JP7446289B2 - 溶融延伸ポリアミドフィラメント - Google Patents
溶融延伸ポリアミドフィラメント Download PDFInfo
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- JP7446289B2 JP7446289B2 JP2021517818A JP2021517818A JP7446289B2 JP 7446289 B2 JP7446289 B2 JP 7446289B2 JP 2021517818 A JP2021517818 A JP 2021517818A JP 2021517818 A JP2021517818 A JP 2021517818A JP 7446289 B2 JP7446289 B2 JP 7446289B2
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- 239000004952 Polyamide Substances 0.000 title claims description 17
- 229920002647 polyamide Polymers 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 5
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- DVPHDWQFZRBFND-DMHDVGBCSA-N 1-o-[2-[(3ar,5r,6s,6ar)-2,2-dimethyl-6-prop-2-enoyloxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-2-[4-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chlorophenyl)-4-oxoazetidin-3-yl]oxy-4-oxobutanoyl]oxyethyl] 4-o-[(2s,3r)-1-butan-2-ylsulfanyl-2-(2-chloropheny Chemical group C1([C@H]2[C@H](C(N2SC(C)CC)=O)OC(=O)CCC(=O)OC(COC(=O)CCC(=O)O[C@@H]2[C@@H](N(C2=O)SC(C)CC)C=2C(=CC=CC=2)Cl)[C@@H]2[C@@H]([C@H]3OC(C)(C)O[C@H]3O2)OC(=O)C=C)=CC=CC=C1Cl DVPHDWQFZRBFND-DMHDVGBCSA-N 0.000 claims 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 229920002614 Polyether block amide Polymers 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- 102100037293 Atrial natriuretic peptide-converting enzyme Human genes 0.000 description 1
- 101710133555 Atrial natriuretic peptide-converting enzyme Proteins 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- IFAWYXIHOVRGHQ-UHFFFAOYSA-N Nonadecandioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCC(O)=O IFAWYXIHOVRGHQ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960002255 azelaic acid Drugs 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/224—Selection or control of the temperature during stretching
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Artificial Filaments (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Polyamides (AREA)
Description
乾式フィラメントをガラス転移温度と融点の間の温度で延伸し、
前記フィラメントを最大引張荷重で、乾式で、100℃未満に冷却して得られる、延伸フィラメント
を提供するものである。
本発明による延伸フィラメントは、高温下でさえも機械的安定性が高いことも利点である。
によって求められることが好ましい。
(式中、γは、0.05~0.95、好ましくは0.1~0.8、より好ましくは0.2~0.7、特に好ましくは0.3~0.6の値である。)
PA 6.10:ベスタミド Terra HS 16(エボニック社)
PA 10.10:ベスタミド Terra DS 18(エボニック社)
PA 12:ベスタミド L2101 nf(エボニック社)
トロガミド:CX7323(エボニック社)
PA 11
DSC:
パーキンエルマー社、ダイアモンドタイプ、自動ピーク認識および自動集積、DIN EN ISO 11357-1:2010に準拠、加熱速度20K/分。
上記のポリアミドを、押出機(コリンE45M)を用いて、融点より5℃~10℃高い温度(例えば、PA12の場合、250℃~260℃)で押し出して、厚さ150μm、350μm、および650μmのリボンを作製し、30℃~40℃に冷却した。
リボンを1.4m/分の速度でカレンダー加工にかけた;幅は35mmであった。
P 1.*はPA 12のサンプルである。
P 2.*はトロガミドのサンプルである。
P 3.*はPA 6.10のサンプルである。
P 4.*はPA 10.10のサンプルである。
P5.*はPA 11のサンプルである。
方法1
引張試験機(ズウィック社、Z101-K)で、実施例1による試験片を140℃で50mm/分の速度で延伸した。引張応力を解除する前に、試験片を室温まで冷却した。冷却は、2分以内にゆっくりと、あるいは10秒以内に素早く行った。
以下の表によるさらなるサンプル:
実施例1によるエンドレス試験片をコイル上に準備し、連続機(リテックドローイング)上で、1rpm~2.5rpmの材料供給速度かつ最大32rpmの引張速度で、延伸率(SF)3.5~8に延伸した。延伸は、60℃~140℃の温度で行われた。
実施例0:連続延伸法-サンプルP 1.*(PA12)、厚さ650μm、幅10mm。
