EP1989333A1 - Process and apparatus for applying a coating to at least one side of a leather and coated leather produced by such a process - Google Patents
Process and apparatus for applying a coating to at least one side of a leather and coated leather produced by such a processInfo
- Publication number
- EP1989333A1 EP1989333A1 EP06723413A EP06723413A EP1989333A1 EP 1989333 A1 EP1989333 A1 EP 1989333A1 EP 06723413 A EP06723413 A EP 06723413A EP 06723413 A EP06723413 A EP 06723413A EP 1989333 A1 EP1989333 A1 EP 1989333A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- leather
- plastic dispersion
- superheated steam
- compact particles
- solidified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
Definitions
- the invention relates to a method and a device for applying a coating, preferably a base coat, to at least one, optionally on both, sides of a leather, namely on the grain side and / or on that side of the scar opposite side of a grain leather, or on a or both sides of a split leather, and a leather produced by such a process and provided with a coating, preferably a base coat.
- a coating preferably a base coat
- a blowing agent-containing compact particles from which microballoons are subsequently formed by application of pressure and heat in the solidified plastic dispersion.
- a foam coating which consists of a hollow microspheres containing solidified plastic dispersion.
- AT 005281 U1 discloses a leather in which the thick foam coating provided on the backside is formed from an aqueous plastic dispersion which, when applied, contains both finished hollow microspheres and compact particles from which hollow microspheres are formed by supplying heat.
- This thick foam coating has a cushioning function, it has more than 10% open cells, and can not be used as a base coat.
- a leather and a method for producing the same has become known, in which the visible side of the opposite rear side of the leather is provided with a foam, which is formed by solidification of a liquid applied, finished hollow microspheres containing plastic material by brief exposure to hot air ,
- the hot air in this case has a temperature of more than 280 0 C, preferably a temperature between 350 ° C and 650 ° C, is thus very hot and dry, which causes the leather, the natural moisture is removed, and that it shrinks and hardens.
- the hollow microspheres become at the top of the foam equipment -
- DE 20318311 U1 discloses a full-grain leather in which defects in the grain layer are corrected by a plastic filling compound, which consists of a
- the grain layer of the leather must be sanded so deep until the entire surface is flat, whereby the quality of the leather is impaired and this significantly loses value.
- the temperature increase required for expanding the o compact particles to form the hollow microspheres does not take place with an economically justifiable application of pressure and heat, so that this lower region has no or only a small number of hollow microspheres. If higher temperatures are used over a relatively long period of time, although hollow microspheres are formed in this region, the leather is even more compacted, resulting in further hardening.
- sicti fully restores the loosening effect.
- the object of the present invention is to avoid the disadvantages of known leather provided with a foam coating and to provide a leather which has a foam coating applied to at least one, optionally applied on both sides, which can be produced in an economical manner which prevents shrinkage and hardening in the formation of the foam coating and in which defects on the upper side of the leather can be eliminated without any existing grain structure being damaged by reworking the upper side.
- Femer it is an object of the invention to provide a leather to which the Losnarbtechnik, which is always present in soft full-grain cowhide, especially in the abdomen, eliminated or at least significantly reduced, and which is provided with a primer coating firmly with the full grain side of the leather is connected, and having a surface on which can be easily applied by any method finishing layers, these finishing layers with the base coating form a close and firm connection.
- the hollow microspheres are formed by the compact dispersion containing plastic dispersion is subjected after its solidification to the action of relaxed superheated steam at a temperature between 80 ° C and 100 0 C.
- the pressure acting on the plastic dispersion in this case is preferably less than 0.1 bar. Optimum values are achieved when the superheated steam is in a period of less than 7
- Seconds preferably less than 3 seconds, on the solidified
- Compact particles without affecting the properties of the leather, cause moisture not to be deprived of moisture to the leather in this operation, but rather to be supplied, thereby preventing hardening and shrinkage of the leather.
- the hot steam exerts in addition to its 5 heat effect as a steam also caused by the moisture softening effect on the solidified plastic dispersion, whereby the hollow microspheres can form in this quickly and optimally and destruction of the shell of the same is avoided.
- the hollow microspheres thus formed are also better than those formed by the application of pressure and heat, by infrared radiation or ⁇ hot air treatment in the known method, and are not destroyed, especially in an application of superheated steam.
- thermoplastic and / or thermoelastic plastic dispersions which contain a propellant comprising compact particles.
- These compact particles consist in known manner of a thermoplastic or plastic copolymer, preferably of polyvinylidene chloride copolymer, containing as propellant, for example, isobutane, and 5 have a size of less than 20 // m, preferably less than 10 microns.
