JP2010236149A - Production method of reduction salting-out keratin fiber - Google Patents
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本発明は、羊毛、毛髪、爪、角等の角質タンパク質の主成分であるケラチンタンパク質を原料とした繊維の製造方法に関するものであり、詳しくは、ケラチンタンパク質含有物質を還元・塩析して得られる還元塩析ケラチンからなる還元塩析ケラチン繊維の製造方法に関するものである。 The present invention relates to a method for producing a fiber using keratin protein, which is a main component of keratin protein such as wool, hair, nails, and horns, as a raw material, and more specifically, obtained by reducing and salting out a keratin protein-containing substance. The present invention relates to a method for producing reduced salting-out keratin fibers comprising reduced salting-out keratin.
羊毛、毛髪、爪、角等のケラチンタンパク質含有物質を還元して得られる還元ケラチンは、タンパク質の主鎖構造であるペプチド結合を分解することなく高分子量のタンパク質が得られること、タンパク質中のシスチンのジスルフィド結合（−Ｓ−Ｓ−結合）を開裂させて活性なチオール基（−ＳＨ基）とすることが可能なことから、産業材料として重要な物質である。かかる還元ケラチンの製造としては、特許文献１の如く、２−メルカプトエタノール等のチオール系化合物、メタ重亜硫酸ナトリウム等の重亜硫酸塩化合物、亜硫酸水素ナトリウム等の亜硫酸塩化合物等を還元剤としてケラチンタンパク質含有物質を還元処理する方法が知られている。また、還元ケラチンからなる繊維の製造方法としては、上記した還元剤を用いた可溶性Ｓ−スルホン化ケラチン誘導体（ブンデ塩）を利用したケラチン繊維の製造方法が知られている（特許文献２）。 Reduced keratin obtained by reducing keratin protein-containing substances such as wool, hair, nails, and horns is capable of obtaining a high molecular weight protein without breaking the peptide bond, which is the main chain structure of the protein, and cystine in the protein. This is an important material as an industrial material because it can be cleaved to form an active thiol group (—SH group). As for the production of such reduced keratin, as in Patent Document 1, a keratin protein using a thiol compound such as 2-mercaptoethanol, a bisulfite compound such as sodium metabisulfite, a sulfite compound such as sodium bisulfite as a reducing agent. A method of reducing the contained material is known. As a method for producing a fiber made of reduced keratin, a method for producing a keratin fiber using a soluble S-sulfonated keratin derivative (Bunde salt) using the above-described reducing agent is known (Patent Document 2).
しかしながら、特許文献１に示された還元剤の内、チオール系のものは、独特の強い刺激臭を有しており、作業者に著しい不快感を与えるため、工業的生産に利用することは困難である。また、亜硫酸塩化合物系の還元剤は、抽出時にＳＯｘ等のガスを発生する等の問題点を有する上、還元力が弱いため、還元処理に長い時間を要するという不具合がある。一方、特許文献２に示された還元塩析ケラチン繊維の製造方法は、可溶性Ｓ−スルホン化ケラチン誘導体からでは可紡性の溶液が得られにくいため、安定した連続した繊維の製造が困難であった。 However, among the reducing agents shown in Patent Document 1, those based on thiols have a unique and strong irritating odor, and give a significant discomfort to the worker. Therefore, it is difficult to use them for industrial production. It is. In addition, the sulfite compound-based reducing agent has problems such as generation of gas such as SOx at the time of extraction, and has a problem that it takes a long time for the reduction treatment because of its weak reducing power. On the other hand, in the method for producing reduced salting-out keratin fibers disclosed in Patent Document 2, it is difficult to obtain a spinnable solution from a soluble S-sulfonated keratin derivative, and thus it is difficult to produce a stable continuous fiber. It was.
本発明の目的は、上記従来の還元ケラチン繊維の製造方法が有する問題点を解消し、ケラチン含有物質の還元塩析工程で不具合を生じさせることなく、安定して強度の高い還元塩析ケラチン繊維を安価かつ容易に製造することが可能な還元ケラチン繊維の製造方法を提供することにある。 An object of the present invention is to eliminate the problems of the conventional method for producing reduced keratin fibers and to reduce the salting-out keratin fibers stably and with high strength without causing problems in the reducing and salting-out process of the keratin-containing substance. It is in providing the manufacturing method of the reduced keratin fiber which can be manufactured cheaply and easily.
本発明の発明者らは、上記従来技術の課題を解決すべく鋭意検討した。その結果、ケラチン含有物質を水性媒体中でタンパク質変性剤、還元剤、界面活性剤の存在下で還元抽出するときに、還元剤として第三級ホスフィン化合物を用いると、１００℃で３０分間程度の短時間の処理で、臭気やガスをほとんど発生させることなく容易にケラチンの抽出作業を行うことができることを見出した。また、上記の如く可溶化還元ケラチン抽出液を得る際に、抽出時に加える界面活性剤の量を調整すること、および、可溶化還元ケラチン抽出液に無機塩を加えて塩析反応により還元塩析ケラチンの溶液またはゾル状物を析出させる際に、無機塩の添加量、塩析後の還元塩析ケラチンの温度、塩析からの経過時間をそれぞれ調整をすることによって、還元塩析ケラチンに紡糸・成形に適した粘性を付与して曳糸性を向上させることが可能であることを見出した。さらに、還元塩析ケラチンからなる紡糸液を、乾式紡糸法、湿式紡糸法、乾湿式紡糸法によって紡糸した後に、紡糸後の還元塩析ケラチンに酸性溶液に接触させることによ って、還元塩析ケラチン繊維の強度を高め得ることを見出した。そして、それらの知見に基づいて、本発明を案出するに至った。 The inventors of the present invention have intensively studied to solve the above problems of the prior art. As a result, when a keratin-containing substance is reductively extracted in an aqueous medium in the presence of a protein denaturant, a reducing agent, and a surfactant, a tertiary phosphine compound is used as a reducing agent at 100 ° C. for about 30 minutes. It has been found that keratin extraction can be carried out easily with little odor and gas generation in a short treatment. In addition, when obtaining a solubilized reduced keratin extract as described above, the amount of surfactant to be added at the time of extraction is adjusted, and an inorganic salt is added to the solubilized reduced keratin extract and reduced salting out by a salting out reaction. When precipitating a keratin solution or sol, spinning the reduced salting-out keratin by adjusting the amount of inorganic salt added, the temperature of the reduced salting-out keratin after salting out, and the elapsed time since salting-out. -It has been found that it is possible to improve the spinnability by imparting a viscosity suitable for molding. Further, after spinning the spinning solution composed of reduced salting out keratin by dry spinning method, wet spinning method, and dry and wet spinning method, the reduced salting out keratin after spinning is brought into contact with an acidic solution, thereby reducing the reduced salt. It has been found that the strength of the deposited keratin fibers can be increased. And based on those knowledge, it came to devise this invention.
