TW205501B - - Google Patents
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- Publication number
- TW205501B TW205501B TW080105226A TW80105226A TW205501B TW 205501 B TW205501 B TW 205501B TW 080105226 A TW080105226 A TW 080105226A TW 80105226 A TW80105226 A TW 80105226A TW 205501 B TW205501 B TW 205501B
- Authority
- TW
- Taiwan
- Prior art keywords
- absorbable
- copolymer
- patent application
- polymer
- item
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 claims description 87
- 229920001577 copolymer Polymers 0.000 claims description 62
- 239000000126 substance Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 39
- 238000011049 filling Methods 0.000 claims description 24
- -1 polyethylene Polymers 0.000 claims description 21
- 229920001519 homopolymer Polymers 0.000 claims description 20
- 230000008439 repair process Effects 0.000 claims description 20
- 229920001400 block copolymer Polymers 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 229920000249 biocompatible polymer Polymers 0.000 claims description 12
- 210000000988 bone and bone Anatomy 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 4
- 229930182843 D-Lactic acid Natural products 0.000 claims description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- 229920000118 poly(D-lactic acid) Polymers 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 2
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
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- 239000004677 Nylon Substances 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
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- 150000001875 compounds Chemical class 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
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- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 241000252234 Hypophthalmichthys nobilis Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000282472 Canis lupus familiaris Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- 238000001727 in vivo Methods 0.000 description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 2
- 150000003903 lactic acid esters Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000006207 propylation Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WWMQIJFJSHVMDM-UHFFFAOYSA-N 2-ethenoxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC=C WWMQIJFJSHVMDM-UHFFFAOYSA-N 0.000 description 1
- QMTRBTDPYXTJEN-UHFFFAOYSA-N 2-ethylhexanoic acid sulfane Chemical compound S.CCCCC(CC)C(O)=O QMTRBTDPYXTJEN-UHFFFAOYSA-N 0.000 description 1
- WTVNUJRNSNVFID-UHFFFAOYSA-N 2-hydroxypropanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)C(O)=O WTVNUJRNSNVFID-UHFFFAOYSA-N 0.000 description 1
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 241000270722 Crocodylidae Species 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 101000606535 Homo sapiens Receptor-type tyrosine-protein phosphatase epsilon Proteins 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
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- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 206010041349 Somnolence Diseases 0.000 description 1
- 241001415849 Strigiformes Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- SIERTXRCLCLPAR-UHFFFAOYSA-N bismuth;propan-2-one Chemical compound [Bi].CC(C)=O SIERTXRCLCLPAR-UHFFFAOYSA-N 0.000 description 1
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- HFNQLYDPNAZRCH-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O.OC(O)=O HFNQLYDPNAZRCH-UHFFFAOYSA-N 0.000 description 1
