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WO2023109547A1 - Prothèse articulaire ayant une couche réticulée en surface et son procédé de fabrication, et ensemble moule de pressage - Google Patents

Prothèse articulaire ayant une couche réticulée en surface et son procédé de fabrication, et ensemble moule de pressage Download PDF

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Publication number
WO2023109547A1
WO2023109547A1 PCT/CN2022/136517 CN2022136517W WO2023109547A1 WO 2023109547 A1 WO2023109547 A1 WO 2023109547A1 CN 2022136517 W CN2022136517 W CN 2022136517W WO 2023109547 A1 WO2023109547 A1 WO 2023109547A1
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WO
WIPO (PCT)
Prior art keywords
layer
cross
linked
molding
joint prosthesis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2022/136517
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English (en)
Chinese (zh)
Inventor
俞天白
潘忠诚
梁柱
姚夏睿
常兆华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Microport Orthorecon Co Ltd
Original Assignee
Suzhou Microport Orthorecon Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Microport Orthorecon Co Ltd filed Critical Suzhou Microport Orthorecon Co Ltd
Publication of WO2023109547A1 publication Critical patent/WO2023109547A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/14—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/36—Moulds for making articles of definite length, i.e. discrete articles

Definitions

  • the application relates to the technical field of medical devices, in particular to a joint prosthesis with a surface cross-linked layer, a preparation method thereof, a molding die assembly, and an artificial joint friction pair.
  • Ultra-high molecular weight polyethylene has been widely used in the field of artificial hip/knee replacement due to its excellent mechanical properties, biocompatibility, self-lubrication and wear resistance.
  • high-energy irradiation is commonly used to treat ultra-high molecular weight polyethylene.
  • Ethylene undergoes radiation crosslinking. However, there will be residual free radicals after irradiation cross-linking, which need to be eliminated, otherwise the performance of the joint prosthesis will be affected.
  • antioxidants-vitamin E to control the degree of irradiation crosslinking of ultra-high molecular weight polyethylene.
  • the basic principle is that the phenolic hydroxyl group on vitamin E can combine with free radicals, so when mixed with ultra-high molecular weight polyethylene, vitamin E can reduce the concentration of free radicals in ultra-high molecular weight polyethylene after irradiation, thereby controlling the concentration of ultra-high molecular weight polyethylene.
  • the crosslink density of polyethylene Although this method can obtain ultra-high molecular weight polyethylene with a certain cross-linking density and reduce the loss of mechanical properties, the improvement of mechanical properties is still relatively limited.
  • the wear resistance of the friction surface of the joint prosthesis is low. When used with metal or ceramic femoral head/condyle, the friction and wear are serious, which affects the service life of the product.
  • the object of the present application includes providing a joint prosthesis with a surface cross-linked layer, a preparation method thereof, a molding die assembly, and a friction pair.
  • the joint prosthesis includes a surface cross-linked layer and a matrix layer, the friction surface of the joint prosthesis is located on the outer surface of the surface cross-linked layer, the UHMWPE in the surface cross-linked layer has a high degree of cross-linking (the degree of cross-linking is higher than that of the base layer), and The overall crosslinking degree of UHMWPE in the base layer is low or there is no crosslinking UHMWPE.
  • the joint prosthesis can be prepared through the following steps: firstly perform pre-compression molding in a low temperature mode to prepare a preformed base layer, then add highly cross-linked UHMWPE powder, and perform compression molding in a high-temperature mode to form a surface cross-linked layer.
  • a joint prosthesis in the first aspect of the present application, includes a surface cross-linked layer and a matrix layer, and the friction surface of the joint prosthesis is located on the outer surface of the surface cross-linked layer;
  • the surface cross-linked layer and the matrix layer each independently comprise UHMWPE and optional auxiliary material components;
  • the UHMWPE in the surface crosslinked layer has a crosslinked structure
  • the UHMWPE in the matrix layer does not have a crosslinked structure or has a crosslinked structure
  • the average degree of crosslinking of the UHMWPE in the surface crosslinked layer is higher than the average degree of crosslinking of the UHMWPE in the base layer.
  • an intermediate cross-linked layer is also included between the surface cross-linked layer and the base layer, and the intermediate cross-linked layer contains UHMWPE and optional auxiliary material components; the intermediate cross-linked layer
  • the average trans-vinylidene index of is recorded as TVI M , and TVI M satisfies greater than TVI B and less than TVI A .
  • the joint prosthesis is prepared by a method comprising the following steps:
  • the preform includes a preformed matrix layer
  • the first cross-linked UHMWPE powder on the preform, and carry out compression molding at the molding temperature to form the surface cross-linked layer; wherein, the first cross-linked UHMWPE powder is in the form of the surface cross-linked The powder required for the layer; the molding temperature is higher than the pre-pressing temperature.
  • the pre-pressing temperature of each pre-pressing molding is independently selected from 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C and any two temperatures in 200°C constitute an interval;
  • the molding temperature is selected from any two temperature intervals of 210°C, 220°C, 230°C, 240°C, 250°C and 260°C;
  • the pre-pressing temperature for each pre-pressing molding is independently 150°C-200°C; during the molding process for forming the surface cross-linked layer, the molding temperature is 210°C-260°C.
  • the preparation method of the joint prosthesis satisfies any one or any suitable combination of the following features:
  • the pre-pressing time of each pre-pressing molding is independently 20min ⁇ 60min;
  • the pre-compression pressure of each pre-compression molding is independently 20MPa ⁇ 40MPa;
  • the compression molding pressure for forming the surface cross-linked layer is 20MPa ⁇ 40MPa;
  • the compression molding time for forming the surface cross-linked layer is 0.5h-1h.
  • the preform further includes a preformed intermediate cross-linked layer.
  • the preform is prepared by a method comprising the following steps:
  • the intermediate cross-linking layer powder is loaded on the preformed base layer at one time or in batches, and the second pre-compression molding is performed one or more times to form the pre-formed intermediate cross-linking layer; wherein, each The pre-pressing temperature of the second pre-pressing molding is independently lower than the molding temperature;
  • the pre-pressing temperature for each second pre-pressing forming is independently 150°C-200°C.
  • the crosslinked UHMWPE in the joint prosthesis is produced by irradiation crosslinking; wherein,
  • the average trans-vinylene index of the surface cross-linked layer is recorded as TVI A , and the TVI A is greater than 0.3; optionally, the TVI A is selected from the following two values to form an interval: 0.32, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.42 and 0.45;
  • the average trans-vinylidene index of the base layer is denoted as TVIB , and the TVIB is less than 0.05.
  • the joint prosthesis satisfies any one or any combination of the following features:
  • the roughness of the friction surface of the joint prosthesis is Ra ⁇ 0.1 ⁇ m; optionally, Ra ⁇ 0.09 ⁇ m; further optionally, Ra ⁇ 0.08 ⁇ m; further optionally, Ra ⁇ 0.07 ⁇ m; further optionally , Ra ⁇ 0.06 ⁇ m; further optionally, Ra ⁇ 0.05 ⁇ m;
  • the thickness of the surface cross-linked layer is selected from the interval consisting of any two thicknesses as follows: 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm , 1.6mm, 1.7mm, 1.8mm, 1.9mm, 2.0mm, 2.1mm, 2.2mm, 2.3mm, 2.4mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm, 2.9mm and 3mm; optionally, the The thickness of the surface cross-linked layer is 0.5 mm to 3 mm.
  • the joint prosthesis satisfies any one or any combination of the following features:
  • trans-vinylene indices of the surface cross-linked layer are all greater than 0.3; optionally, the trans-vinylene indices of the surface cross-linked layer are independently or simultaneously selected from any of the following two Value composition range: 0.32, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.42 and 0.45;
  • the trans-vinylidene index of each part of the base layer is less than 0.05.
  • the intermediate cross-linked layer includes N structural layers, where N is an integer greater than or equal to 1;
  • the average trans-vinylidene index of each structural layer in the direction from the base layer to the surface crosslinked layer is recorded as TVI 1 , TVI 2 , ..., TVI N , are greater than TVI B and less than TVI A , and increase sequentially;
  • the number of times of performing the second pre-press forming is any integer selected from 2 to N.
  • the powder when loading the powder to be formed into the preformed blank, the powder is preheated at 100° C. to 120° C. first.
  • the optional auxiliary material components in each structural layer are each independently selected from the following components: antibacterial agents, anti-inflammatory agents, inorganic fillers, antioxidants;
  • the auxiliary material components are independently selected from the following components: antibacterial agents, anti-inflammatory agents and antioxidants;
  • the mass proportion of the auxiliary material components in any structural layer independently does not exceed 2%; optionally, the mass proportion of the auxiliary material components in any structural layer independently ranges from 0.1% to 2%.
  • the joint prosthesis is a hip joint prosthesis, a knee joint prosthesis, an ankle joint prosthesis or a shoulder joint prosthesis.
  • the joint prosthesis is produced by the preparation method of the second aspect of the present application.
  • a method for preparing a joint prosthesis wherein the joint prosthesis includes a surface cross-linked layer and a matrix layer, and the friction surface of the joint prosthesis is located on the outer surface of the surface cross-linked layer;
  • the preparation method comprises the following steps S100, S200, S300 and S400:
  • S300 Perform radiation cross-linking treatment on the UHMWPE powder under anaerobic conditions, and control the radiation dose according to the target TVI A of the surface cross-linked layer to obtain the first cross-linked UHMWPE powder;
  • S400 Use the first cross-linked UHMWPE powder as a surface cross-linked layer powder, or mix the first cross-linked UHMWPE powder with the required auxiliary materials in the surface cross-linked layer to obtain a surface cross-linked layer powder; then the surface crosslinking layer powder is loaded on the preformed matrix layer to form a surface crosslinking powder layer, so that the surface crosslinking powder layer covers the friction surface forming surface of the mould, and the Compression molding to prepare the joint prosthesis with the surface cross-linked layer and the base layer.
  • the preparation method satisfies any one or any suitable combination of the following features:
  • the pre-compression temperature is 150°C-200°C, optionally, the pre-compression time is 20min-60min; optionally, the temperature adjustment rate is 5°C/min- 10°C/min;
  • Step S300 includes: irradiating and annealing the UHMWPE powder under vacuum conditions to obtain the first cross-linked UHMWPE powder; wherein, the irradiation dose is 30kGy-100kGy, the annealing temperature is 100°C-140°C, Optionally, the annealing time is 4h-10h;
  • step S300 the high-energy rays used for irradiation crosslinking treatment are electron beams or gamma rays;
  • the thickness of the surface cross-linked powder layer is 1 mm to 6 mm; optionally, the thickness of the surface cross-linked powder layer is selected from the following interval consisting of any two thicknesses: 1 mm, 1.5 mm , 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm and 5.5mm;
  • the roughness of the molding surface of the friction surface of the mold is Ra ⁇ 0.1 ⁇ m; optionally, Ra ⁇ 0.09 ⁇ m; further optionally, Ra ⁇ 0.08 ⁇ m; further optionally, Ra ⁇ 0.07 ⁇ m ; Further optionally, Ra ⁇ 0.06 ⁇ m; Further optionally, Ra ⁇ 0.05 ⁇ m;
  • step S400 of performing the compression molding the molding temperature is 210°C-260°C, the molding pressure is 20MPa-40MPa, and the molding time is 0.5h-1h; optionally, the temperature adjustment rate is 5°C/min-10°C /min.
  • a step S220 of preparing an intermediate cross-linked layer is also included, and the intermediate cross-linked layer is located between the base layer and the surface cross-linked layer Between, the average trans-vinylidene index TVI M of the intermediate cross-linked layer satisfies greater than TVI B and less than TVI A ;
  • S220 Perform radiation cross-linking treatment on the UHMWPE powder under anaerobic conditions, control the radiation dose according to the target TVI M of the middle cross-linked layer, and obtain a second cross-linked UHMWPE powder; use the second cross-linked Combine UHMWPE powder and optional auxiliary materials to obtain intermediate cross-linking layer powder; put the intermediate cross-linking layer powder on the preformed base layer, and perform the second pre-compression molding, and the pre-compression temperature is 150°C ⁇ 200°C, optionally, the pre-pressing time is 20min ⁇ 60min.
  • the intermediate cross-linked layer includes N structural layers, where N is an integer greater than or equal to 1;
  • the number of times of performing the second pre-press molding is selected from any integer from 1 to N (further any integer from 2 to N), from the base layer to the surface crosslinking In the direction of the layer, the average trans-vinylene index of each structural layer is greater than TVI B and less than TVI A , and increases sequentially.
  • the powder when loading the powder to be formed into the preformed blank, the powder is preheated at 100° C. to 120° C. first.
  • the joint prosthesis prepared by the preparation method is selected from the joint prosthesis described in the first aspect of the present application.
