JPS61149160A - Biodegradable absorbable sponge and its production - Google Patents
Biodegradable absorbable sponge and its productionInfo
- Publication number
- JPS61149160A JPS61149160A JP59271287A JP27128784A JPS61149160A JP S61149160 A JPS61149160 A JP S61149160A JP 59271287 A JP59271287 A JP 59271287A JP 27128784 A JP27128784 A JP 27128784A JP S61149160 A JPS61149160 A JP S61149160A
- Authority
- JP
- Japan
- Prior art keywords
- lactic acid
- sponge
- biodegradable
- absorbable sponge
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、医療用スポンジおよびその製造法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a medical sponge and a method for manufacturing the same.
さらに詳しくは、安全性の高い生体分解吸収性のス、ボ
ンジとその製造法に関する。More specifically, the present invention relates to highly safe, biodegradable and absorbable soaps and bonds, and a method for producing the same.
医療用スポンジは手術時の止血あるいは血管吻合や生体
の軟組織、例えば肝臓、膵臓等の臓器の縫合時の補綴材
料として使用されろ。Medical sponges are used for hemostasis during surgery, for blood vessel anastomosis, and as prosthetic materials for suturing soft tissues of living bodies, such as the liver and pancreas.
これらの外科手術用スポンジが、例えばポリエチレン等
の非分解吸収性材料からなる場合、生体組織の治癒後、
半永久的に生体内に残存するため細菌の巣窟となる恐れ
があり将来にわたって問題となる。従って現在臨床で使
用されている外科手術用スポンジは分解性のスポンジエ
ルと溶解性のオキシセルである。しかし、スポンジエル
は生体由来高分子材料であるため極めて高価であるのみ
ならず、少なからず抗原性があり、また、オキシセルは
セルロース誘導体であるため生体内では分解吸収されず
単に水に溶解するのみであり、多量に用いられると生体
内に蓄積される問題がある。When these surgical sponges are made of non-degradable and absorbable materials, such as polyethylene, after healing of living tissue,
Since it remains in the body semi-permanently, it may become a breeding ground for bacteria, which will pose a problem in the future. Therefore, the surgical sponges currently in clinical use are degradable Spongel and soluble Oxycel. However, since SpongeL is a bio-derived polymeric material, it is not only extremely expensive, but also has some antigenicity, and Oxycell is a cellulose derivative, so it is not broken down and absorbed in the body, but simply dissolves in water. However, if used in large quantities, there is a problem that it accumulates in the body.
一方、これらに対し生体分解吸収性の合成高分子からな
る組織吸収性スポンジ及びその製造法に関し、特開昭５
１−１１６０７９号があり、これにはポリグリコール酸
あるいは乳酸単位の様な他の単位を１５％まで含むポリ
グリコール酸からなるスポンジについての記載がある。On the other hand, regarding the tissue absorbable sponge made of biodegradable and absorbable synthetic polymer and its manufacturing method, Japanese Patent Laid-Open No. 5
No. 1-116079 describes a sponge made of polyglycolic acid containing up to 15% of polyglycolic acid or other units such as lactic acid units.
しかしながらこれらの材料は結晶構造が極めて緻密なた
め有機溶媒に対する溶解性が極めて劣り、従ってヘキサ
フルオロイソプロピルアルコールまたはへキサフルオロ
アセトンセスキヒトラードのような極めて特殊な有機溶
媒にしか溶解させることができない。そしてこれらの溶
媒はフッソ系の溶媒であるため、極めて刺激性、毒性が
強（皮膚に触れるだけでやけどが生じるほどであり、こ
のような刺激性あるいは毒性が高い溶媒を用いて組織吸
収性のスポンジを製造した場合、スポンジ中の溶媒が完
全に除去されず微量の溶媒が残留したならば、生体組織
に損傷を与え生命の危険さえ脅かすことにもなりかねな
い。However, since these materials have extremely dense crystal structures, their solubility in organic solvents is extremely poor, and therefore they can only be dissolved in very specific organic solvents such as hexafluoroisopropyl alcohol or hexafluoroacetone sesquitride. Since these solvents are fluorine-based solvents, they are extremely irritating and toxic (simply touching the skin can cause burns, and these highly irritating or highly toxic solvents are used to prevent tissue absorption. When a sponge is manufactured, if the solvent in the sponge is not completely removed and a trace amount of solvent remains, it may damage living tissue and even threaten life.
