WO2006032813A1 - Method, production device and silicon elastomer containers for controlled and uniform release of substances into a surrounding medium - Google Patents

Method, production device and silicon elastomer containers for controlled and uniform release of substances into a surrounding medium Download PDF

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Publication number
WO2006032813A1
WO2006032813A1 PCT/FR2005/050754 FR2005050754W WO2006032813A1 WO 2006032813 A1 WO2006032813 A1 WO 2006032813A1 FR 2005050754 W FR2005050754 W FR 2005050754W WO 2006032813 A1 WO2006032813 A1 WO 2006032813A1
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Prior art keywords
substance
tube
pockets
method according
according
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PCT/FR2005/050754
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French (fr)
Inventor
Marc Ferber
Christophe Pottier
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Saint-Gobain Performance Plastics Verneret
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B31/00Packaging articles or materials under special atmospheric or gaseous conditions; Adding propellants to aerosol containers
    • B65B31/04Evacuating, pressurising or gasifying filled containers or wrappers by means of nozzles through which air or other gas, e.g. an inert gas, is withdrawn or supplied
    • B65B31/08Evacuating, pressurising or gasifying filled containers or wrappers by means of nozzles through which air or other gas, e.g. an inert gas, is withdrawn or supplied the nozzle being adapted to pierce the container or wrapper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B9/00Enclosing successive articles, or quantities of material, e.g. liquids or semiliquids, in flat, folded, or tubular webs of flexible sheet material; Subdividing filled flexible tubes to form packages
    • B65B9/10Enclosing successive articles, or quantities of material, in preformed tubular webs, or in webs formed into tubes around filling nozzles, e.g. extruded tubular webs
    • B65B9/24Enclosing successive articles, or quantities of material, in preformed tubular webs, or in webs formed into tubes around filling nozzles, e.g. extruded tubular webs the tubes being formed in situ by extrusion

Abstract

The invention relates to a method and corresponding device for producing a silicon elastomer container for a controlled and substantially uniform release of a substance very often organic, for example a volatile liquid such as a perfume, flavour, insecticide, atmosphere air coolant, etc into surrounding medium. The inventive method consists in extruding a hollow tube, in shaping said tube and a sequence of hollow pockets and filled parts, in vulcanising and in filling the pockets with a substance by means of a suitable system. A container obtainable by means of the inventive method is also disclosed.

Description

PROCESS AND INSTALLATION OF MANUFACTURING AND TANKS

SILICON ELASTOMER FOR CONTROLLED RELEASE AND

REGULAR SUBSTANCES IN THE ENVIRONMENT

The present invention relates to a method and an apparatus connected therewith for producing a silicone elastomer reservoir for controlled and substantially uniform release in a surrounding medium such as air or water from a mostly organic substance, for example a volatile liquid such as a perfume, a flavor, an insecticide, air freshener agent in the atmosphere, etc. The invention also relates to the container obtained by such a method.

It is known that silicone elastomers are permeable to gases and liquids due to their high porosity. Two types of systems are described in the prior art:

- the matrix systems in which the molecule to be broadcast are homogeneously dispersed in the polymer matrix, the diffusion rate being controlled by diffusion through the matrix, - systems in which the molecule to be broadcast are confined within a container consisting at least partly of the silicone elastomer, the diffusion rate being dependent on the permeability AUDITED molecules of the elastomeric wall of the tank.

For example, the Japanese patent JP 57-40558 discloses a material in which a fragrance is dispersed in an elastomeric matrix before crosslinking silicone thereof. Similarly, U.S. Patent 4,725,575 discloses a silicone matrix obtained by vulcanizing special silicone elastomers.

U.S. Patent 4,703,070 discloses a composition for slow diffusion of an organic liquid in the atmosphere, comprising a compatibilizing agent between the silicone matrix and the liquid to be diffused in order to avoid phenomena of exudation of the liquid over time .

U.S. Patent 4,889,285 discloses a tank for the diffusion of a perfume comprising a silicone rubber hollow body and also made of said elastomeric stopper. The device is obtained by molding. According to this technique, molding is carried out of a hollow body (tank) in silicone elastomer and a plug also made of silicone elastomer, together for example by screwing, by clipping or by gluing of the lid with a silicone adhesive after filling the tank with the liquid substance. The number of operations to be performed is according to this significant achievement. In addition, such a process requires most often a resumption of silicone products to bring them into position for performing filling. is easy to understand that such an amount of operation is expensive to implement on an industrial scale. In addition, such a bottle has a certain fragility and the risk of bursting or leaking from the stopper, especially in case of impact or crushing, in particular when bottles are stacked during transportation or storage.