すなわち、本発明の内、請求項１に記載された発明は、ケラチン含有物質を還元処理した後に、得られた還元ケラチンを塩析することによって得られる還元塩析ケラチンを用いて還元塩析ケラチン繊維を製造する方法であって、以下の（ａ）〜（ｃ）の工程を備えたことを特徴とする還元塩析ケラチン繊維の製造方法である。
（ａ）タンパク質変性剤、第三級ホスフィン化合物、および、ケラチン含有物質の質量に対して６０質量％以上１００質量％以下の界面活性剤を加えた水溶液中でケラチン含有物質を還元処理する工程
（ｂ）前記還元処理工程で得られた還元ケラチンを含む水溶液に、０．９Ｍ以上飽和濃度未満に相当する量の無機塩あるいは無機塩の水溶液を添加して、水溶液中のケラチン成分を塩析させることによって還元塩析ケラチンを得る工程
（ｃ）還元塩析ケラチンを繊維状に形成して気中に吐出あるいは所定の濃度に調整した酸性凝固液中に浸漬する工程
That is, among the present invention, the invention described in claim 1 is a reduced salting-out keratin using a reduced salting-out keratin obtained by salting out the obtained reduced keratin after reducing the keratin-containing substance. A method for producing a fiber, comprising the following steps (a) to (c): a method for producing a reduced salting-out keratin fiber.
(A) A step of reducing the keratin-containing substance in an aqueous solution to which 60% by mass to 100% by mass of a surfactant is added with respect to the mass of the protein denaturant, the tertiary phosphine compound, and the keratin-containing substance ( b) Adding an inorganic salt or an aqueous solution of an inorganic salt in an amount corresponding to 0.9 M or more and less than a saturated concentration to the aqueous solution containing the reduced keratin obtained in the reduction treatment step to salt out the keratin component in the aqueous solution. (C) A step of forming reduced salting-out keratin in a fibrous form and discharging it into the air or immersing it in an acidic coagulating liquid adjusted to a predetermined concentration
請求項２に記載された発明は、請求項１に記載された発明において、前記還元処理時に使用するタンパク質変性剤、界面活性剤、第三級ホスフィン化合物が、それぞれ、尿素またはチオ尿素、ドデシル硫酸ナトリウム、トリアルキルホスフィンであるとともに、前記塩析時に用いる無機塩が、硫酸アンモニウムあるいは硫酸ナトリウムであることを特徴とするものである。 The invention described in claim 2 is the invention described in claim 1, wherein the protein denaturant, surfactant, and tertiary phosphine compound used in the reduction treatment are urea, thiourea, dodecyl sulfate, respectively. In addition to sodium and trialkylphosphine, the inorganic salt used for the salting out is ammonium sulfate or sodium sulfate.
請求項３に記載された発明は、請求項１、または請求項２に記載された発明において、（ｄ）繊維状に形成された還元塩析ケラチンにアルデヒド類を接触させて還元塩析ケラチンを架橋する工程を備えたことを特徴とするものである。 The invention described in claim 3 is the invention described in claim 1 or 2, wherein (d) reduced salting-out keratin is obtained by bringing reduced salting-out keratin formed into a fibrous form into contact with aldehydes. It is characterized by comprising a cross-linking step.
請求項１に記載の還元塩析ケラチン繊維の製造方法によれば、ケラチン抽出時の界面活性剤の量、塩析時の無機塩の濃度を特定の範囲に調整することで、還元塩析ケラチンに適度な流動性および粘性を付与し、曳糸性を良好なものとすることによって、還元塩析工程で悪臭やガスの発生等の不具合を生じさせることなく、還元塩析ケラチン繊維を、安定して安価かつ容易に製造することができる。また、界面活性剤にてミセル化されているもののチオール基（ＳＨ基）の反応活性を維持した状態にある還元塩析ケラチンを気中に吐出して乾燥・脱水することによって、ケラチン分子鎖に配向性を付与しチオール基がジスルフィド結合に再架橋する。さらに、酸性凝固液を接触させることによって、還元塩析ケラチンをミセル化していたＳＤＳが凝固液中に溶出し、同時に還元塩析ケラチンが酸変性・固化して繊維状に形成される。このことにより、実用に耐え得る強度を有する還元塩析ケラチン繊維を、安定して安価かつ容易に製造することができる。 According to the method for producing reduced salting-out keratin fibers according to claim 1, the amount of surfactant during keratin extraction and the concentration of inorganic salt during salting-out are adjusted to a specific range, thereby reducing reduced salting-out keratin. By imparting moderate fluidity and viscosity to the fiber and improving the spinnability, the reduced salting-out keratin fibers can be stabilized without causing problems such as malodor and gas generation in the reducing salting-out process. Thus, it can be manufactured inexpensively and easily. In addition, the reduced salting-out keratin, which has been micellized with a surfactant but maintains the reaction activity of the thiol group (SH group), is discharged into the air and dried and dehydrated to form a keratin molecular chain. Alignment is imparted and the thiol group is re-crosslinked to a disulfide bond. Furthermore, by bringing the acidic coagulation liquid into contact, SDS in which the reduced salting-out keratin is micellized is eluted into the coagulating liquid, and at the same time, the reduced salting-out keratin is acid-denatured and solidified to form a fiber. By this, the reduced salting out keratin fiber which has the intensity | strength which can be practically used can be manufactured stably cheaply and cheaply.
