WO2014067201A1 - 吻合器用可吸收缝钉 - Google Patents

吻合器用可吸收缝钉 Download PDF

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Publication number
WO2014067201A1
WO2014067201A1 PCT/CN2012/085453 CN2012085453W WO2014067201A1 WO 2014067201 A1 WO2014067201 A1 WO 2014067201A1 CN 2012085453 W CN2012085453 W CN 2012085453W WO 2014067201 A1 WO2014067201 A1 WO 2014067201A1
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Prior art keywords
magnesium alloy
magnesium
alloy wire
staple
degradable
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PCT/CN2012/085453
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English (en)
French (fr)
Inventor
储成林
薛烽
白晶
施超
王世栋
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东南大学
常州德凯医疗器械有限公司
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Publication of WO2014067201A1 publication Critical patent/WO2014067201A1/zh

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/11—Surgical instruments, devices or methods, e.g. tourniquets for performing anastomosis; Buttons for anastomosis
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/11—Surgical instruments, devices or methods, e.g. tourniquets for performing anastomosis; Buttons for anastomosis
    • A61B17/1114—Surgical instruments, devices or methods, e.g. tourniquets for performing anastomosis; Buttons for anastomosis of the digestive tract, e.g. bowels or oesophagus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
    • A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • 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

Definitions

  • the invention relates to an absorbable staple for an anastomat, a staple body processed from a medical degradable magnesium alloy wire, a degradable bioceramic film bottom layer attached to the surface of the magnesium alloy wire, and a degradable for sealing treatment
  • the surface layer of the polymer can be completely degraded and absorbed in the body environment.
  • it has the necessary acid or alkali corrosion resistance in the early stage of the operation, and can resist the early corrosion damage of the strong acid environment in the stomach, and is suitable for human body.
  • Various kinds of surgery, especially for wound anastomosis after gastrointestinal surgery belong to the technical field of surgical anastomotic suture instruments.
  • the kiss is a tool used by doctors to replace the traditional hand-stitching method and suture the cut tissue or organ with suture. It has the advantages of quick suturing, easy operation and few side effects and surgical complications.
  • the Hungarians made the world's first stapler, which was subsequently improved and gradually promoted in the clinic. Especially in the past ten years, the stapler has become a routine tool for digestive tract surgery in Europe and the United States. Popularization has become an indispensable tool for gastrointestinal surgery. According to the market survey on the sales of medical staplers, the annual amount of staples in the country is more than 5 million sets.
  • the current conventional stapler staples are made of titanium alloy or base metal with excellent chemical stability. After the operation, the staples are long-lived in the patient, which causes the patient to have a long-term foreign body sensation, which may lead to future medical treatment such as nuclear magnetic resonance. During the examination, shadows will be generated in the stapled parts of the body, which will affect the examination effect and accuracy, especially the tissue hyperplasia of the sutured parts, resulting in problems such as postoperative narrowing of the lumen.
  • Magnesium alloys have many performance advantages for implantable devices, such as low modulus of elasticity, about 41-45 GPa, which is closer to human bone than titanium; density is about 1.7-1.9 g/cm 3 , and bone density of human bone is dense. Similar; its specific strength, specific stiffness, tensile strength is usually between 200MPa and 300MPa; with good biocompatibility, magnesium is one of the main metal elements in the human body, for regulating cell growth and maintenance The cell membrane structure plays an important role; the excess magnesium that is decomposed can be excreted through the urine and has good safety.
  • the stapler developed by using magnesium alloy has a bioabsorbable function, avoiding the biosafety hazard caused by long-term existence in the body, and at the same time, can effectively avoid the foreign body sensation and psychological shadow in the postoperative body, and solve the problem that the patient is difficult to carry out in the future. Difficulties in medical examinations such as nuclear magnetic resonance.
  • the corrosion resistance of magnesium alloy is poor, and the biodegradation rate in the human body is too fast, which may cause the magnesium alloy stud to corrode and break before the healing of the surgical suture, and the leakage of the anastomosis occurs.
  • the disclosed utility model "adhesive magnesium alloy staples for staplers (publication number: CN 201617885 In U)"
  • a solution is proposed, in which a U-shaped body of a staple is made of a magnesium alloy wire, and the surface of the magnesium alloy wire is coated with a surface coating having excellent biocompatibility and corrosion resistance.
  • the surface coating is a bioceramic coating, a coating of a pure metal or alloy or an anodized layer of a magnesium alloy.
  • the different physiological environments in the human body especially the gastric and intestinal environment in which the surgical stapler staples are used in large amounts, have great differences in acidity and alkalinity.
  • the pH of the stomach gastric juice is about 1.5
  • the intestinal fluid is alkaline.
  • the ideal absorbable staple surface protective coating must be fully degradable and absorbable in the in vivo environment, and must also provide the necessary acid resistance for the internal bulk magnesium alloy wire of the staple in the early postoperative stage. Or alkali corrosion resistance.
  • bioceramics used to make coatings include degradable hydroxyapatite, tricalcium phosphate, magnesium oxide, etc., and non-degradable alumina, zirconia, titania, etc., the former can be degraded and absorbed in the body, but not Acid corrosion resistant; the latter is resistant to acid corrosion but not to degradation and is not an ideal staple protection coating.
