JP2006219787A - Modified fabric - Google Patents
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- JP2006219787A JP2006219787A JP2005034327A JP2005034327A JP2006219787A JP 2006219787 A JP2006219787 A JP 2006219787A JP 2005034327 A JP2005034327 A JP 2005034327A JP 2005034327 A JP2005034327 A JP 2005034327A JP 2006219787 A JP2006219787 A JP 2006219787A
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本発明は、細胞生育能に優れた非結晶性フィブロイン、及び／又は非結晶性セリシンを付着してなる布帛、及び該布帛を用いたスキンケア用素材並びに医薬用具及び化粧品に関する。 The present invention relates to a fabric formed by attaching amorphous fibroin and / or amorphous sericin having excellent cell growth ability, a skin care material using the fabric, a pharmaceutical device, and a cosmetic.
絹糸は古くから手術糸として使われ、絹タンパクは細胞生育能、抗酸化性、抗菌性、アルコール消化性、抗血液凝固性等の多様な機能を有し、絹タンパクを構成するフィブロインのＨ鎖(分子量３５万)と、Ｌ鎖（分子量２．５万）、及びセリシンのａ成分(分子量４０万)には、正常なヒト皮膚由来の線維芽細胞を生育促進する作用がある（文献１、及び２を参照。）。 Silk thread has long been used as a surgical thread, and silk protein has various functions such as cell growth ability, antioxidant property, antibacterial property, alcohol digestibility, and anticoagulant property, and the H chain of fibroin that constitutes silk protein. (Molecular weight 350,000), L chain (molecular weight 25,000), and a component of sericin (molecular weight 400,000) have the effect of promoting the growth of fibroblasts derived from normal human skin (Reference 1, And 2).
この絹タンパクの有するヒト皮膚細胞生育機能に注目し、繭糸または絹糸を溶解した後に、これを粉末、フィルム、ゲル等に変え、これらをスキンケア素材として創傷被覆材や化粧品として利用するための開発と機能解明の研究が進められてきた（特許文献３乃至５を参照。）。 Focusing on the human skin cell growth function of this silk protein, after dissolving the silk thread or silk thread, it is converted into powder, film, gel, etc., and these are developed for use as wound care materials and cosmetics as skin care materials Studies on functional elucidation have been promoted (see Patent Documents 3 to 5).
しかし従来の繊維表面に絹タンパクがコートされた布帛は、繊維の触感を改質し、繰返し使用することを目的とするため、繊維表面に結晶状態で固着されていた。結晶化した絹タンパクは柔軟性に欠け、皮膚の微妙な凹凸に密着することはできず、皮膚に接する部分は限られているため、絹タンパクの有するヒト皮膚細胞生育機能を発揮するものとはなっていなかった(特許文献６、及び７を参照。)。 However, the conventional fabric in which the surface of the fiber is coated with silk protein has been fixed to the surface of the fiber in a crystalline state in order to improve the feel of the fiber and to be used repeatedly. The crystallized silk protein lacks flexibility, cannot adhere to the delicate unevenness of the skin, and the part that touches the skin is limited. (See Patent Documents 6 and 7).
一方絹タンパクのヒト細胞生育促進能は、絹タンパクの分子量が低下するにともない低下し、分子量２万程度以下では細胞生育促進能はほとんどなくなる、あるいは細胞生育を阻害する（特許文献５を参照。）。絹糸や絹織物の原料となる繭や生糸の乾繭や精練等の加工工程において、絹タンパクの分子量は低下する。また、繭糸や絹糸を粉末、フィルム、ゲル等に変える加工工程（特に繭糸や絹糸の溶解工程）においても絹タンパクの分子量が低下する（非特許文献１、２を参照。）。従って、従来の繭糸や絹糸を、粉末、フィルム、ゲル等に変えて、繊維表面にコーティングされた絹タンパクは、必ずしも充分の細胞生育促進能を有しない。 On the other hand, the ability of silk protein to promote human cell growth decreases as the molecular weight of silk protein decreases, and if the molecular weight is about 20,000 or less, the ability to promote cell growth is almost lost or inhibits cell growth (see Patent Document 5). ). The molecular weight of silk protein decreases in processing processes such as silkworms and raw silk used as raw materials for silk and silk fabrics. In addition, the molecular weight of silk protein is also reduced in a processing step (particularly, a step of dissolving silk yarn or silk yarn) in which silk yarn or silk yarn is changed to powder, film, gel or the like (see Non-Patent Documents 1 and 2). Therefore, the silk protein coated on the fiber surface by changing the conventional silk thread or silk thread into powder, film, gel or the like does not necessarily have sufficient cell growth promoting ability.
本発明は、細胞生育促進能を有する非結晶性フィブロイン及び／又は非結晶性セリシンが付着され、皮膚表面の微妙な凹凸をカバーすることを可能とする布帛を提供することを課題とする。 An object of the present invention is to provide a fabric to which non-crystalline fibroin and / or non-crystalline sericin having cell growth promoting ability is attached and which can cover fine unevenness on the skin surface.
本発明者は、非結晶状態のフィブロイン及び／又はセリシンが、容易に水に溶解し、各種の繊維表面を容易にカバーでき、また、非結晶性のフィブロイン及び／又はセリシンは比較的長期に保管できる特長があることを見出し、本発明をするにいたった。 The inventor of the present invention can easily dissolve amorphous fibroin and / or sericin in water and easily cover various fiber surfaces, and store amorphous fibroin and / or sericin for a relatively long period of time. It was found that there is a feature that can be performed, and the present invention was completed.
即ち本発明は、布帛を構成する繊維または布帛の表面に、非結晶性フィブロイン、及び／又は非結晶性セリシンを付着してなる布帛である。 That is, the present invention is a fabric obtained by adhering amorphous fibroin and / or amorphous sericin to the surface of a fiber or fabric constituting the fabric.
更に前記布帛において、非結晶性フィブロイン、及び／又は非結晶性セリシンは、結晶化度が２0％以下であることが好ましい。 Further, in the fabric, the crystallinity of the amorphous fibroin and / or amorphous sericin is preferably 20% or less.
更に前記布帛において、非結晶性フィブロインの分子量が、５万以上で２０万以下であることが好ましい。 Furthermore, in the fabric, the molecular weight of the amorphous fibroin is preferably 50,000 or more and 200,000 or less.
更に布帛への非結晶性フィブロイン、及び／又は非結晶性セリシンの付着が、布帛に非結晶性フィブロイン、及び／又は非結晶性セリシン水溶液を含浸させることにより、非結晶性フィブロイン、及び／又は非結晶性セリシン付着量が布帛単位体積当り1〜12mg／cm3であることが好ましい。 Furthermore, the adhesion of the amorphous fibroin and / or amorphous sericin to the fabric can be achieved by impregnating the fabric with the amorphous fibroin and / or the amorphous sericin aqueous solution. The amount of crystalline sericin attached is preferably 1 to 12 mg / cm 3 per unit volume of the fabric.
更に前記布帛への非結晶性フィブロイン、及び／又は非結晶性セリシンの付着が、布帛に非結晶性フィブロイン、及び／又は非結晶性セリシンフィルムを付着することにより、非結晶性フィブロイン、及び／又は非結晶性セリシン付着量が布帛単位面積当り1〜10mg／cm2であることが好ましい。 Further, the attachment of amorphous fibroin and / or amorphous sericin to the fabric may be achieved by attaching amorphous fibroin and / or amorphous sericin film to the fabric, and / or amorphous fibroin and / or The amount of non-crystalline sericin attached is preferably 1 to 10 mg / cm 2 per unit area of the fabric.
更に、前記の布帛を用いたスキンケア用素材である。 Furthermore, it is a skin care material using the fabric.
更に、前記の布帛を用いた医療用具、及び／又は化粧品である。 Furthermore, it is a medical device and / or a cosmetic using the above-mentioned fabric.