- plastic dispersion which preferably contains a wetting agent and / or density-increasing additives, such as barite, they penetrate easily into the depressions on the leather surface.
- soft plastic dispersions having a hardness of less than 70 Shore A, which are softened by the action of superheated steam.
- the preferred viscosity of the plastic dispersion in particular when applied to the leather with a spray device or by so-called plush, is in the range between 5 seconds and 15 seconds, measured in a Ford cup with a nozzle diameter of 6 mm.
- the viscosity is between 10 and 40 seconds measured in the Ford cup with 6 mm diameter.
- the applied superheated steam acts on such compact particles in addition to his
- a significant advantage of using the method according to the invention is that the leather for the formation of the hollow microspheres from the compact particles must be subjected to no pressure load, so maintains its original thickness, so that a complete filling of wells in the leather surface is ensured and to achieve a flat Surface post-processing by partial removal of the scar layer is required.
- the use of the method according to the invention also entails the economic advantage that most leather factories in any case have high-pressure steam generators and are therefore able to produce low-pressure steam.
- aqueous, containing a blowing agent containing compact particles, plastic dispersion is applied.
- the application takes place here in thin layers between 0.015 mm and 0.08 mm, either via rollers that rotate in the opposite direction to the transport direction of the leather, or preferably by spraying, because then the thin plastic dispersion better even in fine depressions from the leather surface starting deep in the leather penetrates.
- the application can also be done manually, e.g. by the so-called plush.
- the low-viscosity plastic dispersion penetrates particularly deeply into the finest pinholes.
- this superheated steam supply device has at least one superheated steam line with outlet nozzles or slots directed against the solidified plastic dispersion, from which the superheated steam is sprayed onto the solidified plastic dispersion.
- the hot steam line preferably consists of a tube with a round or rectangular cross section, in which the outlet nozzles or slots are provided, and which is connected to a superheated steam source. It turned out to be J proven advantageous if this tube is formed meander-shaped, wherein the individual
- the hot steam supply device consists of a transport device enclosing hot steam tank
- the superheated steam is supplied via a superheated steam source, so that on the conveyor located, provided with the solidified plastic dispersion leather during the further movement in this hot steam tank with the is acted upon in this superheated steam.
- the superheated steam supply device of a provided with the applied plastic dispersion leather supporting, circulating transport device is arranged adjacent, so that the moving past the superheated steam supply leather is continuously supplied with the superheated steam.
- the transport device preferably consists of a plurality of spaced, parallel, circumferential plastic threads, such as polyamide or polyester threads. These threads are heat resistant, are not destroyed by the hot steam, in contrast to the use of o hot air and infrared radiation, and cause a good support of the leather.
- this arrangement has the advantage that spaces between the threads are kept free, so that it is possible not only the top of the solidified plastic dispersion, but also on the underside, thus supply from all sides, heat through the interstices to the leather 5 passes.
- This transport device is advantageous above all when the hot steam supply device, as mentioned, consists of a hot steam container enclosing the transport device.
- a separate superheated steam supply device which is arranged below the transport device, to be provided, via which heat is supplied to the aqueous plastic dispersion having the compact particles through the leather.
- a warm air duct enclosing the transport device 5 in which the warm air can also get through the spaces between the plastic threads to the leather
- the leather produced by the process according to the invention is characterized characterized in that the superheated steam treated coating has on its surface a homogeneous, nubuck-like, recess-free appearance, such as finely grained grain leather, even having a slight nubuck writing performance, and microscopically the finest pores having an inside diameter of less than 35 has ⁇ m.
- a leather despite its softness is not or almost not losnarbig.
- a finish coat is applied to a basecoat prepared by the methods of the present invention, this leather exhibits an optimum appearance because many small wrinkles are formed during swaging which have the appearance of high-grade full-grain aniline leather.
- the superheated steam treatment also improves the adhesion of the base coat to the leather and, due to the nubuck-like appearance of the surface of the base coat, a subsequently applied finish coat can also be mechanically anchored.
- the thin, consolidated base coat increases in volume after hot steam treatment by more than 15%, preferably more than 25%.
- depressions in the leather surface are filled flat or slightly raised.
- the nubuck-like surface structure is preferably present over the entire surface or almost completely over the leather surface. Since in the coating predominantly closed cells formed by the hollow microspheres are present, such a leather is particularly suitable for the production of automotive components, in which the leather is drawn into molds and optionally backfoamed.
- Fig. 1 shows the principle of the device according to the invention and Fig. 2 shows schematically an embodiment of this device.
- Fig. 3 a particular embodiment of the hot steam supply device according to the invention is shown.
- Fig. 4 shows a further embodiment of the device according to the invention.