請求項２に記載の還元塩析ケラチン繊維の製造方法によれば、還元時に用いるタンパク質変性剤、界面活性剤、第三級ホスフィン化合物として、それぞれ、尿素またはチオ尿素、ドデシル硫酸ナトリウム、トリアルキルホスフィンを用い、塩析時に用いる無機塩として、硫酸アンモニウムあるいは硫酸ナトリウムを用いることによって、還元塩析ケラチン繊維を、より効率的に製造することができる。 According to the method for producing reduced salting-out keratin fibers according to claim 2, urea or thiourea, sodium dodecyl sulfate, trialkylphosphine as the protein denaturant, surfactant and tertiary phosphine compound used at the time of reduction, respectively. By using ammonium sulfate or sodium sulfate as the inorganic salt used during salting out, reduced salting out keratin fibers can be more efficiently produced.
請求項３に記載の還元塩析ケラチン繊維の製造方法によれば、繊維状に形成された還元塩析ケラチンにアルデヒド類を接触させることにより、還元塩析ケラチン繊維の強度をより高いものとすることができる。 According to the method for producing reduced salting-out keratin fibers according to claim 3, the strength of the reduced salting-out keratin fibers is made higher by bringing aldehydes into contact with the reduced salting-out keratin formed in a fibrous form. be able to.
本発明におけるケラチンとは、所謂、硬質ケラチンのことであり、人の毛髪、羊毛、鳥類の羽、動物の爪等の主要なタンパク質成分のことである。また、本発明におけるケラチン含有物質としては、羊毛、人の毛髪、馬毛などの哺乳動物の体毛、動物の爪、角、ひずめ、鳥類の羽、魚類の鱗等を用いることができる。その中でも、羊毛および毛髪を用いると好ましい。なお、それらのケラチン含有物質中において、ケラチンは総重量の３０〜９０％を占め、羊毛や人の毛髪の場合には、約６０〜８５％を占める。したがって、本発明において「ケラチン含有物質の質量に対して６０質量％以上１００質量％以下」とは、ケラチン含有物質が羊毛や人の毛髪である場合には、「ケラチンの純分の質量に対して７１質量％以上１６７質量％以下」であることを意味する。 The keratin in the present invention is so-called hard keratin, and is a major protein component such as human hair, wool, bird feathers, animal nails and the like. In addition, as the keratin-containing substance in the present invention, it is possible to use mammalian hair such as wool, human hair, horse hair, animal nails, horns, hooves, bird feathers, fish scales, and the like. Among these, it is preferable to use wool and hair. In these keratin-containing substances, keratin accounts for 30 to 90% of the total weight, and in the case of wool or human hair, it accounts for about 60 to 85%. Therefore, in the present invention, “60% by mass or more and 100% by mass or less with respect to the mass of the keratin-containing substance” means “when the keratin-containing substance is wool or human hair” 71 mass% or more and 167 mass% or less ”.
また、ケラチン含有物質を還元処理する際に使用するタンパク質変性剤としては、尿素またはチオ尿素を用いることができる。その中でも尿素を用いると、還元処理の効率が上昇するので好ましい。 Moreover, urea or thiourea can be used as a protein denaturant used when reducing a keratin containing substance. Among these, use of urea is preferable because the efficiency of the reduction treatment is increased.
さらに、ケラチン含有物質を還元処理する際に使用する界面活性剤としては、各種の陰イオン界面活性剤、陽イオン界面活性剤、非イオン界面活性剤を用いることができる。その中でも、陰イオン界面活性剤のドデシル硫酸ナトリウム（ＳＤＳ，ＣＡＳ登録番号１５１−２１−３）を用いると、還元処理の効率が上昇するので好ましい。 Furthermore, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used as the surfactant used when reducing the keratin-containing substance. Among these, it is preferable to use an anionic surfactant sodium dodecyl sulfate (SDS, CAS registration number 151-21-3) because the efficiency of the reduction treatment is increased.
また、界面活性剤の量は、ケラチン含有物質の質量に対して６０質量％以上１００質量％以下に調整する必要があり、６０質量％以上９０質量％以下に調整すると還元処理の効率が上昇するので好ましく、７０質量％以上８０質量％以下に調整するとより好ましい。すなわち、ケラチン含有物質として羊毛や人の毛髪を用いる場合には、界面活性剤の量は、ケラチンの純分の質量に対して７１質量％以上１６７質量％以下に調整する必要があり、７１質量％以上１０６質量％以下に調整すると還元処理の効率が上昇するので好ましく、８２質量％以上９４質量％以下に調整するとより好ましい。 Further, the amount of the surfactant needs to be adjusted to 60% by mass or more and 100% by mass or less with respect to the mass of the keratin-containing substance, and when adjusted to 60% by mass or more and 90% by mass or less, the efficiency of the reduction treatment increases. Therefore, it is preferable to adjust to 70% by mass or more and 80% by mass or less. That is, when wool or human hair is used as the keratin-containing substance, the amount of the surfactant must be adjusted to 71% by mass or more and 167% by mass or less with respect to the mass of pure keratin, and 71% by mass. It is preferable to adjust the content to be not less than 106% by mass and not more than 106% by mass because the efficiency of the reduction treatment is increased.
一方、ケラチン含有物質を還元処理する際に使用する第三級ホスフィン化合物としては、下記の一般式（Ｉ）で示すヒドロキシアルキルホスフィン、ヒドロキシアルキル塩化ホスホニウムなどを用いることができる。その中でも、トリス−３−ヒドロキシプロピルホスフィン（ＴＨＰＰ，ＣＡＳ登録番号４７０６−１７−６）を用いると、還元処理の効率が上昇するので好ましい。 On the other hand, as the tertiary phosphine compound used for reducing the keratin-containing substance, hydroxyalkylphosphine, hydroxyalkylphosphonium chloride represented by the following general formula (I) and the like can be used. Among these, it is preferable to use tris-3-hydroxypropylphosphine (THPP, CAS registration number 4706-17-6) because the efficiency of the reduction treatment is increased.