  • pure metals or alloys only magnesium and its alloys have good degradation and absorption properties. Other parts of zinc and iron alloys also have degradation properties, but they are not resistant to acid corrosion. At the same time, many acid-corrosive metals cannot be degraded into titanium or tantalum. Absorbed, so pure metal or alloy is not an ideal staple protective coating.
  • the anodized layer of the magnesium alloy is a loose layer of magnesium oxide, which is obviously not resistant to acid corrosion.
  • the stapler staples used in clinical practice are made of titanium alloy or bismuth metal with excellent stability.
  • the staples exist in the patient for a long time, which causes the patient to have a long-term foreign body sensation, which will lead to the future acceptance of nuclear magnetic resonance.
  • shadows will be generated in the stapled parts of the body, which will affect the examination effect and accuracy. In particular, it may lead to tissue hyperplasia of the sutured parts, resulting in problems such as postoperative narrowing of the lumen.
  • the U-shaped body of the staple is made of magnesium alloy wire, and the surface of the magnesium alloy wire is coated with a biocompatible and corrosion-resistant surface coating, which is a bioceramic coating and a pure metal. Or an alloy coating or an anodized layer of a magnesium alloy.
  • a biocompatible and corrosion-resistant surface coating which is a bioceramic coating and a pure metal.
  • an alloy coating or an anodized layer of a magnesium alloy can be completely degraded and absorbed, its surface coating technical solution cannot guarantee the performance of the absorbable staple in the body environment and is completely degraded and absorbed, and it is necessary in the early postoperative stage. Acid or alkali corrosion resistance.
  • the object of the present invention is to provide an absorbable staple for a stapler and a preparation method thereof, and to provide an overall solution to the above technical problems.
  • the technical solution proposed by the present invention is an absorbable staple for an anastomosis, which is a staple body processed from a medically degradable magnesium alloy wire and attached to a surface of a magnesium alloy wire.
  • the surface polymer surface layer consists of poly-L-lactic acid, or poly (D, L)-lactic acid or a copolymer or mixture of the two, or a copolymer of lactic acid and glycolic acid, has better corrosion resistance than other degradable polymers, and at the same time, the degradable bioceramic film bottom layer is generally rough porous
  • the surface structure, the acid and alkaline corrosive medium in the body easily penetrate into the corrosive magnesium alloy body, and the surface layer of the polylactic acid polymer with corrosion resistance on the surface can effectively seal the pore structure of the bottom surface of the bioceramic film during the coating process.
  • the double-layer protection formed by the surface degradable ceramic coating and the polymer film and the sealing effect of the organic coating on the surface of the inorganic ceramic coating can effectively improve the corrosion resistance of the absorbable staple for the stapler, and the absorbable for controlling the stapler
  • the rate of degradation of the staples, the stapler of the present invention can be completely degraded and absorbed in the body environment, and at the same time, has the necessary acid or alkali corrosion resistance in the early stage of the operation, and can resist the strong acid in the stomach.
  • the early corrosion damage of the environment is suitable for all kinds of surgery in the human body, especially after the digestive tract surgery.
  • the stapler for the stapler of the invention has the staple body processed by the medical degradable magnesium alloy wire, the bottom layer of the degradable bioceramic film attached to the surface of the magnesium alloy wire, and the high degradable for the sealing treatment
  • the molecular surface layer composition, the diameter of the magnesium alloy wire is 0.1mm ⁇ 0.6mm, and the thickness of the bottom layer of the degradable bioceramic film is 0.1 ⁇ m ⁇ 50 ⁇ m, the thickness of the degradable polymer surface layer is from 0.1 ⁇ m to 100 ⁇ m.
  • the magnesium alloy wire is composed of one or a combination of magnesium alloy, magnesium manganese alloy, magnesium zinc alloy, magnesium zirconium alloy, magnesium rare earth alloy, magnesium lithium alloy, magnesium calcium alloy or magnesium silver alloy.
  • the multi-component magnesium alloy is drawn and processed.
  • the surface of the magnesium alloy wire surface of the bioceramic film is prepared by micro-arc oxidation, anodization, electrodeposition, plasma spraying, chemical conversion, ion implantation, sputtering, vapor deposition or biochemical method, and is coated with hydroxyapatite.
  • the degradable polymer surface layer material is poly-L-lactic acid, or poly(D, L)-lactic acid or a copolymer or mixture of the two, or a copolymer of lactic acid and glycolic acid, having a molecular weight of 10,000 to 1,500,000.
  • the preparation method of the absorbable staple for the stapler of the present invention is:
  • the selected magnesium alloy is processed into a magnesium alloy wire
  • the invention relates to an absorbable staple for an anastomat, a staple body processed from a medical degradable magnesium alloy wire, a degradable bioceramic film bottom layer attached to the surface of the magnesium alloy wire, and a sealing hole treatment.
  • Degradation of polymer surface layer composition From the internal magnesium alloy wire to the inorganic ceramic film bottom layer to the polymer surface layer, the materials used are all biodegradable. Therefore, the present invention can be completely degraded and absorbed after in vivo healing in the body without residue.
