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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
• • 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
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • 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
  • 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
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
  • F03D—WIND MOTORS
  • F03D1/00—Wind motors with rotation axis substantially parallel to the air flow entering the rotor 
  • F03D1/06—Rotors
  • F03D1/065—Rotors characterised by their construction elements
  • F03D1/0675—Rotors characterised by their construction elements of the blades
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/07—Parts immersed or impregnated in a matrix
  • B32B2305/076—Prepregs
• • 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
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • 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
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2475/04—Polyurethanes
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/70—Wind energy
  • Y02E10/72—Wind turbines with rotation axis in wind direction
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31511—Of epoxy ether

Definitions

• the invention relates to compositions based on epoxy resins for the production of gel coats and the use of these gel coats for the surface treatment of fiber-reinforced plastics. Moreover, the invention relates to processes for the preparation of the gel coats and to processes for the production of surface-tempered components made of fiber-reinforced plastics, in particular production processes which use prepregs.
• the component surfaces are painted with appropriate coating materials, in particular weather-resistant and corrosion-protecting coatings, e.g. be used based on aliphatic polyurethanes.
• appropriate coating materials in particular weather-resistant and corrosion-protecting coatings, e.g. be used based on aliphatic polyurethanes.
• the surfaces to be painted must be pretreated consuming.
• a paintable surface is usually used in several processes -
• CONFIRMATION COPY received steps. First, the surface of the demolded component is abraded to completely remove any existing mold release agent. Then, the surface is coated or troweled with a putty to balance the surface defects, such as pores or protruding single fibers, that are revealed by the abrasion. After the putty has set, the surface is re-ground to obtain a smooth, paintable surface.
• Gelcoat is a composition based on a resin system that is applied in an in-mold process on surfaces of composite components. Through the use of gelcoats, tempered surfaces are obtained in the manufacturing process of the component, which are smooth and at the same time easy to sand. They can be painted directly after sanding. In general, the gelcoat is applied as a first layer in a component form and as far as precured or gelled that he has the degree of dryness 6 according to DIN 53 150 and meets the mechanical requirements of the other process.
• the fibers are applied in the form of fabrics, nonwovens or sheets, and the laminating resin containing the curable resins used as the matrix. The entire structure is then cured.
• the gelcoat film must be strong enough to allow the fibers to be laid up and, if necessary, removed without damaging the film. ended. For very large shapes such as rotor blades for wind turbines, fiber fabrics or fleeces are usually placed by hand. The gelcoat film must therefore be accessible without damage.
• the filler distributed in the resin system builds up a framework which causes the necessary mechanical stability even at a low pre-hardening or a slight progress of the hardening reaction of the gelcoat. More advantageous is the use of transparent gel coats, since laminating defects such as gas bubbles or dry, not resin-wetted points in the laminate can be detected and repaired immediately after demolding of the component. Transparent gelcoats without fillers have to be pre-cured much more strongly in order to achieve the required stability of the film. However, the greater progress of the curing reaction leads to significantly shorter lamination times.
• the lamination time is the time between the time when the gelcoat film applied to the mold is tack-free and the time at which the gelcoat film must be overlaminated to ensure adhesion between gelcoat and laminate.
• Parent component comprising at least one or more
• Epoxy resins and a hardener component having one or more amines.
• a hardener component having one or more amines.
• gelcoat resin systems based on
• the gel coats based on epoxy resins according to the invention exhibit no monomer emissions. Also, they show little to no shrinkage during the Curing so that stresses in the composite / gelcoat interface are avoided and a stable interface is obtained. Furthermore, composites based on epoxy resins (EP) show good adhesion to the gelcoats according to the invention.
• UP unsaturated polyesters
• EP epoxy resins
• Epoxy resins suitable in accordance with the present invention are aromatic glycidyl compounds, e.g. Glycidyl ether of bisphenol A, glycidyl ether of bisphenol F,
• Phenol novolak glycidyl ethers cresol novolak glycidyl ethers, glyoxoldrapraphenyl tetraglycidyl ethers, p-tert-butyl phenyl glycidyl ethers, cresyl glycidyl ethers, N, N-diglycidyl aniline, p-aminophenol triglycide, 4,4-diamino diphenylmethane tetraglycide, cycloaliphatic glycidyl compounds, such as Tetrahydrophthalic diglycidyl ether, hexahydrophthalic diglycidyl ether, cyclohexane-dimethanol diglycidyl ether, glycidyl ether of hydrogenated bisphenol A and glycidyl ether of hydrogenated bisphenol F, epoxidized cycloolefins, aliphatic
• the composition comprises one or more polyols.
