The invention relates to a method for producing tapelike laminates, to apparatus for carrying out the method, and to uses of the apparatus.
Tapelike laminates, more particularly single-sidedly or double-sidedly adhesive tapes, are produced in accordance with the prior art by means of a method which comprises generally three component steps. In the first component step, a pressure-sensitive adhesive is applied continuously to a tapelike liner material which is moving in its longitudinal direction. Subsequently, the liner material coated with the pressure-sensitive adhesive passes, in the second component step, through a drying apparatus, in which the pressure-sensitive adhesive on the liner material is dried. In the third component step, the top face of the pressure-sensitive adhesive, facing away from the liner material, is laminated with a tapelike carrier material, the carrier material being subjected, immediately prior to lamination, to a corona treatment. The resulting three-layer laminate, comprising the tapelike carrier material, the pressure-sensitive adhesive atop it, and the liner material atop that, is subsequently rolled up into a roll. This method can also be used to produce double-sided adhesive tapes.
This known method has a number of drawbacks. First, the productivity of lines of this kind is comparatively low, since the laminating in the third component step necessitates a lower web speed than is necessary for the coating in the first component step and the drying in the second component step. The laminating is therefore the rate-determining step, and thus limits the productivity of the line for producing the adhesive tape.
Second, it is disadvantageous in certain cases if the liner material passes through the drying apparatus. The temperature prevailing in the drying unit may result in unwanted alteration or destruction of the liner material. For example, drying may result in the liner material drying out. For this reason, in the method described, only certain liner materials can be used, while other liner materials, which on the basis of their properties in the context, for example, of adhesive tapes are desirable, cannot be used. The existing method therefore limits the number of possible liner materials to those which are not deleteriously altered by the coating and drying step.
DE 101 47 036 A1 discloses a method for delaminating and laminating webs. This method uses dehesively treated carrier materials, which are laminated and delaminated, the lamination of the adhesive layer onto the dehesively treated carrier material and the delamination of the carrier material being performed without an interruption to the method.
It is an object of the invention to eliminate the drawbacks inherent in the prior art. The intention more particularly is to specify a method for producing a tapelike laminate where the rate of lamination does not determine the rate of the coating of an adhesive onto a tapelike carrier material and the drying of the laminated adhesive layer. An additional intention is to specify apparatus for carrying out the method, and uses of the apparatus.
This object is achieved by the features of the invention as described hereinbelow.
Provided in accordance with the invention is a method for producing a tapelike laminate which comprises a tapelike carrier material and, on at least one of the surfaces of the tapelike carrier material, a first adhesive layer. The method comprises the following steps:
The method of the invention separates the coating of the carrier material with the adhesive layer and its drying on the carrier layer from the lamination.
Accordingly, step (a), i.e., the coating and drying operation, on the one hand, and steps (b) to (d), i.e., the laminating operation, on the other, are performed separately from one another. With a first unit, therefore, the first adhesive layer can be laminated onto an auxiliary carrier material and then dried. The auxiliary carrier material thus coated is then wound onto a roll. The production of the coated auxiliary carrier material can therefore take place completely independently of the rate at which lamination occurs in steps (b) to (d). Through the separation of these two operations, a considerable gain in speed in the production of tapelike laminates is achieved. This achievement can be attributed to fewer holding points, due for example to the running lengths of the individual materials or to frequent bale changeovers. Furthermore, each operation can be halted and started up again as desired, independently of the other. In addition, the two operations can be separated from one another in terms both of location and of time.
Furthermore, the method of the invention avoids possible faults in the carrier material and thereby saves on costs. If a fault occurs during laminate production in the coating and drying operation and if, accordingly, the production apparatus has to be stopped, faults are formed in the as yet unfinished tapelike laminate, and have to be cut out. Accordingly, with conventional methods, sections—in some cases large—with carrier material have to be cut out and disposed of, since this material is employed in the actual coating and drying operation. With the method of the invention, in contrast, only the substantially less costly auxiliary carrier material has to be cut away.
Furthermore, the auxiliary carrier material generally has substantially longer running lengths than the carrier material, and so, with the method of the invention, in comparison to the prior art, the individual tape sections in the coating and drying operation are substantially longer, and, therefore, the production apparatus has to be stopped less often for the purpose of renewing the tape material. This increases the efficiency of the method.
