JP2013515805A - Treatment method for treating the surface of a fluid dispensing device - Google Patents

Abstract

A treatment method for treating a surface of a fluid dispensing device, wherein the thin film has anti-friction properties on one or more support surfaces of one or more movable parts of the fluid dispensing device that move during operation of the fluid dispensing device. Including a process of forming the film using chemical grafting.
[Selection figure] None

Description

  The present invention relates to a surface treatment method for a fluid administration device.

  Fluid delivery devices are known and typically consist of: That is, a dosing head with one or more reservoirs, a dosing member such as a pump, a valve, a piston moving within the reservoir, and a dosing opening. In some configurations, a side drive system is provided for driving the dispensing member. In a modification, the fluid administration device is an inhaler, and each has a plurality of reservoirs each storing a single amount of powder or liquid, and means for opening and releasing the single dose during continuous driving. It can also be configured. Depending on the type of device, there may also be a frequency counter or indicator for counting or displaying how many doses have been dispensed from the dosing device or not yet administered and left on the dosing device. Thus, the fluid dispensing device has a number of moving parts or moving parts that move relative to each other during actuation. Thus, controlling friction, which can cause undesirable noise and / or malfunction, becomes an important issue. Especially in the field of medicine, the risk of malfunction of the administration device is significant (for example in the case of treatment of seizures such as asthma). Specifically, friction problems occur in pump pistons and valve members, where it is important to avoid clogging of pump pistons and valve members. The same applies to the inhaler, where the means for moving or opening the reservoir and the means for administering a single dose are susceptible to friction. Furthermore, the same is true for the number counter where the user needs to accurately display how many doses remain undosed so as not to misunderstand. Thus, any clogging that occurs as a result of friction can cause damage.

  There are problems with all existing surface treatment methods. As such, some methods are only suitable for use in planes. Also, other methods limit the choice of substrate (eg gold). Polymerization of molecules by plasma is complicated and expensive, and the resulting coating layer is difficult to control, and there is a problem of deterioration over time. Similarly, the polymerization of molecules by UV radiation is complex and expensive and only works when used with photosensitive molecules. The same applies to atom transfer radical polymerization (ATRP), which is complex and expensive. Finally, the electrografting method is complex and requires that the support surface be conductive.

International Publication No. 2008/078052

An object of the present invention is to propose a surface treatment method that does not cause the above problems.
Specifically, an object of the present invention is to provide an effective, long-lasting, non-polluting and easy-to-implement surface treatment method.

  Therefore, the present invention is a processing method for treating the surface of a fluid administration device, wherein the surface of one or more supports of one or more movable parts of the fluid administration device that moves while the fluid administration device is driven A processing method is provided that includes a process of forming a thin film having anti-friction properties using chemical grafting.

Further, as an effective embodiment, the chemical grafting treatment includes a treatment in which the surface of the support in contact with a fluid is brought into contact with a solution containing one or more fixing agents, and the fixing agent is a cleaved aryl salt. And one or more monomers or polymers selected from the group consisting of vinyl-terminated or acrylic-terminated siloxanes.
The thin film is effectively a polymer film containing silicon.

Further, it is effective that the silicon is DM300 or DM1000 silicon.
In the chemical grafting, it is effective to generate a covalent bond between the thin film and a molecule on the surface of the support. This creates a strong and long lasting bond.
The chemical grafting is effectively performed in an aqueous medium. In this way, the chemical action can be used in a pollution-free or safe manner and without any danger to the environment.

In practice, the cleaveable aryl salt is selected from the group consisting of aryldiazonium salts, arylammonium salts, arylphosphonium salts, arylsulfonium salts, and aryliodonium salts.
The cleaveable aryl salt is selected from compounds of the general formula: ArN ₂ ⁺ , X ⁻ (Ar represents an aryl group, X ⁻ represents an anion). The aryl group in the organic compound is a functional group derived from an aromatic ring.

In practice, X ^- anions are selected from the following ones. That is, inorganic anions such as halides such as I ⁻ , Cl ⁻ and Br ⁻ ; halogenoboric acids such as tetrafluoroboric acid; organic anions such as alcoholates, carboxylates, perchlorates and sulfonates.
In practice, the aryl group Ar can be selected from mono- or poly-substituted aromatic groups or heteroaromatic groups composed of aromatic rings having 3 to 8 carbons. The heteroatom of the heteroaromatic compound is selected from N, O, P, and S. Substituents include alkyl groups and one or more heteroatoms (N, O, F, Cl, P, Si, Br, S, etc.).

