U.S. patent application number 13/514152 was filed with the patent office on 2013-04-04 for method for treating the surface of a device for dispensing a fluid product.
This patent application is currently assigned to VALOIS SAS. The applicant listed for this patent is Pascal Bruna, Matthieu Laurent, Fabien Nekelson, Sebastien Roussel, Lorraine Tessier. Invention is credited to Pascal Bruna, Matthieu Laurent, Fabien Nekelson, Sebastien Roussel, Lorraine Tessier.
Application Number | 20130081953 13/514152 |
Document ID | / |
Family ID | 42312784 |
Filed Date | 2013-04-04 |
United States Patent
Application |
20130081953 |
Kind Code |
A1 |
Bruna; Pascal ; et
al. |
April 4, 2013 |
METHOD FOR TREATING THE SURFACE OF A DEVICE FOR DISPENSING A FLUID
PRODUCT
Abstract
A treatment method for treating the surface of a fluid dispenser
device, said method comprising the step of using chemical grafting
to form a thin film on at least one support surface of at least one
movable portion of said device that is movable while said device is
being actuated, said thin film having anti-friction properties.
Inventors: |
Bruna; Pascal; (Sotteville
Les Rouen, FR) ; Laurent; Matthieu; (Vaucresson,
FR) ; Nekelson; Fabien; (Montigny Le Bretonneux,
FR) ; Roussel; Sebastien; (Soisy Sur Seine, FR)
; Tessier; Lorraine; (Montrouge, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Bruna; Pascal
Laurent; Matthieu
Nekelson; Fabien
Roussel; Sebastien
Tessier; Lorraine |
Sotteville Les Rouen
Vaucresson
Montigny Le Bretonneux
Soisy Sur Seine
Montrouge |
|
FR
FR
FR
FR
FR |
|
|
Assignee: |
VALOIS SAS
Le Neubourg
FR
|
Family ID: |
42312784 |
Appl. No.: |
13/514152 |
Filed: |
December 22, 2010 |
PCT Filed: |
December 22, 2010 |
PCT NO: |
PCT/FR10/52888 |
371 Date: |
December 17, 2012 |
Current U.S.
Class: |
205/122 |
Current CPC
Class: |
C25D 5/54 20130101; A61M
11/00 20130101; C25D 7/04 20130101; C25D 3/02 20130101; A61M
2205/0222 20130101; B05D 5/08 20130101; B65D 83/64 20130101; B05B
11/00416 20180801; A61M 15/0071 20140204; C25D 9/02 20130101; C08J
7/16 20130101; B05D 1/18 20130101; A61M 15/00 20130101; B05D
2201/00 20130101; C25D 5/02 20130101 |
Class at
Publication: |
205/122 |
International
Class: |
C25D 7/04 20060101
C25D007/04; C25D 9/02 20060101 C25D009/02; C25D 3/02 20060101
C25D003/02; C25D 5/02 20060101 C25D005/02; C25D 5/54 20060101
C25D005/54 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 23, 2009 |
FR |
0959479 |
Claims
1. A treatment method for treating the surface of a fluid dispenser
device, said method being characterized in that it comprises a step
of using chemical grafting to form a thin film on at least one
support surface of at least one movable portion of said device that
is movable while said device is being actuated, said thin film
having anti-friction properties.
2. A method according to claim 1, wherein said grafting step
comprises putting said surface that is in contact with the fluid
into contact with a solution that includes at least one adhesive
primer, said adhesive primer being a cleavable aryl salt, and at
least one monomer or polymer selected from the group constituted by
vinyl- or acrylic-terminated siloxanes.
3. A method according to claim 1, wherein vinyl- or
acrylic-terminated siloxanes are selected from the group
constituted by: vinyl- or acrylic-terminated polyalkylsiloxanes
such as vinyl- or acrylic-terminated polymethylsiloxane; vinyl- or
acrylic-terminated polydimethylsiloxane such as
polydimethylsiloxane-acrylate (PDMS-acrylate); vinyl- or
acrylic-terminated polyarylsiloxanes such as vinyl- or
acrylic-terminated polyphenylsiloxane such as
polyvinylphenylsiloxane; and vinyl- or acrylic-terminated
polyarylalkylsiloxanes such as vinyl- or acrylic-terminated
polymethylphenylsiloxane.