  • the preparation method satisfies any one or any combination of the following features:
  • the molecular weight of the UHMWPE contained in each step is independently 3 ⁇ 10 6 Da to 5 ⁇ 10 6 Da; the molecular weight may be but not limited to the weight average molecular weight;
  • the average particle size of the powder in each step is independently 100 ⁇ m to 200 ⁇ m.
  • a molding die assembly for preparing the joint prosthesis described in the first aspect of the present application, or for implementing the preparation method described in the second aspect of the present application.
  • it includes a first forming die, a sleeve, a third forming die and a fourth forming die; wherein, the sleeve is hollow tubular, and the first forming die, the third forming die and The outer peripheral contour of the fourth molding die matches the inner cavity contour of the sleeve respectively;
  • the third forming mold is used to form the friction surface of the joint prosthesis, and the roughness of the forming surface of the corresponding friction surface in the third forming mold is Ra ⁇ 0.1 ⁇ m;
  • the first molding die is used to form the surface of the joint prosthesis opposite to the friction surface of the joint prosthesis;
  • the third molding die cooperates with the first molding die to provide a cavity for compression molding
  • the fourth molding die is used to form a preform, and the preform does not include the surface crosslinking layer;
  • the fourth molding die cooperates with the first molding die to provide a cavity for pre-press molding to prepare the pre-form blank.
  • an artificial joint friction pair including a first support body and a second support body, the first support body is the joint prosthesis described in the first aspect of the application, and the second support body
  • the support body is a hard joint component, and the friction surface of the joint prosthesis and the friction surface of the second support body cooperate with each other.
  • This application has changed the traditional method of carrying out radiation cross-linking treatment on the formed UHMWPE joint prosthesis to improve wear resistance, but develops a surface cross-linking technology, by directly cross-linking the UHMWPE powder (which can be preferably , but not limited to radiation cross-linking treatment), and then press molding to control the degree of cross-linking of UHMWPE.
  • UHMWPE powder which can be preferably , but not limited to radiation cross-linking treatment
  • press molding to control the degree of cross-linking of UHMWPE.
  • the joint prosthesis includes a highly cross-linked UHMWPE structural layer (as a surface cross-linked layer that provides the friction surface of the joint prosthesis), and also includes a non-cross-linked or less cross-linked UHMWPE structural layer ( As a matrix layer with good mechanical properties), it can take into account the dual needs of wear resistance and mechanical properties (such as mechanical strength, toughness, fatigue resistance, etc.).
  • This special structural design can be realized by using the aforementioned surface cross-linking technology.
  • the irradiation dose of UHMWPE powder required for the structural layer can be controlled accordingly according to the cross-linking degree of different structural layers, and UHMWPE structural layers with different cross-linking degrees can be obtained after molding.
  • the UHMWPE powder of the base layer no cross-linking treatment may be performed, or only a small amount of radiation cross-linking treatment, or only a slight radiation cross-linking treatment, so as to maintain the mechanical properties of the base layer to a greater extent.
  • a large dose of radiation treatment can be used according to the need for wear resistance, so as to greatly improve the wear resistance of the raw material.
  • the structural layer of the joint prosthesis can be flexibly designed.
  • the cross-linked UHWMPE can be limited to the surface cross-linked layer (at this time, the middle cross-linked layer is not included, and the UHWMPE in the matrix layer has not been irradiated to cross-link), or the matrix layer of non-cross-linked UHMWPE
  • An intermediate cross-linked layer is set between the highly cross-linked surface cross-linked layer to realize the transition change of UHMWPE cross-linked degree between the matrix layer and the surface cross-linked layer, and improve the cohesion between the surface cross-linked layer and the adjacent structural layer .
  • the middle cross-linked layer may also include multiple structural layers to further realize a good performance transition from the base layer to the surface cross-linked layer. Different multi-layer structure designs can be reasonably selected according to the performance requirements of different joint parts.
  • different molding parameters can be used for different structural layers by means of pre-compression molding, so as to realize performance optimization of different structural layers (including but not limited to optimization).
  • the roughness of the molding surface of the friction surface in the mold can be greatly reduced, thereby further improving the wear resistance of the joint prosthesis.
  • FIG. 1 in the following description is only an embodiment of the present application, and those skilled in the art can also obtain other drawings according to FIG. 1 and FIG. 2 without creative effort.
  • Fig. 1 and Fig. 2 are drawn in a simplified form, and are only used for convenience and clarity to assist in explaining the present application.
  • the various dimensions of each component shown in FIGS. 1 and 2 are arbitrarily shown and may be exact or may not be drawn to actual scale.
  • Fig. 1 is the schematic diagram of the molding die of the acetabular cup joint prosthesis of one embodiment of the present application, wherein, 110-the first molding die (mold lower die); 120-sleeve; 130-the third molding die (molding upper die) ; 131-the pressure head of the third molding die; 140-the fourth molding die (pre-press upper die);
  • FIG. 2 is a schematic diagram of a molding die of a knee prosthesis according to an embodiment of the present application, wherein, 210-the first forming die (mold lower die); 220-sleeve; 230-the third forming die (molding upper die); 240 - the fourth molding die (pre-press upper die);
  • Fig. 3 is a schematic diagram of an acetabular cup joint prosthesis prepared according to an embodiment of the present application
  • Fig. 4 is the change diagram of the TVI value with the distance from the friction surface in the joint prosthesis of embodiment 2;
  • Fig. 5 is a graph showing the change of TVI value with the distance from the friction surface in the joint prosthesis of embodiment 3;
  • Fig. 6 is a graph showing the change of TVI value with the distance from the friction surface in the joint prosthesis of embodiment 4;
  • Fig. 7 is a graph showing the variation of TVI value with the distance from the friction surface in the joint prosthesis of Example 5.
  • the terms “and/or”, “or/and”, “and/or” include any one of two or more of the associated listed items, and any of the associated listed items. and all combinations including any combination of any two of the relevant listed items, any more of the relevant listed items, or all of the relevant listed items. It should be noted that when at least three items are connected with at least two conjunctions selected from “and/or”, “or/and”, “and/or”, it should be understood that in this application, the technical solution Undoubtedly include the technical solutions that are all connected by "logic and”, and also undoubtedly include the technical solutions that are all connected by "logic or”. For example, "A and/or B” includes three parallel schemes of A, B and A+B.
  • the technical solution of "A, and/or, B, and/or, C, and/or, D” includes any one of A, B, C, and D (that is, all are connected by "logic or") technical solution), also includes any and all combinations of A, B, C, and D, that is, includes any combination of any two or any three of A, B, C, and D, and also includes A, B, and C , four combinations of D (that is, all use the technical scheme of "logic and" connection).
  • multiple means that the number is greater than 2 or equal to 2.
  • one or more means one or more than two.
  • the terms “first”, “second”, “third”, “fourth” etc. It is for descriptive purposes only and should not be read as indicating or implying relative importance or quantity, nor as implying the importance or quantity of the indicated technical features. Moreover, “first”, “second”, “third”, “fourth” and so on are only for the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on the quantity.
  • the technical features described in open form include closed technical solutions consisting of the enumerated features, as well as open technical solutions including the enumerated features.
  • any step may include a plurality of sub-steps or stages, and these sub-steps or stages are not necessarily executed at the same time, but may be executed at different times, and the order of execution is not necessarily sequential, but It can be performed in turn or alternately with other steps or sub-steps of other steps or a part of stages, or at the same time.
  • N1 ⁇ N2 has the same meaning as “about N1 to about N2” and can be used interchangeably, wherein N1 and N2 are two unequal values; due to the technical One or more factors such as the allowable reasonable deviation, the temperature control accuracy of the instrument, etc., make the approximate value within the approximate range should also be included in the range indicated by the numerical range.
  • the molding temperature is 210°C to 260°C
  • the molding temperature can be understood as “about 210°C to about 260°C”; further, taking the endpoint as “210°C” and its divisor as ⁇ 1°C as an example, "about 210°C
  • the approximate values such as 209°C and 209.5°C within the approximate range indicated by “°C” should also be included in the range indicated by 210°C to 260°C.
  • the temperature parameters in this article are allowed to be treated at a constant temperature, and are also allowed to vary within a certain temperature range. It should be understood that the isothermal treatment described allows the temperature to fluctuate within the precision of the instrument control. It is allowed to fluctuate within the range of ⁇ 5°C, ⁇ 4°C, ⁇ 3°C, ⁇ 2°C, ⁇ 1°C.
  • volume percentage for gas-gas mixture refers to mass percentage wt% for solid phase-solid phase mixture
  • for a solid-liquid mixture refers to mass percent wt% or solid-liquid percent (w/v).
  • % (w/w) and wt % represent percentage by weight.
  • UHMWPE refers to ultra-high molecular weight polyethylene.
  • molecular weight of UHMWPE unless otherwise specified, it generally refers to the weight average molecular weight.
  • the particle size refers to the average particle size unless otherwise specified, and a certain particle size distribution range is allowed, such as ⁇ 10%, ⁇ 5%.
  • a certain particle size distribution range is allowed, such as ⁇ 10%, ⁇ 5%.
  • the average particle size of the powder is allowed to be 200 ⁇ 20 microns, 200 ⁇ 10 microns, etc.
  • excipients refer to ingredients other than UHMWPE, and the form of each auxiliary ingredient at room temperature is not particularly limited, and can be solid, liquid, semi-solid (such as paste), etc.
  • the degree of cross-linking of UHMWPE may refer to the degree of cross-linking obtained by any cross-linking treatment, including the degree of cross-linking caused by irradiation cross-linking treatment.
  • irradiation cross-linking treatment means that, if there is no special limitation, after UHMWPE is irradiated (such as but not limited to ⁇ -ray or electron beam irradiation), CC bonds and CH bonds in the molecule may occur. Breakage produces active free radicals, and the active free radicals between different molecular chains react, which will lead to the formation of cross-linked structures. Usually, the trans-vinylidene structure is an inevitable product of irradiation crosslinking.
  • the trans-vinylidene index (TVI) in UHMWPE monotonically increases with the increase of the irradiation dose. Therefore, in this paper, TVI is used to characterize the cross-linking degree of UHMWPE in the joint prosthesis prepared from UHMWPE powder after irradiation cross-linking treatment. Generally, the larger the TVI, the higher the degree of cross-linking of UHMWPE. Because the degree of crosslinking of UHMWPE after irradiation often corresponds to the level of wear resistance of the joint prosthesis, the higher the degree of crosslinking, the better the wear resistance. Therefore, the higher the TVI value, the better the wear resistance. Abrasive.
  • the TVI should usually be 0, and due to instrument errors and test accuracy, it may also show extremely small TVI values (such as 0.002, 0.003, 0.005).
  • the TVI value can be tested by using or referring to the method of the national pharmaceutical industry standard "YY/T0814-2010".
  • the transvinylene index (TVI) inside UHMWPE is detected by infrared spectroscopy, that is, the ratio of the area of the absorption peak at 965 cm -1 to the total area of the absorption peak between 1330 cm -1 and 1396 cm -1 to determine the absorption of UHMWPE products
  • the dose level of electron beam irradiation reflects the degree of crosslinking of UHMWPE. It is understandable that the degree of cross-linking can also be characterized by other parameters, and the use of different parameters for characterization does not constitute a limitation on the cross-linking process itself; in addition, if other cross-linking methods are used to obtain cross-linked UHMWPE, other methods other than TVI are allowed. way to determine the degree of cross-linking of UHMWPE.
  • degree of crosslinking and “degree of crosslinking” have the same meaning and can be used interchangeably, both refer to the degree of crosslinking.
  • the difference in the degree of cross-linking in this application can be reflected in the density of cross-linking points, the content of cross-linking points, the distribution of cross-linking points and so on.
  • the level of crosslinking degree refers to the difference in the content of crosslinking points unless otherwise specified.
  • the degree of cross-linking can also be reflected by the difference in cross-linking point density.
  • upper in “installed on the preform” and “installed on the preformed base layer” should be understood in a broad sense, referring to the upper side along the direction of gravity, which can be in direct contact or No direct contact.
  • a preformed blank also referred to as a preform
  • the laid surface crosslinking layer powder directly contacts the intermediate crosslinking layer without directly contacting the matrix layer, but in this application Also referred to as “mounting on said preformed substrate layer”.
  • the “friction surface” in this application refers to the surface of the joint prosthesis that is in contact with another joint prosthesis or a human joint. Its shape is not particularly limited and can be adjusted according to the shape of the joint. For example, it can be a concave surface Or the convex surface, which is not particularly limited here, should be understood as being within the protection scope of the present application.
  • the direction from the base layer to the surface cross-linked layer can also be understood as the direction toward the friction surface of the joint prosthesis.
  • a joint prosthesis with a surface cross-linked layer is provided.
  • the joint prosthesis includes a highly cross-linked UHMWPE structural layer (as a joint prosthesis friction surface
  • the surface cross-linked layer also includes non-cross-linked or less cross-linked UHMWPE structure layer (as a matrix layer with good mechanical properties), so that both wear resistance and mechanical properties (such as mechanical strength, toughness, fatigue resistance) etc.) dual needs.
