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
  • A61M15/0028—Inhalators using prepacked dosages, one for each application, e.g. capsules to be perforated or broken-up
  • A61M15/0045—Inhalators using prepacked dosages, one for each application, e.g. capsules to be perforated or broken-up using multiple prepacked dosages on a same carrier, e.g. blisters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
  • C09D5/1675—Polyorganosiloxane-containing compositions
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
• • 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
  • A61M2205/0222—Materials for reducing friction
• • 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
  • 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
  • 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
  • B05D7/02—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 macromolecular substances, e.g. rubber
• • 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
  • B05D7/50—Multilayers
  • B05D7/52—Two layers

Definitions

• the present invention relates to a surface treatment method for fluid dispensing devices.
• Dispensing devices for fluid products are well known. They generally comprise a reservoir, a dispensing member, such as a pump or a valve, and a dispensing head provided with a dispensing orifice.
• the fluid dispensing devices may also be inhalers comprising a plurality of reservoirs each containing an individual dose of powder or liquid, and means for opening and expelling said doses during successive actuations.
• these devices have many parts that come into contact with the fluid during actuation. There is therefore a risk that the product remains glued or hooked to one or more parts of the device before being distributed to the user. This results in a decrease in the dose distributed over the theoretical dose, which can create serious problems, for example for crisis treatments, such as asthma.
• These gluing problems can arise in particular at the level of the tank or tanks, but also at the level of the piston and the pump chamber or the valve and the valve chamber. It is the same in the pushers or dispensing heads.
• the present invention aims to provide a surface treatment method that does not reproduce 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 said device which is in contact with said fluid product during actuation of said device, said thin film having anti-stick properties for said fluid product.
• 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.
• said thin film is a polymeric film comprising silicone.
• said silicone is a grade DM300 or DM1000 silicone
• 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 salts thereof. aryl 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 X " anions are chosen from inorganic anions such as halides, such as I “ , Cl “ and Br " , haloborates such as tetrafluoroborate and organic anions such as alcoholates, carboxylates, perchlorates and sulfonates.
• inorganic anions such as halides, such as I “ , Cl “ and Br "
• haloborates 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 selected from aryl groups substituted with attractant moieties such as NO2, COH, CN, CO2H, 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 diazonium tetrafluoroborate, 2-methyl-4 - [(2-methylphenyl) diazenyl] benzenediazonium sul
• the cleavable aryl salt is selected from the group consisting of 4-nitrophenyldiazonium tetrafluoroborate, 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 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.
• said thin film has a thickness of less than 1 micrometer, between 10 and 800 angstroms.
• said thin film has a thickness between 400 and 1000 angstroms.
• 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, and vinyl-terminated or acrylic-terminated polyarylalkylsiloxanes, such as vinyl-terminated or acrylic-terminated polymethylphenylsiloxane.
• 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.
• 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 prevent contact between the substrate immersed in the solution and the electrodes also immersed in the solution.
• the method further comprises the step of forming by chemical grafting a second thin film on said support surface, said second thin film preventing interactions between said support surface and said fluid product.
• said two thin films are deposited on said support surface during two successive chemical grafting steps each carried out in a single-component bath.
• said two thin films are deposited on said support surface simultaneously during the same chemical grafting step in a multi-component bath.
• said support surface is made of synthetic material, especially comprising polyethylene and / or polypropylene.
• said support surface is made of metallic material.
• said thin film has a thickness of less than 1 micrometer, preferably between 10 and 800 angstroms. No conventional coating technique makes it possible to obtain such thin layers chemically grafted.
• said dispensing device comprises a reservoir containing the fluid, a dispensing member, such as a pump or a valve, fixed on said reservoir, and a dispensing head provided with a dispensing orifice, for actuating said organ of distribution.
• said dispensing device includes a plurality of individual reservoirs each containing a dose of fluid, reservoir opening means, such as a piercing needle, and dose delivery means for dispensing a dose of product. fluid from an individual reservoir open through a dispensing orifice.
• said fluid product is a pharmaceutical fluid product intended to be sprayed nasally or orally.
• a method similar to that described in WO 2008/078052 which describes a method for preparing an organic film on the surface of a solid support under non-electrochemical conditions, can be used.
• this type of process has been adapted to form a thin anti-stick film on moving surfaces when actuating the dispensing devices. above. Such an application of this grafting method had never been considered.
• the process aims to prepare a thin film on the surface of a solid support, in particular polyethylene and / or polypropylene and / or metal.
• 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 the 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 thin film contains silicone.
