Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes
  • C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

• the invention relates to a method for coating a molded part, the use of a silane-modified coating composition for coating a molded part, a device for coating the surface of a molded part and the molded part, which is produced by the process according to the invention.
• the moldings are protected by the coating against external influences, protect them from, for example, corrosion or the damaging effect of UV light, increase the resistance of the molded part surface against mechanical damage or are made for purely optical reasons to improve the appearance of the molded part.
• a coating is applied to the surface for optical reasons and also as protection against the action of UV rays.
• Sill panels, spoilers, tailgates and engine compartment and trunk lid panels, moldings and railings in the roof area, as well as components in the front window of the radiator and the fuel filler flap are painted on a large scale to produce a visually high-quality appearance, in particular visually and in color with the Coated components made of sheet metal of the body and also to protect the plastic from the harmful effects of UV light of the sun.
• Object of the present invention is therefore to provide a method for coating the surface of a molded part, which overcomes the disadvantages mentioned above.
• Another object of the present invention relates to the use of a modified coating agent for coating at least one activated portion of the surface of a molding.
• Another object of the invention is to provide a device for coating the surface of a molded part, in which a molded part according to the inventive method is coatable.
• the object is achieved by the method of coating at least a portion of the surface of a molded part with a coating agent by the following process steps: Providing a molding;
• active centers are formed on this surface, which are present for example in the case of a plastic molding as -OH groups.
• other active centers are formed, which are present for example as carbonyl groups.
• Such a plasma process can be carried out, for example, in a certain vacuum range with the supply of electrical energy in a highly diluted atmosphere of air, oxygen, nitrogen or other gases, such. B. in the low pressure plasma process.
• Another method of activating the portion of the surface of the molding to be coated is flame treatment to deposit an activating agent.
• a flame such as a propane gas flame burning in an atmosphere of air, a volatile silane, or a compound containing titanium or aluminum, is added.
• a silane is formed in the flame SiOx, which is deposited as an activating agent on the activated surface of the molding.
• the activating agent in the form of SiOx firmly adheres to the surface of the molding.
• a compound containing or releasing a halogen, especially fluorine and / or chlorine, a compound containing or releasing oxygen or a strong acid capable of being active type centers is suitable to form on the surface of the molding.
• the aforesaid means of activating the portion of the surface of the molding to be coated, the plasma process, flame-on deposition of an activating agent and treatment with an oxidizing agent may be carried out individually or in any combination with each other to provide active sites on the surface of the molding form.
• a particularly preferred activation of the surface of the molded part to be coated is to expose it to a plasma treatment process.
• the plasma process can be operated as follows: As atmospheric pressure plasma (AD plasma or normal pressure plasma) refers to the special case of a plasma, in which the pressure is approximately equal to the surrounding atmosphere - the so-called normal pressure.
• AD plasma atmospheric pressure plasma
• normal pressure plasma refers to the special case of a plasma, in which the pressure is approximately equal to the surrounding atmosphere - the so-called normal pressure.
• DBE dielectrically impeded discharge
• the plasma nozzle is used industrially for activating and cleaning plastic and metal surfaces before gluing and painting processes.
• web products with treatment widths of several meters can be treated today by juxtaposing many nozzles.
• the modification of the surface achieved by the plasma nozzle can certainly be compared with the effects achieved in the low-pressure plasma.
• the plasma jet can be up to 40 mm long and achieve a treatment width of 15 mm.
• Special rotation systems today allow a treatment width per nozzle of up to 13 cm.
• the plasma source is moved at a distance of 0 to 40 mm at a speed of 5 to 400 m / min relative to the surface of the material to be treated.
• a low-pressure plasma is a plasma in which the pressure is considerably lower than the atmospheric pressure.
• Low-pressure plasmas are among the non-thermal plasmas.
• Typical low-pressure technical plasmas are operated in the pressure range less Pascal, ie at pressures which are lower by a factor of 10,000 than the normal air pressure.
• Typical of low pressure plasmas is a mean free path of the electrons that is larger than the Debye length. In low-pressure plasmas, the typical mean free path is so high because of the low pressure that impact processes are "rare.” Accordingly, the different particle types (heavy particles, electrons) are not in thermal equilibrium, i. H. have different temperatures.
