JP5478895B2 - 医療機器に有用なポリマー材料 - Google Patents
医療機器に有用なポリマー材料 Download PDFInfo
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- 239000002861 polymer material Substances 0.000 title description 2
- 229920001577 copolymer Polymers 0.000 claims description 59
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 claims description 19
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 8
- 210000002435 tendon Anatomy 0.000 claims description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 210000003041 ligament Anatomy 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 4
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- 239000013078 crystal Substances 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 24
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical group O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 13
- 239000000178 monomer Substances 0.000 description 11
- 229940089513 pentadecalactone Drugs 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 206010019909 Hernia Diseases 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 229920000431 shape-memory polymer Polymers 0.000 description 3
- 238000001356 surgical procedure Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000017423 tissue regeneration Effects 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- 230000002792 vascular Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 241000282465 Canis Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 210000003711 chorioallantoic membrane Anatomy 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009658 destructive testing Methods 0.000 description 1
- 239000000032 diagnostic agent Substances 0.000 description 1
- 229940039227 diagnostic agent Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003356 suture material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable materials
- A61L17/10—At least partially resorbable materials containing macromolecular materials
-
- 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
- A61L27/18—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
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
- D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/126—Copolymers block
Description
[背景]
(1)高強度
(2)最適な加水分解安定性、すなわち、外科処置において使用された後であっても、長期間にわたり十分な強度を維持すること
(3)粒子のない分解特性
(4)負荷下での伸長が最小
(5)機械的外力/負荷が変化するサイクルに対する耐久性
(6)高歪み下での安定性。
[発明の簡単な説明]
[発明の詳細な説明]
O=C=N−R−N=C=O
の化合物であり、ここで、Rは、2価の芳香族基又は脂肪族基である。好ましくは、Rは、1〜10の炭素鎖、好ましくは2〜8、より好ましくは4〜7個の炭素原子を有し、好ましくは直鎖の脂肪族である。この炭素鎖は、水素により飽和していてもよく(脂肪族不飽和基)、又はこの鎖は、さらなる置換基、好ましくは、1〜6個、より好ましくは1〜4個の炭素原子を有する鎖長の短いアルキル基、特にメチル基を示してもよい。特に好ましいジイソシアネートは、トリメチルヘキサン−1,6−ジイソシアネートであり、別の例は、ヘキサメチレンジイソシアネートである。
1.生体分解性形状記憶ポリマーの合成
合成の第1段階において、報告された方法(A.Lendlein,P.Neuenschwander,U.W.Suter,Macromol.Chem.Phys.,201,1067,(2000))に従って、開始剤として低分子量ジオールを用いた開環重合によりマクロジオールを合成し、精製した。溶融転移温度(Ttrans)を有する切り替えセグメント(switching segment)(ソフトセグメント)のための前駆体として、オリゴ(ε−カプロラクトン)ジオール(Mn 2000g/mol)を選択した。溶融転移温度(Tm=Tperm)を有する結晶化可能なオリゴ(p−ジオキサノン)ジオール(Mn 4000g/mol)を、物理的な架橋を提供するためのハードセグメントとして選択した。
第2段階において、2つのマクロジオールを以下のようにしてヘキサメチレンジイソシアネートと結合させた:両マクロジオールを等量で1,2−ジクロロエタンに溶解し、80℃まで加熱した。等モル量のヘキサメチレンジイソシアネートを加えた。溶媒及びモノマーを標準的な技術により乾燥し、水を排除して合成を行った。粗生成物をヘキサン中で沈殿させた。得られたポリマーは、約50000g/molの分子量(Mn)を有し、融点Tmは、90℃を超えており、オリゴ(p−ジオキサノン)ジオールセグメントに起因する結晶化度は約35%であった。
