EP2370614B1 - Procede de fabrication d'un corps creux pourvu d'une surface interieure en verre metallisee et corps creux correspondant - Google Patents

Procede de fabrication d'un corps creux pourvu d'une surface interieure en verre metallisee et corps creux correspondant Download PDF

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Publication number
EP2370614B1
EP2370614B1 EP09797113.9A EP09797113A EP2370614B1 EP 2370614 B1 EP2370614 B1 EP 2370614B1 EP 09797113 A EP09797113 A EP 09797113A EP 2370614 B1 EP2370614 B1 EP 2370614B1
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EP
European Patent Office
Prior art keywords
inside surface
metal
cavity
lining
hollow body
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Application number
EP09797113.9A
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German (de)
English (en)
French (fr)
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EP2370614A2 (fr
Inventor
Christophe Jean Wagner
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Verescence France SAS
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Verescence France SAS
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Publication of EP2370614A2 publication Critical patent/EP2370614A2/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1889—Multistep pretreatment with use of metal first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2425/00—Indexing scheme corresponding to the position of each layer within a multilayer coating relative to the surface
    • B05D2425/01—Indexing scheme corresponding to the position of each layer within a multilayer coating relative to the surface top layer/ last layer, i.e. first layer from the top surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/02—Linings or internal coatings

Definitions

  • the present invention relates to the general field of hollow bodies provided with an internal glass surface which can be used in various industrial sectors, such as for example the packaging sector (glass containers, of the flasks or jars type, intended to contain a substance. liquid or pasty, for example a cosmetic or pharmaceutical substance) or construction (hollow glass bricks).
  • the invention also relates to the general technical field of the treatment of glass surfaces, for functional and / or decorative purposes.
  • the invention relates more precisely to a method of manufacturing a hollow body provided with an interior glass surface delimiting a cavity, as well as such a hollow body.
  • glass containers to contain liquid products, in particular in the cosmetic, pharmaceutical or food industries.
  • the use of glass for producing liquid perfume containers is particularly popular, given the noble character generally attributed to glass by consumers, and the objective qualities of transparency, robustness, and mechanical and chemical stability. of this material. This is why all or almost all liquid body perfumes, and in particular perfumes considered to be “ high-end ”, are contained in glass bottles.
  • the aesthetic qualities of a perfume bottle are also extremely important for the overall commercial attractiveness of a perfume. From this perspective, it is therefore essential to provide a perfume bottle whose aesthetics are very distinctly different from that of the bottles of the competition, and which is particularly attractive and enhancing for the perfume contained in the bottle.
  • the second reason relates to the environment to which the glass constituting the perfume bottles is subjected and the general context of use of these bottles.
  • the interior of a perfume bottle is in direct contact with the perfume itself, which usually consists of an alcoholic liquid.
  • the perfume itself which usually consists of an alcoholic liquid.
  • any decoration placed on the inner surface of the bottle in order to be visible by transparency from the outside to the consumer, must withstand being permanently and in the long term bathed in such an alcoholic solution, without disintegrating, disintegrate, decompose or dissolve, which is a real technical challenge.
  • JP-2000129448 discloses a method according to the preamble of claim 1, and a hollow body according to the preamble of claim 16.
  • the document US-6,251,482 describes an example of the manufacture of a mirror in which glass sheets are first polished, rinsed and then sensitized by means of a solution of tin chloride, then rinsed. An acidic aqueous solution of PdCl 2 is then sprayed onto the glass sheets. The glass sheets thus activated then pass to a rinsing station, then to a silvering station where a traditional silvering solution is sprayed so as to form, under conditions of conventional production, a layer containing about 800 to 850 mg / m 2 of silver. The mass of silver deposited is greater by approximately 100 mg / m 2 of silver, that is to say approximately 900 to 950 mg / m 2 of silver.
  • the glass is then rinsed, and directly after rinsing the silver coating, an acidified solution of freshly formed tin chloride is sprayed onto the silver glass sheets moving forward. Other steps are then implemented (spraying with a silane, rinsing, drying, covering with a Levis paint).
  • the objects assigned to the invention therefore aim to remedy the problem set out in the foregoing and to propose a new method of manufacturing a hollow body provided with an interior glass surface, making it possible to obtain a hollow body. particularly attractive from the aesthetic point of view.
  • Another object of the invention aims to provide a new method of manufacturing a hollow body provided with an interior glass surface, which makes it possible to obtain a particularly aesthetic hollow body and resistant to use, both from the point of view of mechanical and chemical point of view.
  • Another object of the invention is to provide a new method of manufacturing a hollow body provided with an interior glass surface, which makes it possible to obtain a particularly aesthetic hollow body extremely quickly and inexpensively.
