Patent Application
20090166936
This invention relates to a sol-gel process for the manufacture of moulds suitable for the formation of materials using photocatalysis processes.
This invention also relates to a pultrusion process, an extrusion process and a moulding process in which a mould manufactured in accordance with the abovementioned method is provided.
In particular the invention lies in the field of the processing of various materials, including composite materials and silicones, and pultrusion, extrusion and moulding processes are of particular interest in that sector.
As is known, composite materials (or reinforced plastics) are obtained through the combination of a thermohardening resin, such as polyesters or epoxides, with a reinforcement based on glass fibre, carbon fibre, fabric or other material. This association imparts particular mechanical strength properties to the material which can be utilized in a wide range of industrial sectors.
As far as silicones are concerned, these are organosilicon compounds comprising polymers based on a silicon-oxygen chain and organic functional groups linked to the silicon atoms; their special feature is that they are particularly resistant to temperature, chemical attack and oxidation, and are excellent electrical insulators. Silicones may be subdivided into various application classes, including liquids, emulsions, lubricants, resins, elastomers. They obviously have very wide application extending from adhesives to lubricants, insulating agents and prostheses.
It is known that in the main industrial processes, and in particular in the processes of pultrusion (for composite materials), extrusion and moulding, both composite materials and silicones undergo a cross-linking treatment known as polymerization which generally takes place through thermal means, in particular by placing the material in contact with a heated mould in which it undergoes polymerization and plastic deformation and in which it takes up the final or semi-final shape of the end product.
In the known art moulds are generally made of metal, because they have to withstand high mechanical loads as a result of the plastic deformation stresses on the material being formed, and thermal loads due to the repeated thermal polymerization cycles which they perform.
Moulds of this type are disadvantageously characterized by a particularly high mass; as a consequence of this moulds made of metal create more than insignificant logistical difficulties.
Furthermore, the manufacture of moulds from metal requires mechanical finishing machining of the rough piece downstream from the operation of casting or plastically deforming the piece in order to obtain a mould which is consistent with a desired shape. Mechanical machining of the mould takes place through the removal of swarf, generally by milling, or, in some cases, by turning or other machining, and is as a result very costly in that it requires complex equipment, particularly when moulds of large size are being machined.
As a result the manufacture of metal moulds has the further disadvantage that it requires rather long machining times; this is another factor having an adverse effect on the costs of manufacture of such moulds, which also reflects the various disadvantages affecting moulds made of metal.
As mentioned previously, there are various processes in industry in which the use of moulds is required; specifically the processes of pultrusion, extrusion and moulding will also be described below with reference to the equipment used. These processes, which are known, constitute the main but not the only methods of producing and forming composite and silicone materials in accordance with processes according to this invention.
Pultrusion is an operation used to manufacture composite materials and is the production process normally used in the production of pipes, articles having a hollow cross section and various sections, in which continuous layers of reinforced fibre are impregnated with catalysed resin and then caused to pass through a heated metal mask using an appropriate machine which “draws” the composite material. A continuous line of product which can then be cut and dispatched for subsequent processing is obtained in this way.
The extrusion process on the other hand consists of feeding the material which has to be shaped, for example a silicone, which is then thrust, for example by means of a piston or continuous thrust means comprising for example rotating screws, through a die having a shape which reproduces the cross section of the required section. Again in this case a continuous line of generally semi-finished product which is then sent to stations for subsequent processing is produced.
Moulding on the other hand consists of placing the material which has to be moulded, for example a silicone, in a mould forcing it to fill it and adopt its shape. The material may for example be injected into the mould while it is in the liquid state. Heating of the mould takes place in parallel with polymerization of the material.
In each of these processes polymerization takes place through a thermal effect and requires a very precise time, which can in some cases be excessive. This has an adverse effect in terms of low productivity and relatively high production costs.
As an alternative to the processes of thermohardening plastics material described, photocatalytic processes for achieving polymerization and, if appropriate, cross-linking of the same, with acceptable results, are known, at least at laboratory level.
Unfortunately these processes have not become industrially established because of intrinsic difficulties with the processes themselves. For example, in a photocatalytic process one appreciable difficulty is the nature of the mould, which must have appreciable optical transparency, and mechanical and thermomechanical strength properties. Not to mention a shape appropriate for the purpose, which might require appreciable sophistication.