In practice, the aryl group is selected from NO ₂ ; COH; CN; CO ₂ H; ketone; ester; amine; and aryl group substituted by an attracting group such as halogen.
In practice, the aryl group is selected from the group consisting of a phenyl group and a nitrophenyl group.
In practice, the cleaveable aryl salt is selected from the group consisting of: phenyldiazonium tetrafluoroborate; 4-nitrophenyldiazonium tetrafluoroborate; 4-bromophenyldiazonium tetrafluoroborate; 4-aminophenyldiazonium chloride. 4-aminomethylphenyldiazonium chloride; 2-methyl-4-chlorophenyldiazonium chloride; tetrafluoroborate 4-benzoylbenzenediazonium; tetrafluoroborate 4-cyanophenyldiazonium; tetrafluoroborate 4-carboxyphenyldiazonium; tetrafluoro 4-acetamidophenyldiazonium borate; diazonium tetraphenylborate 4-phenylacetate; 2-methyl-4-[(2-methylpheny ) Diazenyl] benzene diazonium sulfate; 9,10-dioxo-9,10-dihydro-1-anthracene diazonium chloride; tetrafluoroborate 4-nitronaphthalene diazonium; and, tetrafluoroborate naphthalene diazonium.

In practice, the cleaveable aryl salt is selected from the group consisting of: 4-nitrophenyldiazonium tetrafluoroborate; 4-aminophenyldiazonium chloride; 2-methyl-4-chlorophenyldiazonium chloride; and tetra 4-Carboxyphenyldiazonium fluoroborate.
In practice, the concentration of the cleaveable aryl salt ranges from 5 × 10 ⁻³ mol (M) to 10 ⁻¹ M.

In practice, the concentration of the cleaveable aryl salt is about 5 × 10 ⁻² M.
In practice, the cleaveable aryl salt is prepared in situ.
It is effective that the chemical grafting process is started by chemical activation of a diazonium salt for forming the anchor layer for the thin film.
In addition, it is effective that the chemical grafting process is started by chemical activation.

In practice, the chemical activation is initiated by the presence of a reducing agent in the solution.
In practice, the solution shall consist of a reducing agent.
The term “reducing agent” refers to a compound that donates electrons during a redox reaction. As a feature of the present invention, the redox potential difference of the reducing agent with respect to the redox potential of the cleaveable aryl salt is in the range of 0.3 volts (V) to 3V.

As a feature of the present invention, the reducing agent is iron, zinc or nickel, a reducible metal that can be finely divided, a metal salt that can take the form of metallocene, and hypophosphorous acid or ascorbic acid. Selected from the group consisting of: an organic reducing agent;
In implementation, the concentration of the reducing agent is in the range of 0.005M to 2M.
In the implementation, the concentration of the reducing agent is about 0.6M.

In practice, the thickness of the thin film is less than 1 micrometer (μm), preferably in the range of 10 Å (Å) to 2000 Å. The range of 10 to 800 cm is effective, and the range of 400 to 1000 cm is preferable. It is impossible to obtain such a thin chemical graft layer with conventional coating techniques.
The term “vinyl-terminated or acrylic-terminated siloxane” is a saturated silicon and oxygen hydrogen formed by linear or branched chains of alternating silicon and oxygen atoms, containing a vinyl or acrylic motif at the end. Means a chemical.

  In practice, vinyl-terminated or acrylic-terminated siloxanes are vinyl-terminated or acrylic-terminated polyalkylsiloxanes that are vinyl-terminated or acrylic-terminated polymethylsiloxanes; and vinyl-terminated or poly-terminated siloxanes (PDMS-acrylic acid salts). Acrylic-terminated polydimethylsiloxane; a vinyl-terminated or acrylic-terminated polyarylsiloxane that is a vinyl-terminated or acrylic-terminated polyphenylsiloxane that is polyvinylphenylsiloxane; and a vinyl-terminated or acrylic-terminated polyaryl that is a vinyl-terminated or acrylic-terminated polymethylphenylsiloxane And selected from the group consisting of alkylsiloxanes.