  • the joint prosthesis includes a surface cross-linked layer and a matrix layer, and the friction surface of the joint prosthesis is located on the outer surface of the surface cross-linked layer.
  • the surface crosslinking layer and the matrix layer each independently comprise UHMWPE and optional auxiliary material components.
  • Both the surface cross-linked layer and the matrix layer in this application contain UHMWPE.
  • the degree of crosslinking of UHMWPE in the surface crosslinking layer and the matrix layer is different.
  • the UHMWPE crosslinking degree in the surface crosslinking layer is higher (better wear resistance), and the UHMWPE crosslinking degree in the matrix layer is lower (strength, toughness and other mechanical properties are better) Excellent) or non-crosslinked UHMWPE.
  • the UHMWPE in the surface crosslinked layer has a highly crosslinked structure (the degree of crosslinking is higher than that of the base layer), and the UHMWPE in the base layer does not have a crosslinked structure or has a crosslinked structure (When having a crosslinked structure, it may be preferred but not limited to have a low crosslinked structure, less crosslinked or partially crosslinked structure).
  • the joint prosthesis can reduce the roughness of the joint prosthesis on the basis of avoiding the loss of mechanical properties, and is expected to greatly reduce the amount of friction and wear when used in conjunction with other materials in artificial joint replacement.
  • the average degree of crosslinking of UHMWPE in the surface crosslinked layer is higher than the average degree of crosslinking of UHMWPE in the base layer.
  • the average degree of crosslinking is calculated as the content of crosslinking points, which can be determined by suitable known characterization methods.
  • the cross-linked UHMWPE in the joint prosthesis can be produced by irradiation cross-linking, and further, the corresponding cross-linking degree is characterized by TVI.
  • the average trans-vinylene index of the surface cross-linked layer is recorded as TVI A , which refers to the TVI value measured at different positions of the surface cross-linked layer, and the average value is taken after sampling at multiple positions.
  • TVI A refers to the TVI value measured at different positions of the surface cross-linked layer, and the average value is taken after sampling at multiple positions.
  • at least 3 positions are sampled, and some non-limiting examples thereof include 3, 4, 5, 6, 7, 8, 9, 10 and other sampling positions.
  • Low cross-linking of the base layer refers to a low degree of cross-linking, and less cross-linking refers to a low density of cross-linking points (also manifested as a low degree of cross-linking), which can be achieved by controlling a low irradiation dose to UHMWPE.
  • the partial crosslinking of the matrix layer can be realized by mixing uncrosslinked UHMWPE and crosslinked UHMWPE (preferably, but not limited to low crosslinked UHMWPE).
  • the overall crosslinking degree of the matrix layer can be reflected by the average TVI.
  • the average trans-vinylidene index of the base layer is recorded as TVI B , which refers to the TVI value measured at different positions of the base layer, and the average value is taken after sampling at multiple positions.
  • TVI B refers to the TVI value measured at different positions of the base layer
  • the average value is taken after sampling at multiple positions.
  • at least 3 positions are sampled, and some non-limiting examples thereof include 3, 4, 5, 6, 7, 8, 9, 10 and other sampling positions.
  • a joint prosthesis in some embodiments of the present application, includes a surface cross-linked layer and a base layer, and the friction surface of the joint prosthesis is located on the outer surface of the surface cross-linked layer;
  • the surface cross-linked layer and the base layer each independently comprise UHMWPE and optional auxiliary material components (optionally, the optional auxiliary material components in each structural layer can each independently be selected from the following components: antibacterial agent, anti-inflammatory agents and antioxidants);
  • the UHMWPE in the surface crosslinked layer has a crosslinked structure
  • the UHMWPE in the matrix layer does not have a crosslinked structure or has a crosslinked structure
  • the average degree of crosslinking of the UHMWPE in the surface crosslinked layer is higher than the average degree of crosslinking of the UHMWPE in the base layer.
  • the cross-linked UHMWPE in the joint prosthesis is generated by irradiation cross-linking
  • the joint prosthesis can be prepared by a method comprising the following steps: firstly perform pre-compression molding in low temperature mode to prepare the preformed base layer, then add the first cross-linked UHMWPE powder, in high temperature mode performing compression molding to form the surface cross-linked layer;
  • the first cross-linked UHMWPE powder is prepared by a method comprising the following steps: the UHMWPE powder is subjected to radiation cross-linking treatment under anaerobic conditions, and the irradiation is controlled according to the target TVI A of the surface cross-linked layer. dose, to obtain the first cross-linked UHMWPE powder;
  • the pre-pressing temperature is 150°C-200°C; during the molding process for forming the surface cross-linked layer, the molding temperature is 210°C-260°C
  • the joint prosthesis is prepared by a method comprising the following steps:
  • the preform includes a preformed matrix layer
  • the first cross-linked UHMWPE powder on the preform, and carry out compression molding at the molding temperature to form the surface cross-linked layer; wherein, the first cross-linked UHMWPE powder is in the form of the surface cross-linked The powder required for the layer; the molding temperature is higher than the pre-pressing temperature.
  • the pre-pressing temperature of each pre-pressing molding is independently selected from any two temperatures of 150°C, 160°C, 170°C, 175°C, 180°C, 190°C and 200°C interval.
  • the pre-compression temperature of each pre-compression molding can also be independently set to any one of the aforementioned temperatures.
  • the molding temperature is selected from any two temperatures of 210°C, 220°C, 230°C, 240°C, 250°C and 260°C constitute an interval.
  • the molding temperature can also be set to any one of the aforementioned temperatures.
  • the pre-pressing temperature of each pre-pressing molding is independently 150°C to 200°C; during the molding process of forming the surface cross-linked layer, the molding temperature is 210°C to 260°C.
  • the pre-compression temperature and the molding temperature of each pre-compression molding can be selected from suitable parameters provided herein independently or in combination with each other.
  • the preparation method of the joint prosthesis satisfies any one or any suitable combination of the following features (any of the following features can also be described in more detail according to other descriptions herein):
  • the pre-pressing time of each pre-pressing molding is independently 20min ⁇ 60min;
  • the pre-compression pressure of each pre-compression molding is independently 20MPa ⁇ 40MPa;
  • the compression molding pressure for forming the surface cross-linked layer is 20MPa ⁇ 40MPa;
  • the compression molding time for forming the surface cross-linked layer is 0.5h-1h.
  • the pre-compression temperature of each pre-compression molding and the pre-compression time of each pre-compression molding can be combined in any suitable manner.
  • the pre-pressing temperature of each pre-pressing forming, the pre-pressing time of each pre-pressing forming, and the pre-pressing pressure of each pre-pressing forming may be combined in any suitable manner.
  • the molding temperature and the molding time can be combined in any suitable way.
  • the molding temperature, the molding time and the molding pressure may be combined in any suitable manner.
  • the preform further includes a preformed intermediate cross-linked layer.
  • the preform is prepared by a method comprising the following steps:
  • the intermediate cross-linking layer powder is loaded on the preformed base layer at one time or in batches, and the second pre-compression molding is performed one or more times to form the pre-formed intermediate cross-linking layer; wherein, each The pre-pressing temperature of the second pre-pressing molding is independently lower than the molding temperature.
  • the pre-pressing temperature for each second pre-pressing forming may be independently 150°C to 200°C. It can also be selected from any two temperature intervals selected from 150°C, 160°C, 170°C, 175°C, 180°C, 190°C and 200°C; it can also be set to any one of the aforementioned temperatures.
  • the intermediate cross-linked layer can be prepared by a method including the following steps: UHMWPE powder is subjected to radiation cross-linking treatment under anaerobic conditions, and according to the target of the intermediate cross-linked layer TVI M controls the radiation dose to obtain the second cross-linked UHMWPE powder; use the second cross-linked UHMWPE powder and optional auxiliary materials to obtain the middle cross-linked layer powder; pack the middle cross-linked layer powder Carry out the second pre-compression molding on the pre-formed base layer, the pre-compression temperature is 150°C-200°C, further, the pre-compression time can be 20min-60min
  • TVIA is greater than TVIB.
  • TVI A is greater than 0.3, and can further be greater than 0.32, greater than 0.35, greater than 0.36, 0.3-0.5, 0.3-0.45, 0.3-0.42, 0.35-0.5, 0.35-0.45, etc. , some non-limiting examples such as 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, etc.
  • TVI A is greater than 0.3; further, TVI A can be selected from any of the following values or any two values to form an interval: 0.32, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.42 and 0.45.
  • the TVI B is less than 0.05, and may further be less than 0.05, less than 0.04, less than 0.03 and so on. In some further embodiments, TVI B is 0; in this application, unless otherwise stated, values below the detection limit can be regarded as 0. TVI B is theoretically 0 in the structural layer formed by raw materials that have not been irradiated and cross-linked.
  • TVI A is greater than 0.3 and TVI B is less than 0.05.
  • TVI A is greater than 0.3; alternatively, TVI A is selected from any two numerical intervals as follows: 0.32, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.42 and 0.45;
  • TVI B is less than 0.05.
  • the surface cross-linked layer and the matrix layer in the present application each independently optionally contain auxiliary material components.
  • the surface cross-linked layer may optionally contain auxiliary material components, that is, may or may not contain auxiliary material components.
  • the base layer may optionally contain auxiliary material components, that is, may or may not contain auxiliary material components.
  • the joint prosthesis includes a surface cross-linked layer and a base layer, and the friction surface of the joint prosthesis is located on the outer surface of the surface cross-linked layer;
  • the surface cross-linked layer and the matrix layer each independently comprise UHMWPE and optional auxiliary material components;
  • the UHMWPE in the surface crosslinked layer has a crosslinked structure, and the average trans vinylidene index of the surface crosslinked layer is recorded as TVIA , and the TVIA is greater than 0.3;
  • the UHMWPE in the base layer does not have a cross-linked structure or has a cross-linked structure, and the average trans-vinylidene index of the base layer is recorded as TVI B , and the TVI B is less than 0.05.
  • the trans-vinylidene index everywhere in the surface crosslinked layer satisfies greater than 0.3. For example, at more than 3 sampling points (such as 3, 4, 5, 6, 7, 8, 9, 10 sampling points).
  • the trans-vinylidene index everywhere in the base layer satisfies less than 0.05.
  • at more than 3 sampling points such as 3, 4, 5, 6, 7, 8, 9, 10 sampling points.
  • the trans-vinylidene index is zero everywhere in the base layer. For example, at more than 3 sampling points (such as 3, 4, 5, 6, 7, 8, 9, 10 sampling points).
  • the matrix is uncrosslinked ultra-high molecular weight polyethylene, so the mechanical properties of the joint prosthesis are not affected by the irradiation crosslinking operation, the toughness is good, and the fatigue resistance is excellent. In artificial joint replacement applications, the service life can be effectively extended.
  • the average trans-vinylene index on the outer surface of the surface cross-linked layer is greater than 0.3, and further, it may be preferred (but not limited to) that the trans-vinylene index on the outer surface of the surface cross-linked layer The indices are all greater than 0.3.
  • the outer surface of the base layer has an average trans-vinylidene index of less than 0.05. Further, it may be preferable (but not limited to) that the trans-vinylidene index of all places on the outer surface of the base layer satisfy less than 0.05.
  • the outer surface of the base layer has an average trans-vinylidene index of zero. Further, it may be preferred (but not limited to) that the trans-vinylene index everywhere on the outer surface of the base layer is 0.
  • the joint prosthesis satisfies any one or any combination of the following features:
  • the trans-vinylidene index everywhere in the surface cross-linked layer is greater than 0.3 (the trans-vinylidene index everywhere in the surface cross-linked layer can also be selected from any of the aforementioned suitable ranges or values; some non-limiting For example, the trans-vinylidene index at each place of the surface cross-linked layer can be independently or simultaneously selected from the following two numerical intervals: 0.32, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.42 and 0.45);
  • the trans-vinylidene index of each part of the base layer is less than 0.05.
  • the thickness of the surface cross-linked layer can be flexibly adjusted. If it is too thick, it may affect the overall mechanical properties of the joint prosthesis. If it is too thin, it will affect the durability of the wear resistance. The surface crosslinked layer will be lost due to wear, resulting in the exposure of the adjacent structural layer with a relatively lower degree of crosslinking. The anti-wear performance will be reduced or even seriously deteriorated.
  • the thickness of the surface cross-linked layer is less than or equal to 3 mm. In some embodiments of the present application, the thickness of the surface crosslinked layer is less than 3 mm. In some embodiments of the present application, the thickness of the surface cross-linked layer is greater than or equal to 0.5 mm.
  • the thickness of the surface crosslinked layer is greater than 0.5 mm. In some embodiments of the present application, the thickness of the surface cross-linked layer is 0.5 mm to 3 mm. In some embodiments of the present application, examples of the thickness of the surface crosslinked layer are 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6 mm, 1.7mm, 1.8mm, 1.9mm, 2.0mm, 2.1mm, 2.2mm, 2.3mm, 2.4mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm, 2.9mm, 3mm.
