Absorbable biomedical polymer material, ligation clip, and method for preparing same

Abstract

Provided are an absorbable biomedical polymer material, a ligation clip, and a method for preparing same. The ingredients selected for the absorbable biomedical polymer material consist of a first polymer and a second polymer. The first polymer consists of 50 wt%-100 wt% of poly(L-lactide) and 0 wt%-50 wt% of polyglycolide, and the second polymer is poly(p-dioxanone). The absorbable biomedical polymer material has suitable rigidity and flexibility, and can be used in preparing a medical device, such as a ligation clip. In particular, when containing 2.5 wt%-40 wt% of the first polymer, the ligation clip can readily pierce the fascia, and is less likely to undergo plastic deformation at a bend. Also disclosed are some structural forms of ligation clips and a method for preparing same.

Description

Absorbable biomedical polymer material, ligature clip and preparation method thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of biomedical polymer materials, in particular to an absorbable biomedical polymer material, a ligature clip made of the polymer material and a preparation method of the ligature clip. BACKGROUND

[0002] In the prior art, it is a common practice in the industry to use absorbable biomedical polymer materials such as polylactic acid, poly(p-dioxanone), polyglycolic acid, etc. to prepare various medical devices.

[0003] For example, a Chinese patent application discloses a bioabsorbable polymer composition, a processing method and a medical device obtained therefrom. The new bioabsorbable polymer blend has a first component and a second component, the first polymer contains about 76% to about 92% by weight of a lactide-rich polymer, the lactide-rich polymer contains 80% to 90% by mole of poly(lactide) and 10% to 20% by mole of poly(glycolide). The second polymer is poly(p-dioxanone), which has a maximum weight percentage of about 22%, and the minimum weight percentage depends on the mole amount of poly(lactide) in the lactide-rich polymer. The new polymer blend provides a medical device with dimensional stability, which can be an injection molded staple.

[0004] However, the new polymer blend has high rigidity, but it is difficult to meet the requirements of material toughness of absorbable ligature devices, tissue engineering scaffolds and other medical devices, and plastic deformation easily occurs at the bending part.

[0005] Chinese patent application: Bioabsorbable polymer composition, processing method and medical device obtained therefrom, publication number: CN114316540A, publication date: 20220412. SUMMARY

[0006] The present application aims to provide an absorbable biomedical polymer material with appropriate rigidity and toughness, as well as a ligature clip made of the polymer material and a preparation method of the ligature clip.

[0007] The raw materials selected in the present application are composed of a first polymer and a second polymer. The first polymer is composed of 50wt%-100wt% of poly-L-lactide and 0wt%-50wt% of polyglycolide, and the second polymer is poly-p-dioxanone.

[0008] The absorbable biomedical polymer material is prepared by extruding and granulating the first polymer and the second polymer in a nitrogen atmosphere by an extruder (preferably a twin-screw extruder). The absorbable biomedical polymer material has proper rigidity and toughness, with a tensile strength of 27-95.7 MPa, a bending strength of 23-164 MPa, a compressive strength of 95-557 MPa, and a Vickers hardness of 2.5-19.5 HV.

[0009] The absorbable polymer material is mainly applied to the preparation of medical devices, and the medical devices also have proper rigidity and toughness. Further, the absorbable polymer material can be specifically applied to the preparation of ligature clips. Especially when the ligature clip contains 2.5wt%-40wt% of the first polymer, it is easy to pierce the fascia and not easy to deform plastically at the bending part.

[0010] The detailed technical solutions disclosed in the application are as follows:

[0011] The absorbable biomedical polymer material disclosed in the application is composed of a first polymer and a second polymer;

[0012] Among them, the sum of the weight percentages is 100%;

[0013] The first polymer is composed of 50wt%-100wt% of poly-L-lactide and 0wt%-50wt% of polyglycolide by weight ratio; or

[0014] The first polymer is polymerized from 50wt%-100wt% of L-lactide and 0wt%-50wt% of glycolide by weight ratio;

[0015] The above parallel solutions only differ in the different industry expressions, but the final meanings are the same.

[0016] The second polymer is poly-p-dioxanone.

[0017] Alternatively, the first polymer is composed of 70wt%-100wt% of poly-L-lactide and 0wt%-30wt% of polyglycolide; and the second polymer is poly-p-dioxanone.

[0018] Alternatively, the first polymer is composed of 50wt%-90wt% of poly-L-lactide and 10wt%-50wt% of polyglycolide; and the second polymer is poly-p-dioxanone.

[0019] Alternatively, the first polymer is composed of 75wt%-90wt% of poly-L-lactide and 10wt%-25wt% of polyglycolide; and the second polymer is poly-p-dioxanone.

[0020] Further, the following several ratio embodiments can be selected:

[0021] The weight ratio of the first polymer is 0wt%~80wt% and the weight ratio of the second polymer is 20wt%~100wt% based on the sum of the weight percentages being 100%.

[0022] The weight ratio of the first polymer is 2.5wt%~80wt% and the weight ratio of the second polymer is 20wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0023] The weight ratio of the first polymer is 2.5wt%~70wt% and the weight ratio of the second polymer is 30wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0024] The weight ratio of the first polymer is 2.5wt%~60wt% and the weight ratio of the second polymer is 40wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0025] The weight ratio of the first polymer is 2.5wt%~50wt% and the weight ratio of the second polymer is 50wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0026] The weight ratio of the first polymer is 2.5wt%~40wt% and the weight ratio of the second polymer is 60wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0027] The weight ratio of the first polymer is 2.5wt%~35wt% and the weight ratio of the second polymer is 65wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0028] Based on the same inventive concept, the application also provides a preparation method of the absorbable biomedical polymer material, which is prepared by extruding and granulating the first polymer and the second polymer in a nitrogen atmosphere at 140~160℃, preferably 150℃, by a double-screw extruder.

[0029] The medical devices made of the polymer material mainly include sutures, suspension wires, stent self-sealing nails, flat-head nails, clamps, suture wires, patches, substrates, meshes, tissue engineering scaffolds, ligature clips, and drug delivery devices.

[0030] Specifically, when preparing the ligature clip, the pellets of the absorbable biomedical polymer material after blending and extrusion can be injection molded by an injection molding machine. The four temperature zones in the injection molding machine are set to 30℃~60℃, 130℃~150℃, 140℃~160℃, and 150℃~170℃, respectively. In a specific embodiment, the four temperature zones can be specifically selected as 40℃, 140℃, 150℃, and 160℃.

[0031] Based on the same inventive concept, the application also provides a ligature clip, which is made by injection molding the pellets of the absorbable biomedical polymer material after blending and extrusion.

[0032] The ligature clip disclosed above comprises a ligature clip body, which further comprises a clip body and a locking device for keeping the clip body closed;

[0033] The clip body has a first clip arm and a second clip arm connected in a V shape, and the first clip arm and the second clip arm are both curved arc structures or both are flat structures.