上記一般式（Ｉ）中、Ｒ１，Ｒ２およびＲ３は、炭素数１〜１０のアルキレン基を表す。なお、Ｒ１，Ｒ２およびＲ３が、炭素数１〜６のアルキレン基であると、還元処理の効率が上昇するので好ましい。そのような化合物としては、具体的には、ジメチルヒドロキシメチルホスフィン、ジメチルヒドロキシエチルホスフィン、エチルビス（ヒドロキシエチル）ホスフィン、エチルビス（ヒドロキシプロピル）ホスフィン、トリス（ヒドロキシメチル）ホスフィン、トリス（ヒドロキシエチル）ホスフィン、トリス（ヒドロキシプロピル）ホスフィン、トリス（ヒドロキシオクチル）ホスフィン、トリス（ヒドロキシクロヘキシル）ホスフィン、トリス（ヒドロキシブチル）ホスフィン等を挙げることができる。 In the general formula (I), R 1, R 2 and R 3 represents an alkylene group having 1 to 10 carbon atoms. Note that it is preferable that R 1 , R 2, and R 3 are alkylene groups having 1 to 6 carbon atoms because the efficiency of the reduction treatment is increased. Specific examples of such a compound include dimethylhydroxymethylphosphine, dimethylhydroxyethylphosphine, ethylbis (hydroxyethyl) phosphine, ethylbis (hydroxypropyl) phosphine, tris (hydroxymethyl) phosphine, tris (hydroxyethyl) phosphine, Tris (hydroxypropyl) phosphine, tris (hydroxyoctyl) phosphine, tris (hydroxycyclohexyl) phosphine, tris (hydroxybutyl) phosphine and the like can be mentioned.
一方、還元ケラチンを塩析させる際に添加する無機塩としては、硫酸ナトリウム，硫酸アンモニウム，塩化ナトリウムなどの無機塩を用いることができる。その中でも、硫酸ナトリウムを用いると、塩析処理の効率が上昇するので好ましい。また、無機塩の添加量は、０．９Ｍ以上飽和濃度未満に相当する量の無機塩あるいは無機塩の水溶液とする必要があり、０．９２Ｍ以上１．４Ｍ未満に調整すると、塩析処理の効率が上昇するので好ましく、０．９３Ｍ以上１．１３Ｍ以下に調整するとより好ましい。 On the other hand, inorganic salts such as sodium sulfate, ammonium sulfate, and sodium chloride can be used as the inorganic salt added when salting out reduced keratin. Among these, use of sodium sulfate is preferable because the efficiency of the salting-out treatment is increased. Also, the amount of inorganic salt added must be 0.9M or more and less than the saturation concentration of inorganic salt or an aqueous solution of inorganic salt. Since efficiency increases, it is preferable, and it is more preferable to adjust to 0.93M or more and 1.13M or less.
また、得られた還元塩析ケラチンを、湿式紡糸する際に使用する酸性凝固液としては、トリクロロ酢酸（ＴＣＡ）溶液、グアニジン塩酸溶液、過塩素酸溶液等のタンパク質変性剤の水溶液の他に、塩酸、硫酸、酢酸、リン酸等の酸性物質から選ばれる１種以上からの水溶液を用いることができる。その中でも、ＴＣＡ、硫酸の水溶液を用いると還元塩析ケラチンの凝固効率が上昇して還元塩析ケラチン繊維の強度が高くなるので好ましい。そのように、酸性凝固液として、ＴＣＡの水溶液を用いる場合には、ＴＣＡの濃度を３％以上５０％以下に調整すると、変性・固化効率が良好なものとなるので好ましく、５％以上４０％以下に調整すると特に好ましい。また、酸性凝固液として、硫酸の水溶液を用いる場合には、ＴＣＡの濃度を０．３％以上４０％以下に調整すると、変性・固化効率が良好なものとなるので好ましく、０．５％以上３０％以下に調整すると特に好ましい。 Moreover, as an acidic coagulation liquid used when the obtained reduced salting-out keratin is wet-spun, in addition to an aqueous solution of a protein denaturant such as a trichloroacetic acid (TCA) solution, a guanidine hydrochloric acid solution, or a perchloric acid solution, An aqueous solution of at least one selected from acidic substances such as hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid can be used. Among them, it is preferable to use an aqueous solution of TCA and sulfuric acid because the coagulation efficiency of the reduced salting out keratin is increased and the strength of the reduced salting out keratin fiber is increased. As such, when an aqueous TCA solution is used as the acidic coagulation liquid, it is preferable to adjust the concentration of TCA to 3% or more and 50% or less because the modification / solidification efficiency is improved. Adjustment to the following is particularly preferable. Further, when an aqueous solution of sulfuric acid is used as the acidic coagulating liquid, it is preferable to adjust the TCA concentration to 0.3% or more and 40% or less because the modification / solidification efficiency is improved, and preferably 0.5% or more. It is particularly preferable to adjust it to 30% or less.
さらに、ＴＣＡ、硫酸の水溶液を用いて還元塩析ケラチンを変性・固化させる場合には、ＴＣＡ、硫酸の水溶液からなる凝固液を満たした凝固槽の温度を１０℃以上７０℃以下に調整すると、変性・固化効率が良好なものとなるので好ましく、１７℃以上６０℃以下に調整すると特に好ましい。また、ＴＣＡ、硫酸の水溶液を用いて還元塩析ケラチンを変性・固化させる場合には、変性・固化させる時間（たとえば、ＴＣＡ、硫酸の水溶液からなる凝固液を満たした凝固槽内に浸漬させる時間）を３０秒以上７０分以下に調整すると、変性・固化効率が良好なものとなるので好ましく、１分以上６０分以下に調整すると特に好ましい。 Furthermore, when denaturing and solidifying reduced salting out keratin using an aqueous solution of TCA and sulfuric acid, adjusting the temperature of the coagulation tank filled with the coagulating liquid consisting of an aqueous solution of TCA and sulfuric acid to 10 ° C. or higher and 70 ° C. or lower, This is preferable because the modification / solidification efficiency is good, and it is particularly preferable to adjust to 17 ° C. or more and 60 ° C. or less. In addition, when reducing salting out keratin using TCA and sulfuric acid aqueous solution, the time for denaturation and solidification (for example, the time for immersion in a coagulation tank filled with a coagulating liquid consisting of TCA and sulfuric acid aqueous solution) ) Is adjusted to 30 seconds or more and 70 minutes or less because the modification / solidification efficiency is improved, and is preferably adjusted to 1 minute or more and 60 minutes or less.