In this situation the technical task underlying this invention is to provide a process for the manufacture of moulds which are capable of overcoming the abovementioned disadvantages.
In the context of this technical task it is an important object of the invention to provide a process for the manufacture of moulds which makes it possible to reduce process times and as a consequence to increase productivity, even substantially, in particular in processes of pultrusion, extrusion and moulding using such moulds, achieving the effect of reducing production costs.
Another object of the invention is to provide a process for the manufacture of moulds of smaller mass than conventional metal moulds, while maintaining good mechanical and thermal strength.
Another object of the invention is to provide a process for the manufacture of moulds which eliminates, or at least reduces as far as possible, the need to carry out mechanical machining on the moulds obtained and therefore which reduces the production costs for the moulds themselves.
The technical task specified and the objects specified are substantially achieved through a sol-gel process for the manufacture of moulds having at least one portion transparent to UV rays according to one or more of the technical arrangements claimed below.
Thus the object of the following invention comprises a sol-gel process for the manufacture of moulds having at least one portion transparent to UV rays as claimed below.
The subject of the invention is a sol-gel process for the manufacture of moulds having at least one portion transparent to UV rays, which comprises the following stages:
a) provision of a container (1) which is a negative of the said at least one portion (2a) transparent to UV of the mould (2) which is to be manufactured and internally defining a chamber (3), the said chamber (3) having at least one first surface (3a) which is substantially the negative of a corresponding outer surface (2b) of the said at least one transparent portion (2a) of the mould (2) being manufactured, and at least one second surface (3b) which is substantially a negative of at least one corresponding inner surface (2c) of the said at least one transparent portion (2a) of the mould (2) being manufactured,
b) filling the chamber (3) with a sol,
c) gelling the sol, obtaining the so-called gel,
d) heating the gel and a corresponding solvent for a programmed period of time consequently achieving predetermined temperature and pressure values preferably higher than the critical values for the solvent present in the gel, and evaporation of the said solvent, the said heating giving rise to drying of the gel,
e) densification and/or sintering of the dried gel through heating to a predetermined temperature, preferably higher than the temperature at which drying stage d) takes place, with the consequent formation of the said transparent portion (2a) of the mould, with a vitreous consistency and transparent to at least UV rays, the said mould being suitable for the formation of pultrusion and/or extrusion products and/or the moulding of plastics materials through a process of photocatalytic synthesis.
In the process of the invention the outer surface (2b) of the said at least one transparent portion (2a) of the mould (2) being manufactured can face the external environment in the operating condition of the mould (2) and allow UV rays to pass towards the interior, while the inner surface (2c) of the said at least one transparent portion (2a) of the mould (2) is in the operating condition in contact with the product being formed and polymerized.
In the process according to the invention the container (1) can comprise at least one insert (5) defining the said at least one second surface (3b) of the chamber (3).
In the process according to the invention the said at least one insert (5) can be incompressible.
In the process according to the invention the said at least one insert (5) can be cylindrical.
In the process according to the invention the stage d) of gelling the sol can comprise an operation of extraction of the said at least one insert (5).
In the process according to the invention the extraction of the said at least one insert (5) can take place at a predetermined time in the gelling stage to prevent the formation of cracks in the forming gel.
In the process according to the invention the container (1) can be caused to rotate to assist extraction of the said at least one insert (5) making use of the centrifugal forces acting on the forming gel.
In the process according to the invention the container (1) can be caused to rotate axially so that, under the effect of the centrifugal force, the sol adopts the shape of the container bounded externally by the inner surface of the container and internally by the equipotential surface at right angles to the centrifugal force field.
In the process according to the invention the container (1) can comprise a plurality of inserts (5).
In the process according to the invention stage b) can be preceded by the following stages:
In the process according to the invention a phase c′) in which the solvent is replaced with an aprotic solvent can be included between stage c) and stage d).
In the process according to the invention a stage c″) in which the gel is placed in an autoclave and subjected to a flow of inert gas can be included between stage c′) and stage d).
In the process according to the invention a stage d′) of depressurization of the autoclave with a consequent escape of vapours, with possible recovery of the said vapours, can be included between stage d) and stage e).
In the process according to the invention a stage d″) which consists of flowing an inert gas through the autoclave containing the gel can be included between stage d′) and stage e).