[0034] Further, the inner middle part of the first clip arm and the second clip arm opposite to each other is provided with an inward arc-shaped protrusion, and the outer middle part of the first clip arm and the second clip arm opposite to each other is a flat surface.

[0035] Further, the inner middle part of the first clip arm and the second clip arm opposite to each other is provided with an inward arc-shaped protrusion, and the outer middle part of the first clip arm and the second clip arm opposite to each other is provided with an inward arc-shaped recess.

[0036] Further, the inner side surface of the first clip arm and the second clip arm opposite to each other is provided with anti-skid teeth or anti-skid grooves.

[0037] Further, the connecting part of the first clip arm and the second clip arm is provided with a hollow groove.

[0038] Further, the clip body is further provided with a clamping device;

[0039] The clamping device comprises a first clamping column provided on the left and right sides of the distal end of the first clip arm in the width direction of the clip body, and a second clamping column provided on the left and right sides of the distal end of the second clip arm in the width direction of the clip body.

[0040] Further, the clip body is further provided with a positioning device;

[0041] The positioning device comprises a first positioning groove provided on the inner side of the distal end of the first clip arm and a first positioning protrusion provided on the inner side of the second clip arm and matched with the first positioning groove, and / or a second positioning protrusion provided on the outer side of the distal end of the second clip arm and a second positioning groove provided on the outer side of the first clip arm and matched with the second positioning protrusion.

[0042] Further, the clip body is integrally formed by an injection molding process.

[0043] Further, the locking device comprises a hook part provided on the distal end of the first clip arm and a fitting part provided on the distal end of the second clip arm and matched with the hook part. The hook part is provided with an acute angle cutting structure or a straight line acute edge cutting structure.

[0044] Further, the locking device is further provided with two limiting blocks, which are oppositely arranged on the distal end of the second clamping arm; the hook portion is in clamping cooperation with the two limiting blocks and is limited between the two limiting blocks.

[0045] Further, the locking device is further provided with a penetrating device for cutting off the tissue when the clamping body starts to close; the penetrating device comprises a sharp cutting head arranged at the outer end of the hook portion; when the clamping body starts to close, the sharp cutting head cooperates with the inclined surface on the abutting portion to cut off the tissue.

[0046] The application further discloses another structure of the ligature clip, which comprises a ligature clip body, wherein the ligature clip body comprises an inner clip and a U-shaped outer clip; the inner clip is clamped into the inner side region of the U-shaped outer clip to complete the closing; the outer clip and the inner clip are respectively made by injection molding of the pellets of the absorbable biomedical polymer material after blending and extrusion; and the content of the first polymer in the outer clip is greater than that in the inner clip.

[0047] Further, the outer wall of the inner clip has a groove along the length direction of the inner clip; the inner wall of the U-shaped region of the outer clip has a convex rib matched with the groove; when the convex rib is clamped into the groove and slides along the groove, the inner clip is forced to deform in the outer clip to gradually complete the closing.

[0048] Based on the same inventive concept, the application further provides a ligature clip with antibacterial efficacy, which comprises a ligature clip body consistent with the structure of the ligature clip and an antibacterial agent uniformly dispersed in the ligature clip body. During preparation, the antibacterial agent is uniformly dispersed in the raw material, and after processing or injection molding, the antibacterial agent is uniformly distributed in the entire ligature clip and can be released slowly during the degradation of the ligature clip body; the weight of the antibacterial agent is 0.1wt%-10wt% of the total weight of the ligature clip body.

[0049] In another embodiment, the application further provides a ligature clip with antibacterial efficacy, which comprises a ligature clip body consistent with the structure of the ligature clip and an antibacterial layer attached to the surface of the ligature clip body; the composition of the antibacterial layer comprises an antibacterial agent, and the weight of the antibacterial agent is 0.1wt%-3wt% of the total weight of the ligature clip body.

[0050] Further, the antibacterial agent is one or more of halogenated hydroxyl ether, acyloxy diphenyl ether, vanillin or ethyl vanillin compound, acylanilide, imidazole, thiazole, isothiazolone derivative, quaternary ammonium salt, bisphenol, phenol and combinations thereof.

[0051] Further, the antibacterial agent is a nanoparticle containing any one of silver, cerium, zinc, or a combination thereof; or one or more of tetracycline hydrochloride, neomycin sulfate, chloramphenicol, streptomycin sulfate, penicillin potassium, oxytetracycline hydrochloride, gentamicin sulfate, cephalothin sodium, furanone, rifamycin, benzalkonium chloride, oxacillin sodium, dihydrostreptomycin sulfate, carbenicillin disodium, and furantoin sodium.

[0052] Further, the antibacterial agent is 2,4,4'-trichloro-2'-hydroxy diphenyl ether.

[0053] Further, the composition of the antibacterial layer further comprises a binder and a lubricant.

[0054] The application has the following advantages:

[0055] The absorbable biomedical polymer material provided by the application is composed of a first polymer and a second polymer. The first polymer is composed of 50wt%-100wt% poly-L-lactide and 0wt%-50wt% polyglycolide, and the second polymer is poly-p-dioxanone, with the sum of the weight percentages being 100%. The absorbable biomedical polymer material has certain rigidity and toughness, with a tensile strength of 27-95.7 MPa, a bending strength of 23-164 MPa, a compressive strength of 95-557 MPa, and a Vickers hardness of 2.5-19.5 HV.

[0056] The ligature provided by the application can effectively solve the defects of poor toughness of the same type of material and poor hardness of the existing absorbable ligature material, and help to pierce the fascia during use, thereby improving the mechanical properties of the absorbable ligature. BRIEF DESCRIPTION OF DRAWINGS

[0057] Fig. 1 is a structural schematic diagram of a first form of ligature provided in Example 2 of the application;

[0058] Fig. 2 is a structural schematic diagram of the ligature of the first form provided in Example 2 of the application from another angle;

[0059] Fig. 3 is a structural schematic diagram of an improved type of the ligature of the first form provided in Example 2 of the application (with a reinforcing rib);

[0060] Fig. 4 is a side view of a second form of ligature provided in Example 2 of the application;

[0061] Fig. 5 is a structural schematic diagram of the ligature of the second form provided in Example 2 of the application;

[0062] Fig. 6 is a side view of a third form of ligature provided in Example 2 of the application;

[0063] Fig. 7 is a structural schematic view of a third form of ligature clip provided in Embodiment 2 of the present application;

[0064] Fig. 8 is a structural schematic view of a fourth form of ligature clip provided in Embodiment 2 of the present application;

[0065] Fig. 9 is a structural schematic view of a fifth form of ligature clip provided in Embodiment 2 of the present application;

[0066] Fig. 10 is a structural schematic view of a sixth form of ligature clip provided in Embodiment 2 of the present application;

[0067] Fig. 11 is a structural schematic view of a ligature clip in a free state provided in Embodiment 2 of the present application;

