EP2516521A1 - Method for treating the surface of a device for dispensing a fluid product - Google Patents

Method for treating the surface of a device for dispensing a fluid product

Info

Publication number
EP2516521A1
EP2516521A1 EP10808921A EP10808921A EP2516521A1 EP 2516521 A1 EP2516521 A1 EP 2516521A1 EP 10808921 A EP10808921 A EP 10808921A EP 10808921 A EP10808921 A EP 10808921A EP 2516521 A1 EP2516521 A1 EP 2516521A1
Authority
EP
European Patent Office
Prior art keywords
vinyl
acrylic
terminated
aryl
constituent part
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10808921A
Other languages
German (de)
French (fr)
Inventor
Pascal Bruna
Serge Herry
Matthieu Laurent
Fabien Nekelson
Sébastien ROUSSEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aptar France SAS
Original Assignee
Aptar France SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aptar France SAS filed Critical Aptar France SAS
Publication of EP2516521A1 publication Critical patent/EP2516521A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M15/00—Inhalators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2205/00—General characteristics of the apparatus
    • A61M2205/02—General characteristics of the apparatus characterised by a particular materials
    • A61M2205/0238—General characteristics of the apparatus characterised by a particular materials the material being a coating or protective layer
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M2207/00—Methods of manufacture, assembly or production
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • 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
    • B05D2201/00—Polymeric substrate or laminate
    • 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
    • B05D2202/00—Metallic substrate
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive 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
    • B65D83/00—Containers or packages with special means for dispensing contents
    • B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
    • B65D83/75—Aerosol containers not provided for in groups B65D83/16 - B65D83/74

Definitions

  • the present invention relates to a surface treatment method for fluid dispensing devices.
  • Dispensing devices for fluid products are well known. They may comprise one or more reservoirs, a dispensing member, such as a pump, a valve or a piston displaceable in the reservoir, and a dispensing head provided with a dispensing orifice. These dispensing devices generally comprise component parts made of various materials.
  • the tank may be of plastic or synthetic material, glass or metal.
  • Various parts, such as pistons or seals may be made of flexible plastic materials, such as elastomers.
  • Other parts are generally metallic, for example crimping capsules, springs or balls forming a valve.
  • these interactions may include releasing molecules of these materials into the fluid product. For example, these interactions can degrade certain active ingredients, such as hormones, peptides or enzymes, especially in nasal spray devices.
  • the present invention aims to provide a surface treatment method that avoids the aforementioned drawbacks.
  • the present invention aims to provide a surface treatment method that is effective, durable, non-polluting and simple to achieve.
  • the present invention therefore relates to a surface treatment method of a fluid dispenser device, said method comprising the step of forming by chemical grafting a thin film on at least one support surface of at least a part constituent in contact with said fluid product, said thin film preventing interactions between said fluid product and said constituent part.
  • said grafting step comprises contacting said surface in contact with the fluid product with a solution comprising at least one adhesion primer, said adhesion primer being a cleavable aryl salt and at least one monomer or a polymer selected from the group consisting of vinyl-terminated or acrylic-terminated siloxanes and acrylic or vinyl monomers.
  • said chemical grafting creates covalent bonds between the molecules of said thin film and said support surface. This creates a strong and lasting connection over time.
  • said chemical grafting is carried out in an aqueous medium. This allows a non-polluting or green chemistry, which does not present risks for the environment.
  • the cleavable aryl salt is selected from the group consisting of aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts, aryl sulfonium salts and aryl salts. iodonium.
  • the cleavable aryl salts are chosen from compounds of the general formula ArN 2 + , X " in which Ar represents the aryl group and X " represents an anion.
  • the aryl group in an organic compound is a functional group derived from an aromatic ring.
  • the anions X " are selected from inorganic anions such as halides, such as, Cl" or Br ", the halogenoborates such as tetrafluoroborate and organic anions such as alcoholates, carboxylates, perchlorates and sulfonates.
  • inorganic anions such as halides, such as, Cl" or Br "
  • the halogenoborates such as tetrafluoroborate
  • organic anions such as alcoholates, carboxylates, perchlorates and sulfonates.
  • the Ar aryl groups are chosen from aromatic or heteroaromatic compounds, optionally mono- or polysubstituted, consisting of one or more aromatic rings of 3 to 8 carbons.
  • the heteroatoms of the heteroaomatic compounds are chosen from N, O, P and S.
  • the substituents may contain alkyl groups and one or more heteroatoms such as N, O, F, Cl, P, Si, Br or S.
  • the aryl groups are chosen from aryl groups substituted with attracting groups such as NO 2, COH, CN, CO 2 H, ketones, esters, amines and halogens.
  • the aryl groups are selected from the group consisting of phenyl and nitrophenyl.
  • the cleavable aryl salt is selected from the group consisting of phenyldiazonium tetrafluoroborate, 4-nitrophenyldiazonium tetrafluoroborate, 4-bromophenyldiazonium tetrafluoroborate, 4-aminophenyldiazonium chloride, 4- aminomethylphenyldiazonium, 2-methyl-4-chlorophenyldiazonium chloride, 4-benzoylbenzenediazonium tetrafluoroborate, 4-cyanophenyldiazonium tetrafluoroborate, 4-carboxyphenyldiazonium tetrafluoroborate, 4-acetamidophenyldiazonium tetrafluoroborate, 4-phenylacetic acid tetrafluoroborate diazonium, 2-methyl-4 - [(2-methylphenyl) diazenyl] benzenediazonium sul
  • the cleavable aryl salt is selected from the group consisting of 4-nitrophenyldiazonium tetrafluoroborate, the 4-aminophenyldiazonium chloride, 2-methyl-4-chlorophenyldiazonium chloride, 4-carboxyphenyldiazonium tetrafluoroborate.
  • the salt concentration of cleavable aryl is between 5.10 "3 M and 10" 1 M.
  • the concentration of cleavable aryl salt is of the order of 5.10 -2 M.
  • the cleavable aryl salt is prepared in situ.
  • said chemical grafting step is initiated by chemical activation of a diazonium salt to form an anchoring layer for said thin film.
  • said chemical grafting step is initiated by chemical activation.
  • said chemical activation is initiated by the presence of a reducing agent in the solution.
  • the solution comprises a reducing agent.
  • reducing agent a compound which in an oxidation-reduction reaction yields electrons.
  • the reducing agent has a redox potential whose potential difference with respect to the oxidation-reduction potential of the cleavable aryl salt is between 0.3 V and 3 V.
  • the reducing agent is selected from the group consisting of reducing metals which may be in finely divided form such as iron, zinc, or nickel, a metal salt which may be in the form of metallocene and an organic reducing agent such as hypophosphorous acid, ascorbic acid.
  • the concentration of reducing agent is between 0.005 M and 2 M.
  • the concentration of reducing agent is of the order of 0.6 M.
  • said thin film has a thickness of less than 1 micrometer, between 10 and 2000 angstroms, advantageously between 10 and 800 angstroms, preferably between 400 and 1000 angstroms. No conventional coating technique makes it possible to obtain such thin layers chemically grafted.
  • vinyl or acrylic terminated siloxane means a saturated hydride of silicon and oxygen formed of straight or branched chains, of alternating silicon and oxygen atoms comprising vinyl units or terminal acrylic units.
  • the vinyl-terminated or acrylic-terminated siloxanes are chosen from the group consisting of polyalkylsiloxanes with acrylic or vinyl terminations, such as vinyl-terminated or acrylic-terminated polymethylsiloxane, and vinyl-terminated or acrylic-terminated polydimethylsiloxane, such as polydimethylsiloxane-acrylate (PDMS).
  • polyalkylsiloxanes with acrylic or vinyl terminations such as vinyl-terminated or acrylic-terminated polymethylsiloxane
  • vinyl-terminated or acrylic-terminated polydimethylsiloxane such as polydimethylsiloxane-acrylate (PDMS).
  • vinyl-terminated or acrylic-terminated polyarylsiloxanes such as vinyl-terminated or acrylic-terminated polyphenylsiloxane, such as polyvinylphenylsiloxane, vinyl-terminated or acrylic-terminated polyarylalkylsiloxanes such as vinyl-terminated or acrylic-terminated polymethylphenylsiloxane.
  • the acrylic or vinyl monomer is selected from the group consisting of vinyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylate, and the like.
  • propyl hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and derivatives thereof, acrylamides such as aminoethyl, propyl, butyl, pentyl and hexyl methacrylamides, cyanoacrylates, diacrylates, dimethacrylates, triacrylates, trimethacrylates, tetraacrylates, tetramethacrylates, styrene and its derivatives, parachlorostyrene, pentafluorostyrene, N-vinyl pyrrolidone, 4-vinyl pyridine, 2-vinyl pyridine, vinyl halides, acryloyl and methacryloyl, divinylbenzene.
  • acrylamides such as aminoethyl, propyl, butyl, pentyl and hexyl methacrylamides
  • cyanoacrylates diacrylates, dimethacrylates, tri
  • a potential difference is applied in said solution.
  • potential difference is meant the difference in redox potential measured between two electrodes.
  • the potential difference is applied by a generator connected to two identical or different electrodes immersed in the solution during the soaking step.
  • the electrodes are selected from stainless steel, steel, nickel, platinum, gold, silver, zinc, iron, copper, in pure form or in the form of alloy.
  • the electrodes are made of stainless steel.
  • the potential difference applied by a generator is between 0.1 V and 2 V.
  • it is of the order of 0.7 V.
  • the potential difference is generated by a chemical battery.
