JP2003192807A - Silk protein film and method for producing the same - Google Patents
Silk protein film and method for producing the sameInfo
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- JP2003192807A JP2003192807A JP2001400222A JP2001400222A JP2003192807A JP 2003192807 A JP2003192807 A JP 2003192807A JP 2001400222 A JP2001400222 A JP 2001400222A JP 2001400222 A JP2001400222 A JP 2001400222A JP 2003192807 A JP2003192807 A JP 2003192807A
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- silk protein
- film
- silk
- aqueous solution
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Abstract
(57)【要約】
【課題】 生分解性を有し、環境保全型のタンパク質材
料として、多機能性フィルムへの応用が可能で、製造過
程の簡易化、材料の透明化等が注目される、新しい絹タ
ンパク質フィルムを提供する。
【解決手段】 主として絹タンパク質からなり、炭酸ガ
スが微量にのみ、または存在しない不活性ガス雰囲気条
件で絹タンパク質水溶液を乾燥することによってキャス
トフィルムとする。
(57) [Summary] [Problem] As a biodegradable, environmentally-friendly protein material, it can be applied to multifunctional films, and simplification of the manufacturing process, transparency of the material, etc. are attracting attention. Provide a new silk protein film. SOLUTION: A cast film is mainly formed by drying an aqueous solution of silk protein under an inert gas atmosphere condition in which only a trace amount of carbon dioxide gas or no carbon dioxide gas is present.
Description
【０００１】[0001]
【発明の属する技術分野】この出願の発明は、絹タンパ
ク質フィルムとその製造方法に関するものである。TECHNICAL FIELD The present invention relates to a silk protein film and a method for producing the same.
【０００２】さらに詳しくは、この出願の発明は、生分
解性の環境調和型の新しい材料を提供可能とし、高強
度、高弾性な多機能性フィルムとして、医療材料や食品
材料等として有用な、絹タンパク質フィルムとその製造
方法に関するものである。More specifically, the invention of this application can provide a new biodegradable, environmentally friendly material, which is useful as a high-strength, highly elastic multifunctional film, as a medical material, a food material, or the like. The present invention relates to a silk protein film and a method for producing the same.
【０００３】[0003]
【従来の技術とその課題】従来より、フィルム材料とし
て、合成樹脂や天然樹脂由来の各種のものが知られてお
り、その一種としてタンパク質のフィルムが、不織布や
生体適合性膜として、利用されてきている。そして、コ
ラーゲン等のタンパク質フィルムは、各種の用途におい
て注目されているものである。2. Description of the Related Art Conventionally, various materials derived from synthetic resins and natural resins have been known as film materials, and as one of them, protein films have been used as nonwoven fabrics and biocompatible membranes. ing. Protein films such as collagen have been attracting attention in various applications.
【０００４】しかしながら、従来産業や社会生活におい
て用いられているフィルムの圧倒的に多くのものは、そ
のいずれもが石油系原料等より製造された合成樹脂のフ
ィルムである。これらの合成樹脂フィルムは、資源、エ
ネルギー多消費型であり、廃棄物としての処分が容易で
はない。そこで、生分解性を有し、環境調和型の材料と
してタンパク質フィルムが注目されるところではある
が、従来では、製造工程が多いため、エネルギー多消費
型となり、環境負荷が大きいという問題を有している。However, the overwhelming majority of films conventionally used in industry and social life are all synthetic resin films manufactured from petroleum-based raw materials. These synthetic resin films are a resource and energy consuming type and are not easy to dispose as waste. Therefore, although protein films are biodegradable and are attracting attention as environmentally friendly materials, they have a problem that they are energy-intensive and have a large environmental load because of the large number of manufacturing processes. ing.