[0068] Fig. 12 is a structural schematic view of a ligature clip in a semi-closed state provided in Embodiment 2 of the present application;

[0069] Fig. 13 is a test schematic view of a ligature clip clamping a strip-shaped object in a slip-off prevention performance test provided in Embodiment 2 of the present application;

[0070] Fig. 14 is a test schematic view of a ligature clip clamping a cylindrical metal rod in a test of clamping range and brittle fracture performance provided in Embodiment 2 of the present application;

[0071] Fig. 15 is a structural schematic view of an outer clip of a seventh form of ligature clip provided in Embodiment 2 of the present application;

[0072] Fig. 16 is a structural schematic view of an inner clip of a seventh form of ligature clip provided in Embodiment 2 of the present application;

[0073] Reference Signs:

[0074] 100. clip body; 110. first clip arm; 111. hook portion; 112. pointed cutting head; 113. first clamping post; 114. first positioning groove; 115. reinforcing rib;

[0075] 120. second clip arm; 121. abutting portion; 122. second clamping post; 123. first positioning protrusion;

[0076] 130. anti-slip tooth; 140. limiting block;

[0077] 200. inner clip; 201. groove;

[0078] 300. outer clip; 301. convex rib. DETAILED DESCRIPTION

[0079] In the following, only certain exemplary embodiments are simply described. As those skilled in the art can recognize, the described embodiments can be modified in various different manners without departing from the spirit or scope of the embodiments of the present application. Therefore, the drawings and descriptions are to be considered exemplary in nature rather than limiting.

[0080] The terms "first", "second", etc. are used only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features.

[0081] In the embodiments of the present application, unless explicitly specified and limited, the terms "mounting", "connection" and the like should be understood in a broad sense, for example, can be directly connected, can be indirectly connected through an intermediate medium, can be the internal connection of two elements or the interaction relationship of two elements. For those skilled in the art, the specific meaning of the above terms in the embodiments of the present application can be understood according to the specific circumstances.

[0082] The following disclosure provides many different embodiments or examples for implementing different structures of the embodiments of the present application. In order to simplify the disclosure of the embodiments of the present application, the components and arrangements of specific examples are described below. Of course, they are only examples, and the purpose is not to limit the embodiments of the present application. In addition, the reference numerals of the embodiments of the present application can be repeated in different examples. Such repetition is for the purpose of simplification and clarity, and does not indicate the relationship of the various embodiments discussed.

[0083] Embodiment 1

[0084] The present embodiment provides a bioabsorbable biomedical polymer material, which is composed of a first polymer and a second polymer.

[0085] The first polymer is composed of 50wt%-100wt% of poly-L-lactide (PLA) and 0wt%-50wt% of polyglycolide (PGA), with the sum of weight percentages being 100%, and the intrinsic viscosity being 1.9-3.5 dL / g, which is referred to as PLLGA hereinafter; and the second polymer is poly-p-dioxanone, with the intrinsic viscosity being 1.5-2.5 dL / g (preferably 1.9), which is referred to as PPDO hereinafter.

[0086] Further, the first polymer can be composed of 70wt%-100wt% of poly-L-lactide (PLA) and 0wt%-30wt% of polyglycolide (PGA), with the sum of weight percentages being 100%, and the intrinsic viscosity being 1.9-3.5 dL / g, and the second polymer is poly-p-dioxanone, with the intrinsic viscosity being 1.5-2.5 dL / g (preferably 1.9).

[0087] Further, the first polymer can be composed of 50wt%~90wt% of poly-L-lactide (PLA) and 10wt%~50wt% of polyglycolide (PGA) with the sum of weight percentage being 100%, and the intrinsic viscosity of the first polymer is 1.9~3.5 dL / g, and the second polymer is poly-p-dioxanone with the intrinsic viscosity of 1.5~2.5 dL / g (preferably 1.9).

[0088] Further, the first polymer can be composed of 75wt%~90wt% of poly-L-lactide (PLA) and 10wt%~25wt% of polyglycolide (PGA) with the sum of weight percentage being 100%, and the intrinsic viscosity of the first polymer is 1.9~3.5 dL / g, and the second polymer is poly-p-dioxanone with the intrinsic viscosity of 1.5~2.5 dL / g (preferably 1.9).

[0089] Preferably, the weight ratio of the first polymer is 0wt%~80wt%, and the weight ratio of the second polymer is 20wt%~100wt% with the sum of weight percentage being 100%.

[0090] Preferably, the weight ratio of the first polymer is 0wt%~80wt%, and the weight ratio of the second polymer is 20wt%~100wt% with the sum of weight percentage being 100%.

[0091] More preferably, the weight ratio of the first polymer is 2.5wt%~80wt%, and the weight ratio of the second polymer is 20wt%~97.5wt% with the sum of weight percentage being 100%.

[0092] More preferably, the weight ratio of the first polymer is 2.5wt%~60wt%, and the weight ratio of the second polymer is 40wt%~97.5wt% with the sum of weight percentage being 100%.

[0093] More preferably, the weight ratio of the first polymer is 2.5wt%~50wt%, and the weight ratio of the second polymer is 50wt%~97.5wt% with the sum of weight percentage being 100%.

[0094] More preferably, the weight ratio of the first polymer is 2.5wt%~40wt%, and the weight ratio of the second polymer is 60wt%~97.5wt% with the sum of weight percentage being 100%.

[0095] More preferably, the weight ratio of the first polymer is 2.5wt%~35wt%, and the weight ratio of the second polymer is 65wt%~97.5wt% with the sum of weight percentage being 100%.

[0096] The present embodiment also provides a preparation method of the absorbable biomedical polymer material, which is prepared by extruding and granulating the first polymer and the second polymer in a nitrogen atmosphere at 140~160℃ by a double-screw extruder to obtain the absorbable biomedical polymer material.

[0097] The absorbable biomedical polymer material prepared by the foregoing method can be used for medical devices including sutures, suspension wires, stent self-sealing nails, flat-headed nails, clips, suture wires, patches, substrates, meshes, tissue engineering scaffolds, ligature clips, drug delivery devices, and the like.

[0098] The foregoing medical devices are prepared by injection molding of the pellets of the absorbable biomedical polymer material after blending and extrusion. When injection molding, the four-section temperature range in the injection molding machine can be set to 30-60°C, 130-150°C, 140-160°C, and 150-170°C, respectively. In a specific implementation scenario, when the four-section temperature range is specifically selected to be 40°C, 140°C, 150°C, and 160°C, the medical devices prepared have a better rigidity and toughness that meet the expectations.

[0099] The absorbable biomedical polymer material is described below by more specific examples.

[0100] According to the proportions, the two polymer pellets of PLLGA and / or PPDO are first physically mixed; then, regranulated by a twin-screw extruder under nitrogen protection at 150°C; finally, the polymer blended material after granulation is added to the barrel of an injection molding machine, the four-section temperature range of the injection molding machine is set to 40°C, 140°C, 150°C, and 160°C, respectively, a standard sample is prepared by injection molding, and the mechanical properties thereof are detected after annealing at 60-80°C for 8 hours.