• the polyols may be included in both the parent component and the hardener component. According to the invention, the polyols are preferably used in the parent component. Suitable polyols are, for example, polyacrylate polyols, polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactones and polyurethane polyols. preferred
• average molar masses based on the number average of the polyols are 1000 to 3000, preferably 1500 to 2500, particularly preferably 1800 to 2000, g / mol.
• the polyols are used in amounts of from 2 to 40, preferably from 5 to 30, particularly preferably from 10 to 20, percent by weight of polyols, based on the parent component including the polyols.
• Polytetrahydrofuran polyols are preferably used.
• fillers and / or pigments can be used in small amounts.
• fillers are understood to be particles which are practically insoluble in the application medium and are used to influence optical properties.
• they can also contribute to increasing the volume, to achieving or improving technical properties.
• pigments in the application medium is understood to mean virtually insoluble substances which are used as colorants or colorants.
• compositions are easily clouded with fillers and / or pigments for better handling, so that it is recognizable in the application where material has already been applied.
• the composition according to the invention preferably contains in the main component at most 5, preferably at most 2, more preferably at most 1, very preferably at most 0.5, weight percent fillers and / or pigments based on the parent component. Become bigger
• the composition is intransparent.
• Suitable fillers and pigments are e.g. mineral substances such as kaolin or talc, synthetic substances such as e.g. Barium sulfate or calcium carbonate and the inorganic or organic pigments commonly used in paint production and mixtures thereof. Titanium dioxide or carbon black is preferably used according to the invention.
• the hardener component has one or more amines.
• suitable amines are polyamines from the group of polyethylenepolyamines, for example ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,3-pentanediamine, 2-methylpentamethylenediamine, propyleneamines such as propylenediamine, dipropylenetriamine, diethylaminopropylamine, trimethylhexamethylenediamine, polyethers polyamines, for example polyoxypropylene diamines or polyoxypropylene triamines, polyoxypropylene polyamines, polyoxyethylene polyamines, polytetrahydrofuran polyamines or butanediol ether diamine or N-aminopropylcyclohexylamine, alkylenediamines, for example hexamethylenediamine, trimethylhexamethylenediamine or methylpent
• Cycloaliphatic amines in particular isophorodiamine, are preferably used.
• the amines are used in amounts of from 60 to 100, preferably from 80 to 95, particularly preferably from 85 to 95, percent by weight, based on the hardener component.
• the hardener components according to the invention may contain accelerators.
• Suitable accelerators are tertiary amines such. N, N-dimethylaniline or benzyldimethylamine, alcoholates, imidazoles, Mannich bases such as e.g. Dimethylaminomethylphenol or tris (dimethylamino-methyl) -phenol, boron trifluoride complexes, Broenstedt acids, alkylphenols, polyphenols, onium salts, triarylsulfonium salts, iron-arene complexes or salts of alkali or alkaline earth metals, such as e.g. Lithium bromide or calcium nitrate.
• Preferred accelerators are phenols, polyphenols, alkali and alkaline earth metal salts. Calcium nitrate tetrahydrate is particularly preferably used.
• the accelerators are used in amounts of from 0.2 to 40, preferably from 0.5 to 20, particularly preferably from 1 to 10, percent by weight, based on the hardener component.
• the composition contains plasticizers.
• Suitable plasticizers are polyurethane prepolymers with blocked Isocyanate groups.
• the plasticizers can be used both in the parent component and in the hardener component.
• Isocyanate prepolymers blocked with substituted phenols and / or pyrazoles are preferably used in the parent component, as described in patent application EP 0688803 A1.
• the patent application EP 0688803 A1 is hereby expressly included in the disclosure of the present invention.
• Particularly preferred are linear polymers with alkylphenol-capped terminal isocyanate groups. If the plasticizers are used in the hardener component, preference is given to isocyanate prepolymers whose isocyanate groups are blocked with secondary monoamines, as described in the patent application EP 0457089 A2.
• the plasticizers are used in the hardener component, preference is given to isocyanate prepolymers whose isocyanate groups are blocked with secondary monoamines, as described in the patent application EP 0457089 A
• Patent application EP 0457089 A2 is hereby expressly included in the disclosure of the present invention.