加えて、上記の如く、酸性凝固液中で凝固・変性させた還元塩析ケラチン繊維には、アルデヒド類を接触させることによって、還元塩析ケラチンを架橋するのが好ましい。そのように、還元塩析ケラチンを架橋させる際に使用するアルデヒド類としては、グルタルアルデヒド（ＧＡ）、ホルムアルデヒド、アセトアルデヒド等を挙げることができる。その中でも、ＧＡ、ホルムアルデヒドを用いると、還元塩析ケラチンの凝固効率が上昇して還元塩析ケラチン繊維の強度が高くなるので好ましい。そのように、架橋剤として、ＧＡを用いる場合には、ＧＡの水溶液の濃度を０．５％以上３％以下に調整すると、架橋効率が良好なものとなるので好ましく、１％以上２％以下であると特に好ましい。 In addition, as described above, the reduced salting out keratin is preferably cross-linked by bringing aldehydes into contact with the reduced salting out keratin fibers coagulated and modified in the acidic coagulating liquid. As such, examples of aldehydes used when crosslinking reduced salting-out keratin include glutaraldehyde (GA), formaldehyde, acetaldehyde and the like. Among these, use of GA or formaldehyde is preferable because the coagulation efficiency of the reduced salting out keratin is increased and the strength of the reduced salting out keratin fiber is increased. As such, when GA is used as the cross-linking agent, it is preferable to adjust the concentration of the GA aqueous solution to 0.5% or more and 3% or less because the cross-linking efficiency is improved, and preferably 1% or more and 2% or less. Is particularly preferred.
以下、実施例によって本発明をより詳細に説明するが、本発明は、かかる実施例の態様に何ら限定されるものではなく、本発明の趣旨を逸脱しない範囲で、適宜変更することが可能である。実施例における物性、特性の評価方法は以下の通りである。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the embodiments of the examples, and can be appropriately changed without departing from the spirit of the present invention. is there. Evaluation methods of physical properties and characteristics in the examples are as follows.
＜粘度測定＞
芝浦システム株式会社製 単一円筒型回転粘度計（ビスメトロン粘度計）を用いて、下記の条件において測定した。
試験条件：少量サンプルアダプター 使用ローター ＳＳ３
回転数：０．３ｒｐｍ、温度（以下の実施例・比較例において温度の記述がない場合）：２０℃
<Viscosity measurement>
Using a single cylindrical rotational viscometer (Bismetron viscometer) manufactured by Shibaura System Co., Ltd., measurement was performed under the following conditions.
Test conditions: Small sample adapter Rotor SS3
Rotation speed: 0.3 rpm, temperature (when no temperature is described in the following examples and comparative examples): 20 ° C
＜湿式紡糸における曳糸性＞
液中に直径約３ｍｍのガラス棒先端部を試験液に挿入した後、毎秒約１０ｃｍの速度で上方に引き上げた。そして、その際に形成された液状糸が破断したときの試験液面からガラス棒先端までの距離（以下、破断長さという）を測定した。そして、その破断長さによって、曳糸性を以下の３段階で評価した。
○：破断長さが５０ｃｍ以上
△：破断長さが５ｃｍ以上５０ｃｍ未満
×：破断長さが５未満
<Spinnability in wet spinning>
A glass rod tip having a diameter of about 3 mm was inserted into the test solution and then pulled upward at a speed of about 10 cm per second. And the distance (henceforth a fracture | rupture length) from the test liquid surface when the liquid thread | yarn formed in that case fracture | ruptured to the front-end | tip of a glass rod was measured. And the spinnability was evaluated in the following three stages according to the break length.
○: Breaking length is 50 cm or more Δ: Breaking length is 5 cm or more and less than 50 cm x: Breaking length is less than 5
＜乾式紡糸・湿乾式紡糸における製糸性＞
還元塩析ケラチンを充填したシリンジに圧力を加えて、シリンジの先端の紡糸ノズル（孔径＝０．４ｍｍあるいは０．１ｍｍ）から吐出させた際に、還元塩析ケラチンの連なり度合いによって、以下の２段階で官能評価した。
○：還元塩析ケラチンが連なって繊維状になる
×：還元塩析ケラチンが分断されて繊維状にならない
<Fabricity in dry spinning and wet drying spinning>
When pressure is applied to a syringe filled with reduced salting-out keratin and discharged from the spinning nozzle (hole diameter = 0.4 mm or 0.1 mm) at the tip of the syringe, depending on the degree of chaining of reduced salting-out keratin, the following 2 Sensory evaluation was performed at each stage.
○: Reduced salting-out keratin is continuous and becomes fibrous ×: Reduced salting-out keratin is divided and does not become fibrous
＜繊維の強度＞
株式会社島津製作所製の定速伸長形の引張り試験機（オートグラフ）を用い、日本工業規格ＪＩＳ Ｌ １０１３−１９９９（化学繊維フィラメント糸試験法）の引張強さおよび伸び率の試験方法に準じて、以下の条件下で測定した。なお、単位繊度当たりの破断時の引張強さを強度として求めた。
温度２０℃ 相対湿度６５％
試料のつかみ間隔１０ｍｍ 引張速度：１０ｍｍ／ｍｉｎ
<Fiber strength>
Using a constant speed extension type tensile tester (Autograph) manufactured by Shimadzu Corporation, according to the test method of tensile strength and elongation of Japanese Industrial Standard JIS L 1013-1999 (chemical fiber filament yarn test method) The measurement was performed under the following conditions. The tensile strength at break per unit fineness was determined as the strength.