本発明の布帛は、細胞生育促進能を有する非結晶性フィブロイン及び／又は非結晶性セリシンが付着され、皮膚の小さな凹凸に対し密着して被覆することを可能とし、損傷皮膚の再生のみならず、皮膚表面の目に見えないような多くの傷の再生と、皮膚の健康の向上を可能とする。 The fabric of the present invention adheres to non-crystalline fibroin and / or non-crystalline sericin having the ability to promote cell growth, and allows the skin to be closely attached to small unevenness of the skin. It can regenerate many invisible wounds on the skin surface and improve skin health.
本発明は、細胞生育能、抗酸化性、抗菌性等の細胞生育促進効果を有するフィブロイン及び／又はセリシンを、水と融和する非結晶性の状態で布帛に付着させ、皮膚の小さな凹凸にも密着することを特徴とする布帛である。
以下に本発明について詳細に説明する。
In the present invention, fibroin and / or sericin having cell growth promoting effects such as cell growth ability, antioxidant property, and antibacterial property are attached to a fabric in a non-crystalline state compatible with water, and even on uneven skin. The fabric is characterized by being in close contact.
The present invention is described in detail below.
＜フィブロイン及びセリシン＞
フィブロインは昆虫、クモ等の絹糸虫類が分泌する繊維状たんぱく質である。又、セリシンは、繊維を形成しているフィブロインの外側を覆っているゴム状たんぱく質である。本発明のフィブロイン、及びセリシンは、蚕が吐糸する繭を始めとして、クモやハチ等の絹糸虫類が吐糸する蛋白質繊維を対象とすることができる。
<Fibroin and sericin>
Fibroin is a fibrous protein secreted by silkworms such as insects and spiders. Sericin is a rubbery protein covering the outside of the fibroin forming the fiber. The fibroin and sericin of the present invention can be used for protein fibers spun by silkworms such as spiders and bees, including spiders spited by spiders.
中でも前記フィブロイン、及びセリシンは、家蚕、セリシン蚕、及び野蚕等の、各種蚕が吐糸する繭、繭糸および繭糸の加工物である生糸、絹糸、絹織編物等の未精練物、半精練物、精練物等、並びに前記加工物の繊維屑等である残糸を原料とすることが好ましく、特に家蚕の繭、絹糸等が、入手の容易な点からは好ましい。 Above all, the fibroin and sericin are raw silk, silk thread, silk knitted fabric, etc., unscoured and semi-scoured products such as silkworms, sericin silkworms and wild silkworms. In addition, it is preferable to use a scoured material, etc., and a residual yarn which is fiber scraps of the processed product as raw materials, and in particular, rabbit silkworms, silk yarn and the like are preferable from the viewpoint of easy availability.
＜非結晶性絹タンパク＞
本発明は、前記フィブロイン、及びセリシン（以下両者を含めて、絹タンパクと総称することもある。）が非結晶性であることを特徴とする。本発明において非結晶性とは、結晶化度が５０％未満であることをいい、結晶化度とは、前記絹タンパクを室温の蒸留水中に１０分浸漬したときに、水に溶解しない絹たんぱくの総絹たんぱくに対する質量％をいう。絹タンパクが蒸留水に全く溶解しない場合を結晶化度１００％とし、蒸留水に完全に溶解する場合が結晶化度０％とする。
<Amorphous silk protein>
The present invention is characterized in that the fibroin and sericin (hereinafter sometimes collectively referred to as silk protein) are non-crystalline. In the present invention, non-crystalline means that the degree of crystallinity is less than 50%, and the degree of crystallinity means a silk protein that does not dissolve in water when the silk protein is immersed in distilled water at room temperature for 10 minutes. Refers to the mass% of the total silk protein. When the silk protein does not dissolve in distilled water at all, the crystallinity is 100%, and when completely dissolved in distilled water, the crystallinity is 0%.
本発明において、前記絹たんぱくの結晶化度は、中でも２０％未満であることがより好ましく、更には１０％未満が一層好ましい。特に結晶化度が０％は非結晶といい、極めて好ましい。 In the present invention, the degree of crystallinity of the silk protein is more preferably less than 20%, and even more preferably less than 10%. In particular, a crystallinity of 0% is called amorphous, which is extremely preferable.
前記非結晶性絹タンパクにおいて、非結晶性セリシンは、繭糸、生糸又は生織等のセリシンを含有する原料を、精練することにより得ることができる。精練は本来前記原料からセリシンを除くために行う工程で、その方法としては、アルカリ性ナトリウム塩や石鹸を含む水溶液中で煮沸する場合（アルカリセッケン精練）が、最も一般的な方法である。前記アルカリセッケン精練の他に、アルカリ性ナトリウム塩水溶液のみで精練する場合（アルカリ精練）、加圧熱水（例えば１２０℃の熱水）に浸漬して精練する場合（高圧精練）、酵素で精練する場合（酵素精練）等も用いることができる。中でも加圧熱水のみを用いる高圧精練は、以降の脱塩工程が不用なため、セリシン水溶液を得る方法として好ましい。 In the non-crystalline silk protein, non-crystalline sericin can be obtained by scouring a raw material containing sericin such as warp, raw silk or raw weave. Scouring is a process originally performed to remove sericin from the raw material, and the most common method is a method of boiling in an aqueous solution containing an alkaline sodium salt or soap (alkali soap scouring). In addition to the alkaline soap scouring, when scouring only with an aqueous sodium salt solution (alkali scouring), when scouring by immersing in pressurized hot water (for example, 120 ° C. hot water) (high pressure scouring), scouring with enzymes Cases (enzyme scouring) can also be used. Among them, high-pressure scouring using only pressurized hot water is preferable as a method for obtaining an aqueous sericin solution because the subsequent desalting step is unnecessary.
前記精練することにより、原料から前記の溶液中にセリシンが溶出する。セリシンが溶出した溶液は脱塩することにより、非結晶性セリシン水溶液を得ることができる。前記脱塩は、後記のフィブロインの精製に用いると同様の方法を用いることができる。前記により得た非結晶性セリシン水溶液は、該溶液を煮詰める等により、濃度を調整することができる。 By scouring, sericin is eluted from the raw material into the solution. By demineralizing the solution from which sericin is eluted, an amorphous sericin aqueous solution can be obtained. The desalting can be performed by the same method as used for the purification of fibroin described later. The concentration of the amorphous sericin aqueous solution obtained as described above can be adjusted by boiling the solution.
前記フィブロインは絹糸の主な構成成分であり、一般に天然絹糸の結晶化度は概ね１００％である。水に溶解しているフィブロインは高分子量であるほど、水溶液の状態で置いても、水を含んだゆるやかな結晶となりやすい（以下ゲル化という。）。振動や摩擦あるいは攪拌時のずり(shear)により、フィブロインの一部が容易に結晶化し、水不溶性の塊状物が出現する。前記塊状物とは、フィブロイン水溶液が摩擦等によりずりを加えられた場合に、フィブロインの一部が液体状態から固体に変わることにより生ずる、数ミリないしそれ以下の大きさの繊維化した微細な固体をいう。該塊状物が生じた絹タンパクを皮膚上で摩擦すると、皮膚間のすべりが悪く、ざらざらして手触りが悪くなる。
なお前記セリシン水溶液は、振動、摩擦、あるいは攪拌時のずりにより、手触りを粗にする水不溶性の塊状物が出現することはない。
Fibroin is a main constituent of silk thread, and the crystallinity of natural silk is generally about 100%. The higher the molecular weight of fibroin dissolved in water, the easier it is to form loose crystals containing water even when placed in an aqueous solution (hereinafter referred to as gelation). Due to vibration, friction, or shear during stirring, part of the fibroin is easily crystallized and a water-insoluble mass appears. The lump is a fine solid made into a fiber having a size of several millimeters or less, which is generated when a part of fibroin changes from a liquid state to a solid when a fibroin aqueous solution is sheared by friction or the like. Say. When the silk protein in which the lump is formed is rubbed on the skin, slippage between the skins is poor and rough and the touch is poor.
In the sericin aqueous solution, a water-insoluble lump that roughens the hand does not appear due to vibration, friction, or shear during stirring.