  • the surface polymer surface layer consists of poly-L-lactic acid, or poly (D, L)-lactic acid or a copolymer or mixture of the two, or a copolymer of lactic acid and glycolic acid, is a commonly used surgical suture material, has better corrosion resistance than other degradable polymers such as gelatin, and at the same time,
  • the degraded bioceramic film bottom layer usually has a rough porous surface structure, and the acid and alkaline corrosive medium in the body easily penetrate into the corrosive magnesium alloy body, and the surface corrosion-resistant polylactic acid polymer surface layer can also be used to coat the bioceramic film bottom layer during the coating process. The pore structure of the surface is effectively sealed.
  • the double layer protection formed by the surface degradable ceramic coating and the polymer film and the sealing effect of the organic coating on the surface of the inorganic ceramic coating can effectively improve the absorbable staple for the stapler.
  • Corrosion resistance it has the necessary acid or alkali corrosion resistance in the early stage of operation, can resist the early corrosion damage of the strong acid environment in the stomach, and control the degradation rate of the absorbable staples in the stapler. It is suitable for various operations in the human body. It is used for anastomosis after gastrointestinal surgery.
  • the stapler is composed of a staple body processed from a medical degradable magnesium alloy wire, a bottom layer of a degradable bioceramic film attached to the surface of the magnesium alloy wire, and a degradable polymer surface layer for sealing treatment.
  • the diameter of the magnesium alloy wire is 0.1mm ⁇ 0.6mm
  • the thickness of the bottom layer of the biodegradable bioceramic film is 0.1 ⁇ m.
  • the thickness of the degradable polymer surface layer is from 0.1 ⁇ m to 100 ⁇ m.
  • the magnesium alloy wire is composed of one or a combination of magnesium alloy, magnesium manganese alloy, magnesium zinc alloy, magnesium zirconium alloy, magnesium rare earth alloy, magnesium lithium alloy, magnesium calcium alloy or magnesium silver alloy.
  • the ternary or multi-component magnesium alloy is drawn and processed.
  • the magnesium alloy wire materials involved mainly include: magnesium-aluminum series (except the binary system mainly includes four ternary systems of Mg-Al-Zn, Mg-Al-Mn, Mg-Al-Si, Mg-Al-RE and Multi-component system, representative alloys such as AZ31, AZ61, AZ91, AM60, AE21, AS21, etc., in which the aluminum content is less than 10%, Zn, Mn, Si, RE mass is less than 5%); magnesium manganese series (mainly binary Mg-0.1 ⁇ 2.5% Mn and a ternary or multi-component system composed of a small amount of rare earth, calcium, zinc and other elements, representing alloys such as domestic grades MB1 and MB8); magnesium-zinc series (excluding binary systems mainly including Mg-Zn) -Zr and Mg-Zn-Cu series, representative alloys ZK21, ZK60, ZC62, etc.); magnesium-zirconium series (mainly binary Mg-0.1 ⁇
  • the surface of the magnesium alloy wire surface of the bioceramic film is prepared by micro-arc oxidation, anodization, electrodeposition, plasma spraying, chemical conversion, ion implantation, sputtering, vapor deposition or biochemical method, and is coated with hydroxyapatite.
  • the degradable polymer surface layer material is poly-L-lactic acid, or poly(D, L)-lactic acid or a copolymer or mixture of the two, or a copolymer of lactic acid and glycolic acid, having a molecular weight of 10,000 to 1,500,000.
  • the stapler uses an absorbable staple, which can be prepared by processing a magnesium alloy with a selected component into a magnesium alloy wire; selecting a suitable ceramic coating technique to prepare a desired organism on the surface of the magnesium alloy wire.
  • the bottom layer of the ceramic film using a dip coating, brushing or spraying method, further preparing a degradable polymer surface layer on the surface of the magnesium alloy wire having a bottom surface of the bioceramic film; forming a staple by using the magnesium alloy wire obtained as described above
  • the invention is obtained by drying, testing and disinfecting.
  • the stapler uses an absorbable staple, and the preparation method thereof can also be: drawing and processing the magnesium alloy of the selected component into a magnesium alloy wire; and selecting a suitable ceramic coating technology to surface-treat the magnesium alloy wire. Preparing a desired degradable bioceramic film bottom layer on the surface of the magnesium alloy wire; forming a staple by using the magnesium alloy wire obtained as described above; using a dip coating, brush coating or spraying method to further advance the surface of the obtained nail The surface layer of the degradable polymer is prepared; finally, dried, inspected, and sterilized to obtain the present invention.
  • the surface layer of the degradable polylactic acid has a diameter of ⁇ 0.30 mm, a thickness of the bottom layer of the magnesia ceramic film is about 10 ⁇ m, and a thickness of the surface layer of the degradable polylactic acid is about 10 ⁇ m.
  • the preparation steps of the stapler with the absorbable staples are as follows:
  • step 3) is processed to form a U-shaped structural staple with a magnesium alloy wire
  • U-shaped structural staple body processed by medical degradable AZ91 magnesium alloy wire, and degradable magnesium oxide and hydroxyapatite composite ceramic film bottom layer attached to magnesium alloy wire surface The surface layer of the degradable polylactic acid used for sealing treatment, the diameter of the magnesium alloy wire is ⁇ 0.20 mm, the thickness of the bottom layer of the magnesia and hydroxyapatite composite ceramic film is about 5 ⁇ m, and the thickness of the surface layer of the degradable polylactic acid is About 5 ⁇ m.