The auxiliary carrier material, also referred to as in-process liner, can be re-used. This allows considerable cost savings. Since the auxiliary carrier material is not part of the end product, the carrier material which is used in the end product can be selected independently of whether it is adversely altered by the coating and subsequent drying in the coating and drying operation. In particular, drying-out of the carrier material, and the possible need for it to be re-wetted, are avoided. In the coating and drying operation, the prevailing temperatures, for example, are from 40° to 180° C., while the laminating operation can be performed at room temperature, for example. In the methods known from the prior art, in contrast to the present invention, the carrier material is exposed to the higher temperatures from the coating and drying operation, and so the requirements on the temperature stability of the carrier material are much higher. Furthermore, in the coating and drying operation, the material is subject to irradiation (e.g., EBC irradiation) and to higher mechanical loads than in the laminating operation. Consequently, in accordance with the present invention, the carrier material used can be a material which is not so resistant to radiation and to pressure as the auxiliary carrier material is. In contrast to the coating and drying operation, the laminating operation does not expose the material to any chemical changes. Overall, therefore, the carrier material can be less robust than is necessarily the case with the prior-art method.
The method of the invention can be used to produce, for example, single-sided and double-sided adhesive tapes.
The auxiliary carrier material coated with the adhesive is referred to here as the coated auxiliary carrier material. The auxiliary carrier material preferably has a nonstick coating on both sides, thereby facilitating the transfer of the adhesive layer to the tapelike carrier material.
The term “laying-on” means the laying of a material onto a roller. Where the roller already carries a first material, the laying-on of a second material laminates said second material onto the first material.
In one embodiment of the invention, the method further comprises the steps of
By means of this embodiment of the invention it is possible to produce a double-sided adhesive tape.
Steps (a) and (e), which both belong to the coating and drying operation, can be performed independently of one another before steps (b) to (f). Steps (c), (d), (g) and (f) may be performed on one laminating roller or two laminating rollers.
Advantageously, a tapelike liner material may be laminated onto the first adhesive layer subsequently to step (d). This lamination may take place, for example, on the first laminating roller.
In a likewise preferred embodiment of the invention, especially for producing a double-sided adhesive tape,
Alternatively, in a further preferred embodiment, a double-sided adhesive tape can be produced as follows:
In a further preferred embodiment of the invention for producing a double-sided adhesive tape,
It is possible, furthermore, to subdivide the laminating operation into two method sections, in order to simplify the method conditions. In this case the following is possible:
Alternatively, the following is possible:
The tapelike carrier material is preferably subjected to a corona treatment prior to its lamination. The first adhesive layer and the second adhesive layer may be identical or different. Likewise, the first auxiliary carrier material and the second auxiliary carrier material may be identical or different.
Further provided in accordance with the invention is apparatus for producing a tapelike laminate. The apparatus comprises an accommodating device for the first roll, from which the coated first auxiliary carrier material is unwound; a laminating roller; a lay-on roller for laying the tapelike carrier material and the coated first auxiliary carrier material onto the laminating roller; and a first delaminating device for delaminating the first auxiliary carrier material from the first adhesive layer.
Where a double-sided adhesive tape is to be produced, the apparatus advantageously further comprises an accommodating device for the second roll, from which the coated second auxiliary carrier material is unwound; a lay-on roller for laying-on the coated second auxiliary carrier material; and a second delaminating device for delaminating the second auxiliary carrier material from the second adhesive layer.
Irrespective of whether a single-sided or double-sided adhesive tape is to be produced, there ought to be a lay-on roller for laying-on the liner material.
The delaminating devices may be a roller, more particularly having radii in the range from 5 mm to 100 mm and more preferably in the range from 10 mm to 50 mm, or a rounded wedge, in particular with rounding radii of 1 mm up to a radius equal to that of the roller, and more preferably with radii of 5 mm to 30 mm.
The lay-on rollers are in contact with the laminating roller, specifically in such a way that the axes of the rollers are disposed in parallel, with the disposition of the lay-on rollers being limited by the disposition of the other rollers, those in contact with the laminating roller. Nip adjustment between a lay-on roller and the laminating roller ought to be variable, and lamination can take place with linear pressures of 0 N/mm to 50 N/mm, more preferably with linear pressures of 2 N/mm to 10 N/mm.
