EP3016751B1 - Wärme-lichttrennung für eine uv-strahlungsquelle - Google Patents
Wärme-lichttrennung für eine uv-strahlungsquelle Download PDFInfo
- Publication number
- EP3016751B1 EP3016751B1 EP14734004.6A EP14734004A EP3016751B1 EP 3016751 B1 EP3016751 B1 EP 3016751B1 EP 14734004 A EP14734004 A EP 14734004A EP 3016751 B1 EP3016751 B1 EP 3016751B1
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- EP
- European Patent Office
- Prior art keywords
- radiation
- strips
- mirror
- application
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- 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.)
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/062—Pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B3/00—Drying solid materials or objects by processes involving the application of heat
- F26B3/28—Drying solid materials or objects by processes involving the application of heat by radiation, e.g. from the sun
Definitions
- UV-curing coatings are used in many different areas. Curing is essentially understood to mean the crosslinking of polymer chains. In UV-curing paints, this crosslinking is induced by UV radiation.
- these paints when applied to a workpiece, contain solvents that must be expelled before curing. This expulsion can be accelerated by increasing the temperature beyond the ambient temperature. The higher the temperature, the faster the expulsion of the solvents. However, a certain paint-dependent temperature (glass transition temperature, chemical decomposition temperature) must not be exceeded. Likewise, the deformation temperature of the material of the workpiece must not be exceeded.
- High intensity UV radiation sources are based on gas discharge lamps that emit strong visible light (VIS) and infrared radiation (IR) in addition to the desired UV radiation.
- VIS and IR contribute to a significant additional increase in temperature when curing paints. However, it must be avoided that the temperature rises during the curing process on the glass transition temperature of the paint. It is desirable to suppress this VIS and IR contribution as possible, while losing as little UV radiation as possible.
- Typical UV radiation sources consist of a gas discharge lamp and a reflector element which collects the UV radiation emitted in the direction away from the workpiece and reflects it in the direction of the area of application.
- the propagating to the application UV radiation is thus composed of direct radiation and reflected radiation together.
- the lamp In the case of a substantially linear source, the lamp is substantially tubular. she can but also exist as a series of individual, substantially point-shaped lamps which are arranged in a row.
- the reflector element can be provided with a coating which reflects the VIS and IR radiation as little as possible. This can be done through an absorbing layer, but is preferably carried out as a dichroic thin film coating which on the one hand highly reflects the UV component and transmits VIS and IR, i. deflects away from the field of application.
- a UV source reduces the VIS and IR radiation in the field of application by a factor in the range of 2-5, depending on the reflective element (typically cylindrical elliptic element).
- This deflection mirror should reflect the UV radiation as well as possible, but should reflect the VIS & IR radiation as poorly as possible.
- This deflection mirror is designed as a flat mirror. Usually, a glass plate with dichroic thin film filter coating, which is arranged at an angle of 45 ° to the main beam of the UV source, is used. The application area is then located downstream in the beam path of the UV radiation reflected by the deflection mirror.
- the UV radiation is deflected by this deflection mirror in the 90 °, while the VIS & IR radiation is transmitted and thus not directed to the application area.
- the use of the dichroic deflection mirror leads to an extension of the light path between the UV source and the application, typically by about 70% of the length of the deflection mirror.
- FIG. 1 The corresponding situation is in the FIG. 1 with respect to the reflector radiation and in FIG. 2 with respect to direct radiation.
- the UV radiation is shown as a dotted line, while the radiation of the VIS & IR is shown as a dashed line.
- the total radiation is shown as a solid line.
- the extension of the beam path therefore has the consequence, above all for direct radiation, that the intensity of the UV radiation per unit area (area intensity) is reduced, in particular also in the field of application, due to the opening angle into which the radiation is emitted.
- area intensity intensity of the UV radiation per unit area
- a certain dose is required, which is due to the product of radiation intensity and exposure time (more precisely, by the temporal integral of the intensity).
- the lower areal intensity described above can only be made up by increasing the exposure time to achieve the required dose. This leads to a longer process time and thus to higher process costs.
- the required exposure dose can at best be achieved if the resulting overexposure of the flat areas does not entail any disadvantages, and the minimum necessary intensity can still be achieved. If this is not so, there is still the possibility of rotation of the components during the relative movement of the components to the UV source, but this additional movement means a significant overhead in the mounting of the components and the means for movement, and the disadvantages in a lower arrangement density of the components in the curing plant and a substantial extension of the exposure times.