  • a chemical cell is a cell composed of two electrodes connected by an ion bridge. According to the present invention, the two electrodes are judiciously chosen so that the potential difference is between 0.1 V and 2.5 V.
  • the chemical stack is created between two different electrodes dipping into the solution.
  • the electrodes are selected from nickel, zinc, iron, copper, silver in pure form or in alloy form.
  • the potential difference generated by the chemical battery is between 0.1 V and 1.5 V.
  • the potential difference is of the order of 0.7 V.
  • the electrodes are chemically isolated to avoid any contact between the substrate immersed in the bath of step b) and the electrodes also immersed in the bath of step b).
  • said constituent part is made of metal, in particular a crimping cap, a spring or a ball forming a valve.
  • said constituent part is made of a flexible material, such as an elastomer, in particular a piston or a seal.
  • said constituent part is made of synthetic material, such as polyethylene or polypropylene.
  • said constituent part is made of glass, in particular a reservoir,
  • the method further comprises the step of forming by chemical grafting at least one additional thin film on said support surface.
  • the method comprises the step of forming by chemical grafting a first additional thin film on said support surface, said first additional thin film preventing interactions between said support surface and said fluid product.
  • the method comprises the step of forming by chemical grafting a second additional thin film on said support surface, said second additional thin film limiting the friction between two constituent parts moving relative to each other during the treatment. actuation of the fluid dispensing device.
  • said at least one additional thin film is deposited on said support surface during at least one successive chemical grafting step, each carried out in a single-component bath.
  • said at least one additional thin film is deposited on said support surface simultaneously during the same chemical grafting step in a multi-component bath.
  • said fluid product is a pharmaceutical fluid product intended to be sprayed in particular nasally or orally.
  • the present invention provides a method similar to that described in WO 2008/078052, which describes a method of preparing an organic film on the surface of a solid support under non-electrochemical conditions.
  • this type of process has been found suitable for forming a thin film on surfaces intended to come into contact with a pharmaceutical fluid product in dispensing devices, to prevent interactions with said fluid product.
  • Such an application of this grafting method had never been considered.
  • the process aims to prepare a thin film on the surface of a support which can be made of different materials, such as hard plastics, soft plastics, metal or glass.
  • This method mainly comprises contacting said support surface with a liquid solution.
  • This comprises at least one solvent and at least one adhesion primer allowing the formation of radical entities from the adhesion primer.
  • the "thin film” can be any polymeric film, in particular of organic nature, for example derived from several units of organic chemical species, and covalently bonded to the surface of the support on which the process is carried out. It is particularly a film covalently bonded to the surface of a support and comprising at least one layer of similar structural units of nature. Depending on the thickness of the film, its cohesion is ensured by the covalent bonds that develop between the different units.
  • the solvent employed in the process may be protic or aprotic in nature. It is preferable that the primer is soluble in said solvent.
  • protic solvent is meant a solvent which comprises at least one hydrogen atom capable of being released in the form of a proton.
  • the protic solvent can be chosen from the group consisting of water, deionized water, distilled water, acidified or not, acetic acid, hydroxylated solvents such as methanol and ethanol, low-level liquid glycols. weight such as ethylene glycol, and mixtures thereof.
  • the protic solvent consists only of a protic solvent or a mixture of different protic solvents.
  • the protic solvent or the mixture of protic solvents may be used in admixture with at least one aprotic solvent, it being understood that the resulting mixture has the characteristics of a protic solvent.
  • Acidified water is the preferred protic solvent and, more particularly, acidified distilled water or acidified deionized water.
  • aprotic solvent is meant a solvent which is not considered as protic. Such solvents are not likely to release a proton or accept one under non-extreme conditions.
  • the aprotic solvent is advantageously chosen from dimethylformamide (DMF), acetone and dimethyl sulfoxide (DMSO).
  • adheresion primer corresponds to any organic molecule susceptible, under certain conditions, to chemisorber on the surface of the support by radical reaction such as radical chemical grafting.
  • Such molecules comprise at least one functional group capable of reacting with a radical and also a reactive function with respect to another radical after chemisorption. These molecules are thus capable of forming a film of polymeric nature after grafting of a first molecule on the surface of the support and then reaction with other molecules present in its environment.
  • radical chemical grafting refers in particular to the use of molecular entities having an unpaired electron to form covalent link bonds with a surface, said molecular entities being generated independently of the support surface on which they are to be grafted.
  • the radical reaction leads to the formation of covalent bonds between the support surface in question and the grafted adhesion primer derivative and then between a grafted derivative and molecules present in its environment.
  • the adhesion primer is advantageously a cleavable aryl salt selected from the group consisting of aryl diazonium salts, ammonium aryl salts, aryl phosphonium salts, arylsulphonium salts and aryl iodonium salts.
  • At least one additional thin film is produced by chemical grafting on the same support surface to give at least one other property to this support surface.
  • the fluid product may be likely to stick to a surface with which it is in contact, which may in particular have a detrimental effect on the reproducibility of the dispensed dose.
  • the invention advantageously provides for forming by chemical grafting a first additional thin film which prevents the fluid product from sticking to the support surface.
  • it could also be envisaged to apply a second additional thin film by chemical grafting to give a third property to the support surface. For example, in fluid product dispensing devices, some parts move relative to others, and blockages due to friction may interfere with the proper operation of the device.
  • the invention advantageously provides to form by chemical grafting a second additional thin film which limits the friction between two component parts which move relative to each other during actuation.
  • additional thin films can be applied during successive chemical grafting steps.
  • each chemical grafting step is carried out in a single-component bath.
  • the order of these successive chemical grafting steps can be arbitrary.
  • the thin films additional can also be applied in a single step of chemical grafting, which is then carried out in a multi-component bath. A combination of the two variants is also conceivable.
  • the present invention is applicable to multidose devices, such as pump or valve devices mounted on a reservoir and operated for the successive delivery of doses. It also applies to multi-dose devices comprising a plurality of individual reservoirs each containing a dose of fluid, such as pre-dosed powder inhalers. It also applies to single-dose or bidose devices, in which a piston moves directly into a reservoir each time it is actuated.
  • the invention is particularly applicable to nasal or oral spray devices, ophthalmic dispensing devices and syringe-type needle devices.
  • the invention also relates to the use of a grafting method according to the invention for treating at least one surface of at least one constituent part of a fluid dispenser device in contact with said fluid product, to prevent interactions between said fluid product and said constituent part.
  • EXAMPLE 1 Grafting of a Poly (Butylmethacrylate) (BUMA) Barrier Film on Metal Parts of a Pump
  • BUMA Poly (Butylmethacrylate)
  • By pump is meant a manually operated fluid dispensing device comprising a pump body in which one or several pistons.
  • the sodium dodecyl sulphate (0.283 g, 0.5 ⁇ 10 -3 mol) was solubilized in 33 ml of milliQ water and the butyl methacrylate (0.71 g, 10 -3 mol) is added and emulsified under strong magnetic agitation.
  • the 4-aminobenzoic acid (0.686 g, 7.5 ⁇ 10 -3 mol) was solubilized in a solution of hydrochloric acid (1.9 mL in 30 mL of MQ water) and hypophosphorous acid (3.2 mL). mL, 3.1 10 "2 mol). This solution was added to the BUMA emulsion.
  • Sodium dodecyl benzene sulphonate (0.849 g, 1.5 ⁇ 10 -2 mol) was solubilized in 100 ml of milliQ water and vinyl-terminated poly (dimethylsiloxane) (3 g, 10 g / l) was added and then The mixture was magnetically stirred to form an emulsion.
  • 4-Aminobenzoic acid (2.058 g, 2.25 10 -2 mol) was solubilized in a solution of hydrochloric acid (5.8 mL in 90 mL of MQ water) and hypophosphorous acid (9.7 50% mL) This solution was added to the PDMS emulsion.
  • the preparation of the biphasic solution takes place in two stages.
  • the beaker (1) are added in order and with magnetic stirring (300 rpm), the PDMS-acrylate (1 g / L); Brij® 35 in solution in water at 8.5% wt (4.37 g / L) and 33 mL of water Dl.
  • the emulsification is then sonicated at 40 ° C under a power of 200 W (100%) for 15 minutes.
  • In the beaker (2) are added, with magnetic stirring (300 rpm), nitrobenzene diazonium tetrafluoroborate (0.05 mol / L); 130 mL of Dl water and hydrochloric acid (0.23 mol / L).
  • the contents of the beaker (2) are poured into the emulsion of the beaker (1).
  • the stainless steel blades (x 2), a galvanized steel wire (wound on 10 turns, a length of about 25 to 30 cm) and a Ni wire (wound on 10 turns, a length of about 25 to 30 cm) are placed in the beaker (1). Both wires are connected to a potentiostat and an ammeter is connected in series. The potentiostat imposes a constant potential difference of 0.5 V and the intensity of the current is measured over time via the ammeter.
  • hypophosphorous acid 0.7 mol / L
  • isopropanol in a soxhlet extractor for 16 hours.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to a method for treating the surface of a device for dispensing a fluid product, said method comprising a chemical grafting step in order to form a thin film on at least one supporting surface of at least one component of said device, which is in contact with the fluid product, said thin film preventing interaction between the fluid product and said component.

Description

Procédé de traitement de surface d'un dispositif de distribution de produit fluide  Surface treatment method of a fluid dispensing device
La présente invention concerne un procédé de traitement de surface pour des dispositifs de distribution de produits fluides.  The present invention relates to a surface treatment method for fluid dispensing devices.