In the process according to the invention a stage d′″) which comprises cooling the dried gel and removing it from the autoclave can be included between stage d″) and stage e).
In the process according to the invention the aprotic solvent used in stage c′) can be selected from the group comprising acetone, dioxan and hydrofuran.
In the process according to the invention stage a) also can comprise the operation of positioning and attaching at least one insert (5) within the chamber (3).
In the process according to the invention the mould (2) can be wholly transparent to UV rays.
In the process according to the invention the mould (2) can comprise a portion (2a) which is transparent to at least UV rays and a portion (9) which is not transparent to UV rays.
In the process according to the invention the mould (2) can comprise a half-mould 2a) which is transparent to at least UV rays and a half-mould (9) which is not transparent to UV rays.
In the process according to the invention a surface (9a) of the said portion (9) which is not transparent to UV rays, facing the product being formed, can be coated with a reflecting material (10).
In the process according to the invention the reflecting material (10) can be an aluminium film (10).
A further subject of the invention is a pultrusion process, which comprises the following stages:
A further subject of the invention is an extrusion process, which comprises the following stages:
The material being extruded can belong to the group comprising materials based on silicone and rubber.
A preferably thermohardening catalyst can be added to the material being extruded to polymerize the material being extruded when it is exposed to UV rays.
A further subject of the invention is a moulding process, which comprises the following stages:
The material being moulded can belong to the group comprising materials based on silicone and rubber, or thermohardening materials.
Preferably a thermohardening catalyst can be added to the material being moulded to polymerize the material being moulded when it is exposed to UV rays.
The moulding process to the invention can comprise injection or compression moulding.
A description of a preferred embodiment of a sol-gel process for the manufacture of moulds having at least one portion transparent to UV rays is described below by way of example but not exclusively in accordance with the appended drawings in which:
A preferred embodiment of a sol-gel process for the manufacture of moulds having at least one portion transparent to UV rays according to the invention comprises the following stages:
The colloidal suspension (sol) in stage b) is prepared in a preceding stage a′) by mixing one or more precursors containing metal alkoxides with a solvent. This solvent may be water or a water/alcohol mixture, and gives rise to an aqueous or water/alcohol suspension respectively.
Preferably, also, the metal in each precursor is an element belonging to groups 3, 4, 5 of the Periodic system. The metals generally used for the formation of a precursor are silicon and, sometimes, aluminium.
In order to be able to carry out stage b) it is also necessary that hydrolysis of the suspension produced in stage a′) be carried out in a further preceding stage a″), yielding the sol. This is generally achieved by the addition of an acid or basic catalyst to the suspension. This catalyst is preferably an aqueous solution of hydrochloric acid.
It should also be added that once hydrolysis is complete, before starting gelling, it is possible to add a colloidal suspension of an oxide of a metal present in a precursor of the suspension in paragraph b) to the sol. For example, in the case where a precursor comprising or constituting a silicon alkoxide is used, a colloidal suspension prepared by mixing water, pyrolytic silica and an acid or a base may be added to the sol. This also makes it possible to adjust the pH value of the suspension; it is in fact known that pH is one of the factors having the greatest influence on the gelling stage, in particular the duration of that stage and the strength of the gel obtained. In fact it has been found experimentally that increasing the pH value brings about a reduction in the time required for gelling, achieving a period of the order of a few minutes, and in parallel with this imparts greater strength to the gel obtained, thus making it possible to manufacture products of larger dimensions. In detail the improved results in terms of strength of the gel are obtained from a sol having a pH value of between 3 and 6. In order to increase the pH of the suspension it may be brought into solution in a controlled gradual way with for example ammonium hydroxide.
The sol so obtained can then be poured into container 1 and proceed to the gelling stage. This stage takes place through maintaining the sol at a temperature below 40° C. for a time varying from a few minutes to several hours. The gel so obtained has a gelatinous consistency and a porous structure and is immersed in the solvent, in particular water or a water/alcohol mixture as described previously.
