技术领域technical field
本发明涉及一种双层复合管道支架及其制造方法，特别是涉及一种内层管道是聚对二氧环己酮(PPDO)单丝编织的网格状管道、所述的外层管道为聚乙交酯(PGLA)复丝编织的网格状管道的双层复合管道支架及其制造方法。The present invention relates to a double-layer composite pipeline support and a manufacturing method thereof, in particular to a grid-like pipeline in which the inner pipeline is woven with polydioxanone (PPDO) monofilament, and the outer pipeline is Polyglycolide (PGLA) multifilament braided grid-like pipeline double-layer composite pipeline support and its manufacturing method.
背景技术Background technique
在生物体内，很多的管道直径都在10-20mm之间，属于大管径的管道，比如食管，尿管，大动脉等等。这些管道在发生病变时，多数需行病变切除并实施管道重建。采用人工材料原位重建病变的管道，可减小手术创伤，简化手术操作传统的治疗。许多先天性或后天性食管疾病都需要行食管替代术，食管病变多数需行病变切除并实施食管重建。食管的替代物主要分两大类：一类是用自身的其他组织或器官，另一类是人工的食管替代物。采用人工材料原位重建食管，可减小手术创伤，简化手术操作，对消化功能影响小，具有重要的学术意义和实用价值。人工食管一直是人工器官研究的主要内容和探索的主要课题，20世纪以来人类进行了大量的人工食管实验研究，先后尝试了各种材料来制作人工食管，如：聚乙烯、硅橡胶、硅胶涤纶合成体、膨体聚四氟乙烯、碳素纤维等高分子材料和经处理后的气管或血管等生物材料，并制成各种形状的人工食管，取得了一些成果。高分子材料可以方便的通过各种工艺手段载荷药物，在置入管腔后使药物快速释放或缓释，以促进局部组织的愈合，在血管内可以防止血栓形成、预防血管再狭窄，目前受到材料科学和医学界的广泛关注。In the living body, the diameter of many pipes is between 10-20mm, belonging to large-diameter pipes, such as esophagus, urinary catheter, aorta and so on. Most of these pipelines require lesion resection and pipeline reconstruction when lesions occur. Using artificial materials to reconstruct the diseased pipeline in situ can reduce surgical trauma and simplify traditional treatment. Many congenital or acquired esophageal diseases require esophageal replacement, and most esophageal lesions require lesion resection and esophageal reconstruction. Esophageal substitutes are mainly divided into two categories: one is to use other tissues or organs of oneself, and the other is artificial esophageal substitutes. Using artificial materials to reconstruct the esophagus in situ can reduce surgical trauma, simplify surgical operations, and have little impact on digestive function, which has important academic significance and practical value. Artificial esophagus has always been the main content and subject of artificial organ research. Since the 20th century, humans have carried out a large number of artificial esophagus experimental research, and have tried various materials to make artificial esophagus, such as: polyethylene, silicone rubber, silicone polyester Polymer materials such as synthetic body, expanded polytetrafluoroethylene, carbon fiber, and biological materials such as trachea or blood vessel after processing, and made into artificial esophagus of various shapes, have obtained some results. Polymer materials can be conveniently loaded with drugs through various technological means, and after being inserted into the lumen, the drugs can be released quickly or slowly to promote the healing of local tissues, and can prevent thrombosis and restenosis in blood vessels. Widespread interest in the materials science and medical communities.
人工材料制备的管道支架经历了金属材料、高分子材料、生物材料等几个历程。金属材料制备的管道支架具有很好的力学支撑性能，但是术后愈合之后需要进行第二次手术将支架取出，并且金属材料的生物相容性和载药性能很差。与金属材料相比，可降解的生物材料制备的支架具有优越的性能。可降解高分子材料制备的内支架具有很好的生物相容性，在人体特定的病理过程中在完成对局部管腔的力学支撑和药物释放后支架逐渐被降解，避免了假体置入对人体的长期异物影响，且能较长时间保持狭窄部通畅，改善病人的营养状况，操作简单，病人痛苦减少，同时可防止肿瘤生长发生再狭窄，延缓患者生命。Pipe supports made of artificial materials have gone through several processes such as metal materials, polymer materials, and biological materials. Pipeline stents made of metal materials have good mechanical support properties, but a second operation is required to remove the stent after postoperative healing, and the biocompatibility and drug-loading performance of metal materials are poor. Compared with metal materials, scaffolds made of biodegradable biomaterials have superior performance. The stent made of degradable polymer materials has good biocompatibility. In the specific pathological process of the human body, the stent is gradually degraded after the mechanical support of the local lumen and drug release are completed, which avoids the impact of prosthetic implantation. Long-term impact of foreign bodies in the human body, and can keep the stenosis unobstructed for a long time, improve the nutritional status of the patient, the operation is simple, the patient's pain is reduced, and at the same time, it can prevent restenosis from tumor growth and delay the patient's life.