In practice, a potential difference is applied to the solution.
The term “potential difference” means a redox potential difference measured between two electrodes.
In implementation, the potential difference is applied from a power source connected to the two electrodes, and the two electrodes may be the same or different, and are immersed in the solution during the immersion process.
In practice, the electrodes are selected from among stainless steel, steel, nickel, platinum, gold, silver, zinc, iron and copper. It may be an in pure form or an alloy.

In practice, the electrodes are made of stainless steel.
In implementation, the potential difference applied from the generator is in the range of 0.1V to 2V.
In implementation, the value is about 0.7V.
In practice, the potential difference is caused by a chemical battery.
The term “chemical cell” means a cell consisting of two electrodes interconnected via an ion bridge. The two electrodes in the present invention are appropriately selected so that the potential difference is in the range of 0.1V to 2.5V.

In practice, a chemical cell is formed between two different electrodes immersed in a solution.
In practice, the electrodes are selected from nickel, zinc, iron, copper, and silver. It may be a simple substance or an alloy.
In the implementation, the potential difference generated by the chemical battery is in the range of 0.1V to 1.5V.
In the implementation, the potential difference is about 0.7V.

In practice, the electrodes are chemically insulated so that contact between the substrate in the solution and the electrode immersed in the solution is completely avoided.
In addition, it is effective that the surface of the support is made of a synthetic material, elastomer, glass, or metal made of polyethylene (PE) and / or polypropylene (PP).

In addition, it is effective to further include a process of forming one or more additional thin films on the surface of the support using chemical grafting.
Moreover, it further has a process of forming a first additional thin film on the surface of the support using chemical grafting, and the first additional thin film suppresses the degree of adhesion of the fluid to be administered to the surface of the support. Is effective.

The method further includes forming a second additional thin film on the support surface using chemical grafting, and the second additional thin film prevents an interaction between the support surface and the fluid. It is effective to be a thing.
In a variation, the one or more additional thin films are laminated to the support surface during one or more successive chemical grafting processes each in one single-component bath. And

In another variation, the one or more additional thin films are simultaneously laminated to the support surface during a single chemical grafting process in one multi-component bath) And
The administration device includes a reservoir in which a fluid is stored, an administration member that is a pump or a valve fixed to the reservoir, and an administration head having an administration opening, and the administration head includes the administration head. It is effective to drive the member.

In a variant, the dosing device comprises a plurality of individual reservoirs each storing a volume of fluid, a reservoir opening means being a piercing needle, and one of the opened reservoirs. And a single dose administration means for administering a batch amount of fluid from the administration opening.
In a modified example, the administration device includes a reservoir that stores one or two volumes of fluid, and a piston that moves inside the reservoir each time it is driven.

In addition, it is effective that the administration device has a number counter that counts how many doses are administered from the administration device or how many doses remain in the administration device. is there.
In addition, it is effective that the fluid is a medicine sprayed to the nose or mouth.

  In implementation, a method similar to that described in International Publication No. 2008/078052 can be used. Described in the international publication is a method of providing an organic thin film on the surface of a solid support under non-electrochemical conditions. Surprisingly, this type of method has been found to be suitable for forming a thin film having anti-friction properties on a moving surface during operation of the fluid delivery device. The application of such a grafting method has not been considered so far.

In summary, the present method aims to form a thin film (especially a polyethylene and / or polypropylene membrane) on the surface of a solid support. The method mainly comprises a treatment of immersing the support surface in a liquid solution. The liquid solution includes one or more solvents and one or more fixing agents from which radical entities can be formed.
A “thin film” is an organic polymer film in particular, for example, that originates from a plurality of units of organic chemical species and is covalently bonded to the surface of a support on which the method is performed. . Specifically, it is a membrane having one or more layers which are bonded to the surface of a support in the form of a covalent bond and are composed of structural units of similar properties. Coupling force corresponding to the film thickness is realized by the covalent bond that proceeds between various units. The thin film preferably contains silicon.

The solvent used in connection with the present method may be protic or aprotic. However, it is preferable that the solvent dissolves the fixing agent.
The term “protic solvent” means a solvent containing one or more hydrogen atoms that can be released in proton form. The protic solvent may be selected from the group consisting of: Water; deionized water; distilled water (which may be acidified but not essential); acetic acid; hydroxylated solvents such as methanol and ethanol; low molecular weight liquid glycols such as ethylene glycol; and mixtures thereof. In the first example, the protic solvent may consist of a protic solvent alone or a mixture of different protic solvents. In the following example, one or more aprotic solvents are mixed into a protic solvent or mixture of protic solvents. As will be appreciated, in this case, the resulting mixture must exhibit the characteristics of a protic solvent. Acidified water is a preferred protic solvent, but more specifically, acidified distilled water and acidified deionized water are preferred.