  • the outer surface of the surface crosslinked layer provides a friction surface for the joint prosthesis. Wear resistance can also be optimized by improving the roughness of the friction surfaces of joint prostheses. Improving the roughness of the friction surface of the joint prosthesis on the basis of the surface crosslinking layer can improve the wear resistance of the friction surface from two angles.
  • the control of the roughness of the friction surface of the joint prosthesis can be realized by controlling the surface roughness of the indenter of the corresponding forming die, and the surface roughness of the indenter of the forming die can be reduced by means of polishing or the like.
  • the roughness Ra of the friction surface of the joint prosthesis is ⁇ 0.1 ⁇ m, preferably (but not limited to) less than 0.1 ⁇ m, some non-limiting examples are ⁇ 0.09 ⁇ m, ⁇ 0.08 ⁇ m, ⁇ 0.07 ⁇ m , ⁇ 0.06 ⁇ m, ⁇ 0.05 ⁇ m and other ranges, also for example 0.09 ⁇ m, 0.08 ⁇ m, 0.07 ⁇ m, 0.06 ⁇ m, 0.05 ⁇ m and other values.
  • the joint prosthesis satisfies any one or any combination of the following features:
  • the roughness Ra of the friction surface of the joint prosthesis is less than or equal to 0.1 ⁇ m (further, Ra can also be selected from any suitable range or value mentioned above);
  • the thickness of the surface cross-linked layer is 0.5 mm to 3 mm (further, the thickness of the surface cross-linked layer can also be selected from any suitable range or value mentioned above).
  • the joint prosthesis satisfies any one or any combination of the following features:
  • the roughness of the friction surface of the joint prosthesis is Ra ⁇ 0.1 ⁇ m; optionally, Ra ⁇ 0.09 ⁇ m; further optionally, Ra ⁇ 0.08 ⁇ m; further optionally, Ra ⁇ 0.07 ⁇ m; further optionally , Ra ⁇ 0.06 ⁇ m; further optionally, Ra ⁇ 0.05 ⁇ m;
  • the thickness of the surface cross-linked layer is selected from the interval consisting of any two thicknesses as follows: 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm , 1.6mm, 1.7mm, 1.8mm, 1.9mm, 2.0mm, 2.1mm, 2.2mm, 2.3mm, 2.4mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm, 2.9mm and 3mm; Optionally, all The thickness of the surface cross-linked layer is 0.5 mm to 3 mm.
  • the joint prosthesis includes a base layer and a surface cross-linked layer adjacent to the base layer, at this time, no intermediate cross-linked layer is included between the base layer and the surface cross-linked layer .
  • the UHMWPE in the surface cross-linked layer is highly cross-linked (see above for the preference and examples of TVI A ), while the UHMWPE in the base layer does not have a cross-linked structure, for example, TVI A is greater than 0.3 and TVI B is 0.
  • an intermediate cross-linking layer is further included between the surface cross-linking layer and the base layer.
  • the preform also includes a preformed middle cross-linked layer at this time.
  • the structural layer of the joint prosthesis can be flexibly designed.
  • the cross-linked UHWMPE can be limited to the surface cross-linked layer (at this time, the middle cross-linked layer is not included, and the UHWMPE in the matrix layer has not been irradiated to cross-link), or the matrix layer of non-cross-linked UHMWPE
  • An intermediate cross-linked layer is set between the highly cross-linked surface cross-linked layer to realize the transition change of UHMWPE cross-linked degree between the matrix layer and the surface cross-linked layer, and improve the cohesion between the surface cross-linked layer and the adjacent structural layer .
  • the middle cross-linked layer may also include multiple structural layers to further realize a good performance transition from the base layer to the surface cross-linked layer. Different multi-layer structure designs can be reasonably selected according to the performance requirements of different joint parts.
  • different molding parameters can be used for different structural layers by means of pre-compression molding, so as to realize performance optimization of different structural layers (including but not limited to optimization).
  • the middle cross-linking layer in this application refers to the structural layer whose overall cross-linking degree of UHMWPE is between the matrix layer and the surface cross-linking layer.
  • the average transvinylene index of the middle crosslinked layer is reported as TVIM .
  • TVI M is larger than TVI B and smaller than TVI A .
  • the TVI M is 0.05-0.3, such as 0.08, 0.1, 0.15, 0.2, 0.25 and so on.
  • the middle cross-linked layer contains UHMWPE and optional excipient components.
  • an intermediate cross-linked layer is also included between the surface cross-linked layer and the base layer, and the intermediate cross-linked layer contains UHMWPE and optional auxiliary material components; the intermediate cross-linked layer
  • the average trans-vinylidene index of is recorded as TVI M , and TVI M satisfies greater than TVI B and less than TVI A .
  • the UHMWPE in the matrix layer, the middle cross-linking layer and the surface cross-linking layer are different in at least the overall cross-linking degree.
  • the difference in the degree of crosslinking among the base layer, the middle crosslinked layer and the surface crosslinked layer may lie in one or more aspects of the density of crosslinking points, the content of crosslinking points, the distribution of crosslinking points, and the like.
  • the difference in the degree of crosslinking lies in the density of crosslinking points.
  • the difference in the degree of crosslinking lies in the content of crosslinking points.
  • the difference in the degree of crosslinking lies in the distribution of crosslinking points.
  • the base layer comprises optional excipient ingredients, ie, may or may not contain excipient ingredients.
  • auxiliary material components in the base layer, the middle cross-linked layer and the surface cross-linked layer are independent, and may be the same or different in type, and may be the same or different in content in the structural layer.
  • the optional auxiliary components in each structural layer are each independently selected from the following components: antibacterial agents, anti-inflammatory agents, inorganic fillers, and antioxidants. Adding antibacterial agents and anti-inflammatory agents can improve the safety and success rate of joint prosthesis implantation, and reduce the occurrence of infection and inflammation.
  • the antibacterial agent that can be used in this application can be selected from the group including but not limited to following material: silver ion antibacterial agent, anilides, quaternary ammonium salts etc., existing medical antibacterial agent all can be used as the optional of this application scope.
  • the anti-inflammatory agents that can be used in this application can be selected from the group including but not limited to the following substances: quinolones, macrolides, etc., and the existing anti-inflammatory agents can be used as the optional scope of this application.
  • quinolones such as carbon fiber, graphene, etc.
  • Adding inorganic fillers, such as carbon fiber, graphene, etc. can improve the mechanical properties of the product, and the existing fillers or additives for improving mechanical properties can be used as the optional scope of this application.
  • the auxiliary material components are independently selected from the following components: antibacterial agents, anti-inflammatory agents, inorganic fillers, antioxidants and the like.
  • the auxiliary material components are independently selected from the following components: antibacterial agents, anti-inflammatory agents and antioxidants.
  • the mass proportion of the auxiliary material components in any structural layer is independently no more than 2%; optionally, the mass proportion of the auxiliary material components in any structural layer is independently 0.1% % ⁇ 2%.
  • the mass proportion of the auxiliary material components in any structural layer can be independently selected from any of the following percentages: 0.1%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% %, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, etc.; can also be selected from any two percentages above interval.
  • the corresponding content should not affect the overall function of the structural layer, and can preferably (but not limited to) improve the overall performance of the structural layer.
  • the base layer avoid causing loss of mechanical properties.
  • the surface cross-linked layer it should be avoided to cause a decrease in wear resistance.
  • the mass proportion of auxiliary material components is no more than 2%.
  • the mass proportion of the auxiliary material components is 0.1%-2%.
  • the mass proportion of auxiliary material components is no more than 2%.
  • the mass proportion of auxiliary material components is 0.1%-2%.
  • the mass proportion of the auxiliary material component does not exceed 2%.
  • the mass proportion of the auxiliary material components is 0.1%-2% independently.
  • Each independently exemplifies, for example, 0.1%, 0.5%, 1%, 1.5%, 2% and the like.
  • the middle cross-linked layer includes N structural layers, where N is an integer greater than or equal to 1.
  • the middle cross-linked layer is one cross-linked layer.
  • N is greater than or equal to 2. At this time, there is at least one difference in the chemical composition, component content, crosslinking degree, preparation sequence, etc. of each structural layer of the intermediate crosslinking layer.
  • N is greater than or equal to 2
  • the crosslinking degree of each structural layer of the middle crosslinking layer increases sequentially from the base layer to the surface crosslinking layer.
  • N is greater than or equal to 2
  • the average trans-vinylidene index of each structural layer is recorded as TVI 1 , TVI 2 , ..., TVI N in the direction from the base layer to the surface crosslinking layer.
  • TVI M is 0.05-0.3, also such as 0.08, 0.1, 0.15, 0.2, 0.25 and so on.
  • they are all larger than TVI B and smaller than TVI A , and in some further preferred examples, they also increase sequentially.
  • the number of times of performing the second pre-press forming is any integer selected from 2 to N, and the optional number of times includes but not limited to 2 times.
  • the powder after each pre-press molding is completed, under the condition that the powder is kept in a molten state independently each time, after loading the powder to be formed into the pre-formed blank, continue Subsequent hot pressing operations are carried out at a preset temperature. Further, when loading the powder to be formed into the preformed blank, the powder may be preheated at 100°C to 120°C.
  • the target implantation position of the joint prosthesis is not particularly limited, as long as there is a possibility of joint damage, the joint prosthesis can be implanted.
  • the joint prosthesis is a hip joint prosthesis, a knee joint prosthesis, an ankle joint prosthesis or a shoulder joint prosthesis.
  • One embodiment of the present application provides a joint prosthesis, which includes at least two functional layers containing UHMWPE, wherein the functional layer constituting the friction surface of the joint prosthesis is a cross-linked layer, and along the direction away from the friction surface, The cross-linking degree of UHMWPE in the functional layer decreases successively, and the cross-linking layer is made of UHMWPE powder processed by radiation cross-linking through molding.
  • the number of cross-linked layers is greater than or equal to 2, and the cross-linked degree of polyethylene in at least two layers of UHMWPE is different, wherein the cross-linked layer with the largest cross-linked degree forms the friction surface of the joint prosthesis, and Along the direction away from the friction surface of the joint prosthesis, the cross-linking degree of UHMWPE in each cross-linked layer decreases successively.
  • the functional layer also includes a matrix layer laminated under the crosslinked layer, the matrix layer is made of UHMWPE powder through pre-compression molding, and when it contains multiple crosslinked layers with different crosslinking degrees of UHMWPE, The least crosslinked layer is in contact with the substrate layer.
  • the joint prosthesis is produced by the preparation method of the second aspect of the present application.
  • a method for preparing a joint prosthesis which can be used to prepare the joint prosthesis described in the first aspect of the present application.
  • the surface cross-linking technology can be developed by the method of pre-pressing to realize the preparation of the surface cross-linking layer, and while maintaining the mechanical properties of the matrix layer, the surface cross-linking layer can be endowed with better wear resistance.
  • the structure design of the surface cross-linking layer in this application can be realized by using the surface cross-linking technology provided in this application.
  • the joint prosthesis includes a surface cross-linked layer and a matrix layer, and the friction surface of the joint prosthesis is located on the outer surface of the surface cross-linked layer.
  • the preparation method includes the following steps S100, S200, S300 and S400:
  • S300 Perform radiation cross-linking treatment on the UHMWPE powder under anaerobic conditions, and control the radiation dose according to the target TVI A of the surface cross-linked layer to obtain the first cross-linked UHMWPE powder;
  • S400 Use the first cross-linked UHMWPE powder as a surface cross-linked layer powder, or mix the first cross-linked UHMWPE powder with the required auxiliary materials in the surface cross-linked layer to obtain a surface cross-linked layer powder; then the surface crosslinking layer powder is loaded on the preformed matrix layer to form a surface crosslinking powder layer, so that the surface crosslinking powder layer covers the friction surface forming surface of the mould, and the Compression molding to prepare the joint prosthesis with the surface cross-linked layer and the base layer.
  • this method conveniently arranges the cross-linked layer formed by cross-linked UHMWPE powder on the surface of the joint prosthesis as the surface cross-linked layer, and at the same time provides the friction surface of the joint prosthesis, which can improve the wear resistance of the friction surface, thereby improving the product quality.
  • this method is also convenient to adjust the proportion of the cross-linked layer in the joint prosthesis, and then it is convenient to adjust the performance of the product according to the strength requirements.
  • UHMWPE with a cross-linked structure can be provided by irradiating and cross-linking the UHMWPE powder.
  • a surface cross-linking technology was developed.
  • the surface cross-linking technology provided by this application controls the cross-linking degree of UHMWPE by directly performing radiation cross-linking treatment on UHMWPE powder (preferable, but not limited to radiation cross-linking treatment), and then performing compression molding.
  • radiation crosslinking as an example, by adjusting the radiation dose according to the preset crosslinking degree, powders with different crosslinking degrees can be obtained, and structural layers with corresponding crosslinking degrees can be prepared.