Les dispositifs de distribution de produits fluides sont bien connus. Ils peuvent comporter un ou plusieurs réservoirs, un organe de distribution, tel qu'une pompe, une valve ou un piston déplaçable dans le réservoir, et une tête de distribution pourvue d'un orifice de distribution. Ces dispositifs de distribution comportent généralement des pièces constitutives réalisées en divers matériaux. Ainsi, le réservoir peut être en matériau plastique ou synthétique, en verre ou en métal. Diverses pièces, comme les pistons ou les joints peuvent être en matériaux plastiques souples, tels que des élastomères. D'autres pièces sont généralement métalliques, par exemple les capsules de sertissage, les ressorts ou les billes formant clapet. En particulier dans le domaine pharmaceutique, les risques d'interaction entre le produit fluide à distribuer et ces différents matériaux peuvent être néfastes pour ledit produit fluide. Ces interactions peuvent comprendre des relarguage de molécules de ces matériaux dans le produit fluide. Par exemple, ces interactions peuvent dégrader certains principes actifs, tels que les hormones, les peptides ou les enzymes, notamment dans les dispositifs de pulvérisation nasale.  Dispensing devices for fluid products are well known. They may comprise one or more reservoirs, a dispensing member, such as a pump, a valve or a piston displaceable in the reservoir, and a dispensing head provided with a dispensing orifice. These dispensing devices generally comprise component parts made of various materials. Thus, the tank may be of plastic or synthetic material, glass or metal. Various parts, such as pistons or seals may be made of flexible plastic materials, such as elastomers. Other parts are generally metallic, for example crimping capsules, springs or balls forming a valve. In particular in the pharmaceutical field, the risks of interaction between the fluid product to be dispensed and these different materials can be harmful for said fluid product. These interactions may include releasing molecules of these materials into the fluid product. For example, these interactions can degrade certain active ingredients, such as hormones, peptides or enzymes, especially in nasal spray devices.
Les procédés de traitement de surface existants présentent tous des inconvénients. Ainsi, certains procédés ne sont utilisables que sur des surfaces planes. D'autres procédés imposent un choix limité de substrat, par exemple de l'or. La polymérisation de molécules induite par plasma est complexe, coûteuse, et la couche de revêtement obtenue est difficile à contrôler et présente des problèmes de vieillissement. De même, la polymérisation de molécules induite par ultraviolets est également complexe et coûteuse, et ne fonctionne qu'avec des molécules photosensibles. Il en est de même de la polymérisation radicalaire par transfert d'atomes (ATRP), qui est aussi complexe et coûteuse. Enfin, les procédés d'électro-greffage sont complexes et nécessitent des surfaces de support conductrices. Existing surface treatment methods all have disadvantages. Thus, some processes can only be used on flat surfaces. Other methods require a limited choice of substrate, for example gold. The plasma-induced polymerization of molecules is complex, expensive, and the resulting coating layer is difficult to control and has aging problems. Similarly, ultraviolet-induced polymerization of molecules is also complex and expensive, and only works with photosensitive molecules. The same is true of atom transfer radical polymerization (ATRP), which is also complex and expensive. Finally, electrografting processes are complex and require conductive support surfaces.
La présente invention a pour but de proposer un procédé de traitement de surface qui évite les inconvénients susmentionnés.  The present invention aims to provide a surface treatment method that avoids the aforementioned drawbacks.
En particulier, la présente invention a pour but de fournir un procédé de traitement de surfaces qui soit efficace, durable, non polluant et simple à réaliser.  In particular, the present invention aims to provide a surface treatment method that is effective, durable, non-polluting and simple to achieve.
La présente invention a donc pour objet un procédé de traitement de surface d'un dispositif de distribution de produit fluide, ledit procédé comprenant l'étape de former par greffage chimique un film mince sur au moins une surface de support d'au moins une partie constitutive en contact avec ledit produit fluide, ledit film mince empêchant les interactions entre ledit produit fluide et ladite partie constitutive.  The present invention therefore relates to a surface treatment method of a fluid dispenser device, said method comprising the step of forming by chemical grafting a thin film on at least one support surface of at least a part constituent in contact with said fluid product, said thin film preventing interactions between said fluid product and said constituent part.
Dans un mode de réalisation avantageux, ladite étape de greffage comprend la mise en contact de ladite surface en contact avec le produit fluide avec une solution comprenant au moins un primaire d'adhésion, ledit primaire d'adhésion étant un sel d'aryle clivable et au moins un monomère ou un polymère choisi dans le groupe constitué par les siloxanes à terminaison vinylique ou acrylique et les monomères acryliques ou vinyliques.  In an advantageous embodiment, said grafting step comprises contacting said surface in contact with the fluid product with a solution comprising at least one adhesion primer, said adhesion primer being a cleavable aryl salt and at least one monomer or a polymer selected from the group consisting of vinyl-terminated or acrylic-terminated siloxanes and acrylic or vinyl monomers.
Avantageusement, ledit greffage chimique crée des liaisons covalentes entre les molécules dudit film mince et ladite surface de support. Ceci crée une liaison forte et durable dans le temps.  Advantageously, said chemical grafting creates covalent bonds between the molecules of said thin film and said support surface. This creates a strong and lasting connection over time.
Avantageusement, ledit greffage chimique est réalisé dans un milieu aqueux. Ceci permet une chimie non polluante ou verte, qui ne présente pas de risques pour l'environnement.  Advantageously, said chemical grafting is carried out in an aqueous medium. This allows a non-polluting or green chemistry, which does not present risks for the environment.
Dans un mode de réalisation le sel d'aryle clivable est choisi dans le groupe constitué par les sels d'aryle diazonium, les sels d'aryle ammonium, les sels d'aryle phosphonium, sels d'aryle sulfonium et les sels d'aryle iodonium.  In one embodiment, the cleavable aryl salt is selected from the group consisting of aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts, aryl sulfonium salts and aryl salts. iodonium.
Les sels d'aryles clivables sont choisis parmi les composés de formule générale ArN2 +, X" dans laquelle Ar représente le groupe aryle et X" représente un anion. Le groupe aryle dans un composé organique est un groupe fonctionnel issu d'un noyau aromatique. The cleavable aryl salts are chosen from compounds of the general formula ArN 2 + , X " in which Ar represents the aryl group and X " represents an anion. The aryl group in an organic compound is a functional group derived from an aromatic ring.
Dans un mode de réalisation, les anions X" sont choisis parmi les anions inorganiques tels que les halogénures, comme , CI" et Br", les halogénoborates tels que le tetrafluoroborate et les anions organiques tels que les alcoolates, les carboxylates, les perchlorates et les sulfonates. In one embodiment, the anions X "are selected from inorganic anions such as halides, such as, Cl" or Br ", the halogenoborates such as tetrafluoroborate and organic anions such as alcoholates, carboxylates, perchlorates and sulfonates.
Dans un mode de réalisation, les groupes aryles Ar sont choisis parmi les aromatiques ou hétéroaromatiques, éventuellement mono- ou polysubstitués, constitués d'un ou plusieurs cycles aromatiques de 3 à 8 carbones. Les hétéroatomes des composés hétéroaomatiques sont choisis parmi N, O, P et S. Les substituants peuvent contenir des groupes alkyles et un ou plusieurs hétéroatomes tels que N, O, F, Cl, P, Si, Br ou S.  In one embodiment, the Ar aryl groups are chosen from aromatic or heteroaromatic compounds, optionally mono- or polysubstituted, consisting of one or more aromatic rings of 3 to 8 carbons. The heteroatoms of the heteroaomatic compounds are chosen from N, O, P and S. The substituents may contain alkyl groups and one or more heteroatoms such as N, O, F, Cl, P, Si, Br or S.
Dans un mode de réalisation, les groupes aryles sont choisis parmi les groupes aryles substitués par des groupements attracteurs tels que NO2, COH, CN, CO2H, les cétones, les esters, les aminés et les halogènes. In one embodiment, the aryl groups are chosen from aryl groups substituted with attracting groups such as NO 2, COH, CN, CO 2 H, ketones, esters, amines and halogens.
Dans un mode de réalisation, les groupes aryles sont choisis dans le groupe constitué par le phényle et le nitrophényle.  In one embodiment, the aryl groups are selected from the group consisting of phenyl and nitrophenyl.
Dans un mode de réalisation, le sel d'aryle clivable est choisi dans le groupe constitué par le tétrafluoroborate de phényldiazonium, le tétrafluoroborate de 4-nitrophényldiazonium, le tétrafluoroborate de 4- bromophényldiazonium, le chlorure de 4-aminophényldiazonium, le chlorure de 4-aminométhylphényldiazonium, le chlorure de 2-méthyl-4- chlorophényldiazonium, le tétrafluoroborate de 4-benzoylbenzènediazonium, le tétrafluoroborate de 4-cyanophényldiazonium, le tétrafluoroborate du 4- carboxyphényldiazonium, le tétrafluoroborate de 4- acétamidophényldiazonium, le tétrafluoroborate de l'acide 4-phénylacétique diazonium, le sulfate de 2-méthyl-4-[(2- méthylphényl)diazényl]benzènediazonium, le chlorure de 9,10-dioxo-9,10- dihydro-1 -anthracènediazonium, le tétrafluoroborate de 4- nitronaphtalènediazonium et le tétrafluoroborate de naphtalènediazonium.  In one embodiment, the cleavable aryl salt is selected from the group consisting of phenyldiazonium tetrafluoroborate, 4-nitrophenyldiazonium tetrafluoroborate, 4-bromophenyldiazonium tetrafluoroborate, 4-aminophenyldiazonium chloride, 4- aminomethylphenyldiazonium, 2-methyl-4-chlorophenyldiazonium chloride, 4-benzoylbenzenediazonium tetrafluoroborate, 4-cyanophenyldiazonium tetrafluoroborate, 4-carboxyphenyldiazonium tetrafluoroborate, 4-acetamidophenyldiazonium tetrafluoroborate, 4-phenylacetic acid tetrafluoroborate diazonium, 2-methyl-4 - [(2-methylphenyl) diazenyl] benzenediazonium sulfate, 9,10-dioxo-9,10-dihydro-1-anthracenediazonium chloride, 4-nitronaphthalenediazonium tetrafluoroborate and tetrafluoroborate naphthalenediazonium.