フィブロイン水溶液はフィブロインの分子量が２０万程度以上であれば、ゲル化しやすく、分子量約３７万の未分解フィブロインは、ずりが無くてもゲル化する。このようなゲル化物にずりを加えると、前記塊状物が容易に現れる。大きさが０．１ｍｍ以上の塊状物は前記の通り手触りを粗にするため、軟膏や化粧料としての使用感を低下させる原因となり、スキンケア素材としては不適当である。 The fibroin aqueous solution is easily gelled if the molecular weight of fibroin is about 200,000 or more, and undegraded fibroin having a molecular weight of about 370,000 gels even without shear. When a shear is added to such a gelled material, the lump appears easily. A lump having a size of 0.1 mm or more is not suitable as a skin care material because it causes a rough feel as described above and causes a decrease in the feeling of use as an ointment or cosmetic.
本発明においては、フィブロインのゲル化を防止し非結晶性を高めるために、前記フィブロインの分子量は５万以上で２０万以下が好ましく、７万以上で１０万以下がより好ましい。 In the present invention, the molecular weight of the fibroin is preferably 50,000 or more and 200,000 or less, more preferably 70,000 or more and 100,000 or less, in order to prevent the gelation of fibroin and increase the non-crystallinity.
前記フィブロインの分子量は、前記原料の精練条件、及び後記の精練して得た絹糸の溶解条件により異なるものとなる。フィブロインの分子量を前記の範囲とするためには、原料の精練は、前記アルカリ性ナトリウム塩の中でも炭酸ソーダ水溶液を用いることが、pHに対して適度のバッファー効果があるため好ましい。前記炭酸ソーダの濃度は０．０１％〜１％が好ましく、精練時間は２０分〜９０分が好ましい。前記の範囲以上に炭酸ソーダの濃度を高くし、あるいは精練時間を長くすると、フィブロインの分子量が低下し好ましくない。 The molecular weight of the fibroin varies depending on the scouring conditions of the raw material and the dissolving conditions of the silk thread obtained by scouring described later. In order to make the molecular weight of fibroin within the above range, it is preferable to use a sodium carbonate aqueous solution among the alkaline sodium salts for the scouring of the raw material because it has an appropriate buffer effect on pH. The concentration of the sodium carbonate is preferably 0.01% to 1%, and the scouring time is preferably 20 minutes to 90 minutes. Increasing the concentration of sodium carbonate beyond the above range or lengthening the scouring time is not preferable because the molecular weight of fibroin decreases.
精練して得た絹糸の溶解とは、フィブロインで構成される絹糸等の原料を中性塩で溶解することをいい、その後必要な脱塩を行い、これにより非結晶状態で溶解しているフィブロイン水溶液を得ることができる。前記原料を中性塩溶液に溶解する工程は、
１）攪拌することにより溶解を促進することができる。
２）溶解温度が低いと溶解しにくい。
３）溶解温度が高いと溶解し易いが、分子量低下が起きやすい。
ことから、中性塩の種類と目的とする分子量に応じ、最適の溶解条件を設定する。
Dissolution of silk thread obtained by scouring means dissolving raw materials such as silk thread composed of fibroin with neutral salt, and then performing necessary desalting, thereby fibroin dissolved in an amorphous state. An aqueous solution can be obtained. The step of dissolving the raw material in a neutral salt solution,
1) Dissolution can be promoted by stirring.
2) It is difficult to dissolve when the melting temperature is low.
3) When the dissolution temperature is high, the composition is easily dissolved, but the molecular weight is likely to decrease.
Therefore, optimal dissolution conditions are set according to the type of neutral salt and the target molecular weight.
前記中性塩としては、例えば塩化カルシウム、銅エチレンジアミン、チオシアン酸ナトリウム、チオシアン酸リチウム、臭化リチウム、硝酸マグネシウム等を挙げることができる。コスト面からは塩化カルシュウムが好ましい。 Examples of the neutral salt include calcium chloride, copper ethylenediamine, sodium thiocyanate, lithium thiocyanate, lithium bromide, and magnesium nitrate. In view of cost, calcium chloride is preferable.
前記中性塩は、５０％（重量(g)／容量（ｍｌ））以上の濃度が好ましく、飽和水溶液がより好ましい。中性塩として塩化カルシウムを使う場合は、９５℃以下の温度で、さらには７５〜８５℃程度の温度で行うことが好ましい。臭化リチウムを使う場合は、５０℃程度以下の温度で原料を溶解する等、中性塩の種類によりに溶解条件は異なる。 The neutral salt preferably has a concentration of 50% (weight (g) / volume (ml)) or more, and more preferably a saturated aqueous solution. When calcium chloride is used as the neutral salt, it is preferably carried out at a temperature of 95 ° C. or less, and more preferably at a temperature of about 75 to 85 ° C. When lithium bromide is used, the dissolution conditions differ depending on the type of neutral salt, such as melting the raw material at a temperature of about 50 ° C. or lower.
前記原料を中性塩溶液に溶解する工程において、中性塩にメチルアルコール、エチルアルコール、プロピルアルコール等のアルコール類を添加してもよい。 In the step of dissolving the raw material in a neutral salt solution, alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol may be added to the neutral salt.
原料を中性塩で溶解した溶解液には絹タンパク、中性塩、アルコール等が含まれている。このため、前記溶解液から透析膜や透析装置を用いて、中性塩、アルコール、分子量約１万以下の絹タンパク、及び不溶物除き、目的とする非結晶性絹タンパク水溶液を得ることができる。 The solution obtained by dissolving the raw material with a neutral salt contains silk protein, neutral salt, alcohol and the like. For this reason, neutral salt, alcohol, silk protein having a molecular weight of about 10,000 or less, and insoluble matter can be removed from the solution using a dialysis membrane or a dialysis device to obtain a target amorphous silk protein aqueous solution. .
前記溶解液からの脱塩を蒸留水で透析する場合は、溶解液の約50倍量の蒸留水を透析外液として、２〜４時間毎に蒸留水を４回以上変えるか、これに相当する方法を用いて透析する。脱塩によって非結晶性絹タンパク水溶液を得ることができる。 When dialyzing the desalted solution from the solution with distilled water, approximately 50 times the amount of the solution as distilled water is used as the external solution, or the distilled water is changed at least 4 times every 2 to 4 hours or equivalent. Dialyze using the method described above. An amorphous silk protein aqueous solution can be obtained by desalting.
前記の通り高圧精練は、前記脱塩工程が不用なため、非結晶性セリシン水溶液を得る方法として好ましい。前記高圧精練の場合は高圧にするほど、又長時間処理をするほどフィブロインの分子量が低下するため、温度を115〜125℃として、圧力を2気圧程度に維持したうえで、10〜30分の処理が好ましい。 As described above, high-pressure scouring is preferable as a method for obtaining an amorphous sericin aqueous solution because the desalting step is unnecessary. In the case of the high-pressure scouring, the higher the pressure, the longer the treatment, the lower the molecular weight of fibroin. Therefore, the temperature is set to 115 to 125 ° C., and the pressure is maintained at about 2 atm. Treatment is preferred.
＜非結晶性絹タンパクの繊維への付着＞
本発明は、前記により得た非結晶性絹タンパクを、水と融和する非結晶性の状態で布帛に付着させることを特徴とする。前記非結晶性絹タンパク水溶液としては、前記非結晶性フィブロインのみ、前記非結晶性セリシンのみ、または前記非結晶性フィブロインと前記非結晶性セリシンの混合液のいずれをも用いることができる。
<Adhesion of non-crystalline silk protein to fiber>
The present invention is characterized in that the amorphous silk protein obtained as described above is adhered to a fabric in an amorphous state compatible with water. As the non-crystalline silk protein aqueous solution, any one of the non-crystalline fibroin, the non-crystalline sericin alone, or the mixed liquid of the non-crystalline fibroin and the non-crystalline sericin can be used.