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- ITAHRPSKCCPKOK-UHFFFAOYSA-N ethyl trimethyl silicate Chemical compound CCO[Si](OC)(OC)OC ITAHRPSKCCPKOK-UHFFFAOYSA-N 0.000 description 1
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- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
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- 150000004676 glycans Chemical class 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/064—Surgical staples, i.e. penetrating the tissue
-
- 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
- A61L31/041—Mixtures of macromolecular compounds
-
- 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
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/129—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing macromolecular fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/064—Surgical staples, i.e. penetrating the tissue
- A61B17/0644—Surgical staples, i.e. penetrating the tissue penetrating the tissue, deformable to closed position
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/72—Intramedullary pins, nails or other devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/80—Cortical plates, i.e. bone plates; Instruments for holding or positioning cortical plates, or for compressing bones attached to cortical plates
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- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
- A61B17/86—Pins or screws or threaded wires; nuts therefor
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00004—(bio)absorbable, (bio)resorbable or resorptive
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Description
經濟部中央標準局Μ工消费合作社印製 L05i>0i A6 _B6_ 五、發明説明(1) 本發明係黼於在室谌下經由開裂機制而具有增進之永久 變形能力之可吸狀及部份可吸收聚合物質,本發明亦鬭於 此等物質於需要物質可再成形之翳蕖裝置應用方面之用途 。此種應用之一為常會遇到複辕的破碎位置表面輪麻之可 吸收下額與面的骨酪固定片。另一應用為需要蟮進之韌性 及延展性之可暇收外科夾子及鎖環。 修改玻璃質聚合物質Μ增進堅韌性一事巳為非可吸收聚 合物先前技術所熟知。或許最著名之韌化玻璃質薩膠之實 例為高«擊之聚苯乙烯。許多其他非可吸收聚合物巳予改 良以增進堅韌性或酎衝擊性。通常*在毋聚合物基質中· 併入不連續橡腰都會改進堅韌性及耐衝擊性。_似之理綸 巳應用於熱固性物霣如瑁氧樹_。雖然已有非可吸收橡膠 改霣_膠延展性增之報専•但此改霣之主要目的係為賦予 射銜擊性及堅韌性。此性霣改霣方法並應用於可吸收或非 可吸收之醫藥裝置用途。 說明部份A : 本發明係闞於在室溫時經由開裂機制而具有埔進之永久 變形能力之可吸收聚合物霣。本發明亦闞於此類物質於需 要物質可再成形之》藥裝置應用方面之用途。逋類物霣可 能有用之用途包含下列: l可吸收下顎與面骨骼固定片; 2可吸收骨骼嫌躲或其他栓緊裝置; y* '一一 a可吸收外科夾子及鎖瓖; (請先閲讀背面之注意事項再填窝本頁) 裝< 訂· 線< DP 3 本紙張尺度逍用中國Η家標準(CNS)甲4規格(210x297公放) 經濟部屮央標準局員工消贽合作社印製 ^Ο^ϋί Α6 ___ 五、發明説明(2) 4可吸收嫌酪固定桿或螺嫌。 _然未明確舉列銳明•但已雄知可想慊一些物霣可具有 類似於所例示共聚物之性質。為了具有類似性霣,物霣需 具有連績"硬質"相及”軟霣”相。較佳為此软質相應為 非連績性•雖然此點並非必要。為了形成分開之硬質及软 質枏,此硬»及軟質物種在其最终聚合物形式中,需不為 完全相混溶。最终聚合物形式可為嵌段或接枝共聚物或均 聚物及/或共聚物之摻合物。或者•可相混》之聚合物可 用控制之摻合方法•以孵最终物件中之相灌合滅至最少。 下列為包含於本發明之可能替代物霣: 1·形成"硬質”及”软質"相之嵌段共聚物; A. 硬霣相形成箪艚 L 1 一丙交_,d —丙交》或内消旋一丙交_· 2. dl —丙交酷,d對1之比值為可變, 3- 乙交酯· < 乙交酯與丙交酯之混合物, 5- 可形成玻璃轉化溫度高於室溫之可吸收聚合物 之其他單《或單《混合物* B. 軟質相形成單體 I 碳酸三亞甲酷(1 · 3 —二嗶烷一 2 —酮) 2- 對二啤烷嗣9 1 ,4 一二聘烷一2 —嗣) a ε —己内酯(2 —氧化戊嗣或氧代戊一 2 —酮 ) ( 上述1·2·或3之混合物, (請先閲讀背面之注意事項再填寫本頁) D Ρ - 4 - 本紙張尺度遑用中困囷家標準(CNS)曱4規格(21〇><297公放) 經濟部中央標準局貝工消t合作社印製 £055Ci A 6 _ B6__ 五、發明説明(3 ) 5. 可形成具有玻璃轉化ffl度低於室溫之可吸收聚· 合物之其他犟黼或犟牖潙合物· 2."硬霣”及”軟質"可吸收聚合物之摻合物; A. 硬質相形成聚合物 ! 聚(1—丙交_) •聚(d —丙交驩)或聚( 内消》—丙交_ > 2. 丨一丙交_ · d —丙交酷或内消旋丙交_!之共 聚物· a 聚乙交醮, 4. 丙交__乙交酯共聚物, & 具玻璃轉化溫度高於室漘其他聚合均或共聚物 » B. 软»相形成聚合物 I 聚(碳酸三亞甲期) 2- 聚(對一二嗶烷嗣) 3- 聚(e —己内酯) 4- 上述1,2,或3之共聚物, 5. 具玻璃轉化溫度低於室港之其他聚合物或共聚 物0 較佳物霣之堪揮將視最終物件所需之物理性質而定。 較佳物質將拜所需活體内降解及吸收速率而定。可調整若 干變數Μ獲得所需性質吸收速率已知會受姐合物及结晶性 所影W。例如聚(_丨一丙交酷)之硬筲相,由於其疏水性 ,結晶性質•而提供緩慢之降解速率,而乙交_與<11 一丙 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂- 線·