- Fig. 5 shows a section through a leather, in which defects forming depressions in the grain layer were removed by a known method, and Fig. 6 such a leather whose grain layer with the inventive Procedure was treated.
- Fig. 7 shows in section also a leather whose grain layer has been treated by the method according to the invention.
- a leather 3 is supported on the in a manner not shown, known per se, for example by spraying or by roller application, preferably by a counter to the
- Transport direction 1 rotating applicator roll an aqueous, compact particles containing plastic dispersion 4 was applied, which was solidified by supplying heat, for example by means of hot air.
- the transport device 2 is made Here it is expedient from a plurality of spaced, parallel polyamide or polyester threads between which spaces are kept free. These threads are shown enlarged in the drawing. In practice, its diameter is less than 4 mm.
- a hot steam source hot steam supply means consisting of tubes 5 of any cross-section, which are provided with outlet nozzles or slots 6, from which relaxed superheated steam with little or no pressure Direction to the solidified plastic dispersion 4 emerges.
- the number of tubes 5 arranged one behind the other in the direction of transport 1 depends on the transport speed of the leather 3 and must be selected such that pressurization of the solidified plastic dispersion with relaxed superheated steam is ensured in the short time required for the formation of the hollow microspheres.
- the distance between the outlet nozzles or slots 6 and the solidified o plastic dispersion 4 must be selected so that the hot steam at a temperature of at least 80 0 C impinges on the plastic dispersion.
- hot air drying ducts 9, 10 are provided, in which over the spaces between the polyamide or polyester threads and the bottom 5 of the leather 3 warm air can be supplied.
- the solidification of the plastic dispersion 4 applied to the leather 3 takes place before the formation of the hollow microspheres 7 from the compact particles takes place in the region of the tubes 5; in the hot air drying channel 10, the coating already having a foam structure takes place.
- a hot steam tank 5 ' is provided, which has the transport device 2 directed outlet nozzles or slots 6'.
- the hot steam tank 5 1 is connected to a superheated steam source, so that emerges via the outlet nozzles or slots 6 'superheated steam, which passes over the spaces between the plastic threads to the leather 3 5, so that on the passing through this leather superheated steam formation of the hollow microspheres in the the solidified plastic dispersion filled recesses of the grain layer takes place and the solidified plastic dispersion also of the bottom is foamed.
- Plastic dispersion arranged tubes 5 also a hot steam tank 5 'may be provided, in addition to the hot steam tank 5 1 below the transport device 1 or without such a hot steam tank below the
- Fig. 3 shows an embodiment in which the tubes 5 of the hot steam supply means are arranged meandering and connected at both ends with a superheated steam source 16 such that the superheated steam continuously circulates in the tubes 5 and undergoes no cooling, so that exposure to superheated steam at a constant temperature takes place because the condensed water is converted back into steam.
- the individual pipe sections in this case run transversely to the transport direction.
- Fig. 4 shows a construction according to the invention, wherein the
- Transport device 2 passes through a hot steam tank 17, which with a
- Hot steam source is connected, or in which the steam is generated from demineralized water, so that the superheated steam evenly around the leather with the solidified plastic dispersion thereon.
- the spaces between the plastic threads allow this access of the superheated steam on the underside of the leather.
- the method according to the invention also makes it possible to apply a coating to both sides of a leather, for example for the purpose of correcting defects on the grain side of a grain leather and for attaching foam equipment to the back side opposite this grain side.
- an aqueous, compact particles-containing plastic dispersion is first applied to one side and then to the other side of the leather and allowed to solidify completely, whereupon both sides, preferably simultaneously, can be subjected to the action of relaxed superheated steam.
- hot steam supply means or it is an arrangement of FIG. 4 is used, so that the formation of the hollow microspheres of the compact particles in the existing on both sides of the leather solidified plastic dispersion takes place simultaneously ,
- Fig. 5 shows in cross section a leather with a leather layer 11 and a
- Scar layer 12 which has recesses 13 formed defects.
- these recesses 13 are filled by a solidified plastic dispersion 14, which Contains hollow microspheres.
- These hollow microspheres are formed by compact particles contained in the plastic dispersion by application of pressure and heat.
- the leather layer 11 is compressed, but the leather turns back after pressure relief due to its compressive elasticity, whereas the present in the wells 13 solidified plastic dispersion 14 does not change its volume. For this reason, as is apparent from Fig.
- the wells 13 in the grain layer 12 are not completely filled when using known methods after pressure relief, so that it is necessary to achieve a flat surface, the grain layer 12 to the level of solidified, in grind the plastic dispersion 14 located in the recesses. This will damage the scar layer and significantly reduce the quality of the leather.