前記布帛を構成する繊維としては、天然繊維、合成繊維、またそれらの混合物の、いずれの繊維も用いることができる。中でもレーヨン、コットン、絹糸が好ましい。前記布帛は、編物等の布地でも、不織布でも用いることができる。中でも不織布は布帛内で繊維が均一に分散しているため特に好ましい。 As the fibers constituting the fabric, any of natural fibers, synthetic fibers, and mixtures thereof can be used. Of these, rayon, cotton and silk are preferred. The fabric can be a fabric such as a knitted fabric or a non-woven fabric. Among them, the nonwoven fabric is particularly preferable because the fibers are uniformly dispersed in the fabric.
前記布帛に非結晶性絹タンパクを付着させる方法としては、布帛に非結晶性絹タンパク水溶液を含浸させる方法、布帛表面に非結晶性絹タンパク水溶液を噴霧する方法、及び布帛表面に非結晶性絹フィルムを付着させる方法がある。 As a method of attaching the amorphous silk protein to the cloth, a method of impregnating the cloth with an amorphous silk protein aqueous solution, a method of spraying an amorphous silk protein aqueous solution on the cloth surface, and an amorphous silk on the cloth surface. There is a method of attaching a film.
前記布帛に非結晶性絹タンパク水溶液を含浸させる方法としては、該絹タンパク水溶液中に布帛を浸漬する方法、又は該絹パンパク水溶液を布帛に噴霧する方法が好ましい。前記布帛に絹タンパクを含浸させた後、送風しながら乾燥させることで、布帛を構成する繊維表面に非結晶性絹タンパクが付着される。 As a method of impregnating the cloth with the non-crystalline silk protein aqueous solution, a method of immersing the fabric in the silk protein aqueous solution or a method of spraying the silk pangpak aqueous solution onto the fabric is preferable. After the silk protein is impregnated with the silk fabric, the silk silk protein is adhered to the surface of the fibers constituting the fabric by drying while blowing air.
前記布帛に付着させる非結晶性絹タンパク水溶液の濃度は、０．１〜１５質量％が好ましく、１〜５質量％がより好ましい。非結晶性絹タンパク水溶液の濃度が前記の範囲より濃いと、該水溶液が布帛に浸透しにくくなり、均一な付着が難しくなり、又前記の範囲より薄いと、付着量が少なくなり、いずれも好ましくない。 The concentration of the amorphous silk protein aqueous solution attached to the fabric is preferably 0.1 to 15% by mass, and more preferably 1 to 5% by mass. If the concentration of the non-crystalline silk protein aqueous solution is higher than the above range, the aqueous solution will not easily penetrate into the fabric and uniform adhesion will be difficult. Absent.
前記布帛に絹タンパク水溶液を含浸させる方法の場合は絹タンパクの含浸量は、布帛単位体積当り1〜12mg／cm3が好ましく、２〜６mg／cm3がより好ましい。 In the case of the method of impregnating the cloth with the silk protein aqueous solution, the amount of silk protein impregnated is preferably 1 to 12 mg / cm 3 , more preferably 2 to 6 mg / cm 3 per unit volume of the cloth.
前記絹タンパク水溶液を含浸させる方法の場合は、布帛は厚くなるほど非結晶性絹タンパク水溶液を含浸した後の乾燥時間が長くなり、該乾燥時間が長くなると絹タンパクが結晶化しやすいので、布帛の厚さは５ｍｍ以下が好ましく、より好ましくは２ｍｍ以下である。 In the case of the method of impregnating the silk protein aqueous solution, the thicker the cloth, the longer the drying time after impregnating the amorphous silk protein aqueous solution, and the longer the drying time, the easier it is for the silk protein to crystallize. The thickness is preferably 5 mm or less, more preferably 2 mm or less.
前記布帛に非結晶性絹フィルムを付着させる方法としては、接着剤を用いる方法、又は水で該フィルムの一部を溶解させ付着させる方法を用いることができ、水で付着させる方法がより好ましい。前記接着剤を用いる場合は、接着剤として水溶性の接着剤が好ましい。又前記水で付着させる方法の場合は、布帛に水を含浸させ、そこに非結晶性絹フィルムを押し当てる方法が好ましい。更に前記水に前記水溶性接着剤を適宜配合することも好ましい。該フィルムが付着された布帛を乾燥することで目的の布帛を得ることができる。 As a method of attaching the amorphous silk film to the fabric, a method using an adhesive or a method of dissolving and attaching a part of the film with water can be used, and a method of attaching with water is more preferable. When the adhesive is used, a water-soluble adhesive is preferable as the adhesive. Moreover, in the case of the method of making it adhere with water, the method of impregnating a cloth with water and pressing an amorphous silk film there is preferable. Furthermore, it is also preferable to mix the water-soluble adhesive appropriately in the water. The desired fabric can be obtained by drying the fabric to which the film is attached.
前記非結晶性絹フィルムは、絹タンパク水溶液を平板上に流し、室温で送風しながら乾燥すれば非結晶性絹フィルムが得られる。絹タンパク水溶液の濃度、または平板上に流す時の単位面積当たりの絹タンパク水溶液量等を変えることでフィルムの厚さを変えることができる。フィルムの厚さを厚くすると、フィルムの乾燥に時間がかかり絹タンパクが結晶化し、水不溶性となる。結晶化を防ぐにはフィルムの乾燥を速くする必要がある。 The amorphous silk film can be obtained by pouring an aqueous silk protein solution onto a flat plate and drying it while blowing air at room temperature. The thickness of the film can be changed by changing the concentration of the silk protein aqueous solution or the amount of the silk protein aqueous solution per unit area when flowing on a flat plate. When the thickness of the film is increased, it takes time to dry the film, and the silk protein crystallizes and becomes insoluble in water. In order to prevent crystallization, it is necessary to dry the film quickly.
前記フィルムの厚さは２０〜１２０μｍが好ましく、絹タンパクの布帛単位面積当り付着量は1〜10mg／cm2が好ましく、1〜5mg／cm2がより好ましい。 Thickness is 20~120μm preferably of the film, the fabric per unit area adhered amount of silk protein is preferably 1~10mg / cm 2, 1~5mg / cm 2 is more preferable.
前記布帛に水を含浸させる方法としては、水を布帛に噴霧する方法が好ましい。特に、布帛の表面繊維にのみ、水が付くようにすることが好ましい。噴霧する水の量が多いと、絹フィルムが溶解し、あるいは乾燥中に結晶化し、少なすぎると、絹フィルムが付着しないので、噴霧する水の量は、布帛の表面１００ｃｍ２当たり０．１ｇ〜３ｇが好ましく、中でも０．２ｇ〜２ｇがより好ましい。 As a method of impregnating the fabric with water, a method of spraying water on the fabric is preferable. In particular, it is preferable that water is attached only to the surface fibers of the fabric. If the amount of water to be sprayed is large, the silk film dissolves or crystallizes during drying. If the amount is too small, the silk film does not adhere. Therefore, the amount of water to be sprayed is 0.1 g to 100 cm 2 of the surface of the fabric. 3g is preferable and 0.2g-2g is more preferable especially.
該絹タンパク水溶液には、本発明の作用効果を損なわない範囲で、必要に応じて、保湿剤、抗菌剤、抗炎症財、色素、香料、ビタミン、紫外線吸収材、有機もしくは無機の粉体など、スキンケア用として通常に使用されている成分を適宜配合することができる。また、付着用の水にこれらの成分を適宜配合してもよい。 In the silk protein aqueous solution, a moisturizer, an antibacterial agent, an anti-inflammatory agent, a pigment, a fragrance, a vitamin, an ultraviolet absorber, an organic or inorganic powder, etc. Ingredients usually used for skin care can be appropriately blended. Moreover, you may mix | blend these components suitably with the water for adhesion.
＜本発明の布帛の取扱＞
本発明の布帛は高温、高湿をさけ、暗室に置けば、５年程度の長期にわたって非結晶性絹タンパクの機能を保持することができる。
<Handling of the fabric of the present invention>
The fabric of the present invention can retain the function of the amorphous silk protein for a long period of about 5 years if it is placed in a dark room while avoiding high temperature and high humidity.