4. A method according to claim 1, wherein the cleavable aryl salt
is selected from the group constituted by: aryl diazonium salts;
aryl ammonium salts; aryl phosphonium salts; aryl sulfonium salts;
and aryl iodonium salts.
5. A method according to claim 1, wherein said chemical-grafting
step is initiated by chemical activation.
6. A method according to claim 5, wherein said chemical activation
is initiated by the presence of a reducing agent in the
solution.
7. A method according to claim 6, wherein the reducing agent is
selected from the group constituted by: reducing metals that are
possibly finely divided, such as iron, zinc, or nickel; a metal
salt that is possibly in the form of a metallocene; and an organic
reducing agent such as hypophosphorus acid, or ascorbic acid.
8. A method according to claim 1, wherein a potential difference is
applied in said solution.
9. A method according to claim 8, wherein the potential difference
is applied by a generator that is connected to two electrodes that
are identical or different and that are dipped in the solution.
10. A method according to claim 8, wherein the potential difference
is generated by a chemical cell.
11. A method according to claim 1, wherein said support surface is
made of: synthetic material, in particular comprising polyethylene
and/or polypropylene; elastomer; glass; or metal.
12. A method according to claim 1, wherein said thin film has a
thickness that is less than 1 .mu.m, preferably lying in the range
10 .ANG. to 2000 .ANG..
13. A method according to claim 1, wherein the method further
comprises the step of using chemical grafting to form at least one
additional thin film on said support surface.
14. A method according to claim 13, wherein the method further
comprises the step of using chemical grafting to form a first
additional thin film on said support surface, said first additional
thin film limiting the degree to which the fluid for dispensing
sticks to said support surface.
15. A method according to claim 13, wherein the method further
comprises the step of using chemical grafting to form a second
additional thin film on said support surface, said second
additional thin film preventing interactions between said support
surface and said fluid.
16. A method according to claim 13, wherein said at least one
additional thin film is deposited on said support surface during at
least one successive chemical-grafting step, each step being
performed in a single-component bath.
17. A method according to claim 13, wherein said at least one
additional thin film is deposited on said support surface
simultaneously during a single chemical-grafting step in a
multi-component bath.
18. A method according to claim 1, wherein said dispenser device
comprises: a reservoir containing the fluid; a dispenser member,
such as a pump or a valve, that is fastened on said reservoir; and
a dispenser head that is provided with a dispenser orifice, and
this is for actuating said dispenser member.
19. A method according to claim 1, wherein said dispenser device
comprises: a plurality of individual reservoirs each containing a
dose of fluid; reservoir opening means, such as a perforator
needle; and dose dispenser means for dispensing a dose of fluid
from an individual opened reservoir through a dispenser
orifice.
20. A method according to claim 1, wherein said dispenser device
includes a reservoir containing one or two doses of fluid, and a
piston that moves in said reservoir on each actuation.
21. A method according to claim 1, wherein said dispenser device
includes a dose counter for counting the number of doses that have
been dispensed or that remain to be dispensed from said dispenser
device.
22. A method according to claim 1, wherein said fluid is a liquid
or powder pharmaceutical, in particular for spraying in nasal or
oral manner.
23. The use of a grafting method according to claim 1, in order to
form a thin film on at least one support surface of at least one
movable portion of a fluid dispenser device that is movable while
said device is being actuated, said thin film having anti-friction
properties.
Description
[0001] The present invention relates to a surface treatment method
for fluid dispenser devices.
[0002] Fluid dispenser devices are well known. They generally
comprise: one or more reservoirs; a dispenser member, such as a
pump, a valve, or a piston that moves in the reservoir; and a
dispenser head that is provided with a dispenser orifice. In some
configurations, laterally-actuated systems are provided for
actuating the dispenser member. Alternatively, in a variant, the
fluid dispenser devices may be inhalers including a plurality of
reservoirs each containing an individual dose of powder or liquid,
and means for opening and expelling said doses during successive
actuations. The various devices may also include a dose counter or
indicator for counting or indicating the number of doses that have
been dispensed or that remain to be dispensed from the dispenser
device. Thus, the devices include numerous movable parts or
portions that move relative to one another during actuation.