【０００５】この出願の発明は、以上のとおりの事情に
鑑みてなされたものであり、従来の合成樹脂フィルムに
代わるものとして、生分解性を有し、環境保全型のタン
パク質材料として、医療材料や食品材料等への応用が可
能で、しかも従来のタンパク質材料に代わるものとし
て、製造過程の簡易化、材料の透明化等が注目される、
カイコやクモから得られる絹フイブロインとセリシンを
用いた絹タンパク質材料として、新しい絹タンパク質フ
ィルムを提供することを課題としている。The invention of this application was made in view of the above circumstances, and as an alternative to the conventional synthetic resin film, it has biodegradability and is used as a medical material as an environmentally friendly protein material. As a substitute for conventional protein materials, it can be applied to food materials, food materials, etc., and attention is focused on simplification of the manufacturing process, transparency of materials, etc.
It is an object to provide a new silk protein film as a silk protein material using silk fibroin obtained from silkworms and spiders and sericin.
【０００６】[0006]
【課題を解決するための手段】この出願の発明は、上記
の課題を解決するものとして、第１には、主として絹タ
ンパク質水溶液のキャストフィルムであることを特徴と
する絹タンパク質フィルムを提供し、第２には、絹タン
パク質がフイブロインおよびセリシンの少くともいずれ
かであることを特徴とする絹タンパク質フィルムを、第
３には、絹タンパク質が天然に産出されたもの、および
人為的に合成もしくは改変されたものの少くともいずれ
かであることを特徴とする絹タンパク質フィルムを提供
する。Means for Solving the Problems The invention of the present application is to solve the above-mentioned problems by providing a silk protein film, which is mainly a cast film of a silk protein aqueous solution, Secondly, a silk protein film characterized in that the silk protein is at least one of fibroin and sericin, and thirdly, a silk protein film produced naturally, and artificially synthesized or modified. Provided is a silk protein film characterized by being at least one of the following:
【０００７】また、この出願の発明は、第４には、以上
いずれかの絹タンパク質フィルムの製造方法であって、
主として絹タンパク質の水溶液膜を乾燥することを特徴
とする絹タンパク質フィルムの製造方法を提供し、第５
には、主として絹タンパク質の水溶液膜を乾燥ととも
に、もしくは乾燥後に延伸することを特徴とする絹タン
パク質フィルムの製造方法を提供する。A fourth aspect of the invention of this application is the method for producing a silk protein film according to any one of the above.
Provided is a method for producing a silk protein film, which comprises mainly drying an aqueous solution of silk protein.
Provides a method for producing a silk protein film, which comprises stretching an aqueous silk protein film mainly with or after drying.
【０００８】そして、この出願の発明は、第６には、前
記の絹タンパク質フィルムの製造方法であって炭酸ガス
が存在しないかまたは微量にのみ存在する不活性雰囲気
とすることを特徴とする絹タンパク質フィルムの製造方
法を、第７には、主として窒素ガスの雰囲気とすること
を特徴とする絹タンパク質フィルムの製造方法を提供す
る。A sixth aspect of the invention of this application is a method for producing a silk protein film as described above, characterized in that an inert atmosphere in which carbon dioxide gas is not present or is present in a trace amount is used. Seventh, the method for producing a protein film provides a method for producing a silk protein film, which is characterized in that an atmosphere of nitrogen gas is mainly used.
【０００９】[0009]
【発明の実施の形態】この出願の発明は上記の通りの特
徴を持つものであるが、以下にその実施の形態について
説明する。BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application has the characteristics as described above, and the embodiments thereof will be described below.
【００１０】この出願の発明によれば、タンパク質材料
として、主として絹タンパク質からなるキャストフィル
ムであるものが提供されることになる。絹タンパク質と
しては、カイコやクモから得られる、絹フィブロイン、
あるいは絹フイブロインとセリシンからなる天然生成
物、またはバイオテクノロジー等の方法により合成ない
し改変された絹タンパク質等が例示されることになる。
なお、この出願の発明においては、絹タンパク質からな
る材料は、絹タンパク質が主構成要素であるものを意味
しており、全てが絹タンパク質であるもの、あるいはそ
の一部が絹タンパク質以外の物質、例えば多糖類等によ
り置換されて構成されたもの、絹タンパク質以外の物質
と複合化されたもの等であってよい。According to the invention of this application, the protein material is a cast film mainly made of silk protein. As silk protein, silk fibroin obtained from silkworm or spider,
Alternatively, a natural product composed of silk fibroin and sericin, or a silk protein synthesized or modified by a method such as biotechnology is exemplified.
