JP4520436B2 - Biodegradable honeycomb structure adhesive film - Google Patents
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- JP4520436B2 JP4520436B2 JP2006189071A JP2006189071A JP4520436B2 JP 4520436 B2 JP4520436 B2 JP 4520436B2 JP 2006189071 A JP2006189071 A JP 2006189071A JP 2006189071 A JP2006189071 A JP 2006189071A JP 4520436 B2 JP4520436 B2 JP 4520436B2
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- 239000002313 adhesive film Substances 0.000 title claims description 44
- 229920001610 polycaprolactone Polymers 0.000 claims description 21
- 239000004632 polycaprolactone Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 150000003904 phospholipids Chemical class 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229920003232 aliphatic polyester Polymers 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
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- 229920000642 polymer Polymers 0.000 description 25
- 239000011148 porous material Substances 0.000 description 21
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
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- 229920002988 biodegradable polymer Polymers 0.000 description 15
- 239000004621 biodegradable polymer Substances 0.000 description 15
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- 238000000034 method Methods 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- -1 For example Polymers 0.000 description 12
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- 239000004626 polylactic acid Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JZNWSCPGTDBMEW-UHFFFAOYSA-N Glycerophosphorylethanolamin Natural products NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 150000008104 phosphatidylethanolamines Chemical class 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- TZCPCKNHXULUIY-RGULYWFUSA-N 1,2-distearoyl-sn-glycero-3-phosphoserine Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OC[C@H](N)C(O)=O)OC(=O)CCCCCCCCCCCCCCCCC TZCPCKNHXULUIY-RGULYWFUSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZWZWYGMENQVNFU-UHFFFAOYSA-N Glycerophosphorylserin Natural products OC(=O)C(N)COP(O)(=O)OCC(O)CO ZWZWYGMENQVNFU-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- ATBOMIWRCZXYSZ-XZBBILGWSA-N [1-[2,3-dihydroxypropoxy(hydroxy)phosphoryl]oxy-3-hexadecanoyloxypropan-2-yl] (9e,12e)-octadeca-9,12-dienoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(COP(O)(=O)OCC(O)CO)OC(=O)CCCCCCC\C=C\C\C=C\CCCCC ATBOMIWRCZXYSZ-XZBBILGWSA-N 0.000 description 1
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
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- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Description
本発明は、ポリカプロラクトンをブレンド成分として含有した生分解性ポリマーよりなるハニカム構造接着フィルムに関するものであり、本発明で開示されているフィルムは、接着用途、とりわけ医療用の接着フィルム、インプラント用の接着フィルムとして好ましく利用しうる。以下、本文中のハニカム構造接着フィルムはハニカム構造を有する接着フィルムの意味で用いられる。 The present invention relates to a honeycomb structure adhesive film comprising a biodegradable polymer containing polycaprolactone as a blend component, and the film disclosed in the present invention is used for adhesive applications, particularly medical adhesive films and implants. It can be preferably used as an adhesive film. Hereinafter, the honeycomb structure adhesive film in the text is used to mean an adhesive film having a honeycomb structure.
これまでに、材料の表面にマイクロあるいはナノオーダーでの規則構造やパターニングを形成することにより、細胞の接着性や細胞の増殖能などを制御する技術が開発され、細胞培養のための容器や細胞チップなどの応用へと技術開発が進められている。これらの中で、ハニカム構造フィルムは、疎水性有機溶媒表面上に水滴を形成させることにより形成される微細構造を利用し、細胞培養基材への応用（特許文献１）、電子デバイスへの応用（特許文献２）、血液濾過膜への応用、癒着防止材への応用（特許文献４）などの研究がなされている。 So far, technologies have been developed to control cell adhesion and cell growth ability by forming micro- or nano-order regular structures and patterning on the surface of materials. Technological development is underway for applications such as chips. Among these, the honeycomb structure film uses a fine structure formed by forming water droplets on the surface of the hydrophobic organic solvent, and is applied to a cell culture substrate (Patent Document 1) and an electronic device. (Patent Document 2), application to blood filtration membranes, application to adhesion prevention materials (Patent Document 4) and the like have been studied.
ポリカプロラクトンを利用した例としては、血液濾過膜への応用（特許文献３）が開示されているが、生体への接着に関する記載はない。
乳酸とカプロラクトンからなる共重合体からなら多孔性癒着防止材（特許文献４）が開示されているが、凍結乾燥体からなるフィルムであり、均一なハニカム構造を得ることは出来ない。また、組織への接着性も有しておらず、融着固定することが明記されている。
As an example using polycaprolactone, application to a blood filtration membrane (Patent Document 3) is disclosed, but there is no description regarding adhesion to a living body.
A porous adhesion preventing material (Patent Document 4) is disclosed from a copolymer of lactic acid and caprolactone, but it is a film of a freeze-dried product, and a uniform honeycomb structure cannot be obtained. Moreover, it does not have the adhesiveness to a structure | tissue and it is specified that it fixes by fusion.
本発明者らによるハニカム構造を有する生分解性フィルムおよび癒着防止材に関する特許文献５では、癒着防止材として使用する方法としてハニカム構造体フィルムの開孔部を患部に貼付した後に、ハニカム構造が血液や組織液などの水分を吸着し、患部に定着させていることを開示している。臓器表面の保護をするためのカバー材、あるいは臓器表面での癒着防止効果を高めるために、より柔軟性、接着性が高められたフィルムが求められている。 In Patent Document 5 relating to a biodegradable film having a honeycomb structure and an adhesion preventing material by the present inventors, as a method of using as an adhesion preventing material, the honeycomb structure is blood after the pores of the honeycomb structure film are pasted on the affected area. And adsorbing moisture such as tissue fluid and fixing it to the affected area. There is a need for a cover material for protecting the organ surface, or a film with higher flexibility and adhesion in order to enhance the adhesion preventing effect on the organ surface.