The object of the present invention is to remedy these drawbacks by providing a simplified method of manufacturing an article serving as a reservoir for a substance such as for example an organic volatile liquid, said reservoir being made of a silicone elastomer. The container obtained according to the invention allows to optimize the time the amount of substance diffused to the surroundings. To do this, is adjusted according to the invention the heat exchange area by maximizing the surface portion of the membrane silicone elastomer in contact on its inner face with the substance and on its outer face with the external environment and this , independently of the filling level of said reservoir.

The container obtained according to the invention thus enables a controlled, sustained and substantially constant of the substance to the external environment as long as it remains of product in the reservoir.

More specifically, the invention relates to a silicone elastomer tanks manufacturing process containing a controlled manner to diffuse substance comprising the steps of: a) extruding a hollow tube of silicone elastomer, b) bringing shaped tube, for example by crushing the tube in several places, so as to obtain an alternation of hollow pockets and solid portions forming connection between said pockets, c) curing the silicone elastomer, d) introduction of the substance in hollow pockets by implementation of a system comprising the air replacing means contained in the pouch by the substance to be diffused.

The method may further comprise a step e) of cutting to separate after filling each bag into an individual tank.

In general, said pockets and said solid portions are evenly spaced at the end of step b) shaping of the tube.

According to a possible embodiment, the system used during the step d) comprises at least one needle. For example said needle evacuates the air contained in the bag in a first step then injects the substance. According to another embodiment, one uses at least two needles, at least one needle evacuating air contained in the bag and at least one other needle injecting the substance, preferably simultaneously. According to another embodiment, allowing for example to accelerate the filling rates, one uses at least three needles, at least one needle evacuating air contained in the bag and at least two other needles injecting the substance, preferably simultaneously. According to the method, the size of the needles or is advantageously adjusted and the silicone elastomer selected such that the orifice made by the needle is closed immediately after removal thereof thanks to the elastic properties of the elastomer silicone without any possibility of output or higher leakage of the substance. The needle may be made of any suitable material for this purpose for example a metal such as steel or a ceramic.

For example, the diameter of the extruded hollow tube during the step a) of the process is between 3 and 150 mm, preferably between 3 and 50 mm.

The wall thickness can vary according to the invention between about 0.5 mm and about 10 mm, preferably between 1 and 5 mm and more preferably between about 1 and about 3 mm. Testing by the applicant have shown that the thickness of the tank walls surprisingly not influenced significantly on the drug release kinetics. In particular, thickness of tanks 1, 2 or 3 mm have a substantially identical release kinetics.

On the other hand, the thickness of the wall of the carton is critical from an economic point of view. The applicant has calculated that the cost of the raw material, that is to say of the elastomer itself, entered to a large extent in the overall cost of the process according to the invention. The present method advantageously allows, from a small amount of material, obtaining resistant tanks to shocks or crushing and whose walls are of the order of a millimeter or even less.

Advantageously, during step a) extrusion, the die is configured such that the reservoir has an extra thickness on a portion of its surface. This configuration has the advantage of allowing the use of a minimum amount of elastomer per tank.

It was found that the substance release rate was based on the shape of the tank. More specifically, for the same internal volume, an elongated tank and a small diameter has a much greater release rate than a large diameter reservoir and small length. According to one possible embodiment of the invention, it is thus possible to adjust, in particular during the extrusion and cutting steps, the dimensions of the tanks, particularly their diameter and length, to change and adjust the release kinetics of the substance. Without departing from the scope of the invention, the drug release kinetics can be controlled by varying the temperature applied around the carton.

The invention also relates to an installation suitable for implementing the method and comprising: - an extruder for forming a hollow tube of silicone elastomer, a forming system of the tube so as to obtain a alternating pockets hollow and solid portions forming connection between said pockets, for example a toothed wheel or a system for a plurality of successive crushing of the tube, an oven for the vulcanisation of the elastomer, an automatic filling system comprising pockets e.g. at least one syringe, optionally a cutting device for separating the bags into individual reservoirs. The die of the extruder may be configured such that the obtained hollow tube has an increased thickness over a portion of its surface, for example a projection present on the entire length of said tube, on the inner or outer wall of said tube.