Controlling friction, which may cause unwanted noise and/or
malfunctions, is a major challenge. In particular in the
pharmaceutical field, any risk of the dispenser device
malfunctioning may be critical, e.g. for treating attacks such as
asthma attacks. In particular, the problem of friction may occur at
the pump piston or at the valve member, where it is essential to
avoid the pump piston or valve member jamming. The same applies for
inhalers, in which the means for moving or opening a reservoir, and
the means for dispensing a dose are sensitive to friction, or even
for dose counters that must give the user an accurate indication,
so that the user is not mistaken about the number of doses
remaining to be dispensed. Thus, any blockage as a result of
friction is potentially prejudicial.
[0003] All existing surface treatment methods present drawbacks.
Thus, certain methods are suitable for use only on plane surfaces.
Other methods impose a limited choice of substrate, e.g. gold.
Polymerizing molecules by plasma is complex and costly, and the
coating layer obtained is difficult to control and presents
problems of aging. Likewise, polymerizing molecules by ultraviolet
radiation is also complex and costly, and functions only with
photosensitive molecules. The same applies for atom transfer
radical polymerization (ATRP) that is also complex and costly.
Finally, electrografting methods are complex and require support
surfaces that are conductive.
[0004] An object of the present invention is to propose a surface
treatment method that does not have the above-mentioned
drawbacks.
[0005] In particular, an object of the present invention is to
provide a surface treatment method that is effective, long-lasting,
non-polluting, and simple to perform.
[0006] The present invention thus provides a treatment method for
treating the surface of a fluid dispenser device, said method
comprising the step of using chemical grafting to form a thin film
on at least one support surface of at least one movable portion of
said device that is movable while said device is being actuated,
said thin film having anti-friction properties.
[0007] In an advantageous implementation, said grafting step
comprises putting said surface that is in contact with the fluid
into contact with a solution that includes at least one adhesive
primer, said adhesive primer being a cleavable aryl salt, and at
least one monomer or polymer selected from the group constituted by
vinyl- or acrylic-terminated siloxanes.
[0008] Advantageously, said thin film is a polymeric film that
includes silicone.
[0009] Advantageously, said silicone is a DM300 or DM1000
silicone.
[0010] Advantageously, said chemical grafting creates covalent
bonds between the molecules of said thin film and said support
surface. This creates a strong and long-lasting connection.
[0011] Advantageously, said chemical grafting is performed in an
aqueous medium. This makes it possible to use chemistry that is
non-polluting or green and that does not present any risk to the
environment.
[0012] In an implementation, the cleavable aryl salt is selected
from the group constituted by: aryl diazonium salts; aryl ammonium
salts; aryl phosphonium salts; aryl sulfonium salts; and aryl
iodonium salts.
[0013] The cleavable aryl salts are selected from compounds of
general formula ArN.sub.2.sup.+, X.sup.- in which Ar represents the
aryl group and X.sup.- represents an anion. The aryl group in an
organic compound is a functional group derived from an aromatic
ring.
[0014] In an implementation, X.sup.- anions are selected from:
inorganic anions such as halides, such as I--, Cl--, and Br--;
halogenoborates such as tetrafluoroborate; and organic anions such
as alcoholates, carboxylates, perchlorates, and sulfonates.
[0015] In an implementation, the aryl groups Ar are selected from
possibly mono- or poly-substituted aromatic or heteroaromatic
groups constituted by one or more aromatic rings of 3 to 8 carbons.
The heteroatoms of the heteroaromatic compounds are selected 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.
[0016] In an implementation, the aryl groups are selected from:
aryl groups substituted by attractor groups such as NO.sub.2; COH;
CN; CO.sub.2H; ketones; esters; amines; and halogens.
[0017] In an implementation, the aryl groups are selected from the
group constituted by: phenyl and nitrophenyl groups.
[0018] In an implementation, the cleavable aryl salt is selected
from the group constituted by: phenyldiazonium tetrafluoroborate;
4-nitrophenyldiazonium tetrafluoroborate; 4-bromophenyldiazonium
tetrafluoroborate; 4-aminophenyldiazonium chloride;
4-aminomethylphenyldiazonium chloride;
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 sulfate;
9,10-dioxo-9,10-dihydro-1-anthracenediazonium chloride;
4-nitronaphtalenediazonium tetrafluoroborate; and
naphtalenediazonium tetrafluoroborate.