本発明の目的は接着性に優れた生分解性のハニカム構造を有する接着フィルムを提供することであり、詳細には水分を含有する表面での接着力、とりわけ手術時の臓器表面に対する接着力が改良されたフィルムを提供する事を目的としている。 An object of the present invention is to provide an adhesive film having a biodegradable honeycomb structure excellent in adhesiveness, and in particular, has an adhesive force on a surface containing moisture, particularly an adhesive force on an organ surface during surgery. It aims to provide an improved film.
本発明はポリカプロラクトンを１から８０重量％ブレンド成分として含有する生分解性ポリマー１００重量部とリン脂質０．０１〜１００重量部とを含み、ハニカム構造を有する接着フィルムである。 The present invention is an adhesive film having a honeycomb structure containing 100 parts by weight of a biodegradable polymer containing 1 to 80% by weight of polycaprolactone as a blend component and 0.01 to 100 parts by weight of phospholipid.
本発明のハニカム構造を有する接着フィルムは、ポリカプロラクトンをブレンド成分として含有することにより優れた接着性を有する。それより医療用の材料、とりわけ接着フィルム、インプラント用の接着フィルムとして好ましく利用しうる。また本発明により、各種の用途に応じて任意の接着性を有するフィルムを提供できる。 The adhesive film having a honeycomb structure of the present invention has excellent adhesiveness by containing polycaprolactone as a blend component. It can be preferably used as a medical material, particularly as an adhesive film or an adhesive film for implants. Moreover, according to the present invention, a film having an arbitrary adhesiveness can be provided according to various uses.
以下、本発明について詳述する。
本発明は、ポリカプロラクトンを１から８０重量％ブレンド成分として含有する生分解性ポリマー１００重量部とリン脂質０．０１〜１００重量部とを含み、ハニカム構造を有するフィルムである。
Hereinafter, the present invention will be described in detail.
The present invention is a film having a honeycomb structure containing 100 parts by weight of a biodegradable polymer containing 1 to 80% by weight of polycaprolactone as a blend component and 0.01 to 100 parts by weight of phospholipid.
生分解性ポリマーにおけるポリカプロラクトンの重量比率は、目的に応じて変更することが可能である。より好ましくは５から６０重量％であり、より好ましくは１０から５０重量％である。ポリカプロラクトンの含有量が少ないと、柔軟性が低く、有効な接着強度が得られないことがある。また、ポリカプロラクトンの含有量が多すぎると、疎水性が高すぎて、有効な接着強度が得られないことがある。 The weight ratio of polycaprolactone in the biodegradable polymer can be changed according to the purpose. More preferably, it is 5 to 60% by weight, and more preferably 10 to 50% by weight. When the content of polycaprolactone is small, the flexibility is low and effective adhesive strength may not be obtained. Moreover, when there is too much content of polycaprolactone, hydrophobicity is too high and effective adhesive strength may not be obtained.
ポリカプロラクトン以外の生分解性ポリマー成分としては、
たとえば、ポリ乳酸、乳酸−グリコール酸共重合体、ポリヒドロキシ酪酸、ポリエチレンアジペート、ポリブチレンアジペートなどの生分解性脂肪族ポリエステル、ポリブチレンカーボネート、ポリエチレンカーボネート等の脂肪族ポリカーボネート等が、有機溶媒への溶解性の観点から好ましい。中でも、ポリ乳酸、乳酸−グリコール酸共重合体が入手の容易さ、価格等の観点から望ましい。
As biodegradable polymer components other than polycaprolactone,
For example, polylactic acid, lactic acid-glycolic acid copolymer, polyhydroxybutyric acid, polyethylene adipate, biodegradable aliphatic polyester such as polybutylene adipate, aliphatic polycarbonate such as polybutylene carbonate, polyethylene carbonate, etc. It is preferable from the viewpoint of solubility. Among these, polylactic acid and lactic acid-glycolic acid copolymer are desirable from the viewpoint of availability and price.
本発明のハニカム構造を有するフィルムは、生分解性ポリマー１００重量部に対し、リン脂質０．０１〜１００重量部とを含む。好ましくは０．２〜１０重量部である、より好ましくは、０．５〜２重量部である。リン脂質はハニカム構造を簡便に再現性よく得るために用いられ、また本発明の接着フィルムを医療用接着フィルムとして、好ましくはインプラント用の接着フィルムとして用いるために必須である。リン脂質は、動物組織から抽出したものでも、また人工的に合成して製造したものでもその起源を問うことなく使用できる。リン脂質としてはホスファチジルエタノールアミン、ホスファチジルコリン、ホスファチジルセリン、ホスファチジルグリセロールおよびそれらの誘導体からなる群から選択されてなるものを利用することが望ましい。好ましくはホスファチジルエタノールアミンであり、さらに好ましくはL−α−ホスファチジルエタノールアミン ジオレオイルである。 The film having a honeycomb structure of the present invention includes 0.01 to 100 parts by weight of phospholipid with respect to 100 parts by weight of the biodegradable polymer. Preferably it is 0.2-10 weight part, More preferably, it is 0.5-2 weight part. Phospholipids are used in order to easily obtain a honeycomb structure with good reproducibility, and are essential for using the adhesive film of the present invention as a medical adhesive film, preferably as an adhesive film for implants. Phospholipids can be used regardless of their origin, whether extracted from animal tissue or artificially synthesized. It is desirable to use a phospholipid selected from the group consisting of phosphatidylethanolamine, phosphatidylcholine, phosphatidylserine, phosphatidylglycerol and derivatives thereof. Preferred is phosphatidylethanolamine, and more preferred is L-α-phosphatidylethanolamine dioleoyl.
