Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
  • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
  • C03C21/006—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform an exchange of the type Xn+ ----> nH+
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
  • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
  • A61J1/14—Details; Accessories therefor
  • A61J1/1468—Containers characterised by specific material properties
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
  • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
  • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers

Definitions

• the present invention relates to a method and a device for passivating the inner surface of a glass vial.
• passivation is meant extraction prior to use of the bottle, elements likely to come out of the inner wall of the bottle during contact with the products that will be stored later.
• the extraction must be sufficient for the weight measurements of these elements to be below a certain threshold fixed by the standards in force.
• neutral glass means a glass which releases in time very little sodium or other alkaline and / or alkaline earth ions in the liquid or product which is inside the container.
• soda-lime glass is not neutral in the sense of pharmacopoeia.
• alkali although generally very small are troublesome in the case of bottles intended to contain vaccines or active ingredients, which must remain pure.
• the treatment can also be done during the elaboration of the glass, where precursors are introduced into the oven which will make the obtained glass less subject to this migration.
• An aqueous acidic mixture in the presence of a surfactant is used here for washing.
• the present invention aims to provide a method, a device and a bottle obtained by such a method, better than those previously known to the requirements of practice, in particular in that it does not generate release of harmful products to passivate or protect the inner wall of the vial or container, in that it does not require any violent treatment or mandatory rinsing before and / or after use and that it makes it possible to treat all types of vials, irrespective of the suppliers of these and this generating less breakage or damage containers than in the prior art.
• the invention proceeds from the idea of using the chemical reactions of water with the inner wall of the glass container, reactions that occur with all products containing water (including air wet or steam).
• the invention therefore proposes a process based on the more or less important activation of these reactions, taking into account the composition and alkali concentration of the inner face of the glass vial, so as to allow ion exchange. between the container and the water.
• composition of the glass and in particular the quantity of alkaline and alkaline earth contained in it, naturally influence the resistance to water and the exudation.
• the purpose of the present invention is therefore to implement these principles with the advantages mentioned above and to overcome the drawbacks of the prior art.
• it proposes in particular a method of passivating the inner wall of a glass container adapted to contain a pharmaceutical grade product, characterized in that to passivate and / or inhibit the internal surface of the container, said surface is treated. internal of the container by ion exchange between the container and an aqueous extraction liquid so that the measured hydrolytic resistance of said surface is at least halved.
• the ability to resist the release of elements is multiplied by at least two.
• the hydrolytic resistance is measured before treatment, and after treatment, by determining the amount of sodium oxide and other alkaline or alkaline-earth oxides released during autoclave treatment at 121 ° C. for 60 minutes, the For example, the measurements are then carried out in a manner known per se by flame spectrometry.
• the aqueous extraction liquid is water of quality RI.
• water of quality R corresponds to purified water by distillation, ion exchange, reverse osmosis or by any other appropriate method, from a water intended for human consumption.
• the conductivity of such a water is less than
• the limit on the total organic carbon is set at 0.5 mg / 1.
• the water R must comprise less than 0.1 ppm of heavy metals (Pb) and 0.2 ppm of nitrate.
• the water of quality RI is in turn a water R decarbonated by boiling for 15 minutes, or by any other appropriate method. Its resistivity must be at least 1 M ⁇ .cm, ie a conductivity less than 1 ⁇ S.cit 1 ;
• the internal surface of the container is treated with at least three passages of the bottle in an autoclave, at a temperature greater than 120 ° C., each time for a time greater than one hour, the aqueous extraction liquid being likewise changed every time .
• the idea here is to use the autoclave, which so far has only been used to measure, industrially as a repetitive process proper (ie more than three times in succession, for example five or ten times). times) .
• the autoclave internal water allows the desired chemical reaction, while maintaining the extraction liquid in liquid form at a higher level. temperature thanks to the pressure (which proves to be very effective);
• the extraction liquid is an acidic aqueous solution with pH corrected to 8.
