DK3262207T3 - Højtydende belægning til koldmetalformgivning af højstyrkestål - Google Patents
Højtydende belægning til koldmetalformgivning af højstyrkestål Download PDFInfo
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- DK3262207T3 DK3262207T3 DK16706566.3T DK16706566T DK3262207T3 DK 3262207 T3 DK3262207 T3 DK 3262207T3 DK 16706566 T DK16706566 T DK 16706566T DK 3262207 T3 DK3262207 T3 DK 3262207T3
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0664—Carbonitrides
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3492—Variation of parameters during sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J13/00—Details of machines for forging, pressing, or hammering
- B21J13/02—Dies or mountings therefor
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Physical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Chemical Vapour Deposition (AREA)
Claims (15)
1. Belægning pålagt på en substratoverflade af et metalformgivningsværktøj eller metalformgivningselement til koldformgivning af højstyrkestål, idet belægningen omfatter et nedre lag (20) omfattende CrN og et øvre lag (30) omfattende TiCN, hvor det nedre lag (20) er pålagt tættere på substratet (1) end det øvre lag (30), kendetegnet ved, at: • det nedre lag (20) er fremstillet af oxygenberiget chromnitrid udvisende en kubisk struktur med foretrukket (200) orientering, • det øvre lag (30) er fremstillet af hydrogenberiget titaniumcarbonitrid.
2. Belægning ifølge krav 1, kendetegnet ved, at - det nedre lag (20) har en kemisk sammensætning svarende til formlen CrNyOx, i hvilken 0,20 < x < 0,45, og 0,55 < y < 0,8, hvor x og y er andelene af oxygen og nitrogen i atomprocent, hvis summen af indholdet af de ikke-metalliske belægningsbestanddele N og O i atomprocent regnes for at være 100 atomprocent og følgelig x+y=1, og/eller det nedre lag (20) har en kemisk sammensætning svarende til formlen CrNyOx, i hvilken 0,20 < x < 0,45, og 0,55 < y < 0,8, foretrukket 0,25 < x < 0,40, og 0,60 < y < 0,75, hvor x og y er andelene af oxygen og nitrogen i atomprocent, hvis summen af indholdet af de ikke-metalliske belægningsbestanddele N og O i atomprocent regnes for at være 100 atomprocent og følgelig x+y = 1.
3. Belægning ifølge et hvilket som helst af de foregående krav 1 eller 2, kendetegnet ved, at den kemiske sammensætning af det øvre lag (30) er i overensstemmelse med formlen TiCpNqHz, i hvilken 0,6 < p+q < 0,8, 0,33 < p/q < 4 og 0,2 < z < 0,4, hvor p, q og z henviser til de ikke-metalliske belægningsbestanddele, og summen herafsættes til 100 % i forhold til metalbestanddelen titanium.
4. Belægning ifølge et hvilket som helst af de foregående krav 1 til 3, kendetegnet ved, at det øvre lag (30) udviser en variation af den kemiske sammensætning over lagtykkelsen, hvor nitrogenindholdet falder, og carbonindholdet stiger i retning mod den ydre overflade af det øvre lag (30).
5. Belægning ifølge et hvilket som helst af de foregående krav 1 til 4, kendetegnet ved, at der er tilvejebragt et mellemlag mellem det nedre lag (20) og det øvre lag (30), idet mellemlaget er et flerlagssystem omfattende et første mellemlag (41) tilvejebragt som CrN-lag på det nedre lag (20), et andet mellemlag (42) tilvejebragt som et TiCrN-lag på det første mellemlag (41), og et tredje mellemlag (43) tilvejebragt som et TiCrCN-lag på det andet mellemlag (42).
6. Belægning ifølge krav 5, kendetegnet ved, at det andet mellemlag (42) er udformet som et flerlagssystem omfattende TiN- og CrN-nanolag pålagt skiftevis, og/eller det tredje mellemlag (43) er udformet som et flerlagssystem omfattende TiCN- og CrCN-nanolag pålagt skiftevis.
7. Belægning ifølge et af de foregående krav 5 eller 6, kendetegnet ved, at det tredje mellemlag (43) indeholder hydrogen.
8. Belægning ifølge et af de foregående krav 5 til 7, kendetegnet ved, at carbonindholdet gradvist stiger fra mellemlaget (43) til den ydre overflade af det øvre lag (30).
9. Belægning ifølge et af de foregående krav 2 til 8, hvor - det nedre lag (20) udviser et XRD-intensitetsforhold for (200)/(111) i området fra 10 til 50, foretrukket i intervallet fra 24 til 40, og/eller - det øvre TiCpNq:Hz-lag (30) udviser en kubisk struktur med foretrukket (111) orientering, og et XRD-intensitetsforhold for (111 )/(200) i området fra 5 til 20, foretrukket i intervallet fra 11 til 15.
10. Belægning ifølge et af de foregående krav 2 til 9, hvor - det nedre lag (20) udviser kornstørrelser fra (200)-refleksionen i området mellem 5-30 nm, foretrukket mellem 8-20 nm, mere foretrukket mellem 10-15 nm, og/eller - det øvre lag udviser XRD-kornstørrelser fra (200)-refleksionen i området mellem 5-30 nm, foretrukket mellem 5-20 nm, yderligere foretrukket mellem 5-8 nm.
11. Belægning ifølge et hvilket som helst af de foregående krav, som udviser relative tykkelser på 29-59%, 11-18% og 27-36% af den samlede belægningstykkelse for hhv. det nedre funktionelle lag (20), summen af mellemlagene (41) + (42) + (43) og det ydre funktionelle lag (30).