本発明においてハニカム構造とは、ハニカム状に配置された複数の細孔を有する構造であって、複数の細孔同士の位置関係は、図１に示す正六角形同士の位置関係と対応する。従って、一つ細孔の周辺には６個の細孔が配置されている。図２に円形の細孔がハニカム状に配置された状態を示す。細孔は、実質的に同一形状であることが好ましい。細孔は、好ましくは直径０．１〜１００μｍ、より好ましくは１〜２０μｍ、より好ましくは１〜１５μｍ、さらに好ましくは１〜１０μｍの円形であることが好ましい。細孔の直径（半径）は表面における孔の直径（半径）のことを言う。細孔の半径をｒとし、隣接する細孔の中心間の距離をａとすると、ｒとａとは、１＜ａ／２ｒ＜２で表されることが好ましい。 In the present invention, the honeycomb structure is a structure having a plurality of pores arranged in a honeycomb shape, and the positional relationship between the plurality of pores corresponds to the positional relationship between regular hexagons shown in FIG. Accordingly, six pores are arranged around one pore. FIG. 2 shows a state where circular pores are arranged in a honeycomb shape. It is preferable that the pores have substantially the same shape. The pores are preferably circular having a diameter of 0.1 to 100 μm, more preferably 1 to 20 μm, more preferably 1 to 15 μm, and still more preferably 1 to 10 μm. The diameter (radius) of the pores refers to the diameter (radius) of the pores on the surface. When the radius of the pore is r and the distance between the centers of adjacent pores is a, r and a are preferably represented by 1 <a / 2r <2.
ハニカム構造接着フィルムの製造方法としては、ポリカプロラクトンを１から８０重量％ブレンド成分として含有する生分解性ポリマー、リン脂質、および有機溶媒を含むポリマー溶液を、相対湿度５０〜９５％の大気下で基板上にキャストし、該有機溶媒を徐々に蒸散させ、同時に該キャスト液表面で結露させ、該結露により生じた微小水滴を蒸発させる方法が好ましく挙げられる。 As a method for producing an adhesive film having a honeycomb structure, a polymer solution containing a biodegradable polymer, a phospholipid, and an organic solvent containing 1 to 80% by weight of polycaprolactone as a blend component is used in an atmosphere with a relative humidity of 50 to 95%. A method of casting on a substrate, gradually evaporating the organic solvent, and simultaneously condensing on the surface of the casting solution, and evaporating fine water droplets generated by the condensation is preferable.
該方法において、ポリマー溶液上に微小な水滴粒子を形成させることが必須である事から、使用する有機溶剤としては非水溶性である事が必要である。これらの例としてはクロロホルム、塩化メチレン等のハロゲン系有機溶剤、ベンゼン、トルエン、キシレン等の芳香族炭化水素、酢酸エチル、酢酸ブチル等のエステル類、メチルイソブチルケトン、などの非水溶性ケトン類、二硫化炭素などが挙げられる。これらの有機溶媒は単独で使用しても、又、これらの溶媒を組み合わせた混合溶媒として使用してもかまわない。 In this method, since it is essential to form fine water droplet particles on the polymer solution, the organic solvent to be used must be water-insoluble. Examples thereof include halogen-based organic solvents such as chloroform and methylene chloride, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, and water-insoluble ketones such as methyl isobutyl ketone, Examples include carbon disulfide. These organic solvents may be used alone or as a mixed solvent in which these solvents are combined.
これらに溶解する生分解性ポリマーとリン脂質両者併せてのポリマー濃度は０.０１から１０ｗｔ％、より好ましくは０.０５から５ｗｔ％である。ポリマー濃度が０.０１ｗｔ％より低いと得られるフィルムの力学強度が不足し望ましくない。又、１０ｗｔ％以上ではポリマー濃度が高くなりすぎ、十分なハニカム構造が得られない。又、生分解性ポリマーとリン脂質の組成比は、生分解性ポリマー１００重量部に対して０．０１〜１００重量部のリン脂質を含む。リン脂質が生分解性ポリマーに対して０．０１重量部以下では均一なハニカム構造が得られないことがあり、又、１００重量部以上ではフィルムとしての自己支持性を有しておらず、コストも高く、経済性に乏しい場合がある。 The polymer concentration of both the biodegradable polymer and phospholipid dissolved in these is 0.01 to 10 wt%, more preferably 0.05 to 5 wt%. If the polymer concentration is lower than 0.01 wt%, the resulting film has insufficient mechanical strength, which is not desirable. On the other hand, if it is 10 wt% or more, the polymer concentration becomes too high and a sufficient honeycomb structure cannot be obtained. The composition ratio of the biodegradable polymer and the phospholipid includes 0.01 to 100 parts by weight of phospholipid with respect to 100 parts by weight of the biodegradable polymer. If the phospholipid is 0.01 parts by weight or less with respect to the biodegradable polymer, a uniform honeycomb structure may not be obtained, and if it is 100 parts by weight or more, the film does not have a self-supporting property, and the cost is low. May be poor and economical.
