WO2013183442A1 - Matériau d'ostéosynthèse - Google Patents

Matériau d'ostéosynthèse Download PDF

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Publication number
WO2013183442A1
WO2013183442A1 PCT/JP2013/064086 JP2013064086W WO2013183442A1 WO 2013183442 A1 WO2013183442 A1 WO 2013183442A1 JP 2013064086 W JP2013064086 W JP 2013064086W WO 2013183442 A1 WO2013183442 A1 WO 2013183442A1
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osteosynthesis material
branched polymer
polylactic acid
represent
polymer
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PCT/JP2013/064086
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English (en)
Japanese (ja)
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英俊 有村
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グンゼ株式会社
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Priority to CN201380023397.XA priority Critical patent/CN104284684A/zh
Priority to JP2014519913A priority patent/JPWO2013183442A1/ja
Publication of WO2013183442A1 publication Critical patent/WO2013183442A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Definitions

  • the present invention relates to an osteosynthesis material having both high strength and excellent biodegradability. More specifically, the present invention relates to an osteosynthesis material that has high initial strength and is rapidly decomposed and absorbed in vivo after a certain period of time.
  • a treatment method is generally adopted in which a bone bonding material such as a pin, screw, or plate is implanted and fixed in the bone damage site.
  • a bone bonding material such as a pin, screw, or plate
  • metal and ceramic bone bonding materials have the disadvantage that they are subject to corrosion and damage when placed in vivo for a long period of time, and are more rigid than bone.
  • the bone around the material can be destroyed. Therefore, when metal or ceramic bone bonding materials are used, it is necessary to remove them again by surgery when the bone damage has healed, which places a heavy burden on the patient.
  • osteosynthesis materials using biodegradable absorbable polymers such as polylactic acid have been developed and actually used clinically.
  • Such an osteosynthesis material is hydrolyzed and absorbed by the living body after a certain period of time after being implanted in the living body, so there is no need for reoperation for removing the osteosynthesis material, greatly reducing the burden on the patient. is made of.
  • the glass transition temperature is lower than the body temperature of 37 ° C., so the strength decreases when implanted in a living body, and the site of bone damage or the site of bone damage caused by surgery is reduced. There is a risk of breaking during placement until healing.
  • the conventional osteosynthesis material made of biodegradable absorbable polymer cannot realize both high strength and excellent biodegradable absorbability.
  • the development of an osteosynthesis material that combines decomposition and absorbability is eagerly desired.
  • An object of the present invention is to provide an osteosynthesis having high initial strength and excellent biodegradability.
  • the present inventor has intensively studied to solve the above problems, and as a result, by forming a bone cement using a branched polymer (particularly a star polymer) having an arm portion made of at least three polylactic acids.
  • the inventors have found that the initial strength is high, and that it can be rapidly decomposed and absorbed in vivo after a certain period of time.
  • the present invention has been completed by further studies based on such knowledge.
  • Item 1 An osteosynthesis material comprising a branched polymer having an arm portion composed of at least three polylactic acids.
  • Item 2. Item 2. The osteosynthesis material according to Item 1, wherein the branched polymer is a star polymer having a core portion and an arm portion made of at least three polylactic acids extending from the core portion.
  • the star polymer has a pentaerythritol residue or dipentaerythritol residue as a core portion, and the hydroxyl group of pentaerythritol or dipentaerythritol and the carboxyl group of polylactic acid constituting the arm portion are linked by an ester bond.
  • the osteosynthesis material according to Item 2 which is a structure.
  • Item 4. Item 4. The osteosynthesis material according to Item 2 or 3, wherein the star polymer is a compound represented by the following general formula (1) or (2).
  • n1 to n4 are the same or different and represent an integer of 0 to 4
  • x1 to x4 are the same or different and represent 0 or 1
  • R1 to R4 are the same or different and represent poly It represents lactic acid or a hydrogen atom
  • at least three of R1 to R4 represent polylactic acid.
  • m1 to m8 are the same or different and represent an integer of 0 to 4
  • y1 to y8 are the same or different and represent 0 or 1
  • R5 to R10 are the same or different, It represents polylactic acid or a hydrogen atom, and at least three of R5 to R10 represent polylactic acid.
  • Item 5. The osteosynthesis material according to any one of Items 1 to 4, wherein the polylactic acid constituting the arm portion is poly L-lactic acid.