• corrected with 8 is meant that the pH of the extraction liquid is reduced to
• the acid is, for example, citric or acetic acid
• the container being for example a bottle
• the following steps are carried out at least once:
• the internal face of the bottle is brought into contact by filling, vaporization or trickling of the aqueous extraction liquid into the bottle,
• the bottle is heated with the extraction liquid inside the container and / or while maintaining a saturated atmosphere inside the container, up to a predetermined temperature greater than or equal to 80 ° C. and during a first determined time arranged to prevent thermal shock and respect the internal tensions of the bottle,
• the flask is maintained at this temperature for a second determined time greater than or equal to 30 minutes, (for example 1 to 2 hours), the inside of the flask being kept entirely in contact with said liquid and / or said saturated atmosphere,
• the bottle and the extraction liquid, and / or the saturated atmosphere inside are cooled for a third determined time arranged to prevent thermal shocks and to respect the internal tensions in the bottle and the extraction liquid is emptied if it has not been evaporated in a previous step.
• saturated atmosphere is meant an atmosphere 100% charged with extraction liquid, the latter being maintained for a time arranged to ensure a sufficient contact time for the extraction of alkali from the inner glass wall of the bottle or container.
• the extraction liquid being acid (for example acetic acid)
• the liquid is sprayed into the bottle at a temperature above 80 ° C. (for example 95 ° C.) for the second time determined which is greater than 30 minutes;
• the extraction liquid is introduced into the container in the form of ice;
• the rise in temperature is carried out by an electric cooking arch in a saturated atmosphere.
• the invention also proposes a device implementing the method as described above.
• the invention also proposes a device for passivating the internal surface of glass vials, characterized in that it comprises
• the invention also provides a vial obtained by the method described above.
• pharmaceutical use is meant the use according to version 8 of the European Pharmacopoeia published by the European Directorate for the Quality of Medicines and Health Care.
• not treated with fluorine and / or sulfur is meant not having undergone the passivations known to those skilled in the art to fluorine and / or sulfur.
• the glass vials treated according to the invention for cosmetic, food or pharmaceutical use, have an improved resistance to aging and humidity of the air, which also makes it possible to avoid the known phenomenon. exudation with air and therefore to be able to use the bottles treated several years after treatments without having to clean them.
• the bottles obtained have an improved cleanliness of the internal surface, including through the elimination of dust and particles.
• the container furthermore has and / or moreover a surface composition with a thickness e ⁇ lOpm, for example less than 5 ⁇ m, for example between 0.Olpm and 0.5pm, for example between 0.OOlpm and O.Olpm in alkaline or alkaline earth at least 5% lower than the glass composition in the mass.
• a thickness e ⁇ lOpm for example less than 5 ⁇ m, for example between 0.Olpm and 0.5pm, for example between 0.OOlpm and O.Olpm in alkaline or alkaline earth at least 5% lower than the glass composition in the mass.
• Fig. 1 is a flowchart showing the steps of a passivation method according to one embodiment of the invention.
• FIG. 2 shows a flowchart of the steps of the method according to another embodiment of the invention.
• Figure 3 shows a curve of the evolution of the hydrolytic resistance RH as a function of the treatment conditions.
• FIG. 4 schematically shows in perspective an embodiment of a device implementing the method described with reference to FIG.
• FIG. 5 shows an exploded partial view of an example of an internal container wall according to one embodiment of the invention, as obtained by the method described with reference to FIG.
• FIG. 1 shows the steps of the passivation method according to the embodiment of the invention, more particularly described here, of the internal face of one or more bottles, for example open pharmaceutical bottles, placed on removable rack-type supports. .
• stage 2 After a first step 1 for supplying the bottles, they are filled into aqueous extraction liquid (stage 2), for example water of quality RI.
• the aqueous liquid is sprayed in fog inside the bottles, in a manner known per se, for example by means of individual nozzles automatically positioned in front of the opening of the bottles.
• the spraying is adapted to ensure a continuous thin layer of liquid on a given surface of said flasks, which are then placed in a heating chamber (step 3), confined and maintained at a given hygrometry extraction liquid.
• the hygrometry rate is for example 100%. In this way the contact between the extraction liquid and the inner wall of the bottle is ensured permanently.
• the heating chamber is for example a furnace or an electric arc and / or gas.