In order to be able to proceed to stage d) of drying of the gel it is necessary to provide for replacement of the solvent in that this drying preferably takes place at a temperature and pressure above the critical temperature and pressure for the solvent, and, when excessive water is present, achieving these pressures and temperatures would be extremely harmful to the integrity of the gel, given the agressivity of water towards the gel at high temperatures. In this respect, during a stage c′) between the gelling stage c) and the subsequent stage d) of heating chamber 3 and drying the gel, the solvent present in chamber 3 and in the pores of the gel is replaced by an aprotic solvent, for example by washing the gel. This aprotic solvent is preferably selected from the group comprising acetone, dioxan and hydrofuran and is decidedly less aggressive towards the gel at high temperatures than water.
The gel so prepared, with a level of solvent compatible with the specifications for the solvent extraction autoclave in question at supercritical conditions or “quasi-supercritical” conditions as described in the known art (Joseph G. Van Lierop et al.—U.S. Pat. No. 4,806,328) is placed directly in the autoclave. The gel is then subjected to a further stage c″) of passing through an inert gas, preferably nitrogen, at the pressure necessary to achieve a total pressure greater than the critical pressure for the aprotic solvent when the temperature exceeds the critical temperature for that aprotic solvent. Exceeding the critical conditions in this way has the advantage that a gel which better matches the desired dimensions is obtained in comparison with a gel which is obtained by drying at conditions below the critical conditions.
As an alternative, during stage c″) the inert gas is passed through at the pressure necessary to achieve total pressure and temperature values below the critical values for the aprotic solvent previously introduced, but compatible with the rules for extraction under subcritical conditions described in the known art (U.S. Pat. No. 5,966,832; U.S. Pat. No. 5,875,564; U.S. Pat. No. 5,473,826; U.S. Pat. No. 5,343,633; PCT/EP 2003/014759).
The gel is then heated; after this heating the aprotic solvent evaporates substantially completely and drying of the gel takes place.
Subsequently in a stage d′) the autoclave is depressurized with the consequent escape of vapours.
These vapours may be recovered where this is considered to be convenient or necessary.
In a subsequent stage d″) an inert gas, preferably nitrogen, is caused to flow through the autoclave containing the gel in order to remove residual traces of vapours. In a subsequent stage d′″) the dried gel is cooled and removed from the autoclave. In order to impart the desired transparency properties to the dried gel, a final sintering stage e) is provided in which the gel is heated to a predetermined temperature, preferably higher than the temperature at which drying stage d) takes place, in which vitrification of the gel occurs. Said stage e) is generally effected by placing the gel in a furnace, not illustrated, and increasing the temperature of the furnace above 100° C. and up to even 900° C. in an atmosphere which may also contain oxygen, used to calcine the gel. After this treatment, gases containing chlorine or its precursors may be introduced in order to eliminate any residual hydroxides in the gel, reaching a temperature of between 100° C. and 1250° C. The temperature of the furnace is finally increased to between 900° C. and 1650° C. in such a way as to bring about densification of the gel and therefore its vitrification, obtaining a mould having a vitreous consistency which is transparent to at least UV rays.
Some of the characteristics of the device used to effect the abovementioned process will now be described.
As mentioned previously, the performance of stage a) requires the provision of a container 1, illustrated in
Advantageously chamber 3 is a negative of the final shape or a portion of the final shape of mould 2 which it is desired to obtain, with dimensions which are suitably enlarged to take into account the progressive shrinkage acting on the sol during the gelling stage and subsequent shrinkage associated with the stages of drying and densification and/or sintering. Mould 2 is illustrated in
In detail, chamber 3 has at least a first surface 3a which is substantially of a shape which is a negative of a corresponding outer surface 2b of at least one transparent portion 2a of mould 2 being manufactured, and at least one second surface 3b which is substantially a negative of at least one corresponding inner surface 2c of said at least one transparent portion 2a of mould 2 being manufactured. This inner surface 2c defines a cavity 4, preferably a through cavity, within the mould.
In relation to
In detail, means may be provided externally to mould 2 to generate UV rays. These means for the generation of UV rays must face mould 2, in particular the outer surface 2b of transparent portion 2a. In this way, in the working condition, the UV rays will be directed towards mould 2, and by virtue of the transparency of mould 2 to UV rays will pass through it reaching internal cavity 4. The material which has to be shaped and polymerized, generally a composite material or a silicone, is suitably introduced into cavity 4 to undergo polymerization through the UV rays generated as just described. The material which has to be formed and polymerized is then exposed to the UV rays while it is within the mould. Advantageously polymerization takes place through exposing the material which has to be shaped and polymerized while it is in movement through cavity 4 of mould 2. It is however conceivable that the flow of material which has to be formed and polymerized may be temporarily stopped in order to permit completion of the polymerization process.