[0101] During detection, three standard samples of the same proportions are taken for testing, and the average value of the test results is taken as the detection result. The relevant detection results are shown in Tables 1-8.

[0102] During tensile detection, the loading rate is 3 mm / min. During bending detection, the loading rate is 1 mm / min. During compression detection, the loading rate is 1 mm / min, and the compression degree is 90%.

[0103] In Tables 1-4, the composition of PLLGA in the standard samples (sample numbers 1-12) is all PLA 85wt% and PGA 15wt%. The weight proportion of PLLGA is 0%, 2.5%, 5%, 10%, 20%, 35%, 40%, 50%, 60%, 70%, 80%, and 100%, and the difference lies in the different weight proportions of PLLGA and PPDO.

[0104] In Tables 5-8, the standard samples (sample numbers 13-18) are all PLLGA 40wt% and PPDO 60wt%. The difference lies in the different weight proportions of PLA and PGA in PLLGA.

[0105] Table 1 Tensile data of standard samples of sample numbers 1-12

[0106] Table 1 Tensile data of standard samples of sample numbers 1-12

[0107] Table 2 Bending data of sample No. 1~12 standard sample strips

[0108]

[0109] Table 3 Compression data of sample No. 1~12 standard sample strips

[0110]

[0111] Table 4 Vickers hardness data of sample No. 1~12 standard sample strips

[0112]

[0113] Table 5 Tensile data of sample No. 13~18 standard sample strips

[0114]

[0115] Table 6 Bending data of sample No. 13~18 standard sample strips

[0116]

[0117] Table 7 Compression data of sample No. 13~18 standard sample strips

[0118]

[0119] Table 8 Vickers hardness data of sample No. 13~18 standard sample strips

[0120]

[0121] From the data in the table, it can be seen that by controlling the weight ratio of PLLGA and PPDO and the weight ratio of PLA and PGA in PLLGA, an absorbable biomedical polymer material with appropriate rigidity and toughness can be obtained, which meets the use requirements of medical devices.

[0122] Example 2

[0123] The present embodiment provides a ligature clip. The ligature clip is made of the pellets of the absorbable biomedical polymer material after blending and extrusion by injection molding.

[0124] The absorbable biomedical polymer material is composed of a first polymer and a second polymer.

[0125] The first polymer is composed of 70wt%~100wt% of poly-L-lactide (PLA) and 0wt%~30wt% of polyglycolide (PGA) with an inherent viscosity of 1.9~3.5, hereinafter referred to as PLLGA;

[0126] The second polymer is poly-p-dioxanone with an inherent viscosity of 1.5~2.5, hereinafter referred to as PPDO.

[0127] Preferably, in one embodiment,

[0128] The weight ratio of the first polymer is 2.5wt%~60wt% and the weight ratio of the second polymer is 40wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0129] More preferably, in other embodiments,

[0130] The weight ratio of the first polymer is 2.5wt%~60wt% and the weight ratio of the second polymer is 40wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0131] More preferably, in other embodiments,

[0132] The weight ratio of the first polymer is 2.5wt%~60wt% and the weight ratio of the second polymer is 40wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0133] More preferably, in other embodiments,

[0134] The weight ratio of the first polymer is 2.5wt%~60wt% and the weight ratio of the second polymer is 40wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0135] More preferably, in other embodiments,

[0136] The weight ratio of the first polymer is 2.5wt%~60wt% and the weight ratio of the second polymer is 40wt%~97.5wt% based on the sum of the weight percentages being 100%.

[0137] More preferably, in other embodiments,

[0138] The ligature clip comprises a ligature clip body, which further comprises a clip body 100 and a locking device for keeping the clip body 100 closed.

[0139] The clip body 100 has a first clip arm 110 and a second clip arm 120 connected in a V shape. The first clip arm 110 and the second clip arm 120 are integrally injection molded or connected by elastic hinges at the proximal ends. The opposite inner side surfaces of the first clip arm 110 and the second clip arm 120 are provided with anti-skid teeth 130 or anti-skid grooves.

[0140] The locking device includes a hook portion 111 provided at the distal end of the first clip arm 110 and a fitting portion 121 provided at the distal end of the second clip arm 120 and adapted to the hook portion 111. A penetrating device is also provided on the locking device for cutting off the tissue when the clip body 100 starts to close. The penetrating device specifically includes a sharp cutting head 112 provided at the outer end of the hook portion 111. When the clip body 100 starts to close, the sharp cutting head 112 cooperates with the inclined surface on the fitting portion 121 to cut off the tissue. The clip body 100 also has a clamping device, which includes first clamping columns 113 provided on the left and right sides of the distal end of the first clip arm 110 along the width direction of the clip body 100, and / or second clamping columns 122 provided on the left and right sides of the distal end of the second clip arm 120 along the width direction of the clip body 100.

[0141] Figs. 1-3 show a first form of the ligation clip in the present embodiment. The first clip arm 110 and the second clip arm 120 are curved circular arc structures in the same direction. The connection between the first clip arm 110 and the second clip arm 120 is provided with a hollow groove. The ligation clip shown in Fig. 3 has a reinforcing rib 115 at the inner side of the hook portion 111, which is not provided in the ligation clips shown in Figs. 1 and 2, mainly for strengthening the strength of the hook portion 111 and avoiding side slipping after the first clip arm 110 and the second clip arm 120 are closed.

[0142] Figs. 4-5 show a second form of the ligation clip in the present embodiment. The first clip arm 110 and the second clip arm 120 are both flat structures. The clip body 100 is provided with a positioning device, which includes a first positioning groove 114 provided at the inner side of the distal end of the first clip arm 110 and a first positioning protrusion 123 provided at the inner side of the second clip arm 120 and adapted to the first positioning groove 114.

[0143] Figs. 6-7 show a third form of the ligation clip in the present embodiment. The first clip arm 110 and the second clip arm 120 are both flat structures. The inner middle parts of the opposite inner sides of the first clip arm 110 and the second clip arm 120 are both provided with inward arc-shaped protrusions. The outer middle parts of the opposite outer sides of the first clip arm 110 and the second clip arm 120 are both flat.

[0144] The ligation clip of this form structure is provided with an acute angle cutting structure at the hook portion 111. Furthermore, the locking device is further provided with two limiting blocks 140, which are oppositely arranged on the distal end surface of the second clip arm 120. The hook portion 111 is in clamping cooperation with the two limiting blocks 140 and is limited between the two limiting blocks 140.

[0145] Fig. 8 is a fourth form of the ligation clip in the embodiment. The first clip arm 110 and the second clip arm 120 are both flat structures. Moreover, the opposite inner middle portions of the first clip arm 110 and the second clip arm 120 are both inwardly arc-shaped protrusions. The opposite outer middle portions of the first clip arm 110 and the second clip arm 120 are both flat surfaces.

