not limited to the use of an aqueous emulsion, and it is for example quite possible that the polymerized material is in the form of a suspension of solid particles of polymer in water, or even a solution of said polymer in water. The use of an already polymerized polyurethane, in the aqueous phase, thus makes it easier to apply and obtain the lower layer 5A and to reduce the risks of the operators, since it is an aqueous phase. The upper layer 5B is formed of a polyurethane material functionalized with a compound based on a fluoropolymer, in particular to allow the coating to be sufficiently hydrophobic superficially to allow sterilization, and in particular sterilization 1. The upper layer 5B thus performs various functions, and aims in particular to protect the lower layer 5A, to preserve the adhesion of the latter to the glass wall 2 (in particular by preventing the reaction of the water with the lower layer 5A, which avoids in particular a "swelling" of the lower layer 5A under the effect of water which could lead to a loss of cohesion with the wall 2 of glass) and 25 allow the container 1 thus coated to be sterilized, including by means of aggressive techniques such as sterilization in an autoclave at 121 ° C, in accordance with standards in the pharmaceutical field. In particular, in the case where the lower layer 5A is obtained exclusively by drying a first intermediate product consisting of a dispersion in aqueous phase of an already polymerized material, without subsequent reaction of polymerization or crosslinking, the cohesive film obtained has an elastic and flexible nature that allows good impact protection and effective retention of glass chips and liquid in case of breakage of the glass wall 2. A silane crosslinking additive could be added to the first intermediate product to crosslink the polymerized material after deposition on the glass wall 2.
    [0008] This would improve adhesion, chemical resistance and hydrolytic resistance. On the other hand, such a crosslinking would also tend to make the film forming the lower layer 5A brittle, which would therefore greatly degrade its retention properties. The invention is thus based in particular, in the preferred embodiment described above, on the idea of dispensing with a post-deposit polymerization or crosslinking, and to compensate for the adverse effects of this lack of polymerization or crosslinking by the implementation of of the upper layer 5B which will protect the lower layer 5A, which is in particular likely to be vulnerable to sterilization. Due to the fact that the material forming the upper layer 5B is based on polyurethane, the upper layer 5B can adhere effectively and naturally to the lower layer 5A which is also based on polyurethane. In addition to this compatibility between the lower layers 5A and 5B, obtained by the common presence of polyurethane in the two layers 5A, 5B in question, the composition of the upper layer 5B promotes optimal behavior of the container 1 to sterilization, and in particular sterilization by autoclave. Indeed, functionalization with a fluoropolymer, and in particular with a fluoropolymer which is polytetrafluoroethylene (PTFE), makes it possible to give the coating 5 a surface hydrophobic character, a high blocking resistance and a particularly smooth character. These different properties allow the coating 5 to undergo the stresses inherent in the sterilization operations, that these are of a physical nature (in an autoclave at 121 ° C., or in boiling water, or by microwaves) or chemical (chemical sterilization Cold). In particular, the blocking resistance makes it possible, when several bottles arranged side by side and in contact with each other are sterilized at the same time, to avoid inadvertent adhesion of the containers to one another under the effect of the physico-chemical constraints induced. by sterilization. Preferably, said upper layer material 5B comprises the reaction product of an isocyanate with at least one fluoropolymer substance. More specifically, the upper layer 5B is advantageously obtained by polymerization of a second intermediate product in aqueous phase including at least said isocyanate and said substance based on a fluoropolymer, other components may of course be present elsewhere (such an alcohol to react with the isocyanate and form polyurethane). The second intermediate product is thus deposited on top layer 5B, and then its components co-react to form a fluoropolymer functionalized polyurethane polymer, which is preferably polytetrafluoroethylene (PTFE). The use of PTFE makes it possible to obtain an excellent resistance to the blocking of the top layer 5B, whereas the use of a polyurethane precursor isocyanate makes it possible to ensure the compatibility and thus the adhesion of the surface layer formed in the occurrence by the top layer 5B with the underlayer (lower layer 5A) based on polyurethane. The second intermediate thus advantageously constitutes an aqueous phase protective varnish which, when applied to the underlayer formed by the lower layer 