- a leather 11 is shown with so-called Pinhols 18 shown in cross section, which extend through the grain layer 12 into the leather layer 11 and partially penetrate this leather layer 11 even completely.
- Pinholes 18 are common and depending on the existing number of pinholes, which have a diameter between 0.3 mm and 1, 5 mm, the dermis is inferior to worthless.
- a plastic dispersion is preferably sec with a viscosity of less than 10 as measured in a Ford cup with a nozzle diameter of 6 mm, with a Quersprüh adopted, preferably airless, under pressure as the grain layer 12 of the Leather sprayed,
- the plastic dispersion with the heavy compact particles therein penetrates into the pinholes 18.
- the density of the compact particles is more than 1.2 g / cm 3 and is thus always higher than the density of the plastic, which represents the discontinuous phase of the dispersion.
- the manual plush can also be used to fill in the pinholes.
- Micro hollow spheres unfold optimally in the solidified, under the influence of hot steam softened plastic dispersion.
- the advantages of the invention are also clarified by sanding off the full grain side of leathers, either to achieve a better anchorage of finish 5, or to eliminate defective pits in the surface. Both result in a significant loss of value, because the leather thus produced may not be offered as full-grain leather.
- scarf defects are cured with the foamed base coating and a surface is created which looks like the finely grained grain side of a leather, but at full or near full preservation of the true grain layer.
- the base coat forms the basis for leather with a fine textured or smooth surface.
- Leather with a basecoat produced according to the invention are particularly suitable for the application of an indirect method for forming a finish coat 5 on the base coat, in which process the thin finish coat preferably having a fine-grained surface is first prepared separately on a patterned backing and then adhesively bonded to the nubuck-type primer coat is connected.
- the hot steam is applied directly to the solidified plastic dispersion, for example via steam outlet nozzles or slots depressurized or almost without pressure, wherein the hollow microspheres can form from the compact particles.
- Plastic dispersion is subjected to a short heat treatment, such that forms from the thin water application in less than 25 sec hot steam.
- the leather, especially on its flesh side, moistened shortly before with a more than 90 0 C hot metal plate without pressure or with very low pressure of a maximum of 1 kg / cm 2 are brought into contact or transported through a heated roller.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0012606U AT8974U1 (en) | 2006-02-20 | 2006-02-20 | METHOD AND DEVICE FOR APPLYING A COATING ON AT LEAST ONE PAGE OF A LEATHER, AND COATED LEATHER PRODUCED BY SUCH A METHOD |
PCT/EP2006/002335 WO2007095970A1 (en) | 2006-02-20 | 2006-03-14 | Process and apparatus for applying a coating to at least one side of a leather and coated leather produced by such a process |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1989333A1 true EP1989333A1 (en) | 2008-11-12 |
EP1989333B1 EP1989333B1 (en) | 2010-01-27 |
Family
ID=36600046
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06723413A Not-in-force EP1989333B1 (en) | 2006-02-20 | 2006-03-14 | Process and apparatus for applying a coating to at least one side of a leather and coated leather produced by such a process |
Country Status (11)
Country | Link |
---|---|
US (1) | US8697232B2 (en) |
EP (1) | EP1989333B1 (en) |
KR (1) | KR101168470B1 (en) |
CN (1) | CN101379198B (en) |
AR (1) | AR059582A1 (en) |
AT (2) | AT8974U1 (en) |
BR (1) | BRPI0621357A2 (en) |
DE (2) | DE502006006066D1 (en) |
MX (1) | MX2008010683A (en) |
WO (1) | WO2007095970A1 (en) |
ZA (1) | ZA200806892B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006039261A1 (en) * | 2006-08-22 | 2008-03-06 | Lanxess Deutschland Gmbh | Dressed leather |
US20090205142A1 (en) | 2006-10-11 | 2009-08-20 | Vorlaender Otto | Process for Retanning Leather Using Hollow Microspheres |
