JP6092167B2 - 生体医用フォーム - Google Patents
生体医用フォーム Download PDFInfo
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- JP6092167B2 JP6092167B2 JP2014181958A JP2014181958A JP6092167B2 JP 6092167 B2 JP6092167 B2 JP 6092167B2 JP 2014181958 A JP2014181958 A JP 2014181958A JP 2014181958 A JP2014181958 A JP 2014181958A JP 6092167 B2 JP6092167 B2 JP 6092167B2
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Description
ここで、Rは、1以上の脂肪族ポリエステル、ポリエ−テルエステル、ポリエ−テル、ポリ酸無水物および/またはポリカーボネートから選ばれ、そして少なくとも1のRは親水性セグメントを含み、R’およびR”は独立にC2〜C8アルキレンであり、任意的に、C1〜C10アルキル基または保護されたS、N、P若しくはO残基で置換されたC1〜C10アルキル基で置換されていて、および/またはアルキレン鎖中にS、N、P若しくはO(たとえばエ−テル、エステル、カーボネートおよび/または酸無水物基)を含んでいてもよく、Z1〜Z4は独立にアミド、尿素またはウレタンであり、Q1およびQ2は独立に尿素、ウレタン、アミド、カーボネート、エステルまたは酸無水物であり、nは5〜500の整数であり、pおよびqは独立に0または1であり、但し、qが0であるときは、Rは少なくとも1の結晶性ポリエステル、ポリエ−テルエステルまたはポリ酸無水物セグメントと少なくとも1の非晶質脂肪族ポリエステル、ポリエ−テル、ポリ酸無水物および/またはポリカーボネートセグメントとの混合物である。アルキレン鎖中のO含有残基は、もし存在するならば、好ましくは親水性基、特にエ−テル基である。というのは、当該親水性基は、重合体に低減した分解時間を付与することができるからであり、それは生体移植物への重合体の使用に望ましいことでありうる。
-[R-Q1-R'''-Q2-]n (II)
ここで、R、Q1、Q2およびnは上に記載された通りであり、Q1およびQ2は独立に尿素、ウレタン、アミド、カーボネート、エステルまたは酸無水物、好ましくは尿素、ウレタンまたはアミドであり、R'''は上に記載されたR、R’またはR”から選ばれ、但し、R'''がR’またはR”であるときは、Rは少なくとも1の結晶性ポリエステル、ポリエ−テルエステルまたはポリ酸無水物と少なくとも1の非晶質脂肪族ポリエステル、ポリエ−テル、ポリ酸無水物および/またはポリカーボネートとの混合物である。R'''がRであるときは、少なくとも1の結晶性ポリエステル、ポリエ−テルエステルまたはポリ酸無水物並びに少なくとも1の非晶質脂肪族ポリエステル、ポリエ−テル、ポリ酸無水物および/またはポリカーボネートが当該重合体に備えられている。するとやはり、親水性セグメントは、相分離された重合体の当該非晶質セグメント中に備えられ、そして非晶質および結晶性セグメントは交互になる。
A−R−A’ (III)
式(IV)の1以上のジイソシアネートと、
O=C=N−R’−N=C=O (IV)
そして任意的に式(V)の1以上の鎖延長剤とを反応させることを含む、
B−R’’−B’ (V)
本発明に従う式(I)の相分離された生分解性の重合体の調製方法を提供し、ここでR、R’およびR”は式(I)で定義された通りであり、そしてA、A’、BおよびB’はヒドロキシル、カルボキシルまたはアミンから独立に選ばれる。好ましくは、上の化合物(III)、(IV)(の反応生成物)と(V)との鎖延長反応は、溶媒中で、より好ましくは1,4−ジオキサンまたはトリオキサン中で、さらにより好ましくは1,4−ジオキサン中で実施される。さらにもっと好ましい実施態様では、化合物(III)と(IV)との間の反応はバルクで実施され、その後でいわゆる鎖延長反応が化合物(V)とで溶媒中で実施される。