Sample holding interval 10 mm Tensile speed: 10 mm / min
［実施例１］
尿素２７０ｇ（３Ｍ）（愛知県農業協同組合連合会製「４６．０尿素」）、トリス−３−ヒドロキシプロピルホスフィン（ＴＨＰＰ）４０％水溶液（日本化学工業（株）製「ヒシコーリン（Ｐ−５４０））８５ｇ（純分３４ｇ）（０．１Ｍ）、ドデシル硫酸ナトリウム（ＳＤＳ）３１％水溶液（日華化学（株）製「サンレックスＬ−３０Ｓ）３００ｇ（純分９３ｇ）（羊毛量に対するＳＤＳ純分の質量割合約７５％（Ｗ／Ｗ））に水を添加して、全量を１５００ｍｌに調整することによって抽出溶液を得た。しかる後、その抽出溶液と、羊毛トップ１２５gとを密栓できる回転ポット入れ、１００℃で３０分間回転しながらケラチンの還元抽出処理を行った。そして、抽出処理後に回転ポットごと冷却して、抽出物全容から濾過布にて残渣を圧搾除去することによって、約１０００ｍｌ（約１．１ｋｇ）の還元ケラチン抽出液を回収した。
[Example 1]
270 g of urea (3M) (“46.0 urea” manufactured by Aichi Agricultural Cooperative Federation), 40% aqueous solution of tris-3-hydroxypropylphosphine (THPP) (“Hishicolin (P-540) manufactured by Nippon Chemical Industry Co., Ltd.) ) 85 g (pure content 34 g) (0.1 M), sodium dodecyl sulfate (SDS) 31% aqueous solution (“Sunrex L-30S” manufactured by Nikka Chemical Co., Ltd.) 300 g (pure content 93 g) (SDS pure content relative to the amount of wool The extraction solution was obtained by adjusting the total amount to 1500 ml by adding water to a mass ratio of about 75% (W / W)), and then a rotating pot capable of sealing the extraction solution and 125 g of wool top Then, the keratin was reduced and extracted while rotating at 100 ° C. for 30 minutes, and after the extraction process, the whole rotary pot was cooled, and the residue was pressed from the entire volume of the extract with a filter cloth. By squeezing and removing, about 1000 ml (about 1.1 kg) of reduced keratin extract was recovered.
しかる後、回収した還元ケラチン抽出液約５５ｍｌ（約６０ｇ）をスターラーで攪拌しながら２０％（Ｗ／Ｖ）硫酸ナトリウム溶液を還元ケラチン抽出液に対して２倍量添加して、還元塩析ケラチンを析出させた。この還元塩析ケラチンを６０℃で１０分間保温後、反応液とともに回転数３５００ｒｐｍで１０分間遠心分離し、反応液中から還元塩析ケラチン約１０ｍｌを回収した。そして、２０℃の条件下で塩析させた後、粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元ケラチン抽出液に対する２０％（Ｗ／Ｖ）硫酸ナトリウム溶液の２倍量の添加は、硫酸ナトリウム濃度を０．９４Ｍとしたことに相当するものであった。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例１の方法で製糸した場合の曳糸性が良好であることが分かる。また、２０℃の条件下で塩析後の経過時間による粘度の変化と曳糸性との関係を図１に示す。当該図１から、２０℃の条件では、紡糸および成形加工等に還元塩析ケラチンを使用するには、塩析から１５０分以内の還元塩析ケラチンを用いることが好ましいことが分かる。 Thereafter, about 55 ml (about 60 g) of the recovered reduced keratin extract was stirred with a stirrer, and a 20% (W / V) sodium sulfate solution was added in an amount twice that of the reduced keratin extract to reduce the reduced salting out keratin. Was precipitated. The reduced salting out keratin was kept at 60 ° C. for 10 minutes, and then centrifuged with the reaction solution at 3500 rpm for 10 minutes to recover about 10 ml of reduced salting out keratin from the reaction solution. And after salting out on 20 degreeC conditions, the viscosity and spinnability of the reduced salting-out keratin 30 minutes after the viscosity measurement start were investigated. The addition of twice the 20% (W / V) sodium sulfate solution to the reduced keratin extract was equivalent to a sodium sulfate concentration of 0.94M. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Example 1 is good. Moreover, the relationship between the change of the viscosity by the elapsed time after salting out at 20 degreeC conditions and a spinnability is shown in FIG. From FIG. 1, it can be seen that, under the condition of 20 ° C., it is preferable to use reduced salting-out keratin within 150 minutes from salting out in order to use reduced salting-out keratin for spinning and molding.
［実施例２］
還元ケラチン抽出液を得る際に用いるタンパク質変成剤をチオ尿素に変更した以外は、実施例１と同様にして還元塩析ケラチンを得た。そして、実施例１と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例２の方法で製糸した場合の曳糸性が良好であることが分かる。
[Example 2]
Reduced salting-out keratin was obtained in the same manner as in Example 1 except that the protein denaturant used for obtaining the reduced keratin extract was changed to thiourea. In the same manner as in Example 1, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Example 2 is good.
［実施例３］
還元ケラチン抽出液を用いて還元塩析ケラチンを析出させる際に還元ケラチン抽出液に加える無機塩溶液を２０％（Ｗ／Ｖ）硫酸アンモニウム（（ＮＨ４）２ＳＯ４）溶液に変更した以外は、実施例１と同様にして還元塩析ケラチンを得た。そして、実施例１と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例３の方法で製糸した場合の曳糸性が良好であることが分かる。
[Example 3]
Except for changing the inorganic salt solution added to the reduced keratin extract to 20% (W / V) ammonium sulfate ((NH 4 ) 2 SO 4 ) solution when the reduced salting out keratin is precipitated using the reduced keratin extract, Reduced salting out keratin was obtained in the same manner as in Example 1. In the same manner as in Example 1, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Example 3 is good.
［実施例４］
実施例１と同様な方法で得た還元ケラチン抽出液約１００ｍｌ（約１１０ｇ）を、スターラーで攪拌しながら、２０％硫酸ナトリウム溶液を還元ケラチン抽出液に対して容量比で２倍の比率で添加して還元塩析ケラチンを析出させた。この還元塩析ケチンを反応液とともに回転数３５００ｒｐｍで１０分間遠心分離し、反応液中から還元塩析ラチン約１５ｍｌを回収した。２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例４の方法で製糸した場合の曳糸性が良好であることが分かる。
[Example 4]
About 100 ml (about 110 g) of the reduced keratin extract obtained by the same method as in Example 1 was added with a 20% sodium sulfate solution at a volume ratio of 2 times that of the reduced keratin extract while stirring with a stirrer. Thus, reduced salting out keratin was precipitated. The reduced salting out ketin was centrifuged together with the reaction solution at a rotational speed of 3500 rpm for 10 minutes, and about 15 ml of reduced salting out latin was recovered from the reaction solution. The viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Example 4 is good.