In the invention of this application, the material made of silk protein means that silk protein is a main constituent element, and all are silk proteins, or a part thereof is a substance other than silk protein, For example, it may be one substituted with a polysaccharide or the like, one conjugated with a substance other than silk protein, or the like.
【００１１】この出願の発明は上記のキャストフィルム
として絹タンパク質の水溶液より得られたものである。
絹タンパク質水溶液は、たとえば絹フイブロインの水溶
液として得られる。この場合の絹フイブロインは、カイ
コの絹糸腺という器官において合成されたタンパク質
で、絹糸腺は、後部、中部および前部の三つの器官によ
り構成され、中部絹糸腺（Ｍ）は、さらに後区（Ｍ
Ｐ）、中区（ＭＭ）、前区（ＭＡ）に分類されている。The invention of this application is obtained from an aqueous solution of silk protein as the cast film.
The silk protein aqueous solution is obtained, for example, as an aqueous solution of silk fibroin. In this case, silk fibroin is a protein synthesized in the silk gland organ of silkworm, the silk gland is composed of three organs of the posterior, middle and anterior parts, and the central silk gland (M) is further divided into the posterior segment (M). M
P), Naka Ward (MM), and Previous Ward (MA).
【００１２】フイブロインは、水に溶解し、水溶液とな
る。Fibroin is dissolved in water to form an aqueous solution.
【００１３】この出願の発明において用意される絹タン
パク質の水溶液の濃度については、たとえば１０〜３０
ｗｔ％の高濃度のものをはじめとして、特に限定的では
ない。ほぼ完全な溶解状態にある場合だけでなく、部分
的に溶解し、分散液の状態にあってよい。The concentration of the silk protein aqueous solution prepared in the invention of this application is, for example, 10 to 30.
There is no particular limitation, including a high concentration of wt%. Not only when it is almost completely dissolved, it may be partially dissolved and in the state of dispersion.
【００１４】絹タンパク質キャストフィルムは、各種の
方法、手段によって形成されてよい。The silk protein cast film may be formed by various methods and means.
【００１５】たとえば水溶液の、台板や支持板、あるい
は基板表面への展開によって液膜を形成し、この液膜を
乾燥する方法や、対向するこれらの板状体の隙間に毛管
現象によって液膜を保持し、次いで乾燥する方法、粘度
が高い場合等には、板状体を水溶液中に浸漬し、これを
引上げ、表面に付着している液膜を乾燥する方法、さら
には、スリット開口より水溶液を乾燥域に吐出させてフ
ィルム形成する方法が例示される。これらの各種方法の
実施に際しては、より好適には、炭酸ガスが微量なだけ
存在するや、または存在しない不活性雰囲気条件で絹タ
ンパク質水溶液を乾燥することによってキャストフィル
ムを作製することを特徴とすることができる。For example, a liquid film is formed by spreading an aqueous solution on a base plate, a support plate, or the surface of a substrate, and the liquid film is dried, or a liquid film is formed in the gap between these facing plate-like bodies by a capillary phenomenon. Holding, then drying, when the viscosity is high, etc., immersing the plate-shaped body in an aqueous solution, pulling it up, drying the liquid film adhering to the surface, further, from the slit opening A method of forming a film by discharging the aqueous solution into a dry region is exemplified. In carrying out these various methods, it is more preferable that a cast film is produced by drying the silk protein aqueous solution under an inert atmosphere condition in which a trace amount of carbon dioxide gas exists or does not exist. be able to.