形状記憶特性を定量するために、プログラム及び回復をサイクル熱機械試験により以下のようにして検討した:300〜500μmの厚さを有するフィルムに材料を圧縮した。犬骨形状サンプル(クランプ間長さ:6mm、幅:3mm)をフィルムから打ち抜き、サーモチャンバを備えた引張試験機(K.Sakurai,Y.Shirakawa,T.Kahiwagi,T.Takahashi,Polymer 35,4238(1994)を参照)に載置した。200%の歪みとし、歪み速度10mm・min−1、Tlow=20℃及びThigh=50℃で、試験を行った。サンプルを10分間Tlowで保持し、その後、負荷を取り除いた(H.Tobushi,H.Hara,E.Yamada,S.Hayashi,S.P.I.E.2716,46(1996)を参照)。
この簡単な試験によると、形状記憶は1次元であるが、その効果は3次元で生じるとのことである。効果は、一般的に2つの重要なパラメータを用いて記述される。歪み固定率Rfは、切り替えセグメントが、プログラムプロセスの間に受ける機械的変形を固定する能力を表す。本明細書において記載されるポリマーについて、Rfは約99%である。歪み回復率Rrは、材料がその永久形状を回復する能力を定量化する。Rrは、サイクル数に依存し、非配向の圧縮されたフィルムにおけるポリマー鎖が、サイクルの早い段階で非弾性挙動により再配向することで徐々に100%に近づく。第1サイクルにおいて、Rrは開示されたマルチブロックコポリマーについて約80%であり、第3サイクルでは約100%である。
本明細書に開示されたポリマーの組織適合性を、毒性を評価するのに感度の良い方法である絨毛尿膜試験(CAM試験)(K.Spanel−Borowski,Res.Exp.Med.(Berl)189,69(1989))を用いて調査した。9つの実験を独立して行った。全ての試験において、Folkman(R.Crum,S.Szabo,J.Folkman,Science 230,1375(1985))に従った等級で良好な組織適合性が示された。試験結果によると、血管の数又は形状において検出可能な変化がないか、又はポリマーフィルム(サンプル長:左A0.3cm、右A0.5cm)の下又はその近傍において損傷がないことが示された。陽性のコントロールサンプルについては、A.Lendlein,Chem.in unserer Zeit 33,279(1999)を参照のこと。
高弾性形状記憶熱可塑性プラスチックを、Haake Polylab一軸押出成形機のロッドダイを介して、90℃での押出成形によりモノフィラメントに押出成形した。エチレンオキシドにより45℃で滅菌した縫合糸を、滅菌条件下で、押出成形した繊維に対して制御した応力をかけ、次いで熱クエンチングすることによりプログラムにかけた。これにより、直径0.29mmの縫合糸を得た。ゆるい結び目を固く締め、フィラメントを両端で固定した。フィラメントを40℃より高く温めると、結び目は最大外力を示しながら収縮しており、フィラメントは、実験を10回繰り返した場合でも十分再現性があり、温度とはほとんど独立しており、その間、Tm付近でなくとも形状変化を引き起こすのに十分高かった。この再現性により、フィラメントを縫合糸として用いることが可能となり、このフィラメントは、破壊試験において公知の材料より低い耐久性を有する。
Claims (10)
- p−ジオキサノンから生じる第1の繰り返し単位と、カプロラクトンから生じる第2の繰り返し単位とを含むコポリマーであって、前記コポリマーは少なくとも70℃の融点と、少なくとも25%の全結晶含有量又は少なくとも20%のp−ジオキサノンから生じる繰り返し単位の結晶含有量とを有し、前記第1及び第2の繰り返し単位は、別個のブロックの形態で、コポリマー内に分配されており、p−ジオキサノン及びカプロラクトン以外の他のいかなる繰り返し単位も含まない、コポリマー。
- 少なくとも50000g/molの数平均分子量を有する、請求項1に記載のコポリマー。
- 少なくとも80℃の融点を有する、請求項1又は2に記載のコポリマー。
- 少なくとも35%の結晶化度を有する、請求項1〜3のいずれか一項に記載のコポリマー。
- ポリエステルウレタンであり、2価のウレタンセグメントを介して結合された同一の繰り返し単位のブロックを含む、請求項1〜4のいずれか一項に記載のコポリマー。
- 請求項1〜5のいずれか一項に記載のコポリマーを含む外科用物品。
- 縫合糸、外科用ネット及びメッシュから選択され、補綴腱及び補綴靱帯のための、請求項6に記載の外科用物品。
- 請求項1〜5のいずれか一項に記載のコポリマーから調製され、500〜40μmの平均径を有するフィラメント。
- 1200%未満の伸長度において、1000MPaを超える弾性率及び/又は100MPaを超える引張強度を有する、請求項8に記載のフィラメント。
- 請求項1〜5のいずれか一項に記載のコポリマーを溶融させるステップと、任意選択で、溶融段階又は溶融前のコポリマーとさらなる従来の添加物とを混合するステップと、次いで、紡糸ノズルを介して前記溶融したコポリマーを押出成形するステップと、次いで、前記紡糸されたフィラメントを冷却するステップと、次いで、前記フィラメントを適切な機器に巻き付けるステップとを含む、請求項1〜5のいずれか一項に記載のコポリマーを用いて、請求項8又は9に記載のフィラメントを調製する方法。
Applications Claiming Priority (3)
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EP06002738A EP1818348A1 (en) | 2006-02-10 | 2006-02-10 | Polymer material for useful medical devices |
EP06002738.0 | 2006-02-10 | ||
PCT/EP2007/001194 WO2007090686A1 (en) | 2006-02-10 | 2007-02-12 | Polymer material useful for medical devices |
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JP5478895B2 true JP5478895B2 (ja) | 2014-04-23 |
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JP2008553696A Expired - Fee Related JP5478895B2 (ja) | 2006-02-10 | 2007-02-12 | 医療機器に有用なポリマー材料 |
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US (1) | US8080629B2 (ja) |
EP (2) | EP1818348A1 (ja) |
JP (1) | JP5478895B2 (ja) |