5A, reacts to form a fluoropolymer-functionalized polyurethane-based polymer to obtain a surface finish. the coating 5 is a homogeneous and continuous smooth layer with excellent blocking resistance, which allows the sterilization of the container 1 without significant or permanent degradation of the coating 5. Advantageously, said isocyanate is a blocked isocyanate, preferably by means of an agent adapted blocking agent (for example a blocking agent allowing the blocked isocyanate to be soluble in water). This makes it possible in particular to be able to easily preserve the second intermediate product and to store it over time, while allowing the isocyanate in question to remain reactive and to polymerize when the required conditions are met (for example when the temperature is sufficient ). Preferably, the second intermediate product is free of any free isocyanate and comprises only one (or more) blocked isocyanate. The invention thus makes it possible, in particular in its advantageous embodiment described in the foregoing and illustrated by FIG. 1, to obtain a container 1 which is particularly suitable for pharmaceutical use (since it is resistant to the constraints of sterilization) while being particularly impact resistant and having a remarkable retention ability for glass and liquid breaks. Advantageously, the thickness of the lower layer 5A is greater than that of the upper layer 5B. The lower layer 5A is indeed intended in particular to dampen the shocks and to provide a retention function of any broken glass and fluid, these different functions requiring a sufficiently large thickness of the lower layer 5A. Conversely, the upper layer 5B provides above all a protection of the lower layer 5A and can therefore have a lower thickness.
    [0009] Preferably, the thickness E1 of the lower layer 5A is substantially between 30 and 300 μm. In a particularly advantageous embodiment, the thickness E1 of the lower layer 5A is substantially between 50 and 200 μm, more preferably substantially equal to 100 μm. The aforementioned thickness ranges, which can of course be adapted according to the characteristics of the container 1 to be coated, and in particular the size and weight of the latter, make it possible to obtain optimal protection against shocks and guarantee a uniform performance. sufficient mechanics of the lower layer 5A to ensure the possible retention of broken glass and / or fluid products. Advantageously, the thickness E2 of the upper layer 5B is substantially between 5 and 50 μm, and even more preferably substantially between 10 and 30 μm, preferably substantially equal to 20 μm. For example, for a bottle with a capacity of 100 ml and a mass equal to 89 g, a thickness El of the lower layer 5A advantageously equal to substantially 100 pm will provide good results in terms of protection against shocks and retention. The invention furthermore relates as such to a kit for producing a substantially transparent multilayer protection and retention coating 5, said coating preferably being in accordance with the foregoing description and thus intended to cover externally at least a fraction a glass wall 2 of a container 1, delimiting a receiving cavity 3 for a fluid substance, according to the above description. The kit which is the subject of the invention comprises: a first intermediate product, intended to be applied in the form of a first layer on the glass wall 2, said first intermediate product advantageously consisting of an aqueous phase dispersion of a non-reactive polyurethane whose molar mass is sufficiently high so that simple evaporation of the aqueous phase results in the formation, from said first layer, of a flexible film adhering to the glass wall 2; And a second aqueous phase intermediate product to be applied as a second layer overlying said first layer, said second aqueous phase intermediate including at least one isocyanate (preferably blocked) and a fluoropolymer substance (Preferably polytetrafluoroethylene or PTFE), intended to react together, after application to said first layer of said second intermediate product, to form a polyurethane material functionalized with a fluoropolymer compound. Advantageously, said first and second intermediate products referred to above are in accordance with the detailed description given in the foregoing in relation to the container 1 according to the invention, so that said description also applies integrally to the kit according to the invention. According to yet another aspect, the invention relates to a method of manufacturing a container 1, in which a glass wall 2 delimiting a receiving cavity 3 for a fluid substance is manufactured or supplied. The process in question is advantageously a method of manufacturing a container 1 according to the invention, so that the description set forth in the foregoing in relation to the container 1 according to the invention remains valid and applicable, mutatis mutandis, in the present process. The latter comprises a step of externally covering at least a fraction of the glass wall 2 with a