- a deflection mirror having a substantially concave surface shape. Not only can the curved path compensate the extended beam path readily, but also a partial focusing of the reflected UV radiation, at least in one plane, can be achieved, which leads to an increase of the surface intensity.
- the shape of the curved deflection mirror is dependent on the exact position and orientation of the application.
- the substrate of the curved deflection mirror is preferably permeable to VIS & IR radiation.
- substrate material therefore, for example, glass and plastic come into question, it should be noted that the substrate is exposed to high temperatures and a UV residual.
- a material for the substrate which absorbs VIS & IR efficiently, but this would be strongly heated by the absorbed power and therefore would have to be cooled separately.
- a concavely curved glass surface can be coated with an interference filter.
- the interference filter is constructed, for example, as a thin-film alternating layer system, wherein the near-surface layers provide for the reflection of the UV radiation and the alternating layer system as a whole forms an antireflection layer for the VIS & IR radiation.
- Another challenge is the angular dependence of the optical behavior of the interference filters.
- this embodiment requires so-called gradient filters in order to position-dependent angles of incidence.
- the available coating technology is able to at least partially overcome this problem, even if this involves a great deal of effort and thus, in turn, costs.
- the problem with the curved mirror solution is that, in some applications, sometimes the distance from the radiation source to the area of application of the radiation changes. This is the case, for example, when large substrates provided with a lacquer layer have to be exposed to UV radiation which lie in one plane and UV radiation is to be applied to UV radiation with the same curing apparatus but also small substrates positioned on a spindle the spindle, the substrates and thus the application area are closer to the deflection mirror. In the worst case, it is then necessary to exchange the curved deflection mirror by a deflection mirror with a different curvature. For example, describes US 4644899 A the use of a double mirror configuration and DE 10352184 A1 a configuration with curved reflecting surfaces. There is therefore a need for an easy-to-implement but efficient irradiation device for UV radiation, with which it is achieved that an application area is exposed to UV radiation in sufficient surface intensity.
- the object is achieved according to a preferred embodiment in that a deflecting mirror composed of planar mirror strips is used, wherein the plane mirror strips are inclined relative to one another such that they at least roughly recreate a desired curvature. At least two strips are used, but preferably more than two, and more preferably three strips are used.
- the coating of the mirror strips can be done so that initially flat glass is coated. Such a coated glass plate is then cut into strips and these strips are fastened in a holder element.
- This holder element is designed such that each of the mirror strips with an orientation at a predetermined angle to the main beam of the UV Source comes to rest. The individual angles are chosen so that as much UV radiation falls within the scope of application. Due to the fact that the mirror strips essentially transmit the VIS & IR radiation, this proportion in the field of application remains small in any case.
- the spectral properties of the thin film mirror layer for each mirror strip can be further optimized. It can therefore be coated for each angle a separate glass plate with specifically optimized for this angle thin film interference filter.
- the deflecting mirror according to the invention is then assembled from strips of differently coated glass plates.
- the fastenings with which the mirror strips are fixed to the holder are designed so that they can rotate at least over a certain angular range about an axis parallel to the longer edge of the mirror strips.
- This makes it possible to adjust the modeled curvature of the deflection mirror and thus to optimize the UV radiation power for different application levels.
- adjustable angles of the mirror segments the illumination of the various surface elements of 3-dimensional components with indentations and side surfaces can be made much more uniform and thus improved by adjusting the segments so that the light in a focused form with beam proportions over a wide angular range in the Scope of application. Although this results in a slightly lower intensity for the flat areas, a more homogeneous exposure over the entire surface of the component is achieved.
- This embodiment allows a simple and above all flexible adaptation of the angular distribution and the spatial distribution of the irradiation light.
- the adjustment of the angle of these mirror segments can also be done via externally controllable drives, which opens up the possibility, process-controlled controlling the exposure of different shaped elements to optimize run.
- the mirrors can also be moved through the field of application by means of drives designed in this way, synchronously with a movement of the workpieces. In this way, the illumination of the surface shape of the workpieces can be dynamically adjusted and optimized.
- the substrates are often moved through the application area. For example, on a circular motion when it is mounted on a so-called spindle. As a result, a repetitive exposure of the paint is achieved. With this movement, the undesirable temperature increase is further reduced because the surface may cool during the angular range of rotation away from the field of application.
- the result is a substantially higher UV dose of 79, (compared to 65 for the flat deflecting mirror).
