WO2022142788A1 - Matériau embolique et son procédé de fabrication - Google Patents

Matériau embolique et son procédé de fabrication Download PDF

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Publication number
WO2022142788A1
WO2022142788A1 PCT/CN2021/130763 CN2021130763W WO2022142788A1 WO 2022142788 A1 WO2022142788 A1 WO 2022142788A1 CN 2021130763 W CN2021130763 W CN 2021130763W WO 2022142788 A1 WO2022142788 A1 WO 2022142788A1
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WO
WIPO (PCT)
Prior art keywords
helical
helical member
shaping
wire
emboli
Prior art date
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PCT/CN2021/130763
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English (en)
Chinese (zh)
Inventor
张朔
杨瑞
蔡亮
郭远益
钱少君
Original Assignee
神遁医疗科技(上海)有限公司
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Publication of WO2022142788A1 publication Critical patent/WO2022142788A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/12—Surgical instruments, devices or methods, e.g. tourniquets for ligaturing or otherwise compressing tubular parts of the body, e.g. blood vessels, umbilical cord
    • A61B17/12022—Occluding by internal devices, e.g. balloons or releasable wires
    • A61B17/12099—Occluding by internal devices, e.g. balloons or releasable wires characterised by the location of the occluder
    • A61B17/12109—Occluding by internal devices, e.g. balloons or releasable wires characterised by the location of the occluder in a blood vessel
    • A61B17/12113—Occluding by internal devices, e.g. balloons or releasable wires characterised by the location of the occluder in a blood vessel within an aneurysm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/12—Surgical instruments, devices or methods, e.g. tourniquets for ligaturing or otherwise compressing tubular parts of the body, e.g. blood vessels, umbilical cord
    • A61B17/12022—Occluding by internal devices, e.g. balloons or releasable wires
    • A61B17/12131—Occluding by internal devices, e.g. balloons or releasable wires characterised by the type of occluding device
    • A61B17/1214—Coils or wires
    • A61B17/12145—Coils or wires having a pre-set deployed three-dimensional shape
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/12—Surgical instruments, devices or methods, e.g. tourniquets for ligaturing or otherwise compressing tubular parts of the body, e.g. blood vessels, umbilical cord
    • A61B17/12022—Occluding by internal devices, e.g. balloons or releasable wires
    • A61B17/12131—Occluding by internal devices, e.g. balloons or releasable wires characterised by the type of occluding device
    • A61B17/1214—Coils or wires
    • A61B17/1215—Coils or wires comprising additional materials, e.g. thrombogenic, having filaments, having fibers, being coated
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B2017/00004—(bio)absorbable, (bio)resorbable, resorptive
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B2017/00526—Methods of manufacturing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B2017/00831—Material properties
    • A61B2017/00902—Material properties transparent or translucent
    • A61B2017/00915—Material properties transparent or translucent for radioactive radiation
    • A61B2017/0092—Material properties transparent or translucent for radioactive radiation for X-rays

Definitions

  • the invention relates to the technical field of medical devices, in particular to an intravascular embolus and a preparation method thereof.
  • the bare metal spring coil Axium Prime is made of platinum-tungsten alloy material and prefabricated into a two-dimensional or three-dimensional structure for intraoperative embolization.
  • Bio-modified spring coil Matrix by covering a layer of PLGA (polylactic-co-glycolic acid) biomaterial on the surface of the metal ring, utilizes the thrombosis-inducing and biodegradable properties of the PLGA material itself to reduce the occupancy effect.
  • the hydrogel coil Hydrocoil adds hydrophilic polypropylene hydrogel inside the metal ring. After implantation, the hydrogel absorbs a large amount of water and expands violently, filling the coil cavity completely to reduce the recanalization rate of the aneurysm.
  • the degradable/absorbable spring coil is still in the conceptual stage, and there is no mature market product.
  • spring coils made of absorbable bioactive materials usually have good X-ray permeability, so that the development effect is poor in the actual pushing operation process, which increases the difficulty of the doctor's operation.