  • Another object of the invention aims to provide a new method of manufacturing a hollow body provided with an interior glass surface, which is not only rapid but which also makes it possible to provide said hollow body with a particularly homogeneous decoration. and free from defects.
  • Another object of the invention aims to provide a new method of manufacturing a hollow body provided with an interior glass surface, making it possible to obtain a hollow body which is not only very aesthetic but is also extremely robust and durable. .
  • Another object of the invention aims to provide a new method of manufacturing a hollow body provided with an interior glass surface, making it possible to obtain a hollow body capable of stably and durably accommodating a fluid substance, and in particular a relatively aggressive fluid substance from the chemical point of view.
  • Another object of the invention is to provide a new hollow body provided with an interior glass surface having a particularly attractive appearance.
  • Another object of the invention aims to provide a new hollow body provided with an interior glass surface with a particularly elegant and sought-after decoration, and capable moreover of contributing to the preservation of any substance, in particular medicinal substance, capable of be contained in said hollow body.
  • Another object of the invention is to provide a new hollow body provided with an interior glass surface with a particularly rich and attractive decoration.
  • Another object of the invention aims to provide a new hollow body provided with an interior glass surface capable of reliably and durably containing a fluid substance, and in particular a relatively aggressive fluid substance from the chemical point of view.
  • the invention relates firstly to a method of manufacturing a hollow body 1 provided with an interior glass cavity 2 delimiting a cavity 3.
  • the hollow body 1 preferably constitutes a container 4 designed to contain a liquid or pasty substance in the cavity 3, and in particular an alcoholic liquid such as a body perfume.
  • the container 4 is advantageously intended to be closed by means of a closure member 5, for example constituted by a stopper 5A.
  • the process according to the invention thus consists of a process for manufacturing a bottle intended to contain a liquid or pasty cosmetic substance, and preferably a perfumed alcoholic liquid.
  • the process in accordance with the invention constitutes a process for manufacturing a bottle intended to receive a substance other than cosmetic, and for example a pharmaceutical substance, such as a drug.
  • the hollow body 1 can constitute a hollow glass brick, which can be used in construction and / or decoration, the process according to the invention consisting in this case in a process for manufacturing a hollow glass brick.
  • the method according to the invention naturally comprises first of all a step of manufacturing or supplying a hollow body 1 provided with an interior surface 2 in glass delimiting a cavity 3.
  • glass should be taken here in its classic meaning, and therefore designates a mineral glass.
  • this step of manufacturing or supplying the hollow body 1 with interior glass surface 2 consists of manufacturing or supplying a single-piece hollow body, entirely made of glass, within which the glass is formed. cavity 3.
  • the hollow body 1 is constituted by a single part manufactured in a single block, for example by a blowing or molding process.
  • the production of such a hollow glass body, in particular when said hollow body constitutes a bottle, is perfectly known as such and can be obtained by any conventional glass process.
  • the hollow body 1 delimiting the cavity 3 is made in one piece, and not by assembling independent parts, makes it all the more difficult to decorate the inside of the hollow body 1, in particular when this the latter is provided with a neck (in the case of a bottle for example) which further restricts access to cavity 3.
  • the hollow body 1 is therefore, as explained in the foregoing, provided with a cavity 3 delimited by an interior surface 2, that is to say that the hollow body 1 is hollowed out and as such defines an empty volume in her breast.
  • the hollow body 1 is shaped so that the cavity 3 forms a constriction 6 defining an opening 7 allowing the cavity 3 to be placed in communication with the outside, said opening 7 preferably being intended to cooperate with said closure member 5. to close the hollow body 1 when the latter constitutes a container 4.
  • the cavity 3 forms an empty interior volume which is entirely closed, with the exception of an opening 7 towards the exterior, the section of which is reduced compared to the average section of the cavity 3, as illustrated in the figure
  • Such a configuration is characteristic of a bottle provided with a neck, that is to say a narrow neck making it possible to put the inside of the bottle in communication with the outside.
  • the method further comprises a step of covering at least a fraction of the interior surface 2 with a coating 8 of predominantly metallic composition.
  • a coating 8 of predominantly metallic composition it is also conceivable, in order to obtain specific aesthetic effects, for the composition of the coating 8 to include a (minority) fraction of a dye, for example in the form of a colored pigment dispersed homogeneously in the coating. coating 8, mixed with the metal mainly constituting the latter.
  • the covering step is designed so that substantially all of the interior surface 2 is covered by the coating 8 of predominantly metallic composition, as illustrated in figure 2 .