O=C=N−R’−Z1-R’’-Z2−R’−N=C=O (VI)
あるいはヒドロキシル、カルボキシルまたはアミンの末端基を持つ化合物、すなわち式(VII)の化合物が生成される
B−R’’−Z1−R’−Z2−R’’−B’ (VII)
(ここでR’、R”、Z1、Z2、BおよびB’は上で定義された通りである)。
O=C=N−R’−Z1-R’’-Z2−R’−Z3−R’’ーZ4ーR’−N=C=O (VIII)
(ここでR’、R”およびZ1〜Z4は上で定義された通りである)、この化合物(VIII)は、次に化合物(III)との反応に使用されて、本発明の重合体を生成する。
O=C=N−R’−Z1-R-Z2−R’−N=C=O (IX)
式(VII)の化合物と式(IX)の化合物との間の反応は、セグメント連鎖−R’−R−R’−R”−R’−R”−を持った重合体状の化合物を生成する結果になるだろう。
O=C=N−R’−Z1-R’’-Z2−R’−N=C=O (VI)
ジオールが1,4−ブタンジオール(BDO)であり、そしてジイソシアネートが1,4−ブタンジイソシアネート(BDI)である場合には、この「3ブロック」の鎖延長剤、すなわち中間体ジイソシアネート錯体はBDI−BDO−BDIと名付けられ、そして式(III)の化合物と反応させられると、式(I)に従う重合体を生じることになり、ここでpは0であり、qは1であり、そしてハードセグメントはセグメント連鎖R’−R”−R’を含む。
O=C=N−R’−Z1-R’’-Z2−R’−Z3−R’’ーZ4ーR’−N=C=O (VIII)
B−R’’−Z1−R’−Z2−R’’−B’ (VII)
当該化合物(VII)の例は、反応生成物BDO−BDI−BDOである。
A−R−A’ (III)
1以上の式(IV)のジイソシアネートと、
O=C=N−R’−N=C=O (IV)
そして任意的に1以上の式(V)の鎖延長剤と、
B−R’’−B’ (V)
反応させる段階を含み、これらの式でR、R’およびR”は、式(I)で定義された通りであり、そしてA、A’、BおよびB’は、ヒドロキシル、カルボキシルまたはアミンから独立に選ばれる。好ましくは、上の化合物(III)、(IV)および(V)は溶媒中で、より好ましくは1,4−ジオキサンまたはトリオキサン中で反応させられる。
(50/50)グリコリド−ε−カプロラクトンプレポリマー(Mn=2000)
PEG1000を用いて開始された(50/50グリコリド−ε−カプロラクトン)プレポリマー(Mn=2000)
(20/40/40)ラクチド−グリコリド−ε−カプロラクトンプレポリマー(Mn=2000)
PEG1000を用いて開始された(20/40/40ラクチド−グリコリド−ε−カプロラクトン)プレポリマー(Mn=2000)
PEG1000を用いて開始された(50/50ラクチド−ε−カプロラクトン)プレポリマー(Mn=2000)
(3/1)((50/50)グリコリド−ε−カプロラクトン)/PEG1000(重量/重量)に基づいた、BDI.BDO.BDI.BDO.BDIハードセグメントを持つポリウレタンの1,4−ジオキサン中での合成
(3/1)((20/40/40)ラクチド−グリコリド−ε−カプロラクトン)/PEG1000(重量/重量)に基づいた、BDI.BDO.BDI.BDO.BDIハードセグメントを持つポリウレタンの1,4−ジオキサン中での合成
(1/1)((50/50)ラクチド−ε−カプロラクトン)/PEG1000(重量/重量)に基づいた、BDI.BDO.BDI.BDO.BDIハードセグメントを持つポリウレタンの1,4−ジオキサン中での合成
グリコリドに基づいたフォームの調製
ラクチドに基づいたフォームの調製
。
Claims (26)
- 人体または動物体の洞若しくは他の腔に詰めるのに適した生分解性の吸収体フォームであって、当該フォームが相分離された重合体を含み、当該重合体が非晶質セグメントおよび結晶性セグメントからなり、当該重合体が式(I)を有する、フォーム。
- 当該重合体が、式(III)に従う1以上のプレポリマーと、
A-R-A’ (III)