本発明の目的は、安全性の高い新規な生体分解吸収性ス
ポンジを提供することにある。他の目的は、生体分解吸
収性スポンジの新規な製造法を提供することにある。An object of the present invention is to provide a novel biodegradable and absorbable sponge with high safety. Another object is to provide a novel method for producing biodegradable and absorbable sponges.
〔問題点を解決するための手段および作用〕本発明は、
特定の重合体と特定の溶媒とを組み合わせて選択するこ
とにより、フッ素系の溶媒を用いることなく生体分解吸
収性スポンジを製造するものである。[Means and effects for solving the problems] The present invention has the following features:
By selecting a combination of a specific polymer and a specific solvent, a biodegradable and absorbable sponge can be manufactured without using fluorine-based solvents.
本発明において使用される重合体は、乳酸の単独重合体
および乳酸単位を少なくとも５０モル％含有する乳酸と
ヒドロキシカルボン酸またはラクトンの共重合体からな
る群より選択する必要がある。このような重合体を選択
することによって初めて非フツ素系の溶媒を使用してス
ポンジを製造できるのである。そしてこれらの重合体は
分子量が２，０００〜６００．０００の範囲にあること
が必要である。The polymer used in the present invention should be selected from the group consisting of homopolymers of lactic acid and copolymers of lactic acid and hydroxycarboxylic acids or lactones containing at least 50 mol % of lactic acid units. Only by selecting such a polymer can a sponge be manufactured using a non-fluorine solvent. These polymers must have a molecular weight in the range of 2,000 to 600,000.
分子量が２．０００よりも小さいと、スポンジとして実
用的な強度を有する製品が得られない。また、分子量が
６００，０００よりも大きいと溶媒への溶解性が低下す
るとともに溶液粘度が大きくなり取扱いが困難になるの
で好ましくない。なお、ここでいう乳酸とは、Ｌ−乳酸
、Ｄ−乳酸及びり、Ｌ−乳酸のいずれをも包含するもの
である。If the molecular weight is less than 2.000, a product with practical strength as a sponge cannot be obtained. On the other hand, if the molecular weight is greater than 600,000, the solubility in a solvent will decrease and the solution viscosity will increase, making handling difficult, which is not preferable. In addition, the lactic acid here includes any of L-lactic acid, D-lactic acid, and L-lactic acid.
よりスポンジを得ることができる。溶解液の濃度として
は、１〜５０重量％の範囲が適当である。濃度が１重量
％よりも低いとスポンジの製造が困難になり、また５０
重量％以上の溶液は調製がむずかしい。You can get more sponge. The concentration of the solution is preferably in the range of 1 to 50% by weight. If the concentration is lower than 1% by weight, it will be difficult to manufacture sponges, and if the concentration is lower than 1% by weight,
It is difficult to prepare solutions with a concentration of more than % by weight.
上述した重合体は、ベンゼンおよびジオキサン以外の非
フツ素系溶媒（例えばクロロホルム、塩化メチレン、ア
セトニトリル、テトラヒドロフラン等）にも溶解可能で
あるが、溶媒の凝固点が低（すぎて凍結乾燥が困難であ
るので、溶媒としてはベンゼンまたはジオキサンが適当
なのである。The above-mentioned polymers can also be dissolved in non-fluorine solvents other than benzene and dioxane (e.g., chloroform, methylene chloride, acetonitrile, tetrahydrofuran, etc.), but the freezing point of the solvent is too low (freeze-drying is difficult). Therefore, benzene or dioxane is suitable as the solvent.