Dans un mode de réalisation, le sel d'aryle clivable est choisi dans le groupe constitué par le tétrafluoroborate de 4-nitrophényldiazonium, le chlorure de 4-aminophényldiazonium, le chlorure de 2-méthyl-4- chlorophényldiazonium, le tétrafluoroborate du 4-carboxyphényldiazonium. In one embodiment, the cleavable aryl salt is selected from the group consisting of 4-nitrophenyldiazonium tetrafluoroborate, the 4-aminophenyldiazonium chloride, 2-methyl-4-chlorophenyldiazonium chloride, 4-carboxyphenyldiazonium tetrafluoroborate.
Dans un mode de réalisation, la concentration en sel d'aryle clivable est comprise entre 5.10"3 M et 10"1 M. In one embodiment, the salt concentration of cleavable aryl is between 5.10 "3 M and 10" 1 M.
Dans un mode de réalisation, la concentration en sel d'aryle clivable est de l'ordre de 5.10"2 M. In one embodiment, the concentration of cleavable aryl salt is of the order of 5.10 -2 M.
Dans un mode de réalisation, le sel d'aryle clivable est préparé in situ. In one embodiment, the cleavable aryl salt is prepared in situ.
Avantageusement, ladite étape de greffage chimique est initiée par activation chimique d'un sel de diazonium pour former une couche d'ancrage pour ledit film mince. Advantageously, said chemical grafting step is initiated by chemical activation of a diazonium salt to form an anchoring layer for said thin film.
Avantageusement, ladite étape de greffage chimique est initiée par activation chimique.  Advantageously, said chemical grafting step is initiated by chemical activation.
Dans un mode de réalisation ladite activation chimique est initiée par la présence d'un réducteur dans la solution.  In one embodiment, said chemical activation is initiated by the presence of a reducing agent in the solution.
Dans un mode de réalisation la solution comprend un agent réducteur. In one embodiment, the solution comprises a reducing agent.
Par agent réducteur, on entend un composé qui lors d'une réaction d'oxydoréduction cède des électrons. Selon un aspect de la présente invention, l'agent réducteur présente un potentiel d'oxydoréduction dont la différence de potentiel par rapport au potentiel d'oxydoréduction du sel d'aryle clivable est comprise entre 0,3 V et 3 V. By reducing agent is meant a compound which in an oxidation-reduction reaction yields electrons. According to one aspect of the present invention, the reducing agent has a redox potential whose potential difference with respect to the oxidation-reduction potential of the cleavable aryl salt is between 0.3 V and 3 V.
Selon un aspect de l'invention, l'agent réducteur est choisi dans le groupe constitué par les métaux réducteurs pouvant se présenter sous forme finement divisée tels que du fer, du zinc, ou du nickel, un sel métallique pouvant être sous forme de métallocène et un réducteur organique tel que l'acide hypophosphoreux, l'acide ascorbique.  According to one aspect of the invention, the reducing agent is selected from the group consisting of reducing metals which may be in finely divided form such as iron, zinc, or nickel, a metal salt which may be in the form of metallocene and an organic reducing agent such as hypophosphorous acid, ascorbic acid.
Dans un mode de réalisation, la concentration en agent réducteur est comprise entre 0,005 M et 2 M.  In one embodiment, the concentration of reducing agent is between 0.005 M and 2 M.
Dans un mode de réalisation, la concentration en agent réducteur est de l'ordre de 0,6 M.  In one embodiment, the concentration of reducing agent is of the order of 0.6 M.
Dans un mode de réalisation, ledit film mince a une épaisseur inférieure à 1 micromètre, comprise entre 10 et 2000 angstroms, avantageusement comprise entre 10 et 800 angstroms, de préférence comprise entre 400 et 1000 angstroms. Aucune technique de revêtement classique ne permet d'obtenir des couches aussi minces greffées chimiquement. In one embodiment, said thin film has a thickness of less than 1 micrometer, between 10 and 2000 angstroms, advantageously between 10 and 800 angstroms, preferably between 400 and 1000 angstroms. No conventional coating technique makes it possible to obtain such thin layers chemically grafted.
On entend par siloxane à terminaison vinylique ou acrylique un hydrure saturé de silicium et d'oxygène formé de chaînes droites ou ramifiées, d'atomes de silicium et d'oxygène en alternance comportant des motifs vinyliques ou des motifs acryliques terminaux.  The term "vinyl or acrylic terminated siloxane" means a saturated hydride of silicon and oxygen formed of straight or branched chains, of alternating silicon and oxygen atoms comprising vinyl units or terminal acrylic units.
Dans un mode de réalisation les siloxanes à terminaison vinylique ou acrylique sont choisis dans le groupe constitué par les polyalkylsiloxanes à terminaisons acryliques ou vinyliques tels que le polyméthylsiloxane à terminaisons vinyliques ou acryliques, le polydiméthylsiloxane à terminaisons vinyliques ou acryliques comme le polydiméthylsiloxane-acrylate (PDMS- acrylate), les polyarylsiloxanes à terminaisons vinyliques ou acryliques tels que le polyphénylsiloxane à terminaisons vinyliques ou acryliques comme le polyvinylphénylsiloxane, les polyarylalkylsiloxanes à terminaisons vinyliques ou acryliques tels que le polyméthylphénylsiloxane à terminaisons vinyliques ou acryliques.  In one embodiment, the vinyl-terminated or acrylic-terminated siloxanes are chosen from the group consisting of polyalkylsiloxanes with acrylic or vinyl terminations, such as vinyl-terminated or acrylic-terminated polymethylsiloxane, and vinyl-terminated or acrylic-terminated polydimethylsiloxane, such as polydimethylsiloxane-acrylate (PDMS). acrylate), vinyl-terminated or acrylic-terminated polyarylsiloxanes such as vinyl-terminated or acrylic-terminated polyphenylsiloxane, such as polyvinylphenylsiloxane, vinyl-terminated or acrylic-terminated polyarylalkylsiloxanes such as vinyl-terminated or acrylic-terminated polymethylphenylsiloxane.
Dans un mode de réalisation, le monomère acrylique ou vinylique est choisi dans le groupe constitué par l'acétate de vinyle, l'acrylonitrile, le méthacrylonitrile, le méthacrylate de méthyle, le méthacrylate d'éthyle, le méthacrylate de butyle, le méthacrylate de propyle, le méthacrylate d'hydroxyéthyle, le méthacrylate d'hydroxypropyle, le méthacrylate de glycidyle et leurs dérivés, les acrylamides tels que les méthacrylamides d'aminoéthyle, propyle, butyle, pentyle et hexyle, les cyanoacrylates, les diacrylates, les diméthacrylates, les triacrylates, les triméthacrylates, les tétraacrylates, les tétraméthacrylates, le styrène et ses dérivés, le parachlorostyrène, le pentafluorostyrène, la N-vinyl pyrrolidone, la 4-vinyl pyridine, la 2-vinyl pyridine, les halogénures de vinyle, d'acryloyle et de méthacryloyle, le divinylbenzène.  In one embodiment, the acrylic or vinyl monomer is selected from the group consisting of vinyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylate, and the like. propyl, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and derivatives thereof, acrylamides such as aminoethyl, propyl, butyl, pentyl and hexyl methacrylamides, cyanoacrylates, diacrylates, dimethacrylates, triacrylates, trimethacrylates, tetraacrylates, tetramethacrylates, styrene and its derivatives, parachlorostyrene, pentafluorostyrene, N-vinyl pyrrolidone, 4-vinyl pyridine, 2-vinyl pyridine, vinyl halides, acryloyl and methacryloyl, divinylbenzene.
Dans un mode de réalisation une différence de potentiel est appliquée dans ladite solution. On entend par différence de potentiel, la différence de potentiel d'oxydoréduction mesurée entre deux électrodes. In one embodiment a potential difference is applied in said solution. By potential difference is meant the difference in redox potential measured between two electrodes.
Dans un mode de réalisation, la différence de potentiel est appliquée par un générateur relié à deux électrodes, identiques ou différentes, plongeant dans la solution pendant l'étape de trempage.  In one embodiment, the potential difference is applied by a generator connected to two identical or different electrodes immersed in the solution during the soaking step.
Dans un mode de réalisation, les électrodes sont choisies parmi l'inox, l'acier, le nickel, le platine, l'or, l'argent, le zinc, le fer, le cuivre, sous forme pure ou sous forme d'alliage.  In one embodiment, the electrodes are selected from stainless steel, steel, nickel, platinum, gold, silver, zinc, iron, copper, in pure form or in the form of alloy.
Dans un mode de réalisation, les électrodes sont en inox.  In one embodiment, the electrodes are made of stainless steel.
Dans un mode de réalisation, la différence de potentiel appliquée par un générateur est comprise entre 0,1 V et 2 V.  In one embodiment, the potential difference applied by a generator is between 0.1 V and 2 V.
Dans un mode de réalisation, elle est de l'ordre de 0,7 V.  In one embodiment, it is of the order of 0.7 V.
Dans un mode de réalisation, la différence de potentiel est générée par une pile chimique.  In one embodiment, the potential difference is generated by a chemical battery.