式(IV)の1以上のジイソシアネートと、
O=C=N-R’-N=C=O (IV)
そして任意的に式(V)の1以上の鎖延長剤と
B-R’’-B’ (V)
を反応させることによって得られる、請求項1に従うフォーム(これらの式で、R、R’およびR”は請求項1で定義された通りであり、A、A’、BおよびB’は、各々ヒドロキシルである)。 - 当該重合体が、式(III)に従う少なくとも2の異なったプレポリマーを反応させることによって得られる、請求項2に従うフォーム。
- 当該重合体が、式(III)に従う少なくとも2の異なったプレポリマーと、
A-R-A’ (III)
任意的に式(V)の1以上の化合物と
B-R’’-B’ (V)
をN−ヒドロキシコハク酸イミド、カルボニルジイミダゾール、アルデヒド、マレイミド、ジシクロヘキシルカルボジイミド(DCC)およびこれらの誘導体からなる群から選ばれた活性化剤の存在下に、反応させることによって得られる、請求項1に従うフォーム(これらの式で、R、R”は請求項1で定義された通りであり、A、A’、BおよびB’は、各々ヒドロキシルである)。 - R’が(CH2)4であり、R”が(CH2)4であり、またはR’およびR”の両方が(CH2)4である、請求項1〜4のいずれか1項に従うフォーム。
- 少なくとも1のRが、ラクチド(L、DまたはLD)、グリコリド、ε−カプロラクトン、δ−バレロラクトン、1,5−ジオキセパン−2−オンおよび/またはパラジオキサノン、またはこれらの組み合わせの環状単量体から誘導される、請求項1〜5のいずれか1項に従うフォーム。
- 少なくとも1のRが、ラクチドおよびε−カプロラクトンから誘導され、1000〜4000の分子量を持つ非晶質ポリエステルである、請求項1〜6のいずれか1項に従うフォーム。
- 当該非晶質ポリエステルが、25重量%のラクチド、25重量%のε−カプロラクトンおよび50重量%のポリエチレングリコールを含む、請求項7に従うフォーム。
- 当該非晶質セグメントが、当該フォームがその中に詰められるところの人体または動物体の当該洞若しくは他の腔の温度より低い軟化点を持ち、そして当該結晶性セグメントが、上記温度より高い軟化点を持つ、請求項1〜8のいずれか1項に従うフォーム。
- 当該結晶性セグメントがポリウレタンを含む、請求項1〜9のいずれか1項に従うフォーム。
- 当該親水性セグメントが、ポリエチレングリコール、ポリプロピレングリコールまたはポリブチレングリコールから誘導される、請求項1〜11のいずれか1項に従うフォーム。
- 非晶質セグメントが、ポリエチレングリコールを1〜80重量%で含む、請求項11に従うフォーム。
- フォームが5%未満の膨潤度およびその乾燥重量の15〜25倍の吸収容量を持つことを特徴とする、請求項1〜12のいずれか1項に従うフォーム。
- フォームが0.5〜0.99g/cm3の吸収容量および/または0.01〜0.2g/cm3の密度を持つことを特徴とする、請求項1〜13のいずれか1項に従うフォーム。
- 請求項1で定義された式(I)の相分離された生分解性重合体。
- 請求項1で定義された式(I)の相分離された生分解性重合体の調製方法において、当該方法が重合反応を実施することを含み、当該重合反応が、式(III)
A-R-A’ (III)
の1以上のプレポリマーを、式(IV)
O=C=N-R’-N=C=O (IV)
の1以上のジイソシアネートと、および任意的に式(V)
B-R’’-B’ (V)
の1以上の鎖延長剤と反応させることを含む方法(ここで、R、R’およびR”は請求項1で定義された通りであり、A、A’、BおよびB’は、各々ヒドロキシルである)。 - 式(IV)の1以上のジイソシアネートを式(V)の1以上の鎖延長剤と反応させて、式(VI)、
O=C=N-R’-Z1-R’’-Z2-R’-Z3-R’’-Z4-R’-N=C=O (VI)
(これらの式で、R’、R”、およびZ1〜Z4は請求項1で定義されたとおりである)
の中間体ジイソシアネート錯体を生成させ、続けて当該中間体ジイソシアネート錯体と式(III)のプレポリマーとの間の重合反応を実施することを含む、請求項16に従う方法。 - 式(IV)の1以上のジイソシアネートを式(V)の1以上の鎖延長剤と反応させて、式(VII)、