【００１６】不活性な雰囲気は、たとえば窒素ガスや希
ガスの雰囲気、あるいは真空減圧雰囲気とすることがで
きる。より実際的に好ましくは、窒素ガス雰囲気とする
ことが考慮される。不活性な雰囲気、特に窒素ガス雰囲
気での乾燥によって、高強度、高弾性、そして透明性の
高いキャストフィルムが作製できる。The inert atmosphere can be, for example, an atmosphere of nitrogen gas or a rare gas, or a vacuum reduced pressure atmosphere. More practically, a nitrogen gas atmosphere is considered. By drying in an inert atmosphere, especially a nitrogen gas atmosphere, a cast film having high strength, high elasticity and high transparency can be produced.
【００１７】一方、炭酸ガス中での乾燥の場合には、白
濁の、脆性のあるフィルムが形成されることになる。こ
の白色脆性のフィルムは、この出願の発明者によって、
絹タンパク質水溶液における大気中の炭酸ガスの吸収固
定化に起因することが確認されている。On the other hand, in the case of drying in carbon dioxide gas, a cloudy, brittle film is formed. This white brittle film was developed by the inventor of this application by
It has been confirmed that this is due to absorption and immobilization of carbon dioxide gas in the atmosphere in the silk protein aqueous solution.
【００１８】このようなフィルム作製条件の雰囲気の違
いによって、絹タンパク質水溶液が異なる形態や物性の
キャストフィルムを形成することは、これまで全く知ら
れていないことである。It is not known at all until now that the silk protein aqueous solution forms a cast film having different morphology and physical properties depending on the difference in the atmosphere of the film production conditions.
【００１９】また、高濃度水溶液の場合には、前記の乾
燥時に、あるいは乾燥後に延伸することもできる。この
延伸によって、物理的物性を改変することも可能とな
る。In the case of a high-concentration aqueous solution, stretching can be performed during or after the above-mentioned drying. This stretching also makes it possible to modify physical properties.
【００２０】もちろん、この出願の発明においては、水
溶液のタンパク質濃度によって、フイブロインフィルム
の厚みや乾燥時間を調製することが可能となる。Of course, in the invention of this application, it becomes possible to adjust the thickness and the drying time of the fibroin film depending on the protein concentration of the aqueous solution.
【００２１】たとえば以上のとおりのこの出願の発明に
ついて、さらに実施例に沿って説明する。The invention of this application as described above will be described in more detail with reference to examples.
【００２２】[0022]
【実施例】＜実施例１＞家蚕の中部絹糸腺中区（ＭＭ）
からフイブロインを取出して水中でセリシンを除去し、
水によって、絹フイブロインの濃度１ｗｔ％の水溶液を
調製した。[Example] <Example 1> Middle section of silk gland (MM) in the middle part of silkworm
From the fibroin to remove sericin in water,
An aqueous solution of silk fibroin having a concentration of 1 wt% was prepared with water.
【００２３】この絹フイブロイン水溶液を、ガラス板上
に展開し、常温において乾燥した。その際の雰囲気とし
て、窒素ガス雰囲気または炭酸ガス雰囲気とした。This silk fibroin aqueous solution was spread on a glass plate and dried at room temperature. The atmosphere at that time was a nitrogen gas atmosphere or a carbon dioxide gas atmosphere.
【００２４】その結果、窒素ガス雰囲気での乾燥によっ
て、形態保持性、透明性を有するフイブロインフィルム
が得られた。このものは、動的ヤング率４．３×１０10
ｄｙｎｅ／ｃｍ2であった。As a result, a fibroin film having shape retention and transparency was obtained by drying in a nitrogen gas atmosphere. This product has a dynamic Young's modulus of 4.3 × 10 10.
It was dyne / cm 2 .
【００２５】一方、炭酸ガス雰囲気での乾燥による場合
には、白濁した不透明なフィルムとなることが確認され
た。On the other hand, it was confirmed that when the film was dried in a carbon dioxide gas atmosphere, an opaque film became cloudy.