  • the preparation steps of the stapler with the absorbable staples are as follows:
  • the AZ91 magnesium alloy is drawn and processed into a magnesium alloy wire having a diameter of 0.20 mm;
  • step 3) is processed to form a U-shaped structural staple with a magnesium alloy wire
  • the utility model relates to an U-shaped structural staple body processed by medical degradable AZ31B magnesium alloy wire, and a degradable hydroxyapatite bioceramic film bottom layer attached to the surface of the magnesium alloy wire, which is used for the stapler
  • the surface of the degradable PLGA layer is sealed, the diameter of the magnesium alloy wire is ⁇ 0.25 mm, the thickness of the hydroxyapatite bioceramic film is about 10 ⁇ m, and the thickness of the degradable PLGA surface layer is about 20 ⁇ m.
  • the preparation steps of the stapler with the absorbable staples are as follows:
  • the AZ31B magnesium alloy is drawn and processed into a magnesium alloy wire having a diameter of ⁇ 0.25 mm;
  • step 3) is processed to form a U-shaped structural staple with a magnesium alloy wire
  • U-shaped structural staple body processed by medical degradable AZ91 magnesium alloy wire, and degradable magnesium oxide and hydroxyapatite composite ceramic film bottom layer attached to magnesium alloy wire surface The composition of the degradable PLGA surface layer for sealing treatment, the diameter of the magnesium alloy wire is ⁇ 0.28 mm, the thickness of the bottom layer of the magnesium oxide and hydroxyapatite composite ceramic film is about 10 ⁇ m, and the thickness of the degradable PLGA surface layer is about 10 ⁇ m.
  • the preparation steps of the stapler with the absorbable staples are as follows:
  • the AZ91 magnesium alloy is drawn and processed into a magnesium alloy wire having a diameter of 0.28 mm;
  • step 3) is processed to form a U-shaped structural staple with a magnesium alloy wire

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Abstract