DP 本紙張尺度逍用中國國家標準(CNS)甲4規格(210x297公¢) 經濟部中央標準局貝工消费合作社印製 ^05oui A 6 _B_6_ 五、發明説明(4 ) 交_等量之共聚物•由於其更親水性*非姑晶性霣,而可 搛供快速之降解速率。若鬌要増加塋硬度及強度,則可 加入可吸收饑鰌或鑛維強化物,而製成複合结構°此複合 物之性霣可鞴著在複合物中控制強化物之位置,而獲得缠 一步之改良*例如,若強化物置於曆合繽構之中心面時* 預期複合物之張力(平行豳加於面之力)將比撓曲力(垂 直施加於面之力)更為轚韌,而能》彎曲使其再成形。 本發明掲示由嵌段共聚物所製得之醫藥装置。此嵌段共 聚物係由丙交Κ或丙交釀/乙酯共聚物及低玻璃轉化®度 或橡謬質聚合物如聚碳酸三亞甲酯所構成。就是埴種橡腰 質或柔软嵌段之存在,才會Κ予本申請案中所逋外科修復 裝置在彎曲時之可變形性。 下列具體例概述本發明之Α部份: L包含可變形外科修復装置之製造物件,此可變形外科 修懊裝置係由共聚物所製得*而共聚物係邐自嵌段及接枝 共聚物,此共聚物包含選自包括乙酵酸_及乳酵酸酯鐽 及其混合物之眾多第一鐽脚,及理自包括1 ,3 —二噚烷 —2 —酮;1 ,4 一二啤烷一 2— _及6—己内賄鐽脚之 眾多第二鐽脚,眾多第一鍵聯包含至少約50至約90莫耳% 之共聚物。 2具體例1之物件•其中共聚物為嵌段共聚物。 a具體例2之物件,其中眾多第一鍵聯包含乳__鍵明 〇 4.具體例2之物件•其中眾多第一鐽明ί包含乙酵酸酯鐽 (請先閲讀背面之注意事項再填寫本頁) DP - 6 - 本紙張尺度逍用中困國家標準(CNS)甲4規格(210x297公货) 經濟部屮央楳準局员工消費合作社印製 五、發明説明(5 )聯。 &具«例3或4之物件•其中眾多第二鍵聯包含1 ,3 一二嗶烷一 2—酮鐽職。 &包含可變形费折固定装置之製造物件•可變形#折囲 定裝置侏由共聚物所製得,共聚物選自包括嵌段及接枝共 聚物,此共聚物具有包含乳酸ft鐽聯之眾多第一鐽聯,及 遘自包括1 ,3 —二啤烷一2—嗣及1 ,4一二嗯烷一2 一酮鐽聯之眾多第二鍵_,眾多乳酸鐽_包含50至約80重 最%之共聚物。 7.具體例6之物件,其中共聚物為嵌段共聚物。 a具《例7之物件,其中眾多乳酸鍵賺包含約80重量% 之共聚物。 a具體例8之物件,其中眾多第二鐽明包含1 ,3 —二 晖烷一2 —酮鍵_。 m包含可變形外科修後装置之製造物件,此可變形外科 修復装置係由第一及第二可吸收聚合物之摻合物所製得, 第一可吸收共聚物包含選自包括乙酵酸酷及乳酸醏鐽聯, 及其琨合物之眾多鐽聯•而第二可•吸收聚合物包含選自包 括1 ,3 —二晖烷一 2 —嗣及1 ,4 —二嗶烷_2 —酮及 ε —己内酯鰱聯之眾多鐽聯*第一可吸收共聚物包含至少 約50至約90重量%之摻合物。 11具«例10之物件,其中第一可吸收聚物為均聚物。 12·具體例11之物,其中第一可吸收均聚物基本上係由 乳酸酯鍵_所姐成。 (請先閲讀背面之注意事項再填寫本頁) 裝- DP 7 本紙張尺度逍用中國困家標準(CNS)甲4規格(210x297公货) A6 __B6__ 五、發明説明(e ) ia具«例ίο之物件•其中第一可吸收聚合物為共聚物。 14具體例12之物件,其中第二可吸收聚合物包含選自包 括1 ,3 —二皭烷一 2 —鬵及1 ,4 —二嗶烷一2 —酮鐽 職之眾多鐽馨。 1&具髓例1 ,2,3 · 10 · 11,12或14之物件,其中可 變形外科修復装置為胥折固定裝置。 16·具_例15之物件,其中《折固定裝置為费觴片。 Π-具體例1 ,2,3 · 10,11,12或14之物件,其中可 變形外科修復裝置為夾子。 la具《例1 · 2,3,10· 11,12或14之物件•其中可 變形外科修復裝置為鎖瑭。 la —種用於哺乳物坦織之外科複合结構包括: ®) 由眾多纖維製得之強化姐份,該眾多纖維係由生物 可相容聚合物製得•及 (b) 包含共聚物之生物可吸收姐份, 共聚物係埋自包括嵌段及接枝共聚物*此共聚物包含理自 包括乙酵酸ft及乳酸酯鍵_,及其琨合物之眾多第一鐽聯 ,及選自包括1 ,3—二嗶烷一2 —酮;1 ,4 —二晖烷 一 2 —嗣及e —己内酷鐽_之眾多第二鐽明,眾多第一鍵 鼸包含至少約50至約90莫耳%之共聚物物。 經濟部屮央標準局貝工消t合作社印製 (請先閲讀背面之注意事項再填寫本頁) 20. 具體例19之结構.其中強化姐份係由可吸收之生物可 相容聚合物製得。 21. 具體例20之结構,其中可吸收之生物可相容聚合物係 一 選自包括聚乙酵酸•聚乳酸,聚丁酸羥基酯之均聚物或共
DP 本紙張尺度逍用中國國家標準(CHS)甲4規格(210X297公釐) 經濟部屮央標準局貝工消费合作社印製
OiuCi A6 ____B6_ 五、發明説明(7 ) 聚物,及上述之摻合物,及與聚(1 一乳酸)摻合之聚( d —乳酸)。 22具Μ例13之结構,其中強化姐份係由非可吸收之生物 可相容聚合物製成。 2S具體例22之结構•其中非可吸收之生物可相容聚合物 係選自包括聚對酞酸乙烯_,躲,射綸•聚丙烯·聚乙烯 及聚氧化甲烯及其摻合物。 汉具體例19,20,21,22或23之结構,其中生物可吸收 姐份包括嵌段共聚物。 2&具«例24之结構,其中嵌段共聚物中之眾多第一鍵聯 包含乳酸_鐽聯。 26具體例24之结構,其中嵌段共聚物中之眾多第一鍵_ 包含乙酵酸醮鐽驊。 27.具體例25或26之结構,其中嵌段共聚物中之眾多第二 鍵I»包含1 ,3 —二噚烷一 2 —酮鍵聯。 2Β —種用於哺乳類姐嫌之外科複合结構•包括: (a> 由眾多孅維所製得之強化姐份,此眾多纖維係由生 物可相容聚合物所製得,及 (b) 包含第一及第二可吸收聚合物之摻合物之生物可吸 收姐份,第一可吸收聚合物包含選自包括乙酵酯及 乳酸酯鍵聯,及其混合物之眾多鐽聯,且第二可吸 收聚合物包含堪自包括1 ,3 —二晖烷一 2 —画· 1 ,4 — 烷一2 —嗣及e —己内_雄_之眾多 鍵聯,第一可吸收聚合物包含至少約50至約90重量 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂- 線· DP 9 本紙張尺度逍用中國國家欉準(CNS)甲4規格(210X297公潑) A 6 B6 五、發明説明(8 ) %之摻合物。 2a具黼例28之结禱,其中強化姐份係由可圾收之生物可 相容聚合物所製得。 30L具艚例20之结構,其中可吸收之生物可相容聚合物係 選自包括聚乙酵酸,聚乳酸·聚丁酸羥基賭之均聚物或共 聚物,及上述之摻合物,及與聚(1_乳酸)»合之聚( d 一乳酸)。 31·具體例28之结構,其中強化姐份係由非可吸收之生物 可相容聚合物製得。 32具體例31之结構,其中非可吸收之生物可相容聚合物 係選自包括聚酞酸乙烯釀,躱,酎綸*聚丙烯•.聚乙烯及 聚氣化甲烯及其摻合物。 3a具»例28,29 · 30,31或32之结構,其中生物可吸 收姐份中之第一可吸收聚合物為均聚物。 具《例33之结構,其中生物可吸收姐份中之第一可吸 收均聚物基本上係由乳酸酯鐽驊所姐成。 35具體例28,29 ,30,31或32之结構,其中生物可吸 收姐份中之第一可吸收聚合物為共聚物。 經濟部屮央標準局貝工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 36具«例35 3之结構,其中生物可吸收姐份中之第二可 吸收聚合物包含選自包括1 ,3 —二啤烷一 2 —酮及1 * 4~二嗶烷一2 —酮鍵明之眾多鍵賺。 參考本部份A中,上述次分段5,6,9,10及14·及 一般述於本說明*_中之具體例,有些聚合物已被敉述為一 或多種單«8之鍵聯。這些單體中有些,則被敘為瓌狀酗, DP 1 〇 本紙張尺度逍用中闽國家標準(CNS)甲4規格(210x297公龙) 五、發明説明(9) 如1 ,4一二嚅烷一2—酮。要了解的是熟誧本技藝之任 何人士必然知道如何製得及如何使用此等單鱷·K形成聚 合物鍵驊•因此•使用埴種犟麵命名來說明逭些鐽聯已很 足夠。 參考本部份A中,上述次分段1 ,6 · 10及15之具«例 •應淸楚了解的是外科修復及脅折固定裝置包含•但不限 於本部份A中上述次分段16至8所述之具《例。因此,其 他裝置如#賂扣針,脅胳桿•骨胳鏍絲,套管針·彌補科 管畎物件•及類似或相闞之横製或擠壓成型裝置均在本發 明範内。 參考本部份A中,上述次分段19及28*強化份中之眾 多纖維可為蓆狀,切碎•《織*針織,軍一方向或纖維束 。