传统的食管内支撑物是一根硬质塑料管，置管时需全麻，短期并发症如出血、食管穿孔等可高达5％-30％，与操作有关的死亡率高达16％，术后再狭窄率可达7％-39％；随后，自展式“Z”型支架(Gianturco支架)、自展式金属网装支架(Wall stent)、球囊扩张金属网状支架(Strecker stent)、镍钛热记忆合金支架等多种金属内支架被应用到食管狭窄的治疗。这些支架置入方便，病人痛苦减小，并发症发生率也降低，我国在1983年也开始了应用此疗法治疗晚期食管癌狭窄，但当时放置食管内支架主要由外科开胸手术下进行，创伤大，术后并发症和死亡率高，适应症窄；金属食管内支架主要有不锈钢和镍钛合金两大类，后者具有更多的优越性。镍钛合金的特点是具有奇异的开关功能，即在一定温度下发生相应的变化，超弹性、耐磨性、耐腐蚀性和良好的生物相容性，其网状结构单元具有良好的纵向柔软性和径向支撑力，从而能适应人体食道的自然弯曲和生物蠕动。自展式“Z”型支架(Gianturco支架)用直径0.01英寸的医用不锈钢丝以“Z”字型方式折成短圆柱状，每节长2cm左右，直径14-20mm，根据病变程度可用钢丝或细线连接成多节支架，它的优点是：扩张强度好、弹性好，压缩时不延长，但是柔顺性较差；自展式金属网装支架(Wall stent)用多根直径0.1-0.2mm的医用不锈钢丝编织成网管状，选用不同数目、不同直径的钢丝进行编织，可得到疏密不同、不同弹性的支架，自展式金属网装支架(Wall stent)的优点是纵向柔顺性好，但是弹性不如“Z”型支架；球囊扩张金属网状支架(Strecker stent)是由单根0.1-0.15mm的钛丝或镍钛合金丝编织成网状，该支架经输送管推入狭窄部位后需再插入球囊导管进行被动扩张，才能完全张开。另有一种自膨式的Strecker支架，被压缩于导管表面，再用明胶包埋固定，外面再套以一鞘管，当送至狭窄部位后回撤鞘管，支架表面的明胶遇食管内壁的分泌物溶解，支架自膨；镍钛热记忆合金支架[5]用直径0.35-0.65mm镍钛合金丝绕成密螺旋状，两头扩张成双喇叭口状。该支架在小于4℃时可随意成型，缠绕在胃镜或导管表面，送至狭窄部位，经导管注入热盐水，支架遇热恢复原形，一般恢复温度为37℃-40℃。该支架组织相容性良好，易于释放，常用于吻合口狭窄或短段的良性狭窄；以上为截止1996年金属食道支架应用的主要种类，当时存在的主要问题有：食道支架会发生放置不到位或滑脱大多不易取出；被膜支架能对肿瘤的生长有一定阻止作用，但是比无膜支架更易滑脱，有人安装了勾刺、两头扩大的支架对防止滑脱有一定作用，但使支架更不易取出。The traditional support in the esophagus is a hard plastic tube, which requires general anesthesia, short-term complications such as bleeding, esophageal perforation, etc. can be as high as 5%-30%, and the mortality rate related to the operation is as high as 16%. The restenosis rate can reach 7%-39%; subsequently, self-expanding "Z" stent (Gianturco stent), self-expanding metal mesh stent (Wall stent), balloon-expandable metal mesh stent (Strecker stent), A variety of metal internal stents such as nickel-titanium thermal memory alloy stents have been applied to the treatment of esophageal strictures. These stents are easy to place, less pain for patients, and lower incidence of complications. In 1983, my country also started using this therapy to treat advanced esophageal cancer stenosis. Large, high postoperative complications and mortality, narrow indications; metal esophageal stents mainly include stainless steel and nickel-titanium alloy, the latter has more advantages. Nickel-titanium alloy is characterized by a singular switch function, that is, a corresponding change at a certain temperature, superelasticity, wear resistance, corrosion resistance and good biocompatibility, and its network structure unit has good longitudinal softness It can adapt to the natural bending and biological peristalsis of human esophagus. The self-expanding "Z"-shaped stent (Gianturco stent) is folded into a short cylindrical shape with medical stainless steel wire with a diameter of 0.01 inches in a "Z" shape. Each section is about 2cm long and 14-20mm in diameter. Steel wire or Thin wires are connected into a multi-section stent. Its advantages are: good expansion strength, good elasticity, no extension when compressed, but poor flexibility; self-expanding metal mesh stents (Wall stent) use multiple pieces with a diameter of 0.1-0.2mm Medical stainless steel wires are braided into mesh tubes, and steel wires of different numbers and diameters are used for braiding, and stents with different density and different elasticity can be obtained. The self-expanding metal mesh stent (Wall stent) has the advantage of good longitudinal flexibility. But the elasticity is not as good as the "Z" type stent; the balloon expandable metal mesh stent (Strecker stent) is woven into a net shape by a single 0.1-0.15mm titanium wire or nickel-titanium alloy wire, and the stent is pushed into the narrow part through the delivery tube After that, a balloon catheter needs to be inserted for passive dilation to fully open. There is also a self-expanding Strecker stent, which is compressed on the surface of the catheter, embedded and fixed with gelatin, and covered with a sheath outside. When it is delivered to the stenosis, the sheath is retracted. The gelatin on the surface of the stent meets the inner wall of the esophagus. The secretion dissolves, and the stent expands itself; the nickel-titanium thermal memory alloy stent [5] is wound into a dense spiral with a nickel-titanium alloy wire with a diameter of 0.35-0.65 mm, and the two ends expand into a double bell-mouth shape. The stent can be formed freely when the temperature is less than 4°C, wrapped around the surface of the gastroscope or catheter, sent to the narrow part, injected with hot saline through the catheter, and the stent returns to its original shape when heated, and the recovery temperature is generally 37°C-40°C. The stent has good histocompatibility and is easy to release. It is often used for anastomotic stenosis or short-segment benign stenosis. The above are the main types of metal esophageal stents used until 1996. The main problems at that time were: the esophageal stent would not be placed in place Or slippage is mostly difficult to remove; coated stent can prevent tumor growth to a certain extent, but it is easier to slip off than non-membrane stent.
至今，人工食管的研究已有50多年历史，半个世纪以来国内外各学者采用多种人工材料进行人工食管的研究取得了较大的成果，但仍存在诸多问题。过去的研究主要为机械材料制成的替代物，近期则主要集中在无细胞支架类人工食管和组织工程化人工食管两大类，难点仍是并发症的防治和组织相容性。人工食管留置一段时间后必然会脱落，会发生新生食管狭窄或发生瘘。这些是人工食管动物实验研究的最常见并发症，是人工食管能否进入临床的关键，这也是人工食管研究者所需要解决的问题。So far, the research on artificial esophagus has a history of more than 50 years. Scholars at home and abroad have made great achievements in the research of artificial esophagus by using various artificial materials for half a century, but there are still many problems. In the past, the research was mainly on the substitutes made of mechanical materials. Recently, it mainly focused on the two categories of acellular scaffold artificial esophagus and tissue engineered artificial esophagus. The difficulty is still the prevention and treatment of complications and histocompatibility. The artificial esophagus will fall off after being indwelling for a period of time, and new esophageal stricture or fistula will occur. These are the most common complications of artificial esophagus animal experiments, and are the key to whether artificial esophagus can enter clinical practice. This is also a problem that researchers of artificial esophagus need to solve.