In the non-working condition, cavity 4 is empty and is therefore not filled with any material which has to be formed.
Coupling means, not illustrated, may also be provided to secure mould 2 to a device, for example a pultrusion, extrusion or moulding device.
One of the most critical operations for manufacturing moulds according to the invention is the production of cavity 4, for reasons which will be clarified below.
In order to make the said cavity 4 (see for example
According to a first embodiment illustrated in
In general it is preferable to use cylindrical inserts 5 to generate cylindrical cavities 4 within mould 2 and therefore passages of constant cross section for the material being polymerized which passes through it. As an alternative it is possible to use inserts 5 of a frustoconical shape, not illustrated, which can be more easily removed from the gel but which can only be used in circumstances where a cavity 4 having a variable cross section for passage of the material being polymerized is necessary.
In a wholly similar way it is possible to obtain different embodiments of a wholly transparent mould 2 as illustrated in
When an insert 5 is present, gelling stage d) also provides for an operation of extracting insert 5 from the sol as it is gelling. The removal of inserts 5 has proved to be a quite complex operation in that, while it is forming from the sol, the gel has a “syneresis” stage, that is a stage during which the material of which it is formed “migrates” in the direction of the centre of mass thus reducing its volume. It is obvious that in this situation any inserts 5 present will tend to be tightly gripped by the forming gel, which has a gelatinous and not very strong consistency. It is therefore necessary to remove these inserts 5 before they are excessively gripped by the gel, but in any event not before the gel has developed sufficient robustness to be able to support the presence of an internal cavity 4. It is therefore necessary to remove each insert 5 at a well-specified time in order to avoid irreversible damage to the gel which would compromise its integrity.
For this purpose it is possible to cause container 1 to rotate, preferably about an axis of symmetry of insert 5 which has to be removed, in order to assist removal of said insert 5 making use of the occurrence of centrifugal forces acting on the gelling sol, as illustrated in the known art (U.S. Pat. No. 6,799,442).
In a further version it may be convenient to prepare cylindrical mould 2 completely on the basis of the centrifugal force acting on the sol located in a suitable horizontal cylindrical container which is caused to rotate rapidly axially as described in the known art (U.S. Pat. No. 4,680,045).
In this arrangement the sol, whose volume occupies a predetermined fraction of the volume of the container, under the effect of the centrifugal force adopts the cylindrical shape of the container bounded externally by the inner surface of the container, and internally by the equipotential surface, which is also cylindrical, perpendicular to the centrifugal force field present during the gelling stage.
The process and device described above make it possible to obtain moulds which are wholly transparent to UV rays.
In another embodiment, illustrated in
It is however possible to use a single container to consecutively make the two half-moulds 7.
In accordance with embodiments not illustrated here the process described can be extended to the manufacture of wholly transparent moulds 2 also comprising more than two transparent portions 2a joined together.
As described in the following two embodiments it is also possible to manufacture a mould 2 comprising a portion 2a transparent to UV rays made using the sol-gel process described and a portion 9 which is not transparent to UV rays. This portion 9 which is not transparent to UV rays may be manufactured using conventional materials, for example metal, and may also be machined using machine tools. Advantageously, furthermore, a surface 9a of this non-transparent portion 9 facing the product which has to be shaped and polymerized may be coated with a reflecting material 10 for reasons which will be specified below.
In a further embodiment illustrated in
It is also possible to use moulds 2 obtained as described above in accordance with the process of manufacture to carry out processes having industrial applications in which it is convenient to polymerize the working material through UV rays.
In particular attention is focused on the processes of pultrusion, extrusion and moulding mentioned previously.
A non-restrictive embodiment of a pultrusion process comprises the following stages:
For the industrial application of such a pultrusion process a plurality of continuous fibres, of glass or carbon for example, is provided forming a preferably parallel bundle. These fibres are impregnated with a thermohardening resin, generally a polyester resin. Impregnation of the fibres may for example take place by causing each fibre to pass over one or more rollers impregnated with that resin. It is also possible for the bundle of fibres to be externally bounded by at least one coating layer. The coating layer must however be transparent to at least the UV rays so that polymerization of the fibres through UV rays can take place and therefore justify the use of a mould 2 which is at least partly transparent to UV rays.