The term “aprotic solvent” means a solvent that is not considered protic. Under non-extreme conditions, these solvents are not suitable for proton release and acceptance. The aprotic solvent is effectively selected from dimethylformamide (DMF), acetone, and dimethyl sulfoxide (DMSO).
The term “fixing agent” refers to any organic molecule suitable for chemisorption onto a support surface under certain conditions by radical reactions such as radical chemical grafting.
Such molecules include one or more functional groups suitable for reacting with a radical and a reactive functional group that reacts with another radical after chemisorption. That is, after grafting the first molecule on the support surface, the molecule can form a polymer film and then react with other molecules present in the environment.

  The term “radical chemical grafting” specifically refers to the formation of a bond with the support surface in the form of a covalent bond using a molecular entity having an unpaired electron. The molecular entities in that case are generated independently of the support surface onto which they are grafted. Thus, as a result of the radical reaction, a covalent bond is first formed between the target support surface and the grafted fixer derivative, and then between the grafted derivative and the molecule present in the environment. Formed.

  The term “fixing agent derivative” specifically refers to a chemical unit originating from a fixing agent, which chemically reacts with the surface of the support or other radicals by radical chemical grafting. It happens after As will be apparent to those skilled in the art, the functional group that reacts with another radical after chemical absorption of the fixer derivative is distinct from the functional group associated with covalent bonding to the surface of the support. For the fixing agent, it is effective to select a fixable aryl salt from the group consisting of aryldiazonium salt, arylammonium salt, arylphosphonium salt, arylsulfonium salt, and aryliodonium salt.

Although it is preferable to include silicon in the thin film, silicon can be used for various medical purposes (for example, DM300 or DM1000). Further, as a modified example of direct covalent bonding of silicon to the surface of the support realized in an aqueous medium, a method of immersing silicon in the porous layer previously grafted may be used. Is possible.
In an effective implementation of the invention, chemical grafting is used to form at least one additional thin film on a single support surface. This adds at least one other characteristic to the support surface. The fluid to be administered tends to adhere to the surface with which it comes into contact, which can in particular adversely affect the reproducibility of the single dose administered. As an effective point, according to the present invention, the first additional thin film that prevents the fluid from adhering to the surface of the support can be formed by chemical grafting. In addition, it is also effective to consider a usage in which the support surface is provided with the third characteristic by providing the second additional thin film using chemical grafting. For example, in fluid delivery devices, certain materials will interact when contacted with the fluid to be administered, which may be harmful to the fluid. As another effective point, according to the present invention, the second additional thin film for preventing the interaction between the fluid and the support surface can be formed by chemical grafting. These additional thin films may be provided by a continuous chemical grafting process. Thus, each chemical grafting process may be performed in a single component tank. It should be noted that these successive chemical grafting processes may be performed in any order. In the modified example, as another method, the additional thin film can be provided by a single chemical grafting process. In this case, the chemical grafting process is performed in a multi-component tank. It is also conceivable to combine these two modifications.

  INDUSTRIAL APPLICABILITY The present invention is used in a multi-use type apparatus that has a reservoir in which a pump or a valve is installed and continuously administers a predetermined amount for one operation by driving. The present invention is also used in multi-use devices having multiple separate reservoirs. Such a device is provided with a plurality of storage containers as in the case of a subdivided powder inhaler, and each reservoir stores a single fluid. The present invention is also used in a one-time or two-time device in which the piston moves directly in the reservoir each time it is driven. The invention is used in particular for nasal or oral spray devices, eye drop administration devices, and syringe type needle devices.

  The present invention is further directed to forming a thin film having anti-friction properties on one or more support surfaces of one or more movable parts of the device that move during operation of the fluid delivery device. How to use the method.

The example shown below was performed in a glass container. Unless otherwise specified, these examples were performed under an atmosphere of normal temperature and normal pressure (about 22 ° C., about 1 atmosphere (atm)). Unless otherwise stated, the reagents used were obtained as they were on the market, and no additional purification treatment was performed. Samples were ultrasonically cleaned beforehand in soapy water at 40 ° C.
Example 1-Poly (dimethylsiloxane) membrane grafted onto a part of the pump to smooth the part of the pump The term "pump" means a manual, having a pump body within which one or more pistons slide The fluid administration device.