• compositions according to the invention may comprise the customary additives known to the person skilled in the art.
• rheology additives such as fumed silica, flow control agents or defoamers in the usual amounts can be used.
• the use of epoxy resins and amines in the molar ratio of the epoxide groups to epoxide-reactive NH groups (EP: NH) of from 1 to 0.7 to 1 to 1.4, particularly preferably from 1 to 0.8 to is preferred 1 to 1.3, most preferably from 1 to 0.9 to 1 to 1.2.
• the gel coats which can be prepared from the compositions according to the invention are transparent, ie have little coverability.
• the hiding power of the gel coats according to the invention is determined according to DIN EN ISO 2814 on a check card. Covering the checks could only be determined with layer thicknesses of more than 1 mm.
• the commonly used layer thickness of a gelcoat is significantly lower at about 500 ⁇ m.
• the gelcoats according to the invention have relatively short gelation times. Due to their short fishing times, the occupancy time of the mold is significantly reduced, which allows short mold loading cycles. They are tough in the gelled state as a gelcoat film and not brittle. The comparison with conventional transparent gel coats shows for the gel coats according to the invention a significantly better elongation at break and tear propagation resistance. Also, a repositioning of applied prepregs without damage is possible on the gelcoat films according to the invention.
• the gelcoats according to the invention have the mechanical stability required for the further process steps.
• they also meet the increased requirements for the production of laminates or fiber-reinforced plastic composite components in the prepreg process. They show as well as the usual, filled gel coats good adhesion to the laminate, are well sandable and paintable in the cured state.
• the object underlying the invention is further achieved by the use of the invention suitable gel coats for surface treatment of fiber-reinforced plastic composite components or laminates.
• the gelcoats are preferably applied to surfaces of the components in an internal method.
• the gelcoat film is introduced as the first layer in the component form.
• the composition according to the invention is first introduced into a mold within the pot life.
• the pot life is the period in which the mixture can be processed. It begins with the time at which both reaction components are mixed and ends at the time when the viscosity of the reaction mixture has increased too much to allow the application of a uniformly thick layer.
• the gelled film, the gelcoat film is sufficiently mechanically stable not to be damaged when the laminating resin and fibers are applied, but is still sufficiently reactive to form a stable bond with the laminating resin upon cure.
• Used laminating resins are, for example, epoxy resins, unsaturated polyester resins and vinyl ester resins.
• Used fibers are, for example, fabrics, scrims or nonwovens made of glass, carbon or plastic fibers.
• the contacting of the gelcoat layer with the laminating resin must take place within the lamination time of the gelcoat. Subsequently, laminating resin and gelcoat are completely cured.
• the gelcoats according to the invention are preferably used for the surface treatment of epoxy resin composites, since they show better adhesion to these materials than gelcoats based on other resin systems. In addition, they contain no volatile monomers and are therefore less hazardous to occupational hygiene.
• the object underlying the invention is further achieved by processes for the production of surface-modified fiber-reinforced plastic composite components or laminates.
• the provided components, the parent and the hardener component of the composition according to the invention are mixed.
• the mixture is mixed with the methods of application familiar to the person skilled in the art, such as e.g. Brushing, rolling, spraying or casting introduced as a first layer in a component mold.
• the applied mixture is gelatinized or precured to the gelcoat film.
• the fibers are applied to the gelcoat film in the form of woven, laid or nonwoven fabrics and the laminating resin.
• the entire structure is cured to the component.
• the component is removed from the mold, its surface ground and then painted.
• Fibers and laminating resin can be applied to the gelcoat film in a variety of ways.
• the person skilled in the usual laminating procedures are common, such as vacuum bag method, injection method, infusion method and wet lamination.
• One possibility for producing the fiber composite material is the use of prepregs.
• Prepregs are impregnated Resin fiber mats that are inserted into the component mold. The resin is partially precured and has a relatively high tack at room temperature.
• a problem with the use of prepregs is the repositioning on the gelcoat film. Component molds are usually pretreated with a release agent so that the gelcoat film itself has no adhesion to the mold. If sticky prepreg is placed on the gelcoat and then peeled off again, the gelcoat must not break or break.
• the gelcoat film Since there is no adhesion to the mold, the gelcoat film must be mechanically stable accordingly.