【００２６】このものの強度は測定不可能であって、脆
性が大きいものであった。
＜実施例２＞実施例１と同様にして、中部絹糸腺中区
（ＭＭ）からのフイブロインの水溶液として、濃度が、
０．７２ｗｔ％、１．０１ｗｔ％、および１．５３ｗｔ
％のものを調製し、窒素ガス雰囲気および炭酸ガス雰囲
気の各々で乾燥してキャストフィルムを製造した。The strength of this product was unmeasurable and had a large brittleness. <Example 2> In the same manner as in Example 1, as an aqueous solution of fibroin from the middle section of the central silk gland (MM), the concentration was
0.72 wt%, 1.01 wt%, and 1.53 wt
%, And a cast film was manufactured by drying in a nitrogen gas atmosphere and a carbon dioxide gas atmosphere.
【００２７】図１は、その結果を例示した写真である。FIG. 1 is a photograph illustrating the result.
【００２８】この図１にも例示したように、窒素ガス雰
囲気での乾燥によって、各々の濃度の水溶液から形態保
持性、透明性を有するフイブロインフィルムが得られる
ことと、炭酸ガス雰囲気の場合には、白濁した不透明な
フィルムとなり、脆性の大きなものとなることが確認さ
れた。
＜実施例３＞実施例１と同様にして、中部絹糸腺前区
（ＭＡ）からのフイブロインの、濃度が、０．５２ｗｔ
％、０．７９ｗｔ％、０．８０ｗｔ％、１．１３ｗｔ％
の水溶液を調製し、窒素ガス雰囲気、炭酸ガス雰囲気の
各々で乾燥してキャストフィルムを製造した。As shown in FIG. 1, by drying in a nitrogen gas atmosphere, a fibroin film having shape retention and transparency can be obtained from an aqueous solution of each concentration, and in the case of a carbon dioxide atmosphere. It was confirmed that the film became a cloudy and opaque film and had a large brittleness. <Example 3> In the same manner as in Example 1, the concentration of fibroin from the central area of the central silk gland (MA) was 0.52 wt.
%, 0.79 wt%, 0.80 wt%, 1.13 wt%
Was prepared and dried in a nitrogen gas atmosphere and a carbon dioxide gas atmosphere to produce a cast film.
【００２９】図２は、その結果を例示した写真である。FIG. 2 is a photograph illustrating the result.
【００３０】この図２より、実施例１および実施例２と
同様の結果が得られていることがわかる。
＜実施例４＞実施例１と同様にして、中部絹糸腺後区
（ＭＰ）からのフイブロインの、濃度０．７４ｗｔ％、
１．１１ｗｔ％、１．１４ｗｔ％、１．１５ｗｔ％の水
溶液を調製し、窒素ガス雰囲気、炭酸ガス雰囲気の各々
で乾燥してキャストフィルムを製造した。From FIG. 2, it can be seen that the same results as those in Examples 1 and 2 were obtained. <Example 4> In the same manner as in Example 1, the concentration of fibroin from the posterior segment of the central silk gland (MP) was 0.74 wt%,
An aqueous solution of 1.11 wt%, 1.14 wt% and 1.15 wt% was prepared and dried in each of a nitrogen gas atmosphere and a carbon dioxide gas atmosphere to manufacture a cast film.
【００３１】図３は、その結果を例示した写真である。FIG. 3 is a photograph showing the result.
【００３２】この図３から、実施例１および実施例２、
さらには実施例３と同様の結果が得られていることがわ
かる。From FIG. 3, Example 1 and Example 2,
Furthermore, it can be seen that the same results as in Example 3 are obtained.
【００３３】[0033]
【発明の効果】以上詳しく説明した通り、この出願の発
明によって、生分解性を有し、環境保全型のタンパク質
材料として、多機能性フィルムへの応用が可能で、製造
過程の簡易化、材料の透明化等が注目される、新しい絹
タンパク質フィルムを提供することができる。INDUSTRIAL APPLICABILITY As described in detail above, according to the invention of this application, biodegradable and environmentally friendly protein materials can be applied to multifunctional films, which simplifies the manufacturing process, It is possible to provide a new silk protein film, which is noted for its transparency and the like.