[0146] Compared with the structure form of the ligation clip shown in Fig. 7, the difference is that the cutting structure at the hook portion 111 is a linear sharp edge cutting structure. The other structures are basically the same, that is, the locking device is also provided with two limiting blocks 140, which are oppositely arranged on the distal end surface of the second clip arm 120. The hook portion 111 is in clamping cooperation with the two limiting blocks 140 and is limited between the two limiting blocks 140.

[0147] Fig. 9 is a fifth form of the ligation clip in the embodiment. The first clip arm 110 and the second clip arm 120 are both flat structures. Moreover, the opposite inner middle portions of the first clip arm 110 and the second clip arm 120 are both inwardly arc-shaped protrusions. The opposite outer middle portions of the first clip arm 110 and the second clip arm 120 are both flat surfaces. The hook portion 111 is provided with a linear sharp edge cutting structure. The locking device is also provided with two limiting blocks 140, which are oppositely arranged on the distal end surface of the second clip arm 120. The hook portion 111 is in clamping cooperation with the two limiting blocks 140 and is limited between the two limiting blocks 140.

[0148] Fig. 10 is a sixth form of the ligation clip in the embodiment. The first clip arm 110 and the second clip arm 120 are both flat structures. Moreover, the opposite inner middle portions of the first clip arm 110 and the second clip arm 120 are both inwardly arc-shaped protrusions. The opposite outer middle portions of the first clip arm 110 and the second clip arm 120 are both flat surfaces.

[0149] Compared with the structure form of the ligation clip shown in Fig. 9, the difference is that the cutting structure at the hook portion 111 is an acute angle cutting structure. The hook portion 111 is provided with an acute angle cutting structure, which is slightly different from the hook portion 111 of the aforementioned ligation clip in forming mode, and other structures are basically the same. That is, the locking device is also provided with two limiting blocks 140, which are oppositely arranged on the distal end surface of the second clip arm 120. The hook portion 111 is in clamping cooperation with the two limiting blocks 140 and is limited between the two limiting blocks 140.

[0150] Fig. 14~15 are the seventh structure of the ligature clip shown in this embodiment, including the inner clip 200 and the outer clip 300 in U shape. The outer wall of the inner clip 200 has a groove 201 along its own length direction. The inner wall of the U-shaped region of the outer clip 300 has a convex ridge 301 matched with the groove 201. When the convex ridge 301 is clamped into the groove 201 and slides along the groove 201, the inner clip 200 is forced to deform into the outer clip 300, gradually completing the clamping.

[0151] The outer clip 300 and the inner clip 200 are respectively made by injection molding the pellets of the absorbable biomedical polymer material after blending and extrusion as described above.

[0152] The absorbable biomedical polymer material is composed of a first polymer and a second polymer. Wherein, the first polymer is composed of 70wt%~100wt% of poly-L-lactide (PLA) and 0wt%~30wt% of polyglycolide (PGA) with the sum of weight percentage being 100%, and the intrinsic viscosity is 1.9~3.5, which is referred to as PLLGA hereinafter; the second polymer is poly-p-dioxanone with the intrinsic viscosity being 1.9, which is referred to as PPDO hereinafter. Preferably, the weight ratio of the first polymer is 2.5wt%~80wt% and the weight ratio of the second polymer is 20wt%~97.5wt% with the sum of weight percentage being 100%. More preferably, the weight ratio of the first polymer is 2.5wt%~50wt% and the weight ratio of the second polymer is 50wt%~97.5wt% with the sum of weight percentage being 100%. Wherein, the content of the first polymer in the outer clip 300 is greater than that in the inner clip 200. Even more preferably, the weight percentage of the first polymer in the outer clip 300 is 40wt%~70wt% and the weight percentage of the second polymer is 30wt%~60wt% with the sum of weight percentage being 100%. The weight percentage of the first polymer in the inner clip 200 is 2.5wt%~10wt% and the weight percentage of the second polymer is 90wt%~97.5wt% with the sum of weight percentage being 100%.

[0153] In this embodiment, the ligature clip in the first form is taken as an example, a plurality of samples are injection molded, and the resilience performance test, the anti-slip ability test, and the clamping range and brittle fracture performance test are carried out. The composition of PLLGA in the samples is all PLA 85wt% and PGA 15wt%, and the weight percentage of PLLGA (the ratio of PLLGA to PPDO) is respectively 0%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 80%, and 100%.

[0154] Ligation clip must be in half-closed state through the puncture device into the abdominal cavity when laparoscopic surgery is performed, and it should not fall off from the clip applier when it is reopened, and it should still maintain good tension so as not to fall off or skew from the clip applier when other soft tissues are touched during the operation. Therefore, the resilience performance of the ligation clip when it is restored to the free state after being half-closed is very important.

[0155] Test method of resilience performance: As shown in FIGS. 11-12, FIG. 11 (the ligation clip shown in the figure is not reinforced 115) is the ligation clip in the free state, which is deformed and closed under the action of force F to become the half-closed state of FIG. 12, and then the pressure F is cancelled. The ligation clip will be restored to the free state due to its own elasticity, but due to the plastic deformation during the half-closed process, the ligation clip cannot completely restore to the initial free state of FIG. 10, but the included angle θ of the double arms will be smaller. The more the number of half-closed times, the smaller the included angle θ will be, and when it is small to the limit θ f , the ligation clip will fall off from the tool holding it, losing the value of the operation.

[0156] The resilience performance of different formula proportions of materials is very different. Table 9 is the test results of the resilience performance of PLLGA in different proportions in the composite material.

[0157] Table 9 Effective resilience number of half-closed times Unit: times

[0158]

[0159] It is found from the above table that when the proportion of PLLGA is between 0wt% and 40wt%, the number of effective half-closed times is relatively large, and it has good use value; the composite material with a proportion of 40wt% to 80wt% has a certain resilience performance, but it is not very ideal, but it can be used with difficulty. The resilience of the material above 80wt% is very poor and has no use value.

[0160] After the ligation clip clamps and closes the tubular or strip-shaped biological tissue during the operation, it cannot slip off during or after the operation. Therefore, the positive pressure of the ligation clip on the ligated tissue after being closed and the lateral anti-slip ability must be improved.

[0161] Anti-slip ability test: As shown in FIG. 13, a strip-shaped object with a thickness of 0.2mm and a width of 3mm is used as the clamped object. After the strip-shaped object is clamped and closed by the ligation clip (the clamping position is the same each time), the ligation clip is fixed, one end of the strip-shaped object is pulled by a tension meter (the other end is in a free state), and the strip-shaped object is made to slide on the closed contact surface of the ligation clip. At this time, the pulling force is the maximum pulling force of the anti-slip. The greater the pulling force, the better the anti-slip performance and the tighter the clamping. Table 10 is the test conclusion of the anti-slip ability test when PLLGA occupies different proportions in the composite material.