Finally, the invention relates to a silicone elastomer reservoir containing a substance to be diffused obtainable by a process as described above. The substance to be diffused contained in the container is for example selected from the group consisting of fragrances, flavors, deodorants, absorbers and neutralizing odors, insecticides, antibacterial agents, anti-limescale agents, fungicides, atmosphere fresheners, softeners for clothes, anti-bacterial and anti-microbial, fungal anti¬, anti-parasites (insecticides), limestone anti¬ (water softeners), product water treatment in general (swimming pools, etc ..), fertilizers and other soil treatment products, lubricants.

The invention will be better understood from reading the following description of an exemplary embodiment of the manufacturing unit according to the invention. This example is provided for illustrative purposes only and not under any of the aspects described be considered as limiting the scope of the present invention.

Figure 1 illustrates schematically a succession of steps according to the present process. Figure 2 is a drawing illustrating an elastomeric reservoir obtained according to a first embodiment 1 of the invention.

Figure 3 is a drawing illustrating an elastomeric reservoir obtained according to a second embodiment of the invention.

During a first step, a continuous hollow tube 13 made of silicone elastomer is extruded by conventional techniques. For example and as illustrated by Figure 1, an extruder 1 enables the formation of a section of the hollow tube-type. Leaving the die 2, the unvulcanized elastomer in the form of soft gum is conventionally extruded in the form of a tube passing between the full internal parts corresponding to the inner lumen of the tube and outer of the die 2. This technique is identical to that already known for the production of hollow continuous and silicone tubes.

In a second step, the tube is collapsed on some regularly spaced positions. Thus, individualized immediately on leaving the die from a hollow tube closed cavities or pockets that will then serve as reservoirs for the volatile liquid, as will be described later. The crushing can be done using any technique known in the art, in particular by means of a system comprising a toothed wheel 3 even through conventional systems for a plurality of successive crushing of the tube, such as one or several mechanical jacks or clamping systems.

The profile 4 thus obtained comprises a string of pockets 6 connected by solid portions 5 having undergone crushing and evenly spaced. It is then transferred to a curing furnace 7, wherein the polymer is treated for example by heating or by ultraviolet or infrared radiation 8. In known manner, the treatment of vulcanization of the silicone elastomer is in the crosslinking chains siloxanes, including vinyl functions present on said reaction channels on other channels hydrogen sites with catalyst systems known in this application such as peroxides agents, silicates, platinum agents etc .. the platinum catalysis can be preferred according to certain applications of the invention as it has the advantage of not inducing degradation products may then react with the various components of the substance to spread. The silicone elastomers vulcanization reaction is well known in the art and reference is made to reference books to determine the optimal conditions for its implementation. Examples of vulcanization of a silicone elastomer are also disclosed in US 4,725,575, US 4,703,070 and US 4,889,285 which reference can also refer to the implementation of such a method. Leaving the furnace 7, one obtains a profile 4 'of a silicone elastomer having improved mechanical strength, typically with a Shore-A hardness is between 20 and 80 and the shape is no longer modifiable.

During the next step, the pockets are filled with liquid by a process implementing a system with double needle 9 and 10.

According to the present method, there is obtained a continuous section, elastic and having good mechanical strength wherein successive equidistant solid parts 5 'and 6 pockets. This regular succession advantageously allows to implement in a simple and ingenious automated filling system, each bag is filled sequentially with a needle 10 containing the product and connected to a reservoir (not shown in Figure 1), while other needle 9 allows the simultaneous discharge of the air initially contained in the pocket. The size of the needle is adjusted according to the invention such that the hole made by the needle is closed immediately after removal thereof through the elastic properties of the silicone elastomer, without possibility of exit or higher leakage of liquid. According to the invention, is thus used advantageously as self-sealing properties 1'élastomère for easy filling of the reservoirs. Thus, a remarkably simple system enabling a substantial reduction in costs compared to a conventional method of molding by forming as described in U.S. Patent 4,889,285.

In the example illustrated by Figure 1 discloses a bag filling system comprising two needles. It is however also within the scope of the present invention if only one needle was used, for example allowing the evacuation of air in first and then injecting the substance into a second time.

Of course it is also possible according to the invention to use several needles used for performing the evacuation of air and / or filling of the pockets, for example in order to adapt the duration of this step to the production rate desired or to increase said rate.