  • the aforementioned special structural design can be realized by using the aforementioned surface cross-linking technology.
  • the irradiation dose of UHMWPE powder required for the structural layer can be controlled accordingly according to the cross-linking degree of different structural layers, and UHMWPE structural layers with different cross-linking degrees can be obtained after molding.
  • the UHMWPE powder of the base layer can not be cross-linked, or only a small amount of powder can be irradiated, or only slightly irradiated, so that the mechanical properties of the base layer can be maintained to a greater extent. performance.
  • a large dose of radiation treatment can be used according to the need for wear resistance, so as to greatly improve the wear resistance of the raw material.
  • the radiation cross-linking treatment generally includes the following steps: performing radiation treatment and annealing under oxygen-free conditions.
  • the irradiation treatment in this application is in principle carried out under anaerobic conditions. For example, it can be performed under the protection of an inert gas, such as argon or nitrogen.
  • an inert gas such as argon or nitrogen.
  • it can be carried out under vacuum conditions. It can preferably be carried out under vacuum conditions.
  • High-energy rays are used for irradiation crosslinking.
  • the high-energy rays used herein are electron beams or gamma rays, and electron beam irradiation is preferred.
  • the irradiation dose When performing irradiation treatment, it is usually necessary to control the irradiation dose to control the number of free radicals generated, control the degree of crosslinking of UHMWPE, and then control the degree of crosslinking in the structural layer of the product obtained after molding treatment.
  • the size of the irradiation dose determines the degree of cross-linking of polyethylene powder.
  • the ultra-high molecular weight polyethylene powder is annealed. The purpose of annealing is to make the interchain cross-linking reaction occur freely and eliminate the residual free radicals.
  • the annealing temperature is usually 140°C and below (for example, the annealing temperature is 120°C to 140°C, the annealing time is 4h to 10h, preferably but not limited to 6h).
  • Vacuum annealing may be preferred but not limited to.
  • the ultra-high molecular weight polyethylene powder is vacuum-sealed in an aluminum foil bag to prevent the powder and Oxygen exposure occurs oxidation reaction, and then irradiated and annealed.
  • the molecular weight of the UHMWPE contained in each step is independently 3 ⁇ 10 6 Da ⁇ 5 ⁇ 10 6 Da. For example, 3 million Daltons, 3.5 million Daltons, 4 million Daltons, 4.5 million Daltons, 5 million Daltons, etc.
  • the molecular weight of UHMWPE powder used in different structural layers can be the same or different.
  • the average particle size of the powder in each step is independently 100 ⁇ m to 200 ⁇ m.
  • Smaller particle size is more conducive to improving the compactness of compression molded products.
  • the base layer can be prepared from UHMWPE powder without adding auxiliary materials. At this time, UHMWPE powder is used as the base layer powder.
  • the base layer can also be mixed with UHMWPE powder and the required auxiliary materials in the base layer to obtain the base layer powder.
  • the ultra-high molecular weight polyethylene powder used in the base layer powder has a molecular weight of 3 to 5 million Daltons, such as 3 million Daltons, 3.5 million Daltons, 4 million Daltons, 4.5 million Daltons, 5 million Daltons, etc.
  • the particle size of the UHMWPE powder used for the base layer powder is 100 ⁇ m ⁇ 200 ⁇ m. For example above.
  • the UHMWPE powder used for the matrix layer powder can be completely unirradiated and cross-linked. At this time, it can be considered that UHMWPE does not have a cross-linked structure, and theoretically, the TVI of the prepared base layer is 0, and understandably, theoretically, TVI B is also 0. At this time, the matrix layer can retain the mechanical properties of the UHMWPE matrix to the greatest extent, including but not limited to strength, toughness, fatigue resistance and the like.
  • the UHMWPE powder used in the base layer powder can also be processed by radiation crosslinking, but it can be preferably low crosslinked, less crosslinked or partially crosslinked, so that, on the whole, the degree of crosslinking of UHMWPE in the base layer is lower than Surface cross-linked layer. Low or less crosslinking can be achieved by reducing the radiation dose. Partial cross-linking can be achieved by mixing UHMWPE powder without radiation cross-linking treatment with UHMWPE powder after radiation cross-linking treatment.
  • the irradiation ratio and/or radiation dose of the UHMWPE powder is controlled according to the target TVI B of the base layer.
  • irradiation doses are less than 30GKy, some non-limiting examples are 10GKy, 15GKy, 20GKy, 25GKy, etc.
  • pre-press molding refers to more than one hot press molding during the preparation of the joint prosthesis.
  • the last thermoforming is used to form the target surface cross-linked layer.
  • one or more pre-compression moldings can be carried out to obtain preformed blanks.
  • the preformed blank does not include a surface crosslinked layer and may include a matrix layer and an optional intermediate crosslinked layer.
  • An intermediate cross-linked layer is set between the base layer of non-cross-linked UHMWPE and the highly cross-linked surface cross-linked layer, which can realize the transition change of the cross-linked degree of UHMWPE between the base layer and the surface cross-linked layer, and improve the surface cross-linked layer and the surface cross-linked layer. Cohesion between adjacent structural layers.
  • the middle cross-linked layer may also include multiple structural layers. Further achieve a good performance transition from the base layer to the surface cross-linked layer. Different multi-layer structure designs can be reasonably selected according to the performance requirements of different joint parts.
  • a step S220 of preparing an intermediate cross-linked layer is further included.
  • the middle cross-linked layer is located between the base layer and the surface cross-linked layer, and the cross-linking degree of the middle cross-linked layer is between the base layer and the surface cross-linked layer.
  • the average trans-vinylidene index TVI M of the middle cross-linked layer is greater than TVI B and less than TVI A .
  • the number of structural layers of the middle cross-linked layer is one.
  • the number of structural layers of the middle cross-linked layer is greater than 1, such as 2, 3, 4, 5, 6, etc.
  • the average trans vinylidene index of each structural layer is greater than TVI B and less than TVI A.
  • the average trans vinylidene index of each structural layer in the middle cross-linked layer The vinylidene index increases sequentially from the base layer to the surface cross-linked layer.
  • the powder after each pre-press molding is completed, under the condition that the powder is kept in a molten state independently each time, after loading the powder to be formed into the pre-formed blank, continue Subsequent hot pressing operations are carried out at a preset temperature. Further, when loading the powder to be formed into the preformed blank, the powder is preheated at 100° C. to 120° C. first.
  • a preformed base layer can be obtained after the base layer powder is pre-pressed and formed.
  • a preformed blank including the intermediate cross-linking layer can be prepared by pre-press molding.
  • the number of prepress molding is not particularly limited, and may be one or more times.
  • the corresponding powder materials of each structural layer can be laid according to the preset position, and only one pre-compression molding is performed. It is also possible to carry out an independent pre-press forming for different structures. Some adjacent multiple (two or more) structures can also be layered and pre-pressed once, and some structures can be pre-pressed independently.
  • the number of structural layers of the intermediate cross-linked layer is N (N is an integer greater than 1), and the number of times of pre-pressing can be any integer from 1 to N+1.
  • the base layer and the middle cross-linked layer are independently pre-pressed, and the pre-press of the base layer is recorded as the first pre-press, and the pre-press of the middle cross-linked layer is recorded as For the second pre-press molding.
  • the number of times of the first pre-press forming can be one or more times, that is, the base layer can undergo one or more pre-press forming, especially when some special functional layers (such as reinforcing layers) need to be arranged in the base layer , can be achieved in this way.
  • the number of times of the second pre-press forming can be 0 or 1.
  • the number of times of performing the second pre-press forming is selected from any integer from 1 to N, and further may be any integer from 2 to N.
  • the intermediate cross-linked layer includes N structural layers, where N is an integer greater than or equal to 1;
  • the number of times for the second pre-press forming is selected from any integer from 2 to N, the direction from the base layer to the surface cross-linked layer, the average trans of each structural layer
  • the vinylidene index is greater than TVI B and less than TVI A , and increases successively.
  • the pre-pressing temperature during pre-press molding is lower than the molding temperature for forming the surface cross-linked layer.
  • the pre-compression molding is carried out at a relatively low hot-pressing temperature to effectively avoid the reduction of mechanical properties caused by high temperature.
  • the temperature for pre-press forming is, for example, 150°C to 200°C, some non-limiting examples are 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200° C., etc., can also be selected from the interval formed by any two of the above-mentioned temperatures.
  • a non-limiting example of the time for one pre-compression molding can be 20 minutes to 60 minutes, and some non-limiting examples are 20 minutes, 30 minutes, 40 minutes, 50 minutes, and 60 minutes.
  • the pre-compression temperature is 150° C. to 200° C.
  • the pre-compression time is 20 minutes to 60 minutes.
  • the foregoing pre-compression temperature and pre-compression time may be selected independently or in combination with each other from other descriptions herein.
  • the temperature adjustment rate is 5°C/min ⁇ 10°C/min, some non-limiting examples such as 5°C/min, 6°C/min, 7°C/min, 8°C/min, 10°C/min °C/min etc.
  • the pre-compression temperature, pre-compression time and temperature adjustment rate can be independently or in combination with each other from other descriptions herein suitable choice.
  • the "temperature adjustment rate” refers to the temperature increase rate or the temperature decrease rate unless otherwise specified. Therefore, the “temperature adjustment rate” can also be recorded as the “temperature increase and decrease rate”. In some embodiments, the temperature adjustment rate (ie, the heating and cooling rate) refers to the heating rate.
  • step S220 is used to prepare a preformed blank including an intermediate cross-linked layer.
  • Step S220 Perform irradiation crosslinking treatment on the UHMWPE powder under anaerobic conditions, control the irradiation dose according to the target TVI M of the middle crosslinking layer, and obtain the second crosslinked UHMWPE powder; use the second crosslinked UHMWPE powder material and optional auxiliary materials to obtain the intermediate cross-linking layer powder; the intermediate cross-linking layer powder is loaded on the preformed base layer, and the second pre-compression molding is performed, and the pre-compression temperature is 150 ° C ⁇ 200 ° C , The pre-pressing time is 20min ⁇ 60min.
  • step S300 includes: performing radiation cross-linking treatment on the UHMWPE powder under anaerobic conditions, controlling the radiation dose according to the target TVI A of the surface cross-linked layer, and obtaining the first cross-linked United UHMWPE powder.
  • the molecular weight of the UHMWPE powder used is 3 to 5 million Daltons, such as 3 million Daltons, 3.5 million Daltons, 4 million Daltons, 4.5 million Daltons, and 5 million Daltons. Dalton et al.
  • the particle size of the UHMWPE powder used is 100 ⁇ m-200 ⁇ m.
  • the irradiation cross-linking treatment (including irradiation and annealing) in this application can be preferably carried out under anaerobic conditions, and further can be preferably carried out under vacuum conditions.
  • the UHMWPE powder in step S300, is vacuum-packaged in an aluminum foil bag, and is irradiated and cross-linked by high-energy rays.
  • Putting the UHMWPE powder in a vacuum environment for irradiation treatment can avoid the oxidation reaction of the powder in contact with oxygen, and it is packaged in an aluminum foil bag, which is easy to operate, low in cost, and has a better irradiation treatment effect.
  • step S300 high-energy rays are used for irradiation; further, ultraviolet light irradiation, electron beam irradiation or gamma ray irradiation is used; further, electron beams are used for irradiation to obtain more Excellent irradiation effect.
  • electron beams for irradiation treatment compared with ultraviolet irradiation, there is no need to add additional initiators and organic solvents, which can effectively avoid the harm of chemical residues to the human body.
  • the high-energy rays used for irradiation crosslinking treatment are electron beams or gamma rays.
  • the dose of radiation crosslinking the UHMWPE powder in step S300 should be able to provide enough free radicals to achieve a sufficient degree of crosslinking in the surface crosslinking layer formed by compression molding.
  • the irradiation dose is 30 kGy-100 kGy. Further, it may be 40kGy-100kGy, and further, the irradiation dose is 40kGy-80kGy. For example, 30KGy, 35KGy, 40KGy, 50KGy, 55KGy, 60KGy, 65KGy, 70KGy, 75KGy, 80KGy, 85KGy, 90KGy, 95KGy, 100KGy, etc. In some preferred embodiments, the irradiation dose is 45 kGy or 75 kGy.
  • the control of the cross-linking degree of the cross-linked UHMWPE powder can be realized by controlling the radiation dose, so that the performance of the product can be adjusted according to the needs.
  • the annealing temperature after irradiation may be 100°C-140°C; further, the annealing temperature may be 110°C-130°C; further, the annealing temperature may be 115°C ⁇ 125°C.
  • the annealing temperature after irradiation can be, for example, any temperature such as 100° C., 110° C., 120° C., 130° C., 140° C., and can also be selected from the interval formed by any two of the above-mentioned temperatures. In some preferred embodiments, the annealing temperature may be 120° C., which can better eliminate residual free radicals.