  • the bone cement according to any one of Items 1 to 5, wherein the degree of polymerization (lactide unit) of polylactic acid constituting the arm portion is 80 to 600.
  • Item 7. Item 7.
  • the osteosynthesis material according to any one of Items 1 to 6, which is a pin, screw, plate, screw, screw, cloth, or film.
  • Items 1 to 6 which is a pin, screw, plate, screw, screw, cloth, or film.
  • Items 8 Use of a branched polymer having an arm portion composed of at least three polylactic acids for producing an osteosynthesis.
  • Item 9. A branched polymer having an arm portion composed of at least three polylactic acids, which is used for treatment of bone damage.
  • Item 10 A method for treating bone damage, comprising a step of fixing an osteosynthesis material containing a branched polymer having an arm portion made of at least three polylactic acids to a bone injury site.
  • the osteosynthesis material of the present invention has high initial strength, can be embedded without breaking during surgery, and can stably fix a bone damage site without breaking before the bone damage site heals. . Furthermore, since the bone cement of the present invention is rapidly hydrolyzed and absorbed in the living body after a certain period of time in the living body, the bone joining material remains in the living body for a long time after healing of the bone damage. It is possible to suppress harmful effects caused by
  • osteosynthesis materials made of linear polylactic acid have the drawbacks of being hard and brittle, but the osteosynthesis materials of the present invention have the properties of high flexural modulus and high maximum point stress. It is also excellent in terms of mechanical properties required for osteosynthesis.
  • each press film is immersed in PBS ( ⁇ ) at 37 ° C. for a predetermined period and then the tensile strength is measured.
  • each press film is immersed in 50 ° C. PBS ( ⁇ ) for a predetermined period and then the tensile strength is measured.
  • each press film is immersed in PBS ( ⁇ ) at 65 ° C. for a predetermined period, and the residual weight percentage (%) is measured.
  • each press film was immersed in PBS ( ⁇ ) at 65 ° C. for a predetermined period, and then the reduction rate (%) of the polymer molecular weight was measured.
  • the osteosynthesis material of the present invention is characterized by containing a branched polymer having an arm portion composed of at least three polylactic acids.
  • a branched polymer having an arm portion composed of at least three polylactic acids is characterized by containing a branched polymer having an arm portion composed of at least three polylactic acids.
  • the branched polymer contained in the osteosynthesis material of the present invention has a structure having three or more arm portions made of polylactic acid.
  • the number of arm portions made of polylactic acid may be 3 or more, preferably 3 to 10, more preferably 4 to 8, and particularly preferably 4 to 6.
  • the degree of polymerization of polylactic acid per arm portion is not particularly limited, but is, for example, 80 to 600, preferably 80 to 550, more preferably 80 to 500, and particularly preferably 90 to 200. Can be mentioned.
  • the degree of polymerization of polylactic acid is a lactide unit, and — [CO—CH (CH 3 ) —O—CO—CH (CH 3 ) —O] — is represented as one unit (degree of polymerization 1). .
  • the polymerization degree of the polylactic acid in the arm part is a value measured by NMR.
  • the three or more arm portions in the branched polymer may be composed of polylactic acid having the same molecular weight, or may be composed of polylactic acid having different molecular weights.
  • the arm part in the branched polymer may be any of poly-L-lactic acid, poly-D-lactic acid, poly-D, L-lactic acid, but has high strength and excellent biodegradability.
  • Poly-L-lactic acid is preferably used from the viewpoint of making it better combined.
  • the structure of the branched polymer is not particularly limited as long as it has three or more arm portions made of polylactic acid, and these arm portions are connected to the core portion. Any of a mold, a bottle brush type, a starburst type, etc. may be sufficient. From the viewpoint of combining the high strength and the excellent biodegradable absorbability, the branched polymer structure used in the osteosynthesis material of the present invention preferably includes a star shape.
  • the structure of the core part in the branched polymer is not particularly limited, and may be appropriately designed according to the structure of the branched polymer.
  • a residue of a trihydric or higher polyhydric alcohol or a residue of a trivalent or higher polyvalent amine can be mentioned.
  • the polyhydric alcohol has a structure in which the hydroxyl group of the polyhydric alcohol is linked to the carboxyl group of the polylactic acid constituting the arm by an ester bond. .