发明内容Contents of the invention
本发明的目的是提供一种双层复合管道支架及其制造方法，特别是提供一种内层管道是聚对二氧环己酮(PPDO)单丝编织的网格状管道、所述的外层管道为聚乙交酯(PGLA)复丝编织的网格状管道的双层复合管道支架及其制造方法。本发明的复合管道支架具有更好的弹性回复性能和力学稳定性，在一定范围之内拉伸或者压缩均不会对其造成损坏；并且具有更大的载药能力。The purpose of the present invention is to provide a double-layer composite pipeline support and its manufacturing method, especially to provide a grid-like pipeline in which the inner pipeline is polydioxanone (PPDO) monofilament weaving, and the outer A double-layer composite pipe support in which the layer pipe is a grid-like pipe braided by polyglycolide (PGLA) multifilaments and a manufacturing method thereof. The composite pipe support of the present invention has better elastic recovery performance and mechanical stability, will not be damaged by stretching or compression within a certain range, and has greater drug loading capacity.
本发明的一种双层复合管道支架，由内、外两层管道组合而成，所述的内层管道是聚对二氧环己酮(PPDO)纤维编织的网格状管道，所述的外层管道为聚乙交酯(PGLA)复丝编织的网格状管道；A double-layer composite pipe support of the present invention is composed of inner and outer two-layer pipes, the inner pipe is a grid-like pipe woven with polydioxanone (PPDO) fibers, and the The outer pipe is a grid-like pipe braided by polyglycolide (PGLA) multifilament;
所述的聚对二氧环己酮(PPDO)纤维为单丝；Described polydioxanone (PPDO) fiber is monofilament;
所述的聚乙交酯(PGLA)纤维为复丝；Described polyglycolide (PGLA) fiber is multifilament;
所述的内层管道与所述的外层管道之间具有一定的间隙，间隙为0～0.5mm。There is a certain gap between the inner pipe and the outer pipe, and the gap is 0-0.5 mm.
作为优选的技术方案：As a preferred technical solution:
如上所述的一种双层复合管道支架，所述的内层管道和外层管道等长；所述的内层管道的网格密度为40-48孔/平方厘米，所述的外层管道的网格密度为50-60孔/平方厘米。所述的内层管道和外层管道等长，两层管道在轴向均有较好的延伸性能，随着管道的拉伸管径会变小，管道的网格密度变得稀疏，随着管道的压缩管径会变大，管道的网格密度会变得致密。复合管道支架与单层管道支架相比，网格的横向密度增大了，即网格的网孔变小了；又由于双层的叠加效果，网格的纵向密度也增大了，即网孔之间的空隙也变小了，这些不仅仅有利于提高复合管道支架的径向支撑力，而且提高了其载药性。两层管道之间是通过各自网格上部分交织点无序的缠结在一起的，当沿着轴向拉伸内层管道时，其管径会缩小，与外层管道之间的结合点会减少；当沿着轴向压缩外层管道时，其管径会增大，与内层管道之间的结合点会减少，这样两层管道就会部分分离，两层管道之间产生了很多的空隙，这些空隙有利于更多的液体药物载在上面。A double-layer composite pipe support as described above, the inner pipe and the outer pipe have the same length; the grid density of the inner pipe is 40-48 holes/square centimeter, and the outer pipe The grid density is 50-60 holes/cm2. The inner pipe and the outer pipe are equal in length, and the two pipes have good extension properties in the axial direction. As the pipe is stretched, the pipe diameter becomes smaller, and the grid density of the pipe becomes sparse. The compressed diameter of the pipeline will become larger, and the grid density of the pipeline will become denser. Compared with the single-layer pipe support, the lateral density of the grid increases, that is, the mesh size of the grid becomes smaller; and due to the superposition effect of the double layers, the vertical density of the grid also increases, that is, the grid The gaps between the holes are also reduced, which is not only beneficial to improve the radial support force of the composite pipeline scaffold, but also improves its drug loading. The two layers of pipes are entangled disorderly through some interweaving points on their respective grids. When the inner pipe is stretched along the axial direction, its diameter will shrink, and the junction with the outer pipe will decrease; when the outer pipe is compressed in the axial direction, its diameter will increase, and the junction with the inner pipe will decrease, so that the two layers of pipes will be partially separated, and a lot of pressure will be generated between the two layers of pipes. The gaps, these gaps are conducive to more liquid drugs loaded on it.
如上所述的一种双层复合管道支架，所述的聚对二氧环己酮(PPDO)单丝纤维的直径为0.2-0.4mm。According to the above-mentioned double-layer composite pipe support, the diameter of the polydioxanone (PPDO) monofilament fiber is 0.2-0.4mm.
如上所述的一种双层复合管道支架，所述的聚乙交酯(PGLA)复丝纤维的直径为0.15-0.2mm。According to the above-mentioned double-layer composite pipe support, the diameter of the polyglycolide (PGLA) multifilament fiber is 0.15-0.2mm.
本发明的一种双层复合管道支架，其内层管道和外层管道等长，内层管道的管径小于外层管道的管径，两层管道之间是通过部分网格交织点结合在一起的。两层管道之间具有一定的空间，热定型之后两层管道之间的空隙被固定下来。复合管道的网格密度大于单层管道支架的网格密度，经过热定型之后复合管道支架具有了更好的弹性回复性能和力学稳定性，在一定范围之内拉伸或者压缩均不会对其造成损坏。A double-layer composite pipeline support of the present invention has the same length as the inner pipeline and the outer pipeline, the diameter of the inner pipeline is smaller than the diameter of the outer pipeline, and the two layers of pipelines are connected by partial grid interweaving points. together. There is a certain space between the two layers of pipes, and the gap between the two layers of pipes is fixed after heat setting. The grid density of the composite pipe is higher than that of the single-layer pipe support. After heat setting, the composite pipe support has better elastic recovery performance and mechanical stability, and it will not be stretched or compressed within a certain range. cause damage.