• 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. molecular weights 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 capable, under certain conditions, of chemisorbing on the surface of the solid 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 the support surface, said molecular entities being generated independently of the support surface on which they are intended 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 preferably a cleavable aryl salt selected from the group consisting of aryl diazonium salts, ammonium aryl salts, aryl phosphonium salts, aryl sulphonium salts, and the like. aryl iodonium salts.
• the thin film comprises silicone, which may be of different medical grades, for example DM300 or DM1000.
• silicone which may be of different medical grades, for example DM300 or DM1000.
• At least one second thin film is produced by chemical grafting on the same support surface, to give at least one other property to this support surface.
• the surfaces of elastomers, and in particular the aforementioned seals, metal or glass surfaces, or synthetic surfaces, for example polyethylene or polypropylene are likely to interact with the fluid product, for example by releasing extractables in said fluid product, which can have a detrimental effect on it.
• the invention advantageously provides for forming by chemical grafting a second thin film which prevents interactions between the elastomeric surface and the fluid product.
• This second thin film may be applied during a second chemical grafting step.
• each chemical grafting step is carried out in a single-component bath.
• the order of these two successive chemical grafting steps can be arbitrary.
• the two thin films can also be applied in a single step of chemical grafting, which is then performed in a multi-component bath.
• other additional thin films may also be made by chemical grafting, for example to limit the friction between parts that move during actuation.
• the invention also relates to the use of a grafting method according to the invention for forming a thin film on at least one surface of at least one constituent part of a fluid dispenser device in contact with said fluid product during actuation of said device, said thin film having anti-stick properties for said fluid product.
• the vinyl-terminated poly (dimethylsiloxane) (1.0 g, 5 g / L) was poured into a solution of Brij® (0.874 g to 4.37 g / L) in 70 mL of milliQ water and then the suspension. was magnetically stirred to form an emulsion.
• 4-Aminobenzoic acid (1. 370 g, 10-2 mol) was solubilized in a solution of hydrochloric acid (4.0 mL in 120 mL of MQ water) and hypophosphorous acid (6.3 mL 6.0-10-2 mol). This solution was added to the PDMS emulsion.
• valve a fluid dispensing device containing propellant gas, comprising a valve body in which slides a valve.
• Nitrile and top valve in POM as well as a gold leaf witness Nitrile and top valve in POM as well as a gold leaf witness.
• the following example illustrates how to graft a lubricant coating (PDMS-acrylic) on a thermoplastic such as polyethylene (PE). Cleaning of the PE samples with ethanol, ultrasound (power of 50%, temperature of 40 ° C) for 5 minutes is carried out.
• a lubricant coating PDMS-acrylic
• PE polyethylene
• 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.
• the contents of the beaker (2) are poured into the emulsion of the beaker (1).
• PE samples (x 2), a galvanized steel wire (wound on 10 turns, approximately 25 to 30 cm long) and a Ni wire (wound on 10 turns, a length of about 25 30 cm) are placed in the beaker (1).
• the two wires are connected to each other and an ammeter is connected in series.
• hypophosphorous acid 0.7 mol / L
• the PE samples are removed and rinsed successively with water, with ethanol and finally with isopropanol in a soxhlet extractor for 16 hours.
• the soxhlet consists of a glass body in which the sample is placed, a siphon tube and an adduction tube.
• the soxhlet is placed on a flask (here 500 ml heated and stirred via a balloon heater) containing the solvent (in this case 300 ml of isopropanol) and surmounted by a coolant.
• the solvent vapors pass through the adductor tube, condense in the refrigerant and fall back into the glass body, thus macerating the sample in a pure solvent (heated by the vapors below).
• the condensed solvent accumulates in the extractor until it reaches the top of the siphon tube, which then causes the liquid to return to the flask, accompanied by the substances extracted, and the solvent contained in the flask thus becomes progressively enriched. soluble compounds.
• the solvent then continues to evaporate, while the extracted substances remain in the flask (their boiling temperature must be significantly higher than that of the extracting solvent).
• soxhlet extractor makes it possible to confirm the chemical grafting of PDMS-acrylic on the surface of the PE substrate.
• EXAMPLE 4 Electrocatalyzed Chemical Grafting of a PDMS Acrylic Polymer Film on a Polyethylene Substrate in the Presence of a Potentiostat The following example illustrates how to graft a lubricant coating
• thermoplastic such as polyethylene (PE) in the presence of a potentiostat.
• 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.
• the contents of the beaker (2) are poured into the emulsion of the beaker (1).
• PE samples (x 2), a galvanized steel wire (wound on 10 turns, approximately 25 to 30 cm long) and a Ni wire (wound on 10 turns, a length of about 25 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
• the PE samples are removed and rinsed successively with water (cascade) and then with ethanol (cascade) and finally with isopropanol in a soxhlet extractor for 16 hours.
• soxhlet extractor makes it possible to confirm the chemical grafting of PDMS-acrylic on the surface of the PE substrate.
• the IR spectrum 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.

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• 2009
  • 2009-12-23 FR FR0959496A patent/FR2954328B1/fr active Active
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  • 2010-12-22 US US13/515,673 patent/US20130022750A1/en not_active Abandoned
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