To a solution of Brij® 35 (0.874 g at a rate of 4.37 g / L) in 70 milliliters (mL) of milli-Q (mQ) water, vinyl terminated poly (dimethylsiloxane) (1.0 grams) (G) 5 grams per liter (g / L)) was poured and the suspension thus obtained was magnetically stirred to form an emulsion.
4-aminobenzoic acid (1.370 g, 10 ⁻² mol (mol)) was added to hydrochloric acid (4.0 mL in 120 mL of mQ water) and hypophosphorous acid (6.3 mL, 6.0 × 10 ^−2). mol) solution. The solution was then added to the PDMS emulsion.

Then, 8 mL of an aqueous solution of NaNO ₂ (0.667 g, 9.7 × 10 ⁻³ mol) was added to the emulsion, and then a pump part sample was added.
After reacting for 30 minutes, the sample (ie PP main body; upper piston; lower piston; polyethylene PE tube) was taken out, and 40 ° C. in a plurality of continuous baths containing 1% soap water (Renoclean). Ultrasonic rinsing was carried out at a temperature of 1, and further rinsing was also carried out in a plurality of tanks containing water.

After these parts were dried with compressed air, the presence of PDMS on the sample was confirmed. Confirmation, 1260 per centimeter (cm ^-1), 1110cm ^-1, at 1045cm ^-1, it was carried out by infrared (IR) analysis using specific band of PDMS.
Example 2-The term "valve" in which a poly (dimethylsiloxane) membrane is grafted onto a valve component to smooth the valve component contains the propellant gas and the valve body within which the valve member slides Means a fluid administration device having a configuration.

First, sodium dodecylbenzenesulfonate (1.307 g, 0.015 M,) was dissolved in 175 mL of mQ water. Vinyl terminated poly (dimethylsiloxane) (2.5 g, 10 g / L) was then added and the resulting mixture was magnetically stirred to form an emulsion.
4-aminobenzoic acid (3.462 g, 2.5 × 10 ⁻² mol) was added to hydrochloric acid (9.6 mL in 20 mL mQ water) and hypophosphorous acid (33 mL, 3.1 × 10 ⁻¹ mol). ). The solution was then added to the PDMS emulsion.

Then 10 mL of an aqueous solution of NaNO ₂ in mQ water (1.664 g, 2.37 × 10 ⁻² mol) is added to the emulsion, and then a sample (ie: ethylene propylene diene monomer (EPDM) or nitrile rubber gasket) A top of a valve member made of polyoxymethylene (POM); a gold indicator strip).
After reacting for 15 minutes, a sample was taken out and rinsed continuously in mQ water, ethanol, and hexane.

The presence of PDMS on the gold strip and other samples was then confirmed. Confirmation, 1260cm ^-1, 1110cm ^-1, at 1045cm ^-1, was carried out by IR analysis using the unique band of PDMS.
Example 3 Electrocatalytic Chemical Grafting of Acrylic PDMS Polymer Film on a Polyethylene Substrate This example illustrates a method of grafting a lubricious coating (acrylic PDMS) onto a thermoplastic material such as PE.

First, a PE sample was placed in ethanol and subjected to ultrasonic cleaning for 5 minutes (50% power, temperature was 40 ° C.).
A biphasic solution was prepared in two steps. First, with magnetic stirring at 300 revolutions per minute (rpm), the following were added in order to the beaker (1): PDMS-acrylate (1 g / L); 8.5 wt% (% wt) A solution of Brij 35® in water (4.37 g / L); 33 mL of deionized (DI) water. The emulsion was then emulsified for 15 minutes under ultrasound at a temperature of 40 ° C. and a power of 200 watts (W) (100%).

The following was then added to the beaker (2) with magnetic stirring (300 rpm): nitrobenzenediazonium tetrafluoroborate (0.05 mol / L); 130 mL DI water; hydrochloric acid (0.23 mol / L).
The contents of beaker (2) were poured into the emulsion of beaker (1). And PE samples (2); galvanized wound metal wire (10 turns, ie about 25-30 centimeters (cm)); wound nickel (Ni) wire (10 turns, ie about 25-30 centimeters) (Cm)) was placed in the beaker (1). A metal wire and a nickel wire were connected to each other, and an ammeter was connected in series.