凍結乾燥は、溶液を溶媒の凝固点以下の温度に冷却して
凍結させ、凍結した状態で減圧下に置いて溶媒を昇華さ
せることにより行なう。Freeze-drying is carried out by cooling the solution to a temperature below the freezing point of the solvent to freeze it, and placing the solution in the frozen state under reduced pressure to sublimate the solvent.
以上のようにして、分子量が２，０００〜６００．００
０の範囲にある乳酸重合体あるいは乳酸単位を少なくと
も５０モル％含有する乳酸とヒドロキシカルボン酸また
はラクトンとの共重合体から形成された連続気泡構造を
有するスポンジであって、実質的にフッ素系化合物を含
有しない生体分解吸収性スポンジが得られる。なお、こ
こで実質的にフッ素系化合物を含有しないとは、含有率
がｌＱＰＰｍ以下であることを意味する。As described above, the molecular weight is 2,000 to 600.00.
A sponge having an open cell structure formed from a lactic acid polymer in the range of 0 or a copolymer of lactic acid and hydroxycarboxylic acid or lactone containing at least 50 mol% of lactic acid units, the sponge having a substantially fluorine-based compound. A biodegradable and absorbable sponge containing no . Here, "not containing substantially fluorine-based compounds" means that the content is 1QPPm or less.
本発明のスポンジは、凍結乾燥により製造されるので連
続気泡構造を有しており、柔軟で吸液性に優れ、医療用
スポンジとして優れたものである。Since the sponge of the present invention is manufactured by freeze-drying, it has an open cell structure, is flexible and has excellent liquid absorption properties, and is excellent as a medical sponge.
実施例１゜
ポリーｎ、Ｌ−乳酸（分子量Ｍｗ ＝ ４２．０００
）をジオキサンに溶解させ５重量％濃度の溶液を調整し
該溶液を容器に入れた後冷凍庫にて凍結させその凍結体
を融解させることなく真空ポンプにて昇華乾燥を５時間
行ない、更にスポンジ中の残存溶媒を除去するため４０
’Ｃにて真空乾燥を一昼夜行ないポリーＤ、Ｌ−乳酸の
スポンジを得た。得られたスポンジは連続気泡構造を有
する吸液率の高いものであった。このようにして得たス
ポンジをエチレンオキサイドガスで滅菌した後体重約８
Ｋｇの家兎の背部皮下（背筋筋膜上）にインブラントし
、材料の１ｎｖｉｖｏ分解吸収性と生体組織反応性を観
察し總材料は４ケ月経過後は生体に完全に吸収され、ま
た生体組織の炎症反応は殆んどみられなかった。Example 1 Poly n, L-lactic acid (molecular weight Mw = 42.000
) in dioxane to prepare a solution with a concentration of 5% by weight, put the solution in a container, freeze it in a freezer, sublimate dry it with a vacuum pump for 5 hours without thawing the frozen substance, and then put it in a sponge. 40 to remove residual solvent of
Vacuum drying was carried out for a day and night at 'C' to obtain a poly D, L-lactic acid sponge. The obtained sponge had an open cell structure and a high liquid absorption rate. After sterilizing the sponge thus obtained with ethylene oxide gas, it weighs approximately 8
The material was implanted subcutaneously (on the dorsal fascia) in the back of a domestic rabbit, and the in vivo decomposition and absorption properties and biological tissue reactivity of the material were observed.The material was completely absorbed by the living body after 4 months, and Almost no inflammatory reaction was observed.