眾多纖維亦可由曆合板構成•其中各板由連鑛性,睪一 方向纖維,掮纖孅维或針織物所姐成•且相鄰板間之纖維 方向不必相同。 «括參考本部份A中之次分段19至30·有闞複合结構之 製進需了解的是生物可吸收姐份之熔點須比強化姐份之熔 點低亦可紙括參見實例12。 經濟部屮央標準局β工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 參考本部份A中上述次分段20至29之具體例•應了解的 是除了本部份A中次分段21及30分別所述之聚合物外,亦 可使用其他可吸收聚合物。其他可吸收聚合物包含上述 "部份A說明”中次分段1 A及2A中所述者,此說明並 非唯一的。 本發明將K下列實例作_一步之敘述: DP 11 本紙張尺度逍用中國Β家標準(CNS)甲4規格(210x297公煃) ,〇GbGi Μ 五、發明説明(κ>)» m ι i,—芮夺酗一= 嵌》物 在182 1C攪拌之反應罌中將聚合级1 · 3_二轉嫡一2 —鬭(磺酸三亞甲醣•後文藺稱為TMC > (97.5克, 0.995莫耳 > ,二乙二酵(下文籣稱DEG ) ( 4.20x 102克 ,4·0 xlO·4莫耳),及DabcoT — 9觸媒(由美臞空氣 產物有限公司觭售之2 —乙基己酸亞鍚觸媒配方,後文籣 稱 T — P) ( 1.35χ ΙΟ-2 克,3.3 X 10_*霣耳)混合。升 高濩度至188 t: ·混合物在此溫度攪拌1 -1/2小時加入聚 合级1 —丙交醮•且將漘度升高至200145分練後•聚合 物自反應器中卸出並令其固化。 所得聚合物具有〇.89dl/g (0.5g/dl之濃度於CHCU中 >之固有黏度(後文籣稱IV)。在此實例及《後實例中用 Μ定義共聚物姐成物之習憤為"莫耳%丙交》”。此代表 共聚物中併入某種奠耳%之丙交酯單«所將形成之共聚物 中之單元含量。此共聚物之姐成M UMR偵测發現為 20.7莫耳% 1 —丙交_。 將聚合物溶於二氯甲烷(5g/dl)中,且鏞成約0.003 ...................- .- ...... ...........- - .· . .- : - ...... - .....· . .......... 吋厚度之薄膜。所得物霣發現室溫時為橡稼質。 (請先閲讀背面之注意事項再填寫本頁) 經濟部屮央標準局员工消费合作社印製 DP 12 本紙張尺度逍用中國國家標準(CNS)甲4規格(210><297公龙) 經濟部中央標準局貝工消#合作社印製 205bGl A6 _B_6_ 五、發明説明(11) 實例2 1 _而夺醮一鏞醵三亞明物 HI 聚合级 TMC (97.5 克,0.995 莫耳),DEG (4.20x 102克· 4.0 X 1〇-Α莫耳 > ,及 T - 9 觸媒(1.35χ ΙΟ·2 克,3.3 xl〇-6莫耳 > 於180 Ό攪拌之反應器中灌合及在 40RPM播拌1小畤又20分鐘。加入聚合級1 一丙交酸( 52.5克,0.364莫耳),且將溫度升高至200 。1小時 後,聚合物自反應器中卸出,並令其固化。接著围黼聚合 物在25 t:下減壓去揮發· Μ除去殘餘睪_。 所得共聚物具有〇.64dl/g <0.5g/dl瀟度於CHCU中) 之固有黏度姐合物MR澜定發琨為25.7莫耳%之1 一 丙交_。 將聚合物溶於二氮甲烷(5g/dl) *並鏞成0.003时厚 度之薄_。所得物質在室灌時發規為橡膠質。 窗俐 1 —丙夺曲一破醻三亞申Bfe嵌段共聚1 將聚合级THC( 64.99克,0.637莫耳),DEG(1.83x 10 - 2 克,Ϊ: 7 3 X ί(Τ 4 莫?),及 T — 9 觸媒(8.0 X 1 0 - 3 克· 2.Ox 10_B莫耳)於180 1C攪拌之反應器中混合,並 在40RPM攪拌35分鏟。加人聚合級丨一丙交_ (154.29克 ,1.07舆耳)•且將湄度升高至190 t:。4小時後,聚合 物自反應器中卸出·且令其固化。 (請先閲讀背面之注意事項再填寫本頁) 裝< 訂· 線. DP 13 本紙張尺度逍用中固國家標準(CNS)甲4規格(210x297公 £05501 A6 _BJ_ 五、發明説明(12) 所得共聚物具有1 .〇ldl/g (於CHCU中之濃度為 0.58/<11>之固有黏度姐合物以1({-»)^檢測發現為62.6莫 耳% 1 —丙交酯β 用於测試樣品製備之飾板係使用加热水力壓结機形成。 在200 t:之壓结灌度,約23克之乾聚合物顆粒在饑氟觴 TM (美圃杜邦公司產品)塗覆之脫除期裡織物閨之4 -1/4吋X 4 -1/4时X 1/16吋綱框中,M500磅壓力壓结4 分鐘,接著壓力增加至50 00磅壓結4分鐘。此热»板在冷 凍之鋁板間冷卻。飾板自框架中移出,並於130 t及約 250磅(14psi )颸力下壓結中退火5分鐘。 當此物質在室湛下彎曲時,發現可經由開裂而_行延展 變形。 奮例4· 1 —丙交酷一礓醵三亞田曲描》社轚物 將聚合级1(:(64.99克,0.637奠耳),0£6(1.83乂 1〇-2 克,1.73xl〇-4 荑耳)* 及 T — 9W 媒(2.06x 1〇-2克〉在180 "C攪拌之反應器中混合,及在40 RPM攪拌 35分鐘。加入聚合级1—丙交_ ( 1 54.29克·1.〇7莫耳) 經濟部中央橾準局貝工消t合作社印製 (請先閲讀背面之注意事項再填寫本頁) ,且將溫度升高至190 υ。1小時又45分鐘後•聚合物自 反應器中卸出,並令其固化。將聚合物冷凍研磨並在105 Ό下稟空鲜嫌1Μ、時。 DP 14 本紙張尺度逍用中困國家標準(CNS)甲4規格(210X297公¢) L05iiCl A 6 _B6_ 五、發明説明(13) (請先閲讀背面之注意事項再填寫本頁) 所得共聚物具有1.44dl/g (於CHCU中為0.5g/dl澹度) 之届有黏度,姐成MU MR檢測8現為60.5莫耳% 1 —丙 交_ ° 依據實例3之方法•形成用於瀏試樣品製備之飾板。 當此物質在室溫下《曲時•發現可經由開裂進行延展變 形。
啻期(R 1一丙夺釀一雄醵=西甲曲«»#躉物 將聚合級TMC( 45.94克,0.450|¢耳),DEG(1.59x 102克,1.49x10 — *莫耳〉,及 T — 9 觸媒(l.?lxl〇_2 克,4.48 χ10_β莫耳)於180 拌之反應器中琨合*並 以40RPM播拌30分鐘。加人聚合级1 —丙交IS (151.35克 ,:1.07舆耳)*且將溫度升离至195 t:。2小時後,聚合 物自反應器中卸出*並令其固化。將固體聚合物冷谏研磨 •且接著在105 ΐ:下滅壓去揮發,Μ除去殘餘單體。 所得共聚物具有1.49dl/g (於CHCU中溻度為0.5g/dl) 之固有黏度,姐成以1H-NMR偵測發現為68.3奠耳% I —丙 交酿。 • — - · — - - — — —- - —------------- ------------------------- ------------ _ _________..... 依據霣例3之方法•形成用於廁試樣品製備之飾板。 當物質在室溫下彎曲時,發規可經由闋裂而進行延展變 形° DP - 15 - 本紙張尺度逍用中國國家標準(CNS)甲4規格(210x297公釐) 經濟部屮央標準局貝工消费合作社印製 ^O&bCi. A€ _B6_ 五、發明説明(W) 奮例6. HI —两夺》1 —理_三嵌段社臺物 將聚合级1^(:(33.2克,0.325 舆耳),0£6(1.72乂 102 克,1.62χ1〇-4莫耳),及 T — 9 觸媒(7.6xl0_s 克 ,1.87 χΙΟ _β莫耳)在180 1C擭拌之反應器中港合,及以 401^»1播拌35分鏞》加入聚合级<11一丙交_(186.8克· 1.296莫耳),且將《度升高至195 *C。3小時又40分鏟 後,聚合物自反應器中卸出*並令其固化。將固黼聚合物 冷凍研磨》接著在25 t:下減壓去揮發18小時,Μ除去殘 餘單體。 所得共聚物具有1.05dl/s (在CHCU中為0.5g/dl壤度) 之固有黏度,姐成MI-NMR偵澜發瑀為78.6莫耳%«11-丙 交酯。 依據實例3之方法•形成用於测試樣品製儋之飾板。 當此物質在室潘下彎曲時·發現可經由闋裂而進行延展 變形。 