  • the coating 8 of predominantly metallic composition
  • the coating 8 is of substantially entirely metallic composition, and is preferably constituted by a shiny metal capable of providing a reflecting effect (“ mirror ” effect) such as silver, and to a lesser extent gold, gold. nickel, platinum, zinc and copper. It is in particular perfectly conceivable that, advantageously, the coating 8 is predominantly or even exclusively composed of gold.
  • a gold coating seen from the outside through the transparent wall of the hollow body 1, in fact provides a quite remarkable aesthetic result, the gold being moreover tolerable by the human organism so that it can be placed in direct contact with the substance likely to be contained by the cavity 3 (perfume for example).
  • the coating 8 is advantageously composed of a precious metal (noble metal), such as palladium, rhodium, ruthenium or osmium for example, or of another non-precious metal such as tin or cobalt.
  • a precious metal such as palladium, rhodium, ruthenium or osmium for example
  • another non-precious metal such as tin or cobalt.
  • the covering of the inner surface 2 with such a coating of predominantly metallic composition makes it possible to decorate the hollow body 1 in a particularly original way, insofar as the metallic coating 8 is advantageously visible by transparency through the wall 1A of the hollow body 1 forming the inner surface 2.
  • the inner surface 2 can be made of transparent white glass, it being understood that colored and / or translucent glass can also give good aesthetic results. The characteristics of the glass used, in particular its nature and its thickness, can advantageously influence the original aesthetic effects conferred by the coating 8.
  • the predominantly metallic character of the coating 8 can impart specific functional properties to the hollow body 1 which is provided with it on its inner surface 2.
  • a coating 8 essentially composed of silver allows to impart microbicidal properties to the interior surface 2, which proves to be particularly useful in the pharmaceutical sector.
  • the method in accordance with the invention comprises a washing step, preferably with demineralized water, of the interior glass surface 2, of the hollow body 1.
  • this washing step is carried out using a rinsing liquid (preferably demineralized water) whose pH is substantially greater than or equal to 5, and even more preferably to 5.5.
  • a rinsing liquid preferably demineralized water
  • the choice of such a pH proves to be particularly beneficial because it makes it possible to substantially avoid, in particular when covering with a silver-based coating 8 is implemented, a phenomenon of degradation of the deposited silver layer. on the inner surface 2.
  • this covering step firstly comprises a sub-step for activating the inner surface 2, in order to thus obtain an activated inner surface 2, that is to say which is more chemically reactive than the inner surface. 2 gross.
  • this activation sub-step makes it possible to increase the surface energy of the interior glass surface 2 in order to promote the chemical reactivity of the latter.
  • the activation substep is carried out by bringing the inner surface 2 into contact with a solution of tin chloride (SnCl 2 ) as an activating agent (also called an activating agent), the chloride tin proving to be particularly suitable for the implementation of a process aimed at coating the inner surface 2 with a silver coating.
  • bringing the inner surface 2 into contact with the tin chloride solution forming an activation solution consists in filling the cavity 3 with the tin chloride solution for a time sufficient to allow the activation of the. interior surface 2 and get an interior surface 2 activated.
  • the activation sub-step is carried out by direct contact of the activation solution with the inner surface 2, that is to say in the absence of any intermediate layer (primer layer for example) covering the interior glass surface 2.
  • the tin chloride solution is discharged out of the cavity 3.
  • bringing the interior surface 2 into contact with the activation solution in the occurrence of tin chloride
  • Such vaporization can for example be carried out using a projection nozzle introduced into the hollow body 1 (for example through the opening 7 if said hollow body forms a bottle provided with the opening 7 in question, preferably by the constriction 6 and beyond the latter), a relative rotational and translational movement of the hollow body 1 and of the nozzle being implemented so that the tin chloride solution is sprayed uniformly and homogeneously over the entire interior surface 2 to be treated, regardless of the shape of the cavity 3 defined by the interior surface 2.
  • Bringing the interior surface 2 into contact with the tin chloride solution by vaporization of the latter is particularly advantageous because it allows rapid industrialized treatment, with a quantity of tin chloride solution much lower than that required for the implementation of the other contacting method described above.
  • the covering step then advantageously comprises , after the waiting time mentioned above, a sub-step of rinsing the activated interior surface 2, to remove any residues from the activation solution (which preferably consists of a solution of chloride of tin, as discussed in the above).
  • the activated interior surface 2 comprises an activating layer (not shown) formed by the activating agent at least partially covering the interior surface 2.
  • the step of activation makes it possible to create not an activation layer but activation points (not shown) constituted by the activating agent distributed discretely, and preferably evenly, on the interior surface 2.
  • step covering subsequently comprises a sub-step of grafting said inner surface 2 activated with a grafting agent, thereby obtaining a grafted inner surface 2.