On entend par pile chimique une pile composée de deux électrodes reliées par un pont ionique. Selon la présente invention, les deux électrodes sont judicieusement choisies pour que la différence de potentiel soit comprise entre 0,1 V et 2,5 V.  A chemical cell is a cell composed of two electrodes connected by an ion bridge. According to the present invention, the two electrodes are judiciously chosen so that the potential difference is between 0.1 V and 2.5 V.
Dans un mode de réalisation, la pile chimique est créée entre deux électrodes différentes plongeant dans la solution.  In one embodiment, the chemical stack is created between two different electrodes dipping into the solution.
Dans un mode de réalisation, les électrodes sont choisies parmi le nickel, le zinc, le fer, le cuivre, l'argent sous forme pure ou sous forme d'alliage.  In one embodiment, the electrodes are selected from nickel, zinc, iron, copper, silver in pure form or in alloy form.
Dans un mode de réalisation, la différence de potentiel générée par la pile chimique est comprise entre 0,1 V et 1 ,5 V.  In one embodiment, the potential difference generated by the chemical battery is between 0.1 V and 1.5 V.
Dans un mode de réalisation, la différence de potentiel est de l'ordre de 0,7 V.  In one embodiment, the potential difference is of the order of 0.7 V.
Dans un mode de réalisation, les électrodes sont isolées chimiquement pour éviter tout contact entre le substrat immergé dans le bain de l'étape b) et les électrodes plongées également dans le bain de l'étape b). Selon une variante de réalisation, ladite partie constitutive est en métal, notamment une capsule de sertissage, un ressort ou une bille formant clapet. In one embodiment, the electrodes are chemically isolated to avoid any contact between the substrate immersed in the bath of step b) and the electrodes also immersed in the bath of step b). According to an alternative embodiment, said constituent part is made of metal, in particular a crimping cap, a spring or a ball forming a valve.
Selon une variante de réalisation, ladite partie constitutive est en matériau souple, tel qu'un élastomère, notamment un piston ou un joint.  According to an alternative embodiment, said constituent part is made of a flexible material, such as an elastomer, in particular a piston or a seal.
Selon une variante de réalisation, ladite partie constitutive est en matériau synthétique, tel que le polyéthylène ou le polypropylène.  According to an alternative embodiment, said constituent part is made of synthetic material, such as polyethylene or polypropylene.
Selon une variante de réalisation, ladite partie constitutive est en verre, notamment un réservoir,  According to an alternative embodiment, said constituent part is made of glass, in particular a reservoir,
Avantageusement, le procédé comprend en outre l'étape de former par greffage chimique au moins un film mince supplémentaire sur ladite surface de support.  Advantageously, the method further comprises the step of forming by chemical grafting at least one additional thin film on said support surface.
Avantageusement, le procédé comprend l'étape de former par greffage chimique un premier film mince supplémentaire sur ladite surface de support, ledit premier film mince supplémentaire empêchant les interactions entre ladite surface de support et ledit produit fluide.  Advantageously, the method comprises the step of forming by chemical grafting a first additional thin film on said support surface, said first additional thin film preventing interactions between said support surface and said fluid product.
Avantageusement, le procédé comprend l'étape de former par greffage chimique un second film mince supplémentaire sur ladite surface de support, ledit second film mince supplémentaire limitant les frottements entre deux parties constitutives se déplaçant l'une par rapport à l'autre lors de l'actionnement du dispositif de distribution de produit fluide.  Advantageously, the method comprises the step of forming by chemical grafting a second additional thin film on said support surface, said second additional thin film limiting the friction between two constituent parts moving relative to each other during the treatment. actuation of the fluid dispensing device.
Selon une première variante, ledit au moins un film mince supplémentaire est déposé sur ladite surface de support lors d'au moins une étape de greffage chimique successive réalisée chacune dans un bain mono composant.  According to a first variant, said at least one additional thin film is deposited on said support surface during at least one successive chemical grafting step, each carried out in a single-component bath.
Selon une seconde variante, ledit au moins un film mince supplémentaire est déposé sur ladite surface de support simultanément lors d'une même étape de greffage chimique dans un bain multi composants.  According to a second variant, said at least one additional thin film is deposited on said support surface simultaneously during the same chemical grafting step in a multi-component bath.
Avantageusement, ledit produit fluide est un produit fluide pharmaceutique destiné à être pulvérisé notamment de manière nasale ou orale. Plus particulièrement, la présente invention prévoit d'utiliser un procédé similaire à celui décrit dans le document WO 2008/078052, qui décrit un procédé de préparation d'un film organique à la surface d'un support solide dans des conditions non électrochimiques. De manière surprenante, ce type de procédé s'est avéré adapté pour former un film mince sur des surfaces destinées à venir en contact avec un produit fluide pharmaceutique dans des dispositifs de distribution, pour empêcher les interactions avec ledit produit fluide. Une telle application de ce procédé de greffage n'avait jamais été envisagée. Advantageously, said fluid product is a pharmaceutical fluid product intended to be sprayed in particular nasally or orally. More particularly, the present invention provides a method similar to that described in WO 2008/078052, which describes a method of preparing an organic film on the surface of a solid support under non-electrochemical conditions. Surprisingly, this type of process has been found suitable for forming a thin film on surfaces intended to come into contact with a pharmaceutical fluid product in dispensing devices, to prevent interactions with said fluid product. Such an application of this grafting method had never been considered.
De manière synthétique, le procédé a pour but de préparer un film mince à la surface d'un support qui peut être réalisé en différents matériaux, tel que les plastiques durs, les plastiques mous, le métal ou le verre. Ce procédé comprend principalement une mise en contact de ladite surface de support avec une solution liquide. Celle-ci comprend au moins un solvant et au moins un primaire d'adhésion permettant la formation d'entités radicalaires à partir du primaire d'adhésion.  In a synthetic manner, the process aims to prepare a thin film on the surface of a support which can be made of different materials, such as hard plastics, soft plastics, metal or glass. This method mainly comprises contacting said support surface with a liquid solution. This comprises at least one solvent and at least one adhesion primer allowing the formation of radical entities from the adhesion primer.
Le "film mince" peut être tout film polymérique, notamment de nature organique, par exemple issu de plusieurs unités d'espèces chimiques organiques, et lié de manière covalente à la surface du support sur lequel est effectué le procédé. Il s'agit particulièrement d'un film lié de manière covalente à la surface d'un support et comprenant au moins une couche d'unités structurales de nature similaires. Selon l'épaisseur du film, sa cohésion est assurée par les liaisons covalentes qui se développent entre les différentes unités.  The "thin film" can be any polymeric film, in particular of organic nature, for example derived from several units of organic chemical species, and covalently bonded to the surface of the support on which the process is carried out. It is particularly a film covalently bonded to the surface of a support and comprising at least one layer of similar structural units of nature. Depending on the thickness of the film, its cohesion is ensured by the covalent bonds that develop between the different units.
Le solvant employé dans le cadre du procédé peut être de nature protique ou aprotique. Il est préférable que le primaire soit soluble dans ledit solvant.  The solvent employed in the process may be protic or aprotic in nature. It is preferable that the primer is soluble in said solvent.
Par "solvant protique" on entend un solvant qui comporte au moins un atome d'hydrogène susceptible d'être libéré sous forme de proton. Le solvant protique peut être choisi dans le groupe constitué par l'eau, l'eau désionisée, l'eau distillée, acidifiées ou non, l'acide acétique, les solvants hydroxylés comme le méthanol et l'éthanol, les glycols liquides de faible poids moléculaire tels que l'éthylèneglycol, et leurs mélanges. Dans une première variante, le solvant protique n'est constitué que par un solvant protique ou par un mélange de différents solvants protiques. Dans une autre variante, le solvant protique ou le mélange de solvants protiques peut être utilisé en mélange avec au moins un solvant aprotique, étant entendu que le mélange résultant présente les caractéristiques d'un solvant protique. L'eau acidifiée est le solvant protique préféré et, plus particulièrement, l'eau distillée acidifiée ou l'eau désionisée acidifiée. By "protic solvent" is meant a solvent which comprises at least one hydrogen atom capable of being released in the form of a proton. The protic solvent can be chosen from the group consisting of water, deionized water, distilled water, acidified or not, acetic acid, hydroxylated solvents such as methanol and ethanol, low-level liquid glycols. weight such as ethylene glycol, and mixtures thereof. In a first variant, the protic solvent consists only of a protic solvent or a mixture of different protic solvents. In another variant, the protic solvent or the mixture of protic solvents may be used in admixture with at least one aprotic solvent, it being understood that the resulting mixture has the characteristics of a protic solvent. Acidified water is the preferred protic solvent and, more particularly, acidified distilled water or acidified deionized water.
Par "solvant aprotique" on entend un solvant qui n'est pas considéré comme protique. De tels solvants ne sont pas susceptibles de libérer un proton ou d'en accepter un dans des conditions non extrêmes. Le solvant aprotique est avantageusement choisi parmi la diméthylformamide (DMF), l'acétone et le diméthyl sulfoxyde (DMSO).  By "aprotic solvent" is meant a solvent which is not considered as protic. Such solvents are not likely to release a proton or accept one under non-extreme conditions. The aprotic solvent is advantageously chosen from dimethylformamide (DMF), acetone and dimethyl sulfoxide (DMSO).