In a subsequent step, the pockets 6 'may then be individualized by section of the continuous section in the solid portions 5' using any known technique, for example by means of a cutter, the action of which is symbolized by the arrow 11. is finally obtained of individual reservoirs 12 comprising a silicone elastomer envelope in which is stored and released slowly and steadily over time the volatile substance. The diameter of the individual pockets (or cartons) finally obtained is for example between 3 and 150 mm, in the widest part, preferably between 3 and 50 mm. The length is variable and can be relatively large, depending on the desired application. According to the invention, it is conceivable forms more or less crushed, more or less round and more or less asymmetrical of cartons depending on the desired aesthetic. 2 illustrates a sequence of tanks 6 'from the continuous section bar, before and after individualization.

3 illustrates a particular embodiment of the reservoirs according to the invention. This mode is particularly advantageous when the thickness 100 of the elastomeric wall is low, i.e. typically less than 4 mm, or 3 mm, 2 mm or even 1 mm. The carton has a limited portion of its surface a thickening 101. The filling of the reservoir 12 through the needle 10 and discharging the air by the needle 9 is performed at the thickened portion 101, shown in Figure 3 by a projection 102 present along the entire length of the carton. The width of this thickness is advantageously selected depending on the size of the needle. Such a configuration allows the use of the filling system according to the invention whatever the thickness of the elastomer wall, particularly when it is too small to be adapted to the size of the used needles. Too thin is meant within the meaning of the present invention a thickness such that the elastic properties of the elastomer only allow more effective sealing of the hole after removal of the needle, in the sense previously described. In Figure 3, said increased thickness 101 is shown in the inner wall of the reservoir and is not visible when the latter is filled. Without departing from the invention, the thickness 101 may also be present on the outer wall of the tank.

For example, there was obtained an effective seal as an average wall thickness of 1 mm and a thickness between 0.5 to 1.5 mm.

The thickness can be obtained according to any known technique, preferably by changing suitably the shape of the punch or the die 2 (cf. Figure

D •

The manufacturing method as just described has many advantages: - The system is closed. The needles fit into the pockets and the fill without possibility of contact of the substance to be injected with the outside, which reduces the risks when at least one component of said substance is highly flammable. The amount of product that can come out is small and precautions are therefore much less large. Instead, the filling of an open system such as a bottle obtained by molding is much more problematic because it is difficult or impossible to avoid in this case the contact of the substance with the outside.

- The cartons obtained are translucent and can thus see and control at any time the tank filling level whatever the level of the substance in it, which significantly improves the comfort of use.

- Surface area of ​​possible contact between the silicone membrane into contact with the substance and the outside environment is maximized, regardless of the filling level of the tank, ensuring over time a substantially constant diffusion of the substance into the external environment.

- Treatment for vulcanization of the elastomer is carried out prior to the pockets filling step, thereby avoiding to degrade during this treatment some sensitive molecules such as organic molecules contained in the substance to be diffused and / or possible reaction between the catalyst or a reaction agent with at least one of the constituents of the substance. - The cartons obtained are extremely durable and can be maintained, or compressed positioned in any direction without uncontrolled risk of bursting or leakage of the substance. In particular, tests have shown that a carton according to the invention, of length equal to 12 mm, resisting a load of 50 kg minimum without any leakage of liquid.

- It is possible to produce extremely low wall thickness of tanks. The choice of silicone elastomer used is not limiting of the invention and it may be selected from various known types of elastomers.

According to the invention, it is possible indifferently to use silicone elastomers obtained from composition which crosslink at room temperature (so-called RTV compositions) or at higher temperatures (High Temperature Vulcanizing compositions or HTV) under the effect of different types of catalysts or other crosslinking agents. The elastomers of the HTV type are preferred. Initial elastomer compositions can be selected for cross-linking under the effect of heating or radiation such as UV or IR. According to the invention, can also be used silicone elastomers roughly functionalized being in form mono, bi or tri-components.

According to the invention there may be added fillers such as silica, titanium dioxide or other types of nanofillers to modify the elastomer porosity and modulate the diffusion of species through the wall thereof.

The substance of the invention may be of different types depending on the desired application. One can cite, as non-limiting example, the substances belonging to the families: - artificial fragrances and essential oils,

- neutralizing or odor modifiers,

- flavorings and essences

- softeners for washing machine and dryer, - anti-bacterial and anti-microbial,

- anti-fungal,

- Anti-parasite (insecticide)

- anti-limestone (water softeners),

- water treatment products in general (swimming pools, etc ..)