• a device for treating the surface of components with low-pressure plasma in a fillable with process gas having an opening vacuum chamber is known, wherein the opening of the vacuum chamber before evacuation and the introduction and the ionization of the process gas by means of a in the vacuum chamber arranged and connected to a plasma generator electrode is sealed from the part of the component surface to be treated.
• This known method should be used for large-scale components with reasonable investment costs.
• a device moving the component or the vacuum chamber is used, with which a relative movement between the component surface and the opening of the vacuum chamber is carried out until the entire surface to be treated of the component has been subjected to a treatment.
• a plurality of process bells are coupled to the vacuum chamber via flexible feed lines and used simultaneously to treat the surface of a component or of various components.
• spacers of about 50 cm in length and a T-piece with optional valve-controlled suction of the reaction chamber of the process bell directly through the vacuum pump or indirectly through the vacuum chamber, a plasma activation on polyethylene substrate with air could be detected.
• a process bell was simultaneously used on the opposite surfaces of a relatively thin opaque polyethylene plate for its treatment, air being used as the carrier medium in the reaction chamber of the respective process bell communicating with the vacuum chamber.
• the detection was carried out on the one hand by the optical recognizability of the plasma boundary through the thin opaque polyethylene plate and on the other hand by the representation of the changed wettability of the treated surface by a test ink. Similarly, coating, etching and cleaning processes are possible.
• the evacuation can be canceled after completion of the treatment of the corresponding part of the component surface.
• the dimensions of the reaction chamber of the low-pressure plasma reactor with regard to their length, width and height must correspond to the components to be treated.
• the feed pressure in the reaction chamber of the low pressure plasma reactor is selected in the range of 1 Pa to 1000 Pa.
• Another equally preferred technique for activating the surface of the molded article is to flame the surface to deposit an activating agent.
• a silane is added to the fuel gas during the flaming process.
• the silane is hereby preferably selected from the group of organosilanes and silicon hydrides. From the documents DE 1771145 and DE 3802043 suitable silanes are known for this purpose.
• Silanes can z.
• organo-oxysilane such as tetra (m) ethoxysilane, ethyltriethoxysilane,
• Silanes can z.
• the coating composition contains a silane from the group of the general formula (I) and / or the general formula (II).
• the coating composition contains effective amounts of at least one silane of the general formula (I)
• R 1 hydrocarbon chain with up to 10 C atoms, which is replaced by oxygen or
• Nitrogen can be interrupted,
• R 2 identical or different hydrolyzable groups
• novel coating compositions of silanes (I) depends on the content of the other constituents in the coating composition.
• the coating composition may comprise an effective amount of at least one silane of the general formula (II)
• R 1 hydrocarbon chain with up to 10 C atoms, which is replaced by oxygen or
• Nitrogen can be interrupted,
• R 2 identical or different hydrolyzable groups
• the content of the coating compositions according to the invention on silanes (II) depends on the content of the other constituents in the coating composition.
• compositions according to the invention can be carried out in various ways.
• the modification of the coating agent can be effected by adding the modifying agent (silane (I)) to a conventional coating agent.
• the modification can be carried out by preparation of polymers which is expediently carried out in such a way that a starting polymer containing the modification is prepared from monomers by the (radical) polymerization methods known per se.
• the silanes (II) can be incorporated in a known manner in the art usually within a few minutes.
• silicon-containing monomers preferably ethylenically unsaturated siloxane-containing monomers, such as those mentioned in the document DE-A 195 37 935 are used. The content of this document is referred to in this point.
• the silicon-containing monomers result in improved adhesion of the coatings to various substrates and may, if desired, in amounts of 0.05 to 5.0 wt .-%, preferably 0.1 to 3.0 wt .-%, based on the remaining monomers are used.
• silane (I) for example
• 3-aminopropyltriethoxysilane e.g., trade name DYNASYLAN® AMEO
• N-methyl [3- (trimethoxysilyl) propyl] carbamate e.g., trade name Geniosil GF 60.
• siloxane-containing monomers (II) are examples of siloxane-containing monomers (II).
• Vinyltrimethoxysilane (eg trade name Geniosil XL 10),
• X alkylvinyl
• R1 variable
• R2 alkoxy
• R3 alkyl
• m 2 or
• the modifiers of the general formula (I) and (II) can also with ingredients of conventional coating agents, such as. B. (iso) cyanate advantageously react.