• the flasks are then mounted at a predetermined temperature of between 70.degree. C. and 150.degree. C., for example 80.degree. first time, for example 15 minutes so as to avoid thermal shocks.
• the temperature is controlled in a known manner in itself and the flask is then maintained (step 4) at said determined temperature for a second time determined for example 40 minutes.
• the flasks are then removed from the oven (step 5) or the heating zone thereof, to be cooled for a third time, for example three minutes, again with appropriate kinetics to prevent thermal shock.
• the final temperature obtained after cooling is for example the ambient temperature.
• step 6 if it has not been evaporated (test 7) in a previous step.
• steps 2 to 6 are repeated (test 8) for a predetermined number of times, for example two, so as to obtain a hydrolytic resistance below the predetermined threshold chosen.
• the aqueous extraction liquid is changed each time (reiteration of step 2).
• the flasks are then but not necessarily rinsed and then dried (step 9) before being stored for later use.
• Figure 2 gives the steps of the method according to the embodiment of the invention using an autoclave.
• This one is of a type known in itself. After a first step of supplying the bottles, they are filled into aqueous extraction liquid and are closed, for example by an unsealed aluminum foil (step 2).
• step 3 ' After they are placed in an autoclave (step 3 ').
• the contents of the autoclave are then carried, respecting the temperature rise steps to prevent thermal shock, at the second determined temperature (for example 121 ° C) and the corresponding pressure. It is maintained at these for the second determined time, for example greater than 1 hour (step 4 ').
• the pressure inside the autoclave is adapted to maintain the extraction liquid in the liquid phase.
• the pressure is increased by latm (atmosphere) relative to the ambient atmospheric pressure.
• the flasks are then reduced in temperature, for example to 80 ° C., while respecting the constraints of the glass (step 5 ').
• the bottle is then emptied of its contents (step 6 ') and the steps 2' to 6 'are repeated (line 7') a number of times greater than three, for example five times or ten times (test 8 ').
• the flasks are then evacuated after a possible rinsing (step 9 ').
• FIG. 3 shows the influence of the parameters P of the process on its efficiency.
• the parameters P are the various temperatures and time determined by the process, the pressure conditions used and the composition of the extraction liquid.
• Curve C represents the evolution of the hydrolytic resistance (RH) of the internal walls of the flasks as a function of these parameters.
• the minimum resistance Rh then corresponds to a minimum of subsequent release of elements of the glass in the content.
• the invention provides a method that allows to stay in the (inverted) top of the curve C (hatched line in the figure).
• An embodiment of a device D embodying the method of FIG. 1 will now be described with reference to FIG.
• Device D firstly comprises means 11 for transporting vials 12, such as for example a treadmill.
• the bottles 12 are for example individually arranged on the conveyor belt 11, or inserted into supports (not shown).
• Means 13 for filling and / or spraying / spraying the aqueous extraction liquid 14 into the flasks are provided.
• They are for example formed by injection nozzles 15, which fill or spray a specific amount of liquid 14 in each of the bottles, for example by filling at least 80% of their volume.
• the aqueous extraction liquid is for example water of quality RI or citric acid water with pH corrected to 8.
• the extraction liquid is introduced in the form of crushed ice into the flasks, which, for a given boiling point, lengthens the contact time between the liquid and the inner wall and protects against thermal shocks .
• Device D comprises, disposed downstream of the filling zone on the treadmill, an oven 16.
• the oven 16 is for example a heating arch
• the hot zone successively comprises, in the direction of travel of the treadmill, a first sub-zone 18 for raising the temperature, a second sub-zone 19 for maintaining a given temperature, and a third sub-zone 20 for cooling to ambient temperature. .
• the conveyor belt 11 thus makes the bottles 12 enter the first subarea 18 of the cooking arch 17 which progressively raises the temperature up to a first temperature determined, for example, of 80 ° C.
• the treadmill 11 then causes the bottles 12 to enter the second heating sub-zone 19 which also comprises means 13 'for maintaining the atmosphere of the arch in saturation of the extraction liquid.
• These means 13 comprise means for controlling and supplying extraction liquid to the enclosure of the furnace 17.