[0162] Table 10 Tensile force data

[0163]

[0164] From the above table, the following conclusions can be analyzed and summarized: the higher the proportion of PLLGA increases from 0% to 100%, the greater the anti-slip tensile force is, which is meaningful for firmly clamping the clamped object.

[0165] Clamping range and brittle fracture performance test: as shown in FIG. 14, different diameter cylindrical metal rods are clamped with the ligature clip, and whether it can be smoothly closed is observed. The larger the diameter of the metal rod that can be smoothly clamped, the better the performance is. If it cannot be smoothly clamped or brittle, it means that it cannot be used normally at this diameter. The material formula of the ligature clip is different, and the clamping range of the ligature clip is different.

[0166] Table 11 is the closing condition of clamping a metal rod with a diameter of Φ2.0 mm. Among them, “√” means smooth clamping. “x” means that it cannot be clamped.

[0167] Table 11 Clamping of Φ2.0 mm diameter metal rod closing condition

[0168]

[0169] The size of the ligature clip designed in this test is actually clamped in the operation. After the soft tissue is compacted, the maximum diameter is about 1 millimeter. Therefore, the 2.0 millimeter metal rod diameter used in this experiment is relatively large, which is only used to test the trend of the clamping range of the ligature clip with the change of the material formula.

[0170] From the above test conclusions, it can be seen that the higher the proportion of PLLGA is, the weaker the elasticity is, the greater the plastic deformation after half-closing is, and the higher the possibility of brittle fracture during clamping is, which affects the use effect. However, the higher the proportion of PLLGA is, the higher the hardness is, the greater the clamping force is, and the stronger the anti-slip ability is, which is beneficial to the use effect.

[0171] Based on the test results of the above three important parameters, and considering the test conclusions of other performance parameters, it is analyzed that when the proportion of PLLGA material is 0wt% to 80wt%, the performance of the ligature clip has use value, but when the proportion of PLLGA material is in the range of 0wt% to 40wt% (at this time, the proportion of the corresponding PPDO material is 60wt% to 100wt%), the performance of the ligature clip is the best, and has the most use value in surgery.

[0172] The ligature clip disclosed in the embodiments of the present application effectively solves the defects of poor toughness of the same type of material and poor hardness of the existing absorbable ligature clip material, which helps to pierce the fascia during use and improves the mechanical properties of the absorbable ligature clip.

[0173] Embodiment 3

[0174] The embodiment provides a ligature clip with antibacterial efficacy, which comprises a ligature clip body consistent with the structure of the ligature clip in Embodiment 2, and an antibacterial agent is uniformly dispersed in raw materials in advance in a preparation process, and the antibacterial agent is uniformly distributed in the whole ligature clip after processing or injection molding, and can be released slowly in the degradation process of the ligature clip body; the weight of the antibacterial agent is 0.1wt%-10wt% of the total weight of the ligature clip body.

[0175] During the operation process, bacteria in the surrounding air can enter the operation site and adhere to the medical instrument. Specifically, the bacteria can be transmitted through the implanted medical instrument as a way to enter the surrounding tissue, and the bacteria on the medical instrument can cause infection and trauma of the patient. Therefore, in order to avoid similar complications in the ligature operation, an antibacterial agent can be added to the raw materials in advance in the process of preparing the ligature clip, so that the antibacterial agent is uniformly distributed in the ligature clip body. The antibacterial agent can be halogenated hydroxyl ether, acyloxy diphenyl ether, vanillin or ethyl vanillin compound, acylanilide, imidazole, thiazole, isothiazolone derivative, quaternary ammonium salt, bisphenol, phenol and combination thereof; it can also be a nanoparticle containing any metal ion such as silver, cerium, zinc; it can also be one or more of tetracycline hydrochloride, neomycin sulfate, chloramphenicol, streptomycin sulfate, penicillin potassium, oxytetracycline hydrochloride, gentamicin sulfate, cephalothin sodium, furanone, rifamycin, benzalkonium chloride, oxacillin sodium, dihydrostreptomycin sulfate, carbenicillin disodium and furantoin sodium. The particularly preferred antibacterial agent is 2,4,4'-trichloro-2'-hydroxydiphenyl ether, commonly known as triclosan. Triclosan is a broad-spectrum antibacterial agent, which has been used in various products and can effectively resist common microorganisms. These microorganisms include but are not limited to Staphylococcus, Staphylococcus epidermidis, Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, methicillin-resistant Staphylococcus aureus and combinations thereof.

[0176] The antibacterial agent is uniformly dispersed into the raw materials or the ligature clip body by solvent, melting, extrusion granulation, physical mixing or injection molding, and the content of the antibacterial agent on the final antibacterial ligature clip is about 0.1wt%-10wt%, and the antibacterial agent is gradually released with the degradation of the ligature clip.

[0177] In this embodiment, triclosan is used as the antibacterial agent, the ligature clip with the first structure form in Embodiment 2 (wherein the content of PLLGA is 40wt%) is used as the ligature clip body, and the antibacterial ligature clip with the content of the antibacterial agent of 0.1wt%, 5wt% and 10wt% is respectively formed by melt injection molding method, and then typical gram-negative bacteria (Escherichia coli) and gram-positive bacteria (Staphylococcus aureus) are selected to study the antibacterial ability of the antibacterial ligature clip.

[0178] The specific procedure of the antibacterial test is as follows: first, 0.1 mL of degradation solution around the antibacterial ligature clip is put into a 24-well plate and sterilized in a UV environment for 24 h. Then, 1 mL of E. coli and S. aureus liquid with a concentration of 10 6 CFU / mL is added to the sample, respectively. After 6 h of incubation at 37℃, the liquid in the 24-well plate is stirred to form a mixture. 450 μL of nutrient broth medium is added to a 48-well culture plate, and 50 μL of the above mixture is taken out and added to the 48-well culture plate, respectively. The parallel samples of each group of experiments are set to 5 groups. After 24 h of culture under the same conditions, 100 μL of liquid is taken out and added to a 96-well plate, and the absorbance of the liquid at a wavelength of 630 nm is measured by an enzyme-labeled instrument. The bacteria without the addition of degradation solution are used as the control group. The nutrient broth medium is used as the blank.

[0179] The bacterial killing rate (%) is calculated by the following formula:

[0180] Wherein, Asample, Acontrol and Ablank are the absorbance of the material group, the absorbance of the control group and the absorbance of the nutrient broth, respectively.

[0181] The antibacterial test shows that the antibacterial ligature clip of the embodiment has a sterilization rate of about 25%, 59% and 87.2% on S. aureus, and a sterilization rate of about 13%, 42% and 73% on E. coli, respectively, showing different degrees of antibacterial ability. The specific antibacterial test data is shown in Table 12.