  • a few reports have proposed adding radiopaque components to the degradable coils.
  • the structure of such coils is relatively complex, and the difficulty of connecting and fixing the components is relatively high.
  • the present invention provides an emboli and a preparation method thereof.
  • the visibility of the emboli satisfies the clinical requirements and the supportability and stability in the aneurysm, at least part of the emboli can be gradually degraded and absorbed by the body, It is converted into small molecular substances that are harmless to the body, so as to alleviate the effect of occupying space.
  • the present invention provides a plug, comprising a tubular first helical member having an inner cavity, a second helical member nested on the outer side of the first helical member, and at least partially disposed on the first helical member.
  • a shaping member in an inner cavity of a helical member wherein the first helical member comprises a radiopaque material, the second helical member comprises a bioabsorbable material, and one end of the shaping member is fixed to the first helical member and one end of the second helical member.
  • the first helical member comprises a radiopaque material and the second helical member comprises a bioabsorbable material.
  • the first helical member is a metal member made of one of platinum, iridium, gold, silver, tantalum and tungsten or an alloy thereof.
  • the first helical part is a composite material part doped with a developing substance in a matrix, wherein the developing substance is an iodine contrast agent or barium sulfate, and the matrix is polylactic acid, polyglycolic acid, lactic acid- One or more of glycolic acid copolymer, polydioxanone, polycaprolactone, polyurethane, chitosan and hyaluronic acid.
  • the developing substance is an iodine contrast agent or barium sulfate
  • the matrix is polylactic acid, polyglycolic acid, lactic acid- One or more of glycolic acid copolymer, polydioxanone, polycaprolactone, polyurethane, chitosan and hyaluronic acid.
  • the second helical part is polylactic acid, polyglycolic acid, lactic acid-glycolic acid copolymer, polydioxanone, polycaprolactone, polyurethane, chitosan, hyaluronic acid, magnesium , one or more of magnesium alloys, iron and iron alloys.
  • the shaping member includes at least one shaping wire, wherein the cross section of each shaping wire is circular, oval or polygonal.
  • the material of the shaping part is one or more of cobalt-chromium alloy, nickel-titanium alloy and platinum-tungsten alloy.
  • the shaping member has at least one secondary structure of spiral, wave, tetrahedron, pentahedron and hexahedron.
  • the outer diameter of the second helical part is in the range of 0.005-0.05 inches and the length in the range of 0.5-200 cm, wherein the cross section of the wire material wound around the second helical part is a circle or a circle
  • the diameter or radius of curvature of the wire has a size in the range of 0.0005-0.005 inches.
  • the outer diameter of the first helical member is in the range of 0.002-0.02 inches, and the length is 10%-100% of the length of the tubular structure wound by the second helical member, wherein the winding of the The cross-section of the wire of the first helical member is a circle or part of a circle, and the diameter or radius of curvature of the wire has a size ranging from 0.0003 to 0.003 inches.
  • the shaping member includes at least one shaping wire, and the diameter of the shaping wire does not exceed 90% of the inner diameter of the first helical member.
  • first helical part, the second helical part and the shaping part are coaxial or axially parallel, and/or the axial length of the first helical part is not greater than that of the second helical part The axial length of the part.
  • At least one end of the second helical member is sealed by forming a spherical cap by means of hot melting or dispensing, wherein at least part of the first helical member is wrapped around the spherical cap.
  • one end of the shaping member is fixed to one end of the first helical member and the second helical member through the ball cap.
  • one end of the shaping member is set as an inverted J-shaped hook, and at least a part of the inverted J-shaped hook is wrapped around the ball cap.
  • the plug further comprises a fixing member disposed at least partially in the inner cavity of the first helical member, wherein the fixing member and the first helical member are coaxial or axially parallel.
  • the fixing member is a polymer wire, wherein the material for making the polymer wire is polypropylene, polyester, nylon, polylactic acid, polyglycolic acid, lactic acid-glycolic acid copolymer, polyglycolic acid One or more of caprolactones.