As a final step, after the assembly was prepared, hypophosphorous acid (0.7 mol / L) was added last, thereby initiating the reaction. After reacting for 30 minutes at ambient temperature, the PE sample was taken out. Then, rinsing was successively performed in the order of water, ethanol, and finally isopropanol. The rinse was performed in a Soxhlet extractor for 16 hours.
Soxhlet consists of a glass body, a siphon tube, and a distillation tube in which a sample is placed. A soxhlet was placed on the flask and a condenser was placed on the soxhlet. The said flask is a 500 mL flask specifically heated and stirred with a flask heater, and the solvent (specifically 300 mL isopropanol) is stored.

  When the flask was heated, the solvent became vapor and passed through the distillation tube, condensed in the condenser, returned to the droplets and dropped into the glass body. Thereby, the sample was immersed in pure solvent (heated by the vapor passing under). Condensed solvent accumulates in the extractor, but eventually reaches the top of the siphon tube and the liquid returns to the container with the extractant. Thus, the solvent in the container was gradually enriched with soluble compounds.

That is, while the extractant remained in the container (the boiling point of the extractant must be significantly higher than the boiling point of the extractor solvent), the solvent was continuously vaporized.
By using a Soxhlet extractor, it became possible to confirm the state of chemical grafting of acrylic PDMS on the PE substrate surface.
Analysis by IR spectroscopy was performed. In the infrared spectrum, acrylic PDMS grafting could be confirmed by the presence of a unique band of 1260 cm ^-1 that corresponds to the vibration of the Si-CH ₃ bond.

Example 4 Electrocatalytic Chemical Grafting of Acrylic PDMS Polymer Film on Polyethylene Substrate in an Environment with Potentiostat This example shows a lubricious coating (acrylic PDMS) such as PE in an environment with a potentiostat. A method for grafting onto a thermoplastic material will be described.
First, a PE sample was placed in ethanol and washed for 5 minutes under ultrasound (power: 100 W, temperature: 40 ° C.).

  A biphasic solution was prepared in two steps. Then, with magnetic stirring at 300 rpm (rpm), the following was added in order to the beaker (1): PDMS-acrylate (1 g / L); put into water at a rate of 8.5% wt. Brij 35® solution (4.37 g / L); and 33 mL of DI water. The emulsion was then emulsified for 15 minutes under ultrasound at a temperature of 40 ° C. and a power of 200 watts (W) (100%).

The following was then added to the beaker (2) with magnetic stirring (300 rpm): nitrobenzenediazonium tetrafluoroborate (0.05 mol / L); 130 mL DI water; hydrochloric acid (0.23 mol / L).
The contents of beaker (2) were poured into the emulsion of beaker (1). And PE samples (2 pieces) (ie, galvanized wound metal wire (10 turns, ie about 25-30 centimeters (cm)); wound Ni wire (10 turns, ie about 25-30 centimeters ( cm))) was placed in the beaker (1). A metal wire and a nickel wire were connected with a potentiostat, and an ammeter was connected in series. A constant potential difference of 0.5 V was applied to the potentiostat, and the current was measured with an ammeter over time.

  As a final step, after the assembly was prepared, hypophosphorous acid (0.7 mol / L) was added last, thereby initiating the reaction. After reacting for 30 minutes at ambient temperature, the PE sample was taken out. The rinse was then carried out sequentially in the order of water (a cascade), ethanol (one stage) and finally isopropanol. Rinsing was performed in a soxhlet for 16 hours.

By using a Soxhlet extractor, it became possible to confirm the state of chemical grafting of acrylic PDMS on the PE substrate surface.
Analysis by IR spectroscopy was performed. In the infrared spectrum, acrylic PDMS grafting could be confirmed by the presence of a characteristic band of 1260 cm ⁻¹ that corresponds to the vibration of the Si—CH ₃ bond.

  It will be apparent to those skilled in the art that various modifications can be devised without departing from the scope of the invention as defined by the appended claims.