[0182] Table 12: Sterilization rate statistics table of antibacterial ligature clip

[0183]

[0184] From the above experimental tests, it can be known that the ligature clip disclosed in the present application can effectively kill bacteria to a certain extent after the addition of the antibacterial agent.

[0185] Embodiment 4

[0186] The antibacterial ligature clip provided in the embodiment includes a ligature clip body consistent with the structure of the ligature clip in Embodiment 2, and an antibacterial layer attached to the surface of the ligature clip body; the weight of the antibacterial layer is 0.1 wt% to 3 wt% of the total weight of the antibacterial ligature clip. Compared with Embodiment 3, the antibacterial efficacy of the antibacterial ligature clip disclosed in the embodiment is mainly realized through the antibacterial layer attached to the surface of the ligature clip body.

[0187] The antibacterial agent in the composition of the antibacterial layer in this embodiment is one or a combination of halogenated hydroxyl ether, acyloxy diphenyl ether, vanillin or ethyl vanillin compound, acylanilide, imidazole, thiazole, isothiazolone derivative, quaternary ammonium salt, bisphenol, phenol, or is any one of silver, cerium, zinc, etc. nanoparticles containing metal ions; or is one or more of tetracycline hydrochloride, neomycin sulfate, chloramphenicol, streptomycin sulfate, penicillin potassium, oxytetracycline hydrochloride, gentamicin sulfate, cephalothin sodium, furanone, rifamycin, benzalkonium chloride, oxacillin sodium, dihydrostreptomycin sulfate, carbenicillin disodium, and furantoin sodium. The particularly preferred antibacterial agent is 2,4,4'-trichloro-2'-hydroxydiphenyl ether, commonly known as triclosan. Triclosan is a broad-spectrum antibacterial agent that has been used in a variety of products and can effectively combat common microorganisms. These microorganisms include, but are not limited to, Staphylococcus, Staphylococcus epidermidis, Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, and combinations thereof. In addition to the antibacterial agent, the composition of the antibacterial layer can also include a binder (such as lactide and glycolide polymer) and a lubricant (such as calcium stearate).

[0188] The antibacterial layer in this embodiment is formed by the dipping method, the process is to dissolve the antibacterial agent in a suitable solvent to form a dipping solution, dip the ligature clip body, then dry the dipped ligature clip body to remove the solvent, and the antibacterial agent residue will be evenly coated on the surface of the clip body. The concentration of the antibacterial agent in the dipping solution is about 2wt%~15wt%, and the content of the antibacterial agent on the final antibacterial ligature clip is about 0.1wt%~3wt%.

[0189] In this embodiment, triclosan is used as the antibacterial agent, and the ligature clip with the first structure form in embodiment 2 (wherein the PLLGA content is 40wt%) is used as the ligature clip body. The antibacterial ligature clip with antibacterial agent content of 0.1wt%, 2wt% and 3wt% is respectively formed by the dipping method, and then typical gram-negative bacteria (Escherichia coli) and gram-positive bacteria (Staphylococcus aureus) are selected to study the antibacterial ability of the antibacterial layer.

[0190] The specific process of the antibacterial test is as follows: first, the antibacterial ligature clip is placed in a 24-well plate and sterilized in a UV environment for 24 h. Then, 1 mL of 10 6E. coli and Staphylococcus aureus bacterial solution at 1.0 x 105CFU / mL. After incubation at 37°C for 6 h, the liquid in the 24-well plate was stirred to form a mixture. 450 μL of nutrient broth medium was added to a 48-well culture plate, and 50 μL of the above mixture was taken and added to the 48-well culture plate. The parallel samples of each group of experiments were set to 5 groups. After 24 h of culture under the same conditions, 100 μL of liquid was taken and added to a 96-well plate, and the absorbance of the liquid at a wavelength of 630 nm was measured by an enzyme-labeled instrument. The bacteria without the treatment of the antibacterial ligature clip were used as a control group. The nutrient broth medium was used as a blank.

[0191] The bacterial killing rate (%) was calculated by the following formula:

[0192] Wherein, Asample, Acontrol and Ablank are the absorbance of the material group, the absorbance of the control group and the absorbance of the nutrient broth, respectively.

[0193] The antibacterial test showed that the antibacterial ligature clip of the embodiment had a bacterial killing rate of about 37%, 74%, and 97% for Staphylococcus aureus, and a bacterial killing rate of about 20%, 51%, and 83% for E. coli, respectively, and showed different degrees of antibacterial ability. The specific antibacterial test data are shown in Table 13 below.

[0194] Table 13 Statistical table of bacterial killing rate of antibacterial ligature clip

[0195]

[0196] From the above experimental tests, it can be known that the ligature clip disclosed in the present application can effectively kill bacteria to a certain extent after the addition of the antibacterial agent.

Claims

1. An absorbable biomedical polymer material, comprising a first polymer and a second polymer, characterized in that: Taking the sum of weight percentages as 100%, The weight ratio of the first polymer is 2.5wt%~80wt%, and the weight ratio of the second polymer is 20wt%~97.5wt%; in, The first polymer consists of 50 wt% to 100 wt% of poly-L-lactide and 0 wt% to 50 wt% of polyglycolide; The second polymer is polydioxanone.

2. The absorbable biomedical polymer material according to claim 1, characterized in that: The weight ratio of the first polymer is 2.5 wt % to 70 wt %, and the weight ratio of the second polymer is 30 wt % to 97.5 wt %.

3. The absorbable biomedical polymer material according to claim 2, characterized in that: The weight ratio of the first polymer is 2.5 wt % to 60 wt %, and the weight ratio of the second polymer is 40 wt % to 97.5 wt %.

4. The absorbable biomedical polymer material according to claim 3, characterized in that: The weight ratio of the first polymer is 2.5 wt % to 50 wt %, and the weight ratio of the second polymer is 50 wt % to 97.5 wt %.

5. The absorbable biomedical polymer material according to claim 4, characterized in that: The weight ratio of the first polymer is 2.5 wt % to 40 wt %, and the weight ratio of the second polymer is 60 wt % to 97.5 wt %.

6. The absorbable biomedical polymer material according to claim 5, characterized in that: The weight ratio of the first polymer is 2.5 wt% to 35 wt%, and the weight ratio of the second polymer is 65 wt% to 97.5 wt%.

7. The absorbable biomedical polymer material according to claim 1, characterized in that: The first polymer consists of 70 wt% to 100 wt% of poly-L-lactide and 0 wt% to 30 wt% of polyglycolide.

8. The absorbable biomedical polymer material according to claim 1, characterized in that: The first polymer consists of 50 wt% to 90 wt% of poly-L-lactide and 10 wt% to 50 wt% of polyglycolide.

9. The absorbable biomedical polymer material according to claim 8, characterized in that: The first polymer consists of 75 wt% to 90 wt% of poly-L-lactide and 10 wt% to 25 wt% of polyglycolide.