Roller pairs provided in accordance with the invention consist of two mutually opposing rollers, in which case nip adjustment ought to be variable, and lamination can take place with linear pressures of 0 to 50 N/mm, more preferably with linear pressures of 2 to 10 N/mm.
All rollers can be cooled or heated in a preferred range from −40° C. to 200° C. with oil, water, steam, electrically, or with other temperature-conditioning media; furthermore, the roller surfaces are of steel, stainless steel, chromium-plated steel, dehesively treated steel or stainless steel, or elastic or elastically dehesively treated material having a Shore hardness (A) of 20 to 100, more particularly having a Shore hardness (A) of 60 to 80. The elastic roller covering may be composed preferably of EPDM, VITON, silicone rubber or dehesively treated EPDM, VITON or silicone rubber.
Examples of tapelike carrier material that can be used include nonwovens, papers, oriented PP, HDPE, LDPE, PVC, and PET films, and foams (e.g., PE foams or PVA foams) and woven fabrics, this recitation not being exhaustive. The carrier material is preferably of tear-sensitive and stretch-sensitive design.
As auxiliary carrier material it is preferred to use carrier materials with a nonstick coating on one or both sides, examples being paper, especially coated paper, such as PE paper, and oriented PP, HDPE, LDPE, PVC, MOPP, BOPP, PEN, PMP, PA, and PET films. Particular preference is given to silicone-coated carrier materials and also to carrier materials having silicone-free release layers such as paraffin, Teflon or waxes, for example. Composite materials, such as PET/aluminum sheet, can also be used. The auxiliary carrier material is advantageously designed to have wet strength.
Where the tapelike carrier material, the first auxiliary carrier material and/or the second auxiliary carrier material are composed of paper, the paper preferably has a basis weight of 40 g/m2 to 200 g/m2.
Where the first auxiliary carrier material and/or the second auxiliary carrier material are composed of oriented polypropylene (PP), the latter has a thickness preferably of 40 to 200 μm, preferably 75 to 125 μm. Where the auxiliary carrier materials are composed of polyester carrier webs (PET), they preferably have a thickness of 20 to 200 μm, more preferably 40 to 80 μm. The carrier material, in contrast, may preferably be given a thinner design, with a thickness, for example, of 5 to 50 μm, more particularly 6 to 15 μm. This is made possible by the fact that the carrier material is not exposed to any chemical alterations and is exposed to lower mechanical loads than the auxiliary carrier material.
Preference is given to using double-sidedly and single-sidedly silicone-coated auxiliary carrier materials having release forces, measured in accordance with BDF Test Method JOPMH003, test tape tesa 7475, of between 1 to 60 cN/cm, test tape tesa 7476, between 3 to 100 cN/cm, more preferably with release forces of less than 20 cN/cm, test tape tesa 7475, and less than 30 cN/cm, test tape tesa 7476.
Liner material used may be, for example, siliconized paper, film, e.g., MOPP, PET or PE film, or coated paper.
As adhesive for producing the adhesive layer, it is possible to use not only adhesives based on solvent-containing natural rubber adhesives and acrylate adhesives, but also solvent-free adhesives. An example of solvent-containing adhesives are adhesives based on styrene-isoprene-styrene block copolymers.
The amount of adhesive applied to the carrier material is preferably 15 to 150 g/m2. In a further preferred embodiment, a coatweight of 20 to 90 g/m2 is set.
The coating and drying operation may take place in accordance with known methods. An overview of typical production methods is found, for example, in “Coating Equipment”, Donatas Satas, in Handbook of Pressure Sensitive Adhesives Technology, second edition, edited by Donatas Satas, Van Nostrand Reinhold New York pp. 767-808. The known methods for drying and slitting the adhesive tapes can likewise be found in the Handbook of Pressure Sensitive Adhesive Technology, pages 809-874.
A suitable adhesives is an acrylate hotmelt-based adhesive having a K value of at least 20, more particularly greater than 30 (measured in each case in 1% strength by weight solution in toluene, 25° C.), obtainable by concentrating a solution of such a composition to form a system which can be processed as a hotmelt. An adhesive of this kind is set out in DE 43 13 008 C2. In an intermediate step, the solvent is removed entirely from these acrylate compositions produced in this way.