非結晶性絹タンパクを付着した布帛は，健常な皮膚に対しスキンケア素材として利用するときは、該布帛を皮膚にあて、水や化粧水、消毒液等を該布帛に添加し、非結晶性絹タンパクが溶解、または溶解に近い状態で使われる。このとき溶解した絹タンパクを皮膚上で、皮膚に浸透するようによく伸ばしてもよい。これによって絹タンパクで皮膚が皮膜され、乾燥した後は優れた手触りとなる。 When the fabric with the amorphous silk protein attached is used as a skin care material for healthy skin, the fabric is applied to the skin, and water, lotion, disinfectant, etc. are added to the fabric, and the amorphous silk protein is added. Used when protein is dissolved or nearly dissolved. At this time, the dissolved silk protein may be well stretched so as to penetrate the skin. As a result, the skin is coated with silk protein, and after drying it has an excellent feel.
損傷皮膚に対しては、該布帛を傷口にあて、滲出液などでフィルムを溶解し、傷口を絹タンパクでコートし、創傷被覆材として使う。溶解した絹タンパクが皮膚表面をカバーするように布帛を押し当てる。数分〜数十分間あてた後に、布帛をとり、皮膚を乾燥する。このとき乾燥前に皮膚を軽く洗ってもよい。これによって皮膚は数ミクロン以下のごく薄い絹タンパクで皮膜された状態となる。 For damaged skin, the fabric is applied to the wound, the film is dissolved with exudate and the wound is coated with silk protein, and used as a wound dressing. The fabric is pressed so that the dissolved silk protein covers the skin surface. After several minutes to several tens of minutes, remove the fabric and dry the skin. At this time, the skin may be gently washed before drying. As a result, the skin is coated with a very thin silk protein of several microns or less.
＜分子量と細胞生育能＞
材料として、家蚕の生糸（２７デニール）を用いた。該生糸１００ｇを、０．４％炭酸ソーダ水溶液５ｋｇに入れ、１時間煮沸する精練工程によりセリシンを除き絹糸を得た。該絹糸１５ｇを、塩化カルシウム：エチルアルコール：蒸留水＝１：２：８のモル比からなる溶解液１００ｇに入れ、７５℃〜８５℃で１時間かけて絹糸を溶解した。絹糸の溶解液を透析膜（三光純薬(株)製、ＵＣ３６−３２−１００）に入れ、蒸留水で透析し、濃度が約１１％のフィブロイン水溶液（以下試料ａという。）を得た。この試料ａを蒸留水で希釈して、濃度２％のフィブロイン水溶液（以下試料ｂという。）を得た。
<Molecular weight and cell viability>
The raw silk thread (27 denier) was used as a material. 100 g of the raw silk was put into 5 kg of 0.4% sodium carbonate aqueous solution, and sericin was removed by a scouring process of boiling for 1 hour to obtain a silk thread. 15 g of the silk thread was put into 100 g of a solution having a molar ratio of calcium chloride: ethyl alcohol: distilled water = 1: 2: 8, and the silk thread was dissolved at 75 ° C. to 85 ° C. over 1 hour. The silk solution was placed in a dialysis membrane (UC36-32-100, manufactured by Sanko Junyaku Co., Ltd.) and dialyzed with distilled water to obtain a fibroin aqueous solution (hereinafter referred to as sample a) having a concentration of about 11%. This sample a was diluted with distilled water to obtain a 2% concentration fibroin aqueous solution (hereinafter referred to as sample b).
一方蒸留水１，０００ｇに、家蚕繭から蛹、脱皮殻等の絹以外のものを除いた繭層２０ｇを入れた容器を、オートクレーブ（トミー工業(株)製、ＢＳ−３２５）で、１２０℃、２気圧で、２０分処理をした。この高圧精練処理で繭層のセリシンは蒸留水に溶解し、濃度約０．２％のセリシン水溶液を得た。これを８０℃〜１００℃で煮詰めて、濃度１％のセリシン水溶液（以下試料ｄという。）とした。 On the other hand, a container in which 20 g of a cocoon layer excluding silk such as cocoons and molting shells was added to 1,000 g of distilled water at 120 ° C. with an autoclave (Tomy Industries, Ltd., BS-325). Treated at 2 atmospheres for 20 minutes. By this high-pressure scouring treatment, the sericin in the soot layer was dissolved in distilled water to obtain an aqueous sericin solution having a concentration of about 0.2%. This was boiled at 80 ° C. to 100 ° C. to obtain a 1% sericin aqueous solution (hereinafter referred to as sample d).
前記により得た試料ｂのフィブロインと試料ｄのセリシンについて、分子量（重量平均）と細胞生育能との関係を以下により調べた。
平均分子量測定はゲルクロマトグラフィー（ファルマシアバイオサイエンス(株)製、Superdex 200 Prep grade）を用いた。前記試料ｂと試料ｄを透析膜（三光純薬(株)製、ＵＣ３６−３２−１００）に入れ、試料溶液を８Ｍ尿素/40ｍＭ Tris-H2SO4（ｐＨ８）に置換した。前記試料溶液を置換後の試料ｂと試料ｄについて、前記ゲルクロマトグラフィーを使用し、２７５ｎｍ（0.6ｍｌ／ｍｉｎ）でモニターした。その結果、重量平均分子量は、試料ｂのフィブロインが１３万、試料ｄのセリシンが８万であった。
Regarding the fibroin sample b and the sericin sample d obtained above, the relationship between the molecular weight (weight average) and the cell growth ability was examined as follows.
The average molecular weight was measured by gel chromatography (Pharmacia Biosciences, Superdex 200 Prep grade). Sample b and sample d were placed in a dialysis membrane (UC36-32-100, manufactured by Sanko Junyaku Co., Ltd.), and the sample solution was replaced with 8M urea / 40 mM Tris-H 2 SO 4 (pH 8). Sample b and sample d after replacement of the sample solution were monitored at 275 nm (0.6 ml / min) using the gel chromatography. As a result, the weight average molecular weight was 130,000 for the fibroin sample b and 80,000 for the sericin sample d.
前記試料ｂ、及び試料ｄの細胞生育能を以下により測定した。前記試料ｂ、試料ｄの水溶液を希釈して得た、０．００２５％溶液１ｍｌを、細胞培養用のシャーレ（ベクトンディキンソン(株)製、３５ｍｍφ）に入れ、風乾し、ＰＢＳ(Phosphate-Buffered Saline)２ｍｌで３回洗った後、再度風乾した。前記風乾後の細胞培養用のシャーレに、７０％エタノール溶液を噴霧し、シャーレ内の絹の水不溶化と滅菌を行い、試料ｂ、試料ｄの細胞培養床をコートしたシャーレを作成した。 The cell growth ability of the sample b and the sample d was measured as follows. 1 ml of a 0.0025% solution obtained by diluting the aqueous solutions of Sample b and Sample d was placed in a cell culture petri dish (Becton Dickinson Co., Ltd., 35 mmφ), air-dried, and PBS (Phosphate-Buffered Saline). ) After washing 3 times with 2 ml, air-dried again. A 70% ethanol solution was sprayed on the petri dish for cell culture after air drying, and water insolubilization and sterilization of silk in the petri dish were performed to prepare petri dishes coated with the cell culture beds of samples b and d.
細胞生育能を測定する細胞は、凍結ヒト皮膚線維芽細胞（三光純薬(株)製）を使用した。細胞増殖用の培地は、皮膚線維芽細胞増殖用低血清培地（クラボウ(株)製）を使用した。培養は前記試料ｂと試料ｄをそれぞれコートしたシャーレ１枚に、前記細胞培養用の培地２ｍｌを入れ、７万の前記細胞を接種して３日間培養した。 Frozen human skin fibroblasts (manufactured by Sanko Junyaku Co., Ltd.) were used as cells for measuring cell growth ability. As a medium for cell proliferation, a low serum medium for skin fibroblast proliferation (Kurabo Co., Ltd.) was used. The culture was performed by placing 2 ml of the cell culture medium in one petri dish coated with the sample b and the sample d, inoculating 70,000 cells, and culturing for 3 days.