  • the polymer wire is connected to both ends of the first helical part and the second helical part by physical winding or knotting, so as to fix the first helical part and the second helical part.
  • the second helical part is connected to both ends of the first helical part and the second helical part by physical winding or knotting, so as to fix the first helical part and the second helical part.
  • the polymer filament is knotted by wrapping at least one helix on the first helical member and at least one helix on the second helical member to retain the first helix
  • the member and the second helical member are coaxial or axially parallel.
  • the plug has at least one secondary structure of helical, wavy, tetrahedral, pentahedral and hexahedral.
  • the present invention also provides an embolism, comprising a tubular first helical part with an inner cavity, a second helical part wound around the outer side of the first helical part, and at least partially disposed on the first helical part.
  • a shaping member within the lumen of a helical member and a fixation member disposed at least partially within the lumen of the first helical member wherein: the first helical member comprises a radiopaque material and the second helical member comprises a bioabsorbable material material; the fixing member is respectively connected to both ends of the second helical member by physical winding or knotting; one end of the shaping member is fixed to one end of the first helical member and the second helical member; and At least one end of the second helical part is sealed by forming a spherical cap by means of hot melting or dispensing, and at least a part of the first helical part and the shaping part is wrapped around the spherical cap.
  • the present invention also provides a method for preparing an embolus, which is characterized by comprising the following steps: pre-forming the wound first helical part and the shaping part on a mold according to a preset shape, respectively. ; Set the pre-shaped shaped part in the inner cavity of the pre-shaped first helical part; and set the wound second helical part on the wound of the first helical part outside.
  • the emboli preparation method further includes: disposing a fixing member in the inner cavity of the first helical member; The two ends of the first helical part and the second helical part are respectively connected in a knotted manner; and one end of the shaping part is fixed together with one end of the first and second helical parts.
  • the way of tying the polymer wire with the first helical part and the second helical part is that the polymer wire simultaneously ties at least one turn of the helical and the second helical part on the first helical part. At least one turn of the helix on the second helical part is knotted to keep the first helical part and the second helical part coaxial or axially parallel.
  • emboli provided by the present invention and the preparation method thereof have the following advantages:
  • the above-mentioned emboli adopts a double-layer structure of bioabsorbable material and metal opaque material, so that the emboli maintains the good development and support characteristics of traditional metal coils, while the bioabsorbable material is partially It can be partially degraded and absorbed within a certain period of time, which can effectively alleviate the problems of large aneurysms, such as the mass effect that may cause compression of surrounding tissues and nerves.
  • the stereotyped parts provided in the double-layer helical structure of the above-mentioned emboli not only have good visibility, but also have a three-dimensional pre-shaped structure that can improve the stability of the emboli, so that it can have better performance in aneurysms. supportive.
  • FIG. 1 is a partial cross-sectional view of an embolus according to an embodiment of the present invention.
  • Figure 2 is a cross-sectional view of the embolic device shown in Figure 1;
  • FIG. 3 is a cross-sectional view of an embolic device according to another embodiment of the present invention.
  • distal end and proximal end are used; “proximal end” is the end close to the medical device operator; “distal end” is the end away from the medical device operator.
  • distal end is the end close to the medical device operator; “distal end” is the end away from the medical device operator.
  • the core idea of the present invention is to provide an embolus, comprising a tubular first helical part with an inner lumen, a second helical part nested on the outer side of the first helical part, and at least partially disposed in the first helical part
  • a shaping member in the lumen of the member wherein the first helical member comprises a radiopaque material, the second helical member comprises a bioabsorbable material, and one end of the shaping member is fixed to the first helical member and one end of the second helical member.
  • the first helical member includes a radiopaque material and the second helical member includes a bioabsorbable material.
  • the present invention also provides an embolism, comprising a tubular first helical member having an inner cavity, a second helical member wound around the outer side of the first helical member, and at least partially disposed on the first helical member.