protective and retaining coating. As previously discussed, the protective and retaining coating 5 is a substantially transparent multilayer coating which comprises a bottom layer 5A covering the glass wall 2 and an upper layer 5B covering said bottom layer 5A, said bottom layer 5A being formed of a polyurethane-based flexible material adhered to the glass wall 2 while the upper layer 5B is formed of a polyurethane material functionalized with a fluoropolymer-based compound, in particular to allow the coating to be sufficiently hydrophobic superficially to allow sterilization, and in particular autoclave sterilization, of the container 1. Advantageously, said covering step itself comprises a step of forming the lower layer 5A during which: A first intermediate product consisting of a dispersion in the aqueous phase of an unreacted polymerized material active is applied to the glass wall 2, in the form of a first layer, for example by spraying. The first intermediate product, which is advantageously in accordance with the foregoing description exposed in relation to the container 1 according to the invention, can be deposited on the glass wall 2 while the latter is at ambient temperature or, on the contrary, has undergone preheating so that its temperature is higher than the ambient temperature. Preferably, the glass wall 2 is treated with corona or plasma before the application of the first intermediate product, in order to improve wettability and adhesion. The first intermediate product can for example be applied by an electrostatic spraying technique to the bowl or disk, which proves particularly advantageous in terms of cost and industrialization, but a pneumatic spray application could also be perfectly suitable, it being understood that the invention is in no way limited to a particular technique of application. - The first intermediate product thus applied, preferably in the form of a homogeneous first continuous and uniform layer, on the glass wall 2, is then dried, for example in the open air or forced (by contribution of heat and / or submission to an air flow), so as to evaporate the aqueous phase (desolvation operation, which can be performed after removal of the second layer mentioned below), the molar mass of said polymerized material 3031740 being high enough that the mere evaporation of the aqueous phase resulting from said drying results in the formation of a film forming the lower layer 5A, as explained in the foregoing. As previously discussed in connection with the description of the container 1 according to the invention, the polymerized material dispersed in the aqueous phase to form the first intermediate product has already reacted, and is therefore no longer reactive, i.e. it is already polymerized and will not undergo, after application of the first intermediate product on the glass wall 2, subsequent reaction, in particular polymerization or crosslinking. Preferably, the flexible and cohesive film forming the lower layer 5A is thus obtained solely by evaporation of the aqueous phase of the first intermediate product, without being implemented, after application of the first intermediate product on the glass wall 2, a subsequent polymerization or crosslinking reaction, which makes it possible to obtain a sufficiently flexible envelope to ensure good shock absorption and efficient retention of glass breakage and liquid, possibly to the detriment of chemical resistance properties and to water, and thus to sterilization. This vulnerability is, however, overcome by means of the upper layer 5B, as explained above, and whose preferred training modalities will be set out below. Preferably, the aqueous phase dispersion forming the first intermediate product is an aqueous emulsion of said polymerized material, so that liquid or semi-liquid particles thereof are dispersed in an aqueous phase. As recalled above, however, the invention is not limited to the use of an emulsion and the dispersion in question could quite well consist of a suspension or a solution for example. The use of an emulsion is, however, advantageous in terms of industrialization and application technique of the first intermediate product, especially by spraying. Advantageously, the first intermediate product has a viscosity at 20 ° C. which is between substantially 800 and 2000 mPa.s, preferably between substantially 1000 and 1800 mPa.s, which makes it easy to apply the first intermediate product 3031740. on the glass wall 2 in a thin layer, homogeneous and uniform, in particular by means of spray instruments as mentioned above. For this purpose, it is particularly advantageous that the first intermediate product has a viscosity at 20 ° C which is between substantially 1300 and 1400 mPa.s. Advantageously, the first intermediate product has a solids content of between 20 and 70% by weight, and preferably between 30 and 60% by weight, even more preferably between 45 and 55% by weight, so as to allow by simple evaporation of the aqueous phase, obtaining a homogeneous and cohesive film 10 for forming the lower layer 5A and