本发明还提供了一种双层复合管道支架的制造方法，以金属管道作为管芯，在编织机上首先用聚对二氧环己酮(PPDO)编织内层管道支架，编织好之后，再以内层管道支架作为管芯，在其外面用所述的聚乙交酯(PGLA)编织外层管道支架；将编织好的双层复合支架连同金属管芯一起从编织机上取下来，然后从管道的两端沿着轴向分别拉伸内层的聚对二氧环己酮(PPDO)支架两端至原来长度的1.05-1.1倍，用夹子夹住聚对二氧环己酮(PPDO)管道与金属管芯，使聚对二氧环己酮(PPDO)两端固定在金属管芯上不回弹；把上述用夹子固定好的双层管道支架放到烘箱中进行热定型，定型温度为80°-85°，定型时间是15-20分钟；定型好待冷却之后将双层复合管道支架从金属管芯上面褪下来，将复合管道的两端剪齐，即制作成功双层复合管道支架；The present invention also provides a method for manufacturing a double-layer composite pipeline support. Metal pipes are used as tube cores, and polydioxanone (PPDO) is used to weave the inner layer pipeline support on a braiding machine. The layer pipe support is used as the tube core, and the outer layer of the pipe support is braided with the polyglycolide (PGLA) outside it; Stretch the two ends of the polydioxanone (PPDO) stent in the inner layer along the axial direction to 1.05-1.1 times the original length, clamp the polydioxanone (PPDO) pipe and Metal pipe core, so that the two ends of polydioxanone (PPDO) are fixed on the metal pipe core without rebound; the above-mentioned double-layer pipe support fixed with clips is placed in an oven for heat setting, and the setting temperature is 80 °-85°, the setting time is 15-20 minutes; after the setting is ready to cool, the double-layer composite pipe support is removed from the metal tube core, and the two ends of the composite pipe are cut evenly, and the double-layer composite pipe support is successfully produced;
其中，所述的聚对二氧环己酮(PPDO)纤维为单丝；所述的聚乙交酯(PGLA)纤维为复丝。Wherein, the polydioxanone (PPDO) fiber is monofilament; the polyglycolide (PGLA) fiber is multifilament.
如上所述的一种双层复合管道支架的制造方法，所述的内层管道的网格密度为36-45孔/平方厘米，所述的外层管道的网格密度为45-55孔/平方厘米。According to a method for manufacturing a double-layer composite pipe support as described above, the mesh density of the inner pipe is 36-45 holes/square centimeter, and the mesh density of the outer pipe is 45-55 holes/square centimeter. square centimeters.
如上所述的一种双层复合管道支架的制造方法，所述的聚对二氧环己酮(PPDO)单丝纤维的直径为0.2-0.4mm；所述的聚乙交酯(PGLA)复丝纤维的直径为0.15-0.2mm。A method for manufacturing a double-layer composite pipeline support as described above, the diameter of the monofilament fiber of the polydioxanone (PPDO) is 0.2-0.4mm; the composite polyglycolide (PGLA) The diameter of the silk fiber is 0.15-0.2mm.
本发明又提供了一种双层复合管道支架的制造方法，具体步骤为：以金属管道作为管芯，在编织机上首先用聚对二氧环己酮(PPDO)单丝纤维编织内层管道支架，编织好之后，再以内层管道支架作为管芯，在其外面用所述的聚乙交酯(PGLA)复丝编织外层管道支架；将编织好的双层复合支架连同金属管芯一起从编织机上取下来，然后从管道的两端沿着轴向分别压缩外层的PGLA支架至原来长度的0.9倍，用夹子分别夹住聚乙交酯(PGLA)管道与内层管道，使其两端固定在内层管道上不回弹；把上述用夹子固定好的双层支架放到烘箱中进行热定型，定型温度为80°-85°，定型时间是15-20分钟；定型好待冷却之后将双层复合管道支架从金属管芯上面褪下来，将复合管道的两端剪齐，即制作成功双层复合管道支架；The present invention also provides a method for manufacturing a double-layer composite pipe support, the specific steps are: using a metal pipe as a tube core, first weaving the inner pipe support with polydioxanone (PPDO) monofilament fibers on a braiding machine After weaving, use the inner pipe support as the pipe core, and weave the outer pipe support with the polyglycolide (PGLA) multifilament on the outside; the braided double-layer composite support together with the metal pipe core Remove it from the braiding machine, then compress the outer PGLA stent axially from both ends of the pipe to 0.9 times the original length, and clamp the polyglycolide (PGLA) pipe and the inner pipe with clips, so that the two The end is fixed on the inner pipe without rebounding; put the above-mentioned double-layer bracket fixed with clips into an oven for heat setting, the setting temperature is 80°-85°, and the setting time is 15-20 minutes; set the shape and wait for cooling Then remove the double-layer composite pipe support from the metal tube core, cut both ends of the composite pipe evenly, and then successfully make the double-layer composite pipe support;
其中，所述的聚对二氧环己酮(PPDO)纤维为单丝；所述的聚乙交酯(PGLA)纤维为复丝。Wherein, the polydioxanone (PPDO) fiber is monofilament; the polyglycolide (PGLA) fiber is multifilament.
如上所述的一种双层复合管道支架的制造方法，所述的内层管道的网格密度为15-20孔/平方厘米，所述的外层管道的网格密度为14-22孔/平方厘米。According to the manufacturing method of a double-layer composite pipe support as described above, the mesh density of the inner pipe is 15-20 holes/square centimeter, and the mesh density of the outer pipe is 14-22 holes/square centimeter. square centimeters.
如上所述的一种双层复合管道支架的制造方法，所述的聚对二氧环己酮(PPDO)单丝纤维的直径为0.2-0.4mm；所述的聚乙交酯(PGLA)复丝纤维的直径为0.15-0.2mm。A method for manufacturing a double-layer composite pipeline support as described above, the diameter of the monofilament fiber of the polydioxanone (PPDO) is 0.2-0.4mm; the composite polyglycolide (PGLA) The diameter of the silk fiber is 0.15-0.2mm.
按本发明所提供的方法所制成的复合管道的内层管道和外层管道等长，外层管道的管径大于内层管道的管径，两层管道之间是通过部分网格交织点结合在一起的。两层管道之间具有一定的空间，热定型之后两层管道之间的空隙被固定下来。复合管道的网格密度大于单层管道支架的网格密度，经过热定型之后复合管道支架具有了更好的弹性回复性能和力学稳定性，在一定范围之内拉伸或者压缩均不会对其造成损坏。The inner layer pipe and the outer layer pipe of the composite pipe made by the method provided by the present invention are equal in length, the pipe diameter of the outer layer pipe is larger than the pipe diameter of the inner layer pipe, and the part grid interweaving point is passed between the two layers of pipes Combined. There is a certain space between the two layers of pipes, and the gap between the two layers of pipes is fixed after heat setting. The grid density of the composite pipe is higher than that of the single-layer pipe support. After heat setting, the composite pipe support has better elastic recovery performance and mechanical stability, and it will not be stretched or compressed within a certain range. cause damage.