  • the grafting sub-step thus makes it possible to chemically graft a grafting agent onto the activated inner surface 2, by chemical reaction between the grafting agent and the activated inner surface 2, said reaction leading to the formation of chemical bonds between the. grafting agent and the inner surface 2 activated.
  • the grafting sub-step allows the establishment of chemical bonds between the grafting agent and the activating agent.
  • the grafting solution comes to cling directly to the inner surface 2.
  • the grafting agent is based on palladium.
  • the grafting sub-step comprises bringing the activated inner surface 2 into contact with a grafting solution, which preferably consists of a solution of palladium chloride (PdCl 2 ).
  • a grafting solution which preferably consists of a solution of palladium chloride (PdCl 2 ).
  • this bringing the activated inner surface 2 into contact with a grafting solution is carried out by filling the cavity 3 with said grafting solution, and preferably by completely filling (to the brim) of said cavity 3. .
  • the filling of the cavity 3 with the grafting solution is carried out in an automated manner.
  • this filling is carried out using a filling machine (filling machine) comprising, as illustrated in figure 3 , a central nozzle 9 through which passes and flows the grafting solution (preferably consisting of a solution of palladium chloride) towards and in the cavity 3, and a peripheral suction nozzle 10, concentric and coaxial with the central nozzle 9, intended to suck up any overflow of grafting solution.
  • a filling machine comprising, as illustrated in figure 3 , a central nozzle 9 through which passes and flows the grafting solution (preferably consisting of a solution of palladium chloride) towards and in the cavity 3, and a peripheral suction nozzle 10, concentric and coaxial with the central nozzle 9, intended to suck up any overflow of grafting solution.
  • the double nozzle is intended to come into contact with the opening 7 giving access to the cavity 3 so that the peripheral suction nozzle 10, the diameter of which is adapted to that of the opening 7, prevents a possible overflow of the grafting solution out of the container 4.
  • the introduction of the grafting solution through the central nozzle 9 and the suction through the peripheral nozzle 10 are preferably carried out simultaneously.
  • the double nozzle is designed to allow direct contact of the grafting solution with the interior surface 2 whatever the shape of the hollow body 1, in particular if it constitutes a bottle 4 with a constriction 6.
  • the grafting agent is designed to form a grafting layer (not shown) which advantageously covers, at least partially, the activating agent (which is in the form of a layer of activation or a distribution of activation points) which is attached directly to the interior surface 2.
  • the interior surface 2 is thus covered, at least in part, by said activation and grafting layers, which are preferably superimposed.
  • the grafting step allows the grafting agent to form chemical bonds with the activating agent at the activation points (or layer) present on the inner surface 2, so that s 'establish chemical bonds between the activating agent and the grafting agent to form attachment points for the metallic coating.
  • the palladium chloride solution is left for a sufficient contact time (for example of the order of about twenty or thirty. seconds) to make bonds between palladium and tin.
  • the method according to the invention comprises a step of recovering the grafting solution after its brought into contact with the activated interior surface 2, insofar as this recovered solution can be used again to graft another interior surface of another hollow body.
  • a quantity of approximately 2 ml of palladium is necessary to treat a vial whose capacity, that is to say the volume of cavity 3, is 130 ml.
  • bringing the activated interior surface 2 into contact with the grafting solution consists of spraying the palladium chloride solution onto the activated interior surface 2, that is, that is to say in spraying said solution of palladium chloride on the activated interior surface 2 in the form of fine droplets (spray).
  • Such vaporization can for example be carried out using a projection nozzle introduced into the hollow body 1 (for example through the opening 7 if said hollow body forms a bottle provided with the opening 7 in question, preferably by the constriction 6 and beyond the latter), a relative rotational and translational movement of the hollow body 1 and of the nozzle being implemented so that the palladium chloride solution is sprayed uniformly and homogeneously on the entire interior surface 2 activated to be treated.
  • Bringing the activated interior surface 2 into contact with the palladium chloride solution by vaporization of the latter is particularly advantageous because it allows rapid industrialized treatment, with a quantity of palladium chloride solution much less than that required for the setting. implementation of the other contacting method described above.
  • the process in accordance with The invention comprises, after the grafting sub-step, a step of rinsing the grafted interior surface 2 to remove the residues of the grafting solution.
  • a step of rinsing the grafted interior surface 2 to remove the residues of the grafting solution.
  • the rinsing step removes chlorine residues and leaves only the palladium on the interior surface 2.
  • the activation sub-step is implemented before the grafting sub-step, as described above, so as to obtain an interior surface 2 which is activated and then grafted.