to adhere for this purpose directly to the glass wall 2. In a particularly preferred embodiment, the first intermediate product has a dry extract equal to 48% by weight. Preferably, the first intermediate product is deposited on the surface of the glass wall 2 in the form of a first layer whose thickness is chosen so that after drying of the first intermediate product and evaporation of the aqueous phase, the thickness of the resulting lower layer 5A is substantially between 30 and 300 μm, preferably between 50 and 200 μm, and even more preferably substantially equal to 100 μm, as previously mentioned in relation to the description of the container 1 according to to the invention. Advantageously, in order to protect the lower layer 5A, the recovery step referred to above also comprises a step of forming the upper layer 5B during which: A second intermediate product in aqueous phase including at least one isocyanate (which is preferably a blocked isocyanate for the reasons set forth above) and a fluoropolymer substance (which is preferably polytetrafluoroethylene (PTFE) for the reasons also set forth in the foregoing), is applied to said first layer by example immediately after application of said first layer, when the latter is still wet, or after a waiting time (for example several tens of minutes) for an application of the second intermediate product on the first dry layer. The second intermediate product is advantageously applied to the first layer by means similar to those used to apply the first intermediate product, and for example by spraying, and in particular by electrostatic spraying with the bowl or disk (as long as the second layer is applied to the first layer still wet (application "wet wet"), that is to say still containing enough water to allow the electrostatic process to function properly), a pneumatic spray application may be preferred ( especially when the second layer is applied after complete drying of the first layer which is then already completely desolvated and forms the lower layer 5A). Said second intermediate product thus applied, preferably in the form of a uniform and homogeneous thin layer, to the first layer (wet or dry), is then subjected to a treatment which causes the reaction of at least said isocyanate with the fluoropolymer-based material for forming said polyurethane material functionalized with a fluoropolymer compound (preferably PTFE). In other words, once the second intermediate product has been applied to the first layer, a polymerization reaction occurs in said second intermediate product, resulting in the conversion of the isocyanate / fluoropolymer mixture into a polyurethane functionalized with a compound based on said fluoropolymer. . This reaction can occur spontaneously, for example, under the effect of the exposure of the second intermediate product to the free air in a thin layer, in which case the treatment in question consists only in leaving the second product in the open air. intermediate applied on the first layer so that it reacts spontaneously. Alternatively, according to a preferred embodiment of the invention, the treatment resulting in the aforementioned reaction is rather a heat treatment to reach a threshold temperature from which the isocyanate will polymerize and react with the fluoropolymer. For example, the treatment includes a step of cooking the container 1 on which said second intermediate product is applied, at a temperature sufficient to trigger the aforementioned reaction, said temperature being for example between substantially 90 ° C. and 200 ° C., preferably between 120 ° C and 180 ° C, even more preferably between 142 ° C and 170 ° C. This cooking step can be performed in traditional hot air oven or by any other means (infrared heating ...). This baking step thus makes it possible to obtain a smooth surface layer with excellent blocking resistance as well as a hydrophobic character, making it possible to sterilize the container 1, including in an autoclave. Preferably, before carrying out the firing step causing the aforesaid reaction within said second intermediate product, a desolvation step is carried out, in particular if the second intermediate product has been applied to the first intermediate product still wet, so as to to dry both the second layer and (especially) the first layer. This operation may for example last several tens of minutes, especially if it is carried out naturally in the open air, this time being able to be reduced by implementing a mixing of the surrounding air and / or at a rise in the ambient temperature (lower at 100 ° C, however). However, it is perfectly possible to proceed with the desolvation (for 15 to 30 min for example depending on the temperature conditions and mixing of the air) of the first layer before application of the second layer. Once the second layer has been deposited, desolvation is then carried out (for 5 to 10 min, for example, depending on the temperature and air mixing conditions) thereof and then on a firing to initiate the evoked polymerization reaction. previously.