- the VIS & IR dose increases slightly to 28 (compared to 25 for the flat deflection mirror).
- the UV dose in the scope can be further improved.
- a UV dose of 83 is obtained, ie a 30% increase over the flat deflecting mirror, while the VIS and IR dose increases only to about 29.
- an intensity threshold of UV radiation must be exceeded for a certain period of time. While in the case of the flat deflecting mirror for the example given an intensity maximum of approximately 45 units is achieved, a value of approximately 60 is achieved for the deflecting mirror, which consists of two mirror strips, and in the FIG. 3 In the case shown with three stiffeners, even a value of about 80 is achieved. Thus, by dividing the dichroic mirror into stripes, almost the same areal intensity as in the case of a structure without this mirror can be achieved.
- a higher efficiency of the UV light guide in the field of application has the advantage that necessary cooling of the system and in particular the application area in which the substrates provided with temperature-sensitive paint are on the one hand smaller dimensions and less expensive to build, and on the other hand in the Application can be operated with less energy consumption.
- the entire waste heat of the curing process must be dissipated with strong air cooling in order to keep the temperature increase in the application area low.
- intensive filtering must prevent dust particles from entering the stream and thus the paint surfaces that are initially in a viscous state and sticking there. Any reduction of the necessary air flow by reducing the unwanted radiation or improving the efficiency in the UV light guide, as shown in the invention, leads to a possible reduction of these necessary air flows.
- FIG. 4 a holder for the mirror strips shown.
- the holder comprises fixing elements 3, 7, 9 and 11, which are arranged on the strip at the shorter edge, for example clamped.
- the fixing element 3 of a strip is connected to the fixing element 7 of an adjacent strip via webs 13, 17 connected by means of a joint 15.
- the fixing element 9 of the central strip is in this case connected to the fixing element 11 of the other adjacent strip via webs 19, 23 connected by means of a joint 21.
- the outer strips of the deflecting mirror have additional fixing elements 25 and 29.
- These fixing elements are fixed to circular arcs 27, 31. They can be moved to adjustment along these circular arcs and then fixed.
- Circular arc 27 belongs to a theoretical circle whose center lies in the joint 15.
- Circular arc 31 belongs to a theoretical circle whose center lies in the joint 21.
- such a holder is provided on both sides of the mirror strip thus arranged.
- FIG. 5 a corresponding plan view is shown. With this bracket, the inclination of the mirror strips can be easily adjusted and adjusted.
- Another aspect of the present invention relates to facilities and process for controllable illumination of workpieces with UV light for curing UV-sensitive surface finishes
- this aspect relates to UV exposure devices for curing UV-sensitive coating layers on surfaces, with a focus on homogeneous or a particular profile following illumination of the paint surfaces on a 3-dimensional workpiece
- paints used are applied by spraying, dipping or painting as a film on the components to be coated and then brought with a curing process in the final state with the desired properties.
- energy is added to the paint film to accelerate the curing process.
- thermal energy is supplied in the form of infrared radiation or by means of a heated gas (air). With suitable ovens or infrared radiators, the lacquer layer can be cured relatively uniformly even on more complex surface geometries.
- the component For more complex surface geometries, the component must also be rotated and / or tilted relative to the UV source, which is a particular challenge for the mechanics of mounting the component in the curing system, which naturally leads to limitations in the Uniformity and uniformity of the properties and quality characteristics of the cured films, or limits the processable surface shapes.
- Essential film properties of the cured paint film require a minimum dose of UV light, the changes with over-exposure may be low for these properties. Thus, a lack of UV light at certain points on the surface of the component can be compensated by a longer exposure time, whereby other areas are overexposed. For properties that are more critically dose dependent, the result is a loss of homogeneity
- a more homogeneous illumination can be achieved by repeatedly rotating holders for the components.
- Such fixtures and equipment are costly to purchase, demanding to handle and usually inflexible to use.
- the utilization of the maximum through the plant loading area with components is lower.
- FIG. 6a shows schematically the arrangement in one Curing unit with UV light source.
- the UV light of the UV lamp is collected via a reflector and guided into an application area in which the paint film is exposed on components and thus cured.
- the components in the area of application heat up so that the entire light radiation of the UV source in this area of the room is largely absorbed.
- the paint films are temperature sensitive and the temperature must not exceed a maximum value. This problem is mitigated by cyclically moving the components through the application area, thus allowing the components to cool off during the time they are not within the range of application. For components of limited size, this cyclic movement is preferably on a circular path by mounting the components on a drum and moving this drum about its axis.