奮俐7 1 一丙夺曲一 I»期三亞甲曲嵌»共聚物 將 W 爸组 T M C ( BT 2 冤—Τ—Τ: Μ 茸 1 0 - 2 克,1 · 6 2 X 1 0 - 4 莫耳),及 T — 9 «I 媒(7 . 6 X 1 0 - 3 克,1.87xlO_B莫耳)於180 1C攪拌之反應器中混合•並 在40RPM下攪拌35分鐘。加人聚合级I —丙交酯(186.8 •声一 克· 1 . 296奠耳),且將溫度升高至195 1C。3小時又40 (請先閱讀背面之注意事項再填寫本頁) 裝. 訂- 線- DP - 16 - 本紙張尺度边用中國國家標準(CNS)甲4規格(210X297公龙) 經濟部屮央標準局貞工消费合作社印製 Α6 Β6 五、發明説明(i5) 分鏟後,聚合物自反應器中卸出,並令其固化。將固Μ聚 合物冷凍研磨•接謇在105 υ下減壓去揮發18小時,以除 去殘餘犟Μ。 所得共聚物具有1.5 6dl/g (於CHCU中為0.5g/dl «度) 之固有黏度,姐成MU MR偵測發現為79.1荑耳% 1 _丙 交ft。 依據實例3之方法,形成用於测試樣品製備之鲰板。 當此物質在室潘下彎曲時,發現可經由開裂而進行延展 變形。 窨俐ft 1 一丙夺醸一》醻三亞甲_嵌段共»物_ 將聚合級 TMC (16.1克,0.158 莫耳),DEG (1.67x 10-2克,1.57xl0-4莫耳),及T一9觸媒(6.37x 10-3克,1.57xl〇-B荑耳)於180 C攪拌之反應器中混合 ,及在40RPM攪拌27分鏟。加人聚合級丨一丙交醏( 203.9克,1.415莫耳),且將溫度升高至195 。6小時
後,聚合物自反應器中卸出,並令其固化。將固體聚合物 冷凍研磨·接著在100 C下減壓去揮發18小時’ W移除殘 餘單體Q 所得共聚物具有1.41dl/g (於CHCU中為0.5g/dl瀠度) 之固有黏度,狙成M UMR偵測發現為89.6舆耳%丨-丙 交酯。 __ 依據實例3之方法,形成用於測試樣品製備之飾板。 DP - 17 - 本紙張尺度逍用中國Η家標準(CNS)甲4規格(210x297公釐) (請先閱讀背面之注意事項再填寫本頁) 裝· A6 _B_6_ 五、發明説明(16) 當此物霣在室湛下彎曲時,發現在破裂前會進行少許延 展變形及闋裂。 窗例9 1 — W夺曲一 gf_三亞甲曲嵌段共蟹物 將聚合级TMC(7.66克,0.075奠耳>*DEG(1.69x 1〇-2克,1.59x10—莫耳),及 T — 9 觸媒(1.82x 10-2克*4.45 xl0_e奠耳)於180 υ攪拌之反應器中港合 ,並在40RPM攪拌21分鐘。加入聚合級1 一丙交W ( 205.34克,1 . 425莫耳),且將通度升髙至195 t:。3小 時又40分鏟後,聚合物自反應器中卸出•並令其固化。將 固«聚合物冷凍研磨,接著在100 υ下減壓去揮發18小時 ,以除去殘餘單體。 所得共聚物具有1.6 5dl/g (於CHCU中為0.5g/<H«度) 之固有黏度,姐成M M-HMR偵拥發現為95.3奠耳% 1 —丙 交釀。 依據實例3之方法•形成用於测試樣品製備之飾板。 當此物霣在室溢下彎曲時*未發現會進行延展變形。 經潦部屮央標準局貝工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) I 一丙夺fe — TMC共«物夕熟分析 K差動掃瞄量熱計(DSC)分析《例3至9所得之共聚 物樣品。掃瞄條件為-40¾至200 t:在氮氣中最低為20*0 。可形成兩僩無晶形相之該等共聚物可由兩個玻璃轉化溫 DP - 18 - 本紙張尺度边用中國Η家標準(CNS)甲4規格(210X297公货) ^05U0i A 6 B6 五、發明説明(17) 經濟部屮央標準局貝工消f合作社印製 度(Tg(l)及 Tg(21))確 定 。除了使用 d 1 - -丙 交 酯所 製 得之 實例 5 以 外 ,所有實例 亦 具有Μ熔點 (Τ·)及 熔 融病 (Δ Hf)為特微之结 晶相。此分析之结果示於 表] L c ► 表 1 聚合 物 1 — 丙交_ Tg (1) Tg(21) (Τ·) (△ Hf ) 實例 奠 耳96 (V ) (V ) (Ό ) (卡/克) 3 62 .5 ~ 8.8 55. 8 167 . 6 7 . 28 4 60 .5 -12.5 57. 8 171 . 4 8. 76 5 68 .3 -10.3 57. 3 171 . 1 8 . 86 6 78 .8 (dl) -4.1 49. 6 -- - - 7 79 .1 -12.5 59 . 4 172. 7 11. 63 8 89 .6 -- 60 . 3 175 . 0 11. 85 9 95 .3 — 65 · 8 174. 8 12 · 12 窨例1 1 丙 交 IS — TMQ # K物之椭» 蒯試 將 實 例 4 至8所製得 之 飾板切成澜 試用樣 品 Μ便 依 據 ASTH 方法D638 (拉張) 及D790 (撓曲) 試驗< /此測試之 结果 包 含 於 表2中。拉 張 測試共使用 5個複 製 品, 且 其平 均值 列 於 表 2 。 表2中 所 列之撓曲值 為4個 複 製品 之 平均 值0 DP 19 本紙張尺度边用中國國家標準(CNS)甲4規格(210x297公货) (請先閱讀背面之注意事項再填寫本頁) 裝· *?τ_ 線-
66 AB 五、發明説明(18) 教_2. 枪#feM (ASTM Dfi^) 樣品 1-丙交_ 荑數 跛裂時之 屈伏時之 強度 應力 強度 應力 實例 莫耳% (103 psi) (103 psi) (101 96) (103 psi) (96) 4 60.5 240 4.6 10 4.9 3.9 5 68.3 310 5.7 12 6.3 3.7 6 78.8(dl) 400 4.4 2.0 6.6 2.4 7 79.1 400 6.3 0.5 7.6 2.7 8 89.6 480 7.3 0.43 8.7 2.4 9 95.3 520 8.1 0.18 — . — 擁曲结果CASTM 790 4 60.5 260 7.5 12 9.0 5.5 5 68.3 340 9.4 12 11.4 5.1 6 78.8(dl) 390 7.7 11 10.4 3.8 7 7S.1 480 11.8 12 14.7 4.8 8 89.6 620 17.2 6.15 18.1 4.8 9 95.3 710 14:5 2.16 一 -- 經濟部屮央標準局A工消f合作社印製 (請先閱讀背面之注意事項再填寫本頁) DP - 20 本紙張尺度逍用中國圉家標準(CNS)曱4規格(210X297公釐) 200bGl A6 __B6_ 五、發明説明(19) 撓曲及拉萇结果表示具有60至90重量%丙交酯之共聚物 會形成經由開裂而進行延展變形之物質。於骨骼板應用上 被铒為需具有最高棋數及屈伏強度,而同時保持延展性。 骨骼板應用之較佳姐成,在兩交酗一 TMC嵌段共聚物之情 形而言,因此將為80至9 0%丙交»。丙交醏90%以上時, 樣品將喪失延展性,而丙交醣80%M下時,横數及屈伏強 度膊持績降低,而不具撓曲被裂時之應力所潢I得之Μ展性 之任何優點。 奮锎1 梅合物脚推 複合物係以下列方式製得。膊聚(乙酵_) (PGA)饑 維(100克/丹尼)》繞在7-3/4吋平方之不携綱板上。 期維覆蓋緬板之兩蠼3” X 7-3/4”部份,而畏尺度與纖维 排成一嫌。用於此搡作之纖維重悬為12.0克。 經濟部中央標準局R工消费合作社印製 (請先閲讀背面之注意事項再填寫本頁) 於二氯甲烷中製備實例7聚合物之l〇g/dl溶液然後將聚 合物刷於纖維上並Μ空氣乾烽。重複數次。此物質接著於 170 υ之加熱壓结拥中凝固•並冷卻至室溫。此使纖維可 切剌*並自板之前端及後皤移除兩個半段。另外之聚合物 溶液則施用於兩段上。繼纘此播作,直至加至纖维上之聚 合物總最為19.0克為止。兩個半段在170 t:之潙度下*興 空®结成1/16时厚度。褸合物自壓结櫬中取出•且在110 C之空氣烘箱中退20分鐘。複合物中PGA之終重量份為 39%。 DP 21. 本紙張尺度逍用中國a家樣準<CNS)甲4規格(210X297公釐) 205bGi A 6 B6 五、發明説明(20) 將此板切成l/2"xl/$”拉張試驗檨品*並依ASTM D638 (美_,賓州,美圏試驗材料協會 > 進行测試。拉伸棋數 為 0·99χ10β psi ,且拉張強度為 37.0xl03 psi。 兩届拉張樣品在Instron試驗機(美國Instron有限公 司)中撓曲予Μ應變至5%。當負載解除時•樣品永久變 形成約2%應變。搞曲棋數為1.27xlOe psi且5%應變 之捎曲應力為21 . 6 X 103 ps i 。