    [0010] Advantageously, the second intermediate product has a viscosity at 20 ° C. which is between substantially 5 and 30 mPa.s, preferably between substantially 10 and 20 mPa.s, in order to facilitate the application, in particular by spraying and covering easily. homogeneously and uniformly, the first layer. For this purpose, the viscosity at 20 ° C of the second intermediate product is even more preferably between substantially 14 and 15 mPa.s. Advantageously, the second intermediate product has a solids content of between 10 and 60% by weight, preferably between 20 and 50% by weight, even more preferably between 25 and 40% by weight. A solids content of, for example, 32% by weight gives excellent results, both in terms of industrialization and the properties of the coating obtained. Advantageously, the second intermediate product is applied to the first layer so that the thickness of the upper layer 5B that it allows to obtain is substantially between 5 and 50 pm, preferably substantially between 10 and 30 pm. , and even more preferably substantially equal to 20 pm, so as to effectively protect the underlayer (lower layer 5A) without constituting an unnecessary or inconvenient extra thickness. Ultimately, the use of a multilayer coating, and in particular a bilayer coating with an undercoating essentially mechanical function (shock absorption, retention) covered with a protective varnish (surface layer) 10 having a very good resistance to blocking and a smooth and hydrophobic character, formed directly on the glass wall 2 of the container 1 and adhering directly to the latter, provides a simple and industrialisabie a container 1 perfectly suitable for pharmaceutical use especially to contain within it cytotoxic liquid products (anticancer drugs for example). The examples and test reports set out below make it possible to better appreciate the practical contribution of the invention. The tests were carried out with 100 ml glass vials of which a first series of 20 vials was covered with a protective and retaining coating according to the invention, while another series of identical vials ( 20 bottles of 100 ml also) remained free of coating. The flasks belonging to the series of flasks according to the invention will hereinafter be referred to as "plasticized flasks", whereas the bottles of simple glass, devoid of coating, will be designated by the term "unplasticized flasks". The coating of the plasticized flasks is a bilayer coating with a lower layer thickness 5A substantially equal to 100 μm, while the upper layer 5B has a thickness substantially equal to 30 μm. The lower layer 5A is formed of a polyurethane adhering directly to the glass wall 2 and is obtained by drying a first intermediate product consisting of an aqueous emulsion of a polyurethane-based material which has already been completely polymerized, with a solids content. Substantially equal to 48% by weight, which includes 3 to 10% by weight of co-solvent, preferably 5% by weight of co-solvent, and whose viscosity at 20 ° C is preferably between 1300 and 1400 rnPa.s. As for the surface layer (upper layer 5B), it is in this case obtained by baking a second intermediate product in aqueous phase applied in the form of a second layer covering the first layer intended to form the lower layer 5A this second intermediate product in aqueous phase including a blocked isocyanate and PTFE, as well as possibly other compounds (alcohol ...) which will react together under the effect of the temperature, and in this case under the effect of heating at a temperature of between 142 ° C. and 170 ° C.) so as to obtain, by polymerization, a polyurethane-based varnish functionalized with PTFE. The second intermediate product in aqueous phase has a solids content substantially equal to 32% by weight, and a viscosity of the order of 14 to 15 mPa.s at 20 ° C. The two series of vials referred to above, plasticized and unplasticized, are first subjected to drop tests carried out on a test bench in which each bottle is positioned vertically and guided so as to fall on a stainless steel plate, with A drop height equal to 1.5 m. Each vial subjected to this drop test is filled to 80% of its capacity to the brim. The results of these drop tests are as follows: 40% (ie 8 bottles out of 20) of the plasticized flasks have broken, whereas 75% (that is to say 15 out of 20 flasks) unplasticized vials broke. The breakage rate is therefore much higher for the unplasticized bottles, which confirms that the coating 5 contributes to reinforcing the glass wall 2, in particular by filling in the microcracks on the surface. The aforementioned drop tests have also shown that when the bottle breaks and is not plasticized, it explodes systematically. On the other hand, when plasticized in accordance with the invention, glass breakage is systematically retained and the flask retains its integrity. With sufficient coating thickness, the liquid is also retained. In this case, the results in terms of retention were as follows: out of the 8 vials that broke, 7 retained both broken glass and liquid, while only one detained only broken glass. glass.
    [0011] Finally, various sterilization tests of vials coated in accordance with the invention were conducted, and concluded that the containers according to the invention support the main types of sterilization, as set out in Table 1 below.