有益效果Beneficial effect
聚对二氧环己酮(PPDO)是一种单丝，该纤维具有较高的强度，用其编织的管道支架力学支撑性能较好，但是由于该纤维是一种单丝，表面光滑，故其编织的管道支架载药性很差；聚乙交酯(PGLA)是一种复丝，用其编织的管道支架载药性良好，但是仅用该材料编织的管道支架支撑力却非常小，将两种材料结合在一起，采用包覆的方式来编织双层复合管道支架，这样不仅仅提高了管道支架的力学性能，同时在编织后采用轴向拉伸内层管道或者轴向压缩外层管道支架的方式来提高双层支架之间的空隙率，这样又大大提高了管道支架的载药性能，从而形成的复合管道支架兼具了较大的力学性能和良好的载药性能的双重优点。Polydioxanone (PPDO) is a kind of monofilament, the fiber has high strength, and the mechanical support performance of the pipe support braided with it is better, but because the fiber is a kind of monofilament, the surface is smooth, so The drug-loading capacity of the braided pipeline stent is very poor; polyglycolide (PGLA) is a kind of multifilament, and the drug-loading property of the pipeline stent braided with it is good, but the supporting force of the pipeline stent braided only with this material is very small. The two materials are combined together, and the double-layer composite pipe support is braided in a cladding method, which not only improves the mechanical properties of the pipe support, but also uses axial stretching of the inner pipe or axial compression of the outer pipe support after braiding. In this way, the drug-loading performance of the pipeline scaffold is greatly improved, and the composite pipeline scaffold formed has the dual advantages of large mechanical properties and good drug-loading performance.
具体实施方式Detailed ways
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
一种双层复合管道支架，由内、外两层管道组合而成，内层管道是聚对二氧环己酮纤维编织的网格状管道，外层管道是聚乙交酯纤维编织的网格状管道；聚对二氧环己酮纤维为单丝，直径为0.2mm，聚乙交酯纤维为复丝，直径0.15mm；内层管道和外层管道等长。这种双层复合管道支架的制造方法是：以金属管道作为管芯，在编织机上首先用聚对二氧环己酮纤维编织内层管道支架，内层管道的网格密度为48孔/平方厘米；编织好之后，再以内层管道支架作为管芯，在其外面用聚乙交酯纤维编织外层管道支架，外层管道的网格密度为60孔/平方厘米；将编织好的双层复合管道支架连同金属管芯一起从编织机上取下来，然后从管道的两端沿着轴向分别拉伸内层管道支架两端至原来长度的1.1倍，用夹子夹住内层管道支架与金属管芯，使内层管道支架两端固定在金属管芯上不回弹；把上述用夹子固定好的双层管道支架放到烘箱中进行热定型，定型温度为85°，定型时间是20分钟；定型好待冷却之后将双层复合管道支架从金属管芯上面褪下来，此时，内层管道与所述的外层管道之间具有一定的间隙，间隙为0.5mm；将复合管道的两端剪齐，即制作成功双层复合管道支架。将该制作成功的双层复合管道支架进行载药实验，经测试该管道的载药率达到86.04％。用直径为0.2mm的聚对二氧环己酮纤维编织的单层管道支架，经载药测试后发现其载药率仅为50.32％。A double-layer composite pipe support, which is composed of inner and outer pipes, the inner pipe is a grid-like pipe woven by polydioxanone fiber, and the outer pipe is a net woven by polyglycolide fiber Lattice pipe; the polydioxanone fiber is a monofilament with a diameter of 0.2mm, and the polyglycolide fiber is a multifilament with a diameter of 0.15mm; the inner pipe and the outer pipe are equal in length. The manufacturing method of this double-layer composite pipe support is as follows: use metal pipe as the tube core, first use polydioxanone fiber to weave the inner layer pipe support on the braiding machine, and the grid density of the inner layer pipe is 48 holes/square cm; after weaving, use the inner layer pipe support as the tube core, weave the outer layer pipe support with polyglycolide fiber outside it, and the grid density of the outer layer pipe is 60 holes/square centimeter; Take the composite pipe support together with the metal pipe core from the braiding machine, and then stretch the two ends of the inner pipe support to 1.1 times the original length from both ends of the pipe along the axial direction, and clamp the inner pipe support and the metal pipe support with clips. Pipe core, so that the two ends of the inner pipe support are fixed on the metal pipe core without rebound; put the above-mentioned double-layer pipe support fixed with clips into an oven for heat setting, the setting temperature is 85°, and the setting time is 20 minutes After finalizing the shape and waiting for cooling, the double-layer composite pipe support is taken off from the metal pipe core. At this time, there is a certain gap between the inner layer pipe and the outer layer pipe, and the gap is 0.5mm; The ends are cut neatly, and the double-layer composite pipe support is successfully produced. The drug-loading experiment was carried out on the successfully fabricated double-layer composite pipeline stent, and the drug-loading rate of the pipeline reached 86.04%. The single-layer pipeline scaffold braided with polydioxanone fibers with a diameter of 0.2 mm was found to have a drug-loading rate of only 50.32% after a drug-loading test.