捕份R 先前技藝掲示某種含有0.05至20%對肽酸乙烯酯( 經濟部中央標準局员工消t合作社印製 (請先閲讀背面之注意事項再填寫本頁) ” PTFE”微纖維顆粒之非可吸收物質。PTFE被择述為可用 作為改良某種熱塑性物霣之黏度及熔融彌性之添加劑。先 前技術亦掲示一種製造含10至20%PTFE及热醴性聚合物之 橫製姐合物之方法。此姐合物纆發現可提供增強之衡擊強 度。先前技術亦擢示一種於其中併入0.1至2.0 % PTPE乳 液之聚對ft酸乙烯醮之姐合物。此PTFE添加劑據稱改良加 工性能。其亦掲示PTFE又可出乎意料地it加最终姐合物之 最终伸長率。在任何先前技藝中,並未提及此等物霣作為 可變形物件之有用性而且亦未提及其B藥產物之有用性 ,¥ ¥ i ¥¥¥—¥ 物。總 i ¥ 玉,冤 •無一提及此可吸收物質輿PTFE结合作為B蕖裝置之有用 性。此可吸收物霣與PTFE在室溫時經由開裂而圼永久變形 DP 22 本紙張尺度逍用中國國家標準(CNS)甲4規格(210x297公釐) 20i3b〇l A6 ___B6_ 五、發明説明(21) 下列具《例観述本發明部份B : L包含可變形外科修復装置之W造物件,此可變形外科 修復裝置係由可吸收物霣所製得•此可吸收物質具有包含 選自包括乙酵酸酯,乳酸ft,1 ,3 —二嚅烷一2 —钃及 1 * 4 一二噚烷一 2 —酮鲢W之鐽賺之聚合物,此外科修 復裝置又可由非可吸收物霣製得。 2:具《例1之物件,其中非可吸收物霣包含由氟化破氬 化合物所製得之聚合物。 a具體例2之物件•其中可吸收物霣包括均聚物。 4具《例3之物件*其中可吸收物霣包含基本上由乙酵 酸酯鐽聯所姐成之均聚物。 &具«例1 ,2或3之物件,其中可吸收物霣包含基本 上由乳酸醮鍵職所姐成之均聚物。 a具體例1或2之物件,其中可吸收物質包含由乙酵酸 醮及乳酵酸醮鰱脚所構成之共聚物。 7. —種包含可變形姐織修復裝置之製造物件•此可變形 姐纖修復裝置係由可吸收物質所製得,可吸收物霣具有基 本由選自包括乙酵酸賭•乳酸酯及1 ,4 一二晖烷一 2 — 酮«脚之«聯所姐成之第一均聚物·並與包含選自包括乙 酵《酗,,厂;3—=二 — 2 ΐ —,—7 = ^ 經濟部屮央標準局A工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 啤烷一2 —嗣及e —己内酷鍵聪之至少兩種不同鐽聯之第 二共聚物摻合*此姐嫌修復裝置又可由非可吸收物質製得 〇 a具體例7之物件•其中非可吸收物質包含由氟化碳氫 DP - 23 - 本紙張尺度逍用中a B家標準(CNS)甲4規格(210x297公龙) 五、發明説明(22) 化合物所製得之聚合物。 a具艚例8之物件,其中第一均聚物基本由乙酵酸釀鐽 職所組成。。 m具《例7或8之物件,其中第一均嫌物基本上由乳酸 «鰱_所姐成。 ϋ具《例9之物件,其中第二共聚物包含乙酵酸醮及礦 酸三甲酯鐽聯。 12. 具*例7,8 · 9或11之物件,其中第二共聚物包 含乙酵酸tt及乳酸__聯。 13. 具《例2 · 3,4,8,9或11之物件,其中非可 吸收物質為聚四氟乙烯。 14. 一種包含可變形外科修復裝置之製造物件,此可變 形外科修復装置係由可吸收物質製得,此可吸收物質具有 包含選自包括乙酵酸醮,乳酸_及1 ,4 一二晖烷一2 — 酮鍵_之鐽聯之第一均聚物•並與包含選自包括乙醇酸酯 經濟部屮央櫺準局β工消f合作社印製 (請先閲讀背面之注意事項再填寫本頁) ,乳酸醏,1 ,3 -二嗶烷一 2 -酮,1 ,4 一二啤烷一 2 —酮及e _己内醏«聯之至少兩種不同«聯之第二共聚 物摻合;此可變形外科修復裝置又可由非可吸收物質製得 *此非可吸收物霣包含選自包括聚四氟乙烯之聚合物及氟 化乙烯一丙烯共聚物;此非可吸收物霣占裝置_重量之約 0.01% Μ下至約1 %以下。 15. 具體例14之物件,其中第一均聚物基本上是由乙酵 酸酗踺聯所姐成。_ 16. 具《例14之物件,其中第一均聚物基本上是由乳酸 DP - 24 - 本紙張尺度边用中國國家標準(CNS)曱4規格(210X297公龙) £05ϋ0ΐ Α6 __ 五、發明説明(23) _鰱_所姐成。 17. 具《例15之物件•其中第二共聚物包含乙酵酸W及 碳酸三亞甲釀鍵驊。 18. 具《例14, 15, 16或17之物件•其中非可吸收物霣 為聚四氟乙烯〇 19. 具艚例18之物件•其中非可吸收物霣占裝置重量之 約0.02%Μ上至約0.5 下。 20. 具《例19之物件,其中非可吸收物霣占約0.1 %。 21. 具體例 2,3,4,8,9,11,14, 15或 17 之物 件,其中非可吸收物霣為微粉碎者。 22. 具體例 2,3,4,8 · 9 · 11,14, 15 或 17 之物 件,其中非可圾收物侏呈微原纖吠。 23. 具 *1 例 2,3,4,8,9,11,14, 15或 17之物 件,其中可變形修復裝置為脅折固定裝置。 24. 具《例23之物件,其中骨折固定裝置為#骼板。 2 5 .具體例 2,3,4,8,9,11,14 , 15 或 17 之物 件,其中可變形修復裝置為夾子。 26.具腰例 2,3 · 4,8,9,11,14, 15 或 17 之物 件,其中可變形修復裝置為鎖瑁。 ......-· — · —*——· —· — - - —----— ·- ----------- ..—- -. ...... . . . .· .... ........... ......- — - „. ___________ , _— 經濟部屮央楳準局貝工消费合作社印製 (請先閲讀背面之注意事項再填寫本頁) ( 參考本部份Β之上述次分段1至7之具«例,將可清楚 了解此非可吸收物質係限於可促進開裂之物霣之非可吸收 姐合物。聚合物物質之開裂櫬制已為本技藝所热知,但須 注意的是先前技HJS乎總是明告此開裂機制並非為儇點。 因此•本申謫案所說明之本發明已知先前技藝即告知者完 DP - 25 - 本紙張尺度边用中國Η家標準(CNS)甲4規格(210x297公龙) 205b0i A 6 B6 經濟部屮央標準局员工消费合作社印製 五、發明説明(24) 全不同。 參考本部份B中上述次分段1 · 7及14之具《例•且通 常述於本銳明害中者*某些聚合物巳被敘述為一或多種單 Μ之鐽職。埴些單體之某些被敘述為環狀醮,如1 · 4 一 二嗶烷一 2 __。須了解的是热悉本技藝者纗對知道如何 製得及如何使用埴些犟體,以形成聚合物鍵馨,因此•使 用埴種單«命名來說明道些鐽驊巳很足狗。 參考本部份Β中上述次分段1 ,7,14及23之具嬲例, 將可淸楚了解外科修復•姐孅修復及骨折固定装置包含, 但不限於:述於本部份Β中上述次分段24至26+具讎例。 因此,其他装置,如#骼扣針,骨骼桿,骨翳螵絲,套 針,彌補管物件及類似或相闢横製或擠壓成型装置都在本 發明之範麵内。 參考本部份Β中上述次分段21及22之具體例’微细碎狀 或微原纖狀之氟化碳值化合物之敘迷,及特別是聚四氟乙 烯已掲示於先前技β中。 部份Β敘I 本發明係闞於部份可吸收聚合物質,其具有在室溫時, 久一¥ i三Μ力。* i i赤tt於此 類物質於需要物質可再成型之》葯裝置應用方面之用途, 造類物質可使用之臁用包含下列: 1. 下顎與面贵骼,定板。 2. 骨骼孀躲或其他栓緊裝置。 (請先閱讀背面之注意事項再填寫本頁) 裝· 訂_ DP 26 本紙張尺度逍用中H a家標準(CNS)甲4規格(210X297公¢) 經濟部中央標準局员工消費合作社印製 £05S〇i A6 ___B6_ 五、發明説明) 3.外科夾子及纈環。 _然並未明確舉例說明•但認知可想像一些可擁有與所 睾例姐合物類似性霣之物質。為了具有類似性霣,物霣霈 具有連鑛”硬質"相及”軟:霣”相。