本发明公开了一种吻合器用可吸收缝钉，由医用可降解镁合金丝材加工而成的缝钉本体、附着在镁合金丝材表面的可降解生物陶瓷薄膜底层、用于封孔处理的可降解高分子表面层组成。表面可降解陶瓷涂层与高分子薄膜形成的双层保护以及有机涂层对无机陶瓷涂层表面的封孔效应能有效改善吻合器用可吸收缝钉耐腐蚀性能，控制缝钉的降解速度。本发明公开的吻合器用可吸收缝钉在体内环境下能被完全降解吸收，同时，在术后的早期阶段又具有必需的耐酸或耐碱腐蚀性能，能抵抗胃内强酸环境的早期腐蚀破坏，适用于人体内各种手术尤其是消化道手术后吻合缝合用。

Description

吻合器用可吸收缝钉 技术领域
本发明一种吻合器用可吸收缝钉，由医用可降解镁合金丝材加工而成的缝钉本体、附着在镁合金丝材表面的可降解生物陶瓷薄膜底层、用于封孔处理的可降解高分子表面层组成，在体内环境下能被完全降解吸收，同时，在术后的早期阶段又具有必需的耐酸或耐碱腐蚀性能，能抵抗胃内强酸环境的早期腐蚀破坏，适用于人体内各种手术尤其是消化道手术后的伤口吻合缝合用，属于手术吻合缝合器械技术领域。
 背景技术
吻（缝）合器是医生用以代替传统手工缝合方法，采用缝钉缝合已切开的组织或器官的工具，具有缝合快速、操作简便及很少有副作用和手术并发症等优点。1908年，匈牙利人制造了世界上第一个缝合器，随后不断改进，并逐渐在临床推广，尤其是在近十年内，吻合器在欧美国家已经成为消化道手术的常规工具，在国内也逐渐普及，已经成为胃肠道手术必不可少的工具。据针对医用吻合器销售情况的市场调查，全国每年吻合缝钉的用量在500万套以上。
但目前的传统吻合器缝钉均采用化学稳定性极好的钛合金或钽金属制作，手术后缝钉在病患体内长期存在，致使患者长期有异物感，也会导致未来接受核磁共振等医疗检查时会在体内缝钉部位产生暗影，影响检查效果和准确性，特别是可能会导致缝合部位的组织增生，造成术后腔道狭窄等问题。
近年来，可降解镁合金在可吸收植入器械方面的应用前景受到了全世界研究者的广泛关注。镁合金用于植入器械具有很多性能优势，例如弹性模量低，约为41~45GPa,比钛金属更接近于人骨；其密度在1.7~1.9g/cm3左右，和人骨密质骨密度相近；其比强度、比刚度较高，拉伸强度通常在200MPa到300MPa之间；具有良好的生物相容性，镁是人体内几个主要的金属元素之一，对于调节细胞的生长和维持细胞膜结构有重要作用；降解析出的过量镁可以通过尿液排出体外，具有良好的安全性。
因此，采用镁合金研制的吻合器用具有生物可吸收功能，避免长期存在于体内带来的生物安全隐患，同时，能有效避免术后的体内异物感及心理阴影，同时解决了患者在未来难以进行核磁共振等医疗检查的困难。但镁合金耐腐蚀性能较差，在人体内生物降解速度过快，易导致镁合金缝钉在手术缝合口愈合前就腐蚀断裂，发生吻合口的泄漏。
已公开的实用新型“吻合器用可吸收镁合金缝钉（公开号：CN 201617885 U）”中，提出了一种解决技术方案，即采用镁合金丝材制作缝钉U形本体，在镁合金丝材表面包覆有生物相容性优良且具有抗腐蚀性能的表面涂层，特别指出该表面涂层是生物陶瓷涂层、纯金属或合金的镀层或镁合金的阳极氧化层。
人体内不同的生理环境，尤其是手术吻合器缝钉大量使用的胃、肠环境在酸碱性方面存在巨大差异，例如胃部胃液的pH值在1.5左右,而肠液又显碱性。显然，理想的可吸收缝钉表面保护涂层在体内环境下必须能被完全可降解吸收的前提下，还必须能在术后的早期阶段能为缝钉内部本体镁合金丝材提供必需的耐酸或耐碱腐蚀性能。
通常，用于制作涂层的生物陶瓷包括可降解的羟基磷灰石、磷酸三钙、氧化镁等以及不可降解的氧化铝、氧化锆、氧化钛等，前者在体内可被降解吸收，但不耐酸腐蚀；后者耐酸腐蚀，但不能被降解吸收，均不是理想的缝钉保护涂层。纯金属或合金中，只有镁及其合金具有很好的降解吸收性能，其它部分锌、铁合金也有降解性能，但均不耐酸腐蚀，同时，很多耐酸腐蚀的金属入钛、钽等又不能被降解吸收，所以纯金属或合金也不是理想的缝钉保护涂层。镁合金的阳极氧化层是疏松的氧化镁层，显然，不能耐酸腐蚀。
目前，临床使用的吻合器缝钉均采用稳定性极好的钛合金、或钽金属制作，手术后缝钉在病患体内长期存在，致使患者长期有异物感，也会导致未来接受核磁共振等医疗检查时会在体内缝钉部位产生暗影，影响检查效果和准确性，特别是可能会导致缝合部位的组织增生，造成术后腔道狭窄等问题。
已公开实用新型CN 201617885 U，采用镁合金丝材制作缝钉U形本体，在镁合金丝材表面包覆有生物相容性优良且具有抗腐蚀性能的表面涂层，该表面涂层是生物陶瓷涂层、纯金属或合金的镀层或镁合金的阳极氧化层。虽然镁合金丝材U形本体能被完全降解吸收，但其表面涂层技术方案却不能保证可吸收缝钉在体内环境下同时具有完全被降解吸收的性能和在术后早期阶段又具有必需的耐酸或耐碱腐蚀性能。
 技术问题
本发明的目的是提供一种吻合器用可吸收缝钉及其制备方法，对上述技术问题提供一种整体解决技术方案。
技术解决方案