  • the amino group of the polyvalent amine is linked to the polylactic acid carboxyl group constituting the arm part by an amide bond. Become a structure.
  • the compound constituting the core in the branched polymer include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, triglycerin, sorbitol, poly (vinyl alcohol), and poly (hydroxyethyl methacrylate). ), Poly (hydroxypropyl methacrylate); monosaccharides such as glucose, galactose, mannose and fructose; and trihydric or higher polyhydric alcohols such as disaccharides such as lactose, sucrose and maltose.
  • Preferred examples of the branched polymer used in the osteosynthesis material of the present invention include pentaerythritol residues, or star polymers having a dipentaerythritol residue as a core, that is, each hydroxyl group of pentaerythritol or dipentaerythritol.
  • branched polymer a star polymer represented by the following general formula (1) or (2) is exemplified.
  • n1 to n4 are the same or different and represent an integer of 0 to 4.
  • n1 to n4 are preferably integers of 0 to 2, and more preferably 0.
  • x1 to x4 are the same or different and represent 0 or 1. x1 to x4 are preferably 0.
  • R1 to R4 are the same or different and represent polylactic acid or a hydrogen atom, and at least three of R1 to R4 represent polylactic acid.
  • Preferable examples of the star polymer represented by the general formula (1) include those in which all of R1 to R4 are polylactic acid.
  • the at least three polylactic acids constituting R1 to R4 may have the same molecular weight, or may have different molecular weights.
  • the molecular weight of at least three polylactic acids constituting R1 to R4, the types of optical isomers of the constituent monomers, etc. are as described above.
  • m1 to m8 are the same or different and represent an integer of 0 to 4.
  • m1 to m3 and m6 to m8 are preferably integers of 0 to 2, more preferably 0.
  • m4 and m5 are preferably integers of 1 to 3, and more preferably 1.
  • y1 to y8 are the same or different and represent 0 or 1. Y1 to y8 are preferably 0.
  • R5 to R10 are the same or different and represent polylactic acid or a hydrogen atom, and at least three of R5 to R10 represent polylactic acid.
  • the star polymer represented by the general formula (1) at least four of R5 to R10 are preferably polylactic acid, more preferably at least five are polylactic acid, and all of these are polylactic acid. Those are particularly preferred.
  • the at least three polylactic acids constituting R5 to R10 may have the same molecular weight, or may have different molecular weights. With respect to at least three polylactic acids constituting R5 to R10, the molecular weight, the type of optical isomers of the constituent monomers, etc. are as described above.
  • the branched polymer can be produced by a known method. Specifically, as a method for producing the branched polymer, a method of ring-opening polymerization of lactide using a catalyst in the presence of a compound constituting the core part, and a method in which lactic acid is directly polymerized in the presence of the compound constituting the core part. Examples thereof include a method of dehydrating condensation polymerization by a condensation method.
  • Examples of the catalyst used for ring-opening polymerization of lactide include, for example, tin 2-ethylhexanoate, tin (II) octylate, triphenyltin acetate, tin oxide, dibutyltin oxide, tin oxalate, tin chloride, dibutyltin dilaurate, Examples thereof include metal catalysts such as thorium ethoxide, potassium tert-butoxide, triethylaluminum, tetrabutyl titanate, and bismuth; organic base catalysts such as organic onium salts.
  • the osteosynthesis material of the present invention may be composed only of the branched polymer, but may contain other biodegradable absorbable polymers as necessary.
  • the other biodegradable absorbable polymers include polylactic acid, lactic acid-glycolic acid copolymer, polyglycolic acid, lactic acid- ⁇ -caprolactone copolymer, glycolic acid- ⁇ -caprolactone copolymer, polydioxanone, and the like. Is mentioned.
  • polylactic acid is preferably used for the purpose of adjusting the strength of the osteosynthesis because it can moderate the degradation rate of the osteosynthesis of the present invention.
  • the polylactic acid contained as necessary in the osteosynthesis material of the present invention may be any of poly-L-lactic acid, poly-D-lactic acid, poly-D, L-lactic acid, preferably Poly-L-lactic acid is exemplified.
  • the weight average molecular weight of the polylactic acid is not particularly limited, and examples thereof include 150,000 to 500,000, preferably 180,000 to 450,000, and more preferably 200,000 to 400,000.
