JPH11217506A - Silk-containing solution, silk-containing resin composition, silk-containing molded product and preparation of silk-containing solution - Google Patents
Silk-containing solution, silk-containing resin composition, silk-containing molded product and preparation of silk-containing solutionInfo
- Publication number
- JPH11217506A JPH11217506A JP2320398A JP2320398A JPH11217506A JP H11217506 A JPH11217506 A JP H11217506A JP 2320398 A JP2320398 A JP 2320398A JP 2320398 A JP2320398 A JP 2320398A JP H11217506 A JPH11217506 A JP H11217506A
- Authority
- JP
- Japan
- Prior art keywords
- silk
- solution
- resin composition
- containing solution
- silk fibroin
- Prior art date
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- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シルク含有溶液、
シルク含有樹脂組成物、シルク含有成形品及びシルク含
有溶液の調製方法に関し、合成皮革、人工皮革、レザー
等の仕上げ剤、等に応用できる。The present invention relates to a silk-containing solution,
The method for preparing a silk-containing resin composition, a silk-containing molded product, and a silk-containing solution can be applied to finishing agents for synthetic leather, artificial leather, leather, and the like.
【０００２】[0002]
【背景技術及び発明が解決しようとする課題】合成樹脂
製品に吸・放湿性、良タッチ感、制電性、等を付与して
製品の付加価値を高めるため、天然タンパク質粉末を含
有する各種製品が市場に出回るようになってきている。
例えば、コラーゲンやシルクの粉末を合成樹脂に練り混
み、このコラーゲン等を含有する樹脂を使用して成形さ
れたプラスチック成形品、シート、フィルム、等があ
る。従来使用されていた天然タンパク質粉末は、粉砕に
よって平均粒径数μｍのオーダーとされたものである。BACKGROUND ART Various products containing natural protein powder in order to increase the added value of products by imparting moisture absorption / desorption properties, good touch feeling, antistatic properties, etc. to synthetic resin products. Are coming to market.
For example, there are plastic molded articles, sheets, films, and the like formed by mixing collagen or silk powder into a synthetic resin, and molding using a resin containing the collagen or the like. Conventionally used natural protein powders have an average particle size of several μm by grinding.
【０００３】しかし、従来の天然タンパク質粉末を含有
する樹脂成形品の場合、吸・放湿性、タッチ感等の向上
効果は得られるが、天然タンパク質粉末の粒径が比較的
大きいため、引張り強度等の物性は低下するという問題
点があった。一方、物性を低下させない程度に天然タン
パク質粉末を少量含有させた場合には、天然タンパク質
の特性を充分発現させることができなくなる。なお、シ
ルクを水に溶かした水溶液を水系樹脂に混入し、これを
使用して成形品やシートを得る技術が提案されている
が、適用可能な樹脂は水系樹脂の場合に限られる。[0003] However, in the case of a conventional resin molded product containing a natural protein powder, the effect of improving the absorption and desorption of moisture and the feeling of touch can be obtained. However, there was a problem that the physical properties of the rubber composition deteriorated. On the other hand, when the natural protein powder is contained in a small amount to the extent that the physical properties are not deteriorated, the characteristics of the natural protein cannot be sufficiently exhibited. A technique has been proposed in which an aqueous solution obtained by dissolving silk in water is mixed with an aqueous resin and a molded product or sheet is obtained using the aqueous solution. However, the applicable resin is limited to an aqueous resin.
【０００４】そこで、本発明は、物性を低下させること
なく、シルクの特性を発揮させることができるシルク含
有溶液、シルク含有樹脂組成物、シルク含有成形品及び
シルク含有溶液の調製方法を提供することを目的とす
る。Accordingly, an object of the present invention is to provide a silk-containing solution, a silk-containing resin composition, a silk-containing molded article, and a method of preparing a silk-containing solution that can exhibit the properties of silk without deteriorating physical properties. With the goal.
【０００５】[0005]
【課題を解決するための手段】本発明の第１発明に係る
シルク含有溶液は、シルクが有機溶剤中に溶解している
ことを特徴とする。前記シルクとしては、精製されたタ
ンパク質であるシルクフィブロインを使用するのが好ま
しい。The silk-containing solution according to the first invention of the present invention is characterized in that silk is dissolved in an organic solvent. As the silk, it is preferable to use silk fibroin which is a purified protein.