ハニカム構造フィルムの製造方法としては該ポリマー有機溶媒溶液を基板上にキャストしハニカム構造フィルムを調製する方法が好ましく挙げられる。該基板としてはガラス、金属、シリコンウェハー等の無機材料、ポリプロピレン、ポリエチレン、ポリエーテルケトン等の耐有機溶剤製に優れた高分子、水、流動パラフィン、液状ポリエーテル等の液体が使用できる。中でも、基材に水を使用した場合、該ハニカム構造体の特徴である自立性を生かすことで、該構造体を単独で容易に基板から取り出すことが出来、好適である。 As a method for producing a honeycomb structure film, a method of preparing the honeycomb structure film by casting the polymer organic solvent solution on a substrate is preferable. As the substrate, there can be used inorganic materials such as glass, metal, silicon wafers, liquids such as polymer, water, liquid paraffin, liquid polyether and the like, which are excellent in organic solvent resistant materials such as polypropylene, polyethylene, polyetherketone. In particular, when water is used as the base material, it is preferable that the structure can be easily taken out from the substrate by taking advantage of the self-supporting property of the honeycomb structure.
本発明で、ハニカム構造が形成される機構は次のように考えられる。疎水性有機溶媒が蒸発するとき、潜熱を奪う為に、キャストフィルム表面の温度が下がり、微小な水の液滴がポリマー溶液表面に凝集、付着する。ポリマー溶液中の親水性部分の働きによって水と疎水性有機溶媒の間の表面張力が減少し、このため、水微粒子は凝集して1つの塊になろうとし、安定化する。溶媒が蒸発するに伴い、ヘキサゴナルの形をした液滴が最密充填した形で並び、最後に、水が飛び、ポリマーが規則正しくハニカム状に並んだ形として残る。従って、該フィルムを調製するためには相対湿度が３０から１００％の範囲にある水蒸気を吹き付けることが望ましい。相対湿度は好ましくは５０〜９５％、より好ましくは５０〜９０％である。相対湿度が３０%以下ではキャストフィルム上への結露が不十分になり作製が難しい場合がある。このようにしてできるハニカム構造体中個々のハニカムの空隙内径は０．１から１００μｍである。このようにして作製したハニカム構造接着フィルムは、表面がハニカム構造を有し、膜厚が充分厚い場合は、基盤に接していた裏面は孔が貫通していない平らな面となる。また、膜厚が水滴の大きさよりも薄い場合は孔が貫通したフィルムが得られる。 In the present invention, the mechanism for forming the honeycomb structure is considered as follows. When the hydrophobic organic solvent evaporates, in order to take away latent heat, the temperature of the cast film surface decreases, and minute water droplets aggregate and adhere to the polymer solution surface. The surface tension between the water and the hydrophobic organic solvent is reduced by the action of the hydrophilic portion in the polymer solution, so that the water fine particles are aggregated to become one lump and stabilize. As the solvent evaporates, the hexagonal-shaped droplets are arranged in a close-packed form, and finally, water is ejected, leaving the polymer in a regular honeycomb-like form. Therefore, it is desirable to spray water vapor having a relative humidity in the range of 30 to 100% in order to prepare the film. The relative humidity is preferably 50 to 95%, more preferably 50 to 90%. When the relative humidity is 30% or less, the condensation on the cast film is insufficient and the production may be difficult. The void inner diameter of each honeycomb in the honeycomb structure thus formed is 0.1 to 100 μm. When the surface of the honeycomb structure adhesive film produced in this way has a honeycomb structure and the film thickness is sufficiently thick, the back surface in contact with the substrate is a flat surface without holes. Moreover, when the film thickness is thinner than the size of the water droplet, a film having holes penetrating is obtained.
本発明の接着フィルムは水分を含有する表面での接着力、とりわけ手術時の臓器表面に対する接着力に優れている。具体的にはハニカムフィルムの開孔部を被接着表面に貼付する。このときハニカム構造に血液や組織液などの水分を吸収し接着性を帯びるが、本発明の接着フィルムは構成するポリマーがポリカプロラクトンをブレンド成分として有することにより、優れた接着性を有する。 The adhesive film of the present invention is excellent in the adhesive force on the surface containing moisture, particularly the adhesive force on the organ surface during surgery. Specifically, the hole portion of the honeycomb film is attached to the adherend surface. At this time, the honeycomb structure absorbs moisture such as blood and tissue fluid and has adhesiveness. However, the adhesive film of the present invention has excellent adhesiveness because the polymer constituting it has polycaprolactone as a blend component.
また、本接着フィルムを使用直前まで表面を保護するために、フィルムの両面を剥離シートで保護することも可能である。本ハニカム構造接着フィルムは、両面の表裏面の構造が違うため、ハニカム構造面の保護用剥離シートが容易に剥離でき、使用面を適用部位に貼付した後に、残る剥離シートを容易に剥離することができる。 Further, in order to protect the surface of the adhesive film until just before use, both surfaces of the film can be protected with a release sheet. Since this honeycomb structure adhesive film has different structures on both sides, the protective release sheet on the honeycomb structure surface can be easily peeled off, and the remaining release sheet can be easily peeled off after the used surface is attached to the application site. Can do.
本発明におけるハニカム構造接着フィルムの膜厚は、通常１〜１０μｍであり、これに基体フィルムを積層させて積層体を形成させることにより任意の厚みを有する積層フィルムを得ることができる。すなわち本発明はハニカム構造を有する接着フィルムと基体層とを含む積層体からなる接着フィルムを含む。 The film thickness of the honeycomb structure adhesive film in the present invention is usually 1 to 10 μm, and a laminated film having an arbitrary thickness can be obtained by laminating a base film thereon to form a laminated body. That is, the present invention includes an adhesive film comprising a laminate including an adhesive film having a honeycomb structure and a base layer.