［実施例５］
還元ケラチン抽出液を用いて還元塩析ケラチンを析出させる際に添加する２０％硫酸ナトリウム溶液の量を、還元ケラチン抽出液に対する容量比で３倍に変更した以外は、実施例２と同様にして還元塩析ケラチンを得た。そして、実施例２と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例５の方法で製糸した場合の曳糸性が良好であることが分かる。
[Example 5]
Except that the amount of 20% sodium sulfate solution added when the reduced salting out keratin was precipitated using the reduced keratin extract was changed to 3 times the volume ratio to the reduced keratin extract, the same as in Example 2. Reduced salting out keratin was obtained. Then, in the same manner as in Example 2, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Example 5 is good.
［実施例６］
還元ケラチン抽出液を用いて還元塩析ケラチンを析出させる際に添加する２０％硫酸ナトリウム溶液の量を、還元ケラチン抽出液に対する容量比で４倍に変更した以外は、実施例２と同様にして還元塩析ケラチンを得た。そして、実施例２と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例６の方法で製糸した場合の曳糸性が良好であることが分かる。
[Example 6]
Except that the amount of 20% sodium sulfate solution added when the reduced salting out keratin was precipitated using the reduced keratin extract was changed to 4 times the volume ratio with respect to the reduced keratin extract, the same as in Example 2. Reduced salting out keratin was obtained. Then, in the same manner as in Example 2, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Example 6 is good.
［実施例７］
尿素５４ｇ（３Ｍ）、ＴＨＰＰ１７ｇ（純分６．８ｇ）、羊毛量に対してＳＤＳ６０％（Ｗ／Ｗ）（羊毛２５ｇとしてＳＤＳ３１％水溶液４８．４ｇ）（ＳＤＳ純分１５．０ｇ）を入れ、最後に水を添加し全量を３００ｍｌとした溶液と羊毛トップ２５ｇとを密栓できる回転ポット入れて、１００℃で３０分間回転しながらケラチンの還元抽出処理を行った。抽出処理後に回転ポットごと冷却して、抽出物全容から濾過布にて残渣を圧搾除去して、還元ケラチン抽出液を回収した。そして、得られた還元ケラチン抽出液約５５ｍｌ（約６０ｇ）をスターラーで攪拌しながら２０％硫酸ナトリウム溶液を還元ケラチン抽出液に対して２倍量添加して、還元塩析ケラチンを析出させた。この還元塩析ケラチンを６０℃で１０分間保温後、反応液とともに回転数３５００ｒｐｍで１０分間遠心分離し、反応液中から還元塩析ケラチン約１０ｍｌを回収した。粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例７の方法で製糸した場合の曳糸性が良好であることが分かる。
[Example 7]
Urea 54g (3M), THPP 17g (pure content 6.8g),
［実施例８］
還元ケラチン抽出液を用いて還元塩析ケラチンを析出させる際に還元ケラチン抽出液に加える界面活性剤（ＳＤＳ）の量を７５％に変更した以外は、実施例７と同様にして還元塩析ケラチンを得た。そして、実施例７と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例８の方法で製糸した場合の曳糸性が良好であることが分かる。
[Example 8]
Reduced salting out keratin in the same manner as in Example 7 except that the amount of surfactant (SDS) added to the reduced keratin extract was changed to 75% when the reduced salting out keratin was precipitated using the reduced keratin extract. Got. In the same manner as in Example 7, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Example 8 is good.
［実施例９］
還元ケラチン抽出液を用いて還元塩析ケラチンを析出させる際に還元ケラチン抽出液に加える界面活性剤（ＳＤＳ）の量を１００％に変更した以外は、実施例７と同様にして還元塩析ケラチンを得た。そして、実施例７と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から実施例８の方法で製糸した場合の曳糸性が良好であることが分かる。
[Example 9]
Reduced salting out keratin in the same manner as in Example 7 except that the amount of surfactant (SDS) added to the reduced keratin extract was changed to 100% when reducing salted out keratin was precipitated using the reduced keratin extract. Got. In the same manner as in Example 7, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Example 8 is good.
［実施例１０］
実施例１と同様な方法で得られた還元塩析ケラチンを、加圧可能なステンレス容器に入れて、０．１ＭＰａの圧縮空気圧力を加えながら孔径０．４ｍｍの紡糸ノズル（６孔）から、下方大気中に吐出させた（乾式紡糸）。なお、かかる乾式紡糸の際には、事前に液の吐出状態を確認した上で加温または冷却することによって還元塩析ケラチン紡糸液の粘度を調整した。そして、吐出された繊維状の還元塩析ケラチンを、室温約１５℃の大気中で固化させながら、ノズル下方約３ｍのテフロン（登録商標）シート上に回収することによって還元塩析ケラチン繊維を得た。なお、製糸性は良好であり、強度試験を実施し得る還元塩析ケラチン繊維が得られた。そして、上記した方法によって、得られた還元塩析ケラチン繊維の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表１に示す。
[Example 10]
Reduced salting-out keratin obtained by the same method as in Example 1 is put into a pressurizable stainless steel container, and while applying a compressed air pressure of 0.1 MPa, from a spinning nozzle having a hole diameter of 0.4 mm (6 holes), It was discharged into the lower atmosphere (dry spinning). In the case of such dry spinning, the viscosity of the reduced salting-out keratin spinning solution was adjusted by heating or cooling after confirming the discharge state of the solution in advance. The discharged fibrous salted-out salted keratin is collected on a Teflon (registered trademark) sheet about 3 m below the nozzle while solidifying in an atmosphere at room temperature of about 15 ° C. to obtain a reduced salted-out keratin fiber. It was. In addition, the spinnability was good, and reduced salting out keratin fibers capable of performing a strength test were obtained. And the intensity | strength of the reduced salting-out keratin fiber obtained by the above-mentioned method was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 1 together with the spinning conditions.