【０００６】前記有機溶剤としては、例えばジメチルホ
ルムアミド（ＤＭＦ）、メチルエチルケトン（ＭＥ
Ｋ）、トルエン、キシレン、シクロヘキサノン、酢酸ブ
チル、等を使用できる。これらのうち、１種の溶剤又は
２種以上の溶剤の混合液を使用する。本発明のシルク含
有溶液は、シルクが有機溶剤中に分子レベルで溶解して
いるため、これを使用した樹脂組成物等においてもシル
クを分子レベルで分散させることができる。また、この
シルク含有溶液は、溶剤系であるため、水系以外の溶剤
系樹脂に使用することができる。As the organic solvent, for example, dimethylformamide (DMF), methyl ethyl ketone (ME
K), toluene, xylene, cyclohexanone, butyl acetate and the like can be used. Among these, one kind of solvent or a mixture of two or more kinds of solvents is used. In the silk-containing solution of the present invention, since silk is dissolved in an organic solvent at a molecular level, silk can be dispersed at a molecular level even in a resin composition or the like using the same. Since the silk-containing solution is a solvent-based solution, it can be used for a solvent-based resin other than an aqueous-based resin.
【０００７】本発明の第２発明に係るシルク含有樹脂組
成物は、第１発明のシルク含有溶液と、溶剤系樹脂とを
含むことを特徴とする。前記溶剤系樹脂としては、ウレ
タン樹脂、アクリル樹脂、塩化ビニル樹脂、等を挙げる
ことができる。本発明のシルク含有樹脂組成物は、溶剤
系樹脂を攪拌しながら前記シルク含有溶液を徐々に加え
ることにより調製することができる。このシルク含有樹
脂組成物は、それ自体表面仕上げ剤として使用し、レザ
ー、フィルム、シート、等に対してグラビアコーティン
グ法等で塗布することができる。[0007] A silk-containing resin composition according to a second invention of the present invention is characterized by containing the silk-containing solution of the first invention and a solvent-based resin. Examples of the solvent-based resin include a urethane resin, an acrylic resin, and a vinyl chloride resin. The silk-containing resin composition of the present invention can be prepared by gradually adding the silk-containing solution while stirring the solvent-based resin. The silk-containing resin composition itself can be used as a surface finish, and can be applied to leather, films, sheets, and the like by a gravure coating method or the like.
【０００８】本発明の第３発明に係るシルク含有成形品
は、第２発明のシルク含有樹脂組成物により成形された
ものである。例えば、前記シルク含有樹脂組成物を使用
し、離型紙上にナイフコーティング法等により塗布して
フィルムやシートを作製することができる。また、前記
シルク含有樹脂組成物を使用し、基布にコーティングや
ラミネーション等を行って合成皮革や人工皮革を作製す
ることができる。[0008] The silk-containing molded article according to the third invention of the present invention is formed by the silk-containing resin composition of the second invention. For example, a film or sheet can be prepared by using the above-mentioned silk-containing resin composition and applying it on release paper by a knife coating method or the like. Further, a synthetic leather or an artificial leather can be produced by using the silk-containing resin composition and coating or laminating the base cloth.
【０００９】本発明の第４発明に係るシルク含有溶液の
調製方法は、シルクを水に溶解した後、このシルク水溶
液に有機溶剤を加え、このシルク混合液から水分を除去
することを特徴とする。本発明によれば、一旦、シルク
水溶液にした後、有機溶剤を加えて、このシルク混合液
から水分を除去するようにしたため、溶剤系のシルク含
有溶液が得られるようになる。A method for preparing a silk-containing solution according to a fourth invention of the present invention is characterized in that after dissolving silk in water, an organic solvent is added to the silk aqueous solution to remove water from the silk mixture. . According to the present invention, once a silk aqueous solution is formed, an organic solvent is added to remove water from the silk mixed solution, so that a solvent-based silk-containing solution can be obtained.