  • the grafting sub-step is advantageously carried out before said activation sub-step or simultaneously with the latter.
  • the latter lead to the formation, on the inner surface 2, of anchoring points for the metallic coating 8, said anchoring points being composed of agents of 'activation and grafting, which are advantageously linked together.
  • the operation of bringing the grafted interior surface 2 into contact with the solution containing metal ions, for example in the form of at least one metal salt is carried out by filling, possibly complete (to the brim) of the cavity 3 with said solution containing metal ions.
  • the reducing agent which is preferably a gluconate, is then introduced into the solution filling the cavity 3 in order to convert the metal ions (consisting for example of silver Ag + ions) into metal (consisting for example of silver) which will be attached to the grafting agent (consisting for example of palladium, which gives excellent results in order to obtain a silver coating 8).
  • the solution containing metal ions preferably contains, in the case of a solution intended to produce a silver coating 8, approximately 2 ml of silver for a flask to be treated, the capacity of which (volume of the cavity 3) is approximately 130 ml.
  • said solution containing silver ions comprises at least silver nitrate (AgNO 3 ). Carrying out the metallization by subjecting the interior surface 2 to a liquid solution proves to be particularly advantageous from an industrial point of view, because of its simplicity and its competitive cost.
  • this metallization by simply filling the bottle with different solutions (activation solution, grafting solution and metallization solution) does not require any complex and expensive industrial means, and only requires basic and robust equipment, which can be easily automated.
  • the process according to the invention exhibits, in its most advantageous embodiments described in the foregoing, excellent industrial efficiency, with high productivity. high allowing high production rates and a relatively low cost price, for an excellent result, in particular aesthetic.
  • the vaporization of said activation and grafting solution using a nozzle 9 facilitates the implementation of the method of the invention, whatever the shape of the hollow body 1, in particular if it comprises a throttling 6.
  • the covering step comprises, before implementation of the metallization sub-step, a sub-step of baking the hollow body 1 (that is to say in this case of the container 4) aimed at raising the temperature of the interior surface 2.
  • this baking sub-step is preferably carried out at a temperature substantially between 20 and 100 °, preferably around 80 ° C, so that the hollow body 1 leaves the oven at a temperature preferably between 30 and 80 ° C, and for example substantially equal to 60 ° C.
  • the metallization sub-step is then carried out on the hollow body 1 (that is to say the bottle in the example illustrated in the figures) while still hot, which makes it possible to accelerate the reduction reaction which transforms the silver ions. in metallic silver.
  • the reaction of transformation of the silver ions into metallic silver can only last about twenty seconds while at room temperature ( about 20 ° C) it could have lasted much longer (for example about 1 hour).
  • the metallization sub-step also comprises an operation of stirring, preferably mechanized, of the grafted interior surface 2, while it is in contact with said solution containing both the metal ions and the reducing agent, to obtain a substantially homogeneous metal deposit on the interior surface 2 grafted.
  • the hollow body 1, that is to say advantageously the container 4 is stirred, shaken, so that the metal resulting from the reduction reaction is distributed evenly over the entire interior surface 2 concerned.
  • the stirring operation makes it possible to obtain a silver coating on the interior surface 2, the thickness E 1 of which is particularly uniform over the entire surface. treated surface.
  • the stirring operation is preferably mechanized, or even automated, using conventional means making it possible to hold the bottle 4 and to shake it. This does of course absolutely not exclude that the stirring operation can be carried out manually.
  • the implementation of a mechanized stirring allows a significant gain in productivity, since combined with the implementation of an automated filling of grafting solution (using a filler, as explained in the above ), it turns out to be possible to treat ten vials (with a capacity of 130 ml) per minute, while reducing the quantities of solution containing metal ions and reducing agent.
  • the metallization sub-step is carried out so that the inner wall 2 is covered by the coating 8 in a surface quantity greater than or equal to 1000 mg / m 2 .
  • the surface quantity is substantially greater than or equal to 1500 mg / m 2 , preferably substantially greater than or equal to 2000 mg / m 2 .
  • Such a surface quantity for the coating 8 advantageously makes it possible to obtain a reflective and opaque coating 8, without having to resort to additional layers. Obtaining these reflective and opaque characters is particularly appreciable from an aesthetic point of view, and also makes it possible to advantageously contribute to preserving the qualities of the liquid or pasty substance contained in the hollow body 1, in particular when it is acts of perfume, preventing the light from reaching it.
  • the use of such a surface amount also allows the coating to be properly maintained on the inner surface 2, without significant risk of untimely detachment.
  • a surface quantity of metal approximately equal to 1,200 mg / m 2 is very particularly preferred, both in terms of decorative effect and of mechanical and chemical resistance.