实施例2Example 2
一种双层复合管道支架，由内、外两层管道组合而成，内层管道是聚对二氧环己酮纤维编织的网格状管道，外层管道为聚乙交酯纤维编织的网格状管道；聚对二氧环己酮纤维为单丝，直径为0.3mm，聚乙交酯纤维为复丝，直径0.18mm；内层管道和外层管道等长。这种双层复合管道支架的制造方法是：以金属管道作为管芯，在编织机上首先用聚对二氧环己酮纤维编织内层管道支架，内层管道的网格密度为44孔/平方厘米；编织好之后，再以内层管道支架作为管芯，在其外面用聚乙交酯纤维编织外层管道支架，外层管道的网格密度为55孔/平方厘米；将编织好的双层复合管道支架连同金属管芯一起从编织机上取下来，然后从管道的两端沿着轴向分别拉伸内层管道支架两端至原来长度的1.05倍，用夹子夹住内层管道支架与金属管芯，使内层管道支架两端固定在金属管芯上不回弹；把上述用夹子固定好的双层管道支架放到烘箱中进行热定型，定型温度为83°，定型时间是18分钟；定型好待冷却之后将双层复合管道支架从金属管芯上面褪下来，此时，内层管道与所述的外层管道之间具有一定的间隙，间隙为0.4mm；将复合管道的两端剪齐，即制作成功双层复合管道支架。将该制作成功的双层复合管道支架进行载药实验，经测试该管道的载药率达到75.38％，用直径为0.3mm的聚对二氧环己酮纤维编织的单层管道支架，经载药测试后发现其载药率仅为43.34％。A double-layer composite pipe support, which is composed of inner and outer pipes, the inner pipe is a grid-like pipe woven by polydioxanone fiber, and the outer pipe is a net woven by polyglycolide fiber Lattice pipe; the polydioxanone fiber is a monofilament with a diameter of 0.3mm, and the polyglycolide fiber is a multifilament with a diameter of 0.18mm; the inner pipe and the outer pipe are equal in length. The manufacturing method of this double-layer composite pipe support is as follows: use metal pipe as the tube core, first use polydioxanone fiber to weave the inner layer pipe support on the braiding machine, and the grid density of the inner layer pipe is 44 holes/square cm; after weaving, use the inner layer pipe support as the tube core, weave the outer layer pipe support with polyglycolide fiber outside it, and the grid density of the outer layer pipe is 55 holes/square centimeter; Take the composite pipe support together with the metal pipe core from the braiding machine, then stretch the two ends of the inner pipe support from both ends of the pipe along the axial direction to 1.05 times the original length, and clamp the inner pipe support and the metal pipe support with clips. Pipe core, so that both ends of the inner pipe support are fixed on the metal pipe core without rebound; put the above-mentioned double-layer pipe support fixed with clips into an oven for heat setting, the setting temperature is 83°, and the setting time is 18 minutes After finalizing the shape and waiting for cooling, the double-layer composite pipe support is taken off from the metal tube core. At this time, there is a certain gap between the inner layer pipe and the outer layer pipe, and the gap is 0.4mm; The ends are cut neatly, and the double-layer composite pipe support is successfully produced. The drug-loading experiment was carried out on the successfully produced double-layer composite pipeline scaffold, and the drug-loading rate of the pipeline was tested to reach 75.38%. After drug testing, it was found that its drug loading rate was only 43.34%.
实施例3Example 3
一种双层复合管道支架，由内、外两层管道组合而成，内层管道是聚对二氧环己酮纤维编织的网格状管道，外层管道为聚乙交酯纤维编织的网格状管道；聚对二氧环己酮纤维为单丝，直径为0.4mm，聚乙交酯纤维为复丝，直径0.20mm；内层管道和外层管道等长。这种双层复合管道支架的制造方法是：以金属管道作为管芯，在编织机上首先用聚对二氧环己酮纤维编织内层管道支架，内层管道的网格密度为40孔/平方厘米；编织好之后，再以内层管道支架作为管芯，在其外面用聚乙交酯纤维编织外层管道支架，外层管道的网格密度为50孔/平方厘米；将编织好的双层复合管道支架连同金属管芯一起从编织机上取下来，然后从管道的两端沿着轴向分别拉伸内层管道支架两端至原来长度的1.00倍，用夹子夹住内层管道支架与金属管芯，使内层管道支架两端固定在金属管芯上不回弹；把上述用夹子固定好的双层管道支架放到烘箱中进行热定型，定型温度为80°，定型时间是15分钟；定型好待冷却之后将双层复合管道支架从金属管芯上面褪下来，此时，内层管道与所述的外层管道之间具有一定的间隙，间隙为0.3mm；将复合管道的两端剪齐，即制作成功双层复合管道支架。将该制作成功的双层复合管道支架进行载药实验，经测试该管道的载药率达到61.22％，用直径为0.4mm的聚对二氧环己酮纤维编织的单层管道支架，经载药测试后发现其载药率仅为40.32％。A double-layer composite pipe support, which is composed of inner and outer pipes, the inner pipe is a grid-like pipe woven by polydioxanone fiber, and the outer pipe is a net woven by polyglycolide fiber Lattice pipe; the polydioxanone fiber is a monofilament with a diameter of 0.4mm, and the polyglycolide fiber is a multifilament with a diameter of 0.20mm; the inner pipe and the outer pipe are equal in length. The manufacturing method of this double-layer composite pipe support is: use the metal pipe as the tube core, first weave the inner layer pipe support with polydioxanone fiber on the braiding machine, and the grid density of the inner layer pipe is 40 holes/square cm; after weaving, use the inner layer pipe support as the tube core, weave the outer layer pipe support with polyglycolide fiber outside it, and the mesh density of the outer layer pipe is 50 holes/square centimeter; Take the composite pipe support together with the metal tube core from the braiding machine, then stretch the two ends of the inner pipe support to 1.00 times the original length from both ends of the pipe along the axial direction, and clamp the inner pipe support and the metal pipe support with clips. Pipe core, so that the two ends of the inner pipe support are fixed on the metal pipe core without rebound; put the above-mentioned double-layer pipe support fixed with clips into an oven for heat setting, the setting temperature is 80°, and the setting time is 15 minutes After finalizing the shape and waiting for cooling, the double-layer composite pipe support is taken off from the metal tube core. At this time, there is a certain gap between the inner layer pipe and the outer layer pipe, and the gap is 0.3mm; The ends are cut neatly, and the double-layer composite pipe support is successfully produced. The drug-loading experiment was carried out on the successfully produced double-layer composite pipeline scaffold, and the drug-loading rate of the pipeline reached 61.22%. The single-layer pipeline scaffold braided with polydioxanone fibers with a diameter of 0.4mm was After drug testing, it was found that its drug loading rate was only 40.32%.