積層フィルムを構成する場合、基体フィルムはいずれのポリマーでも良いが、好ましくは合成高分子、本発明の接着フィルムを医療用接着フィルムとして、好ましくはインプラント用の接着フィルムとして用いるためにより好ましくは生分解性ポリマーが用いられる。生分解性ポリマーとしてはポリ乳酸、乳酸−グリコール酸共重合体、ポリヒドロキシ酪酸、ポリカプロラクトン、ポリエチレンアジペート、ポリブチレンアジペートなどの生分解性脂肪族ポリエステル、ポリブチレンカーボネート、ポリエチレンカーボネート等の脂肪族ポリカーボネート等が、有機溶媒への溶解性の観点から好ましい。中でも、ポリ乳酸、乳酸−グリコール酸共重合体、ポリカプロラクトンが入手の容易さ、価格等の観点から望ましい。 When constituting a laminated film, the base film may be any polymer, but is preferably a synthetic polymer, more preferably biodegradable because the adhesive film of the present invention is used as a medical adhesive film, preferably as an adhesive film for implants. A functional polymer is used. Biodegradable polymers include polylactic acid, lactic acid-glycolic acid copolymer, polyhydroxybutyric acid, polycaprolactone, polyethylene adipate, polybutylene adipate and other aliphatic biodegradable polyesters, polybutylene carbonate, polyethylene carbonate and other aliphatic polycarbonates Etc. are preferred from the viewpoint of solubility in organic solvents. Among these, polylactic acid, lactic acid-glycolic acid copolymer, and polycaprolactone are desirable from the viewpoint of availability, price, and the like.
基体フィルムの作成方法としては、特に限定されないが、たとえばキャスト法や溶融成型法などが選択することができる。キャストフィルムを作成する場合に使用する有機溶媒としては、揮発性溶媒が好ましい。本発明で溶液を形成する揮発性溶媒とは、常圧での沸点が２００℃以下であり、２７℃で液体である物質である。揮発性溶媒としては、脂肪族ポリエステルを溶解することができるものであれば特に限定されない。揮発性溶媒としては、例えば塩化メチレン、クロロホルム、アセトン、メタノール、エタノール、プロパノール、イソプロパノール、トルエン、テトラヒドロフラン、1,1,1,3,3,3−ヘキサフルオロイソプロパノール、水、1,4−ジオキサン、四塩化炭素、シクロヘキサン、シクロヘキサノン、N,N−ジメチルホルムアミド、アセトニトリルなどが挙げられる。これらのうち、脂肪族ポリエステルの溶解性等から、塩化メチレン、クロロホルム、アセトンが特に好ましい。これらの溶媒は単独で用いても良く、複数の溶媒を組み合わせても良い。 The method for producing the base film is not particularly limited, and for example, a casting method or a melt molding method can be selected. As an organic solvent used when producing a cast film, a volatile solvent is preferable. The volatile solvent that forms a solution in the present invention is a substance that has a boiling point of 200 ° C. or less at normal pressure and is liquid at 27 ° C. The volatile solvent is not particularly limited as long as it can dissolve the aliphatic polyester. Examples of volatile solvents include methylene chloride, chloroform, acetone, methanol, ethanol, propanol, isopropanol, toluene, tetrahydrofuran, 1,1,1,3,3,3-hexafluoroisopropanol, water, 1,4-dioxane, Examples thereof include carbon tetrachloride, cyclohexane, cyclohexanone, N, N-dimethylformamide, acetonitrile and the like. Among these, methylene chloride, chloroform, and acetone are particularly preferable in view of the solubility of the aliphatic polyester. These solvents may be used alone, or a plurality of solvents may be combined.
積層フィルムとする場合、ハニカム構造接着フィルムを、少なくとも１層の基体フィルム上に積層することにより得ることができる。図３にその模式図を記す。
すなわち積層フィルムの製造方法として好ましく挙げられるのは、ポリカプロラクトンを１から８０重量％ブレンド成分として含有する生分解性ポリマー、リン脂質、および有機溶媒を含むポリマー溶液を、相対湿度５０〜９５％の大気下で基板上にキャストし、該有機溶媒を徐々に蒸散させ、同時に該キャスト液表面で結露させ、該結露により生じた微小水滴を蒸発させることで得られる生分解性ポリマーからなるハニカム構造接着フィルムを、少なくとも１層の生分解性ポリマーからなる基体フィルム上に積層する方法である。
In the case of a laminated film, the honeycomb structure adhesive film can be obtained by laminating on at least one base film. The schematic diagram is shown in FIG.
That is, a preferable method for producing a laminated film is that a polymer solution containing a biodegradable polymer, a phospholipid, and an organic solvent containing 1 to 80% by weight of polycaprolactone as a blend component has a relative humidity of 50 to 95%. Honeycomb structure adhesion consisting of biodegradable polymer obtained by casting on a substrate in the atmosphere, gradually evaporating the organic solvent, condensing at the casting liquid surface, and evaporating minute water droplets generated by the condensation In this method, the film is laminated on a base film made of at least one biodegradable polymer.