前記３日間培養後の繊維芽細胞数の測定は、前記細胞培養用のシャーレ１枚につき前記細胞培養用の培地２ｍｌとアラマブルー（IWAKI(株)製）０．１ｍｌを加え、３７℃で２時間静置後に、分光光度計（島津製作所製、UV-1200）を使用し、５７０ｎｍ、及び６００ｎｍの吸光度から計算した色素の還元量を生育細胞数とした。 The number of fibroblasts after 3 days of culture was measured by adding 2 ml of the cell culture medium and 0.1 ml of Arama Blue (manufactured by IWAKI Co., Ltd.) per 37 petri dish for cell culture at 37 ° C. for 2 hours. After standing, using a spectrophotometer (manufactured by Shimadzu Corporation, UV-1200), the reduction amount of the pigment calculated from the absorbance at 570 nm and 600 nm was defined as the number of growing cells.
絹タンパクをコートしなかった以外は、前記試料ｂと試料ｄをコートしたシャーレと同様の処理をしたものを対照区とし、試料ｂ、試料ｄをコートしたシャーレ、及び対照区の細胞生育数を測定した。その結果、細胞生育数は対照区（１００％）に対し、試料ｂは１５１％、試料ｄは１２７％であった。 The control group was treated with the petri dish coated with the sample b and the sample d except that the silk protein was not coated, and the cell growth numbers of the petri dish coated with the sample b and the sample d and the control plot were determined. It was measured. As a result, the number of cell growth was 151% for sample b and 127% for sample d with respect to the control group (100%).
＜絹タンパクの分子量と水溶液状態での摩擦による塊状物の出現＞
蒸留水１，０００ｃｃ中に炭酸ソーダ０．５ｇを入れ、煮沸（１００℃）した。前記煮沸液中に、家蚕の繭層１０．０ｇを浸漬、攪拌して、繭層を精練した。前記精練時間を変えてフィブロイン分子量の異なる絹糸を作製した。前記精練時間は（１）５分、（２）２０分、（３）６０分、（４）９０分、（５）１３０分、（６）１８０分とした。
前記絹糸の練減りは（試料１）２２．３％、（試料２）２４．５％、（試料３）２５．１％、（試料４）２５．５％、（試料５）２５．９％、（試料６）２６．２％であった。従って（１）、及び（２）についてはセリシンが１〜３％程度含まれ、（３）〜（６）は９９％以上がフィブロインと考えられる。
<Appearance of mass by silk protein molecular weight and friction in aqueous solution>
0.5 g of sodium carbonate was put in 1,000 cc of distilled water and boiled (100 ° C.). In the boiling solution, 10.0 g of the rabbit cocoon layer was immersed and stirred to refine the cocoon layer. Silk fibers having different fibroin molecular weights were prepared by changing the scouring time. The scouring time was (1) 5 minutes, (2) 20 minutes, (3) 60 minutes, (4) 90 minutes, (5) 130 minutes, and (6) 180 minutes.
The reduction of the silk thread was (Sample 1) 22.3%, (Sample 2) 24.5%, (Sample 3) 25.1%, (Sample 4) 25.5%, (Sample 5) 25.9% (Sample 6) of 26.2%. Accordingly, (1) and (2) contain about 1 to 3% sericin, and (3) to (6) are considered to be 99% or more fibroin.
前記（１）〜（６）の各試料２ｇを、９ＭLiSCN５０ｍｌに溶解し、溶解液を５０倍量の蒸留水で４回透析し、各試料の水溶液とした。該各試料の水溶液について、絹タンパクの分子量と水溶液状態での摩擦による塊状物の出現を調べた。 2 g of each sample of (1) to (6) was dissolved in 50 ml of 9M LiSCN, and the solution was dialyzed 4 times with 50 times the amount of distilled water to obtain an aqueous solution of each sample. The aqueous solution of each sample was examined for the molecular weight of silk protein and the appearance of lumps due to friction in the aqueous solution state.
分子量（重量平均）の測定は、実施例１と同様とした。
次に、試料１〜６の水溶液４０ｇをコーヒーミキサー（シバタ(株)製、パーソナルミルＳＣＭ−４０Ａ）に入れ２０秒攪拌した。攪拌した液を手にとって摩擦し、ざらつくかどうかで、手触りを悪くする塊状物が出来ているかを判断した。塊状物の大きさは、撹拌した液を実態顕微鏡（オリンパス、JM）下で観察し、塊状物の中で大きい方のサイズを測定した。さらに撹拌後の液をガーゼでろ過し、乾燥後にガーゼに付着した塊状物を含む絹タンパクの重さを測定した。結果を表１に示す。
The molecular weight (weight average) was measured in the same manner as in Example 1.
Next, 40 g of the aqueous solutions of Samples 1 to 6 were placed in a coffee mixer (manufactured by Shibata Co., Ltd., Personal Mill SCM-40A) and stirred for 20 seconds. It was judged whether or not a lump that made the touch worse by rubbing the stirred liquid against the hand. Regarding the size of the lump, the stirred liquid was observed under an actual microscope (Olympus, JM), and the larger size of the lump was measured. Furthermore, the liquid after stirring was filtered with gauze, and the weight of the silk protein containing the lump which adhered to gauze after drying was measured. The results are shown in Table 1.
表1から、分子量が２０万程度以上では、分子量の高いほどフィブロイン水溶液の撹拌による塊状物の出現が容易で、且つ塊状物の大きさは大きい。分子量が２０万程度以下では、撹拌による塊状物の出現は見られなかった。 From Table 1, when the molecular weight is about 200,000 or more, the higher the molecular weight, the easier the appearance of the lump by stirring the fibroin aqueous solution, and the lump size is large. When the molecular weight was about 200,000 or less, no lump appeared due to stirring.
＜布帛の改質＞
フィブロイン水溶液による布帛の改質を行った。布帛は、厚さ１．２５ｍｍ、大きさ１０ｃｍ×１０ｃｍ、重さ０．９５ｇのレーヨンとコットンの混合繊維による不織布を用いた。フィブロイン水溶液は、実施例1における試料ｂと同様にして作製した。該布帛を２％フィブロイン水溶液に１０分間浸漬し、引き上げてから絞る程度を試料1から試料9までの9段階として、フィブロイン水溶液の含浸程度の異なる布帛を作製した。フィブロイン水溶液を含浸した布帛の重さを測定し、含浸後の布帛の重さと含浸前の布帛の重さとの差を、フィブロイン水溶液の含浸量として含浸量を測定し、単位体積（ｃｍ３）当りの含浸量（ｍｇ）を算出した。又該含浸量の2％をフィブロイン付着量とし、単位体積（ｃｍ３）当りの付着量（ｍｇ）を算出した。
<Modification of fabric>
The fabric was modified with an aqueous fibroin solution. As the fabric, a nonwoven fabric made of a mixed fiber of rayon and cotton having a thickness of 1.25 mm, a size of 10 cm × 10 cm, and a weight of 0.95 g was used. The aqueous fibroin solution was prepared in the same manner as Sample b in Example 1. The fabric was soaked in a 2% fibroin aqueous solution for 10 minutes, drawn up and then squeezed into nine stages from sample 1 to sample 9, and fabrics having different degrees of impregnation with the fibroin aqueous solution were prepared. Measuring the weight of the fabric impregnated with fibroin aqueous solution, the difference between the weight of the weight and before impregnation of the fabric of the fabric after impregnation, to measure the impregnation amount as impregnation amount of fibroin, unit volume (cm 3) per The amount of impregnation (mg) was calculated. Further, 2% of the impregnation amount was defined as the fibroin adhesion amount, and the adhesion amount (mg) per unit volume (cm 3 ) was calculated.