10. A ligation clip made of the absorbable biomedical polymer material according to any one of claims 1 to 9, characterized in that: include: Ligating clip body; The ligation clip body includes a clip body and a locking device for keeping the clip body closed; The clamping body comprises a first clamping arm and a second clamping arm connected in a V-shape, wherein the first clamping arm and the second clamping arm are arc structures curved in the same direction or are both straight structures; The locking device includes a hook portion provided at the distal end of the first clamp arm and a fitting portion provided at the distal end of the second clamp arm and adapted to fit with the hook portion, wherein the hook portion is provided with an acute-angle cutting structure or a linear sharp-edge cutting structure; and Two limit blocks, which are oppositely arranged on the distal ends of the second clamping arm; The hook portion is engaged with the two limit blocks and is limited between the two limit blocks.

11. The ligation clip according to claim 10, characterized in that: When the first clamping arm and the second clamping arm are arc structures curved in the same direction; A hollow groove is provided at the connection between the first clamping arm and the second clamping arm; A reinforcing rib is also provided on the inner side of the hook portion.

12. The ligation clip according to claim 10, characterized in that : The clamping body is also provided with a clamping device; The clamping device includes first clamping posts provided on the left and right sides of the distal end of the first clamping arm along the width direction of the clamping body; or The clamping device includes first clamping posts arranged on the left and right sides of the distal end of the first clamping arm along the width direction of the clamping body; and second clamping posts arranged on the left and right sides of the distal end of the second clamping arm along the width direction of the clamping body.

13. The ligation clip according to claim 10, characterized in that : The clamping body is also provided with a positioning device; The positioning device includes a first positioning groove arranged on the inner side of the distal end of the first clamp arm and a first positioning protrusion arranged on the inner side of the second clamp arm and adapted to the first positioning groove, and / or a second positioning protrusion arranged on the outer side of the distal end of the second clamp arm and a second positioning groove arranged on the outer side of the first clamp arm and adapted to the second positioning protrusion.

14. The ligation clip according to claim 10, characterized in that: The locking device is also provided with a penetrating device for cooperating with and cutting off tissue when the clamp body begins to close; The penetrating device comprises a pointed cutting head arranged at the outer end of the hook portion; when the clamp body begins to close, the pointed cutting head cooperates with the inclined surface on the fitting portion to cut off the tissue.

15. The ligation clip according to any one of claims 10 to 14, characterized in that: An antibacterial layer is attached to the surface of the ligation clip body, and the composition of the antibacterial layer includes an antibacterial agent, and the weight of the antibacterial agent is 0.1wt% to 3wt% of the total weight of the ligation clip body; or, An antibacterial agent is uniformly dispersed in the ligation clip body, and the weight of the antibacterial agent is 0.1 wt % to 10 wt % of the entire weight of the ligation clip body.

16. The ligation clip according to claim 15, characterized in that: The antibacterial agent is one or more of halogenated hydroxy ethers, acyloxydiphenyl ethers, vanillin, ethyl vanillin compounds, acylanilides, imidazoles, thiazoles, isothiazolone derivatives, quaternary ammonium salts, bisguanidines, and phenols.

17. The ligation clip according to claim 15, characterized in that: The antibacterial agent is nanoparticles containing any one metal ion of silver, cerium, zinc or a combination thereof.

18. The ligation clip according to claim 15, characterized in that: The antibacterial agent is one or more of tetracycline hydrochloride, neomycin sulfate, chloramphenicol, streptomycin sulfate, penicillin potassium, oxytetracycline hydrochloride, gentamicin sulfate, ceftriaxone sodium, furanone, rifamycin, benzyl ammonium chloride, oxacillin sodium, dihydrostreptomycin sulfate, carbenicillin disodium and nitrofurantoin sodium.

19. The ligation clip according to claim 15, characterized in that: The antibacterial agent is 2,4,4'-trichloro-2'-hydroxydiphenyl ether.

20. The ligation clip according to claim 15, characterized in that: The antibacterial layer also comprises an adhesive and a lubricant.

21. A ligation clip made of the absorbable biomedical polymer material according to any one of claims 1 to 9, characterized in that: include: A ligation clamp body, comprising an inner clamp and a U-shaped outer clamp; The content of the first polymer in the outer compartment is greater than the content of the first polymer in the inner compartment.

22. The ligation clip according to claim 21, characterized in that: The outer wall of the inner clip has a groove along its own length direction, and the inner wall of the U-shaped area of ​​the outer clip has a ridge that matches the groove; When the ridge is inserted into the groove and slides along the groove, the inner clip is forcibly deformed and positioned inside the outer clip, thereby completing the clamping.

23. The ligation clip according to claim 21 or 22, characterized in that: An antibacterial layer is attached to the surface of the ligation clip body, and the composition of the antibacterial layer includes an antibacterial agent, and the weight of the antibacterial agent is 0.1wt% to 3wt% of the total weight of the ligation clip body; or, An antibacterial agent is uniformly dispersed in the ligation clip body, and the weight of the antibacterial agent is 0.1 wt % to 10 wt % of the entire weight of the ligation clip body.

24. The ligation clip according to claim 23, characterized in that: The antibacterial agent is one or more of halogenated hydroxy ethers, acyloxydiphenyl ethers, vanillin, ethyl vanillin compounds, acylanilides, imidazoles, thiazoles, isothiazolone derivatives, quaternary ammonium salts, bisguanidines, and phenols.

25. The ligation clip according to claim 23, characterized in that: The antibacterial agent is nanoparticles containing any one metal ion of silver, cerium, zinc or a combination thereof.

26. The ligation clip according to claim 23, characterized in that: The antibacterial agent is one or more of tetracycline hydrochloride, neomycin sulfate, chloramphenicol, streptomycin sulfate, penicillin potassium, oxytetracycline hydrochloride, gentamicin sulfate, ceftriaxone sodium, furanone, rifamycin, benzyl ammonium chloride, oxacillin sodium, dihydrostreptomycin sulfate, carbenicillin disodium and nitrofurantoin sodium.

27. The ligation clip according to claim 23, characterized in that: The antibacterial agent is 2,4,4'-trichloro-2'-hydroxydiphenyl ether.

28. The ligation clip according to claim 23, characterized in that: The antibacterial layer also comprises an adhesive and a lubricant.

29. A method for preparing a ligation clip, for preparing the ligation clip according to any one of claims 10 to 28, characterized in that: The first polymer and the second polymer are first extruded into granules by an extruder in a nitrogen atmosphere, and then injection molded by an injection molding machine; in, The temperature of the nitrogen atmosphere is 140-160°C; The injection molding machine is provided with four temperature zones, and the temperature ranges thereof are respectively set to 30°C-60°C, 130°C-150°C, 140°C-160°C and 150°C-170°C.

30. The method for preparing the ligation clip according to claim 29, characterized in that: The temperatures of the four temperature zones in the injection molding machine are set to 40° C., 140° C., 150° C. and 160° C. respectively.

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