[0019] In an implementation, the cleavable aryl salt is selected
from the group constituted by: 4-nitrophenyldiazonium
tetrafluoroborate; 4-aminophenyldiazonium chloride;
2-methyl-4-chlorophenyldiazonium chloride; and
4-carboxyphenyldiazonium tetrafluoroborate.
[0020] In an implementation, the cleavable aryl salt concentration
lies in the range 5.times.10.sup.-3 molar (M) to 10.sup.-1 M.
[0021] In an implementation, the cleavable aryl salt concentration
is about 5.times.10.sup.-2 M.
[0022] In an implementation, the cleavable aryl salt is prepared in
situ.
[0023] Advantageously, said chemical-grafting step is initiated by
chemically activating a diazonium salt so as to form an anchor
layer for said thin film.
[0024] Advantageously, said chemical-grafting step is initiated by
chemical activation.
[0025] In an implementation, said chemical activation is initiated
by the presence of a reducing agent in the solution.
[0026] In an implementation, the solution comprises a reducing
agent.
[0027] The term "reducing agent" means a compound that donates
electrons during a redox reaction. In an aspect of the present
invention, the reducing agent presents a redox potential difference
relative to the redox potential of the cleavable aryl salt, that
lies in the range 0.3 volts (V) to 3 V.
[0028] In an aspect of the invention, the reducing agent is
selected from the group constituted by: reducing metals that are
possibly finely divided, such as iron, zinc, or nickel; a metal
salt that is possibly in the form of a metallocene; and an organic
reducing agent such as hypophosphorus acid, or ascorbic acid.
[0029] In an implementation, the reducing agent concentration lies
in the range 0.005 M to 2 M.
[0030] In an implementation, the reducing agent concentration is
about 0.6 M.
[0031] In an implementation, said thin film has a thickness that is
less than 1 micrometer (.mu.m), and that lies in the range 10
angstroms (.ANG.) to 2000 .ANG., advantageously lies in the range
10 .ANG. to 800 .ANG., preferably lies in the range 400 .ANG. to
1000 .ANG.. No conventional coating technique makes it possible to
obtain chemically-grafted layers that are as thin.
[0032] The term "vinyl- or acrylic-terminated siloxane" means a
saturated silicon and oxygen hydride that is formed with straight
or branched chains of alternating silicon and oxygen atoms and
including terminating vinyl or acrylic motifs.
[0033] In an implementation, vinyl- or acrylic-terminated siloxanes
are selected from the group constituted by: vinyl- or
acrylic-terminated polyalkylsiloxanes such as vinyl- or
acrylic-terminated polymethylsiloxane; vinyl- or acrylic-terminated
polydimethylsiloxane such as polydimethylsiloxane-acrylate
(PDMS-acrylate); vinyl- or acrylic-terminated polyarylsiloxanes
such as vinyl- or acrylic-terminated polyphenylsiloxane such as
polyvinylphenylsiloxane; and vinyl- or acrylic-terminated
polyarylalkylsiloxanes such as vinyl- or acrylic-terminated
polymethylphenylsiloxane.
[0034] In an implementation, a potential difference is applied in
said solution.
[0035] The term "potential difference" means the redox potential
difference measured between two electrodes.
[0036] In an implementation, the potential difference is applied by
a generator that is connected to two electrodes that are identical
or different and that are dipped in the solution during the dipping
step.
[0037] In an implementation, the electrodes are selected from:
stainless steel; steel; nickel; platinum; gold; silver; zinc; iron;
and copper; in pure form or in alloy form.
[0038] In an implementation, the electrodes are made of stainless
steel.
[0039] In an implementation, the potential difference applied by a
generator lies in the range 0.1 V to 2 V.
[0040] In an implementation, it is about 0.7 V.
[0041] In an implementation, the potential difference is generated
by a chemical cell.
[0042] The term "chemical cell" means a cell that is made up of two
electrodes that are interconnected via an ionic bridge. In the
present invention, the two electrodes are selected appropriately
for the potential difference to lie in the range 0.1 V to 2.5
V.
[0043] In an implementation, the chemical cell is created between
two different electrodes that are dipped in the solution.
[0044] In an implementation, the electrodes are selected from:
nickel; zinc; iron; copper; and silver; in pure form or in alloy
form.
[0045] In an implementation, the potential difference generated by
the chemical cell lies in the range 0.1 V to 1.5 V.
[0046] In an implementation, the potential difference is about 0.7
V.