• the gelcoats according to the invention form films which have the required mechanical properties, so that they are preferably used in prepreg processes.
• the compositions of the invention require only short gelation times. Since the curing process in the prepreg process is significantly faster than in the other processes, they are also particularly suitable in this regard for use in these processes.
• the elongation at break is determined by mandrel bending test according to the test specification DIN EN ISO 1519.
• DIN EN ISO 1519 test specification
• metal plates on which the coating to be examined has been applied are bent around a mandrel.
• the tear strength is determined by tear propagation tests in accordance with the test specification DIN EN ISO 13937-2. It measures the force that must be expended to increase a crack in the coating being tested. The higher the force applied, the tighter the coating is.
• the prepreg repositionability is determined by the following experimental setup, which simulates a laminate construction in a component form.
• a release agent is applied on a sufficiently large metal plate.
• an area of 1 m 2 is coated on the thus prepared plate with a gelcoat composition.
• the composition is gelated to the gelcoat film at the given temperature and duration.
• a prepreg in DIN A4 size is placed in the middle and pressed with a defined force for 1 minute. Subsequently, will pulled off the prepreg at an angle of 90 ° jerky.
• the visible damages of the gelcoat film are evaluated as follows:
• Tables 2a and 2b show the results of the tests on gelcoat films that have been gelled under different conditions.
• the gelcoats according to the invention show markedly improved values in terms of elongation at break and tear propagation resistance.
• the detachment of an applied and pressed pre-preg does not damage the gel coats according to the invention. They can thus be used without the usual disadvantages in prepreg process.
• the gelcoat compositions are introduced into a mold and gelled, and prepreg is applied to the resulting gelcoat film.
• the mold is closed, a vacuum bag applied and evacuated.
• the entire structure is cured, the conditions of curing by the prepreg used are given.
• the following tests are carried out on the cured laminates.
• the elongation at break is determined by the above-mentioned mandrel bending test.
• metal strips were coated with gelcoat, the gel coat was gelled and cured under temperature conditions as were used in the curing of the prepreg laminates.
• the adhesive strength of the gelcoat on the laminate is determined by tear-off tests according to the test specification DIN EN ISO 4624. The higher the tension to tear off the punch, the stronger the adhesion.
• the sandability or abrasion and their paintability or the adhesion of coatings on the surfaces are determined.
• the abrasion resistance is determined according to the test specification ASTM D 4060 with a S33 wheel, 500 revolutions, 1000 g load, gravimetrically. The larger the weight difference, the higher the abrasion and the better the sanding ability.
• the laminate surfaces are first sanded with 180 grit sandpaper. Then the sanding dust is removed and the surface is painted with a suitable, commercially available varnish. After complete curing of the lacquer layer, the adhesion or adhesive strength is determined by tear tests according to the test specification DIN EN ISO 4624. The higher the tension to tear off the punch, the stronger the adhesion.
• Table 3 shows the results of the surface-modified laminates according to the invention in comparison to the customary surface-modified laminates.
• the laminates according to the invention like the conventional laminates, meet all requirements with regard to adhesion, sandability and paintability.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Sustainable Development (AREA)
• Sustainable Energy (AREA)
• Combustion & Propulsion (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Paints Or Removers (AREA)
• Reinforced Plastic Materials (AREA)
• Laminated Bodies (AREA)
• Moulding By Coating Moulds (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2012
  • 2012-05-21 DE DE102012010583A patent/DE102012010583A1/de not_active Withdrawn
• 2013
  • 2013-05-21 EP EP13735186.2A patent/EP2852643A1/de not_active Withdrawn
  • 2013-05-21 DE DE112013002600.7T patent/DE112013002600A5/de not_active Withdrawn
  • 2013-05-21 BR BR112014028806-2A patent/BR112014028806A2/pt not_active IP Right Cessation
  • 2013-05-21 US US14/402,314 patent/US10023762B2/en not_active Expired - Fee Related
  • 2013-05-21 MX MX2014009966A patent/MX367174B/es active IP Right Grant
  • 2013-05-21 WO PCT/DE2013/000272 patent/WO2013174362A1/de active Application Filing
  • 2013-05-21 KR KR1020147031176A patent/KR101738485B1/ko active IP Right Grant
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  • 2013-05-21 IN IN7594DEN2014 patent/IN2014DN07594A/en unknown
• 2015
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