本發明中之軟質相為 PTFE。此PTFE已與可形成硬霣相之一般堅硬可吸收物質調 合,此調合偽藉著在PTFE粉末之存在下,豳用剪力至熔鼬 聚合物中而達成。下列為包含在本發明中之替代物質: 硬質相形成可吸收聚合物 1.聚(1-丙交酯•聚(d —丙交酯)成聚(内消旋一 丙交酯> 2.1 —丙交酯及d —丙交_之共聚物 3. 聚乙交酯 4. 丙交__乙交_共聚物 5. 被玻璃轉化湩度高於室溫之其他聚合物或共聚物。 較佳物霣之揮將視最終物件所需之物理性質而定。較 佳物霣亦將由所需活體内降解及吸收速率所決定。可調轚 若干變數Μ獲得所需性霣。吸收速率已知會受姐成及结晶 性所影響,例如,聚(丨一丙交酯〉之硬霣相由於其疏水 及结晶性霣,故可提供埋慢之降解速率•而乙交酯輿d 1 —丙交醏等量之共聚物εϊ :故 可提供快速之降解速率。若需要增加堅韌性或強度*可添 加期維或嫌物強化物,以製成複合结構。複合物性質之進 一步改良可藉著控.荆複合物中強化物之位置而達成,例如 若強化物置於層合结構之中心面時,預期裡合物在拉張方 (請先閲讀背面之注意事項再填寫本頁) 裝. 訂· 線- DP - 27 - 本紙張尺度通用中國Η家標準(CNS)甲4規格(210x297公釐) 經濟部中央標準局貝工消t合作社印製 A6 _____B6_ 五、發明説明(26) 面(平行豳加於面之力)將仕撓曲方面(垂直胞加於面之· 力)更具堅«•而可鞴彎曲再塑型。 本發明HIM下列賁例敘述: 含0.1 %_覦轤之»乙交_ 將購自美國Davis及Geek Vayne, NJ之聚乙交酯(63克 >置入美_C. W. Brabender儀器公司,NJ製造之電子薩 性記錄器钃之混合頭中。將聚合物加热至其熔融溫度,並 在40 γρ·下混合,同時加入0.063克之嫌氟觴TMDLX 6000粉末(美國杜邦公司)。棍合速宰増加至75 ΓΡΒ混合 2分鐘,且將熔融酒合物自混合頭移出•並冷卻至室《。 奮例14 含0.1 %繕覦艟7·夺醮 使用實例13之步驟,Μ製備0.63克鐵氟》ITMDLX 6000粉 末於63克聚乙交酯中之摻合物。 窨例1 5 食0.1 %供龜W之聚7· 1» —(ϋ曲一—i二ϋΤι»至亞 甲 _ ) ( 50/ 50审· bh 例) 使用貢例13之步驟,Μ將0.1重躉%之鐵氟篛*^01^ 6000粉末混合人5g/ 50重量比例之聚乙交醋及聚(乙交醏 -共一碳酸三亞甲K)摻合物中。50/ 50重量比例之摻合 DP - 28 - 本紙張尺度边用中國國家標準(CNS)甲4規格(210X297公龙) (請先閲讀背面之注意事項再填寫本頁) 裝- ,可* A 6 B6 五、發明説明(27) 物係得自美園Davis及Geek, Vayne N.J.公司0 窗拥1 fi 含0.1 %議觎鱷夕嫌乙夺tt/g (乙夺曲一共一«_三gg 申曲 1 ( 75/25¾ 噩 fch «η 使用實例13之步驟,以將0.1重量%之鐵氟^TMD LX 6000粉末混合人75/ 25重量比例之聚乙交醏及聚(乙交酯 一共一礙酸三亞甲_)摻合物中。 竇例17 描製《6板 將實例13至16之聚合物-嫌氟籠TM摻合物棋製成1/16" 厚板*其法係在用1/16时厚度隔條隔開之兩Η塗覆著嫌鎮 籠"^之《板間,在230 υ之溫度及5 55 psi之壓力下將各 摻合物加热1分鏟。 令飾板冷卻至室灌,接著切成1/4时宽之長條,用以手 工測試此條狀物在周園湛度下如何可易於變形〇手工澜試之 结果概述於表I 。 ~ — " -----— — ...- - —------------- _______ 經濟部+央標準局员工消费合作社印製 (請先閱讀背面之注意事項再填寫本頁) SLM—li &J§Ll 對照姐長條係依上述實例17之步驟,由不含級氟龍TM 顆粒之聚乙交酯製,。對照姐長條接著K上述方法進行手 工澜試。對照姐長條之手工澜試结果概述於表3。 DP 29 本紙張尺度逍用中S困家標準(CHS)甲4規格(210x297公釐) 205501
66 AB 五、發明説明(28) 表-_3— 洽可彩成可曲收麕会物 實例 聚合物 嫌氟觴Vt% 最大變曲度 註解
PGA .0 90-100 當彎曲超 過 90-100 時破裂 (請先閲讀背面之注意事項再填寫本頁)
2 PGA 0 . 180 部份回彌 (約 25X) 3 3 50/50重量 0 比例之 PGA/P (GLY/THC)42 摻合物 180 回彌(大於 50% ) 75/75重量 比例之 180 回彈(大於 經濟部屮央標準局CX工消费合作社印製 5
DP PGA/P (GLY/TMC) 摻合物 P G A對照矩U 〇 30 50% ) 些微變形 破裂
,〇5bOX A6 B6 五、發明説明(29) (1) PGA :聚乙交_ (2) |>(6 17/1»<(:):述於美«專利第4,429.080號之聚(乙 交酯-共一碳酸三亞甲酯)此専利併於此以供參考。 (3) 在釋除進行180"彎曲所需之力時,某些摺璗長條即 打開。 (請先閲讀背面之注意事項再填寫本頁) 裝· 線· 經濟部中央標準局Μ工消费合作社印製
DP 31 太板彷疋泞m巾团团玄燸規格(2〗0父297公修)
Claims (1)
- «專婀肀爾業 y#正本(f么年·>月)^ A7 B7 C7 D7 六'申請專利範® 1 ·—種可變形外科修復裝置,其由包含眾多第一及第二鍵 聯之可吸收共聚物或由第一及第二聚合物之可吸收摻合 物所製得,此共聚物第一鍵聪及摻合物中之第一聚合物 係選自包括乙醇酸酯及乳酸酯鍵聯,及其混合物;而共 聚物第二鍵聯及摻合物中之第二聚合物係選自包括1 , 3 —二啤烷一 2 —嗣,1 ,4 一二噚烷_2 —嗣及4 一 己內酯鍵聯,眾多第一鍵聯或第一聚合物占各該共聚物 或摻合物之至少50至90莫耳%。 2. 根據申請專利範圍第1項之装置,其中可吸收共聚物為 嵌段或接枝共聚物。 3. 根據申請專利範圍第2項之装置·其中可吸收共聚物為 嵌段共聚物,而該眾多第一鍵聯包含乳酸酯鍵聯,且第 二鍵聯包含1 ,3 —二嗶烷一 2 —嗣鍵聯。 4. 根據申請專利範圍第1項之装置,其中可吸收摻合物中 之該第一聚合物為基本上由乳酸酯鍵聯所構成之均聚物 〇 , 5. 根據申請專利範圍第1項之裝置,與由生物可相容聚合 物製成之眾多纖維所製得之強化姐份姐合。 绥濟部中央搮準扃印^ (請先閱讀背面之注意事項再填寫本頁) 6. 根據申請專利範圍第5項之装置,其中強化姐份或由選 自包括聚乙酵酸*聚乳酸*聚丁酸羥基酯之均聚物或共 聚物及彼等之摻合物,及聚(1-乳酸)摻合聚(d-乳酸)之 可吸收生物可相容聚合物製成,或由選自包括聚fe酸乙 烯酯,絳,耐綸,聚乙烯,聚丙烯及聚氧化甲烯及其摻 合物之非可吸收生物可相容聚合物製成。 DP 甲 4(210X297 公尨) {' · y^< *·*· ft · Α7 Β7 C7 D7 六、申請專利乾圓 經濟部中央橾準局印裝 7 ‘ 根據申請專利範圍第1項之裝置,尚可由非可吸收物質 製得。 8 ·根據申請專利範圍第7項之装置,具有摻合第二可吸收 共聚物之第一可吸收均聚物.且非可吸收物質包含由氟 化碳氫化合物1製得之聚合物。 9 ·根據申請専利範圔第8項之裝置,其中第一均聚物基本 上是由乙酵酯鐽聯所姐成。 10·根據申請專利範園第8項之装置,其中第二共聚物包含 選自包括乙醇酸酯,乳酸酯,1 , 3 —二噚烷一2 —酮, 1 ,4 —二鸣烷—2 —萌及ε —己丙酯鍵聯之至少兩種 不同鐽聯,且氟化碳氫化合物聚合物係選自包括聚四氟 乙烯及氟化乙烯-丙烯共聚物,而此非可吸收物質占該 裝置重量之0.01%以上至1 %以下。 11. 根據申請專利範圍第10項之裝置,其中第二共聚物包含 乙酵酸酯及碳酸三亞甲酯鍵聯,且該非可吸收物質為聚 四氟乙烯。 12. 根據申請專利範圍第10項之裝置,其中該非可吸收物質 占該装置重量之0.02%以上至0.5 下,且係圼微粉 碎狀或微原嫌狀。 13. 根據申請專利範圃第1至12項中任一項之裝置,其為一 種夾子。 14. 根據申請專利範圍第1至12項中任一項之裝置,其為一 種鎖環。 15. 根據申請專利範圍第1至12項中任一項之裝置,其為一 DP 甲 4(210X297 公廣) {請先閱讀背面之注意事項再瑱寫本頁) •裝· •打· .綠. A? B7 20i3b0i c? D7 六、申請專利範® 置 装 定 固 折 骨 種 係 置 裝。 定絲 固螺 折骼 骨骨 中及 其桿 ’骼 置# 装, 之針 項扣 15骼 第骨 圍 , 範板 利骼 專骨 請括 申包 據自 根選 (請先閑讀背面之注意事邛再填寫本頁) -¾. •綠· 經濟部中央標準局印裝 31 甲4(210X297 公尨)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US07/548,802 US5080665A (en) | 1990-07-06 | 1990-07-06 | Deformable, absorbable surgical device |