[0047] In an implementation, the electrodes are chemically isolated
so as to avoid any contact between the substrate that is immersed
in the solution and the electrodes that are also dipped in the
solution.
[0048] Advantageously, said support surface is made of: synthetic
material, in particular comprising polyethylene (PE) and/or
polypropylene (PP); elastomer; glass; or metal.
[0049] Advantageously, the method further comprises the step of
using chemical grafting to form at least one additional thin film
on said support surface.
[0050] Advantageously, the method further comprises the step of
using chemical grafting to form a first additional thin film on
said support surface, said first additional thin film limiting the
degree to which the fluid for dispensing sticks to said support
surface.
[0051] Advantageously, the method further comprises the step of
using chemical grafting to form a second additional thin film on
said support surface, said second additional thin film preventing
interactions between said support surface and said fluid.
[0052] In a variant, said at least one additional thin film is
deposited on said support surface during at least one successive
chemical-grafting step, each step being performed in a
single-component bath.
[0053] In another variant, said at least one additional thin film
is deposited on said support surface simultaneously during a single
chemical-grafting step in a multi-component bath.
[0054] Advantageously, said dispenser device comprises: a reservoir
containing the fluid; a dispenser member, such as a pump or a
valve, that is fastened on said reservoir; and a dispenser head
that is provided with a dispenser orifice, and this is for
actuating said dispenser member.
[0055] In a variant, said dispenser device comprises: a plurality
of individual reservoirs each containing a dose of fluid; reservoir
opening means, such as a perforator needle; and dose dispenser
means for dispensing a dose of fluid from an individual opened
reservoir through a dispenser orifice.
[0056] In a variant, said dispenser device includes a reservoir
containing one or two doses of fluid, and a piston that moves in
said reservoir on each actuation.
[0057] Advantageously, said dispenser device includes a dose
counter for counting the number of doses that have been dispensed
or that remain to be dispensed from said dispenser device.
[0058] Advantageously, said fluid is a pharmaceutical, in
particular for spraying in nasal or oral manner.
[0059] In an implementation, it is possible to use a method similar
to the method described in document WO 2008/078052, which describes
a method of preparing an organic film on the surface of a solid
support under non-electrochemical conditions. Surprisingly, that
type of method turns out to be suitable for forming a thin
anti-friction film on surfaces that are movable during the
actuation of the above-mentioned dispenser devices. Such an
application of that grafting method has not previously been
envisaged.
[0060] To summarize, the method seeks to prepare a thin film, in
particular a film made of polyethylene and/or polypropylene, on the
surface of a solid support. The method mainly comprises putting
said support surface into contact with a liquid solution. The
liquid solution includes at least one solvent and at least one
adhesive primer, enabling radical entities to be formed from the
adhesive primer.
[0061] The "thin film" may be any polymeric film, in particular of
organic nature, e.g. resulting from a plurality of units of organic
chemical species, and bonded in covalent manner to the surface of
the support on which the method is performed. In particular, it is
a film that is bonded in covalent manner to the surface of the
support, and that includes at least one layer of structural units
of similar nature. Depending on the thickness of the film, its
cohesion is provided by covalent bonds that develop between the
various units. Preferably, the thin film contains silicone.
[0062] The solvent used in the context of the method may be of
protic or aprotic nature. It is preferable for the primer to be
soluble in said solvent.
[0063] The term "protic solvent" means a solvent that includes at
least one hydrogen atom that is capable of being released in the
form of a proton. The protic solvent may be selected from the group
constituted by: water; deionized water; optionally-acidified
distilled water; acetic acid; hydroxylated solvents such as
methanol and ethanol; liquid glycols of small molecular weight such
as ethyleneglycol; and mixtures thereof. In a first variant, the
protic solvent is constituted solely by a protic solvent or by a
mixture of different protic solvents. In another variant, the
protic solvent or the mixture of protic solvents may be mixed with
at least one aprotic solvent, it being understood that the
resulting mixture should present the characteristics of a protic
solvent. Acidified water is the preferred protic solvent, and more
particularly, acidified distilled water or acidified deionized
water.
[0064] The term "aprotic solvent" means a solvent that is
considered as not being protic. Under non-extreme conditions, such
solvents are not suitable for releasing a proton or for accepting
one. The aprotic solvent is advantageously selected from:
dimethylformamide (DMF); acetone; and dimethyl sulfoxide
(DMSO).