12. Fremgangsmåde til at pålægge substratoverflader på et formgivningsværktøj eller formgivningselement 1 med en belægning ifølge et af de foregående krav, hvor fremgangsmåden omfatter: - indføring af værktøjerne eller elementerne, som skal påføres belægning, i et vakuum-coatingkammer - afgasning af coatingkammeret, - opvarmning og argonion-ætsning af substratoverfladerne, som skal påføres belægning - anvendelse af PVD-processer til pålægning af belægningslagene, kendetegnet ved, at PVD-processerne er katodefordampning og/eller -forstøvning og/eller HIPIMS-processer eller en kombination heraf, og der er tilført negativ forspænding til substratet, som skal påføres belægning, og den negative forspænding holdes konstant på en første værdi mellem -40 og -100 V under pålægningen af det nedre lag (20), og den negative forspænding øges til en anden værdi mellem - 70 og -150 V og holdes konstant til pålægning af det yderste funktionelle lag (30), hvor den anden værdi er højere end den første værdi.
13. Fremgangsmåde ifølge krav 12, kendetegnet ved, at den negative forspænding gradvist stiger indefra det andet mellemlag (42).
14. Fremgangsmåde ifølge et hvilket som helst af de foregående krav 12 eller 13, hvor der anvendes en procesgas omfattende acetylen til formgivning af mellemlaget (43) og/eller det øvre lag (30).
15. Fremgangsmåde ifølge krav 14, hvor acetylen-flowet gradvist stiger fra pålægning af mellemlaget 43 imod pålægning af den ydre overflade af det øvre lag (30).
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US201562120011P | 2015-02-24 | 2015-02-24 | |
PCT/EP2016/053503 WO2016135047A1 (en) | 2015-02-24 | 2016-02-19 | High performance coating for high-strength steel cold metal forming |
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US (1) | US10626505B2 (da) |
EP (1) | EP3262207B1 (da) |
JP (1) | JP6876611B2 (da) |
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CN (1) | CN107532277B (da) |
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CA (1) | CA2973927C (da) |
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PH (1) | PH12017501354A1 (da) |
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CN110431254A (zh) * | 2017-04-07 | 2019-11-08 | 山特维克知识产权股份有限公司 | 涂层切削工具 |
US11136672B2 (en) | 2018-08-30 | 2021-10-05 | Apple Inc. | Electronic devices having corrosion-resistant coatings |
CN113366148B (zh) * | 2019-02-01 | 2023-10-31 | 欧瑞康表面处理解决方案股份公司普费菲孔 | 用于对涂覆和未涂覆的超高强度钢制钣金进行压制硬化的高性能工具涂层 |
DE102019113117B4 (de) * | 2019-05-17 | 2023-12-28 | voestalpine eifeler Vacotec GmbH | Verfahren zum Herstellen eines Kaltumformwerkzeugs sowie Kaltumformwerkzeug |
CN114207177A (zh) * | 2019-05-29 | 2022-03-18 | 欧瑞康表面处理解决方案股份公司普费菲孔 | 具有增强的性能和延长的使用寿命的涂覆成形工具 |
US20220379385A1 (en) * | 2020-06-04 | 2022-12-01 | Sumitomo Electric Hardmetal Corp. | Cutting tool |
CN112725792B (zh) * | 2020-12-28 | 2022-07-26 | 成都美奢锐新材料有限公司 | 一种氮化铬-碳氮化钛基金属陶瓷复合涂层的制备方法 |
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-
2016
- 2016-02-19 BR BR112017015891-4A patent/BR112017015891B1/pt active IP Right Grant
- 2016-02-19 WO PCT/EP2016/053503 patent/WO2016135047A1/en active Application Filing
- 2016-02-19 US US15/553,214 patent/US10626505B2/en active Active
- 2016-02-19 KR KR1020177021097A patent/KR102561370B1/ko active IP Right Grant
- 2016-02-19 CA CA2973927A patent/CA2973927C/en active Active
- 2016-02-19 PL PL16706566T patent/PL3262207T3/pl unknown
- 2016-02-19 TR TR2019/02064T patent/TR201902064T4/tr unknown
- 2016-02-19 JP JP2017544742A patent/JP6876611B2/ja active Active
- 2016-02-19 DK DK16706566.3T patent/DK3262207T3/da active
- 2016-02-19 ES ES16706566T patent/ES2709986T3/es active Active
- 2016-02-19 HU HUE16706566A patent/HUE042602T2/hu unknown
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- 2016-02-19 CN CN201680012806.XA patent/CN107532277B/zh active Active
- 2016-02-19 EP EP16706566.3A patent/EP3262207B1/en active Active
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Also Published As
Publication number | Publication date |
---|---|
BR112017015891B1 (pt) | 2021-05-04 |
PL3262207T3 (pl) | 2019-05-31 |
CA2973927C (en) | 2023-03-14 |
JP6876611B2 (ja) | 2021-05-26 |
US20180237922A1 (en) | 2018-08-23 |
EP3262207B1 (en) | 2018-12-12 |
JP2018509528A (ja) | 2018-04-05 |
AR103753A1 (es) | 2017-05-31 |
TR201902064T4 (tr) | 2019-03-21 |
EP3262207A1 (en) | 2018-01-03 |
BR112017015891A2 (pt) | 2018-04-10 |
CA2973927A1 (en) | 2016-09-01 |
KR20170121741A (ko) | 2017-11-02 |
CN107532277B (zh) | 2020-06-05 |
CN107532277A (zh) | 2018-01-02 |
KR102561370B1 (ko) | 2023-07-28 |
WO2016135047A1 (en) | 2016-09-01 |
MX2017010865A (es) | 2017-12-07 |
PH12017501354A1 (en) | 2017-12-11 |
US10626505B2 (en) | 2020-04-21 |
ES2709986T3 (es) | 2019-04-22 |
HUE042602T2 (hu) | 2019-07-29 |
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