【００１０】[0010]
【発明の実施の形態】本実施形態に係るシルク含有溶液
は、シルクが有機溶剤中に溶解しているものである。前
記シルクとしては、シルクフィブロインを使用し、前記
有機溶剤としては、ジメチルホルムアミド（ＤＭＦ）等
を使用する。本実施形態に係るシルク含有樹脂組成物
は、前記シルク含有溶液と、溶剤系樹脂とを含むもので
ある。前記溶剤系樹脂は、ウレタン樹脂、等である。BEST MODE FOR CARRYING OUT THE INVENTION The silk-containing solution according to the present embodiment is one in which silk is dissolved in an organic solvent. Silk fibroin is used as the silk, and dimethylformamide (DMF) or the like is used as the organic solvent. The silk-containing resin composition according to the present embodiment includes the silk-containing solution and a solvent-based resin. The solvent-based resin is a urethane resin or the like.
【００１１】本実施形態に係るシルク含有成形品は、前
記シルク含有樹脂組成物を使用して作製されたものであ
る。前記シルク含有成形品の具体例は、フィルム、シー
ト、合成皮革、人工皮革等である。本成形品によれば、
シルクが樹脂中に分子レベルで分散しているため、樹脂
の物性を低下させないで、成形品にシルクの有する吸・
放湿性、良タッチ感、制電性、等を付与することが可能
になる。The silk-containing molded article according to the present embodiment is produced using the silk-containing resin composition. Specific examples of the silk-containing molded product include a film, a sheet, synthetic leather, and artificial leather. According to the molded article,
Because the silk is dispersed in the resin at the molecular level, it does not impair the physical properties of the resin.
Moisture release properties, good touch feeling, antistatic properties, and the like can be provided.
【００１２】本実施形態に係るシルク含有溶液の調製方
法は、シルクを水に溶解した後、このシルク水溶液に有
機溶剤を加え、このシルク混合液から水分を除去するこ
とを特徴とする。具体的には、例えば、塩化カルシウ
ム、エタノール及び水よりなる混合溶液を用意し、この
混合溶液にシルクフィブロインを溶解したものを流水透
析して、シルクフィブロイン水溶液を調製する。次に、
有機溶剤をシルクフィブロイン水溶液に添加した後、こ
のシルク混合液をデシケータ等内に入れて乾燥すること
により水分を除去する。この際、減圧乾燥を行うことに
より脱水時間を短縮することができる。The method for preparing a silk-containing solution according to the present embodiment is characterized in that after dissolving silk in water, an organic solvent is added to the silk aqueous solution to remove water from the silk mixture. Specifically, for example, a mixed solution of calcium chloride, ethanol and water is prepared, and a solution obtained by dissolving silk fibroin in the mixed solution is dialyzed with running water to prepare an aqueous solution of silk fibroin. next,
After the organic solvent is added to the aqueous solution of silk fibroin, the silk mixture is placed in a desiccator or the like and dried to remove water. At this time, dehydration time can be shortened by performing drying under reduced pressure.
【００１３】[0013]
【実施例】［実施例１］下記の方法によりシルクフィブ
ロイン含有溶液を調製した。精練によりセリシンを除去
したシルクフィブロインと、塩化カルシウム：エタノー
ル：水＝８：５：６（重量比）の割合で混合した混合溶
液を用意し、この混合溶液中に前記シルクフィブロイン
を入れ、70℃、３時間の条件で溶解した。次に、この溶
液を室温で４日間流水透析して、シルクフィブロイン水
溶液を得た後、透析用セロファンチューブに入れたまま
送風して濃縮した。この濃縮によって、シルクフィブロ
インの濃度は、約８wt％となっていた。EXAMPLES Example 1 A silk fibroin-containing solution was prepared by the following method. A mixed solution was prepared by mixing silk fibroin from which sericin had been removed by scouring and calcium chloride: ethanol: water = 8: 5: 6 (weight ratio), and the silk fibroin was put into the mixed solution, and 70 ° C. And dissolved for 3 hours. Next, this solution was dialyzed with running water at room temperature for 4 days to obtain an aqueous solution of silk fibroin, which was then blown and concentrated while remaining in a cellophane tube for dialysis. This concentration resulted in a silk fibroin concentration of about 8 wt%.