In the acrylate hotmelt-based adhesive, benzoin derivatives may be copolymerized, examples being benzoin acrylate or benzoin methacrylate, acrylic esters or methacrylic esters. Benzoin derivatives of this kind are described in EP 0 578 151 A.
The acrylate hotmelt-based adhesive may be UV-crosslinked. Other types of crosslinking, however, are also possible, an example being electron beam crosslinking.
One particularly preferred embodiment uses, as self-adhesives, copolymers of (meth)acrylic acid and the esters thereof having 1 to 25 C atoms, maleic, fumaric and/or itaconic acid and/or their esters, substituted (meth)acrylamides, maleic anhydride, and other vinyl compounds, such as vinyl esters, more particularly vinyl acetate, vinyl alcohols and/or vinyl ethers. The residual solvent content ought to be below 1% by weight.
It is additionally possible to use an adhesive composed of the group of natural rubbers or synthetic rubbers or of any desired blend of natural rubbers and/or synthetic rubbers, it being possible in principle to select the natural rubber or rubbers from all available grades such as, for example, crepe, RSS, ADS, TSR or CV products, depending on required level of purity and of viscosity, and to select the synthetic rubber or rubbers from the group of randomly copolymerized styrene-butadiene rubbers (SBR), butadiene rubbers (BR), synthetic polyisoprenes (IR), butyl rubbers (IIR), halogenated butyl rubbers (XIIR), acrylate rubbers (ACM), ethylene-vinyl acetate copolymers (EVA), and polyurethanes and/or blends thereof.
With further preference, thermoplastic elastomers may be added to the rubbers for the purpose of improving the processing properties, with a weight fraction of 10% to 50% by weight, based on the total elastomer fraction.
Representatives that may be mentioned at this point include in particular the especially compatible styrene-isoprene-styrene (SIS) and styrene-butadiene-styrene (SBS) types.
Tackifying resins which can be used include, without exception, all tackifier resins that are already known and are described in the literature. As representatives, mention may be made of rosins, their disproportionated, hydrogenated, polymerized, and esterified derivatives and salts, the aliphatic and aromatic hydrocarbon resins, terpene resins and terpene-phenolic resins. Any desired combinations of these and further resins may be used in order to adjust the properties of the resultant adhesive in accordance with requirements. Reference may be made expressly to the depiction of the state of the art in “Handbook of Pressure Sensitive Adhesive Technologies” by Donatas Satas (von Nostrand, 1989).
The invention is illustrated below with reference to embodiments, referring to the drawings. In those drawings
In principle, the production of the coated first auxiliary carrier material 9 is the same as that of the coated second auxiliary carrier material 10; the materials used, like a material of the auxiliary carrier material and the material of the adhesive layer, and also the method of conditions, may vary.
According to
The tapelike carrier material 12 coated with the first adhesive layer is guided, on the first laminating roller, to a second lay-on roller 17. By means of this lay-on roller 17, the liner material 18, which is unwound from a stock roll 19, is laminated onto the first adhesive layer.
The resulting laminate precursor 21, which has the layer construction tapelike carrier material/first adhesive layer/liner material, is then guided from the first laminating roller 14 to the second laminating roller 20, the liner material 18 now facing the second laminating roller. The second laminating roller 20 and the first laminating roller 14 are disposed in parallel to one another at the same height.
Following the second laminating roller 20 now, in web direction, is the third lay-on roller 22, which laminates the coded second auxiliary carrier material 10 onto that surface of the tapelike carrier material that does not bear the first adhesive layer. The second adhesive layer of the coated second auxiliary carrier material is facing the tapelike carrier material 12. The coated second auxiliary carrier material 10 is unwound from a stock roll 8″. There then follows, in web direction, the second delaminating roller 23, which delaminates the auxiliary carrier material 2″ from the second adhesive layer. The second adhesive layer remains on the tapelike carrier material and is guided on together with it, while the delaminated second auxiliary carrier material 2″ is wound up onto a further stock roll 1″ and can be supplied again to the coating and drying operation (
Following in web direction is the second lay-on roller 33, which laminates the coated second auxiliary carrier material 10 onto that surface of the tapelike carrier material 12 that does not bear the first adhesive layer. Here, the second adhesive layer of the coated second auxiliary carrier material 10 is facing the tapelike carrier material 12. The coated second auxiliary carrier material 10 is unwound from a stock roll 8″. There follows in web direction the first delaminating roller 23, which delaminates the auxiliary carrier material 2″ from the second adhesive layer. The second adhesive layer remains on the tapelike carrier material 12 and is guided on together with it, while the delaminated second auxiliary carrier material 2″ is wound onto a further stock roll 1″ and can be supplied again to the coating and drying operation (
The laminate precursor, with the construction first auxiliary carrier material/first adhesive layer/tapelike carrier material/second adhesive layer/liner material, is guided on the laminating roller 31 to a third lay-on roller 35. By means of this lay-on roller 35, the liner material 18, which is unwound from a stock roll 19, is laminated onto the second adhesive layer.