【図１】中部絹糸腺中区（ＭＭ）の絹タンパク質の濃度
の異なる水溶液より窒素ガスおよび炭酸ガスの各々の雰
囲気下で製造したキャストフィルムを例示した写真であ
る。FIG. 1 is a photograph showing an example of a cast film produced from an aqueous solution having different silk protein concentrations in the middle silk gland (MM) under nitrogen gas atmosphere and carbon dioxide gas atmosphere.
【図２】中部絹糸腺前区（ＭＡ）の絹タンパク質の濃度
の異なる水溶液より窒素ガスおよび炭酸ガスの各々の雰
囲気下で製造したキャストフィルムを例示した写真であ
る。FIG. 2 is a photograph exemplifying cast films produced from aqueous solutions having different silk protein concentrations in the central silk gland anterior region (MA) under nitrogen gas and carbon dioxide gas atmospheres.
【図３】中部絹糸腺後区（ＭＰ）の絹タンパク質の濃度
の異なる水溶液より窒素ガスおよび炭酸ガスの各々の雰
囲気下で製造したキャストフィルムを例示した写真であ
る。FIG. 3 is a photograph showing an example of cast films produced from aqueous solutions having different silk protein concentrations in the middle silk gland posterior segment (MP) under nitrogen gas and carbon dioxide gas atmospheres.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田中 稔久 茨城県つくば市観音台２−１−２ 独立行 政法人農業生物資源研究所 生体高分子研 究グループ内 Ｆターム(参考） 4C081 AA06 BC04 CD33 DA02 EA02 EA11 4F071 AA70 AE19 AH04 BA02 BB02 BB07 BC01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Toshihisa Tanaka 2-1-2 Kannondai, Tsukuba City, Ibaraki Prefecture Agricultural Bioresource Research Institute, Biopolymer Research Institute Research group F-term (reference) 4C081 AA06 BC04 CD33 DA02 EA02 EA11 4F071 AA70 AE19 AH04 BA02 BB02 BB07 BC01
Claims (7)
フィルムであることを特徴とする絹タンパク質フィル
ム。1. A silk protein film which is mainly a cast film of a silk protein aqueous solution.
シンの少くともいずれかであることを特徴とする請求項
１の絹タンパク質フィルム。2. The silk protein film according to claim 1, wherein the silk protein is at least one of fibroin and sericin.
および人為的に合成もしくは改変されたものの少くとも
いずれかであることを特徴とする請求項１または２の絹
タンパク質フィルム。3. A naturally occurring silk protein,
And at least one artificially synthesized or modified. 3. The silk protein film according to claim 1 or 2, wherein
ク質フィルムの製造方法であって、主として絹タンパク
質の水溶液膜を乾燥することを特徴とする絹タンパク質
フィルムの製造方法。4. The method for producing a silk protein film according to claim 1, wherein the aqueous solution film of silk protein is mainly dried.
ク質フィルムの製造方法であって、主として絹タンパク
質の水溶液膜を乾燥とともに、もしくは乾燥後に延伸す
ることを特徴とする絹タンパク質フィルムの製造方法。5. The method for producing a silk protein film according to any one of claims 1 to 3, wherein the aqueous solution film of silk protein is mainly stretched with or after drying. .
ムの製造方法であって、炭酸ガスが存在しないかまたは
微量にのみ存在する不活性雰囲気とすることを特徴とす
る絹タンパク質フィルムの製造方法。6. The method for producing a silk protein film according to claim 4 or 5, wherein an inert atmosphere in which carbon dioxide gas is not present or is present in a trace amount is used.
特徴とする絹タンパク質フィルムの製造方法。7. A method for producing a silk protein film, which comprises mainly using a nitrogen gas atmosphere.
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