  • a shaping member in the lumen of a helical member and a fixing member at least partially disposed in the lumen of the first helical member, wherein:
  • the first helical member includes a radiopaque material and the second helical member includes a bioabsorbable material;
  • the fixing parts are respectively connected to both ends of the second helical part by means of physical winding or knotting;
  • One end of the shaping member is fixed to one end of the first helical member and the second helical member;
  • At least one end of the second helical part is formed into a spherical cap by means of hot melting or dispensing for end capping, and at least a part of the first helical part and the shaping part is wrapped around the spherical cap.
  • the embolus in the present application can be a coil applied to the treatment of intracranial vascular diseases, which is used to treat vascular diseases such as intracranial aneurysms.
  • the vascular implant can also be applied to the treatment of non-intracranial vascular aneurysms and other diseases.
  • the biological material in the double-layer structure can be gradually degraded and absorbed by the body, and converted into small molecular substances that are harmless to the body, thereby reducing the effect of occupying space.
  • the shaped parts arranged in the double-layer helical structure can not only improve the supportability and stability of the emboli during surgical operations, but also have certain radiographic visibility.
  • FIG. 1 is a partial cross-sectional view of an embolic device 10 according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of the plug 10 shown in FIG. 1 .
  • the emboli 10 is an elongated device of greater length extending from its proximal end 160 to its distal end 140 .
  • the proximal end of the plug 10 is arranged to connect with a pusher (not shown) of the plug 10 .
  • the plug 10 includes a tubular first helical member 100 having an inner lumen 110, a second helical member 120 nested on the outer side of the first helical member 100, and a second helical member 120 disposed at least partially within the lumen 110 of the first helical member 100.
  • Forming part 130 .
  • the first helical part 100 , the second helical part 120 and the shaping part 130 are coaxial or axially parallel.
  • the first helical member 100 includes a radiopaque material.
  • the first helical member 100 is a metal member made of one of platinum, iridium, gold, silver, tantalum and tungsten or an alloy thereof, and the metal wire made of the above-mentioned materials is in a core of a predetermined diameter.
  • the first helical member 100 is formed by helical winding on the column.
  • the pitch of the coil of the first helical part 100 may be uniform, may also be gradually changed along the length of the coil, and may also have different pitches in different sections of the coil.
  • the first helical part 100 is a composite material part with a matrix doped with a developing substance, wherein the developing substance can be an iodine contrast agent or barium sulfate, and the matrix can be polylactic acid, polyglycolic acid, lactic acid-hydroxyl One or more of acetic acid copolymer, polydioxanone, polycaprolactone, polyurethane, chitosan and hyaluronic acid.
  • the first helical part 100 is formed by helically winding a filamentary composite material part on a stem of predetermined diameter.
  • the second helical member 120 includes a bioabsorbable material, which may be polylactic acid, polyglycolic acid, lactic acid-co-glycolic acid, polydioxanone, polycaprolactone One or more of ester, polyurethane, chitosan, hyaluronic acid, magnesium, magnesium alloy, iron and iron alloy.
  • the above-mentioned second helical part 120 can also be modified, for example, some active substances, which can be growth factors or certain drug molecules, are loaded inside or on the surface of the second helical part 120.
  • the second helical part 120 is formed by helically winding a polymer or metal wire made of the above-mentioned materials on a core column with a predetermined diameter. It can be understood that the pitch of the coils of the second helical part 120 may be uniform, may also be gradual along the length of the coil, and may also have different pitches in different sections of the coil.
  • the volume of the second helical member 120 made of bioabsorbable material accounts for a percentage of the total volume of the entire emboli 10 ranging from 30% to 90%.
  • the emboli 10 using the double-layer structure of bioabsorbable material and metal opaque material maintains the better developing and supporting characteristics of traditional metal coils, and the bioabsorbable material part can be used within a certain period of time. It is partially degraded and absorbed, which can effectively alleviate problems such as mass effect that may cause compression of surrounding tissues and nerves for large aneurysms.
  • the outer diameter of the first helical member 100 is in the range of 0.002-0.02 inches
  • the cross-section of the wire wound around the first helical member 100 is a circle or a portion of a circle
  • the diameter or curvature of the wire is The size range of 2 times the radius is 0.0003-0.003 inches.