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TW205501B true TW205501B (zh) | 1993-05-11 |
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TW080105226A TW205501B (zh) | 1990-07-06 | 1991-07-05 |
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EP (1) | EP0460439B1 (zh) |
JP (1) | JPH04231963A (zh) |
KR (1) | KR0173469B1 (zh) |
AU (2) | AU652761B2 (zh) |
BR (1) | BR9102855A (zh) |
CA (1) | CA2046192C (zh) |
DE (1) | DE69133073T2 (zh) |
DK (1) | DK0460439T3 (zh) |
ES (1) | ES2177519T3 (zh) |
FI (1) | FI913284A (zh) |
IL (1) | IL98146A (zh) |
MX (1) | MX166882B (zh) |
NO (1) | NO912635L (zh) |
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ZA (1) | ZA915229B (zh) |
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- 1990-07-06 US US07/548,802 patent/US5080665A/en not_active Expired - Lifetime
-
1991
- 1991-05-15 IL IL9814691A patent/IL98146A/en active IP Right Grant
- 1991-05-17 DK DK91107998T patent/DK0460439T3/da active
- 1991-05-17 DE DE69133073T patent/DE69133073T2/de not_active Expired - Lifetime
- 1991-05-17 EP EP91107998A patent/EP0460439B1/en not_active Expired - Lifetime
- 1991-05-17 ES ES91107998T patent/ES2177519T3/es not_active Expired - Lifetime
- 1991-06-24 MX MX2636391A patent/MX166882B/es unknown
- 1991-07-02 JP JP91187004A patent/JPH04231963A/ja active Pending
- 1991-07-04 CA CA002046192A patent/CA2046192C/en not_active Expired - Lifetime
- 1991-07-04 PT PT98204A patent/PT98204A/pt not_active Application Discontinuation
- 1991-07-05 FI FI913284A patent/FI913284A/fi not_active Application Discontinuation
- 1991-07-05 TW TW080105226A patent/TW205501B/zh active
- 1991-07-05 AU AU80220/91A patent/AU652761B2/en not_active Ceased
- 1991-07-05 NO NO91912635A patent/NO912635L/no unknown
- 1991-07-05 KR KR1019910011408A patent/KR0173469B1/ko not_active IP Right Cessation
- 1991-07-05 ZA ZA915229A patent/ZA915229B/xx unknown
- 1991-07-05 BR BR919102855A patent/BR9102855A/pt not_active Application Discontinuation
-
1992
- 1992-01-13 US US07/821,731 patent/US5376102A/en not_active Expired - Lifetime
-
1994
- 1994-12-09 AU AU80347/94A patent/AU680060B2/en not_active Ceased
-
1998
- 1998-01-09 US US09/005,143 patent/US6130271A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
FI913284A (fi) | 1992-01-07 |
KR920002101A (ko) | 1992-02-28 |
NO912635D0 (no) | 1991-07-05 |
JPH04231963A (ja) | 1992-08-20 |
US6130271A (en) | 2000-10-10 |
EP0460439A3 (en) | 1992-03-25 |
NO912635L (no) | 1992-01-07 |
IL98146A0 (en) | 1992-06-21 |
AU8022091A (en) | 1992-01-09 |
US5080665A (en) | 1992-01-14 |
EP0460439B1 (en) | 2002-07-24 |
PT98204A (pt) | 1993-08-31 |
CA2046192C (en) | 2003-12-30 |
US5376102A (en) | 1994-12-27 |
EP0460439A2 (en) | 1991-12-11 |
FI913284A0 (fi) | 1991-07-05 |
MX166882B (es) | 1993-02-10 |
AU680060B2 (en) | 1997-07-17 |
BR9102855A (pt) | 1992-02-04 |
DK0460439T3 (da) | 2002-11-04 |
AU8034794A (en) | 1995-02-16 |
DE69133073D1 (de) | 2002-08-29 |
ZA915229B (en) | 1992-04-29 |
ES2177519T3 (es) | 2002-12-16 |
AU652761B2 (en) | 1994-09-08 |
IL98146A (en) | 1996-01-31 |
CA2046192A1 (en) | 1992-01-07 |
DE69133073T2 (de) | 2002-11-14 |
KR0173469B1 (ko) | 1999-03-20 |
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