DE102007011555A1 (en) | 2007-03-09 | 2008-09-11 | Lanxess Deutschland Gmbh | Retanning leather, useful in e.g. auto and glove, comprises treating tanned leather in aqueous liquor in the presence of hollow micro spheres filled with blowing agent, drying the obtained leather and treating with infrared radiation |
KR101360376B1 (en) | 2013-07-19 | 2014-02-21 | 홍종희 | Leather having printing layer on flesh side and method of printing on flesh side of leather |
CN104307710B (en) * | 2014-09-22 | 2016-06-08 | 浙江西雅普康大制革有限公司 | Bubble removing equipment and control method thereof for synthetic leather processing |
JP6507587B2 (en) * | 2014-11-18 | 2019-05-08 | 凸版印刷株式会社 | Coating method and method of producing foam wallpaper |
KR102139536B1 (en) * | 2019-05-10 | 2020-07-29 | 주식회사 노비아레텍 | Method of manufacturing a expandable grain leather with the light weight |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2247320A1 (en) * | 1972-09-27 | 1974-03-28 | Hans F Arendt | UNIVERSAL MACHINE FOR THE CONTINUOUS EQUIPMENT OF TEXTILE, SYNTHETIC LEATHER AND SIMILAR. RAILWAYS |
IT1006448B (en) * | 1974-04-12 | 1976-09-30 | Schaefer H | FLAT BODIES IN LEATHER OR LEATHER-LIKE WITH EXPANDED COATING OF WATER DISPERSIONS OF PLASTIC MATERIAL AND PROCESS FOR PREPARING THEM |
DE3229150C2 (en) * | 1982-08-04 | 1986-04-10 | Helmut 6780 Pirmasens Schaefer | Method and device for dressing split leather |
ES2000118T3 (en) * | 1986-03-15 | 1992-05-16 | J. H. Benecke Ag | NUBUK TYPE SUBSTRATE OR VELVET LEATHER OR TEXTILE VELVET AS WELL AS A MANUFACTURING PROCEDURE. |
GB8802745D0 (en) * | 1988-02-06 | 1988-03-09 | Raymond Wilson Ltd | Leather treatment |
JPH04168200A (en) * | 1990-10-30 | 1992-06-16 | Henkel Hakusui Kk | Flexible filler for leather |
DE19718772B4 (en) * | 1997-05-03 | 2015-08-20 | Dieffenbacher GmbH Maschinen- und Anlagenbau | Process and plant for the production of wood-based panels |
EP1279746A1 (en) * | 2001-12-21 | 2003-01-29 | AKZO Nobel N.V. | Process for preparation of leather |
AT6040U1 (en) * | 2002-04-19 | 2003-03-25 | Schaefer Philipp | LEATHER AND METHOD FOR PRODUCING THE SAME |
AT7186U1 (en) * | 2003-10-20 | 2004-11-25 | Basf Ag | METHOD FOR ELIMINATING DEFECTS IN THE SCAR LAYER OF A FULL-SCARED LEATHER, AND LEATHER WHICH DEFECTS IN THE SCAR LAYER ARE ELIMINATED |
-
2006
- 2006-02-20 AT AT0012606U patent/AT8974U1/en not_active IP Right Cessation
- 2006-03-14 WO PCT/EP2006/002335 patent/WO2007095970A1/en active Application Filing
- 2006-03-14 KR KR1020087022836A patent/KR101168470B1/en not_active IP Right Cessation
- 2006-03-14 BR BRPI0621357-0A patent/BRPI0621357A2/en not_active IP Right Cessation
- 2006-03-14 DE DE502006006066T patent/DE502006006066D1/en active Active
- 2006-03-14 MX MX2008010683A patent/MX2008010683A/en active IP Right Grant
- 2006-03-14 US US12/279,191 patent/US8697232B2/en not_active Expired - Fee Related
- 2006-03-14 AT AT06723413T patent/ATE456679T1/en active
- 2006-03-14 CN CN2006800530374A patent/CN101379198B/en not_active Expired - Fee Related
- 2006-03-14 EP EP06723413A patent/EP1989333B1/en not_active Not-in-force
- 2006-04-03 DE DE202006005330U patent/DE202006005330U1/en not_active Expired - Lifetime
-
2007
- 2007-02-19 AR ARP070100701A patent/AR059582A1/en active IP Right Grant
-
2008
- 2008-08-11 ZA ZA200806892A patent/ZA200806892B/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO2007095970A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20100021722A1 (en) | 2010-01-28 |
CN101379198A (en) | 2009-03-04 |
WO2007095970A1 (en) | 2007-08-30 |
DE202006005330U1 (en) | 2006-06-08 |
KR101168470B1 (en) | 2012-07-26 |
ZA200806892B (en) | 2009-10-28 |
EP1989333B1 (en) | 2010-01-27 |
CN101379198B (en) | 2011-12-14 |
DE502006006066D1 (en) | 2010-03-18 |
AR059582A1 (en) | 2008-04-16 |
AT8974U1 (en) | 2007-03-15 |
KR20080095910A (en) | 2008-10-29 |
MX2008010683A (en) | 2008-09-01 |
ATE456679T1 (en) | 2010-02-15 |
US8697232B2 (en) | 2014-04-15 |
BRPI0621357A2 (en) | 2011-12-06 |
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