• the extraction liquid 14 is acetic acid introduced in fog into the chamber and therefore the bottles, at a temperature above 80.degree. C. (for example 95.degree. determined second time which is greater than 30 minutes.
• injection nozzles (not shown) acid mist placed directly inside the hot zone (oven or arch).
• the treadmill 11 at a speed and / or a length adapted so that the bottles 12 remain in said arch 17 for a certain time in particular at the desired operating temperatures.
• the treadmill 11 is then passed through the vials 12 the third hot sub-zone 20 comprising means for cooling said vials.
• These means may be in the open air or in a controlled atmosphere.
• the control on / off
• the speed and / or the length of the treadmill 11 must allow a rise / fall in temperature sufficiently slow to prevent thermal shock but adapted to the reaction kinetics.
• the operation of the treadmill is therefore programmed and controlled accordingly.
• the flasks are emptied after treatment and closed for example by an aluminum foil 21 during their descent in temperature, which will allow to maintain their inner wall in an aseptic medium.
• the device also includes, if necessary, means 22 for tilting the bottles in a manner known per se, for emptying them for example above a storage tank 23, before placing them in another workstation.
• the other workstation may be a packaging unit.
• it may be another treatment device D and / or gripping means for returning the bottles to the beginning of the chain to repeat the treatment a specified number of times.
• the bottle 25 (shown in sectional view, exploded, partial) is formed of glass 26 consisting of a chemical network whose forming ions provide the structure and modifying ions, of weaker chemical bond with the network, and which form the elements (residual chemical species released) whose invention proposes in particular to reduce the amount released.
• the forming ions are SiO 2, Al 2 O 3 present at almost 74% of the total mass and B 2 O 3 present at almost 12%.
• the network modifying ions are, for example, Na 2 O and / or K 2 O up to the percentage remaining.
• the inner surface 27 of the container 25 carries out an ion exchange between the container and an aqueous liquid 14 of extraction so that the hydrolytic resistance of said surface 27 is at less divided by two in absolute value (resistance capacity multiplied by 2).
• the ion exchange thus produces a passivation of the container.
• the bottle of FIG. 5 has been treated by a process according to the invention.
• said flasks 25 are subsequently untreated, they are then devoid of sulfur and / or fluorine and have a hydrolytic resistance R H of less than 50% of the lower limit indicated by the European Pharmacopoeia for this type of flask and glass.
• the vials after treatment with the invention has a hydrolytic inner wall resistance of at least less than 20% of the lower limit indicated by the European Pharmacopoeia.
• Each implementation corresponds to specific parameter conditions specified in the "Test conditions" column.
• the reference conditions are those considered above as the normal conditions giving a basic hydrolytic resistance R0, with a bottle stored empty after cooling for several weeks (having therefore undergone natural aging under normal storage conditions at fairly long open air).
• the measurements carried out show that the embodiment of the test 7 in which the process is carried out by an autoclave with water of quality RI at 121 ° C. for three cycles of one hour makes it possible to reduce nearly three times the hydrolytic resistance and thus make it almost three times better.
• the present invention is not limited to the embodiments more particularly described. On the contrary, it embraces all the variants and in particular those in which the number of cycles, the temperatures, the pressures, and the durations are determined differently, depending on the glass and the desired results, those in which the container is a pot or another container. in glass, and those where the hot sub-zones themselves comprise sub-zones of variation of the temperature downhill and / or in mounting said temperatures.

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• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Pharmacology & Pharmacy (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Surface Treatment Of Glass (AREA)
• Medical Preparation Storing Or Oral Administration Devices (AREA)
• Cleaning By Liquid Or Steam (AREA)
• Details Of Rigid Or Semi-Rigid Containers (AREA)

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• 2014
  • 2014-02-18 FR FR1451304A patent/FR3017613B1/fr active Active
• 2015
  • 2015-02-18 US US15/119,212 patent/US20170008797A1/en not_active Abandoned
  • 2015-02-18 JP JP2016553495A patent/JP2017512173A/ja active Pending
  • 2015-02-18 EP EP15709274.3A patent/EP3107873B1/fr active Active
  • 2015-02-18 WO PCT/FR2015/050395 patent/WO2015124865A1/fr not_active Ceased

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