  • the value of 1200 mg / m 2 proves to be particularly optimal in the case of a process aimed at covering the inner wall 2 with a silver coating 8.
  • the metallization sub-step comprises a final operation of emptying the cavity 3 consisting in evacuating the solution containing the metal ions and the reducing agent from the bottle.
  • the solution thus recovered can optionally be reused for the metallization of another interior surface 2 of another bottle.
  • the emptying operation in question is only carried out once the solution contained in cavity 3 (mixture of solutions containing silver ions and of a reducing agent) has a clear, translucent appearance, indicative of the completion of the chemical reaction and therefore of the recovery process.
  • the metallized inner surface 2 is then washed to remove the residues of the reducing agent.
  • the method according to the invention finally comprises a baking step, subsequent to the metallization sub-step, in which the metallized inner surface 2 is baked in order to dry and harden the metal film present on the inner surface 2 as a consequence of the implementation of the metallization sub-step, said metallic film constituting the coating 8.
  • the bottle 4 with its metallized inner surface 2 is fired at a temperature of between substantially 50 and 300 ° C, preferably about 180 ° C, for about 30 minutes, which results in a dry and hard silver film on the inner surface 2.
  • the silver coating 8 thus obtained is extremely sturdy attached to the inner surface 2 of the. vial, and satisfies the so-called “ adhesive tape resistance ” test consisting of applying a piece of adhesive tape to the coating 8 covering the inner wall 2, then removing this adhesive tape without the adhesive being significantly torn off. 8 silver coating.
  • the coating obtained also withstands the so-called “ pencil point ” test, that is to say that it is not appreciably scratched when it is scratched by the lead of a pencil. 5H hardness paper.
  • a silvery coating 8 obtained in accordance with what is explained in the foregoing perfectly tolerates being brought into contact for a long time with an alcoholic liquid, and in particular with a perfume.
  • a silver coating deposited on the inner surface 2 of a glass bottle, in accordance with the method according to the invention proves to be quite stable when it is immersed in an alcoholic juice for at least six months at temperature. ambient, and for at least three months at 45 ° C. Additional steps can moreover be optionally implemented at the end of the cooking step.
  • the laser beam advantageously takes its source outside the hollow body 1 and passes through the wall 1A of the latter to reach the coating 8 from the outside of the hollow body 1 to modify, preferably eliminate, at least partly said coating 8.
  • the coating 8 it is thus possible to remove, at least partially, the coating 8 in order to create an aesthetic decorative pattern created from the differences between the inner surface 2 covered by the coating 8 and that not covered.
  • a fiber laser for example an Nd-Yag type laser, placed outside the hollow body 1 and emitting a laser beam capable of passing through the wall. 1A.
  • the method can advantageously comprise, at its start, a prior operation of coloring the interior surface 2, by covering with the latter with a colored layer, by any means known in the field, in order to obtain a colored interior surface 2.
  • the step of covering with the coating 8 is then carried out on this colored interior surface 2, which leads to obtaining an interior surface 2 covered with a stack of two successive layers, namely a colored layer and a coating 8 of predominantly metallic composition.
  • a stack of two successive layers namely a colored layer and a coating 8 of predominantly metallic composition.
  • the method of the invention can advantageously comprise a sub-step of protecting said coating 8 by a protective layer (not shown) which comes into direct contact with the liquid or pasty substance contained in said hollow body 1.
  • the protective layer On the one hand protects said coating 8 from any incompatibility with said liquid or pasty substance, and on the other hand said liquid or pasty substance from any risk of altering its properties on contact with said coating 8.
  • the protective layer is composed, for example, of a vitreous layer obtained by a sol-gel process, of a varnish, of a protective lacquer, of metal oxides or of a plastic material obtained by plasticization.
  • the process has been described essentially with regard to a preferred variant aiming to cover the interior surface with silver 2.
  • the process can be implemented with other metals, such as gold, copper, nickel, zinc or platinum, for example, by adapting in particular the nature and composition of the activating and grafting agents and the reducing agent.
  • the manufacturing process of the invention comprises substantially identical steps whatever the nature of the metallic coating.
  • first comparative table indicates, purely by way of illustration, examples of processes in accordance with the invention making it possible to obtain a metallic coating 8 comprising silver, copper (copper 1 or copper 2), gold or nickel: ⁇ u> Table 1 ⁇ /u> STEP SILVER COPPER COPPER II GOLD NICKEL 1 Rinsing Rinsing Rinsing Rinsing 2 Activation Activation Activation Activation 3 Rinsing Rinsing Rinsing Rinsing 4 Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Grafting Graf
  • This first table makes it possible to highlight the process steps which are substantially identical from one metal to another.