Claims (23)

A treatment method for treating a surface of a fluid administration device, comprising:
Forming a thin film having anti-friction properties on one or more support surfaces of one or more movable parts of the fluid delivery device that moves during operation of the fluid delivery device using a chemical graft;
A processing method characterized by the above. The chemical grafting process includes a process of bringing the support surface in contact with a fluid into contact with a solution containing one or more fixing agents;
The fixer is a cleable aryl salt and is one or more monomers or polymers selected from the group consisting of vinyl-terminated or acrylic-terminated siloxanes;
The processing method according to claim 1. Vinyl-terminated or acrylic-terminated siloxanes
A vinyl terminated or acrylic terminated polyalkylsiloxane which is a vinyl terminated or acrylic terminated polymethylsiloxane;
A vinyl-terminated or acrylic-terminated polydimethylsiloxane that is polydimethylsiloxane-acrylate (PDMS-acrylate);
A vinyl-terminated or acrylic-terminated polyarylsiloxane that is a vinyl-terminated or acrylic-terminated polyphenylsiloxane that is polyvinylphenylsiloxane;
A vinyl-terminated or acrylic-terminated polyarylalkylsiloxane which is a vinyl-terminated or acrylic-terminated polymethylphenylsiloxane;
Being selected from the group consisting of
The processing method according to claim 1. The cleaveable aryl salt is selected from the group consisting of aryldiazonium salts, arylammonium salts, arylphosphonium salts, arylsulfonium salts, and aryliodonium salts;
The processing method according to any one of claims 1 to 3. The chemical grafting process is initiated by chemical activation;
The processing method according to any one of claims 1 to 4, wherein: The chemical activation is initiated by the presence of a reducing agent in solution;
The processing method according to claim 5. The reducing agent is
A reduced metal that can be finely divided, which is iron, zinc or nickel;
A metal salt capable of taking the form of a metallocene,
An organic reducing agent that is hypophosphorous acid or ascorbic acid;
Being selected from the group consisting of
The processing method according to claim 6. A potential difference is applied to the solution;
The processing method according to claim 1, wherein: The potential difference is applied from a power source connected to the two electrodes, and the two electrodes may be the same or different and are immersed in the solution,
The processing method according to claim 8. The potential difference is generated by a chemical battery,
The processing method according to claim 8. The support surface is made of a synthetic material, elastomer, glass, or metal, particularly composed of polyethylene and / or polypropylene,
The processing method according to any one of claims 1 to 10, wherein: The thickness of the thin film is less than 1 μm, preferably in the range of 10 to 2000 mm,
The processing method according to any one of claims 1 to 11, wherein: Further comprising the step of forming one or more additional thin films on the surface of the support using chemical grafting;
The processing method according to any one of claims 1 to 12. The method further includes forming a first additional thin film on the surface of the support using chemical grafting, and the first additional thin film suppresses the degree of adhesion of the fluid to be administered to the surface of the support. Being
The processing method according to claim 13. The method further includes forming a second additional thin film on the surface of the support using chemical grafting, and the second additional thin film prevents an interaction between the surface of the support and the fluid. There is,
The processing method according to claim 13 or 14. The one or more additional thin films are laminated to the surface of the support while one or more successive chemical grafting processes are each performed in a single component bath;
The processing method according to any one of claims 13 to 15. The one or more additional thin films are simultaneously laminated to the support surface during one chemical grafting process in one multi-component bath;
The processing method according to any one of claims 13 to 15. The dosing device includes a reservoir in which a fluid is stored, a dosing member that is a pump or a valve fixed to the reservoir, and a dosing head with a dosing opening, the dosing head including the dosing member. To drive,
The processing method according to any one of claims 1 to 17, wherein: The dosing device comprises a plurality of individual reservoirs each storing a volume of fluid, a reservoir opening means being a piercing needle, and a volume of a single reservoir opened. Having a single dose means for dispensing fluid from a dose opening;
The processing method according to any one of claims 1 to 17, wherein: The dosing device has a reservoir storing a volume of fluid for one or two doses, and a piston that moves inside the reservoir each time it is driven;
The processing method according to any one of claims 1 to 17, wherein: The administration device has a number counter that counts how many doses have been administered from the administration device or how many doses remain in the administration device;
The processing method according to any one of claims 1 to 20, wherein: The fluid is in particular a liquid or powder medicament sprayed on the nose or mouth,
The processing method according to any one of claims 1 to 21, wherein:   23. Use of the grafting method according to any one of claims 1 to 22 on one or more support surfaces of one or more movable parts of the fluid administration device that move during operation of the fluid administration device. Use for the purpose of forming a thin film having anti-friction properties.