実施例２゜
ポリ−Ｌ−乳酸（分子量Ｍｗ ＝ ４０，０００ ）を
溶媒としてベンゼンを用いた以外は実施例１．と同様な
操作をすることによりポリ−Ｌ−乳酸スポンジが得られ
た。得られたスポンジは連続気泡構造を有する吸液率の
高いものであった。この材料は １ｎｎｖｏ分解吸収性
と生体組織反応性を実施例１と同様な方法にて観察した
。材料の生体内分解吸収性は、実施例１のポリーＤ、Ｌ
→Ｌ酸スポンジより遅く約１０ケ月を要した。Example 2 Example 1 except that poly-L-lactic acid (molecular weight Mw = 40,000) was used as a solvent and benzene was used. A poly-L-lactic acid sponge was obtained by performing the same operation as above. The obtained sponge had an open cell structure and a high liquid absorption rate. This material was observed for its 1 nnvo degradability and reactivity in living tissue in the same manner as in Example 1. The biodegradability of the material was determined by Poly D and L in Example 1.
→It took about 10 months, slower than L-acid sponge.
実施例３゜
Ｄ、Ｌ−乳酸−グリコール酸共重合体（８０：２０）（
分子量Ｍｗ ＝ ８９．０００ ）を実施例１と同様な
操作をすることにより乳酸−グリコール酸スポンジが得
られた。得られたスポンジは連続気泡構造を有する吸液
率の高いものであった。この材料の１ｎｖｉｖｏ分解吸
収性と生体組織反応性・左実施例１．と同様な方法にて
観察した。材料の生体内分解吸収性は、実施例１のポリ
ー〇、Ｌ−乳酸スポンジより早く２ケ月経過後は生体に
完全に吸収され、また生体組織の炎症反応は殆どみられ
なかった。Example 3゜D, L-lactic acid-glycolic acid copolymer (80:20) (
A lactic acid-glycolic acid sponge was obtained by performing the same operation as in Example 1. The obtained sponge had an open cell structure and a high liquid absorption rate. In vivo decomposition and absorption properties of this material and reactivity to living tissues - Example 1 on the left. Observation was made in the same manner. The biodegradability of the material was faster than that of the polylactic acid sponge of Example 1, and it was completely absorbed by the living body after two months, and almost no inflammatory reaction was observed in the living tissue.
実施例４
Ｄ、Ｌ−乳酸−ε−カプロラクトン共重合体（８０：２
０）（分子量Ｍｗ ＝ ４４−０００ ）を実施例１．
と同様な操作をすることにより、乳酸−ε−カプロラク
トン共重合体スポンジが得られた。得られたスポンジは
連続気泡構造を有する吸液率の高いものであった。この
材料のｉｎ ｖｉｖｏ分解吸収性と生体組織反応性を実
施例１と同様な方法にて観察した。Example 4 D,L-lactic acid-ε-caprolactone copolymer (80:2
0) (molecular weight Mw = 44-000) in Example 1.
A lactic acid-ε-caprolactone copolymer sponge was obtained by performing the same operation as above. The obtained sponge had an open cell structure and a high liquid absorption rate. The in vivo decomposition and absorption properties and biological tissue reactivity of this material were observed in the same manner as in Example 1.
材料の生体内分解吸収性は実施例２のポリ−Ｌ−乳酸ス
ポンジより早く８ケ月経過後は生体に完全に吸収され、
また、生体組織の炎症反応は殆どみられなかった。The biodegradability of the material is faster than that of the poly-L-lactic acid sponge of Example 2, and it is completely absorbed by the body after 8 months.
In addition, almost no inflammatory reaction was observed in living tissues.
本発明のスポンジはフッ素系化合物を含有していないの
で、生体に対して安全に使用することができる。また、
柔軟で吸液性に優れているので各種の医療用途に好適で
ある。さらに、製造の際にフッ素系の溶媒を使用しない
ので、環境に対しても安全である。Since the sponge of the present invention does not contain fluorine compounds, it can be safely used for living organisms. Also,
It is flexible and has excellent liquid absorption properties, making it suitable for various medical applications. Furthermore, since fluorine-based solvents are not used during production, it is safe for the environment.
また、重合体の構成単位や組成比、分子量等を変えるこ
とにより、力学的性質や生体分解吸収速度を制御できる
ので、多様な使用部位や目的に対応できる利点がある。Furthermore, by changing the structural units, composition ratio, molecular weight, etc. of the polymer, the mechanical properties and biodegradation and absorption rate can be controlled, so there is an advantage that it can be used in a variety of sites and purposes.