The bundle of impregnated fibres is then delivered to mould 2. In particular the fibres are forcibly introduced into mould 2 by exerting a pulling force in a direction of progress.
In mould 2 the fibres converge and are coated by the coating layers if these are present, giving rise to a composite material. These may also be provided for subsequent compacting of the fibres. In addition to this means may also subsequently be used to shape or dimension the compacted composite material.
A non-restrictive embodiment of an extrusion process comprises the following stages:
Similarly to the pultrusion process, in an extrusion process a mould 2 which is at least partly transparent to UV rays manufactured as described previously is provided.
The material being extruded preferably belongs to the group comprising materials based on silicone and there is provision for the addition of a catalyst, for example a thermohardening catalyst, to polymerize the material being moulded when it is exposed to UV rays. The material which is to be extruded is also preferably present in a semi-liquid state or in any event has sufficient malleability to be plastically deformed.
Thrust means to force the material being extruded to pass through mould 2 are also provided. In this respect the mould must have a through cavity 4 shaped to plastically deform the material being extruded.
The thrust means may be provided by means of pistons or rotary screws.
A thrust in the direction of mould 2 is therefore applied to the material being extruded by the thrust means, forcing it to pass through mould 2 and imposing plastic deformation upon it.
While the material being extruded passes through mould 2 it is exposed to UV rays which activate its polymerization.
A non-restrictive embodiment of a moulding process comprises the following stages:
Similarly to the pultrusion and extrusion processes, in a moulding process a mould which is at least partly transparent to UV rays manufactured in accordance with what has been described previously is provided. The mould is constructed as at least two portions which can be joined together, of which at least one is transparent to UV rays, and defines within it a cavity 4 which can be wholly exposed to UV rays.
The material which has to be moulded preferably belongs to the group of materials based on silicone and rubbers and provision is made for the addition of a catalyst, for example a thermohardening catalyst, to polymerize the material being moulded when exposed to UV rays. The material being moulded is also preferably present in a semi-liquid state or in any event has sufficient malleability to be forced to fill the cavity present within the mould.
The process provides for insertion of the material to be moulded within cavity 4. This takes place preferably through at least one hole made in at least one portion of the mould through which it is injected under pressure within cavity 4. The material being moulded is then forced to match the shape of cavity 4.
Once injection has taken place it is then possible to polymerize the material by exposing it to UV rays while it is still in cavity 4.
Obviously the mould used may be used for the injection moulding of thermohardening materials.
In addition to this the technology mentioned above also makes possible the compression moulding of thermohardening material.
It should also be noted that inserts, for example of metal, but advantageously also of quartz, may be positioned within the mould in order to be able to obtain hollow pieces.
This invention provides major advantages.
First of all the use of moulds which are transparent to UV rays makes it possible to polymerize the material being formed by UV rays while it still lies in the mould and this appreciably reduces processing times, in particular because of the possibility of using UV rays whose polymerizing action is appreciably faster than in the case where heated moulds are used. This has the advantageous effect of substantially increasing the productivity of production plants such as, as in the examples mentioned, pultrusion, extrusion and moulding plants.
In addition to this, the material which has to be shaped and polymerized may be advantageously exposed to UV rays while it is in movement within the mould, thus bringing about the advantage of regularizing production and further increasing productivity.
A further advantage is provided by reducing the production costs of the moulds, in that the sol-gel process for the manufacture of moulds transparent to UV provides as a result moulds having a surface which is defined with high accuracy and which does not require any further machining by machine tools. Economic advantage also lies in the fact that the substantial increase in productivity also has a positive effect in a tangible reduction in costs per unit product, in particular fixed costs, including the costs of making the moulds.
These moulds are subject to shrinkage during the stages of gelling, drying and sintering, but the amount of such reduction in size is considered in advance by suitably increasing the initial dimensions of the chamber which contains the sol. The final effect is therefore that of obtaining moulds with high dimensional accuracy and high transparency and sharpness.
Finally, the manufacture of moulds by the sol-gel technique substantially reduces the mass of such moulds, solving the problems arising in logistics from heavy metal moulds.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005A002333 | Dec 2005 | IT | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2006/068139 | 11/6/2006 | WO | 00 | 7/31/2008 |