  • the annealing time after irradiation can be 4h-10h; further, the annealing time can be 5h-9h. For example, 4h, 5h, 6h, 7h, 8h, 9h, 10h etc.
  • the annealing temperature may be 120° C.
  • the annealing time may be 4 hours to 10 hours, and further may be 6 hours.
  • step S300 includes: irradiating and annealing the UHMWPE powder under vacuum conditions to obtain the first cross-linked UHMWPE powder; wherein, the irradiation dose can be 30 kGy-100 kGy , the annealing temperature may be 100°C-140°C, and the annealing time may be 4h-10h.
  • the preference and examples of each parameter can refer to the description above and below.
  • the high-energy rays used are electron beams or gamma rays, and electron beam irradiation can be preferred; further, the irradiation dose can be 30kGy-100kGy, for example, 30kGy, 40kGy, 45kGy, 50kGy, 60kGy , 65kGy, 70kGy, 75kGy, 80kGy, 85kGy, 90kGy, 95kGy, 100kGy, etc., can also be selected from the interval formed by any two radiation doses mentioned above; It may be 4h to 10h (it may be preferred but not limited to 6h).
  • the surface cross-linked layer is formed by the last hot pressing, and the obtained surface cross-linked layer is made of highly cross-linked UHMWPE powder, and is used to provide the friction surface of the joint prosthesis. Therefore, the surface cross-linked layer
  • a forming die with a frictional forming surface is installed for molding processing. During the molding process, force is directly applied to the surface cross-linked layer powder. After the molding is completed, you can get Surface cross-linked layer with friction surface of joint prosthesis. By reducing the roughness of the molding surface of the friction surface (for example, after polishing treatment), the friction surface of the joint prosthesis with low roughness can be obtained, and the wear resistance of the joint prosthesis can be further improved.
  • the surface crosslinked layer forms the friction surface of the joint prosthesis.
  • step S400 includes: using the first cross-linked UHMWPE powder as the surface cross-linked layer powder, or mixing the first cross-linked UHMWPE powder with the required auxiliary materials in the surface cross-linked layer, Obtain the surface cross-linking layer powder; then put the surface cross-linking layer powder on the preformed base layer to form a surface cross-linking powder layer, make the surface cross-linking powder layer cover the friction surface molding surface of the mold, and carry out molding Molded to prepare a joint prosthesis with a surface cross-linked layer and a matrix layer.
  • the temperature needs to be controlled within a certain temperature range, so as to ensure the mechanical properties of the joint prosthesis and improve its wear resistance.
  • the inventors have found through research that the molding temperature has a certain influence on the performance of the joint prosthesis. If the temperature is too low, the roughness of the friction surface will increase, and if the temperature is too high, the mechanical properties will decrease.
  • the molding temperature may preferably be 210°C to 260°C. Without limitation, such as 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C, 260°C, etc.
  • the rate of temperature rise and fall (that is, the rate of temperature adjustment, which can be the rate of temperature increase) can be 5°C/min to 10°C/min, for example, 5°C/min, 6°C/min, 7°C/min, 8°C/min, 9°C/min, 10°C/min, etc.
  • the compression molding pressure may be 20MPa-40MPa, such as 20MPa, 22MPa, 25MPa, 28MPa, 30MPa, 35MPa, 40MPa, etc.
  • the compression molding time may be 0.5h-1h, such as 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h and so on.
  • the molding temperature is 210°C-260°C
  • the molding pressure is 20MPa-40MPa
  • the molding time can be 0.5h-1h.
  • the molding temperature is 210°C-260°C
  • the molding pressure is 20MPa-40MPa
  • the molding time is 0.5h-1h; further, the heating and cooling rate ( That is, the temperature adjustment rate (which may be the temperature rise rate) may be 5° C./min ⁇ 10° C./min.
  • the thickness of the powder of the surface crosslinking layer (that is, the thickness of the material, also referred to as the thickness of the surface crosslinking powder layer) is mainly determined according to the preset thickness of the surface crosslinking layer.
  • the feeding thickness of the surface crosslinking layer powder determines the thickness of the surface crosslinking layer in the obtained joint prosthesis product.
  • the non-limiting example of the thickness of the feed is 0.5mm-6mm, and 1mm-6mm, further examples are 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm, 6mm, etc., the surface
  • the thickness of the cross-linked powder layer can also be selected from the interval formed by any two thicknesses mentioned above, such as 0.5mm-3mm.
  • the roughness Ra of the molding surface of the friction surface of the mold is less than or equal to 0.1 ⁇ m, preferably less than 0.1 ⁇ m.
  • examples include ranges such as Ra ⁇ 0.09 ⁇ m, Ra ⁇ 0.08 ⁇ m, Ra ⁇ 0.07 ⁇ m, Ra ⁇ 0.06 ⁇ m, Ra ⁇ 0.05 ⁇ m, and other values such as 0.09 ⁇ m, 0.08 ⁇ m, 0.07 ⁇ m, 0.06 ⁇ m, and 0.05 ⁇ m.
  • the preformed blank undergoes the following changes: melting first, and then merging with the surface cross-linking layer.
  • the powder is kept in a melt state, and after the powder to be formed is loaded into the pre-formed blank, continue Subsequent hot pressing operations are carried out at a preset temperature.
  • the powder is first preheated (such as 100°C to 120°C) to prevent the cold material from contacting the hot preformed blank. , leading to local cooling and crystallization of the preform, avoiding adverse effects on the bonding strength between different structural layers.
  • the inventors of the present application speculate that the pre-compression molding process in this application may lead to changes in the interface structure of the joint prosthesis, thereby affecting the overall mechanical properties of the joint prosthesis; While the cross-linked layer improves the wear resistance of the surface, it also enables the formation of a uniform and stable interface layer between the surface cross-linked layer and the adjacent structural layer (such as the matrix layer or the middle cross-linked layer), thus giving the joint prosthesis an overall Better mechanical properties.
  • the pre-pressing temperature is 150°C to 200°C
  • the pre-pressing time can be 20min to 60min
  • the temperature is 210°C-260°C
  • the molding pressure is 20MPa-40MPa
  • the molding time is 0.5h-1h.
  • the heating and cooling rate ie temperature adjustment rate
  • a multi-layer cross-linked layer (including a surface cross-linked layer and an intermediate cross-linked layer) is prepared, wherein the cross-linked layer with the highest degree of cross-linking forms the friction surface of the joint prosthesis, and Along the direction away from the friction surface, the cross-linking degree of the multi-layer cross-linked layer decreases successively.
  • the wear resistance of the friction surface can be effectively improved, and the friction and wear resistance of the friction surface can be improved; while the cross-linked layer far away from the friction surface adopts a lower cross-linking degree
  • the cross-linked UHMWPE powder can effectively avoid the loss of mechanical properties and improve the comprehensive performance of joint prosthesis.
  • the crosslinking degree gradient of UHMWPE in the multi-layer crosslinking layer decreases gradually.
  • the multi-layer cross-linked layers are respectively the first cross-linked layer, the second cross-linked layer...the Mth cross-linked layer, forming the corresponding cross-linked layer
  • the cross-linked UHMWPE powder is the first cross-linked UHMWPE powder, the second cross-linked UHMWPE powder...the Mth cross-linked UHMWPE powder; M is an integer greater than or equal to 2; wherein, the M-1st cross-linked The degree of crosslinking of the UHMWPE powder is less than the Mth crosslinked UHMWPE powder; the preparation method comprises the following steps:
  • S202B adding a second cross-linked UHMWPE powder on the first cross-linked layer, and performing pre-press molding to obtain a second cross-linked layer;
  • S203B Repeatedly adding the M-1 cross-linked UHMWPE powder on the M-2 cross-linked layer in sequence, and performing pre-press molding to obtain the M-1 cross-linked layer;
  • S204B Add the M-th cross-linked UHMWPE powder on the M-1 cross-linked layer, and carry out compression molding to obtain the M-th cross-linked layer; wherein, the M-th cross-linked layer with the largest degree of cross-linking forms the friction surface of the joint prosthesis .
  • step S201B-step S204B a joint prosthesis whose degree of cross-linking increases sequentially from the first cross-linked layer to the Mth cross-linked layer is formed.
  • the joint prosthesis has multiple layers, and the pre-compression molding method is used to prepare the remaining layers except the last layer, and the last layer (such as the Mth cross-linked layer in step S201B to step S204B) is prepared using Method of compression molding.
  • the molding conditions for preparing the last layer of the joint prosthesis are: molding temperature 210°C-260°C, heating and cooling rate 5°C/min-10°C/min, molding pressure 20MPa-40MPa, molding time 0.5h- 1h; the compression molding (ie pre-compression molding) conditions of the remaining layers are: molding temperature 150°C-200°C, time 20min-60min.
  • the last layer of the joint prosthesis can be the cross-linked layer, or the matrix layer in the subsequent steps, which is determined according to the actual situation of the product, and is not specifically limited here, and it should be understood that all of them are included in this application. within the scope of protection.
  • lower temperature compression molding ie pre-compression molding
  • the above compression molding conditions for the last layer the reduction in mechanical properties caused by high temperature can be effectively avoided.
  • the molding temperature of the last layer of the joint prosthesis is 210°C-260°C; further, the molding temperature is 220°C-250°C; further, the molding temperature is 235°C-245°C; Further, the molding temperature is 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C or 255°C.
  • the molding temperature has a certain influence on the performance of joint prosthesis.
  • the temperature is too low, it will easily lead to the increase of the roughness of the friction surface, and if it is too high, it will easily lead to the decrease of mechanical properties. It is preferable to control the molding temperature within the above range In order to ensure the mechanical properties of the joint prosthesis and improve its wear resistance.
  • the heating and cooling rate of the last layer of the joint prosthesis is 5°C/min, 6°C/min, 7°C/min, 8°C/min, 9°C/min or 10°C/min.
  • the molding pressure for preparing the last layer of the joint prosthesis is 25MPa-35MPa; further, the molding pressure is 20MPa, 25MPa, 26MPa, 28MPa, 30MPa, 32MPa or 35MPa.
  • the molding conditions of the remaining layers are: molding temperature 160°C-190°C; further, molding temperature 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C or 195°C .
  • a compression mold is used for compression molding; further, the roughness of the surface of the compression mold that is in contact with the powder to be molded is Ra ⁇ 0.1 ⁇ m; in some embodiments, the compression molding The roughness of the surface of the indenter used for molding of the mold is Ra ⁇ 0.1 ⁇ m.
  • the roughness of the joint prosthesis can be effectively reduced and the friction and wear can be reduced by adopting the molding die with the surface roughness of the indenter Ra ⁇ 0.1 ⁇ m for compression molding.
  • the joint prosthesis of the present application is prepared using a molding mold as shown in Figure 1 and Figure 2, and the molding mold includes a first forming mold 110 (or 210), a sleeve 120 (or 220) and a third forming mold Die 130 (or 230), the sleeve is hollow tubular, the first molding die can cooperate with the second molding die to form a cavity for placing the powder to be molded, and the third molding die includes a pressure head for molding. The head can cooperate with the cavity to form a molding cavity corresponding to the shape of the joint prosthesis; wherein, the roughness of the surface of the pressure head is Ra ⁇ 0.1 ⁇ m.
  • the third molding die can pass through the hollow inner cavity of the sleeve under the action of external force.
  • a cavity is formed by combining the first molding die and the sleeve, and the powder to be molded (such as cross-linked UHMWPE powder or ultra-high molecular weight polyethylene powder) is added to the cavity, and the pressure of the third molding die Under the action of a certain temperature and pressure, molding is carried out, and then the third molding mold, the formed joint prosthesis and the first molding mold are pressed out from the hollow inner cavity of the sleeve by using a hot press, etc. Form the joint prosthesis in the desired shape.
  • the powder to be molded such as cross-linked UHMWPE powder or ultra-high molecular weight polyethylene powder
  • the shape of the molded cavity formed by the cooperation of the indenter and the cavity is not particularly limited, and can be determined according to the shape of the prepared joint prosthesis. There is no special limitation here, and it should be understood that all are within the scope of protection of this application. .
  • the first molding die includes a concave portion, and the concave portion of the first molding die and the hollow inner cavity of the sleeve can jointly form a cavity for placing the powder to be molded; in some embodiments, the concave portion is used for The roughness of the inner surface forming the molding cavity is Ra ⁇ 0.1 ⁇ m.
  • the compression mold further includes a fourth molding die 140 (or 240 ), which is used for pre-compression molding; further, the fourth molding die is stepped to facilitate the operation of pre-compression molding.
  • a cross-linked layer is formed on the base layer.
  • the cross-linked layer by disposing the cross-linked layer on the base layer formed by uncross-linked ultra-high molecular weight polyethylene powder, damage to the mechanical properties of the joint prosthesis can be effectively avoided, and the joint prosthesis can be improved.
  • the toughness of the body can effectively improve the service life of the joint prosthesis.