实施例4Example 4
一种双层复合管道支架，由内、外两层管道组合而成，内层管道是聚对二氧环己酮纤维编织的网格状管道，外层管道是聚乙交酯纤维编织的网格状管道；聚对二氧环己酮纤维为单丝，直径为0.2mm，聚乙交酯纤维为复丝，直径0.15mm；内层管道和外层管道等长。这种双层复合管道支架的制造方法是：以金属管道作为管芯，在编织机上首先用聚对二氧环己酮纤维编织内层管道支架，内层管道的网格密度为48孔/平方厘米；编织好之后，再以内层管道支架作为管芯，在其外面用聚乙交酯纤维编织外层管道支架，外层管道的网格密度为60孔/平方厘米；将编织好的双层复合管道支架连同金属管芯一起从编织机上取下来，然后从管道的两端沿着轴向分别压缩外层管道支架至原来长度的0.85倍，用夹子夹住内层管道支架与金属管芯，使内层管道支架两端固定在金属管芯上不回弹；把上述用夹子固定好的双层管道支架放到烘箱中进行热定型，定型温度为85°，定型时间是20分钟；定型好待冷却之后将双层复合管道支架从金属管芯上面褪下来，此时，内层管道与所述的外层管道之间具有一定的间隙，间隙为0.5mm；将复合管道的两端剪齐，即制作成功双层复合管道支架。将该制作成功的双层复合管道支架进行载药实验，经测试该管道的载药率达到87.23％。用直径为0.2mm的聚对二氧环己酮纤维编织的单层管道支架，经载药测试后发现其载药率仅为52.33％。A double-layer composite pipe support, which is composed of inner and outer pipes, the inner pipe is a grid-like pipe woven by polydioxanone fiber, and the outer pipe is a net woven by polyglycolide fiber Lattice pipe; the polydioxanone fiber is a monofilament with a diameter of 0.2mm, and the polyglycolide fiber is a multifilament with a diameter of 0.15mm; the inner pipe and the outer pipe are equal in length. The manufacturing method of this double-layer composite pipe support is as follows: use metal pipe as the tube core, first use polydioxanone fiber to weave the inner layer pipe support on the braiding machine, and the grid density of the inner layer pipe is 48 holes/square cm; after weaving, use the inner layer pipe support as the tube core, weave the outer layer pipe support with polyglycolide fiber outside it, and the grid density of the outer layer pipe is 60 holes/square centimeter; The composite pipe support together with the metal pipe core is removed from the braiding machine, and then the outer pipe support is compressed axially from both ends of the pipe to 0.85 times the original length, and the inner pipe support and the metal pipe core are clamped with clips. Fix the two ends of the inner pipe support on the metal tube core without springback; put the above-mentioned double-layer pipe support fixed with clips into an oven for heat setting, the setting temperature is 85°, and the setting time is 20 minutes; the setting is good After cooling, remove the double-layer composite pipe support from the metal tube core. At this time, there is a certain gap between the inner pipe and the outer pipe, and the gap is 0.5mm; cut both ends of the composite pipe , that is, the double-layer composite pipe support was successfully produced. The drug-loading experiment was carried out on the successfully fabricated double-layer composite pipeline stent, and the drug-loading rate of the pipeline reached 87.23%. The single-layer pipeline scaffold braided with polydioxanone fibers with a diameter of 0.2mm was found to have a drug-loading rate of only 52.33% after a drug-loading test.
实施例5Example 5
一种双层复合管道支架，由内、外两层管道组合而成，内层管道是聚对二氧环己酮纤维编织的网格状管道，外层管道是聚乙交酯纤维编织的网格状管道；聚对二氧环己酮纤维为单丝，直径为0.2mm，聚乙交酯纤维为复丝，直径0.15mm；内层管道和外层管道等长。这种双层复合管道支架的制造方法是：以金属管道作为管芯，在编织机上首先用聚对二氧环己酮纤维编织内层管道支架，内层管道的网格密度为48孔/平方厘米；编织好之后，再以内层管道支架作为管芯，在其外面用聚乙交酯纤维编织外层管道支架，外层管道的网格密度为60孔/平方厘米；将编织好的双层复合管道支架连同金属管芯一起从编织机上取下来，然后从管道的两端沿着轴向分别压缩外层管道支架至原来长度的0.87倍，用夹子夹住内层管道支架与金属管芯，使内层管道支架两端固定在金属管芯上不回弹；把上述用夹子固定好的双层管道支架放到烘箱中进行热定型，定型温度为85°，定型时间是20分钟；定型好待冷却之后将双层复合管道支架从金属管芯上面褪下来，此时，内层管道与所述的外层管道之间具有一定的间隙，间隙为0.5mm；将复合管道的两端剪齐，即制作成功双层复合管道支架。将该制作成功的双层复合管道支架进行载药实验，经测试该管道的载药率达到86.65％。用直径为0.2mm的聚对二氧环己酮纤维编织的单层管道支架，经载药测试后发现其载药率仅为51.54％。A double-layer composite pipe support, which is composed of inner and outer pipes, the inner pipe is a grid-like pipe woven by polydioxanone fiber, and the outer pipe is a net woven by polyglycolide fiber Lattice pipe; the polydioxanone fiber is a monofilament with a diameter of 0.2mm, and the polyglycolide fiber is a multifilament with a diameter of 0.15mm; the inner pipe and the outer pipe are equal in length. The manufacturing method of this double-layer composite pipe support is as follows: use metal pipe as the tube core, first use polydioxanone fiber to weave the inner layer pipe support on the braiding machine, and the grid density of the inner layer pipe is 48 holes/square cm; after weaving, use the inner layer pipe support as the tube core, weave the outer layer pipe support with polyglycolide fiber outside it, and the grid density of the outer layer pipe is 60 holes/square centimeter; The composite pipe support together with the metal pipe core is removed from the braiding machine, and then the outer pipe support is compressed to 0.87 times the original length from both ends of the pipe along the axial direction, and the inner pipe support and the metal pipe core are clamped with clips. Fix the two ends of the inner pipe support on the metal tube core without springback; put the above-mentioned double-layer pipe support fixed with clips into an oven for heat setting, the setting temperature is 85°, and the setting time is 20 minutes; the setting is good After cooling, remove the double-layer composite pipe support from the metal tube core. At this time, there is a certain gap between the inner pipe and the outer pipe, and the gap is 0.5mm; cut both ends of the composite pipe , that is, the double-layer composite pipe support was successfully fabricated. The drug-loading experiment was carried out on the successfully fabricated double-layer composite pipeline stent, and the drug-loading rate of the pipeline reached 86.65%. The single-layer pipeline scaffold braided with polydioxanone fibers with a diameter of 0.2 mm was found to have a drug-loading rate of only 51.54% after a drug-loading test.