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US8357767B2 (en) * | 2007-10-03 | 2013-01-22 | Polynovo Biomaterials Limited | High modulus polyurethane and polyurethane/urea compositions |
US20090093606A1 (en) * | 2007-10-09 | 2009-04-09 | The Hong Kong Polytechnic University | Shape memory fibers prepared via wet, reaction, dry, melt, and electro spinning |
EP2075272A1 (en) | 2007-12-28 | 2009-07-01 | Mnemoscience GmbH | Shape memory polymer networks from crosslinkable thermoplasts |
EP2075273A1 (en) | 2007-12-28 | 2009-07-01 | Mnemoscience GmbH | Multiple shape memory polymer networks |
EP2075279A1 (en) | 2007-12-28 | 2009-07-01 | Mnemoscience GmbH | Production of shape memory polymer articles by molding processes |
US8889193B2 (en) | 2010-02-25 | 2014-11-18 | The Johns Hopkins University | Sustained delivery of therapeutic agents to an eye compartment |
US20110282365A1 (en) * | 2010-05-14 | 2011-11-17 | Ahmad Robert Hadba | Surgical Implants |
WO2012109363A2 (en) | 2011-02-08 | 2012-08-16 | The Johns Hopkins University | Mucus penetrating gene carriers |
EA030318B1 (ru) | 2012-03-16 | 2018-07-31 | Дзе Джонс Хопкинс Юниверсити | Конъюгаты нелинейного мультиблочного сополимера с лекарственным средством для доставки активных агентов |
JP5883539B2 (ja) | 2012-03-16 | 2016-03-15 | ザ・ジョンズ・ホプキンス・ユニバーシティー | Hif−1阻害剤の送達のための放出制御製剤 |
US9533068B2 (en) | 2012-05-04 | 2017-01-03 | The Johns Hopkins University | Drug loaded microfiber sutures for ophthalmic application |
US10568975B2 (en) | 2013-02-05 | 2020-02-25 | The Johns Hopkins University | Nanoparticles for magnetic resonance imaging tracking and methods of making and using thereof |
US10485757B2 (en) | 2015-01-27 | 2019-11-26 | The Johns Hopkins University | Hypotonic hydrogel formulations for enhanced transport of active agents at mucosal surfaces |
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US4643191A (en) * | 1985-11-29 | 1987-02-17 | Ethicon, Inc. | Crystalline copolymers of p-dioxanone and lactide and surgical devices made therefrom |
US6486295B1 (en) * | 2000-01-24 | 2002-11-26 | Richard A. Gross | Lipase-catalyzed transesterifications to regulate copolymer structure |
DE10217350C1 (de) * | 2002-04-18 | 2003-12-18 | Mnemoscience Gmbh | Polyesterurethane |
US20030236319A1 (en) * | 2002-06-25 | 2003-12-25 | Hye-Sung Yoon | Block copolymers for surgical articles |
US6794484B2 (en) * | 2002-06-28 | 2004-09-21 | Ethicon, Inc. | Crystallizable polylactone copolymers prepared from mono- and di-functional polymerization initiators |
DE10316573A1 (de) * | 2003-04-10 | 2004-11-04 | Mnemoscience Gmbh | Blends mit Form-Gedächtnis-Eigenschaften |
DE10334784A1 (de) * | 2003-07-30 | 2005-03-03 | Mnemoscience Gmbh | Kosmetische Zusammensetzung mit Polyol/Polyester Blockpolymeren |
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- 2007-02-12 EP EP07703423.9A patent/EP1981928B1/en active Active
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JP2009526108A (ja) | 2009-07-16 |
EP1981928A1 (en) | 2008-10-22 |
US20090234375A1 (en) | 2009-09-17 |
US8080629B2 (en) | 2011-12-20 |
EP1981928B1 (en) | 2020-05-06 |
EP1818348A1 (en) | 2007-08-15 |
WO2007090686A1 (en) | 2007-08-16 |
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