Following in web direction is the second delaminating roller 36, which delaminates the auxiliary carrier material 2 from the first adhesive layer. The adhesive layer remains on the tapelike carrier material 12 and is guided on together with it, while the delaminated first auxiliary carrier material 2 is wound up on a further stock roll 1′ and can be supplied again to the coating and drying operation (
The resulting laminate 21 has the construction first adhesive layer/tapelike carrier material/second adhesive layer/liner material, and constitutes the completed tapelike laminate, i.e., the laminate end product 24, which is wound onto a stock roll 25.
There follows in web direction a first delaminating device, consisting of a roller pair 44, 45, which is used to delaminate the first auxiliary carrier material 2 from the first pressure-sensitive adhesive. This is followed by a third roller pair 46, 47, which laminates the liner material 18 onto the first adhesive layer. At the last roller pair 48, 49 in web direction, i.e., at the second delaminating device, the remaining second auxiliary carrier material 2″ is delaminated. The resulting laminate has the construction liner material/first adhesive layer/tapelike carrier material/second adhesive layer, and constitutes the completed tapelike laminate, i.e., the laminate end product 24, which is wound up onto a stock roll 25.
The resulting laminate precursor, with the layer construction tapelike carrier material/first adhesive layer/first auxiliary carrier material, is then supplied to a laminating roller 52, where a lay-on roller 53 laminates the coated second auxiliary carrier material 10 onto that surface of the tapelike carrier material 1 that does not bear the first adhesive layer, specifically in such a way that the second adhesive layer is facing the tapelike carrier material 12. Following the laminating roller 52 in web direction is a first delaminating roller 54, which delaminates the second auxiliary carrier material from the second adhesive layer. The remaining laminate precursor 55 has the construction first auxiliary carrier material/first adhesive layer/tapelike carrier material/second adhesive layer, and is wound up onto a stock roll 56.
In the second method section, which is shown in
In the second method section, shown in
For this purpose, instead of the stock roll 11 used in the first method section, the stock roll 56 is charged with the laminate precursor 55. The roller pair 50, 51 laminates the coated second auxiliary carrier material (which in this case is the same as the coated first auxiliary carrier material 9) onto the laminate precursor 55, specifically in such a way that the second adhesive layer is facing the tapelike carrier material 12. The coated second auxiliary carrier material 10 is unwound from a stock roll 8″, which has been loaded in place of the stock roll 8. Since, in this case, the coated second auxiliary carrier material 10 is the same as the coated first auxiliary carrier material 9, however, there is no need for the stock rolls to be replaced.
The resulting laminate precursor, with the layer construction second auxiliary carrier material/second adhesive layer/tapelike carrier material/first adhesive layer/liner material, is then supplied to the laminating roller 52, where, by means of the delaminating roller 54, the second auxiliary carrier material 2″ is delaminated from the second adhesive layer and wound onto the stock roll 1″, which has been loaded in place of the stock roll 1′, although in this case there is no need for this on account of the two coated auxiliary carrier materials being the same. The laminate obtained has the construction first adhesive layer/tapelike carrier material/second adhesive layer/liner material, and constitutes the completed tapelike laminate, i.e., the laminate end product 24, which is wound onto a stock roll 25.
In the second method section, which is shown in
The tapelike carrier material 12 coated with the first adhesive layer is guided on the first laminating roller 70 to a second lay-on roller 73. This lay-on roller 73 laminates the liner material 18, which is unwound from a stock roll 19, onto the first adhesive layer.