[0065] The term "adhesive primer" corresponds to any organic
molecule that is suitable, under certain conditions, for
chemisorbing onto the support surface by a radical reaction, such
as radical chemical grafting. Such molecules include at least a
functional group that is suitable for reacting with a radical, and
also a reactive function that reacts with another radical after
chemiabsorption. Thus, after grafting a first molecule to the
surface of the support, the molecules are capable of forming a
polymeric film, and then of reacting with other molecules that are
present in its environment.
[0066] The term "radical chemical grafting" refers, in particular,
to the use of molecular entities that possess an unpaired electron
in order to form bonds with the support surface of the
covalent-bond type, said molecular entities being generated
independently of the support surface onto which they are to be
grafted. Thus, the radical reaction leads to covalent bonds being
formed between the support surface under consideration and the
derivative of the grafted adhesive primer, and then between a
grafted derivative and molecules that are present in its
environment.
[0067] The term "derivative of the adhesive primer" means a
chemical unit resulting from the adhesive primer, after said
adhesive primer has reacted by radical chemical grafting, in
particular with the support surface, or with another radical. To
the person skilled in the art, it is clear that the function that
is reactive with another radical after chemiabsorption of the
derivative of the adhesive primer is different from the function
involved in the covalent bonding, in particular with the support
surface. Advantageously, the adhesive primer is a cleavable aryl
salt selected from the group constituted by: aryl diazonium salts;
aryl ammonium salts; aryl phosphonium salts; aryl sulfonium salts;
and aryl iodonium salts.
[0068] Preferably, the thin film includes silicone that may be of
various medical grades, e.g. DM300 or DM1000. As a variant to the
direct covalent bonds of the silicone on the support surface, as
obtained in an aqueous medium, it is also possible to use a method
of impregnating a porous layer that has previously been grafted
with silicone.
[0069] In an advantageous implementation of the invention, chemical
grafting is used to form at least one additional thin film on a
single support surface, so as to give at least one other property
to the support surface. Thus, the fluid for dispensing may tend to
stick to a surface with which it is in contact, and this may, in
particular, have a harmful effect on the reproducibility of the
dispensed dose. The invention advantageously makes provision for
using chemical grafting to form a first additional thin film that
prevents the fluid from sticking to the support surface.
Advantageously, it is also possible to envisage using chemical
grafting to apply a second additional thin film, so as to give a
third property to the support surface. For example, in fluid
dispenser devices, certain materials interact with the fluid for
dispensing in the event of coming into contact therewith, and this
may be harmful to the fluid. The invention advantageously makes
provision for using chemical grafting to form a second additional
thin film that prevents interaction between the fluid and the
support surface. The additional thin films may be applied during
successive chemical-grafting steps. Each chemical-grafting step may
then be performed in a single-component bath. It should be observed
that the successive chemical-grafting steps may be performed in any
order. In a variant, the additional thin films may alternatively be
applied during a single chemical-grafting step that is thus
performed in a multi-component bath. A combination of the two
variants may also be envisaged.
[0070] The present invention applies to multidose devices, such as
devices having a pump or a valve mounted on a reservoir, and that
are actuated so as to dispense successive doses. It also applies to
multidose devices that include a plurality of individual
reservoirs, each containing a dose of fluid, such as pre-dosed
powder inhalers. It also applies to uni-dose or bi-dose devices in
which a piston moves directly in a reservoir on each actuation. In
particular, the invention applies to nasal or oral spray devices,
to opthalmic dispenser devices, and to needle devices of the
syringe type.
[0071] The invention also relates to the use of a grafting method
of the invention in order to form a thin film on at least one
support surface of at least one movable portion of a fluid
dispenser device that is movable while said device is being
actuated, said thin film having anti-friction properties.
[0072] The following examples were performed in a glass vessel.
Unless indicated to the contrary, they were performed under normal
temperature and pressure conditions (about 22.degree. C. under
about 1 atmosphere (atm)) in ambient air. Unless mentioned to the
contrary, the reagents used were obtained directly on the market
without additional purification. The samples were subjected
beforehand to washing under ultrasound in soapy water at 40.degree.
C.