  • the osteosynthesis material of the present invention contains a biodegradable absorbable polymer other than the branched polymer
  • the content thereof is not particularly limited.
  • the osteosynthesis material of the present invention may contain, as necessary, components showing affinity with bone tissues such as tricalcium phosphate, tetracalcium phosphate, calcium hydrogen phosphate, and hydroxyapatite; a cell growth factor, a growth factor, An antibacterial agent, antibiotics, etc. may be contained or surface-coated.
  • the glass transition temperature of the osteosynthesis material of the present invention is determined depending on the type of branched polymer used, but is usually 40 ° C. or higher, preferably 45 to 65 ° C., more preferably 50 to 60 ° C.
  • the glass transition temperature is a value measured by DSC (differential scanning calorimetry).
  • the osteosynthesis material of the present invention has the property of being rapidly decomposed after a certain period of time after being implanted in a living body, and as a suitable example of the degradation characteristics of the osteosynthesis material of the present invention,
  • the weight residual ratio when immersed in a phosphate buffer solution (PBS ( ⁇ ), pH 7.4) for 36 days at 65 ° C. is usually 90% or less, preferably 0 to 89%, more preferably 0 to 85%. Can be mentioned.
  • the weight residual ratio (%) is a value calculated according to the following formula.
  • the shape of the osteosynthesis material of the present invention is not particularly limited as long as it can be implanted in a living body and fix a bone damage site.
  • a pin, screw, plate, screw, screw, cloth Shape, film shape and the like for example, a pin, screw, plate, screw, screw, cloth Shape, film shape and the like.
  • the bone bonding material of the present invention can have high strength, among the shapes, pins, screws, plates, screws, and the like that are required to maintain high strength until the bone damage site is healed, and A screw is illustrated as a suitable shape in the osteosynthesis of this invention.
  • the osteosynthesis material of the present invention is manufactured by molding by a known method. Specifically, the osteosynthesis material of the present invention is manufactured by preparing a pellet containing the branched polymer and other biodegradable absorbable polymer contained as necessary, and molding the pellet into a predetermined shape.
  • Synthesis Example 1 Synthesis of 4-armPLLA L, L-lactide 2000 g (13.9 mol), pentaerythritol 2.36 g (1.7 ⁇ 10 ⁇ 2 mol), and tin 2-ethylhexanoate (L, L-lactide) 100 ppm per unit weight) was placed in a separable flask and dried overnight under vacuum. Thereafter, the inside of the container was filled with nitrogen, immersed in an oil bath set at 125 ° C., and polymerized for 2 days. The branched polymer (4-armPLLA) obtained after the completion of the polymerization was pulverized with a rotary pulverizer having a mesh size of 3 mm to obtain pulverized pieces.
  • the obtained branched polymer (4-armPLLA) was analyzed by NMR (solvent: deuterated chloroform, measurement nucleus: 1H, integration number: 128), the degree of hydroxyl group substitution, the average number of arm parts made of polylactic acid, and one arm part.
  • the degree of polymerization of polylactic acid per unit (lactide unit) and the number average molecular weight were determined.
  • the number average molecular weight, the weight average molecular weight, and dispersion degree were calculated
  • required by GPC are the values of standard polystyrene conversion.
  • the DSC Different Scanning Calorimetry
  • the crystallinity (Xc (%)) was calculated according to the following formula.
  • Xc (%) ⁇ H1st (J / g) / ⁇ 93.6 (J / g) ⁇ ⁇ 100
  • Synthesis Example 2 Synthesis of 6-armPLLA L, L-lactide 2000 g (13.9 mol), dipentaerythritol 4.52 g (1.7 ⁇ 10 -2 mol), and tin 2-ethylhexanoate (L, L- 100 ppm per lactide unit weight) was placed in a separable flask and dried overnight under vacuum. Thereafter, the inside of the container was filled with nitrogen, immersed in an oil bath set at 125 ° C., and polymerized for 2 days. The branched polymer (6-armPLLA) obtained after completion of the polymerization was pulverized by a rotary pulverizer having a mesh size of 3 mm to obtain pulverized pieces.
  • the obtained branched polymer (6-armPLLA) was analyzed by NMR, GPC, and DSC under the same conditions as in Synthesis Example 1. The results are shown in Table 2.