• Analogous titanium or aluminum compounds can also be used.
• Polymers containing monomers (II) can be prepared in various ways.
• polymers containing monomers (II) by polymerization such.
• B. solution polymerization or emulsion polymerization are prepared.
• Polymers can also be modified with modifiers of the general formula (I) and (II) after the polymerization.
• Coating agents are prepared in a conventional manner. Depending on the application, application and desired property profile, they contain binders, pigments, fillers, extenders, auxiliaries, additives and optionally other starting materials. The manufacturing process is common.
• Coating agents in liquid form are basically possible on the basis of solvents and water-based.
• the present invention can be applied to both solventborne (solventborne) and waterborne (hydrosol) systems.
• solvent-based coating compositions contain solvents (mixtures) as the liquid phase.
• solvent-based paint system usually contain binders, pigments, fillers, extenders, auxiliaries, additives and optionally other starting materials. They can be made in a variety of ways.
• hydro lacquer systems contain water as the liquid phase.
• hydro lacquer systems usually contain binders, pigments, fillers, extenders, auxiliaries, additives and optionally other starting materials.
• An example of another feedstock may optionally be the addition of small quantities to be solvent. Reason for this can be in the processing, can also be in the film formation.
• Hydro lacquer systems can be produced in a variety of ways.
• the modification of the coating compositions according to the invention is not limited to those binders which come into contact with the activated surface. These may generally be primers or first coats. Coating agents applied to the primer or first coat as a second coat can also be modified. The intermediate adhesion between the primer or first coating and the secondary coating is improved, especially when both the coating agent serving as a primer or first coating and the coating composition of the second coating are modified according to the invention. Accordingly, in multi-layered structures of the coating system, it is also possible to modify third, fourth and further coatings according to the present invention.
• the intermediate adhesion between the primer or primer coating and the secondary coating is also improved if the surface has not been activated, especially if both the primer or primer coating agent and the coating agent of the Second coating is modified according to the invention.
• silane in the activation phase of the plastic surface and the application of a mixture consisting of binder, optionally pigments, fillers, additives and application of a modification according to the invention, after solidification of the coating agent, a significant improvement in the adhesion properties. This is significantly better than solely the use of the silane in the activation phase of the plastic surface or alone the application of a mixture consisting of binder, optionally pigments, fillers, additives and an organosilicon compound, from which a silanol is formed by hydrolysis.
• This improvement is significantly better than solely the use of the silane in the activation phase of the plastic surface or alone the application of a mixture consisting of binder, optionally pigments, fillers, additives and an organosilicon compound, from which a silanol is formed by hydrolysis.
• An improvement in the intermediate adhesion with the agents according to the invention is significantly better than conventional systems.
• siloxane bridges occurs between the activated surface of the molding and the silane of the coating agent.
• Solidification of the coating agent can be customized according to logistics, manufacturing equipment, process parameters and other variables required for the application and the desired property profile.
• the coating of plastic parts may be mentioned. After provision of the molding this can be stored under certain conditions for months, in practice, the storage time but should move in the range of minutes to days. After activation of the portion of the surface of the molded part to be coated, it may be stored for a long time under certain conditions prior to coating, but in practice the storage time should be in the range of minutes to days.
• the solidification of the coating agent is carried out.
• the coating of the activated portion of the surface of the molding is possible by various techniques.
• the coating can be carried out by rolling, spraying, dipping, brushing, rolling or other conditions that meet the requirements.
• the solidification of the coating agent on the activated portion of the surface of the molding can be carried out by various techniques. For example, solidification may be performed by irradiation, exposure to heat, ventilation to remove vaporizing portions contained in the coating agent, or convection.
• the invention achieves the object of specifying the use of a silane-modified coating agent for coating at least one activated portion of the surface of a molding according to the method as described above.
• the object of the invention is to provide the use of a modified coating agent for coating at least one activated portion of the surface of a molding, the method - as described above - is applied.
• the invention also achieves the object of specifying a device for coating at least a portion of the surface of a molded part with a coating agent.
• a device for coating at least a portion of the surface of a molded part with a coating agent has a device for activating the portion of the surface of the molded part to be coated and a device for coating th the activated portion of the surface of the molding with the coating agent according to the method described above.