- FIG Fig. 6b An extended embodiment of a curing unit is shown in FIG Fig. 6b shown.
- a dichroic mirror permeable to the UV light and the IR radiation of the UV lamp, the unwanted VIS and IR radiation is led away from the area of application, whereby the temperature rise during the curing process can be further limited.
- the power of the UV source is changed synchronously with the movement of the component.
- the power is set according to a certain temporal curve.
- a sinusoidal waveform is chosen, whereby the phase is kept in a constant relationship to the rotational movement of the drum ( FIG. 9 ).
- the frequency of this modulation of the UV light output is given by the arrangement of the components on the drum, it being assumed that the distance between the components on the circumference of the drum is kept small in the sense of a dense loading.
- the modulation thus continues to run continuously with each of the components that run sequentially through the application area.
- FIG. 10 is shown the result for the local distribution of the UV radiation dose on the surface of the assumed components, depending for the configuration of Fig. 6a and Fig. 6b .
- the course of the dose from the center to the edge has now almost been eliminated.
- This result is achieved in this case with a modulation amplitude of the UV light output of about 35% relative to the constant value.
- the phase of the modulation waveform is chosen so that the modulation power is minimal at the time when the component is at a minimum distance from the UV light source, ie the normal parallel to the axis of the UV light distribution.
- any periodic waveform can be used which is in a defined phase relationship to the substrate movement. Both amplitude and phase may themselves be modulated, assuming a frequency that matches or is a multiple of that frequency of the component movement over the range of application.
- the waveform in this case contains higher harmonic components, each with a specific, fixed phase, so that the synchronization with the component movement is maintained.
- the principle of synchronous UV light power modulation for influencing the UV dose on paint films on component surfaces disposed on a rotating drum can also be used to provide an inhomogeneous distribution equalize the dose over the circumference of the drum.
- Such inhomogeneity may arise due to mechanical inaccuracies, alignment and alignment errors, ect.
- a deviation from a concentricity d..h non-constant rotational angular velocity
- the UV dose on the components outside the drum can be selectively controlled to provide a more uniform dose distribution across the width of the components.
- the phase of the modulation must be determined from the actual values of a rotation angle sensor which is rigidly connected to the axis of the drum.
- Controlling the UV dose across the width of the device using synchronous modulation of the UV light output is not limited to eliminating non-uniformity of the UV dose, but can also be used to force a desired dose distribution across the device to enhance or attenuate a desired property of the cured lacquer film which can be influenced by the UV dose or UV intensity on the surface of the component.
- this can be adjusted via the modulation amplitude and the modulation phase, assuming that the fundamental frequency of the modulation is determined by the occupation of the drum with components and the rotational speed of the drum. Both the modulation amplitude and the modulation phase can themselves be synchronously modulated again, the fundamental frequency again having to correspond to the frequency of movement of the components through the field of application.
- Another advantage of this synchronous modulation can be that much less different, adapted to the individual components mounts may be necessary in a manufacturing environment in which a variety of components must be exposed. By adapting the modulation curve shapes in the recipe process, dose profiles on different components fixed with the same holders can be compensated.