【００１４】次に、このシルクフィブロイン水溶液に約
２倍量のＤＭＦを加え、五酸化リン（Ｐ2Ｏ5）の入った
デシケータ内で脱水し、約４wt％のシルクフィブロイン
含有溶液を得た。このシルクフィブロイン含有溶液を使
用し、固形分30wt％のポリウレタン樹脂（溶媒：ＤＭ
Ｆ、大日本インキ化学工業（株）製クリスボンS-750
［商品名］）にシルクフィブロイン含有溶液を混合して
シルクフィブロイン含有樹脂組成物を得た。全固形分中
のシルクフィブロイン濃度は、５wt％であった。このシ
ルクフィブロイン含有樹脂組成物を離型紙上にバーコー
タで塗布した後、80℃で乾燥して厚さ約20μｍのフィル
ムを作製した。Next, about 2 times the amount of DMF was added to the silk fibroin aqueous solution and dehydrated in a desiccator containing phosphorus pentoxide (P 2 O 5 ) to obtain a solution containing about 4 wt% silk fibroin. Using this silk fibroin-containing solution, a polyurethane resin having a solid content of 30 wt% (solvent: DM
F, Crisbon S-750 manufactured by Dainippon Ink and Chemicals, Inc.
[Product name]) was mixed with a silk fibroin-containing solution to obtain a silk fibroin-containing resin composition. The silk fibroin concentration in the total solid content was 5% by weight. The silk fibroin-containing resin composition was applied on release paper with a bar coater, and then dried at 80 ° C. to produce a film having a thickness of about 20 μm.
【００１５】［比較例１］シルクフィブロイン含有溶液
を含まない、実施例１に係るポリウレタン樹脂を使用
し、実施例１と同様の製法でフィルムを得た。Comparative Example 1 A film was obtained in the same manner as in Example 1 except that the polyurethane resin according to Example 1 was used without containing the solution containing silk fibroin.
【００１６】［比較例２］実施例１において、シルクフ
ィブロイン含有溶液の代わりにシルクフィブロインパウ
ダー（平均粒径５μｍ）を配合し、実施例１と同様の製
法でフィルムを得た。Comparative Example 2 Silk fibroin powder (average particle size: 5 μm) was blended in place of the silk fibroin-containing solution in Example 1, and a film was obtained in the same manner as in Example 1.
【００１７】［特性の測定、評価］上記実施例１及び比
較例１、２で得られたフィルムについて、透湿度、引張
り強度、伸度、表面タッチ感及び透明性を測定又は評価
した。前記透湿度は、JIS L-1099 A法に準拠して測定
した。前記引張り強度と伸度は、JIS K-7311に準拠し
て測定した。[Measurement and Evaluation of Characteristics] The films obtained in Example 1 and Comparative Examples 1 and 2 were measured or evaluated for moisture permeability, tensile strength, elongation, surface touch feeling, and transparency. The moisture permeability was measured according to JIS L-1099A method. The tensile strength and elongation were measured according to JIS K-7311.
【００１８】前記表面タッチ感は、ランダムに選んだ10
人に試料の表面を手で触ってもらい、その時の感触の評
価を平均点で表したものである。感触の評価基準は次の
通りである。 ５点…非常にタッチ感が良い。４点…タッチ感が良い。
３点…普通。２点…タッチ感が悪い。１点…非常にタッ
チ感が悪い。 前記透明性は、肉眼で判断した。[0018] The surface touch sensation is randomly selected 10
A person touches the surface of the sample with his / her hand, and the evaluation of the touch at that time is represented by an average score. The evaluation criteria for feel are as follows. 5 points: Very good touch feeling. 4 points: Touch feeling is good.
3 points ... normal. 2 points: Touch feeling is poor. 1 point: Touch feeling is very poor. The transparency was judged visually.
【００１９】[0019]
【表１】 [Table 1]
【００２０】表１より、実施例１のフィルムによれば、
シルクフィブロイン含有溶液を使用して作製されたもの
であるため、ウレタン樹脂とシルクフィブロインとが分
子レベルで混合されており、良好な物性や高い透明性を
維持したまま、透湿性とタッチ感が向上していることが
わかる。From Table 1, according to the film of Example 1,
Since it is made using a solution containing silk fibroin, urethane resin and silk fibroin are mixed at the molecular level, improving moisture permeability and touch feeling while maintaining good physical properties and high transparency You can see that it is doing.
【００２１】一方、比較例１のフィルムによれば、シル
クフィブロインを含有していないため、透湿度が低い。
比較例２のフィルムによれば、溶剤に溶解していないシ
ルクフィブロインを使用して作製されたものであるた
め、透湿性とタッチ感は良好であるが、物性に関しては
不良である。On the other hand, the film of Comparative Example 1 has low moisture permeability because it does not contain silk fibroin.