その後、前記布帛を広げ、室温において扇風機で送風しながら２時間乾燥し、フィブロイン付着量の異なる布帛（以下改質布帛という。）を作製し、乾燥後の各改質布帛の重量（Ｙ２ｇ）を測定した。次に該布帛を、蒸留水に１０分間浸漬した後、前記と同様に乾燥し、乾燥後の布帛の重量（Ｚｇ）を測定し、絹タンパクの結晶化度（％）を、下記式1により計算した。
結晶化度（％）＝１−（Ｙ２−Ｚ）／（Ｙ２−0.95）×１００ （式１）
なお、結晶化度が０％とは完全に絹タンパクが蒸留水中に溶解することをいい、結晶化度が１００％とは全く絹タンパクが蒸留水に溶解しないことをいう。
結果を表２に示す。
Thereafter, the fabric is spread and dried for 2 hours while blowing with a fan at room temperature to produce fabrics with different fibroin adhesion amounts (hereinafter referred to as modified fabrics), and the weight of each modified fabric after drying (Y 2 g). ) Was measured. Next, the fabric was immersed in distilled water for 10 minutes, dried in the same manner as described above, the weight (Zg) of the dried fabric was measured, and the crystallinity (%) of the silk protein was determined by the following formula 1. Calculated.
Crystallinity (%) = 1− (Y 2 −Z) / (Y 2 −0.95) × 100 (Formula 1)
The crystallinity of 0% means that the silk protein is completely dissolved in distilled water, and the crystallinity of 100% means that the silk protein is not dissolved in distilled water.
The results are shown in Table 2.
さらに、各改質布帛に蒸留水を添加した後の布帛の手触りを、触感と柔軟性により調査した。試料9の改質布帛は、布帛の柔軟性が改質前より固く、スキンケア素材としては不適当であった。試料１〜８の改質布帛は、柔軟性が改質前より向上し、試料１〜７の改質布帛は、柔軟性が改質前より一層向上し、溶解した絹タンパクのために手触りは布帛の改質前より良くなった。特に試料１〜５の改質布帛は、改質布帛の手触りがきわめて優れていた。 Furthermore, the touch of the fabric after adding distilled water to each modified fabric was investigated by tactile sensation and flexibility. The modified fabric of Sample 9 was unsuitable as a skin care material because the fabric was softer than before the modification. The modified fabrics of Samples 1 to 8 are more flexible than before modification, and the modified fabrics of Samples 1 to 7 are more flexible than before modification. Better than before the fabric modification. In particular, the modified fabrics of Samples 1 to 5 were extremely excellent in the touch of the modified fabric.
＜布帛の厚さと絹タンパクとの関係＞
布帛の厚さを変えて、改質布帛の効果を調査した。布帛A、布帛Bについては実施例3に用いたと同様の不織布を用い、布帛C、布帛Dについては絹糸による不織布を用いた。各布帛の大きさは１０ｃｍ×１０ｃｍとし、厚さ（ｍｍ）、及び重量（ｇ）は、布帛Ａ：０．２５ｍｍ、０．３６ｇ、布帛Ｂ：１．２５ｍｍ、０．９５ｇ、布帛Ｃ：３．８０ｍｍ、３．４０ｇ、布帛Ｄ：６．２０ｍｍ、５．５１ｇを用い、該各布帛に絹タンパクを付着した。
<Relationship between fabric thickness and silk protein>
The effect of the modified fabric was investigated by changing the thickness of the fabric. For fabric A and fabric B, the same non-woven fabric as used in Example 3 was used, and for fabric C and fabric D, a non-woven fabric made of silk thread was used. The size of each fabric is 10 cm × 10 cm, and the thickness (mm) and weight (g) are Fabric A: 0.25 mm, 0.36 g, Fabric B: 1.25 mm, 0.95 g, Fabric C: 3 .80 mm, 3.40 g, Fabric D: 6.20 mm, 5.51 g were used, and silk protein was adhered to each fabric.
前記布帛へ付着させる絹タンパク水溶液は、実施例１において作製した、１１％フィブロイン水溶液（以下試料aという。）、２％フィブロイン水溶液（以下試料bという。）、１％セリシン水溶液（以下試料dという。）、及び試料ｂと試料dを同量混合したフィブロインとセリシン混合液（以下試料cという。）を用いた。前記各布帛を、前記各試料に１０分間浸漬した後に引き上げ、ろ紙の間に挟み、上から荷重（２００ｇ／１０cm×１０cm）を１分間かけて軽く絞った後に、実施例3と同様に絹タンパク水溶液の単位体積（ｃｍ３）当りの含浸量（ｍｇ）、及び絹タンパクの単位体積（ｃｍ３）当りの付着量（ｍｇ）を算出した。 The silk protein aqueous solution to be attached to the fabric was prepared in Example 1 by using an 11% fibroin aqueous solution (hereinafter referred to as sample a), a 2% fibroin aqueous solution (hereinafter referred to as sample b), and a 1% sericin aqueous solution (hereinafter referred to as sample d). ), And a fibroin and sericin mixed solution (hereinafter referred to as sample c) in which the same amount of sample b and sample d was mixed. Each fabric is dipped in each sample for 10 minutes and then pulled up, sandwiched between filter papers, lightly squeezed over 1 minute from the top (200 g / 10 cm × 10 cm), and then silk protein as in Example 3. The amount of impregnation (mg) per unit volume (cm 3 ) of the aqueous solution and the amount of adhesion (mg) per unit volume (cm 3 ) of silk protein were calculated.
各布帛について、実施例3と同様に、前記各布帛に付着した絹タンパクの結晶化度（％）を測定した。
結果を表3に示す。
For each fabric, the crystallinity (%) of silk protein adhering to each fabric was measured in the same manner as in Example 3.
The results are shown in Table 3.
表3に結果から、布帛Ａ〜Ｃの蒸留水中における結晶化度は、いずれも４％以下であり、布帛Ｄの結晶化度は、いずれも２０％以上であった。 From the results shown in Table 3, the crystallization degree of the fabrics A to C in distilled water was 4% or less, and the crystallization degree of the fabric D was 20% or more.
つぎに、これらの布帛を皮膚上に置き、絹タンパクが溶解するように蒸留水を添加し、溶出した絹タンパクを皮膚によく押し当てた。また、布帛を左右に動かした。布帛を皮膚上に10分置いた後、これを取り、皮膚を乾燥した。その結果、布帛Ａ〜Ｃは、いずれも皮膚に付着した絹タンパクのために、皮膚は優れた肌触りとなった。特に、結晶化度が５％未満の布帛を使用した場合、皮膚は極めて優れた肌触りと光沢になった。 Next, these fabrics were placed on the skin, distilled water was added so that the silk protein was dissolved, and the eluted silk protein was well pressed against the skin. The fabric was moved left and right. After placing the fabric on the skin for 10 minutes, it was removed and the skin was dried. As a result, the fabrics A to C all had excellent skin feel because of the silk protein adhering to the skin. In particular, when a fabric having a crystallinity of less than 5% was used, the skin became extremely soft and glossy.
実施例4に使用した布帛Ａと同様の不織布を用い、該布帛に、実施例4に使用した試料ｂと同様の２％フィブロイン水溶液を、該布帛の表面から噴霧した。前記フィブロイン水溶液の布帛１００ｃｍ２あたりの噴霧量は、処理1：０．６５ｇ、処理２：１．７３ｇ、処理３：７．２４ｇの３種類とし、単位面積あたりのフィブロイン付着量（mg／cm2）を算出した。なお単位面積あたりのフィブロイン付着量は、フィブロインが布帛表面にのみ付着したものとして計算した。噴霧後にこれらを、実施例3と同様に乾燥した。乾燥後の布帛を実施例3と同様にして、付着したフィブロインの結晶化度を測定した。
結果を表4に示す。
A non-woven fabric similar to the fabric A used in Example 4 was used, and a 2% fibroin aqueous solution similar to the sample b used in Example 4 was sprayed onto the fabric from the surface of the fabric. The amount of the fibroin aqueous solution sprayed per 100 cm 2 of fabric is three types of treatment 1: 0.65 g, treatment 2: 1.73 g, and treatment 3: 7.24 g, and the fibroin adhesion amount per unit area (mg / cm 2 ) Was calculated. The fibroin adhesion amount per unit area was calculated on the assumption that fibroin adhered only to the fabric surface. After spraying, they were dried as in Example 3. The dried fabric was treated in the same manner as in Example 3, and the crystallinity of the attached fibroin was measured.
The results are shown in Table 4.