  • Synthesis Example 3 Synthesis of linear PLLA L, L-lactide 2000 g (13.9 mol), 1-dodecanol 3.2 g (1.7 ⁇ 10 ⁇ 2 mol), and tin 2-ethylhexanoate (L, L— 100 ppm per lactide unit weight) was placed in a separable flask and dried overnight under vacuum. Thereafter, the inside of the container was filled with nitrogen, immersed in an oil bath set at 125 ° C., and polymerized for 2 days. The linear polylactic acid (linear PLLA) obtained after completion of the polymerization was pulverized by a rotary pulverizer having a mesh size of 3 mm to obtain pulverized pieces.
  • linear PLLA linear PLLA
  • linear polylactic acid (linear PLLA) was analyzed by GPC and DSC under the same conditions as in Synthesis Example 1. The results are shown in Table 3.
  • Example 1 Preparation of 4-armPLLA Press Film 4-armPLLA obtained in Synthesis Example 1 was prepared into a press film having an average thickness of 300 ⁇ m using a heating press machine (Tester Sangyo Co., Ltd. ACM press machine 30T 400C). Specifically, 6-armPLLA 6 g was sandwiched between two 200 mm ⁇ 200 mm ⁇ 0.2 mm aluminum plates and two SUS plates (200 mm ⁇ 200 mm ⁇ 5 mm) and set in a heating press set to 200 ° C. The upper and lower SUS plates were brought into contact with the press surface to melt each polylactic acid over 5 minutes, and then pressurized with a pressure of 20 kgf / m 2 for 1 minute, and then rapidly cooled with ice. Thereafter, heat setting was performed under vacuum at 90 ° C. while sandwiched between aluminum plates. It was 57 degreeC when the glass transition temperature of the obtained film was measured by DSC.
  • a heating press machine Teester Sangyo Co., Ltd. ACM press
  • Example 2 Preparation of 6-armPLLA Press Film Using 6-armPLLA 6 g obtained in Synthesis Example 2, a press film was processed in the same manner as in Example 1. It was 55 degreeC when the glass transition temperature of the obtained film was measured by DSC.
  • Example 3 Preparation of Mixed Press Film of 4-armPLLA and Linear PLLA After thoroughly mixing 2 g of 4-armPLLA obtained in Synthesis Example 1 and 4 g of linear PLLA obtained in Synthesis Example 3, the Example 1 was processed into a press film by the same method. It was 60 degreeC when the glass transition temperature of the obtained film was measured by DSC.
  • Example 4 Preparation of mixed press film of 6-armPLLA and linear PLLA After thoroughly mixing 2 g of 6-armPLLA obtained in Synthesis Example 2 and 4 g of linear PLLA obtained in Synthesis Example 3, Example 1 was processed into a press film by the same method. It was 60 degreeC when the glass transition temperature of the obtained film was measured by DSC.
  • Comparative Example 1 Preparation of linear PLLA press film Using 6 g of linear PLLA obtained in Synthesis Example 3, the film was processed into a press film in the same manner as in Example 1. It was 63 degreeC when the glass transition temperature of the obtained film was measured by DSC.
  • Test Example 1 Evaluation of initial strength and strength after storage The press film obtained above was cut into a 10 mm ⁇ 40 mm strip and the tensile strength was measured (initial strength). Next, the press film cut into strips was immersed in PBS (-) at 37 ° C, and after 1 month, 2 months, and 3 months, each press film was taken out from PBS and dried, and then the tensile strength at break was measured. (Strength after storage). Similarly, a press film cut into strips was immersed in PBS ( ⁇ ) at 50 ° C. for 3 weeks, and then the tensile fracture was measured (strength after storage). The test under the conditions immersed in PBS ( ⁇ ) at 37 ° C.
  • Example 1-2 and Comparative Example 1 The press films of Examples 1-4 and Comparative Example 1 were used.
  • the tensile strength at break was measured using a universal tensile testing machine (Shimadzu Corporation EZ-Graph) under the conditions of a distance between chucks of 15 mm and a tensile speed of 10 mm / min. From the calculation by Arrhenius plot, it is known that the condition of immersing in PBS ( ⁇ ) at 50 ° C. for 3 weeks substantially corresponds to the condition of immersing in PBS ( ⁇ ) at 37 ° C. for 3 months.
  • FIG. 1 shows the test results under conditions immersed in PBS ( ⁇ ) at 37 ° C.