  • the following second comparative table specifies the products and the reagents advantageously used during the steps described in the first table: ⁇ u> Table 2 ⁇ /u> COMPONENTS STEP SILVER COPPER I COPPER II GOLD NICKEL Metallic salt 7 Ag + Cu 2+ or Cu + Cu 2+ or Cu + Au + or Au 3+ Neither 2+ Complexing agent 7 EDTA and other amino complexing agents, rochelle salt, gluconate, organic acids, ammonia, organic acids Reducing agent 8 Formaldehyde, gluconate, hydrazine, hydroxylamine, dimethylamine borane, borohydride, glyoxylic acid, hypophosphorous acid or its salts
  • the metal salt is mixed with a complexing agent in solution in order to facilitate the subsequent reduction reaction.
  • a complexing agent in solution in order to facilitate the subsequent reduction reaction.
  • the complexing and reducing agents indicated in the second table are given purely as an indication and it is also perfectly conceivable to deposit the metal with several complexing agent - reducing agent pairs. There are also other reducing agents which are particularly effective and can lead to the reduction of metal salts. Likewise, there is a wide range of complexing agents which can be used with the metal salt solution for the reduction reaction.
  • the pH is adjusted to be within the operating range of the reducing agent.
  • the invention also relates as such to a hollow body 1 capable of being obtained by the method in accordance with the invention described in the foregoing, and preferably directly obtained by the method in question.
  • the hollow body 1 is provided with an interior surface 2 made of glass defining a cavity 3, at least a fraction of which is covered by a coating 8 of predominantly metallic composition.
  • the coating 8 is mainly made of a metal taken from the following group: silver, gold, copper, nickel, zinc, platinum.
  • the metallization of the inner surface of the hollow body 1 makes it possible to obtain, as explained in the above in relation to the process, an excellent decorative effect.
  • the coating 8 is advantageously visible by transparency through the wall 1A delimiting the cavity 3.
  • the inner face of this wall 1A corresponds to the inner wall 2 on which the coating 8 is deposited.
  • This wall 1A also has an outer face. opposite 11 on which it is possible to affix, by any known means, a marking 12, and preferably a marking 12 for decorative purposes.
  • the marking 12 is thus separated from the metallic coating 8 by the thickness E 2 of the wall 1A defining the cavity 3.
  • the marking 12 is thus reflected on the coating 8, in particular when the latter is a silver coating which provides an excellent. "mirror " effect, so that the user perceives both the marking 12 but also its distant reflection 13 and / or its shadow on the coating 8, which is particularly attractive from an aesthetic point of view.
  • the marking 12 can be produced by screen printing, the screen printing operation being followed by baking which also contributes to reinforcing the strength and stability of the coating 8.
  • the coating 8 covers the internal surface 2 with a basis weight substantially greater than or equal to 800 mg / m 2 , and preferably substantially greater than or equal to 1000 mg / m 2 , a value approximately equal to 1200 mg / m 2 being preferred for reasons of strength and aesthetics, in particular when the coating consists predominantly of silver.
  • the interior surface 2 is substantially completely covered by the coating 8, as illustrated in figure 2 , while the thickness E 1 of said coating 8 is advantageously substantially uniform.
  • the coating 8 it is entirely conceivable that only a fraction of the inner surface 2 is covered by the coating 8, such a selective covering being obtained for example by temporary masking of the fraction of the inner surface 2 which is not intended to be covered by the coating 8. It is thus conceivable that the non-covered areas of the inner surface 2 draw a decorative pattern.
  • part of the coating 8 to be cut using a laser beam as mentioned above.
  • the hollow body 1 in accordance with the invention comprises a single piece of glass within which the cavity 3 is formed.
  • the hollow body 1 is also preferably designed to be gripped and handled by hand.
  • the hollow body 1 preferably constitutes a container 4 designed to contain a liquid or pasty substance in the cavity 3, and in particular an alcoholic liquid such as a body perfume, said container being intended to be closed using a closure member 5.
  • the cavity 3 advantageously forms a constriction 6 defining an opening 7 making it possible to put the cavity 3 in communication with the outside , said opening 7 being intended to cooperate with the closure member 5, preferably constituted by a plug 5A, to close said container.
  • the hollow body 1 thus constitutes a bottle 4, which comprises a constriction 6 forming a neck at the level of its opening 7, intended for the storage and distribution of a liquid body perfume, it being understood that the hollow body 1 is preferably designed so that the coating 8 is in contact, and preferably in direct contact, with said liquid or pasty substance.