Le terme "primaire d'adhésion" correspond à toute molécule organique susceptible, sous certaines conditions, de se chimisorber à la surface du support par réaction radicalaire tel qu'un greffage chimique radicalaire. De telles molécules comportent au moins un groupe fonctionnel susceptible de réagir avec un radical et également une fonction réactive vis-à-vis d'un autre radical après chimisorption. Ces molécules sont ainsi capables de former un film de nature polymérique après greffage d'une première molécule à la surface du support puis réaction avec d'autres molécules présentes dans son environnement.  The term "adhesion primer" corresponds to any organic molecule susceptible, under certain conditions, to chemisorber on the surface of the support by radical reaction such as radical chemical grafting. Such molecules comprise at least one functional group capable of reacting with a radical and also a reactive function with respect to another radical after chemisorption. These molecules are thus capable of forming a film of polymeric nature after grafting of a first molecule on the surface of the support and then reaction with other molecules present in its environment.
Le terme "greffage chimique radicalaire" se réfère notamment à l'utilisation d'entités moléculaires possédant un électron non apparié pour former des liaisons de type liaison covalente avec une surface, lesdites entités moléculaires étant générées indépendamment de la surface de support sur laquelle elles sont destinées à être greffées. Ainsi, la réaction radicalaire conduit à la formation de liaisons covalentes entre la surface de support concernée et le dérivé du primaire d'adhésion greffé puis entre un dérivé greffé et des molécules présentes dans son environnement.  The term "radical chemical grafting" refers in particular to the use of molecular entities having an unpaired electron to form covalent link bonds with a surface, said molecular entities being generated independently of the support surface on which they are to be grafted. Thus, the radical reaction leads to the formation of covalent bonds between the support surface in question and the grafted adhesion primer derivative and then between a grafted derivative and molecules present in its environment.
Par "dérivé du primaire d'adhésion" on entend une unité chimique résultant du primaire d'adhésion, après que ce dernier a réagi par greffage chimique radicalaire notamment avec la surface du support, ou avec un autre radical. Il est clair pour l'homme du métier que la fonction réactive vis-à-vis d'un autre radical après chimisorption du dérivé du primaire d'adhésion est différente de la fonction impliquée dans la liaison covalente notamment avec la surface du support. Le primaire d'adhésion est avantageusement un sel d'aryle clivable choisi dans le groupe constitué par les sels d'aryle diazonium, les sels d'aryle d'ammonium, les sels d'aryle phosphonium, les sels d'aryle sulfonium et les sels d'aryle iodonium. By "derivative of the adhesion primer" is meant a chemical unit resulting from the adhesion primer, after the latter has reacted by grafting radical chemical especially with the surface of the support, or with another radical. It is clear to those skilled in the art that the reactive function with respect to another radical after chemisorption of the adhesion primer derivative is different from the function involved in the covalent bond, especially with the surface of the support. The adhesion primer is advantageously a cleavable aryl salt selected from the group consisting of aryl diazonium salts, ammonium aryl salts, aryl phosphonium salts, arylsulphonium salts and aryl iodonium salts.
En variante aux liaisons covalentes directes sur la surface de support, obtenues en milieu aqueux, on peut aussi utiliser un procédé d'imprégnation d'une couche poreuse préalablement greffée.  As an alternative to the direct covalent bonds on the support surface, obtained in an aqueous medium, it is also possible to use a process for impregnating a previously grafted porous layer.
Dans un mode de réalisation avantageux de l'invention, au moins un film mince supplémentaire est réalisé par greffage chimique sur la même surface de support pour donner au moins une autre propriété à cette surface de support. Ainsi, le produit fluide peut être susceptible de coller à une surface avec laquelle il est en contact, ce qui peut notamment avoir un effet néfaste sur la reproductibilité de la dose distribuée. L'invention prévoit avantageusement de former par greffage chimique un premier film mince supplémentaire qui empêche le collage du produit fluide sur la surface de support. Avantageusement, on pourrait aussi envisager d'appliquer un second film mince supplémentaire par greffage chimique pour donner une troisième propriété à la surface de support. Par exemple, dans les dispositifs de distributions de produit fluides, certaines pièces se déplacent par rapport à d'autres, et des blocages dus aux frottements sont susceptibles de gêner le bon fonctionnement du dispositif. L'invention prévoit avantageusement de former par greffage chimique un second film mince supplémentaire qui limite les frottements entre deux pièces constitutives qui se déplacent l'une par rapport à l'autre lors de l'actionnement. Ces films minces supplémentaires peuvent être appliqués lors d'étapes de greffage chimique successives. Dans ce cas, chaque étape de greffage chimique est réalisée dans un bain mono composant. Il est à noter que l'ordre des ces étapes successives de greffage chimique peut être quelconque. En variante, les films minces supplémentaires peuvent aussi être appliqués lors d'une seule et même étape de greffage chimique, qui est alors réalisée dans un bain multi composants. Une combinaison des deux variantes est aussi envisageable. In an advantageous embodiment of the invention, at least one additional thin film is produced by chemical grafting on the same support surface to give at least one other property to this support surface. Thus, the fluid product may be likely to stick to a surface with which it is in contact, which may in particular have a detrimental effect on the reproducibility of the dispensed dose. The invention advantageously provides for forming by chemical grafting a first additional thin film which prevents the fluid product from sticking to the support surface. Advantageously, it could also be envisaged to apply a second additional thin film by chemical grafting to give a third property to the support surface. For example, in fluid product dispensing devices, some parts move relative to others, and blockages due to friction may interfere with the proper operation of the device. The invention advantageously provides to form by chemical grafting a second additional thin film which limits the friction between two component parts which move relative to each other during actuation. These additional thin films can be applied during successive chemical grafting steps. In this case, each chemical grafting step is carried out in a single-component bath. It should be noted that the order of these successive chemical grafting steps can be arbitrary. Alternatively, the thin films additional can also be applied in a single step of chemical grafting, which is then carried out in a multi-component bath. A combination of the two variants is also conceivable.
La présente invention s'applique aux dispositifs multidoses, tels que les dispositifs à pompe ou valve monté sur un réservoir et actionnés pour la distribution successive de doses. Elle s'applique aussi aux dispositifs multidoses comportant une pluralité de réservoirs individuels contenant chacun une dose de produit fluide, tel que les inhalateurs de poudre prédosée. Elle s'applique également aux dispositifs unidoses ou bidoses, dans lesquels un piston se déplace directement dans un réservoir à chaque actionnement. L'invention s'applique en particulier aux dispositifs de pulvérisation nasale ou orale, aux dispositifs de distribution à usage ophtalmique et aux dispositifs à aiguille, type seringue.  The present invention is applicable to multidose devices, such as pump or valve devices mounted on a reservoir and operated for the successive delivery of doses. It also applies to multi-dose devices comprising a plurality of individual reservoirs each containing a dose of fluid, such as pre-dosed powder inhalers. It also applies to single-dose or bidose devices, in which a piston moves directly into a reservoir each time it is actuated. The invention is particularly applicable to nasal or oral spray devices, ophthalmic dispensing devices and syringe-type needle devices.
L'invention concerne également l'utilisation d'un procédé de greffage selon l'invention pour traiter au moins une surface d'au moins une partie constitutive d'un dispositif de distribution de produit fluide en contact avec ledit produit fluide, pour empêcher les interactions entre ledit produit fluide et ladite partie constitutive.  The invention also relates to the use of a grafting method according to the invention for treating at least one surface of at least one constituent part of a fluid dispenser device in contact with said fluid product, to prevent interactions between said fluid product and said constituent part.
Les exemples qui suivent ont été réalisés dans une cuve en verre. Sauf précision contraire, ils ont été réalisés dans des conditions normales de température et de pression (environ 23 °C sous environ 1 atm) à l'air ambiant. Sauf mention contraire, les réactifs employés ont été directement obtenus dans le commerce sans purification supplémentaire. Les échantillons en acier ont aux préalables subits un traitement UV-ozone pendant 10 mn à température ambiante.  The following examples were carried out in a glass vessel. Unless otherwise specified, they were made under normal conditions of temperature and pressure (about 23 ° C. under about 1 atm) in ambient air. Unless otherwise stated, the reagents employed were directly obtained commercially without further purification. The steel samples have under preliminary UV-ozone treatment for 10 minutes at room temperature.
Exemple 1 - Greffage d'un film barrière en Poly(Butylméthacrylate) (BUMA) sur des pièces en métal d'une pompe Par pompe on entend un dispositif de distribution de produit fluide actionné manuellement, comportant un corps de pompe dans lequel coulisse un ou plusieurs pistons. Le sodium dodécyl sulfate (0,283 g, 0,5 10"3 mol) a été solubilisé dans 33 mL d'eau milliQ puis le butyl méthacrylate (0,71 1 g, 5 10"3 mol) est ajouté et mis en émulsion sous forte agitation magnétique. EXAMPLE 1 Grafting of a Poly (Butylmethacrylate) (BUMA) Barrier Film on Metal Parts of a Pump By pump is meant a manually operated fluid dispensing device comprising a pump body in which one or several pistons. The sodium dodecyl sulphate (0.283 g, 0.5 × 10 -3 mol) was solubilized in 33 ml of milliQ water and the butyl methacrylate (0.71 g, 10 -3 mol) is added and emulsified under strong magnetic agitation.
L'acide 4-aminobenzoïque (0,686 g, 7,5 10"3 mol) a été solubilisé dans une solution d'acide chlorhydrique (1 ,9 mL dans 30 ml d'eau MQ) et d'acide hypophosphoreux (3,2 mL, 3,1 10"2 mol). Cette solution a été ajoutée à l'émulsion de BUMA. The 4-aminobenzoic acid (0.686 g, 7.5 × 10 -3 mol) was solubilized in a solution of hydrochloric acid (1.9 mL in 30 mL of MQ water) and hypophosphorous acid (3.2 mL). mL, 3.1 10 "2 mol). This solution was added to the BUMA emulsion.