    [0012] Sterilization Conditions Observations Autoclave 30min 121 ° C 2 bars Presence of water vapor Light flat observed at the contact areas when the vials touch, due to softening of the PU at a temperature of 121 ° C Sterilizer 5 min in a large sterilizer Bleaching machine that electric electric baby bottles disappears after a few (steam) minutes at room temperature Microwave 4 min at 8501 / V in a microwave sterilizer for baby bottles (water vapor) Cold chemical 30 min in a solution No modification / sodium hypochlorite degradation of the coating is observed Table 1 In the foregoing, it has been described a coating 5 having a homogeneous visual appearance. However, it is perfectly possible to introduce, for example, pigments into the lower layer 5A and / or into the upper layer 5B, in order to obtain a more or less translucent colored coating, or UV protection. Different effects and textures can also be sought and obtained, for example by means of the inclusion of particles or flakes. The coating 5 according to the invention is also suitable for the application on its upper layer 5B of a decoration, for example by screen printing or any other known technique. Finally, the idea of using a simple dispersion in the aqueous phase of a polyurethane already polymerized (making it unnecessary to use catalysts) whose molar mass is sufficiently high for the simple evaporation of the aqueous phase leads to forming a cohesive flexible film adhering to the glass wall 2, constitutes an invention as such.
    [0013] Therefore, as such constitutes an independent invention a container comprising a glass wall delimiting a receiving cavity for a liquid substance, said container further comprising a protective and retaining coating which externally covers at least a fraction of said glass wall, said protective and retaining coating being a multilayer coating which comprises on the one hand a lower layer obtained by drying a first intermediate product consisting of a dispersion in aqueous phase of an already polymerized material (non-reactive) based on polyurethane whose molar mass is sufficiently high for the simple evaporation of the aqueous phase resulting from said drying causes the formation of a film forming said lower layer and on the other hand an upper layer (with or without fluoropolymer) covering said bottom layer to protect it.
    权利要求:
    Claims (23)
    [0001]
    CLAIMS1 - A container (1) comprising a glass wall (2) defining a receiving cavity (3) for a fluid substance, said container (1) further comprising a coating (5) protection and retention which covers the outside of the at least a fraction of said glass wall (2), said container (1) being characterized in that said protective and retaining coating (5) is a substantially transparent multilayer coating which comprises a bottom layer (5A) covering the wall glass (2) and an upper layer (5B) covering said lower layer (5A), said lower layer (5A) being formed of a flexible polyurethane material adhered to said glass wall (2) while said top layer (5B) is formed of a polyurethane material functionalized with a fluoropolymer compound.
    [0002]
    2 - container (1) according to claim 1 characterized in that the thickness (El) of said lower layer (5A) is greater than that (E2) of the upper layer (5B).
    [0003]
    3 - container (1) according to claim 1 or 2 characterized in that the thickness (El) of said lower layer (5A) is substantially between 30 and 300 pm.
    [0004]
    4 - container (1) according to claim 3 characterized in that the thickness (El) of said lower layer (5A) is substantially between 50 and 200 pm, preferably substantially equal to 100 pm.
    [0005]
    5 - container (1) according to one of claims 1 to 4 characterized in that the thickness (E2) of said upper layer (5B) is substantially between 5 and 50 pm.
    [0006]
    6 - container (1) according to claim 5 characterized in that the thickness (E2) of said upper layer (5B) is substantially between 10 and 30 pm, preferably substantially equal to 20 pm.
    [0007]
    7 - container (1) according to one of claims I to 6 characterized in that said coating (5) is a bilayer coating, the lower layer (5A) adhering directly to the glass wall (2) while the upper layer (5B) forms the surface layer of the coating (5).
    [0008]
    8 - Container (1) according to one of claims 1 to 7 characterized in that said flexible material forming the lower layer (5A) is obtained by drying a first intermediate product consisting of an aqueous dispersion of a material non-reactive polymerization whose molar mass is sufficiently high that the mere evaporation of the aqueous phase resulting from said drying causes the formation of a film forming said lower layer (5A).
    [0009]
    9 - Container (I) according to claim 8 characterized in that said dispersion is an aqueous emulsion of said polymerized material.
    [0010]
    10 - Container (1) according to one of claims I to 9 characterized in that said fluoropolymer is polytetrafluoroethylene (PTFE).
    [0011]
    11 - Container (1) according to one of claims 1 to 10 characterized in that said material forming the upper layer (5B) comprises the reaction product of an isocyanate with at least one substance based on a fluoropolymer.
    [0012]
    12 - container (1) according to claim 11 characterized in that said material forming the upper layer is obtained by polymerization of a second intermediate product in the aqueous phase including at least said isocyanate and said substance based on a fluoropolymer.