• the invention also includes a molded part whose surface is at least partially coated with a coating agent, wherein the molded part according to the inventive method - as described above - is made.
• the invention is preferably used in the painting of components for the automotive industry, in particular exterior attachments to the body of plastic, such as bumper panels, fenders, door and sill panels, spoilers, hatchback and engine compartment and trunk lid panels, moldings and relin ge in the roof area , as well as components in the area of the windscreen, the radiator and tank flaps.
• the invention can also be used in other areas.
• the invention can also be used in the loading of buildings, as well as on metallic bodies and surfaces.
• the invention relates to the following examples.
• the examples are only for description and in no way limit the scope of the plastic surfaces or coatings of the invention.
• the adhesion-modified coating compositions and the other coating compositions used can be based on solvent or based on water.
• adhesion-modified coating compositions and also the other coating agents used are ready for application in liquid form. They contain binders, pigments, fillers, additives and additives.
• a multi-layer coating structure can be selected.
• the present invention shows that the modification of one or more coating layers, whether it be primer and / or basecoat and / or clearcoat, has better adhesion and improved properties than comparable structures without modification.
• inventive modification of more than one lacquer layer such.
• a two-layer construction is established - basecoat
• the present invention shows that the modification of one or both paint layers has better adhesion and improved properties than comparable structures without modification.
• the inventive modification of more than one lacquer layer such. B. the modification of the basecoat according to the invention and the modification of the clearcoat according to the invention not only the adhesion to the substrate, but also the intermediate adhesion is improved.
• the same substrate of polypropylene, filler, pigment, stabilizer, processing aids, copolymer was extruded in a typical composition for auto parts to be painted, and injection molded into 20 cm * 5 cm * 0.3 cm plates.
• the panels produced were fired and then provided with coating agents or subjected to a plasma treatment and then provided with coating agents.
• Plasma The plasma treatment was in a device PA 2000 from the company. Plasma Technology at 0.1 mbar under oxygen atmosphere for 1 min. performed at 3 kW.
• the platelets were coated with primer, basecoat and clearcoat under the following conditions:
• Primer Wörwag adhesive primer slate gray conductive, in the cloister were sprayed with the gun so that the layer thickness of 12 ⁇ were reached. It was dried for 25 min at 85 ° C and then the basecoat was applied, depending on the examples.
• Basecoat Wörwag basecoat iridium silver DAG T4, in the cloister was sprayed with the gun so that the layer thickness of 15 ⁇ were reached. It was dried for 20 min at 75 ° C and then the clearcoat was applied.
• Clear coat Wörwag high gloss clear coat 11141, in the cloister was sprayed with the gun so that the layer thickness of 30 pm was reached. It was dried for 30 min at 85 ° C.
• Modified primer 1452 g of the untreated primer Wörwag adhesive primer slate gray conductive were mixed with 11 g of GF 60 while stirring and prepared for 1 hour with stirring. From the modified primer were sprayed in a cloister with the gun so that the layer thickness of 12 pm was reached. It was dried for 25 min at 85 ° C and then the basecoat was applied, depending on the examples.
• Modified basecoat 1517 g of the untreated Wörwag basecoat iridium silver DAG T4 were mixed with 10 g of GF 60 while stirring and prepared for 1 hour while stirring. The modified basecoat was sprayed in a cloister with the gun so that the layer thickness of 15 ⁇ m was reached. It was dried for 20 min at 75 ° C and then the clearcoat was applied.
• Plasma activation by plasma treatment (see above)
• the coated panels were subjected to the following tests: Steam Jet Test (HDW)
• Test specimen was loaded with specified test parameters (volume flow, temperature, jet length and width, DIN 55662).
• the unit pressure was regulated with the prescribed nozzle so that the specified volume flow was maintained.
• An indication of the test pressure was deliberately omitted, as this is defined by the volume flow and the test nozzle.
• Test nozzle was used according to DBL 54 6
• the test duration was 3 cycles. Each cycle consisted of 15 h 105 ° C; 30 min. 23 ⁇ 2 ° C; 8 h - 40 ° C; 30 min. 23 ⁇ 2 ° C, followed by the above-described steam jet test.