  • the method of the present application can realize the regulation and control of related performances of the joint prosthesis by adjusting the thicknesses of the cross-linked layer and the base layer, and is easy to operate and has a higher application space.
  • the UHMWPE powders subjected to radiation crosslinking treatment in steps S100, S300, and S220 can be the same or different, and are not specifically limited here, and should be understood as being within the protection scope of the present application .
  • a post-processing step may also be included before the step of demoulding, for example, using machining on the joint prosthesis to eliminate the margin.
  • the preparation method satisfies any one or any suitable combination of the following features:
  • the pre-compression temperature is 150°C-200°C, optionally, the pre-compression time is 20min-60min; optionally, the temperature adjustment rate is 5°C/min- 10°C/min;
  • Step S300 includes: irradiating and annealing the UHMWPE powder under vacuum conditions to obtain the first cross-linked UHMWPE powder; wherein, the irradiation dose is 30kGy-100kGy, the annealing temperature is 100°C-140°C, Optionally, the annealing time is 4h-10h;
  • step S300 the high-energy rays used for irradiation crosslinking treatment are electron beams or gamma rays;
  • the thickness of the surface cross-linked powder layer is 1 mm to 6 mm; optionally, the thickness of the surface cross-linked powder layer is selected from the following interval consisting of any two thicknesses: 1 mm, 1.5 mm , 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm and 5.5mm;
  • the roughness of the molding surface of the friction surface of the mold is Ra ⁇ 0.1 ⁇ m; optionally, Ra ⁇ 0.09 ⁇ m; further optionally, Ra ⁇ 0.08 ⁇ m; further optionally, Ra ⁇ 0.07 ⁇ m ; Further optionally, Ra ⁇ 0.06 ⁇ m; Further optionally, Ra ⁇ 0.05 ⁇ m;
  • step S400 of performing the compression molding the molding temperature is 210°C-260°C, the molding pressure is 20MPa-40MPa, and the molding time is 0.5h-1h; optionally, the temperature adjustment rate is 5°C/min-10°C /min.
  • the joint prosthesis prepared by the preparation method described in the second aspect of the present application is selected from the joint prosthesis described in the first aspect of the present application.
  • Another embodiment of the present application provides a joint prosthesis prepared by the above preparation method.
  • the joint prosthesis not only has excellent friction and wear resistance, but also has excellent mechanical properties, good toughness, and excellent fatigue resistance. In artificial joint replacement applications, the service life can be effectively extended.
  • the joint prosthesis is a hip prosthesis, a knee prosthesis, an ankle prosthesis, or a shoulder prosthesis.
  • a molding die assembly for preparing the joint prosthesis described in the first aspect of the present application, or for implementing the preparation method described in the second aspect of the present application.
  • the molding die assembly includes a first molding die, a sleeve, a third molding die, and a fourth molding die; wherein, the sleeve is hollow tubular, and the first molding die, The outer peripheral contours of the third molding die and the fourth molding die are respectively matched with the inner cavity contour of the sleeve;
  • the third forming mold is used to form the friction surface of the joint prosthesis, and the roughness of the friction surface forming surface in the third forming mold is Ra ⁇ 0.1 ⁇ m;
  • the first molding die is used to form the surface of the joint prosthesis opposite to the friction surface of the joint prosthesis;
  • the third molding die cooperates with the first molding die to provide a cavity for the compression molding
  • the fourth molding die is used to form a preform, and the preform does not include the surface crosslinking layer;
  • the fourth molding die cooperates with the first molding die to provide a cavity for pre-press molding to prepare the pre-form blank.
  • the fourth forming mold used in this application is designed according to the structural characteristics of the joint prosthesis, has a stepped structure, and is used for pre-compression molding.
  • the designed step is for easy demoulding.
  • the roughness of the molding surface of the friction surface in the mold By controlling the roughness of the molding surface of the friction surface in the mold (such as reducing the roughness by polishing), the roughness of the friction surface of the joint prosthesis can be greatly reduced, thereby further improving the wear resistance of the joint prosthesis.
  • Preferred and examples of the roughness of the friction surface and the molding surface of the mold include but are not limited to the above.
  • the first molding die is used as a lower die
  • the third molding die is used as a molding upper die for preparing a surface cross-linked layer
  • the fourth molding die is used as a pre-pressing upper die (also referred to as a pre-pressing upper die). mold).
  • the acetabular cup joint prosthesis is prepared by using the molding die shown in FIG.
  • the sleeve is used for fixing the radial relative positions of the lower die, the upper die for molding and the upper die for pre-pressing, so as to form a cavity with a certain shape according to the specificity of the joint prosthesis.
  • the inner cavity contour of the sleeve 120 matches the outer peripheral contours of the first forming die 110 , the third forming die 130 , and the fourth forming die 140 (non-stepped parts).
  • the stepped structure of the fourth molding die 140 is for easy demoulding.
  • the indenter 131 of the third molding die is used to form the friction surface of the joint prosthesis.
  • FIG. 3 A schematic diagram of an acetabular cup joint prosthesis prepared by using the molding die assembly shown in FIG. 1 according to an embodiment of the present application is shown in FIG. 3 .
  • the knee joint prosthesis is prepared by using the molding die shown in FIG.
  • the fourth molding die 240 of the die the sleeve is used to fix the radial relative positions of the mold lower mold, the molding upper mold and the pre-pressing upper mold, so as to form a mold cavity with a certain shape according to the specific shape of the joint prosthesis.
  • the inner cavity contour of the sleeve 220 matches the outer peripheral contours of the first forming die 210 , the third forming die 230 and the fourth forming die 240 (non-stepped parts).
  • the step of the fourth molding die 240 is for easy demoulding.
  • the indenter of the third molding die 230 is used to form the friction surface of the joint prosthesis.
  • the indenter of the third molding die 230 is ground and polished, and the surface roughness Ra ⁇ 0.1 ⁇ m.
  • the matching gap between the first molding die (the lower die) and the sleeve is 0.02mm-0.05mm, so as to avoid overflow during the molding process.
  • the matching gap between the third molding die (upper molding die) and the sleeve is 0.02 mm to 0.05 mm to prevent overflow during molding.
  • the matching gap between the step structure of the fourth molding die (pre-pressing upper die) and the sleeve is 0.08mm-0.10mm, which is convenient for demolding after pre-pressing molding.
  • a method comprising the following steps is used to prepare an artificial hip joint liner or a knee joint liner:
  • the UHMWPE powder is vacuum-packed in an aluminum foil bag, irradiated and cross-linked by high-energy rays; after the irradiation, it is annealed.
  • the high-energy rays used are electron beams or gamma rays, and electron beam irradiation can be preferred; the irradiation dose is 30kGy-100kGy, such as 45kGy, 75kGy, etc.; the annealing temperature is 120°C, and the annealing time is 4h-10h, which can be Preferably but not limited to 6h.
  • the mold for pre-compression molding includes three modules of mold lower mold 110, sleeve 120, and pre-compression upper mold 140 (or three modules of mold lower mold 210, sleeve 220, and pre-compression upper mold 240);
  • the matching gap between the lower mold 110 and the sleeve 120 (or between the lower mold 210 and the sleeve 220) is 0.02mm to 0.05mm to avoid overflow during the molding process;
  • pre-press the upper mold 140 (or pre-press The upper mold 240) is designed according to the structural characteristics of the joint prosthesis, has a stepped structure, and has a matching gap with the sleeve 120 (or sleeve 220) of 0.08mm-0.1mm, which is convenient for demoulding after pre-pressing.
  • the temperature of the pre-compression molding used is 150° C. to 200° C., and the pre-compression time is 20 minutes to 60 minutes; after the pre-compression molding, the pre-compression upper mold 140 (or the pre-compression upper mold 240 ) is taken out.
  • the cavity volume between the upper mold and the lower mold determines the shape of the joint prosthesis blank, and the fit gap between the upper mold and the sleeve is 0.02mm to 0.05mm to prevent overflow during the molding process. material;
  • the molding temperature is 210°C-260°C
  • the heating and cooling rate is 5°C/min-10°C/min
  • the molding pressure is 20MPa-40MPa
  • the molding time is 0.5h-1h.
  • an artificial joint friction pair including a first support body and a second support body, the first support body is the joint prosthesis described in the first aspect of the application, and the second support body
  • the support body is a hard joint component, and the friction surface of the joint prosthesis and the friction surface of the second support body cooperate with each other.
  • the hard joint component can use the hard end material in the existing "soft-hard” combination friction pair.
  • Said "soft” and “hard” are relative terms.
  • the material of the soft end can be preferably but not limited to UHMWPE, PEEK and the like.
  • An example of the material of the hard end is hard metal, and further, metal materials such as cobalt-chromium-molybdenum alloy. Hard materials such as ceramics can also be used.
  • the invention provides a joint prosthesis with a surface cross-linked layer, a preparation method thereof, a molding die assembly, and a friction pair.
  • the joint prosthesis includes a surface cross-linked layer and a matrix layer, the friction surface of the joint prosthesis is located on the outer surface of the surface cross-linked layer, the UHMWPE in the surface cross-linked layer has a high degree of cross-linking (the degree of cross-linking is higher than that of the base layer), and The overall crosslinking degree of UHMWPE in the base layer is low or there is no crosslinking UHMWPE.
  • the joint prosthesis can be prepared through the following steps: firstly perform pre-compression molding in a low temperature mode to prepare a preformed base layer, then add highly cross-linked UHMWPE powder, and perform compression molding in a high-temperature mode to form a surface cross-linked layer.
  • the measurement parameters related to raw material components may have slight deviations within the weighing accuracy range unless otherwise specified. Involves temperature and time parameters, allowing for acceptable deviations due to instrumental test accuracy or operational accuracy.
  • the molded acetabular socket was tested by using the Form Talysurf roughness tester of the British Taylor company's inductive roughness profiler. The roughness of the friction surface of the cup lining product is measured.
  • the ultra-high molecular weight polyethylene products are cross-linked by electron beam irradiation, refer to the YY/T0814-2010 method, and detect the trans-vinylidene index (TVI) inside the ultra-high molecular weight polyethylene by infrared spectroscopy, which is 965cm -1
  • the ratio of the absorption peak area to the total absorption peak area between 1330cm -1 and 1396cm -1 is used to determine the level of electron beam irradiation dose absorbed by ultra-high molecular weight polyethylene products, which in turn reflects the crosslinking degree of crosslinked HMWPE powder.
  • the molecular weight of the ultra-high molecular weight polyethylene powder without irradiation crosslinking treatment is 3 to 5 million Daltons, and further, the average molecular weight is 3.5 million Daltons.
  • Embodiment 1 Cross-linked UHMWPE prepares joint prosthesis (acetabular cup liner, different molding temperatures)
  • the ultra-high molecular weight polyethylene powder is vacuum-packed in an aluminum foil bag, and electron beams are used to irradiate to obtain a cross-linked UHMWPE powder.
  • the annealing temperature after irradiation was 120°C for 9 hours.
  • the temperature during molding was set to 190°C and 250°C respectively, and other conditions were kept the same: the heating and cooling rate was 10°C/min, the molding pressure was 40MPa, and the holding time was 45min.
  • the acetabular cup joint prosthesis was obtained (i.e. acetabular cup lining products).
  • the roughness test results show that, at a molding temperature of 250°C, the friction surface roughness Ra of the acetabular cup liner product is 0.08 micron, which is consistent with the surface roughness Ra of the indenter 131 of the third molding die being 0.1 micron, indicating that The surface roughness of the pressing head for molding the third molding die 130 determines the roughness of the friction surface of the acetabular cup liner product.
  • the roughness Ra of the friction surface of the acetabular cup lining product is 0.23 microns. Increase. It shows that the molding temperature will affect the performance of the joint prosthesis, and the preferred molding temperature is 210°C-260°C.
  • the ultra-high molecular weight polyethylene powder is vacuum-packed in an aluminum foil bag, and electron beams are used to irradiate to obtain a cross-linked UHMWPE powder.
  • the annealing temperature after irradiation was 120°C for 4 hours.
  • the molding molds used to prepare the acetabular cup joint prosthesis are the first molding mold 110, the sleeve 120 and the third molding mold 130 shown in Figure 1.
  • the molding temperature is 250° C.
  • the heating and cooling rate is 10° C./min
  • the molding pressure is 40 MPa
  • the molding time is 30 minutes.
  • Acetabular cup lining products and knee joint liner products are obtained after compression molding.
  • the roughness test results show that the friction surface roughness Ra of the acetabular cup lining product is 0.05-0.10 microns, which is basically the same as the surface roughness Ra of the indenter is 0.1 micron, indicating that the surface roughness of the indenter is the same as that of the acetabular cup.
  • the roughness of the lining friction surface is related.