実施例2からの試験片を10cmの長さに切断した。実施例2、方法1による試験片を両端で切断した。試験片を、熱オーブンに、引張荷重なしで、自由に移動できる方法で個別に横置きし、80℃と120℃の温度で5時間保管した。
引張試験
DIN 527-5:1997に準拠したダンベル状試験片(試験片A)を、延伸リボンから打ち抜いた;厚さは、延伸実験の結果のものであり、変更されなかった。引張強さを3つの試験片で測定し、いずれの場合もズウィック引張試験機を使用して、異なる温度で測定した。試験速度=5mm/分、クランプ長さ=120mm、およびインクリメンタルゲージの測定長さ=75mm。
温度23℃、相対湿度50%。
Claims (8)
- 少なくとも80重量%の直鎖状、分岐鎖状または環状の脂肪族または半芳香族ポリアミドを含む延伸フィラメントの製造方法であり、
乾式フィラメントをガラス転移温度と融点の間の温度で延伸し、
延伸したフィラメントを、前記延伸時の全引張荷重下で、水を使用せずに乾式で100℃未満に冷却する、延伸フィラメントの製造方法。 - 前記延伸時の最小延伸温度Tstr,minが式(1):
によって求められる、請求項1記載の延伸フィラメントの製造方法。 - ガラス転移温度より高く、融点より低い温度に加熱された場合に、引張方向の収縮性/弛緩性が低く、延伸された長さに対して最大6%である、請求項1または請求項2記載の延伸フィラメントの製造方法。
- ガラス転移温度より高く、延伸時の温度より低い温度に加熱された場合に、引張方向の収縮性/弛緩性が低く、延伸された長さに対して最大6%である、請求項1または請求項2記載の延伸フィラメントの製造方法。
- 前記ポリアミド、アミノカルボン酸、もしくはラクタムのモノマー、またはこの種の異なるモノマーの混合物の炭素原子の算術平均が少なくとも7.0であり、ジアミンとジカルボン酸の組み合わせである場合、ジアミンとジカルボン酸の炭素原子の算術平均が少なくとも7.0である、請求項1~請求項4のいずれか1項記載の延伸フィラメントの製造方法。
- 前記延伸において、前記乾式フィラメントを少なくとも2.5倍延伸する、請求項1~請求項5のいずれか1項記載の延伸フィラメントの製造方法。
- 複合材料の製造のための、請求項1~請求項6のいずれか1項記載の延伸フィラメントの製造方法により製造された延伸フィラメントの使用。
- 巻線層の製造のための、請求項1~請求項6のいずれか1項記載の延伸フィラメントの製造方法により製造された延伸フィラメントの使用。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18199730.5 | 2018-10-10 | ||
EP18199730.5A EP3636808A1 (de) | 2018-10-10 | 2018-10-10 | Gereckte polyamidfilamente |
PCT/EP2019/077341 WO2020074572A1 (de) | 2018-10-10 | 2019-10-09 | Schmelzvereckte polyamidfilamente |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2022503967A JP2022503967A (ja) | 2022-01-12 |
JP7446289B2 true JP7446289B2 (ja) | 2024-03-08 |
Family
ID=63921499
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2021517818A Active JP7446289B2 (ja) | 2018-10-10 | 2019-10-09 | 溶融延伸ポリアミドフィラメント |
Country Status (10)
Country | Link |
---|---|
US (1) | US20210381135A1 (ja) |
EP (2) | EP3636808A1 (ja) |
JP (1) | JP7446289B2 (ja) |
KR (1) | KR20210069705A (ja) |
CN (1) | CN112955588B (ja) |
AR (1) | AR116725A1 (ja) |
BR (1) | BR112021006566A2 (ja) |
CA (1) | CA3115386A1 (ja) |
MX (1) | MX2021004065A (ja) |
WO (1) | WO2020074572A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3640376A1 (de) | 2018-10-17 | 2020-04-22 | Evonik Operations GmbH | Gereckte aromatische polyether |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180344489A1 (en) | 2017-06-01 | 2018-12-06 | Korea Institute Of Science And Technology | Biodegradable stent and preparation method thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US2298868A (en) | 1940-04-03 | 1942-10-13 | Du Pont | Synthetic polyamide filaments of high impact strength and process of making same |
BE464568A (ja) * | 1944-09-15 | |||
GB885513A (en) * | 1957-04-08 | 1961-12-28 | Dunlop Rubber Co | Hot stretching of fibres |
US3393252A (en) | 1967-04-19 | 1968-07-16 | Du Pont | Melt blend of polyamides |
GB1150860A (en) * | 1967-12-28 | 1969-05-07 | Du Pont | Polyamide Filaments and process for making them |
US3869430A (en) | 1971-08-17 | 1975-03-04 | Du Pont | High modulus, high tenacity poly(p-phenylene terephthalamide) fiber |
US5011645A (en) * | 1989-05-04 | 1991-04-30 | E. I. Du Pont De Nemours And Company | Process for preparing nylon staple fiber |