本発明におけるハニカム構造接着フィルムおよび少なくとも一層の基体フィルムの積層方法としては、特に限定されないが、たとえば、基体フィルムを作製した上に別に作製しておいたハニカム構造接着フィルムを積層後、熱圧着により貼付させることができる。
熱圧着の温度は特に制限はないが、ハニカム構造接着フィルムの材質や、基体フィルムの材質のガラス転移点よりも高い温度であることが好ましい。熱圧着をより効率的に進めるために、必要に応じてシリコンゴムなどの弾性体を圧着時にはり合わせてプレスすることも可能である。
The method for laminating the honeycomb structure adhesive film and at least one substrate film in the present invention is not particularly limited. For example, after the substrate film is produced and the honeycomb structure adhesive film prepared separately is laminated, thermocompression bonding is performed. Can be affixed.
The temperature for thermocompression bonding is not particularly limited, but is preferably higher than the glass transition point of the material for the honeycomb structure adhesive film or the material for the substrate film. In order to proceed the thermocompression bonding more efficiently, it is possible to press an elastic body such as silicon rubber together as needed during the compression bonding.
積層接着フィルム全体の膜厚は１０μｍ以上であることが好ましく、より好ましくは１５μｍ以上である。ハニカム構造接着フィルムは上述のとおり通常１〜１０μｍであることから、基体フィルムの膜厚は適宜選択できる。基体フィルムの膜厚の上限は特に限定されず、用途に応じて調整することが出来る。必要に応じてキャスト法や溶融法により、必要となる積層接着フィルム全体フィルムの厚みから、ハニカム構接着造フィルムの厚みを除いた膜厚に設定し作成することができる。また、基体フィルムは必要に応じて、ハニカム構造接着フィルムを積層させる前に、それ自身を積層させてもよい。 The total thickness of the laminated adhesive film is preferably 10 μm or more, more preferably 15 μm or more. Since the honeycomb structure adhesive film is usually 1 to 10 μm as described above, the thickness of the base film can be appropriately selected. The upper limit of the film thickness of a base film is not specifically limited, It can adjust according to a use. If necessary, the film thickness can be prepared by setting the film thickness excluding the thickness of the entire laminated adhesive film from the required thickness of the laminated adhesive film by a casting method or a melting method. In addition, the base film may be laminated as needed before the honeycomb structure adhesive film is laminated.
また、ハニカム構造接着フィルムを基体フィルムの両面に存在させることもできる。例えば図４に示すように、基体フィルムの上下にハニカム構造フィルムを積層させることもでき、またハニカム構造接着フィルムどうしを積層することもできる。ハニカム構造接着フィルムどうしを積層する場合は一方のハニカム構造接着フィルムが基体フィルムとなっている。 In addition, the honeycomb structure adhesive film can be present on both sides of the base film. For example, as shown in FIG. 4, honeycomb structure films can be laminated on the top and bottom of the base film, and honeycomb structure adhesive films can be laminated. When the honeycomb structure adhesive films are laminated, one of the honeycomb structure adhesive films is a base film.
両面をハニカム層とする場合、２つの表面を構成する層は同一の材質および／またはハニカム孔径を有していても、それぞれ異なった材質および／またはハニカム孔径を有していても良く、種々の目的に合わせて適当な構成とすることができる。
基体フィルムはハニカム構造接着フィルムと同一の高分子でも、異種高分子でもよい。たとえば、基体フィルムの分解をより早くさせたい場合は、基体フィルムの高分子にポリ乳酸を使用するなど、使用目的により自由に選択することができる。
When both sides are formed as a honeycomb layer, the layers constituting the two surfaces may have the same material and / or honeycomb pore diameter, or may have different materials and / or honeycomb pore diameters. It can be set as a suitable structure according to the objective.
The base film may be the same polymer as the honeycomb structure adhesive film or a different polymer. For example, when it is desired to decompose the base film faster, it can be freely selected depending on the purpose of use, such as using polylactic acid as a polymer for the base film.
以下に実施例を示し、本発明を更に具体的に説明するが、本発明はこれら実施例の記載に限定されるものではない。 Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.
[実施例１]
ポリ乳酸（Mｗ＝２０２，０００：島津製作所）とポリカプロラクトン（Mw=７００，０００〜１，０００，０００：和光純薬）のブレンド体（ブレンドの重量比；ポリ乳酸：ポリカプロラクトン＝８８：１２のクロロホルム溶液（５ｇ／L）に、ホスファチジルエタノールアミン−ジオレオイルをポリマーに対し１／２００の割合（重量）で混合し、ポリマー溶液を調製した。ポリマー溶液をガラス基板上にキャストし、液状膜を得た。
[Example 1]
Blend of polylactic acid (Mw = 202,000: Shimadzu Corporation) and polycaprolactone (Mw = 700,000 to 1,000,000: Wako Pure Chemical Industries) (weight ratio of blend; polylactic acid: polycaprolactone = 88: 12 A phosphatidylethanolamine-dioleoyl was mixed with a chloroform solution (5 g / L) in a ratio (weight) of 1/200 to the polymer to prepare a polymer solution, which was cast on a glass substrate to form a liquid film. Obtained.
次に、液状膜を室温、湿度７０％の水蒸気を吹き付け、溶媒を徐々に蒸発ささせると共に水蒸気を液状膜表面に結露させ水滴を形成させ、ついで水滴を蒸発させフィルムを調製した。
得られたフィルムは、全表面に孔径約５．５μｍの細孔が均一にハニカム状に配置された凹凸部を有し、裏面は平滑で、厚さ１０μｍの非貫通フィルムであった。フィルムの凹凸部の顕微鏡写真を図５に示す。
Next, water vapor was sprayed on the liquid film at room temperature and humidity of 70% to gradually evaporate the solvent and to condense the water vapor on the surface of the liquid film to form water droplets, and then the water droplets were evaporated to prepare a film.