针对上述问题，本发明提出的技术解决方案是一种吻合器用可吸收缝钉，该吻合器用缝钉由医用可降解镁合金丝材加工而成的缝钉本体、附着在镁合金丝材表面的可降解生物陶瓷薄膜底层、用于封孔处理的可降解高分子表面层组成。表面高分子表面层由聚L-乳酸，或者聚(D, L)-乳酸或者是两者的共聚物或混合物，或者为乳酸同乙醇酸的共聚物，具有比其他可降解聚合物更好的耐腐蚀性能，同时，可降解生物陶瓷薄膜底层通常具有粗糙多孔的表面结构，体内酸、碱性腐蚀介质易渗入腐蚀镁合金本体，而表面耐腐蚀的聚乳酸高分子表面层在涂覆过程中还能对生物陶瓷薄膜底层表面的孔结构进行有效封孔处理，因此，表面可降解陶瓷涂层与高分子薄膜形成的双层保护以及有机涂层对无机陶瓷涂层表面的封孔效应能有效改善吻合器用可吸收缝钉耐腐蚀性能，控制吻合器用可吸收缝钉的降解速度，本发明一种吻合器用可吸收缝钉在体内环境下能被完全降解吸收，同时，在术后的早期阶段又具有必需的耐酸或耐碱腐蚀性能，能抵抗胃内强酸环境的早期腐蚀破坏，适用于人体内各种手术尤其是消化道手术后吻合缝合用。
本发明的吻合器用可吸收缝钉，由医用可降解镁合金丝材加工而成的缝钉本体、附着在镁合金丝材表面的可降解生物陶瓷薄膜底层、用于封孔处理的可降解高分子表面层组成，镁合金丝材的直径为0.1mm~0.6mm，可降解生物陶瓷薄膜底层的厚度为0.1μm ~50μm，可降解高分子表面层的厚度为0.1μm ~100μm。
所述及的镁合金丝材由镁铝合金、镁锰合金、镁锌合金、镁锆合金、镁稀土合金、镁锂合金、镁钙合金或镁银合金的一种或由这些体系组合而成的多元系镁合金经拉拔、加工而成。
所述及的镁合金丝材表面生物陶瓷薄膜底层通过微弧氧化、阳极氧化、电沉积、等离子喷涂、化学转化、离子注入、溅射、气相沉积或生物化学方法制备，为羟基磷灰石涂层、磷酸三钙涂层、氧化镁涂层或含氟防护层，以控制镁合金丝材的降解速度和镁离子的溶出速度。
所述及的可降解高分子表面层材料为聚L-乳酸，或者聚(D, L)-乳酸或者是两者的共聚物或混合物，或者为乳酸同乙醇酸的共聚物，聚合物分子量为1万~150万。
本发明的吻合器用可吸收缝钉的制备方法是：
1）首先将选好成分的镁合金加工成镁合金丝材；
2）选择陶瓷涂层技术，在镁合金丝材表面制备出所需的生物陶瓷薄膜底层；
3）采用浸涂、刷涂或喷涂方法，在表面有生物陶瓷薄膜底层的镁合金丝材表面进一步制备出可降解高分子表面层；
4）用步骤3）获得的镁合金丝材成型加工出缝钉；
5）最后经干燥、检验、消毒，获得吻合器用可吸收缝钉。
或：
1）首先将选好成分的镁合金拉拔、加工成镁合金丝材；
2）选择陶瓷涂层技术对镁合金丝材进行表面处理，在镁合金丝材表面制
备出所需的可降解生物陶瓷薄膜底层；
3）用步骤2）获得的镁合金丝材成型加工出缝钉；
4）采用浸涂、刷涂或喷涂方法，在用步骤3）获得的缝钉表面进一步制备出可降解高分子表面层；
5）最后经干燥、检验、消毒，获得吻合器用可吸收缝钉。
 有益效果
本发明是一种吻合器用可吸收缝钉，由医用可降解镁合金丝材加工而成的缝钉本体、附着在镁合金丝材表面的可降解生物陶瓷薄膜底层、用于封孔处理的可降解高分子表面层组成。从内部镁合金丝材到无机陶瓷薄膜底层到高分子表面层，所采用的材料均为生物可降解，因此，本发明在体内手术愈合后能被完全降解吸收掉，无残余。
同时，表面高分子表面层由聚L-乳酸，或者聚(D, L)-乳酸或者是两者的共聚物或混合物，或者为乳酸同乙醇酸的共聚物，是常用手术缝合线材料，具有比其他可降解聚合物例如明胶更好的耐腐蚀性能，同时，可降解生物陶瓷薄膜底层通常具有粗糙多孔的表面结构，体内酸、碱性腐蚀介质易渗入腐蚀镁合金本体，而表面耐腐蚀的聚乳酸高分子表面层在涂覆过程中还能对生物陶瓷薄膜底层表面的孔结构进行有效封孔处理，因此，表面可降解陶瓷涂层与高分子薄膜形成的双层保护以及有机涂层对无机陶瓷涂层表面的封孔效应能有效改善吻合器用可吸收缝钉耐腐蚀性能，在术后的早期阶段具有必需的耐酸或耐碱腐蚀性能，能抵抗胃内强酸环境的早期腐蚀破坏，控制吻合器用可吸收缝钉的降解速度，适用于人体内各种手术尤其是消化道手术后吻合缝合用。
 本发明的实施方式
本发明通过以下技术方案加以实现：
该吻合器用缝钉由医用可降解镁合金丝材加工而成的缝钉本体、附着在镁合金丝材表面的可降解生物陶瓷薄膜底层、用于封孔处理的可降解高分子表面层组成，镁合金丝材的直径为0.1mm~0.6mm，可降解生物陶瓷薄膜底层的厚度为0.1μm ~50μm，可降解高分子表面层的厚度为0.1μm ~100μm。
所述及的镁合金丝材由镁铝合金、镁锰合金、镁锌合金、镁锆合金、镁稀土合金、镁锂合金、镁钙合金或镁银合金的一种或由这些体系组合而成的三元或多元系镁合金经拉拔、加工而成。