The resulting laminate precursor 21, which has the layer construction tapelike carrier material/first adhesive layer/liner material, is then guided from the first laminating roller 70 to the second laminating roller 74. There, the laminate precursor 21 is made by means of a third lay-on roller 75 onto the coated second auxiliary carrier material 10, which is supplied simultaneously to the third lay-on roller 75; the coated second auxiliary carrier material 10 is facing the second laminating roller 74, and the second adhesive layer is facing away from the second laminating roller 74 and is facing the tapelike carrier material 12 of the laminate precursor 21. The second laminating roller 74 and the first laminating roller 70 are disposed parallel to one another but at different heights—specifically, laminating roller 70 above laminating roller 74.
The second laminating roller 20 is then followed in web direction by the second delaminating roller 76, which delaminates the auxiliary carrier material 2″ from the second adhesive layer. The second adhesive layer remains on the tapelike carrier material 12 and is guided on together with it, while the delaminated second auxiliary carrier material 2″ is wound onto a further stock roll 1″ and can be supplied again to the coating and drying operation (
The double-sided adhesive tape is produced starting from a PET film carrier material 12 μm thick. For effective adhesive anchorage, the PET film is first corona-pretreated on both sides. Then a roller pair laminates a first auxiliary carrier material onto the carrier material. The auxiliary carrier material used is a double-sidedly siliconized MOPP film in a thickness of 100 μm, which has been coated on one side with an adhesive in a thickness of 100 g/m2. In a further step, a second auxiliary carrier material, which is identical to the first auxiliary carrier material, is laminated onto the other side of the carrier material. Thereafter, using a further roller pair, the first auxiliary carrier material is delaminated from the first pressure-sensitive adhesive, and then a liner material is laminated onto the delaminated side. For the liner material, a siliconized MOPP film in 80 μm thickness is used. In a last step, then, a further roller pair delaminates the second auxiliary carrier material, and at the same time the laminate obtained (double-sided adhesive tape) is wound onto a stock roll.
1 Stock roll for auxiliary carrier material 2
2 First auxiliary carrier material
2″ Second auxiliary carrier material
3 Adhesive
4 Adhesive layer
5, 6 Roller pair
7 Dryer
8 Stock roll for the coated first auxiliary carrier material 9
8″ Stock roll for the coated second auxiliary carrier material 10
9 Coated first auxiliary carrier material
10 Coated second auxiliary carrier material
11 Stock roll for the tapelike carrier material
12 Tapelike carrier material
13 Corona treatment
14 First laminating roller
15 First lay-on roller
16 First delaminating roller
17 Second lay-on roller
18 Liner material
19 Stock roll for the liner material
20 Second laminating roller
21 Laminate precursor
22 Third lay-on roller
23 Second delaminating roller
24 Laminate end product
25 Stock roll for the laminate end product
31 Laminating roller
32 First lay-on roller
33 Second lay-on roller
34 First delaminating roller
35 Third lay-on roller
36 Second delaminating roller
40, 41 First roller pair
42, 43 Second roller pair
44, 45 First delaminating device
46, 47 Third roller pair
48, 49 Second delaminating device
50, 51 Roller pair
52 Laminating roller
53 Lay-on roller
54 Delaminating roller
55 Laminate precursor
56 Stock roll for the laminate precursor
60 Laminating roller
61 First lay-on roller
62 Delaminating roller
63 Second lay-on roller
70 First laminating roller
71 First lay-on roller
72 First delaminating roller
73 Second lay-on roller
74 Second laminating roller
75 Third lay-on roller
76 Second delaminating roller
T Tapelike carrier material 1
PL Auxiliary carrier material 2, 2″ (=in-process liner)
PL1 First auxiliary carrier material 2 (=in-process liner without adhesive layer)
PL1+MaS Coated first auxiliary carrier material 9 (=in-process liner coated with first adhesive layer)
PL2 Second auxiliary carrier material 2″ (=in-process liner without adhesive layer)
PL2+MaS Coated second auxiliary carrier material 20 (=in-process liner coated with second adhesive layer)
E Liner material 18 (=end-customer liner)
tesa Tapelike laminate (=laminate end product)
K Laminating point (K1=laminating point 1, K2=laminating point 2, etc.)
D Delaminating point (D1=delaminating point 1, D2=delaminating point 2, etc.)
Number | Date | Country | Kind |
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10 2008 038 595.6 | Aug 2008 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP2009/060095 | 8/4/2009 | WO | 00 | 1/11/2011 |