US5104969A (en) * | 1989-10-20 | 1992-04-14 | E. I. Du Pont De Nemours And Company | Low shrinkage, high tenacity poly(epsilon-caproamide) yarn and process for making same |
US5106946A (en) * | 1989-10-20 | 1992-04-21 | E. I. Du Pont De Nemours And Company | High tenacity, high modulus polyamide yarn and process for making same |
CA2040133A1 (en) * | 1990-05-11 | 1991-11-12 | F. Holmes Simons | Spinning process for producing high strength, high modulus, low shrinkage synthetic yarns |
JPH05156513A (ja) * | 1991-12-04 | 1993-06-22 | Asahi Chem Ind Co Ltd | 高強度ポリアミド繊維及びその製造方法 |
DE19705113C2 (de) * | 1997-02-12 | 1999-04-29 | Freudenberg Carl Fa | Verstreckvorrichtung und Verfahren zur Herstellung verstreckter Kunststoffilamente |
AR041322A1 (es) | 2002-09-27 | 2005-05-11 | Lankhorst Indutech Bv | Metodo para reforzar un articulo |
US20110207907A1 (en) | 2008-11-20 | 2011-08-25 | Joseph Arnold Paul Maria Simmelink | Gel spun polyethylene fiber |
CN102465353B (zh) * | 2010-11-18 | 2014-04-16 | 上海杰事杰新材料(集团)股份有限公司 | 一种均聚半芳香族聚酰胺纤维及其制备方法 |
EP2864109B1 (en) | 2012-06-22 | 2021-08-25 | Katholieke Universiteit Leuven K.U. Leuven R&D | Hybrid self-reinforced composite material |
WO2015107024A1 (en) | 2014-01-17 | 2015-07-23 | Dsm Ip Assets B.V. | Polyamide fibers |
US10689778B2 (en) * | 2014-12-19 | 2020-06-23 | Truetzschler Gmbh & Co. Kg | Process and apparatus for the production of a low-shrinkage aliphatic polyamide yarn, and low-shrinkage yarn |
-
2018
- 2018-10-10 EP EP18199730.5A patent/EP3636808A1/de not_active Withdrawn
-
2019
- 2019-10-09 WO PCT/EP2019/077341 patent/WO2020074572A1/de unknown
- 2019-10-09 CA CA3115386A patent/CA3115386A1/en active Pending
- 2019-10-09 EP EP19783050.8A patent/EP3864200A1/de active Pending
- 2019-10-09 KR KR1020217013492A patent/KR20210069705A/ko not_active Application Discontinuation
- 2019-10-09 BR BR112021006566-0A patent/BR112021006566A2/pt active Search and Examination
- 2019-10-09 MX MX2021004065A patent/MX2021004065A/es unknown
- 2019-10-09 CN CN201980066665.3A patent/CN112955588B/zh active Active
- 2019-10-09 AR ARP190102869A patent/AR116725A1/es active IP Right Grant
- 2019-10-09 US US17/281,927 patent/US20210381135A1/en active Pending
- 2019-10-09 JP JP2021517818A patent/JP7446289B2/ja active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180344489A1 (en) | 2017-06-01 | 2018-12-06 | Korea Institute Of Science And Technology | Biodegradable stent and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
US20210381135A1 (en) | 2021-12-09 |
BR112021006566A2 (pt) | 2021-07-13 |
CA3115386A1 (en) | 2020-04-16 |
AR116725A1 (es) | 2021-06-09 |
CN112955588B (zh) | 2024-01-05 |
CN112955588A (zh) | 2021-06-11 |
WO2020074572A1 (de) | 2020-04-16 |
MX2021004065A (es) | 2021-06-04 |
JP2022503967A (ja) | 2022-01-12 |
EP3864200A1 (de) | 2021-08-18 |
EP3636808A1 (de) | 2020-04-15 |
KR20210069705A (ko) | 2021-06-11 |
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