The obtained film had a concavo-convex portion in which pores having a pore diameter of approximately 5.5 μm were uniformly arranged in a honeycomb shape on the entire surface, the back surface was smooth, and was a non-penetrating film having a thickness of 10 μm. A photomicrograph of the uneven portion of the film is shown in FIG.
作製したフィルムの接着強度を以下の方法で測定した。フィルムを２×２cm２にカットし、これを２×３ｃｍ２にカットしたキャストフィルムに貼り付け５０ ℃，１０min.熱セットした。レオメーターSR5のバーにクリップのついた糸の一方を固定し、このクリップにフィルムを挟み、フィルムを鶏肉（精肉、胸肉）に貼り付けた。測定を開始し、フィルムが剥がれたときの降伏応力を算出し、接着強度とした。接着強度は測定回数５回の平均値より求めたところ、３５８K0 2/Paであった。 The adhesive strength of the produced film was measured by the following method. The film was cut into 2 × 2 cm 2 , attached to a cast film cut into 2 × 3 cm 2, and heat set at 50 ° C. for 10 min. One thread with a clip was fixed to the bar of the rheometer SR5, a film was sandwiched between the clips, and the film was affixed to chicken (meat, breast). The measurement was started and the yield stress when the film was peeled off was calculated as the adhesive strength. The bond strength was 358 K 0 2 / Pa as determined from the average value of 5 measurements.
[実施例２]
ポリ乳酸（Mｗ＝２０２，０００：島津製作所）とポリカプロラクトン（Mw=７００，０００〜１，０００，０００：和光純薬）のブレンド体（ブレンドの重量比；ポリ乳酸：ポリカプロラクトン＝５０：５０のクロロホルム溶液（５ｇ／L）に、ホスファチジルエタノールアミン−ジオレオイルをポリマーに対し１／２００の割合（重量）で混合し、ポリマー溶液を調製した。ポリマー溶液をガラス基板上にキャストし、液状膜を得た。
[Example 2]
Blend of polylactic acid (Mw = 202,000: Shimadzu Corporation) and polycaprolactone (Mw = 700,000 to 1,000,000: Wako Pure Chemical Industries) (weight ratio of blend; polylactic acid: polycaprolactone = 50: 50 A phosphatidylethanolamine-dioleoyl was mixed with a chloroform solution (5 g / L) in a ratio (weight) of 1/200 to the polymer to prepare a polymer solution, which was cast on a glass substrate to form a liquid film. Obtained.
次に、液状膜を室温、湿度７０％の水蒸気を吹き付け、溶媒を徐々に蒸発ささせると共に水蒸気を液状膜表面に結露させ水滴を形成させ、ついで水滴を蒸発させフィルムを調製した。
得られたフィルムは、全表面に孔径約５μｍの細孔が均一にハニカム状に配置された凹凸部を有し、裏面は平滑で、厚さ１０μｍの非貫通フィルムであった。フィルムの凹凸部の顕微鏡写真を図６に示す。
Next, water vapor was sprayed on the liquid film at room temperature and humidity of 70% to gradually evaporate the solvent and to condense the water vapor on the surface of the liquid film to form water droplets, and then the water droplets were evaporated to prepare a film.
The obtained film was a non-penetrating film having a concavo-convex portion in which pores having a pore diameter of about 5 μm were uniformly arranged in a honeycomb shape on the entire surface, a smooth back surface, and a thickness of 10 μm. A photomicrograph of the uneven portion of the film is shown in FIG.
作製したフィルムの接着強度を以下の方法で測定した。フィルムを２×２cm２にカットし、これを２×３ｃｍ２にカットしたキャストフィルムに貼り付け５０ ℃，１０min.熱セットした。レオメーターSR5のバーにクリップのついた糸の一方を固定し、このクリップにフィルムを挟み、フィルムを鶏肉（精肉、胸肉）に貼り付けた。測定を開始し、フィルムが剥がれたときの降伏応力を算出し、接着強度とした。接着強度は測定回数５回の平均値より求めたところ、５２８K0 2/Paであった。 The adhesive strength of the produced film was measured by the following method. The film was cut into 2 × 2 cm 2 , attached to a cast film cut into 2 × 3 cm 2, and heat set at 50 ° C. for 10 min. One thread with a clip was fixed to the bar of the rheometer SR5, a film was sandwiched between the clips, and the film was affixed to chicken (meat, breast). The measurement was started and the yield stress when the film was peeled off was calculated as the adhesive strength. The adhesion strength was 528 K 0 2 / Pa as determined from the average value of the number of measurements 5 times.
[実施例３]
ポリ乳酸（Mｗ＝２０２，０００：島津製作所）とポリカプロラクトン（Mw=７００，０００〜１，０００，０００：和光純薬）のブレンド体（ブレンドの重量比；ポリ乳酸：ポリカプロラクトン＝２０：８０のクロロホルム溶液（５ｇ／L）に、ホスファチジルエタノールアミン−ジオレオイルをポリマーに対し１／２００の割合（重量）で混合し、ポリマー溶液を調製した。ポリマー溶液をガラス基板上にキャストし、液状膜を得た。
[Example 3]
Blend of polylactic acid (Mw = 202,000: Shimadzu Corporation) and polycaprolactone (Mw = 700,000 to 1,000,000: Wako Pure Chemical Industries) (weight ratio of blend; polylactic acid: polycaprolactone = 20: 80 A phosphatidylethanolamine-dioleoyl was mixed with a chloroform solution (5 g / L) in a ratio (weight) of 1/200 to the polymer to prepare a polymer solution, which was cast on a glass substrate to form a liquid film. Obtained.