    [0013]
    13 - Container (1) according to claim 11 or 12 characterized in that said isocyanate is a blocked isocyanate.
    [0014]
    14 - Container (1) according to one of claims 1 to 13 characterized in that it forms a container designed to contain a liquid substance for pharmaceutical use.
    [0015]
    15 - Kit for manufacturing a coating (5) of protection and multilayer retention substantially transparent intended to cover externally at least a fraction 303 1 740 26 of a glass wall (2) of a container (1), said glass wall (2) delimiting a receiving cavity (3) for a fluid substance, said kit comprising: - a first intermediate product intended to be applied in the form of a first layer on the glass wall (2), said first intermediate product 5 consisting of an aqueous phase dispersion of a non-reactive polyurethane whose molar mass is sufficiently high so that simple evaporation of the aqueous phase results in the formation, from said first layer, of a flexible film adhering to the glass wall (2); and a second aqueous phase intermediate product to be applied in the form of a second layer covering said first layer, said second aqueous phase intermediate including at least one isocyanate and a fluoropolymer substance for reacting together, after application to said first layer of said second intermediate product, to form a polyurethane material functionalized by a fluoropolymer compound.
    [0016]
    16 - Kit according to claim 15 characterized in that said fluoropolymer is polytetrafluoroethylene (PTFE).
    [0017]
    17 - Kit according to claim 15 or 16 characterized in that said isocyanate is a blocked isocyanate. 20
    [0018]
    18 - Method for manufacturing a container (1), in which a glass wall (2) delimiting a receiving cavity (3) for a fluid substance is manufactured or supplied, said method comprising an external recovery step of at least a fraction of said glass wall (2) by a protective and retaining coating (5), said method being characterized in that said protective and retaining coating (5) is a substantially transparent multilayer coating which comprises a lower layer (5A) covering the glass wall (2) and an upper layer (5B) covering said lower layer (5A), said lower layer (5A) being formed of a flexible polyurethane material adhered to said glass wall (2) while said top layer (5B) is formed of a polyurethane material functionalized with a fluoropolymer compound.
    [0019]
    19 - Process according to claim 18 characterized in that said covering step comprises a step of forming said lower layer (5A) during which: a first intermediate product consisting of a dispersion in aqueous phase of a non-reactive polymerized material is applied to the glass wall (2) in the form of a first layer, for example by spraying, - said first intermediate product thus applied to the glass wall (2) is dried, the molar mass of said polymerized material being sufficiently high that the mere evaporation of the aqueous phase resulting from said drying results in the formation of a film forming said lower layer (5A).
    [0020]
    20 - Process according to claim 19 characterized in that said dispersion is an aqueous emulsion of said polymerized material.
    [0021]
    Method according to claim 19 or 20, characterized in that said first intermediate product has a viscosity at 20 ° C which is between approximately 800 and 2000 mPa · s, preferably between approximately 1000 and 1800 mPa · s, even more preferentially between substantially 1300 and 1400 mPa.s.
    [0022]
    22. The process as claimed in claim 19, wherein said first intermediate product has a solids content of between 20 and 70% by weight, preferably between 30 and 60% by weight, more preferably still. between 45 and 55% by weight, for example 48% by weight.