A cette émulsion, ont été ajouté une solution de NaNO2 (0,328 g, 4,8 10"3 mol) dans 30 mL d'eau MQ puis les échantillons de billes et ressorts en inox 316 L de la pompe. To this emulsion, a solution of NaNO 2 (0.328 g, 4.8 × 10 -3 mol) in 30 ml of MQ water was added, followed by samples of 316 L stainless steel balls and springs from the pump.
Après 30 minutes de réaction, les échantillons ont été retirés puis rincés successivement par une solution aqueuse de liquide vaisselle Palmolive à 10% sous agitation magnétique à 40 °C, Jet de cette solution à 10%, bain d'eau MQ puis séchage sous Azote.  After 30 minutes of reaction, the samples were removed and then rinsed successively with an aqueous solution of 10% Palmolive dishwashing liquid with magnetic stirring at 40 ° C., jet of this 10% solution, MQ water bath and then drying under nitrogen. .
Les analyses par spectrométrie IRRAS (Hypérion) d'une bille confirme le greffage. Les bandes spécifiques d'un film de BUMA à 1716 cm"1 , sont présentes. Analyzes by IRRAS spectrometry (Hyperion) of a marble confirm the grafting. The specific bands of a BUMA film at 1716 cm -1 are present.
L'efficacité du greffage sur les échantillons a été vérifiée par un test de passivation. Pour cela, 100 g d'échantillon sont mis à minéraliser dans une solution d'acide chlorhydrique à 0,1 M pendant 15 h à 40 °C. 2 mL de cette solution ont été prélevés. Le pH a été ajusté à 3,5 à l'aide d'une solution d'acétate de sodium à 250 g/L. 1 mL d'une solution de 1 ,10-phénanthroline a été ajouté pour vérifier la présence d'ions ferreux (couleur rouge). Exemple 2 - Greffage d'un film barrière en Poly(Diméthylsiloxane) The grafting efficiency on the samples was verified by a passivation test. For this, 100 g of sample are mineralized in a solution of 0.1 M hydrochloric acid for 15 h at 40 ° C. 2 ml of this solution were taken. The pH was adjusted to 3.5 with a 250 g / L sodium acetate solution. 1 ml of a solution of 1,10-phenanthroline was added to check for the presence of ferrous ions (red color). EXAMPLE 2 Grafting of a Poly (Dimethylsiloxane) Barrier Film
(PDMS) sur des pièces en métal d'une pompe (PDMS) on metal parts of a pump
Le sodium dodécyle benzène sulfonate (0,849g, 1 ,5 10"2 mol) a été solubilisé dans 100 mL d'eau milliQ. Le poly(diméthylsiloxane) à terminaisons vinyliques (3 g, à 10g/L) a été ajouté puis le mélange a été mis sous agitation magnétique pour former une émulsion. L'acide 4-aminobenzoïque (2,058 g, 2,25 10"2 mol) a été solubilisé dans une solution d'acide chlorhydnque (5,8 mL dans 90 ml d'eau MQ) et d'acide hypophosphoreux (9,7 mL à 50%). Cette solution a été ajoutée à l'émulsion de PDMS. Sodium dodecyl benzene sulphonate (0.849 g, 1.5 × 10 -2 mol) was solubilized in 100 ml of milliQ water and vinyl-terminated poly (dimethylsiloxane) (3 g, 10 g / l) was added and then The mixture was magnetically stirred to form an emulsion. 4-Aminobenzoic acid (2.058 g, 2.25 10 -2 mol) was solubilized in a solution of hydrochloric acid (5.8 mL in 90 mL of MQ water) and hypophosphorous acid (9.7 50% mL) This solution was added to the PDMS emulsion.
A cette solution, ont été ajoutés 90 mL d'une solution aqueuse de NaNO2 (0,984 g, 1 ,44 10"2 mol) suivi des billes et des ressorts en inox 316 L. To this solution was added 90 ml of an aqueous solution of NaNO 2 (0.984 g, 1.44 × 10 -2 mol) followed by 316 L stainless steel balls and springs.
Après 30 minutes de réaction, les échantillons ont été retirés puis rincés successivement par une solution de Liquide Vaisselle Palmolive à 10% sous agitation US à 40 °C, jet de cette solution à 10%, bain d'eau puis séchage sous Azote.  After 30 minutes of reaction, the samples were removed and then rinsed successively with a solution of 10% Palmolive Liquid Dilute with US agitation at 40 ° C., jet of this 10% solution, water bath and then drying under nitrogen.
Ces échantillons traités ont également passé avec succès le test de passivation, les résultats obtenus sont rassemblés dans le tableau suivant :  These treated samples have also successfully passed the passivation test, the results obtained are summarized in the following table:
Test passivation  Passivation test
Revêtement Sans revêtement Avec revêtement pBUMA Ή-+ 000  Coating Uncoated With coating pBUMA Ή- + 000
PDMS Ή-+ 000  PDMS Ή- + 000
Test positif (corrosion) Positive test (corrosion)
000 Test négatif (pas de corrosion)  000 Negative test (no corrosion)
Exemple 3 : Greffage chimique d'un film polymère en PDMS- acrylique sur une lame d'inox en présence d'une différence de potentiel Example 3 Chemical grafting of a PDMS-Acrylic Polymer Film on a Stainless Steel Blade in the Presence of a Potential Difference
Un nettoyage des lames d'inox à l'éthanol, aux ultrasons (puissance de 100 W, température de 40°C) pendant 5 minutes est effectué. Cleaning the stainless steel blades with ethanol, ultrasound (power 100 W, temperature 40 ° C) for 5 minutes is performed.
La préparation de la solution biphasique s'opère en deux temps. Dans le bêcher (1 ), sont ajoutés, dans l'ordre et sous agitation magnétique (300 rpm), du PDMS-acrylate (1 g/L) ; du Brij® 35 en solution dans l'eau à 8,5% wt (4,37 g/L) et 33 mL d'eau Dl. L'émulsification se fait ensuite aux ultrasons à 40°C sous une puissance de 200 W (100 %) pendant 15 minutes. Dans le bêcher (2), sont ajoutés, sous agitation magnétique (300 rpm), le nitrobenzene diazonium tetrafluoroborate (0.05 mol/L) ; 130 mL d'eau Dl et l'acide chlorhydrique (0.23 mol/L). The preparation of the biphasic solution takes place in two stages. In the beaker (1) are added in order and with magnetic stirring (300 rpm), the PDMS-acrylate (1 g / L); Brij® 35 in solution in water at 8.5% wt (4.37 g / L) and 33 mL of water Dl. The emulsification is then sonicated at 40 ° C under a power of 200 W (100%) for 15 minutes. In the beaker (2) are added, with magnetic stirring (300 rpm), nitrobenzene diazonium tetrafluoroborate (0.05 mol / L); 130 mL of Dl water and hydrochloric acid (0.23 mol / L).
Le contenu du bêcher (2) est versé dans l'émulsion du bêcher (1 ). Les lames d'inox(x 2), un fil d'acier galvanisé (enroulé sur 10 spires, soit une longueur d'environ 25 à 30 cm) et un fil de Ni (enroulé sur 10 spires, soit une longueur d'environ 25 à 30 cm) sont placés dans le bêcher (1 ). Les deux fils sont reliés à un potentiostat et un ampèremètre est branché en série. Le potentiostat impose une différence de potentiel constante de 0.5 V et l'intensité du courant est mesurée au cours du temps via l'ampèremètre.  The contents of the beaker (2) are poured into the emulsion of the beaker (1). The stainless steel blades (x 2), a galvanized steel wire (wound on 10 turns, a length of about 25 to 30 cm) and a Ni wire (wound on 10 turns, a length of about 25 to 30 cm) are placed in the beaker (1). Both wires are connected to a potentiostat and an ammeter is connected in series. The potentiostat imposes a constant potential difference of 0.5 V and the intensity of the current is measured over time via the ammeter.
Enfin, une fois le montage prêt, l'acide hypophosphoreux (0.7 mol/L) est ajouté en dernier ce qui marque le début de la réaction. Après 30 minutes de réaction à température ambiante, les lames d'inox sont retirés et rincés successivement à l'eau (cascade) puis à l'éthanol (cascade) et enfin à l'isopropanol dans un extracteur de soxhlet pendant 16 heures.  Finally, once the assembly is ready, the hypophosphorous acid (0.7 mol / L) is added last which marks the beginning of the reaction. After 30 minutes of reaction at ambient temperature, the stainless steel blades are removed and rinsed successively with water (cascade) and then with ethanol (cascade) and finally with isopropanol in a soxhlet extractor for 16 hours.
L'utilisation d'un extracteur de soxhlet permet de confirmer le greffage chimique de PDMS-acrylique à la surface de la lame d'inox.  The use of a soxhlet extractor makes it possible to confirm the chemical grafting of PDMS-acrylic on the surface of the stainless steel blade.
Une analyse par spectroscopie IR est réalisée qui permet de confirmer le greffage de PDMS-acrylique par la présence de la bande caractéristique à 1260 cm"1 correspondant à la vibration de la liaison Si-CH3. An IR spectroscopic analysis is performed which makes it possible to confirm the grafting of PDMS-acrylic by the presence of the characteristic band at 1260 cm -1 corresponding to the vibration of the Si-CH 3 bond.
Ces lames d'inox ont également passé avec succès le test de passivation.  These stainless steel blades have also passed the passivation test.