所涉及镁合金丝材材质主要包括：镁铝系列（除二元体系外主要包括Mg-Al-Zn，Mg-Al-Mn，Mg-Al-Si，Mg-Al-RE四个三元体系以及多元体系，代表性合金如AZ31，AZ61，AZ91，AM60，AE21，AS21等，其中含铝质量低于10%，Zn、Mn、Si、RE质量小于5%）；镁锰系列（主要是二元Mg-0.1~2.5%Mn以及添加少量稀土、钙、锌等元素组成的三元系或多元系，代表合金如国内牌号MB1和MB8）；镁锌系列（除二元体系外主要包括Mg-Zn-Zr和Mg-Zn-Cu系列，代表性合金ZK21，ZK60，ZC62等）；镁锆系列（主要是二元Mg-0.1~2%Zr及添加少量稀土、锌等元素组成的三元系或多元系，代表合金如K1A等）；镁稀土系列（主要是二元Mg-0.1~5%RE）及添加少量铝、锆、钙、锌等元素组成的三元系或多元系）；镁锂合金（主要是二元Mg-1~15%Li及添加少量铝、稀土、锌和硅等元素组成的三元系或多元系，代表合金如LA91，LAZ933等）；镁钙系列（主要是二元Mg-0.1~10%Ca及添加少量稀土、锆、锌等元素组成的三元系或多元系）；镁银系列（主要是二元Mg-0.1~12%Ag及添加少量稀土、锆、锌等元素组成的三元系或多元系，代表合金如QE22等）等不同的合金体系的一种或者由这些体系组成的三元系和多元系镁合金。
所述及的镁合金丝材表面生物陶瓷薄膜底层通过微弧氧化、阳极氧化、电沉积、等离子喷涂、化学转化、离子注入、溅射、气相沉积或生物化学方法制备，为羟基磷灰石涂层、磷酸三钙涂层、氧化镁涂层或含氟防护层，以控制镁合金丝材的降解速度和镁离子的溶出速度。
所述及的可降解高分子表面层材料为聚L-乳酸，或者聚(D, L)-乳酸或者是两者的共聚物或混合物，或者为乳酸同乙醇酸的共聚物，聚合物分子量为1万~150万。
所述的吻合器用可吸收缝钉，其制备方法可以是：将选好成分的镁合金加工成镁合金丝材；选择合适的陶瓷涂层技术，在镁合金丝材表面制备出所需的生物陶瓷薄膜底层；采用浸涂、刷涂或喷涂方法，在表面有生物陶瓷薄膜底层的镁合金丝材表面进一步制备出可降解高分子表面层；用前述获得的镁合金丝材成型加工出缝钉；最后经干燥、检验、消毒，获得本发明。
所述的吻合器用可吸收缝钉，其制备方法也可以是：将选好成分的镁合金拉拔、加工成镁合金丝材；选择合适的陶瓷涂层技术对镁合金丝材进行表面处理，在镁合金丝材表面制备出所需的可降解生物陶瓷薄膜底层；用前述获得的镁合金丝材成型加工出缝钉；采用浸涂、刷涂或喷涂方法，在前述获得的缝钉表面进一步制备出可降解高分子表面层；最后经干燥、检验、消毒，获得本发明。
实施例1
一种吻合器用可吸收缝钉，由医用可降解AZ31B镁合金丝材加工而成的U型结构缝钉本体、附着在镁合金丝材表面的可降解氧化镁陶瓷薄膜底层、用于封孔处理的可降解聚乳酸表面层组成，镁合金丝材的直径为φ0.30mm，氧化镁陶瓷薄膜底层厚度约为10μm，可降解聚乳酸表面层的厚度约为10μm。
所述的吻合器用可吸收缝钉的制备步骤如下：
1）首先将AZ31B镁合金拉拔、加工成直径为φ0.30mm的镁合金丝材；
2）用10g/L硅酸钠和2g/L NaOH作为微弧氧化电解液体系，将镁合金丝材浸于其中，施加400V电压，进行10分钟的微弧氧化处理，使其表面原位生成氧化镁生物陶瓷底层；
3）将10克可降解聚乳酸溶于50ml的氯仿中，将步骤2）处理过的镁合金丝材浸泡在该溶液中，浸泡时间为1.0分钟，可进行多次浸泡，每两次浸泡之间取出镁合金丝材，并在空气中挥发掉溶剂，可降解表面层的厚度控制在10mm 左右；
4）将步骤3）处理过用镁合金丝材成型加工出U型结构缝钉；
5）最后经干燥、检验、消毒，获得本发明。
实施例2
一种吻合器用可吸收缝钉，由医用可降解AZ91镁合金丝材加工而成的U型结构缝钉本体、附着在镁合金丝材表面的可降解氧化镁和羟基磷灰石复合陶瓷薄膜底层、用于封孔处理的可降解聚乳酸表面层组成，镁合金丝材的直径为φ0.20mm，氧化镁和羟基磷灰石复合陶瓷薄膜底层厚度约为5μm，可降解聚乳酸表面层的厚度约为5μ m。
所述的吻合器用可吸收缝钉的制备步骤如下：
1）首先将AZ91镁合金拉拔、加工成直径为φ0.20mm的镁合金丝材；
2）用10g/L硅酸钠、3g/L羟基磷灰石纳米粉体、2g/L NaOH作为微弧氧化电解液体系，将镁合金丝材浸于其中，施加400V电压，进行5分钟的微弧氧化处理，使其表面原位生成一层氧化镁和羟基磷灰石复合陶瓷底层；
3）将10克可降解聚乳酸高分子材料进行高温熔化，用该熔融态聚乳酸刷涂或浸涂步骤2）处理过的镁合金丝材，经凝固固化，可降解表面层的厚度控制在5mm 左右；
4）将步骤3）处理过用镁合金丝材成型加工出U型结构缝钉；
5）最后经干燥、检验、消毒，获得本发明。
实施例3