According to the film of Comparative Example 2, since the film was produced using silk fibroin not dissolved in a solvent, the film had good moisture permeability and touch feeling, but was poor in physical properties.
【００２２】［実施例２］実施例１に係るシルクフィブ
ロイン含有溶液を使用し、ウレタン樹脂（溶媒：ＤＭ
Ｆ、セイコー化成（株）製ラッキースキンU-65［商品
名］）にシルクフィブロイン含有溶液を混合してシルク
フィブロイン含有樹脂組成物を得た。全固形分中のシル
クフィブロイン濃度は、５wt％であった。このシルクフ
ィブロイン含有樹脂組成物を使用し、グラビアコーティ
ング機で手帳の表装用のポリ塩化ビニルレザー上に塗布
量が20g／m2となるように塗布した。Example 2 Using the silk fibroin-containing solution according to Example 1, a urethane resin (solvent: DM
F. A silk fibroin-containing resin composition was obtained by mixing silk fibroin-containing solution with Lucky Skin U-65 (trade name) manufactured by Seiko Chemical Co., Ltd.). The silk fibroin concentration in the total solid content was 5% by weight. Using the silk fibroin-containing resin composition, a gravure coating machine was used to coat the surface of a notebook with polyvinyl chloride leather at a coating amount of 20 g / m 2 .
【００２３】［比較例３］シルクフィブロイン含有溶液
を含まない、実施例２に係るポリウレタン樹脂を使用
し、実施例２と同様の製法でポリ塩化ビニルレザー上に
塗布した。Comparative Example 3 Using the polyurethane resin according to Example 2, which did not contain the silk fibroin-containing solution, was applied on polyvinyl chloride leather in the same manner as in Example 2.
【００２４】［比較例４］実施例２において、シルクフ
ィブロイン含有溶液の代わりにシルクフィブロインパウ
ダー（平均粒径５μｍ）を配合し、このシルクフィブロ
イン含有樹脂組成物を実施例２と同様の製法でポリ塩化
ビニルレザー上に塗布した。Comparative Example 4 In Example 2, silk fibroin powder (average particle size: 5 μm) was blended in place of the silk fibroin-containing solution, and the silk fibroin-containing resin composition was prepared in the same manner as in Example 2. Coated on vinyl chloride leather.
【００２５】［特性の測定、評価］上記実施例２及び比
較例３、４で得られたレザーについて、表面タッチ感を
評価し、また実用テストを行った。前記実用テストは、
前記コーティングされたポリ塩化ビニルレザーで作製さ
れた手帳表装に対して、折り曲げを何回か繰り返すこと
により行い、その際の折曲げ部分の変化を確認した。[Measurement and Evaluation of Characteristics] The leathers obtained in Example 2 and Comparative Examples 3 and 4 were evaluated for surface touch feeling and subjected to practical tests. The practical test,
The notebook was made of the coated polyvinyl chloride leather, and was repeatedly bent several times to confirm the change in the bent portion.
【００２６】[0026]
【表２】 [Table 2]
【００２７】表２より、実施例２に係るレザーは、シル
クフィブロイン含有溶液を使用して作製されたものであ
るため、タッチ感を向上させることができる。また、繰
り返し折り曲げても大丈夫であり、実用に充分耐え得る
ものである。From Table 2, it can be seen that the leather according to Example 2 was produced by using a solution containing silk fibroin, so that the touch feeling can be improved. Further, it is safe to bend repeatedly, and can withstand practical use.
【００２８】一方、比較例３のレザーは、実用性に問題
はないが、シルクフィブロインを含有していないため、
タッチ感が不良である。比較例４のレザーは、溶剤に溶
解していないシルクフィブロインを使用して作製された
ものであるため、タッチ感は良好であるが、折曲げ部が
白化して実用にならなかった。On the other hand, although the leather of Comparative Example 3 has no problem in practicality, it does not contain silk fibroin.
Touch feeling is poor. Since the leather of Comparative Example 4 was produced using silk fibroin not dissolved in the solvent, the touch feeling was good, but the bent portion was whitened and was not practical.
【００２９】[0029]
【発明の効果】本発明に係るシルク含有溶液、シルク含
有樹脂組成物、シルク含有成形品及びシルク含有溶液の
調製方法によれば、物性を低下させることなく、シルク
の特性を発揮させることができる。According to the method for preparing a silk-containing solution, a silk-containing resin composition, a silk-containing molded article and a silk-containing solution according to the present invention, the properties of silk can be exhibited without deteriorating physical properties. .