次に、液状膜を室温、湿度７０％の水蒸気を吹き付け、溶媒を徐々に蒸発ささせると共に水蒸気を液状膜表面に結露させ水滴を形成させ、ついで水滴を蒸発させフィルムを調製した。
得られたフィルムは、全表面に孔径約６．５μｍの細孔が均一にハニカム状に配置された凹凸部を有し、裏面は平滑で、厚さ１０μｍの非貫通フィルムであった。フィルムの凹凸部の顕微鏡写真を図７に示す。
Next, water vapor was sprayed on the liquid film at room temperature and humidity of 70% to gradually evaporate the solvent and to condense the water vapor on the surface of the liquid film to form water droplets, and then the water droplets were evaporated to prepare a film.
The obtained film was a non-penetrating film having a concavo-convex portion in which pores having a pore diameter of about 6.5 μm were uniformly arranged in a honeycomb shape on the entire surface, a smooth back surface, and a thickness of 10 μm. A photomicrograph of the uneven portion of the film is shown in FIG.
作製したフィルムの接着強度を以下の方法で測定した。フィルムを２×２cm２にカットし、これを２×３ｃｍ２にカットしたキャストフィルムに貼り付け５０ ℃，１０min.熱セットした。レオメーターSR5のバーにクリップのついた糸の一方を固定し、このクリップにフィルムを挟み、フィルムを鶏肉（精肉、胸肉）に貼り付けた。測定を開始し、フィルムが剥がれたときの降伏応力を算出し、接着強度とした。接着強度は測定回数５回の平均値より求めたところ、３６７K0 2/Paであった。 The adhesive strength of the produced film was measured by the following method. The film was cut into 2 × 2 cm 2 , attached to a cast film cut into 2 × 3 cm 2, and heat set at 50 ° C. for 10 min. One thread with a clip was fixed to the bar of the rheometer SR5, a film was sandwiched between the clips, and the film was affixed to chicken (meat, breast). The measurement was started and the yield stress when the film was peeled off was calculated as the adhesive strength. The bond strength was 367 K 0 2 / Pa as determined from the average value of 5 measurements.
[比較例１]
ポリ乳酸（Mｗ＝２０２，０００：島津製作所）のクロロホルム溶液（５ｇ／L）に、ホスファチジルエタノールアミン−ジオレオイルをポリマーに対し１／２００の割合（重量）で混合し、ポリマー溶液を調製した。ポリマー溶液をガラス基板上にキャストし、液状膜を得た。
次に、液状膜を室温、湿度７０％の水蒸気を吹き付け、溶媒を徐々に蒸発ささせると共に水蒸気を液状膜表面に結露させ水滴を形成させ、ついで水滴を蒸発させフィルムを調製した。
[Comparative Example 1]
A polymer solution was prepared by mixing phosphatidylethanolamine-dioleoyl with a chloroform solution (5 g / L) of polylactic acid (Mw = 202,000: Shimadzu Corporation) at a ratio (weight) of 1/200 to the polymer. The polymer solution was cast on a glass substrate to obtain a liquid film.
Next, water vapor was sprayed on the liquid film at room temperature and humidity of 70% to gradually evaporate the solvent and to condense the water vapor on the surface of the liquid film to form water droplets, and then the water droplets were evaporated to prepare a film.
作製したフィルムの接着強度を以下の方法で測定した。フィルムを２×２cm２にカットし、これを２×３ｃｍ２にカットしたキャストフィルムに貼り付け５０ ℃，１０min.熱セットした。レオメーターSR5のバーにクリップのついた糸の一方を固定し、このクリップにフィルムを挟み、フィルムを（精肉、胸肉）に貼り付けた。測定を開始し、フィルムが剥がれたときの降伏応力を算出し、接着強度とした。接着強度は測定回数５回の平均値より求めたところ、１９３K0 2/Paであった。 The adhesive strength of the produced film was measured by the following method. The film was cut into 2 × 2 cm 2 , attached to a cast film cut into 2 × 3 cm 2, and heat set at 50 ° C. for 10 min. One thread with a clip was fixed to the bar of the rheometer SR5, a film was sandwiched between the clips, and the film was affixed to (meat, breast). The measurement was started and the yield stress when the film was peeled off was calculated as the adhesive strength. The bond strength was 193 K 0 2 / Pa as determined from the average value of 5 measurements.
本発明で開示されているフィルムは、接着用途、とりわけ医療用の接着フィルム、インプラント用の接着フィルムとして好ましく利用しうる。例えば、手術を行った後に、欠損したり、収縮して縫合できない部分の代用として使用することができる。また、様々な外科的手術時に生じる癒着を防止するために使用することもできる。また、手術時の手術用具固定材として使用することもできる。また、縫合部のシーリング材として使用することもできる。本フィルムは接着性を有しているため、縫合せずに体内に留置することが出来、医師の手間、手術時間の短縮、患者のQOLの向上に役立てることが可能である。 The film disclosed in the present invention can be preferably used as an adhesive application, particularly as a medical adhesive film or an implant adhesive film. For example, it can be used as a substitute for a portion that is lost or contracted and cannot be sutured after surgery. It can also be used to prevent adhesions that occur during various surgical procedures. It can also be used as a surgical tool fixing material during surgery. It can also be used as a sealing material for a stitched portion. Since this film has adhesiveness, it can be left in the body without suturing, and can be used for reducing the labor of the doctor, shortening the operation time, and improving the QOL of the patient.
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