  • the hollow body 1 is designed so that the coating 8 itself directly defines the cavity 3, that is to say that it forms the outermost layer of the inner wall 2, intended to be in contact with the substance contained in said cavity 3.
  • the coating 8 is itself covered with a protective layer, for example based on metal oxides (titanium oxide for example).
  • the invention finds its industrial application in the design and manufacture of hollow bodies provided with an interior glass surface which can be used in various industrial sectors, in particular in the packaging or construction sector.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Surface Treatment Of Glass (AREA)
  • Chemically Coating (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Joining Of Glass To Other Materials (AREA)
EP09797113.9A 2008-11-27 2009-11-27 Procede de fabrication d'un corps creux pourvu d'une surface interieure en verre metallisee et corps creux correspondant Active EP2370614B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0806660A FR2938850B1 (fr) 2008-11-27 2008-11-27 Procede de fabrication d'un corps creux pourvu d'une surface interieure en verre metallisee et corps creux correspondant
PCT/FR2009/052327 WO2010061150A2 (fr) 2008-11-27 2009-11-27 Procede de fabrication d'un corps creux pourvu d'une surface interieure en verre metallisee et corps creux correspondant

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EP2370614A2 EP2370614A2 (fr) 2011-10-05
EP2370614B1 true EP2370614B1 (fr) 2020-10-21

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US (1) US8962076B2 (enrdf_load_stackoverflow)
EP (1) EP2370614B1 (enrdf_load_stackoverflow)
JP (1) JP5918536B2 (enrdf_load_stackoverflow)
FR (1) FR2938850B1 (enrdf_load_stackoverflow)
WO (1) WO2010061150A2 (enrdf_load_stackoverflow)

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Publication number Priority date Publication date Assignee Title
FR3051689B1 (fr) 2016-05-26 2020-02-14 Glass Surface Technology Procede, dispositif de marquage d'au moins une face interne d'un recipient, et recipient correspondant.
US11421857B2 (en) * 2020-03-31 2022-08-23 One Offs Plus, LLC Methods for decorating a translucent container
FR3114522B1 (fr) * 2020-09-25 2023-06-16 Verescence France Procede et installation de fabrication d’un recipient decore pour produit cosmetique
CZ2023373A3 (cs) * 2023-10-02 2025-04-09 Ego 93, S.R.O. Roztok pro úpravu povrchu před vyloučením odrazivé vrstvy stříbra a způsob jeho přípravy

Citations (3)

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US6251482B1 (en) * 1994-05-12 2001-06-26 Glaverbel Forming a silver coating on a vitreous substrate
US6257732B1 (en) * 1999-09-29 2001-07-10 American Spray Coating Method for forming a metallic mirror surface and solutions for the same
US20040223238A1 (en) * 1994-05-12 2004-11-11 Pierre Laroche Forming a silver coating on a vitreous substrate

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DE9409613U1 (de) * 1994-06-20 1994-11-03 Köhnlein, Rolf, Ing.grad., 75385 Bad Teinach-Zavelstein Metallisierte Kunststoffflasche
KR100260956B1 (ko) * 1995-09-13 2000-09-01 쓰치야 히로오 합성수지제 단열 이중벽 용기 및 합성수지제 단열 이중벽 덮개
JP2000129448A (ja) * 1998-10-23 2000-05-09 Inoac Corp 内面にめっき層を有する容器及びその製造方法
FR2787742B1 (fr) * 1998-12-28 2001-03-16 Toly Products France Materiau plastique non metallisable lors de la realisation d'objets composites a revetement metallique selectif, les objets composites ainsi obtenus et leur procede de preparation
CZ289551B6 (cs) * 2000-08-02 2002-02-13 Irisa, Výrobní Dru®Stvo Způsob výroby vánočních ozdob a přípravky pro jejich upevňování při provádění tohoto způsobu
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US6251482B1 (en) * 1994-05-12 2001-06-26 Glaverbel Forming a silver coating on a vitreous substrate
US20040223238A1 (en) * 1994-05-12 2004-11-11 Pierre Laroche Forming a silver coating on a vitreous substrate
US6257732B1 (en) * 1999-09-29 2001-07-10 American Spray Coating Method for forming a metallic mirror surface and solutions for the same

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Publication number Publication date
JP2012509836A (ja) 2012-04-26
US20110220535A1 (en) 2011-09-15
FR2938850A1 (fr) 2010-05-28
WO2010061150A2 (fr) 2010-06-03
EP2370614A2 (fr) 2011-10-05
JP5918536B2 (ja) 2016-05-18
WO2010061150A3 (fr) 2010-08-26
US8962076B2 (en) 2015-02-24
FR2938850B1 (fr) 2011-04-29

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