EXAMPLE 1
Grafting a Poly(Dimethylsiloxane) Film onto Parts of a Pump so as
to Lubricate it
[0073] The term "pump" means a fluid dispenser device that is
actuated manually, and that includes a pump body in which one or
more pistons slide.
[0074] Vinyl-terminated poly(dimethylsiloxane) (1.0 gram (g), 5
grams per liter (g/L)) was poured into a solution of Brij.RTM. 35
(0.874 g at 4.37 g/L) in 70 milliliters (mL) of milliQ (mQ) water,
then the suspension was stirred magnetically so as to form an
emulsion.
[0075] 4-aminobenzoic acid (1.370 g, 10.sup.-2 moles (mol)) was
dissolved in a solution of hydrochloric acid (4.0 mL in 120 mL of
mQ water) and of hypophosphorus acid (6.3 mL, 6.0.times.10.sup.-2
mol). That solution was added to the PDMS emulsion.
[0076] To that emulsion there were added 8 mL of an aqueous
solution of NaNO.sub.2 (0.667 g, 9.7.times.10.sup.-3 mol), and then
the pump-part samples.
[0077] After 30 minutes of reaction, the samples, namely: a body
made of PP; an upper piston; a lower piston; and a tube made of
polyethylene PE; were removed, then rinsed in successive baths of
soapy water (Renoclean) at 1% under ultrasound at 40.degree. C.,
and baths of water.
[0078] After drying the parts with compressed air, the presence of
PDMS on the samples was confirmed by infrared (IR) analysis by
means of PDMS-specific bands at 1260 per centimeter (cm.sup.-1),
1110 cm.sup.-1, and 1045 cm.sup.-1.
EXAMPLE 2
Grafting a Poly(Dimethylsiloxane) Film onto Parts of a Valve so as
to Lubricate it
[0079] The term "valve" means a fluid dispenser device that
contains propellant gases, and that includes a valve body in which
a valve member slides.
[0080] Sodium dodecyl benzene sulfonate (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 added, then the mixture
was stirred magnetically so as to form an emulsion.
[0081] 4-aminobenzoic acid (3.462 g, 2.5.times.10.sup.-2 mol) was
dissolved in a solution of hydrochloric acid (9.6 mL in 20 mL of mQ
water) and of hypophosphorus acid (33 mL, 3.1.times.10.sup.-1 mol).
That solution was added to the PDMS emulsion.
[0082] To that emulsion there were added 10 mL of a solution of
NaNO.sub.2 (1.664 g, 2.37.times.10.sup.-2 mol) in mQ water, and
then the samples, namely: ethylene propylene diene monomer (EPDM)
or nitrile rubber gaskets; a valve member top made of
polyoxymethylene (POM); and a gold indicator strip.
[0083] After 15 minutes of reaction, the samples were removed, then
rinsed successively in mQ water, in ethanol, and in hexane.
[0084] The presence of PDMS on the gold strip and on the other
samples was confirmed by IR analysis with PDMS-specific bands at
1260 cm.sup.-1, 1110 cm.sup.-1, and 1045 cm.sup.-1.
EXAMPLE 3
Electrocatalyzed Chemical Grafting of a Polymer Film Made of
Acrylic-PDMS onto a Polyethylene Substrate
[0085] This example explains how to graft a lubricating coating
(acrylic-PDMS) onto a thermoplastic such as PE.
[0086] The PE samples were washed in ethanol, under ultrasound (at
50% power, temperature at 40.degree. C.) for 5 minutes.
[0087] The biphasic solution was prepared in two stages. The
following were added to a beaker (1), in order and under magnetic
stirring (at 300 revolutions per minute (rpm)): PDMS-acrylate (1
g/L); Brij.RTM. 35 in solution in water at 8.5% by weight (% wt)
(4.37 g/L); and 33 mL of deionized (DI) water. Emulsification then
took place under ultrasound at 40.degree. C. and at a power of 200
watts (W) (100%) for 15 minutes.
[0088] The following were added to a beaker (2), under magnetic
stirring (at 300 rpm): nitrobenzene diazonium tetrafluoroborate
(0.05 mol/L); 130 mL of DI water; and hydrochloric acid (0.23
mol/L).
[0089] The content of beaker (2) was poured into the emulsion of
beaker (1). The PE samples (.times.2); a winding of galvanized
steel wire (ten turns, i.e. a length of about 25 centimeters (cm)
to 30 cm); and a winding of nickel (Ni) wire (ten turns, i.e. a
length of about 25 cm to 30 cm); were placed in beaker (1). The two
wires were connected together and an ammeter was connected in
series.