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- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Coating Apparatus (AREA)
- Optical Elements Other Than Lenses (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
- Mounting And Adjusting Of Optical Elements (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL14734004T PL3016751T3 (pl) | 2013-07-03 | 2014-06-30 | Oddzielanie ciepła i światła dla źródła promieniowania uv |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361842576P | 2013-07-03 | 2013-07-03 | |
DE102013011066.1A DE102013011066A1 (de) | 2013-07-03 | 2013-07-03 | Wärme-Lichttrennung für eine UV-Strahlungsquelle |
PCT/EP2014/001779 WO2015000574A1 (de) | 2013-07-03 | 2014-06-30 | Wärme-lichttrennung für eine uv-strahlungsquelle |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3016751A1 EP3016751A1 (de) | 2016-05-11 |
EP3016751B1 true EP3016751B1 (de) | 2019-07-03 |
Family
ID=52105892
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14734004.6A Active EP3016751B1 (de) | 2013-07-03 | 2014-06-30 | Wärme-lichttrennung für eine uv-strahlungsquelle |
Country Status (15)
Country | Link |
---|---|
US (1) | US11052423B2 (es) |
EP (1) | EP3016751B1 (es) |
JP (1) | JP6768505B2 (es) |
KR (1) | KR102328419B1 (es) |
CN (1) | CN105722607B (es) |
BR (1) | BR112015032873B1 (es) |
CA (1) | CA2917069C (es) |
DE (1) | DE102013011066A1 (es) |
ES (1) | ES2749119T3 (es) |
HU (1) | HUE047192T2 (es) |
MX (1) | MX2016000223A (es) |
PL (1) | PL3016751T3 (es) |
PT (1) | PT3016751T (es) |
RU (1) | RU2659261C2 (es) |
WO (1) | WO2015000574A1 (es) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102015016730A1 (de) | 2015-12-22 | 2017-06-22 | Oerlikon Surface Solutions Ag, Pfäffikon | UV-Aushärtevorrichtung mit geteilten UV-Umlenkspiegeln |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009046407A1 (de) * | 2009-11-04 | 2011-05-05 | Dürr Systems GmbH | Vorrichtung zur Strahlungsbehandlung einer Beschichtung |
Family Cites Families (74)
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US2140069A (en) * | 1936-02-05 | 1938-12-13 | Cyrus R Bostwick | Triplicate folding hand mirror |
US3171403A (en) * | 1962-05-17 | 1965-03-02 | John C Drescher | Solar heating systems |
US3712980A (en) * | 1971-01-25 | 1973-01-23 | Kollmorgen Corp | Reflector arrangement for attenuating selected components of spectral radiation |
US4048490A (en) * | 1976-06-11 | 1977-09-13 | Union Carbide Corporation | Apparatus for delivering relatively cold UV to a substrate |
US4146308A (en) * | 1978-01-18 | 1979-03-27 | Trina, Inc. | Foldable mirror construction |
AT355200B (de) * | 1978-01-23 | 1980-02-25 | Espe Pharm Praep | Bestrahlungsgeraet zum aushaerten von durch strahlung haertbaren massen |
US4408595A (en) * | 1978-09-05 | 1983-10-11 | Broyles Howard F | Turret mounted solar concentrator with boom mounted secondary mirror or collector |
US4277141A (en) * | 1979-03-28 | 1981-07-07 | Tropel, Inc. | Multifaceted mirror and assembly fixture and method of making such mirror |
US4487479A (en) * | 1983-03-10 | 1984-12-11 | Tolomeo Sr Joseph F | Hunter's rear viewing mirror device |
JPH0646304B2 (ja) * | 1984-07-31 | 1994-06-15 | 東芝ライテック株式会社 | 紫外線硬化用照射装置 |
CH660489A5 (de) * | 1984-08-31 | 1987-04-30 | Bernhard Glaus | Verfahren und vorrichtung zum aushaerten polymerisierbarer beschichtungsmassen auf nicht textilen substraten. |
US4602321A (en) * | 1985-02-28 | 1986-07-22 | Vari-Lite, Inc. | Light source having automatically variable hue, saturation and beam divergence |
US4643544A (en) * | 1985-11-21 | 1987-02-17 | Loughran William P | Three view in one mirror |
US4864145A (en) * | 1986-10-31 | 1989-09-05 | Burgio Joseph T Jr | Apparatus and method for curing photosensitive coatings |
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2014
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DE102009046407A1 (de) * | 2009-11-04 | 2011-05-05 | Dürr Systems GmbH | Vorrichtung zur Strahlungsbehandlung einer Beschichtung |
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HUE047192T2 (hu) | 2020-04-28 |
CN105722607A (zh) | 2016-06-29 |
MX2016000223A (es) | 2016-06-15 |
RU2016103245A (ru) | 2017-08-08 |
PL3016751T3 (pl) | 2019-12-31 |
CA2917069C (en) | 2021-02-16 |
RU2659261C2 (ru) | 2018-06-29 |
EP3016751A1 (de) | 2016-05-11 |
WO2015000574A1 (de) | 2015-01-08 |
US20160368021A1 (en) | 2016-12-22 |
JP2016530550A (ja) | 2016-09-29 |
JP6768505B2 (ja) | 2020-10-14 |
KR20160029819A (ko) | 2016-03-15 |
PT3016751T (pt) | 2019-11-11 |
DE102013011066A1 (de) | 2015-01-08 |
CN105722607B (zh) | 2019-06-18 |
BR112015032873A2 (pt) | 2017-07-25 |
BR112015032873B1 (pt) | 2022-04-12 |
ES2749119T3 (es) | 2020-03-19 |
CA2917069A1 (en) | 2015-01-08 |
KR102328419B1 (ko) | 2021-11-19 |
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