Diverses modifications sont également possibles pour un homme du métier sans sortir du cadre de la présente invention tel que défini par les revendications annexées.  Various modifications are also possible for a person skilled in the art without departing from the scope of the present invention as defined by the appended claims.

Claims

Revendications claims
1 . - Procédé de traitement de surface d'un dispositif de distribution de produit fluide, caractérisé en ce que ledit procédé comprend l'étape de former par greffage chimique un film mince sur au moins une surface de support d'au moins une partie constitutive en contact avec ledit produit fluide, ledit film mince empêchant les interactions entre ledit produit fluide et ladite partie constitutive. 1. - Surface treatment method of a fluid dispenser device, characterized in that said method comprises the step of forming by chemical grafting a thin film on at least one support surface of at least one constituent part in contact with said fluid product, said thin film preventing interactions between said fluid product and said constituent part.
2. - Procédé selon la revendication 1 , dans lequel ladite étape de greffage comprend la mise en contact de ladite surface en contact avec le produit fluide avec une solution comprenant au moins un primaire d'adhésion, ledit primaire d'adhésion étant un sel d'aryle clivable et au moins un monomère ou un polymère choisi dans le groupe constitué par les siloxanes à terminaison vinylique ou acrylique et les monomères acryliques ou vinyliques.. 2. - Method according to claim 1, wherein said step of grafting comprises contacting said surface in contact with the fluid product with a solution comprising at least one adhesion primer, said adhesion primer being a sodium salt. cleavable aryl and at least one monomer or polymer selected from the group consisting of vinyl-terminated or acrylic-terminated siloxanes and acrylic or vinyl monomers.
3. - Procédé selon la revendication 1 ou 2, dans lequel ledit greffage chimique crée des liaisons covalentes entre les molécules dudit film mince et ladite surface de support. 3. - The method of claim 1 or 2, wherein said chemical grafting creates covalent bonds between the molecules of said thin film and said support surface.
4.- Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit greffage chimique est réalisé dans un milieu aqueux. 4. A process according to any one of the preceding claims, wherein said chemical grafting is carried out in an aqueous medium.
5. - Procédé selon l'une quelconque des revendications précédentes, dans lequel le sel d'aryle clivable est choisi dans le groupe constitué par les sels d'aryle diazonium, les sels d'aryle ammonium, les sels d'aryle phosphonium, les sels d'aryle sulfonium et les sels d'aryle iodonium. 5. A process according to any one of the preceding claims, wherein the cleavable aryl salt is selected from the group consisting of aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts, aryl sulfonium salts and aryl iodonium salts.
6. - Procédé selon l'une quelconque des revendications précédentes, dans lequel l'agent réducteur est choisi dans le groupe constitué par les métaux réducteurs pouvant se présenter sous forme finement divisée tels que du fer, du zinc, ou du nickel, un sel métallique pouvant être sous forme de métallocène et un réducteur organique tel que l'acide hypophosphoreux, l'acide ascorbique. 6. - Process according to any one of the preceding claims, wherein the reducing agent is selected from the group consisting of reducing metals which may be in finely divided form such iron, zinc or nickel, a metal salt which may be in the form of metallocene and an organic reducing agent such as hypophosphorous acid, ascorbic acid.
7.- Procédé selon l'une quelconque des revendications précédentes, dans lequel ladite étape de greffage chimique est initiée par activation chimique. 7. A process according to any one of the preceding claims, wherein said chemical grafting step is initiated by chemical activation.
8. - Procédé selon la revendication 7, dans lequel ladite activation chimique est initiée par la présence d'un réducteur dans la solution. 8. - The method of claim 7, wherein said chemical activation is initiated by the presence of a reductant in the solution.
9. - Procédé selon l'une quelconque des revendications précédentes, dans lequel les siloxanes à terminaison vinylique ou acrylique sont choisis dans le groupe constitué par les polyalkylsiloxanes à terminaisons acryliques ou vinyliques tels que le polyméthylsiloxane à terminaisons vinyliques ou acryliques, le polydiméthylsiloxane à terminaisons vinyliques ou acryliques comme le polydiméthylsiloxane-acrylate (PDMS-acrylate), les polyarylsiloxanes à terminaisons vinyliques ou acryliques tels que le polyphénylsiloxane à terminaisons vinyliques ou acryliques comme le polyvinylphénylsiloxane, les polyarylalkylsiloxanes à terminaisons vinyliques ou acryliques tels que le polyméthylphénylsiloxane à terminaisons vinyliques ou acryliques. 9. The process as claimed in any one of the preceding claims, in which the vinyl-terminated or acrylic-terminated siloxanes are chosen from the group consisting of polyalkylsiloxanes with acrylic or vinyl terminations, such as vinyl-terminated or acrylic-terminated polymethylsiloxane, and terminated polydimethylsiloxane. vinyl or acrylic such as polydimethylsiloxane-acrylate (PDMS-acrylate), vinyl-terminated or acrylic-terminated polyarylsiloxanes such as polyphenylsiloxane with vinyl or acrylic terminations such as polyvinylphenylsiloxane, polyarylalkylsiloxanes with vinyl or acrylic terminations, such as vinyl-terminated or acrylic-terminated polymethylphenylsiloxane .
10. - Procédé selon l'une quelconque des revendications précédentes, dans lequel le monomère acrylique ou vinylique est choisi dans le groupe constitué par l'acétate de vinyle, l'acrylonitrile, le méthacrylonitrile, le méthacrylate de méthyle, le méthacrylate d'éthyle, le méthacrylate de butyle, le méthacrylate de propyle, le méthacrylate d'hydroxyéthyle, le méthacrylate d'hydroxypropyle, le méthacrylate de glycidyle et leurs dérivés, les acrylamides tels que les méthacrylamides d'aminoéthyle, propyle, butyle, pentyle et hexyle, les cyanoacrylates, les diacrylates, les diméthacrylates, les triacrylates, les triméthacrylates, les tétraacrylates, les tétraméthacrylates, le styrène et ses dérivés, le parachl orostyrène, le pentafluorostyrène, la N-vinyl pyrrolidone, la 4-vinyl pyridine, la 2-vinyl pyridine, les halogénures de vinyle, d'acryloyle et de méthacryloyle, le divinylbenzène. The process of any one of the preceding claims, wherein the acrylic or vinyl monomer is selected from the group consisting of vinyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate. , butyl methacrylate, propyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and derivatives thereof, acrylamides such as aminoethyl, propyl, butyl, pentyl and hexyl methacrylamides; cyanoacrylates, diacrylates, dimethacrylates, triacrylates, trimethacrylates, tetraacrylates, tetramethacrylates, styrene and its derivatives, parachlorostyrene, pentafluorostyrene, N-vinyl pyrrolidone, 4-vinyl pyridine, 2-vinyl pyridine, vinyl halides, acryloyl and methacryloyl, divinylbenzene.
1 1 .- Procédé selon l'une quelconque des revendications précédentes, dans lequel une différence de potentiel est appliquée dans ladite solution. Method according to any one of the preceding claims, wherein a potential difference is applied in said solution.
12. - Procédé selon la revendication 1 1 , dans lequel la différence de potentiel est appliquée par un générateur relié à deux électrodes, identiques ou différentes, plongeant dans la solution pendant l'étape de trempage 12. - Method according to claim 1 1, wherein the potential difference is applied by a generator connected to two electrodes, identical or different, plunging into the solution during the soaking step
13. - Procédé selon la revendication 1 1 , dans lequel la différence de potentiel est générée par une pile chimique. 13. - The method of claim 1 1, wherein the potential difference is generated by a chemical battery.
14.- Procédé selon l'une quelconque des revendications précédentes, dans lequel ladite partie constitutive est en métal, notamment une capsule de sertissage, un ressort ou une bille formant clapet. 14. A process according to any one of the preceding claims, wherein said constituent part is made of metal, in particular a crimping cap, a spring or a ball forming a valve.
15. - Procédé selon l'une quelconque des revendications 1 à 13, dans lequel ladite partie constitutive est en matériau souple, tel qu'un élastomère, notamment un piston ou un joint. 15. - Process according to any one of claims 1 to 13, wherein said constituent part is of flexible material, such as an elastomer, in particular a piston or a seal.
16. - Procédé selon l'une quelconque des revendications 1 à 13, dans lequel ladite partie constitutive est en matériau synthétique, tel que le polyéthylène ou le polypropylène. 16. - Method according to any one of claims 1 to 13, wherein said constituent part is made of synthetic material, such as polyethylene or polypropylene.
17. - Procédé selon l'une quelconque des revendications 1 à 13, dans lequel ladite partie constitutive est en verre, notamment un réservoir. 17. - Method according to any one of claims 1 to 13, wherein said constituent part is glass, including a reservoir.
18.- Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit film mince a une épaisseur inférieure à 1 micromètre, de préférence comprise entre 10 et 2000 angstrôms. 18. A process according to any one of the preceding claims, wherein said thin film has a thickness of less than 1 micrometer, preferably between 10 and 2000 angstroms.
19.- Utilisation d'un procédé de greffage selon l'une quelconque des revendications précédentes, pour traiter au moins une surface d'au moins une partie constitutive d'un dispositif de distribution de produit fluide en contact avec ledit produit fluide, pour empêcher les interactions entre ledit produit fluide et ladite partie constitutive. 19.- Use of a grafting method according to any one of the preceding claims, for treating at least one surface of at least one constituent part of a fluid dispenser device in contact with said fluid product, to prevent the interactions between said fluid product and said constituent part.
EP10808921A 2009-12-23 2010-12-22 Method for treating the surface of a device for dispensing a fluid product Withdrawn EP2516521A1 (en)

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FR2954330A1 (en) 2011-06-24
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