- fertilizers and other soil treatment products,

- continuous lubrication for lubricants.

Reference may be made to EP 1,060,751 for examples of such substances.

The broadcast substance may comprise a single compound or a mixture of compounds and solvent, for example included in the previously mentioned group.

The present invention particularly the carton from the present method can be used for many applications. Among these include, for example:

- perfume applications in a washing machine or dryer, dishwasher, of atmosphere fresheners (air freshener) or deodorants in rooms or enclosed spaces such as kitchens, toilets, toilets public, cars, buildings, offices etc. - applications in various technologies and technical materials, eg seals releasing lubricants, water filters releasing fungicides, water treatment devices (aquaculture, swimming pools), the processing of limestone in various household appliances (irons , boilers, coffee machines) etc.

- applications in agriculture, environment, medical, hygiene, for example to the slow diffusion of pesticides in the fields of antimicrobials on farms, schools, hospitals, refrigerators, air conditioning systems etc.

The following examples, not limiting the invention, are given in order to illustrate the advantages of the manufacturing method described above and the products obtained by its implementation.

Example 1:

Elastomer HTV silicone composition on a basis of the product sold by the company Rhodia Silicones under reference RODORSIL catalyzed peroxide is extruded in a hollow section (tube) by an extruder of the single screw type, and some parts are crushed by a toothed wheel to provide continuous profile comprising a succession of pockets whose average width is 25mm and crushing whose spacing is 50mm. The wall thickness is 3mm. The profile thus obtained is treated (cured) at a temperature of 300 0 C in an oven of the infrared type for two minutes. Leaving the furnace is recovered an enhanced mechanical strength profile (Shore 60 A). A double needle system allows replacement of the air by an organophilic perfume base containing 70% of a perfume dispersed fishing flavor base in a solvent, dipropylene glycol methyl ether. The profile thus obtained is cut into lending units or cartons for use. A photograph of the through runner and an individual carton after cutting is provided in Figure 2. 5 grams of the base are injected carton. Each carton is then weighed regularly for 45 days to control the perfume release kinetics. a substantially linear and constant variation is observed over time, at about 75 to 70 micrograms of the substance released daily. The substance percentage of regression line released vs. time and fitted by the least squares method has a coefficient of determination R 2 equal to 0.95, justifying an almost linear release kinetics over time. After 45 days 3.25 grams of perfume were released, corresponding to 65% of the amount initially stored.

Of crushing tests showed that the reservoir thus obtained could carry a load of 80 kg, but without risk of bursting or leakage of the substance.

Example 2:

Example 1 above was repeated, but the extruder die has been modified so that the thickness of the wall is 1 mm. Furthermore the inner portion of the die (the punch) at the extruder outlet includes a deep groove 1 mm wide and 5 mm, so that the tube has on its inner wall an internal projection corresponds to a thickness of 1 mm, according to Figure 3. the amount of elastomer used and is thus almost divided by three as compared to example 1.

After heat treatment, the tubes are filled with the same amount of the perfume base organophilic of Example 1, by the double needle system, at the thickened region of the container.

The substance of the release kinetics is surprisingly substantially identical to that described in 1'exemple 1.

Of crushing tests showed that the resulting tank could carry a load of 50 kg, but without risk of bursting or leakage of the substance.