Claims (4)
を特徴とするシルク含有溶液。1. A silk-containing solution, wherein the silk is dissolved in an organic solvent.
剤系樹脂とを含むことを特徴とするシルク含有樹脂組成
物。2. A silk-containing resin composition comprising the silk-containing solution according to claim 1 and a solvent-based resin.
を使用して作製されたシルク含有成形品。3. A silk-containing molded article produced using the silk-containing resin composition according to claim 2.
溶液に有機溶剤を加え、このシルク混合液から水分を除
去することを特徴とするシルク含有溶液の調製方法。4. A method for preparing a silk-containing solution, comprising dissolving silk in water, adding an organic solvent to the silk aqueous solution, and removing water from the silk mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02320398A JP4095704B2 (en) | 1998-02-04 | 1998-02-04 | Silk-containing resin composition, silk-containing molded article, and method for producing silk-containing resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02320398A JP4095704B2 (en) | 1998-02-04 | 1998-02-04 | Silk-containing resin composition, silk-containing molded article, and method for producing silk-containing resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11217506A true JPH11217506A (en) | 1999-08-10 |
| JP4095704B2 JP4095704B2 (en) | 2008-06-04 |
Family
ID=12104121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02320398A Expired - Fee Related JP4095704B2 (en) | 1998-02-04 | 1998-02-04 | Silk-containing resin composition, silk-containing molded article, and method for producing silk-containing resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4095704B2 (en) |
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| WO2014175179A1 (en) * | 2013-04-25 | 2014-10-30 | スパイバー株式会社 | Polypeptide particle and method for producing same |
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| WO2019119009A1 (en) * | 2017-12-19 | 2019-06-27 | Universität Innsbruck | Method for producing a leather substitute |
| JPWO2018123953A1 (en) * | 2016-12-27 | 2019-10-31 | Ｓｐｉｂｅｒ株式会社 | Protein recovery method |
| US10975206B2 (en) | 2015-04-09 | 2021-04-13 | Spiber Inc. | Polar solvent solution and production method thereof |
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1998
- 1998-02-04 JP JP02320398A patent/JP4095704B2/en not_active Expired - Fee Related
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| WO2013065650A1 (en) * | 2011-11-02 | 2013-05-10 | スパイバー株式会社 | Polypeptide solution, artificial polypeptide fiber production method using same, and polypeptide refining method |
| US9051453B2 (en) | 2011-11-02 | 2015-06-09 | Spiber Inc. | Polypeptide solution, artificial polypeptide fiber production method and polypeptide purification method using same |
| WO2014175179A1 (en) * | 2013-04-25 | 2014-10-30 | スパイバー株式会社 | Polypeptide particle and method for producing same |
| JP5823079B2 (en) * | 2013-04-25 | 2015-11-25 | Ｓｐｉｂｅｒ株式会社 | Method for producing polypeptide particles |
| JPWO2014175179A1 (en) * | 2013-04-25 | 2017-02-23 | Ｓｐｉｂｅｒ株式会社 | Method for producing polypeptide particles |
| US9732125B2 (en) | 2013-04-25 | 2017-08-15 | Spiber Inc. | Polypeptide particle and method for producing same |
| US9968682B2 (en) | 2013-04-25 | 2018-05-15 | Spiber Inc. | Polypeptide hydrogel and method for producing same |
| US10065997B2 (en) | 2013-04-25 | 2018-09-04 | Spiber Inc. | Polypeptide porous body and method for producing same |
| US10975206B2 (en) | 2015-04-09 | 2021-04-13 | Spiber Inc. | Polar solvent solution and production method thereof |
| US11668024B2 (en) | 2015-04-09 | 2023-06-06 | Spiber, Inc. | Polar solvent solution and production method thereof |
| JPWO2018123953A1 (en) * | 2016-12-27 | 2019-10-31 | Ｓｐｉｂｅｒ株式会社 | Protein recovery method |
| WO2019119009A1 (en) * | 2017-12-19 | 2019-06-27 | Universität Innsbruck | Method for producing a leather substitute |
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|---|---|
| JP4095704B2 (en) | 2008-06-04 |
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