  • the outer diameter of the second helical member 120 is in the range of 0.005-0.05 inches
  • the cross-section of the wire wound around the second helical member 120 is a circle or part of a circle, and the diameter of the wire is twice the size of the radius of curvature The range is 0.0005-0.005 inches.
  • the second helical part 120 is wrapped outside the first helical part 100 , and the axial length of the first helical part 100 is not greater than the axial length of the second helical part 120 .
  • the length of the second helical part 120 is in the range of 0.5-200 cm.
  • the length of the first helical part 100 is slightly shorter than the length of the second helical part 120, which is 10% of the length of the tubular structure wound by the second helical part 120- 100%.
  • the distal end 132 of the shaping member 130 is fixed to the distal ends 140 of the first helical member 100 and the second helical member 120 , and the proximal end 134 of the shaping member 130 is a free end, which is provided on the first helical member 100 . in the proximal lumen 110 .
  • the distal end 132 of the shaping member 130 is provided as an inverted J-shaped hook, which is connected with at least one coil of the distal end 140 of the first helical member 100, such as the last coil, and then is heated by melting or spotting
  • An atraumatic distal tip is formed on the distal ends 140 of the first helical member 100 and the second helical member 120 by means of glue, and the distal end 132 of the shaping member 130 is attached to the distal end of the first helical member 100 and the second helical member 120.
  • the ends 140 are firmly joined to each other, ie, at least a portion of the inverted J-shaped hook and the distal ends 140 of the first and second helical members 100, 120 are wrapped around the atraumatic distal tip.
  • the atraumatic distal tip can be the spherical cap 150 shown in Figure 2, or it can be a conical or oval closed end.
  • the atraumatic distal tip may be formed from a polymeric material such as polyester, acrylic adhesive, or other polymeric material suitable for hot melt or dispensing.
  • the distal end 132 of the shaping member 130 can also be connected to the distal end 140 of the first helical member 100 and the second helical member 120 by other means, such as straight, inverted J, or other shapes
  • the distal end 132 of the shaping member 130 is directly wrapped and fixed by the ball cap 150; or the distal end 132 of the shaping member 130 is first connected to at least one coil of the second helical member 120 and then wrapped and fixed by the ball cap 150;
  • the shaping part 130 is connected to at least one end of the first helical part 100 and the second helical part 120 in a knotted manner.
  • the proximal end 134 of the shaping member 130 is connected to the proximal end 160 of the first helical member 100, and the distal end 132 is the free end.
  • the proximal end 134 and the distal end 132 may also be connected to the proximal end 160 and the distal end 140 of the first helical member 100, respectively.
  • the shaping member 130 includes at least one shaping wire, wherein the cross-section of each shaping wire is circular, oval or polygonal, and its diameter does not exceed 90% of the inner diameter of the first helical member 100, wherein, The inner diameter of the first helical member 100 is in the range of 0.001-0.01 inches.
  • the material for forming the shaping part 130 is memory alloy, which can be one or more of cobalt-chromium alloy, nickel-titanium alloy and platinum-tungsten alloy.
  • the shaping member 130 made of the above-mentioned materials not only enhances the visibility of the double-layer helical structure in blood vessels and aneurysms, but also can perform three-dimensional pre-sizing of the memory alloy, which is used to improve the stability of the emboli 10 and make it in the artery.
  • the tumor can have better support.
  • the shaping member 130 may be pre-shaped to have at least one secondary structure of helical, wavy, tetrahedral, pentahedral, and hexahedral.
  • FIG. 3 is a cross-sectional view of an embolic device 10 according to another embodiment of the present invention.
  • the plug 10 includes a tubular first helical member 100 having an inner lumen 110 , a second helical member 120 nested on the outer side of the first helical member 100 , and a second helical member 120 disposed at least partially in the lumen 110 of the first helical member 100 .
  • the shaping part 130 and the fixing part 170 at least partially placed in the inner cavity 110 of the first helical part 100 .