  • FIG. 2 shows the results of tests under conditions immersed in PBS ( ⁇ ) at 50 ° C.
  • the press film prepared using the branched polymer obtained in Synthesis Examples 1 and 2 showed the same initial strength as the press film prepared using linear PLLA.
  • the press film prepared using the branched polymer obtained in Synthesis Examples 1 and 2 is one month or 2 times in PBS ( ⁇ ) at 37 ° C. compared to the press film prepared using linear PLLA. It was shown that the strength decrease after immersion for months was large (see FIG. 1).
  • the mixed press film of the branched polymer obtained in Synthesis Example 1 or 2 and the linear PLLA is compared with the press film produced with the branched polymer obtained in Synthesis Example 1 or 2 after storage. It was shown that the strength decrease after storage was larger than that of the press film prepared using linear PLLA (see FIG. 2).
  • the press film prepared using the branched polymer obtained in Synthesis Examples 1 and 2 has a high initial strength and has a property of being rapidly decomposed after a certain period of time. It was confirmed that it can be suitably used as a material.
  • Test Example 2 Evaluation of weight reduction rate after storage of press film
  • Each press film of Example 1-4 and Comparative Example 1 was cut into 10 mm ⁇ 40 mm strips, which were cut into PBS ( ⁇ ) at 65 ° C. for a predetermined period. Soaked. After immersing in PBS ( ⁇ ) at 65 ° C. for 6, 12, and 36 days, each press film is taken out from PBS ( ⁇ ), washed and dried, and then weighed to determine the remaining weight percentage (%). It was. Further, after immersion for 6, 12, and 36 days, about 10 mg pieces were collected from each press film, and using this as a sample, the weight average molecular weight of the polymer remaining by the GPC method was measured.
  • the rate of decrease in the weight average molecular weight of the polymer after the immersion relative to the weight average molecular weight of the polymer before the immersion was determined as a decrease rate (%) of the polymer molecular weight. From the calculation by Arrhenius plot, the conditions of 6-12, 36 days immersion in PBS (-) at 65 ° C are almost equivalent to 6-12 months of PBS (-) at 37 ° C respectively. I know that
  • Example 5 Preparation of 4-armPLLA rolled plate Using 4-armPLLA obtained in Synthesis Example 1 as a raw material polymer and molding using an injection molding machine and a rolling machine, a plate of 10 mm x 60 mm x 2 mm Manufactured.
  • Example 6 Preparation of 6-armPLLA rolled plate A plate was prepared in the same manner as in Example 5 using 6-armPLLA obtained in Synthesis Example 2.
  • Comparative Example 2 Preparation of linear PLLA rolled plate A plate was prepared in the same manner as in Example 5 using the linear PLLA obtained in Synthesis Example 3.
  • Test Example 3 Evaluation of Mechanical Properties of Rolled Plates
  • the rolled plates of Example 5-6 and Comparative Example 2 were subjected to a three-point bending test using a small universal testing machine (Ez Graph Shimadzu Corporation) to determine the flexural modulus ( GPa), maximum point stress (MPa), and energy (J) up to the maximum point were measured.
  • Ez Graph Shimadzu Corporation Ez Graph Shimadzu Corporation
  • Table 4 shows the obtained results. From this result, it is understood that the rolled plate (Example 5-6) prepared using a branched polymer has both a high flexural modulus and a maximum point stress, and has desirable mechanical properties as an osteosynthesis material. It was.

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Abstract

L'invention a pour objectif de fournir un matériau d'ostéosynthèse qui présente une résistance initiale élevée, et qui en outre combine d'excellentes propriétés biodégradables et bioabsorbables. Ce matériau d'ostéosynthèse est formé par mise en œuvre d'un polymère ramifié (plus spécifiquement, un polymère en étoile) qui possède des parties branche constituées d'au moins trois acides polyactiques, permettant ainsi de lui conférer des caractéristiques telles qu'une résistance initiale élevée, et une dégradation et une absorption rapide à l'intérieur d'un organisme vivant après écoulement d'une durée fixe.
PCT/JP2013/064086 2012-06-07 2013-05-21 Matériau d'ostéosynthèse WO2013183442A1 (fr)

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CN114712559A (zh) * 2022-05-05 2022-07-08 湖北翎美生物科技有限公司 一种体内可促进胶原稳定再生的可注射聚左旋乳酸微球及其制备和应用

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