B-R’’-Z1-R’-Z2-R’’-B’ (VII)
の中間錯体を生成させることを含む方法において、当該方法がさらに、式(IV)の1以上のジイソシアネートを式(III)の1以上のプレポリマーと反応させて、式(IX)、
O=C=N-R’-Q1-R-Q2-R’-N=C=O (IX)
(ここで、R、R’、Q1、Q2、Z1およびZ2は請求項1で定義されたとおりである。)の中間体ジイソシアネート錯体を生成させ、続けて式(VII)の当該中間錯体と式(IX)の当該中間体ジイソシアネート錯体との間の重合反応を実施することを含む、請求項16に従う方法。 - 当該重合反応が15℃〜90℃の温度で実施される、請求項16〜18のいずれか1項に従う方法。
- 請求項15に従う相分離された生分解性重合体を用意し、そして当該重合体をフォームへと形成することを含む、請求項1〜14のいずれか1項に従う フォームの調製方法。
- 当該重合体が溶融され、そしてガスの助けを受けてフォームへと押出される、請求項20に従う方法。
- 当該重合体が溶媒中の当該重合体の溶液として用意され、そして当該フォームが当該溶液を凍結し、そして溶媒を凍結乾燥によって昇華することによって調製される、請求項20に従う方法。
- 請求項16〜19のいずれか1項の方法に従い相分離された生分解性重合体をバルクで調製し、そして当該重合反応の間に二酸化炭素の現場(インシチュー)生成を許すことを含む、請求項1〜14のいずれか1項に従うフォームの調製方法。
- 当該溶媒が1,4−ジオキサンである、請求項22に従う方法。
- 請求項1〜14のいずれか1項に従うフォームを、止血スポンジとして、創傷被覆材料として、動物体(ヒトを除く)の洞若しくは他の腔のパッキングとして、鼻ドレッシング材として、外耳用のパッキングとして、歯科手術においてまたは薬物送達媒体として使用する方法。
- 請求項15に従う相分離された生分解性重合体を、請求項1〜14のいずれか1項に従うフォームの製造に使用する方法。
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JP2006519633A (ja) | 2006-08-31 |
US20060008419A1 (en) | 2006-01-12 |
CN1771061B (zh) | 2010-05-12 |
DK1581268T3 (da) | 2011-08-15 |
US20210402047A1 (en) | 2021-12-30 |
JP2015006428A (ja) | 2015-01-15 |
DE602004032514D1 (de) | 2011-06-16 |
US11911524B2 (en) | 2024-02-27 |
US20150273102A1 (en) | 2015-10-01 |
CN101816801B (zh) | 2012-11-14 |
EP1581268B1 (en) | 2011-05-04 |
JP2011251150A (ja) | 2011-12-15 |
WO2004062704A1 (en) | 2004-07-29 |
EP1581268A1 (en) | 2005-10-05 |
US11147898B2 (en) | 2021-10-19 |
US20200069835A1 (en) | 2020-03-05 |
AU2004204561A1 (en) | 2004-07-29 |
CN101816801A (zh) | 2010-09-01 |
CA2512896A1 (en) | 2004-07-29 |
CN1771061A (zh) | 2006-05-10 |
ES2365709T3 (es) | 2011-10-10 |
US10507260B2 (en) | 2019-12-17 |
CA2512896C (en) | 2012-10-16 |
JP5528656B2 (ja) | 2014-06-25 |
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