  • the structures and usage of the first helical member 100 , the second helical member 120 and the shaping member 130 are substantially the same as those in the embodiment shown in FIG. 2 , and will not be repeated here.
  • the fixed member 170 and the first helical member 100 are coaxial or axially parallel.
  • the fixing member 170 may be a polymer wire material, and the material of the polymer wire material is polypropylene, polyester, nylon, polylactic acid, polyglycolic acid, lactic acid-glycolic acid copolymer, polyhexamethylene One or more of the lactones.
  • the polymer wire is connected to both ends of the first helical part 100 and the second helical part 120 by physical winding or knotting, respectively, so as to fix the first helical part 100 and the second helical part 120 .
  • the fixing member 170 is knotted with the first helical member 100 and the second helical member 120 in a manner that the fixing member 170 simultaneously ties at least one turn of the helix on the first helical member 100 and the second helix on the second helical member 120 . At least one turn of the helix is knotted to keep the first helical part 100 and the second helical part 120 coaxially or axially parallel. It can be understood that the connection position of the fixing member 170 with the first helical member 100 and/or the second helical member 120 is not limited to that shown in FIG. 3 , and the fixing member 170 can be knotted at any position on the circumference of the helical member.
  • the fixing member 170 may be connected with the shaping member 130 to stabilize the fixing member 170 , the first helical member 100 and the shaping member 130 effect.
  • the knotting manner of the fixing member 170 with the first helical member 100 and the second helical member 120 may also be: the fixing member 170 only ties at least one turn of the helical member or the second helical member on the first helical member 100 . At least one turn of the helix on the 120 is knotted.
  • the present invention also provides a method for preparing an emboli 10, with reference to FIG. 3, which mainly includes the following steps:
  • the wound first helical part 100 and the shaping part 130 are respectively pre-shaped on the mold according to preset shapes, wherein the preset shapes can be helical, wave, tetrahedron, At least one of the pentahedron and the hexahedron, the preset shapes of the first helical part 100 and the shaping part 130 are also corresponding to each other.

Abstract

Matériau embolique et son procédé de fabrication ; le matériau embolique comprend un premier composant hélicoïdal tubulaire (100) ayant une cavité interne (110), un second composant hélicoïdal (120) ajusté sur la face latérale externe du premier composant hélicoïdal (100), et un composant de mise en forme (130) au moins partiellement disposé dans la cavité interne (110) du premier composant hélicoïdal (100) ; le premier composant hélicoïdal (100) comprenant un matériau radio-opaque, le second composant hélicoïdal (120) comprenant un matériau bioabsorbable, et une extrémité du composant de mise en forme (130) étant fixée à une extrémité du premier composant hélicoïdal (100) et à une extrémité du second composant hélicoïdal (120). Dans le matériau embolique (10) ayant une structure à double couche, le composant de mise en forme (130) est fourni, de telle sorte que le matériau embolique (10) a les performances de dégradation et de soulagement de l'effet d'occupation d'espace, et présente les caractéristiques telles que de bonnes performances de développement et des performances de soutien dans un anévrisme.
PCT/CN2021/130763 2020-12-31 2021-11-15 Matériau embolique et son procédé de fabrication WO2022142788A1 (fr)

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CN202011624572.9A CN112641484A (zh) 2020-12-31 2020-12-31 一种栓塞物及其制备方法

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CN112656476A (zh) * 2020-12-31 2021-04-16 微创神通医疗科技（上海）有限公司 一种栓塞物及其制备方法
CN113303859B (zh) * 2020-12-31 2023-06-30 神遁医疗科技(上海)有限公司 一种栓塞物及其制备方法
CN116672022A (zh) * 2021-12-20 2023-09-01 神遁医疗科技(上海)有限公司 一种栓塞物及其制备方法
CN114176698B (zh) * 2021-12-20 2024-04-26 神遁医疗科技(上海)有限公司 一种栓塞物
CN115054307A (zh) * 2022-06-30 2022-09-16 上海微创医疗器械（集团）有限公司 封堵植入物及其制备方法

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