一种吻合器用可吸收缝钉，由医用可降解AZ31B镁合金丝材加工而成的U型结构缝钉本体、附着在镁合金丝材表面的可降解羟基磷灰石生物陶瓷薄膜底层、用于封孔处理的可降解PLGA表面层组成，镁合金丝材的直径为φ0.25mm，羟基磷灰石生物陶瓷薄膜底层厚度约为10μm，可降解PLGA表面层的厚度约为20μm。
所述的吻合器用可吸收缝钉的制备步骤如下：
1）首先将AZ31B镁合金拉拔、加工成直径为φ0.25mm的镁合金丝材；
2）在含有6g/L羟基磷灰石纳米粉体的电解液体系，用电沉积技术在镁合金丝材表面电沉积羟基磷灰石生物陶瓷底层；
3）将10克可降解PLGA溶于50ml的氯仿中，将步骤2）处理过的镁合金丝材浸泡在该溶液中，浸泡时间为1.5分钟，可进行多次浸泡，每两次浸泡之间取出镁合金丝材，并在空气中挥发掉溶剂，可降解表面层的厚度控制在20mm左右；
4）将步骤3）处理过用镁合金丝材成型加工出U型结构缝钉；
5）最后经干燥、检验、消毒，获得本发明。
实施例4
一种吻合器用可吸收缝钉，由医用可降解AZ91镁合金丝材加工而成的U型结构缝钉本体、附着在镁合金丝材表面的可降解氧化镁和羟基磷灰石复合陶瓷薄膜底层、用于封孔处理的可降解PLGA表面层组成，镁合金丝材的直径为φ0.28mm，氧化镁和羟基磷灰石复合陶瓷薄膜底层厚度约为10μm，可降解PLGA表面层的厚度约为10μm。
所述的吻合器用可吸收缝钉的制备步骤如下：
1）首先将AZ91镁合金拉拔、加工成直径为φ0.28mm的镁合金丝材；
2）用10g/L硅酸钠、3g/L羟基磷灰石纳米粉体、2g/L NaOH作为微弧氧化电解液体系，将镁合金丝材浸于其中，施加400V电压，进行10分钟的微弧氧化处理，使其表面原位生成一层氧化镁和羟基磷灰石复合陶瓷底层；
3）将10克可降解PLGA高分子材料进行高温熔化，用该熔融态PLGA刷涂或浸涂步骤2）处理过的镁合金丝材，经凝固固化，可降解表面层的厚度控制在10mm 左右；
4）将步骤3）处理过用镁合金丝材成型加工出U型结构缝钉；
5）最后经干燥、检验、消毒，获得本发明。
显然，本发明的上述实施例仅仅是为了清楚说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，还可在上述说明的基础上做出其它不同形式的变化或变动，这里无需也无法对所有实施方式予以穷举，而这些属于本发明的精神所引申出的显而易见的变化或变动仍处于本发明的保护范围内。

Claims (6)

  1. 一种吻合器用可吸收缝钉，其特征在于，该吻合器用缝钉由医用可降解镁合金丝材加工而成的缝钉本体、附着在镁合金丝材表面的可降解生物陶瓷薄膜底层、用于封孔处理的可降解高分子表面层组成，镁合金丝材的直径为0.1mm~0.6mm，可降解生物陶瓷薄膜底层的厚度为0.1μm ~50μm，可降解高分子表面层的厚度为0.1μm ~100μm。
  2. 如权利要求1所述的吻合器用可吸收缝钉，其特征在于，所述及的镁合金丝材由镁铝合金、镁锰合金、镁锌合金、镁锆合金、镁稀土合金、镁锂合金、镁钙合金或镁银合金的一种或由这些体系组合而成的多元系镁合金经拉拔、加工而成。
  3. 如权利要求1所述的吻合器用可吸收缝钉，其特征在于，所述及的镁合金丝材表面生物陶瓷薄膜底层通过微弧氧化、阳极氧化、电沉积、等离子喷涂、化学转化、离子注入、溅射、气相沉积或生物化学方法制备，为羟基磷灰石涂层、磷酸三钙涂层、氧化镁涂层或含氟防护层，以控制镁合金丝材的降解速度和镁离子的溶出速度。
  4. 如权利要求1所述的吻合器用可吸收缝钉，其特征在于，所述及的可降解高分子表面层材料为聚L-乳酸，或者聚(D, L)-乳酸或者是两者的共聚物或混合物，或者为乳酸同乙醇酸的共聚物，聚合物分子量为1万~150万。
  5. 一种如权利要求1所述的吻合器用可吸收缝钉的制备方法，其特征在于其制备的步骤是：
    1）首先将选好成分的镁合金加工成镁合金丝材；
    2）选择陶瓷涂层技术，在镁合金丝材表面制备出所需的生物陶瓷薄膜底层；
    3）采用浸涂、刷涂或喷涂方法，在表面有生物陶瓷薄膜底层的镁合金丝材表面进一步制备出可降解高分子表面层；
    4）用步骤3）获得的镁合金丝材成型加工出缝钉；
    5）最后经干燥、检验、消毒，获得吻合器用可吸收缝钉。
  6. 一种如权利要求1所述的吻合器用可吸收缝钉的制备方法，其特征在于其制备的步骤为：
    1）首先将选好成分的镁合金拉拔、加工成镁合金丝材；
    2）选择陶瓷涂层技术对镁合金丝材进行表面处理，在镁合金丝材表面制
    备出所需的可降解生物陶瓷薄膜底层；
    3）用步骤2）获得的镁合金丝材成型加工出缝钉；
    4）采用浸涂、刷涂或喷涂方法，在用步骤3）获得的缝钉表面进一步制备出可降解高分子表面层；
    5）最后经干燥、检验、消毒，获得吻合器用可吸收缝钉。
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