• the area to be assessed was cleaned with isopropanol before attachment of the cross-hatch and dried at 23 ⁇ 2 ° C for about 15 min.
• the cross-hatching was carried out with a multi-cutter device, cutting distance 1, 5 mm (regardless of the coating thicknesses) at right angles. The depth of cut was up to the substrate.
• Tesaband type 4657 gray from Beiersdorf Hamburg
• the 19 mm wide Tesaband type 4657 gray was used for the cross-hatch cut with tape tear test. Prior to application of the tape, care was taken to ensure that the scratch marks reaching into the substrate were brushed with an additional suitable article, e.g. Fingernail were smoothed. It was ensured that the Tesaband the entire surface of the painting was applied, was pressed firmly by hand, and was pressed with the fingernail firmly into the scratches and was abruptly, at high speed, torn vertically upwards. When cross-hatching the Tesaband was stuck in accordance with the scratches in the longitudinal and transverse directions and demolished.
• silane in the activation phase of the plastic surface or the sole application of a mixture consisting of binder, optionally pigments, fillers, additives and an organosilicon compound, from which a silanol is formed by hydrolysis, do not lead to the above-indicated adhesion improvement.
• 1a and 1b is a schematic cross-sectional view of a molded part with its
• FIGS. 2a and 2b show a schematic cross-sectional view of a molded part with an activated surface
• 3a and 3b show a schematic cross-sectional view of a molded part with an activated surface, wherein a drop of the coating agent approaches the surface;
• FIGS. 1 a and 1 b schematically show a molded part 1 in a cross-sectional view, which has a surface 2.
• the index a stands for the activation of the surface by a plasma treatment and the index b for an activation of the surface by a flame on deposition of an activating agent.
• FIGS. 2a and 2b show schematically in a cross-sectional view that after an activation step on the surface 2 of the molded part 1 -OH groups are formed.
• the -OH groups are isolated on the surface 2 of the molded part 1 before.
• Fig. 2b is additionally shown that an SiOx particles 3 is adhered to the surface 2 of the molded part 1.
• the SiOx particle 3 has been formed by flame deposition with deposition of the SiO x particle serving as the activating agent and deposited on the surface 2 of the molded article 1.
• the SiOx particle 3 has on its surface in turn -OH groups, one of which is shown in FIG. 2b.
• FIGS. 3 a and 3 b show that a silane-modified coating agent 4 in the form of a droplet approximates the activated surface 2 of the molded part 1.
• the silane-modified coating agent 4 in a painting z. B. divided by a sputtering technique in the form of drops and has been accelerated in the direction of the activated surface 2 of the molding 1.
• the silane-modified coating agent 4 is in this case moved in the direction of the activated surface 2 of the molded part 1.
• the activated surface 2 of the molded part 1 comprises -OH groups or, as shown in FIG. 3 b, an SiO x particle 3 adhering to the surface 2, which itself Having -OH groups.
• FIGS. 4 a and 4 b show, in a schematic cross-sectional view, that the coating agent 5 is brought into contact with the surface 2 of the molded part 1 and wets the surface 2 of the molded article 1 and has spread on the surface 2.
• silane groups contained in the silane-modified coating agent 4 as shown in FIGS. 3 a and 3b, which are schematically denoted by Si, have, together with the -OH groups formed there through the activation of the surface 2, siloxane bridges characterized as silicon. O, abreacted.
• silane of the coating agent 4 in FIG. 3b has also reacted here with the -OH group of the SiOx particle 3 on the surface 2 of the molded part 1 to form a siloxane bridge, designated Si-O.
• the significantly improved adhesion of the coating agent 5 on the surface 2 of the molded part 1 is achieved.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Medicinal Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paints Or Removers (AREA)

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• 2012
  • 2012-05-21 DE DE102012104357A patent/DE102012104357A1/de not_active Withdrawn
  • 2012-07-03 DE DE202012102438U patent/DE202012102438U1/de not_active Expired - Lifetime
• 2013
  • 2013-05-16 WO PCT/EP2013/001444 patent/WO2013174491A1/fr not_active Ceased
  • 2013-05-16 DE DE112013002592.2T patent/DE112013002592A5/de not_active Withdrawn
  • 2013-05-16 WO PCT/EP2013/001445 patent/WO2013174492A1/fr not_active Ceased

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