实施例6Example 6
一种双层复合管道支架，由内、外两层管道组合而成，内层管道是聚对二氧环己酮纤维编织的网格状管道，外层管道是聚乙交酯纤维编织的网格状管道；聚对二氧环己酮纤维为单丝，直径为0.2mm，聚乙交酯纤维为复丝，直径0.15mm；内层管道和外层管道等长。这种双层复合管道支架的制造方法是：以金属管道作为管芯，在编织机上首先用聚对二氧环己酮纤维编织内层管道支架，内层管道的网格密度为48孔/平方厘米；编织好之后，再以内层管道支架作为管芯，在其外面用聚乙交酯纤维编织外层管道支架，外层管道的网格密度为60孔/平方厘米；将编织好的双层复合管道支架连同金属管芯一起从编织机上取下来，然后从管道的两端沿着轴向分别压缩外层管道支架至原来长度的0.85倍，用夹子夹住内层管道支架与金属管芯，使内层管道支架两端固定在金属管芯上不回弹；把上述用夹子固定好的双层管道支架放到烘箱中进行热定型，定型温度为85°，定型时间是20分钟；定型好待冷却之后将双层复合管道支架从金属管芯上面褪下来，此时，内层管道与所述的外层管道之间具有一定的间隙，间隙为0.5mm；将复合管道的两端剪齐，即制作成功双层复合管道支架。将该制作成功的双层复合管道支架进行载药实验，经测试该管道的载药率达到85.65％。用直径为0.2mm的聚对二氧环己酮纤维编织的单层管道支架，经载药测试后发现其载药率仅为50.95％。A double-layer composite pipe support, which is composed of inner and outer pipes, the inner pipe is a grid-like pipe woven by polydioxanone fiber, and the outer pipe is a net woven by polyglycolide fiber Lattice pipe; the polydioxanone fiber is a monofilament with a diameter of 0.2mm, and the polyglycolide fiber is a multifilament with a diameter of 0.15mm; the inner pipe and the outer pipe are equal in length. The manufacturing method of this double-layer composite pipe support is as follows: use metal pipe as the tube core, first use polydioxanone fiber to weave the inner layer pipe support on the braiding machine, and the grid density of the inner layer pipe is 48 holes/square cm; after weaving, use the inner layer pipe support as the tube core, weave the outer layer pipe support with polyglycolide fiber outside it, and the grid density of the outer layer pipe is 60 holes/square centimeter; The composite pipe support together with the metal pipe core is removed from the braiding machine, and then the outer pipe support is compressed axially from both ends of the pipe to 0.85 times the original length, and the inner pipe support and the metal pipe core are clamped with clips. Fix the two ends of the inner pipe support on the metal tube core without springback; put the above-mentioned double-layer pipe support fixed with clips into an oven for heat setting, the setting temperature is 85°, and the setting time is 20 minutes; the setting is good After cooling, remove the double-layer composite pipe support from the metal tube core. At this time, there is a certain gap between the inner pipe and the outer pipe, and the gap is 0.5mm; cut both ends of the composite pipe , that is, the double-layer composite pipe support was successfully produced. The drug-loading experiment was carried out on the successfully fabricated double-layer composite pipeline stent, and the drug-loading rate of the pipeline reached 85.65%. The single-layer pipe scaffold woven with polydioxanone fibers with a diameter of 0.2mm was found to have a drug-loading rate of only 50.95% after a drug-loading test.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100782556ACN102160830B (en) | 2011-03-30 | 2011-03-30 | Double-layer compound pipeline bracket and manufacturing method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100782556ACN102160830B (en) | 2011-03-30 | 2011-03-30 | Double-layer compound pipeline bracket and manufacturing method thereof |
| Publication Number | Publication Date |
|---|---|
| CN102160830Atrue CN102160830A (en) | 2011-08-24 |
| CN102160830B CN102160830B (en) | 2013-07-10 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100782556AActiveCN102160830B (en) | 2011-03-30 | 2011-03-30 | Double-layer compound pipeline bracket and manufacturing method thereof |
| Country | Link |
|---|---|
| CN (1) | CN102160830B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103656838A (en)* | 2013-12-31 | 2014-03-26 | 易生科技(北京)有限公司 | Guide pipe of special ball bag structure |
| CN113599035A (en)* | 2021-09-02 | 2021-11-05 | 东莞颠覆产品设计有限公司 | Support and application |
| WO2024082640A1 (en)* | 2022-10-19 | 2024-04-25 | 常州乐奥医疗科技股份有限公司 | Method for manufacturing biliary tract stent and biliary tract stent |
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| CN101496753A (en)* | 2008-01-29 | 2009-08-05 | 太雄医疗器株式会社 | Double-tube type stent |
| CN101496754A (en)* | 2008-01-29 | 2009-08-05 | 太雄医疗器株式会社 | Biodegradable double stent |
| US20090312834A1 (en)* | 2008-06-16 | 2009-12-17 | Boston Scientific Scimed, Inc. | Continuous double layered stent for migration resistance |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101496753A (en)* | 2008-01-29 | 2009-08-05 | 太雄医疗器株式会社 | Double-tube type stent |
| CN101496754A (en)* | 2008-01-29 | 2009-08-05 | 太雄医疗器株式会社 | Biodegradable double stent |
| US20090312834A1 (en)* | 2008-06-16 | 2009-12-17 | Boston Scientific Scimed, Inc. | Continuous double layered stent for migration resistance |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103656838A (en)* | 2013-12-31 | 2014-03-26 | 易生科技(北京)有限公司 | Guide pipe of special ball bag structure |
| CN113599035A (en)* | 2021-09-02 | 2021-11-05 | 东莞颠覆产品设计有限公司 | Support and application |
| WO2024082640A1 (en)* | 2022-10-19 | 2024-04-25 | 常州乐奥医疗科技股份有限公司 | Method for manufacturing biliary tract stent and biliary tract stent |
| Publication number | Publication date |
|---|---|
| CN102160830B (en) | 2013-07-10 |
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