[0090] Finally, once the assembly was ready, hypophosphorus acid
(0.7 mol/L) was added last, thereby marking the start of the
reaction. After 30 minutes of reaction at ambient temperature, the
PE samples were removed, then rinsed successively in water, in
ethanol, and finally in isopropanol, in a soxhlet extractor for 16
hours.
[0091] The soxhlet was composed of: a glass body in which the
sample was placed; a siphon-tube; and a distillation tube. The
soxhlet was placed on a flask (specifically a 500 mL flask heated
and stirred via a flask heater) containing the solvent
(specifically 300 mL of isopropanol) and surmounted by a
condenser.
[0092] When the flask was heated, the solvent vapor passed via the
distillation tube, condensed in the condenser, and dropped back
into the glass body, thereby soaking the sample in pure solvent
(heated by the underlying vapor). The condensed solvent accumulated
in the extractor until it reached the top of the siphon-tube which
then caused the liquid to return to the vessel, accompanied by
extracted substances, and the solvent contained in the vessel was
thus enriched progressively with soluble compounds.
[0093] The solvent thus continued to evaporate, while the extracted
substances remained in the vessel (their boiling temperature needs
to be significantly higher than the boiling temperature of the
extractor solvent).
[0094] The use of a soxhlet extractor made it possible to confirm
the chemical grafting of acrylic-PDMS on the surface of the PE
substrate.
[0095] An analysis by IR spectroscopy was performed. The infrared
spectrum made it possible to confirm the grafting of acrylic-PDMS
by the presence of the characteristic band at 1260 cm.sup.-1
corresponding to the vibration of the Si--CH.sub.3 bond.
EXAMPLE 4
Electrocatalyzed Chemical Grafting of a Polymer Film Made of
Acrylic-PDMS onto a Polyethylene Substrate in the Presence of a
Potentiostat
[0096] This example explains how to graft a lubricating coating
(acrylic-PDMS) onto a thermoplastic such as PE in the presence of a
potentiostat.
[0097] The PE samples were washed in ethanol, under ultrasound
(power at 100 W, temperature at 40.degree. C.) for 5 minutes.
[0098] The biphasic solution was prepared in two stages. The
following were added to a beaker (1), in order and under magnetic
stirring (at 300 rpm): PDMS-acrylate (1 g/L); Brij.RTM. 35 in
solution in water at 8.5% wt (4.37 g/L); and 33 mL of DI water.
Emulsification then took place under ultrasound at 40.degree. C.
and at a power of 200 W (100%) for 15 minutes.
[0099] The following were added to a beaker (2), under magnetic
stirring (at 300 rpm): nitrobenzene diazonium tetrafluoroborate
(0.05 mol/L); 130 mL of DI water; and hydrochloric acid (0.23
mol/L).
[0100] The content of beaker (2) was poured into the emulsion of
beaker (1). The PE samples (.times.2); a winding of galvanized
steel wire (ten turns, i.e. a length of about 25 cm to 30 cm); and
a winding of Ni wire (ten turns, i.e. a length of about 25 cm to 30
cm); were placed in beaker (1). The two wires were connected to a
potentiostat and an ammeter was connected in series. The
potentiostat imposed a constant potential difference of 0.5 V and
the current over time was measured by the ammeter.
[0101] Finally, once the assembly was ready, hypophosphorus acid
(0.7 mol/L) was added last, thereby marking the start of the
reaction. After 30 minutes of reaction at ambient temperature, the
PE samples were removed, then rinsed successively in water (a
cascade), then in ethanol (a cascade), and finally in isopropanol,
in a soxhlet extractor for 16 hours.
[0102] The use of a soxhlet extractor made it possible to confirm
the chemical grafting of acrylic-PDMS on the surface of the PE
substrate.
[0103] An analysis by IR spectroscopy was performed. The IR
spectrum made it possible to confirm the grafting of acrylic-PDMS
by the presence of the characteristic band at 1260 cm.sup.-1
corresponding to the vibration of the Si--CH.sub.3 bond.
[0104] Various modifications may also be envisaged by a person
skilled in the art, without going beyond the ambit of the present
invention, as defined by the accompanying claims.
* * * * *