次に、これらの布帛を腕に巻き、蒸留水を５ｇ添加した。布帛から流出してきたフィブロイン水溶液が皮膚に浸透するように布帛を皮膚に押し当て、30秒間摩擦した。その後、そのまま１０分間置いてから布帛を取り、腕を乾燥し、腕の手触り感を調べたところ、処理1では改質による手触りにはほとんど変化が無かった。処理２では、腕は極めて手触りが良くなり、快適感のある状態に変わった。しかし、処理３では、布帛は硬くなり、手触りは低下した。 Next, these fabrics were wound around the arm and 5 g of distilled water was added. The fabric was pressed against the skin so that the fibroin aqueous solution flowing out from the fabric penetrated into the skin, and rubbed for 30 seconds. Then, after leaving for 10 minutes as it was, the fabric was taken out, the arm was dried, and the feel of the arm was examined. In treatment 1, there was almost no change in the touch due to the modification. In the process 2, the arm became extremely comfortable and changed to a comfortable state. However, in treatment 3, the fabric became stiff and the feel decreased.
＜非結晶性絹フィルムの作成と布帛への付着及び利用＞
実施例４に使用した試料ａと試料ｃの絹タンパク水溶液を用い、非結晶性絹フィルムを作成した。フィルム１として、前記試料ａの水溶液１００ｇを１５００ｃｍ２のプラスチック板上に、フィルム２として、前記試料ｃの水溶液２００ｇを３００ｃｍ２のプラスチック板上にそれぞれ流し、室温（２０℃、５０％ＲＨ）環境下で、送風しながら乾燥した。得られたフィルム各１ｇを蒸留水５００ｇに浸漬したところ、いずれのフィルムも５分以内に完全に蒸留水に溶解した。つまり、非結晶絹フィルムが得られた。
<Creation of non-crystalline silk film and adhesion to fabric>
Using the silk protein aqueous solutions of Sample a and Sample c used in Example 4, an amorphous silk film was prepared. As film 1, 100 g of the aqueous solution of sample a was poured onto a 1500 cm 2 plastic plate, and as film 2, 200 g of the aqueous solution of sample c was poured onto a 300 cm 2 plastic plate. Below, it dried with ventilation. When 1 g of each of the obtained films was immersed in 500 g of distilled water, all the films were completely dissolved in distilled water within 5 minutes. That is, an amorphous silk film was obtained.
前記フィルム１、及びフィルム２を、布帛に付着した。布帛は実施例３において用いた布帛Ｂと同様で、１０ｃｍ×１０ｃｍのサイズの不織布を用いた。該布帛に、蒸留水（０．４ｇ）を細かい霧状にして噴霧し、この上に前記フィルム１、及びフィルム２を軽く押し当てたところ、わずかな水滴がフィルムの一部を溶解し布帛の繊維にフィルムが付着した。前記フィルム１、及びフィルム２が付着した布帛の絹タンパク量は、前記試料ａが１．３３μｇ、試料ｃが１０．００μｇである。この後は送風しながら布帛を速やかに乾燥することでフィルムは布帛に接着し、いずれのフィルムも非結晶性は保たれた。
結果を表５に示す。
The film 1 and the film 2 were attached to the fabric. The fabric was the same as the fabric B used in Example 3, and a nonwoven fabric having a size of 10 cm × 10 cm was used. Distilled water (0.4 g) was sprayed in a fine mist on the fabric, and when the film 1 and the film 2 were lightly pressed onto the fabric, slight water droplets dissolved a part of the film and A film adhered to the fiber. The silk protein content of the fabric to which the films 1 and 2 are attached is 1.33 μg for the sample a and 10.00 μg for the sample c. Thereafter, the fabric was quickly dried while blowing air, whereby the film adhered to the fabric, and all the films were kept non-crystalline.
The results are shown in Table 5.
皮膚上にできた直径４ｍｍの水泡が破けて痛いところに、フィルム１を付着した布帛（２ｃｍ×２ｃｍ）をあて、粘着テープで止めたところ、傷口の滲出液をフィルムが吸収し、フィルムが溶解して傷口をカバーした。この状態で数分後には痛みは無くなった。そのまま５日間置いたところ、水疱の後には薄皮ができ傷は治りつつあった。 When the water bubble with a diameter of 4mm on the skin breaks and hurts, the fabric (2cm x 2cm) to which the film 1 is attached is applied and stopped with an adhesive tape. The film absorbs the exudate from the wound and the film dissolves. And covered the wound. The pain disappeared after a few minutes in this state. When left for 5 days, a thin skin was formed after the blister and the wound was healing.
一方、フィルム２を付着した布帛（５ｃｍ×１０ｃｍ）を額にあて、布帛の上から化粧水６ｇを添加して、絹タンパクを溶解し、溶出した絹タンパクが皮膚に浸透するように布帛を額に押し当て、また上下左右に動かし、そのまま置いた。このとき、額にはずりや摩擦による絹タンパクの塊状物は現れなかった。１０分後に布帛をとり、額を乾燥したところ、額は手触りと光沢に極めて優れ、快適感のある皮膚となった。 On the other hand, the fabric (5 cm × 10 cm) to which the film 2 is attached is applied to the forehead, 6 g of skin lotion is added from above the fabric, the silk protein is dissolved, and the fabric is placed so that the eluted silk protein penetrates into the skin. And then moved up, down, left and right, and left as it was. At this time, a lump of silk protein due to slipping or friction did not appear on the forehead. After 10 minutes, the fabric was taken out and the forehead was dried. As a result, the forehead was extremely excellent in touch and gloss, and became a comfortable skin.
本発明の、非結晶性絹タンパクを付着した布帛は、皮膚上でこの布帛に水又は化粧水などを添加して、絹タンパクを溶解し、溶解された絹タンパクを皮膚にコーティングする。また、皮膚上の水あるいは滲出液で絹タンパクを溶解し、溶解液で皮膚をコーティングする方法で使用する。絹タンパクは皮膚細胞生育促進能を有していることから、皮膚上の小さな傷の治癒促進にも効果的であり、スキンケア素材として優れている。
In the fabric of the present invention to which the amorphous silk protein is adhered, water or lotion is added to the fabric on the skin to dissolve the silk protein, and the dissolved silk protein is coated on the skin. The silk protein is dissolved with water or exudate on the skin, and the skin is coated with the solution. Since silk protein has the ability to promote the growth of skin cells, it is effective in promoting the healing of small wounds on the skin and is an excellent skin care material.
Claims (7)
A medical device and / or a cosmetic using the fabric according to any one of claims 1 to 7.
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| JPS56140176A (en) * | 1980-04-03 | 1981-11-02 | Hideo Kakigi | Surface treatment of polyester or polyether molded product |
| JPH1170160A (en) * | 1997-06-18 | 1999-03-16 | Norin Suisansyo Sanshi Konchu Nogyo Gijutsu Kenkyusho | Occlusive dressing consisting essentially of silk fibroin and silk sericin and its production |
| JP2002302879A (en) * | 2001-04-05 | 2002-10-18 | Kuraray Co Ltd | Leathery sheet |
| JP2003226614A (en) * | 2001-11-29 | 2003-08-12 | National Institute Of Agrobiological Sciences | Emulsifier having skin cell growth promoting property and method for producing the same |
| JP2003171876A (en) * | 2001-12-05 | 2003-06-20 | Imai Senshoku Kk | Sericin fibroin-adhered acrylic article and polyamide article, and method for producing the same |
| JP2003342835A (en) * | 2002-05-23 | 2003-12-03 | National Institute Of Agrobiological Sciences | Biocompatible core-sheath type conjugate fiber, biocompatible synthetic fiber and method for producing the same |
| JP2004250821A (en) * | 2003-02-20 | 2004-09-09 | Shiga Pref Gov | Method for treating fiber assembly and the resultant sericin-treated fiber assembly |
| JP2004250405A (en) * | 2003-02-21 | 2004-09-09 | Oodoreman:Kk | Cosmetic containing noncrystalline silk fibroin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020204057A1 (en) * | 2019-04-02 | 2020-10-08 | 株式会社島精機製作所 | Non-woven fabric and method for manufacturing same |
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| JP4875305B2 (en) | 2012-02-15 |
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