Claims (4)
る乳酸重合体あるいは乳酸単位を少なくとも５０モル％
含有する乳酸とヒドロキシカルボン酸またはラクトンと
の共重合体から形成された連続気泡構造を有するスポン
ジであって、実質的にフッ素系化合物を含有しないこと
を特徴とする生体分解吸収性スポンジ。(1) At least 50 mol% of lactic acid polymer or lactic acid units with a molecular weight in the range of 2,000 to 600,000
A biodegradable and absorbable sponge having an open cell structure formed from a copolymer of lactic acid and hydroxycarboxylic acid or lactone, which is characterized in that it contains substantially no fluorine-based compounds.
請求の範囲第１項記載の生体分解吸収性スポンジ。(2) The biodegradable and absorbable sponge according to claim 1, wherein the hydroxycarboxylic acid is glycolic acid.
範囲第１項記載の生体分解吸収性スポンジ。(3) The biodegradable absorbable sponge according to claim 1, wherein the lactone is ε-caprolactone.
る乳酸重合体あるいは乳酸単位を少なくとも５０モル％
含有する乳酸とヒドロキシカルボン酸またはラクトンと
の共重合体をベンゼンまたはジオキサンに１〜５０重量
％の濃度範囲になるように溶解させ、かかる溶液を凍結
乾燥させることを特徴とする実質的にフッ素系化合物を
含有しない生体分解吸収性スポンジの製造法。(4) At least 50 mol% of lactic acid polymer or lactic acid units with a molecular weight in the range of 2,000 to 600,000
Substantially fluorinated material characterized by dissolving a copolymer of lactic acid and hydroxycarboxylic acid or lactone in benzene or dioxane to a concentration range of 1 to 50% by weight, and freeze-drying the solution. A method for producing a biodegradable absorbable sponge that does not contain any compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59271287A JPS61149160A (en) | 1984-12-22 | 1984-12-22 | Biodegradable absorbable sponge and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59271287A JPS61149160A (en) | 1984-12-22 | 1984-12-22 | Biodegradable absorbable sponge and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61149160A true JPS61149160A (en) | 1986-07-07 |
| JPS6364988B2 JPS6364988B2 (en) | 1988-12-14 |
Family
ID=17497955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59271287A Granted JPS61149160A (en) | 1984-12-22 | 1984-12-22 | Biodegradable absorbable sponge and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61149160A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6456055A (en) * | 1987-08-26 | 1989-03-02 | Nippon Medical Supply | Medical molded article composed of lactic acid/epsilon-caprolactone copolymer and its preparation |
| JP2005034239A (en) * | 2003-07-16 | 2005-02-10 | Gunze Ltd | Base material for artificial blood vessel |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0566356U (en) * | 1992-02-14 | 1993-09-03 | エヌ・オー・ケー・メグラスティック株式会社 | Anti-vibration mount |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4848717A (en) * | 1971-10-18 | 1973-07-10 | ||
| JPS51116079A (en) * | 1974-03-25 | 1976-10-13 | American Cyanamid Co | Tissueeabsorptive sponge and method of manufacturing same |
-
1984
- 1984-12-22 JP JP59271287A patent/JPS61149160A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4848717A (en) * | 1971-10-18 | 1973-07-10 | ||
| JPS51116079A (en) * | 1974-03-25 | 1976-10-13 | American Cyanamid Co | Tissueeabsorptive sponge and method of manufacturing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6456055A (en) * | 1987-08-26 | 1989-03-02 | Nippon Medical Supply | Medical molded article composed of lactic acid/epsilon-caprolactone copolymer and its preparation |
| JP2005034239A (en) * | 2003-07-16 | 2005-02-10 | Gunze Ltd | Base material for artificial blood vessel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6364988B2 (en) | 1988-12-14 |
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