  • the molding molds used to prepare the knee joint prosthesis are the first molding mold 210, the sleeve 220 and the third molding mold 230 shown in Figure 2 (see Example 1 for more detailed operation methods)
  • the friction surface roughness Ra of the knee joint pad product is 0.06-0.1 micron, which is basically the same as the surface roughness Ra of the indenter is 0.1 micron, indicating that the surface roughness of the indenter is related to the roughness of the friction surface of the knee joint pad product.
  • A is the change of the TVI value of the trans vinylidene index with the distance away from the friction surface of the acetabular cup lining product (2.1.)
  • B is the change of the TVI value of the trans vinylidene index with the distance away from the product of the knee joint liner (2.1. 2.2.) Variation of the friction surface distance. It can be seen from Figure 4 that both TVI values are in the range of 0.38 to 0.39, indicating that the entire acetabular cup lining product and knee joint liner product have undergone a high degree of cross-linking of ultra-high molecular weight polyethylene, forming UHMWPE high Cross-linked joint prosthesis.
  • Embodiment 3 preparation has the articular prosthesis of surface cross-linking layer (precompression molding, artificial acetabular cup liner)
  • the roughness test results show that the roughness Ra of the friction surface of the acetabular cup liner product is 0.10 micron, which is consistent with the surface roughness (0.10 micron) of the indenter.
  • the molded acetabular cup liner ultra-high molecular weight polyethylene samples were characterized by infrared spectroscopy, and the change of trans vinylidene index TVI value with the distance from the friction surface of the acetabular cup liner was obtained. The result is shown in Figure 5.
  • the trans-vinylidene index can be detected in the depth range of 1mm from the friction surface of the acetabular cup lining, but no trans-vinylidene index can be detected in the remaining depth range. It can be seen that the thickness of the surface cross-linked layer is about 2mm . This result indicates the successful preparation of UHMWPE acetabular cup liner products with a surface cross-linked layer.
  • Embodiment 4 preparation has the articular prosthesis (precompression molding, artificial knee liner) with surface cross-linked layer
  • the roughness test results show that the roughness Ra of the friction surface of the knee pad product is 0.09 microns, which is consistent with the surface roughness Ra (0.10 microns) of the indenter.
  • the molded ultra-high molecular weight polyethylene samples of knee joint pads were characterized by infrared spectroscopy, and the change of TVI value of trans vinylidene index with the distance from the friction surface of knee joint pads was obtained.
  • the result is shown in Figure 6.
  • the trans-vinylidene index can be detected in the depth range of 1 mm from the friction surface of the knee joint pad, while no trans-vinylidene index can be detected in the remaining depth range. It can be seen that the thickness of the surface cross-linked layer is about 1 mm. This result indicates that the surface cross-linked ultra-high molecular weight polyethylene knee pad product was successfully prepared.
  • Embodiment 5 preparation has the joint prosthesis (artificial acetabular cup liner) of intermediate cross-linking layer
  • the electron beam irradiation dose is 75kGy, and the annealing after irradiation The temperature is 120°C and the time is 9 hours to obtain the first cross-linked UHMWPE powder;
  • the second ultra-high molecular weight polyethylene powder is irradiated and cross-linked, placed in a vacuum package in an aluminum foil bag, and irradiated with electron beams , carry out irradiation crosslinking, the electron beam irradiation dose is 45kGy, the annealing temperature after irradiation is 120°C, and the time is 9h, to obtain the second crosslinked UHMWPE powder.
  • the molded acetabular cup liner ultra-high molecular weight polyethylene samples were characterized by infrared spectroscopy, and the change of trans vinylidene index TVI value with the distance from the friction surface of the acetabular cup liner was obtained.
  • the result is shown in Figure 7.
  • the trans-vinylidene index was 0.38 in the depth range of 1 mm from the friction surface of the acetabular cup lining, and 0.23 in the depth range of 1-2 mm, while no trans-vinylidene index was detected in the remaining depth range. It can be seen that The thicknesses of the middle cross-linked layer and the surface cross-linked layer are about 1 mm, respectively. This result indicates that the ultra-high molecular weight polyethylene acetabular cup liner product with a gradient of cross-linking degree along the direction away from the friction surface was successfully prepared.
  • Embodiments 7, 8, and 9 respectively omit the pre-compression molding process on the basis of Examples 3-5, adopt the same powder, the same amount of material, and adopt the same conditions as the last step of compression molding in Examples 3-5 Perform one-time thermocompression molding.
  • the roughness test results show that the roughness Ra of the friction surface of the acetabular cup liner product is 0.10 micron, which is consistent with the surface roughness (0.10 micron) of the indenter.
  • the molded acetabular cup liner ultra-high molecular weight polyethylene samples were characterized by infrared spectroscopy, and the change of trans vinylidene index TVI value with the distance from the friction surface of the acetabular cup liner was obtained.
  • the test results are similar to those shown in Figure 5.
  • the roughness test results show that the roughness Ra of the friction surface of the knee pad product is 0.09 microns, which is consistent with the surface roughness Ra (0.10 microns) of the indenter.
  • the molded ultra-high molecular weight polyethylene samples of knee joint pads were characterized by infrared spectroscopy, and the change of TVI value of trans vinylidene index with the distance from the friction surface of knee joint pads was obtained.
  • the test results are similar to those shown in Figure 6.
  • the electron beam irradiation dose is 75kGy, and the annealing after irradiation The temperature is 120°C and the time is 9 hours to obtain the first cross-linked UHMWPE powder;
  • the second ultra-high molecular weight polyethylene powder is irradiated and cross-linked, placed in a vacuum package in an aluminum foil bag, and irradiated with electron beams , carry out irradiation crosslinking, the electron beam irradiation dose is 45kGy, the annealing temperature after irradiation is 120°C, and the time is 9h, to obtain the second crosslinked UHMWPE powder.
  • an ultra-high molecular weight polyethylene artificial acetabular cup liner product with a middle cross-linking layer and a surface cross-linking layer (with multi-layer cross-linking layers, UHMWPE in the matrix layer is not cross-linked, and the middle cross-linking layer
  • the degree of crosslinking of UHMWPE is lower than that of UHMWPE in the surface crosslinked layer).
  • the molded acetabular cup liner ultra-high molecular weight polyethylene samples were characterized by infrared spectroscopy, and the change of trans vinylidene index TVI value with the distance from the friction surface of the acetabular cup liner was obtained.
  • the test results are similar to those shown in Figure 7.
  • Comparative example 1 Traditional method: first prepare the joint prosthesis, and then perform irradiation cross-linking treatment (acetabular cup joint prosthesis)
  • the compression molding mold used is the first forming mold 110 shown in Figure 1, the sleeve 120 and the third forming mold 130, in more detail, the first forming mold 110 and the sleeve 120 are combined to form a cavity, and the uncrosslinked UHMWPE powder is added into the cavity, and molded under the molding conditions through the action of the pressure head of the third forming die 130, and then the third forming die 130, the joint prosthesis and the first forming die 110 are separated from each other by using a hot press.
  • the hollow interior of the sleeve 120 is pressed out. Among them, the temperature during compression molding was set at 250°C, the heating and cooling rate was 10°C/min, the molding pressure was 40MPa, and the holding time was 45min.
  • the acetabular cup lining product is recorded as comparative example 1b).
  • the molded acetabular cup joint prosthesis was cross-linked by electron beam irradiation, the dose of electron beam irradiation was 75kGy, and the annealing temperature after irradiation was 120°C for 9 hours.
  • the results of the roughness test show that at a molding temperature of 250° C., the friction surface roughness Ra of the acetabular cup liner product is 0.09 microns, which is consistent with the surface roughness Ra of the pressure head of the third molding die 130 being 0.1 microns.
  • Comparative example 2 Traditional method: first prepare the joint prosthesis, and then perform irradiation cross-linking treatment (knee joint prosthesis)
  • the compression molding mold used is the first forming mold 210 shown in Figure 2, the sleeve 220 and the third forming mold 230, in more detail, the first forming mold 210 and the sleeve 220 are combined to form a cavity, and the uncrosslinked UHMWPE powder is added into the cavity, and molded under the molding conditions through the action of the pressure head of the third forming die 230, and then the third forming die 230, the joint prosthesis and the first forming die 210 are removed from the The hollow interior of the sleeve 220 is pressed out. Among them, the temperature during compression molding was set at 250°C, the heating and cooling rate was 10°C/min, the molding pressure was 40MPa, and the holding time was 45min.
  • the joint liner product is denoted as comparative example 2b).
  • the molded knee joint liner blank prosthesis was cross-linked by electron beam irradiation, the dose of electron beam irradiation was 75kGy, and the annealing temperature after irradiation was 120°C for 9 hours.
  • the roughness test results show that at a molding temperature of 250° C., the friction surface roughness Ra of the knee pad product is 0.09 microns, which is consistent with the surface roughness Ra of the pressure head of the third molding die 230 being 0.1 microns.
  • the infrared test results show that the TVI value of the trans vinylidene index changes little with the distance away from the friction surface of the knee joint pad product, and is in the range of 0.38 to 0.39, indicating that ultra-high molecular weight polymerization has occurred in the entire knee joint pad product.
  • Ethylene was crosslinked and no surface crosslinked layer was formed.
  • the preparation process is basically the same as in Example 1. The difference is that when performing compression molding, the surface roughness of the acetabular cup liner indenter is 0.85 microns, and that of the knee joint liner is 0.92 microns.
  • the roughness test results show that the friction surface roughness Ra of the acetabular cup lining product is 0.79 microns, and the friction surface roughness Ra of the knee joint liner product is 0.89 microns, which is basically consistent with the surface roughness of the indenter, indicating that the indenter is Surface roughness is related to the roughness of the friction surfaces of acetabular cup liners and knee liner products.
  • Embodiment 6 Investigation about prepress molding parameters
  • the molding temperature is 240° C.
  • the heating and cooling rate is 5° C./min
  • the molding pressure is 30 MPa
  • the molding time is 30 minutes.
  • the preparation method is basically the same as that in 6.1. Example, the difference is that the temperature of pre-compression molding in step (2) is 175°C.
  • the preparation method is basically the same as that in 6.1. Example, the difference is that the pre-pressing temperature in step (2) is 200°C.
  • the preparation method is basically the same as that in 6.1. Example, the difference is that the temperature of pre-compression molding in step (2) is 140°C.
  • the preparation method is basically the same as that in 6.1. Example, the difference is that the temperature of pre-compression molding in step (2) is 220°C.
  • Embodiment 7 Mechanical performance test
  • the cobalt chromium molybdenum ball head was combined with the molded acetabular cup liner for hip wear testing, and the cobalt chromium molybdenum femoral condyle and molded knee liner were combined for knee wear testing.
  • the friction and wear testing machine is controlled by displacement, wears 5 million times, and weighs every 500,000 times. The results are shown in Table 1.
  • Comparative Example 1b and Comparative Example 2b do not have a surface cross-linked layer, and the results show that the wear resistance is poor.
  • Example 6.1 The pre-pressing temperature is too low, the fusion of powder particles is poor, and the difference between the cross-linked layer and the cross-linked layer is large during the second molding, and the overall impact toughness of the material is not as good as that of Example 6.2.
  • Example 6.3 The pre-pressing temperature is too high, the powder particles are completely melted, and when the cross-linking powder is added for the second time for high-pressure exhaust, the matrix melt is prone to produce extrusion flow, which is not conducive to the formation of a better bonding layer, and the overall impact of the material Toughness is not as good as Example 6.2.
  • the joint prostheses of Example 3, Example 4, and Example 5 have good wear resistance and excellent mechanical properties at the same time, which is brought about by the design of the surface cross-linked layer realized by the pre-compression molding technology in this application .
  • Examples 3-5 adopted the pre-compression molding technology provided by the present application to form a surface cross-linked layer, and the results showed that compared with Comparative Examples 1b and 2b, the joint prosthesis prepared also had a significant improvement in wear resistance. Compared with Examples 7-9, it also shows overall better mechanical properties.

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Abstract

La présente invention concerne une prothèse articulaire ayant une couche réticulée en surface et son procédé de fabrication, et un ensemble moule de pressage pour fabriquer la prothèse articulaire. La prothèse d'articulation comprend une couche réticulée en surface et une couche de matrice, une face de frottement de la prothèse d'articulation étant située sur une surface externe de la couche réticulée en surface, l'UHMWPE dans la couche réticulée en surface ayant un degré élevé de réticulation, et l'UHMWPE dans la couche de matrice ayant un faible degré de réticulation globale ou pas de réticulation.
PCT/CN2022/136517 2021-12-13 2022-12-05 Prothèse articulaire ayant une couche réticulée en surface et son procédé de fabrication, et ensemble moule de pressage Ceased WO2023109547A1 (fr)

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CN114344568B (zh) * 2021-12-13 2023-03-17 苏州微创关节医疗科技有限公司 具有表面交联层的关节假体及其制备方法和模压模具组件
CN119217630B (zh) * 2024-09-24 2025-12-09 北京安通忆泰医疗科技有限公司 一种高交联超高分子量聚乙烯膝关节衬垫的成型方法

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