    [0023]
    Method according to one of Claims 18 to 22, characterized in that the thickness of said lower layer (5A) is substantially between 30 and 300 μm, preferably substantially between 50 and 200 μm, and still more preferably substantially equal to 100 pm.24 - Process according to one of claims 18 to 23 characterized in that said covering step comprises a step of forming said upper layer (5B) during which: a second intermediate product in aqueous phase including at least one isocyanate and a substance based on a fluoropolymer is applied to said first layer, - said second intermediate product thus applied to said first layer is subjected to a treatment which causes the reaction of at least said isocyanate with the substance to fluoropolymer base for forming said polyurethane material functionalized with a fluoropolymer compound. 25 - Process according to claim 24 characterized in that said treatment includes a step of cooking said container (1) on which is applied said second intermediate product at a temperature sufficient to trigger said reaction, said temperature being for example between substantially 90 ° C and 200 ° C, preferably between 120 ° C and 180 ° C, even more preferably between 140 ° C and 170 ° C. 26 - Method according to one of claims 18 to 25 characterized in that said fluoropolymer is polytetrafluoroethylene (PTFE). 27 - Method according to one of claims 24 to 26 characterized in that said isocyanate is a blocked isocyanate. 28 - Method according to one of claims 24 to 27 characterized in that said second intermediate product has a viscosity at 20 ° C which is between substantially 5 and 30 mPa.s, preferably between substantially 10 and 20 mPa.s, even more preferably between substantially 14 and 15 mPa.s. Process according to one of Claims 24 to 28, characterized in that the said second intermediate product has a solids content of between 10 and 60% by weight, preferably between 20 and 50% by weight, even more preferably between 25 and 40% by weight, for example 32% by weight.30 -Procédé according to one of claims 18 to 29 characterized in that the thickness of said upper layer is substantially between 5 and 50 gin, preferably substantially between 10 and 30 pnn, still more preferably substantially equal to 20 pm.5
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    同族专利:
    公开号 | 公开日
    EP3045401A1|2016-07-20|
    JP2016132508A|2016-07-25|
    FR3031740B1|2017-02-24|
    CA2917451A1|2016-07-15|
    US20160206508A1|2016-07-21|
    CN105800043A|2016-07-27|
    引用文献:
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    FR2221414A1|1972-12-23|1974-10-11|Toyo Ink Mfg Co|
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    FR2970468A1|2011-01-18|2012-07-20|Sgd Sa|Container i.e. glass bottle, for containing e.g. drug, has barrier layer interposed between plastic coating of wall and informative and/or decorative medium such as paper label, to limit migration of component of coating toward label|
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    CN203127473U|2013-03-19|2013-08-14|王一鸣|Case for contain packed meal|FR3041956B1|2015-10-06|2017-12-01|Sgd Sa|METHOD FOR RECOVERING A GLASS ARTICLE|
    CN106275733B|2016-08-31|2019-03-26|中国标准化研究院|A kind of vial and preparation method thereof for that can reduce to the loss of expensive powdered samples|
    WO2018140698A1|2017-01-27|2018-08-02|Tedia Company, Inc.|Chemical reagent bottle internally coated with a fluoropolymer|
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    法律状态:
    2016-01-28| PLFP| Fee payment|Year of fee payment: 2 |
    2016-07-22| PLSC| Publication of the preliminary search report|Effective date: 20160722 |
    2017-01-26| PLFP| Fee payment|Year of fee payment: 3 |
    2018-01-18| PLFP| Fee payment|Year of fee payment: 4 |
    2020-01-23| PLFP| Fee payment|Year of fee payment: 6 |
    2021-01-27| PLFP| Fee payment|Year of fee payment: 7 |
    2022-01-24| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1550325A|FR3031740B1|2015-01-15|2015-01-15|CONTAINER COVERED WITH PROTECTIVE AND RETENTION COATING, KIT FOR MANUFACTURING PROTECTIVE COATING AND RETENTION COATING, AND MANUFACTURING METHOD THEREOF|FR1550325A| FR3031740B1|2015-01-15|2015-01-15|CONTAINER COVERED WITH PROTECTIVE AND RETENTION COATING, KIT FOR MANUFACTURING PROTECTIVE COATING AND RETENTION COATING, AND MANUFACTURING METHOD THEREOF|
    CN201510290331.8A| CN105800043A|2015-01-15|2015-05-29|Container covered with a protection and retention coating, a kit for manufacturing protection and retention coating, and related manufacturing method|
    EP16150947.6A| EP3045401A1|2015-01-15|2016-01-12|Container covered with a protecting and retaining coating, kit for producing a protecting and retaining coating and method for manufacturing same|
    JP2016004507A| JP2016132508A|2015-01-15|2016-01-13|Container covered with protective holding coating, kit for manufacturing protective holding coating, and related manufacturing method|
    CA2917451A| CA2917451A1|2015-01-15|2016-01-13|A container covered with a protection and retention coating, a kit for manufacturing a protection and retention coating, and a related manufacturing method|
    US14/995,731| US20160206508A1|2015-01-15|2016-01-14|Container covered with a protection and retention coating, a kit for manufacturing a protection and retention coating, and a related manufacturing method|
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