Claims

1 - Process for producing silicone elastomeric tanks containing a controlled manner to diffuse substance comprising the steps of: a) extruding a hollow tube of silicone elastomer, b) shaping of the tube, for example by crushing of the tube in several places, so as to obtain an alternation of hollow pockets and solid portions forming connection between said pockets, c) curing the silicone elastomer, d) introduction of the substance into the hollow pockets by implementation a system comprising the air replacing means contained in the pouch by the substance to be diffused.
2 - The method of claim 1 further comprising a step e) cutting to separate after filling each bag into an individual tank.
3 - The method of claim 1 or 2 wherein said pockets and said solid portions are evenly spaced at the end of step b) of the shaping tube. 4 - Method according to one of claims 1 to 3 wherein the system used during the step d) comprises at least one needle.
5 - Method according to one of claims 1 to 3 wherein the system used during the step d) comprises at least two needles, at least one needle evacuating air contained in the bag and at least one needle injecting the substance.
6 - Process according to claim 4 or 5 wherein the size of the or needles is adjusted and silicone 1'élastomère selected such that the orifice made by the needle is closed immediately after removal thereof through elastic properties of the silicone elastomer, without possibility of exit or higher leakage of the substance.
7 - Method according to one of claims 5 or 6 wherein the evacuation of air and the injection of the substance are simultaneous.
8 - Method according to one of the preceding claims, wherein the diameter of the extruded hollow tube during the step a) is between 3 and 150 mm. 9 - Method according to one of the preceding claims, wherein the thickness of the wall of the tank is between 0.5 and 10 mm, preferably between 1 and 5 mm.
10 - Method according to one of the preceding claims, wherein the extruded tube during step a) extrusion has a thickness over a portion of its surface.
11 - Method according to one of the preceding claims, wherein one adjusts the dimensions of the tanks, particularly their diameter and length, to change and adjust the release kinetics of the substance.
12 - Device for implementing the method according to claims 1 to 11 comprising: - an extruder (1) for the shaping of a hollow tube (13) of silicone elastomer,
- a system of shaping the tube so as to obtain an alternation of hollow pockets and solid portions forming connection between said pockets, for example a toothed wheel (3) or a system allowing several successive crushing of the tube,
- a furnace (7) for the vulcanisation of the elastomer,
- an automatic filling system pockets (9, 10), - optionally a cutting device for separating the bags into individual reservoirs. 13 - Device according to claim 12, wherein the die of the extruder is configured in such a way that the resulting hollow tube has a thickness
(101) over a portion of its surface, for example a projection (102) has over the entire length of said tube, on the inner or outer wall of said tube.
14 - silicone elastomeric reservoir containing a substance to be diffused obtainable by a process according to claims 1 to 11 or a plant according to claim 12 or 13.
15 - container according to claim 14 wherein the substance is selected from the group consisting of fragrances, flavors, deodorants, absorbers and neutralizing odors, insecticides, antibacterial agents, anti-limescale agents, fungicides, atmosphere fresheners, softeners for clothes, anti-bacterial and anti-microbial, fungal anti¬, anti-parasites (insecticides), limestone anti¬ (water softeners), products water treatment in general (swimming pools, etc ..), fertilizers and other soil treatment products, lubricants.
PCT/FR2005/050754 2004-09-17 2005-09-16 Method, production device and silicon elastomer containers for controlled and uniform release of substances into a surrounding medium WO2006032813A1 (en)

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FR0452088A FR2875431B1 (en) 2004-09-17 2004-09-17 Method, manufacturing facility and reservoirs silicone elastomer for the controlled and steady release of substances into the surrounding medium
FR0452088 2004-09-17

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965642A (en) * 1974-08-22 1976-06-29 Hills Research & Development, Inc. Method and apparatus for filling plastic bags with liquid or particulate material
US4725575A (en) * 1986-12-10 1988-02-16 Union Camp Corporation Silicone rubber dispensers of volatile organic liquids
US4889285A (en) * 1985-10-15 1989-12-26 Union Camp Corporation Device for dispensing volatile fragrances
US5641004A (en) * 1994-04-26 1997-06-24 Py; Daniel Process for filling a sealed receptacle under aseptic conditions
DE19941200A1 (en) * 1999-08-30 2001-03-15 Mutschlechner Ilona Air deodorizing device dealing with e.g. paint, mold or nicotine odors, comprises a volatile deodorant in a closed sheath allowing diffusion

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3299603A (en) * 1962-03-12 1967-01-24 Continental Can Co Method of filling pouches
US3561186A (en) * 1968-04-17 1971-02-09 Donald E Pickering Method of evacuating hollow bodies

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3965642A (en) * 1974-08-22 1976-06-29 Hills Research & Development, Inc. Method and apparatus for filling plastic bags with liquid or particulate material
US4889285A (en) * 1985-10-15 1989-12-26 Union Camp Corporation Device for dispensing volatile fragrances
US4725575A (en) * 1986-12-10 1988-02-16 Union Camp Corporation Silicone rubber dispensers of volatile organic liquids
US5641004A (en) * 1994-04-26 1997-06-24 Py; Daniel Process for filling a sealed receptacle under aseptic conditions
DE19941200A1 (en) * 1999-08-30 2001-03-15 Mutschlechner Ilona Air deodorizing device dealing with e.g. paint, mold or nicotine odors, comprises a volatile deodorant in a closed sheath allowing diffusion

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