［実施例１１］
実施例１０と同様な方法で得られた還元塩析ケラチン繊維を、１０分間５％（Ｗ／Ｖ）トリクロロ酢酸（ＴＣＡ）溶液に浸漬し不溶化させ、しかる後に、１％グルタルアルデヒド（ＧＡ）水溶液に１分浸漬し架橋させた後に、室温中で十分に乾燥させた。そして、還元塩析ケラチン繊維（不溶化および架橋したもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表１に示す。表１から不溶化および架橋した還元塩析ケラチン繊維は、そのような処理を施さなかった還元塩析ケラチン繊維に比べて高い強度を有していることが分かる。
[Example 11]
The reduced salted-out keratin fibers obtained by the same method as in Example 10 were soaked in a 5% (W / V) trichloroacetic acid (TCA) solution for 10 minutes to be insolubilized, and then 1% glutaraldehyde (GA) aqueous solution. After being immersed in 1 minute for crosslinking, it was sufficiently dried at room temperature. Then, the strength of the reduced salting out keratin fibers (insolubilized and crosslinked) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 1 together with the spinning conditions. It can be seen from Table 1 that the reduced salted-out keratin fibers that have been insolubilized and crosslinked have higher strength than the reduced salted-out keratin fibers that have not been subjected to such treatment.
［実施例１２］
実施例１１と同様な方法で得られた還元塩析ケラチン繊維（不溶化・架橋したもの）を、室温中で手によって約３．２倍延伸した。そして、還元塩析ケラチン繊維（不溶化、架橋および延伸したもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表１に示す。表１から延伸した還元塩析ケラチン繊維は、延伸しなかった還元塩析ケラチン繊維（不溶化・架橋しなかったもの、および、不溶化・架橋したもの）に比べて高い強度を有していることが分かる。
[Example 12]
Reduced salted-out keratin fibers (insolubilized and cross-linked) obtained by the same method as in Example 11 were stretched about 3.2 times by hand at room temperature. Then, the strength of the reduced salting out keratin fibers (insolubilized, crosslinked and stretched) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 1 together with the spinning conditions. The reduced salted-out keratin fibers stretched from Table 1 have higher strength than reduced salted-out keratin fibers that were not stretched (those that were not insolubilized / crosslinked and those that were insolubilized / crosslinked). I understand.
［実施例１３］
実施例１と同様な方法で得られた還元塩析ケラチンをシリンジに入れ、そのシリンジを約０．１ＭＰａに加圧しながら、先端の孔径０．４ｍｍの紡糸ノズル（１孔）を、凝固槽内に満たした約１７℃の液温で５％のＴＣＡ溶液からなる第一凝固液中に挿入した状態で、シリンジ内の還元塩析ケラチンを吐出させた。凝固液中で吐出した還元塩析ケラチンは直ちに酸変性・固化し、ケラチン繊維が得られた。その後、糸速度約１．４ｍ／分で吐出させながら凝固液中で約８０ｃｍの長さに亘って酸変性させつつ延伸した後、凝固槽の外からガイドを経由して気中に引き出して、ケラチン繊維を回転ローラーに巻き取った。このケラチン繊維をさらに第二凝固液として５％のＴＣＡ溶液へ１０分間浸漬し、その後１％ＧＡ溶液中に1分間浸漬し水洗いして乾燥させた。そして、得られた還元塩析ケラチン繊維（酸変性・延伸したもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表１に示す。
[Example 13]
The reduced salting-out keratin obtained by the same method as in Example 1 was put in a syringe, and while the syringe was pressurized to about 0.1 MPa, a spinning nozzle (one hole) having a tip diameter of 0.4 mm was placed in the coagulation tank. The reduced salting-out keratin in the syringe was discharged in a state of being inserted into a first coagulation liquid consisting of a 5% TCA solution at a liquid temperature of about 17 ° C. filled with 1. The reduced salting-out keratin discharged in the coagulation liquid was immediately acid-denatured and solidified to obtain keratin fibers. Then, after being stretched while being acid-modified over a length of about 80 cm in the coagulation liquid while discharging at a yarn speed of about 1.4 m / min, it is drawn out from the outside of the coagulation tank into the air via a guide, Keratin fibers were wound on a rotating roller. This keratin fiber was further immersed in a 5% TCA solution as a second coagulation solution for 10 minutes, then immersed in a 1% GA solution for 1 minute, washed with water and dried. And the intensity | strength of the obtained reduced salting-out keratin fiber (what was acid-modified and extended | stretched) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 1 together with the spinning conditions.
［実施例１４］
第一凝固液、第二凝固液として用いるＴＣＡ溶液の濃度を１０％に変更した以外は、実施例１３と同様にして還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（酸変性・延伸したもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表１に示す。表１から１０％のＴＣＡ溶液の凝固液を用いて凝固させた場合の還元塩析ケラチン繊維は、５％のＴＣＡ溶液の凝固液を用いて凝固させた場合の還元塩析ケラチン繊維に比べて高い強度を有していることが分かる。
[Example 14]
Reduced salting-out keratin fibers were obtained in the same manner as in Example 13 except that the concentration of the TCA solution used as the first coagulation liquid and the second coagulation liquid was changed to 10%. Then, the strength of the reduced salting out keratin fibers (acid-modified and stretched) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 1 together with the spinning conditions. From Table 1, the reduced salting out keratin fibers when coagulated using a coagulating solution of 10% TCA solution are compared to the reducing salting out keratin fibers coagulated using a coagulating solution of 5% TCA solution. It turns out that it has high intensity | strength.
［実施例１５］
ケラチン含有物質を羊毛トップから廃棄人毛に変更し、実施例１の方法と同様な方法で還元ケラチン抽出液約１５００ｍｌ（約１５８０ｇ）を得た。還元ケラチン抽出液約１００ｍｌ（約１０５ｇ）をスターラーで攪拌しながら、２０％硫酸ナトリウム溶液を還元ケラチン抽出液に対して容量比で３倍量を添加して還元塩析ケラチンを析出させた。この還元塩析ケラチンを反応液とともに回転数３５００ｒｐｍで１０分間心分離し、反応液中から還元塩析ケラチン約１０ｍｌを回収した。しかる後、その還元塩析ケラチン液を、加圧できるシリンジに入れて、０．３ＭＰａに加圧しながら孔径約１．０ｍｍの紡糸ノズル（１孔）から、約１７℃に調節された３０％硫酸溶液からなる凝固液を満たしたシャーレ内に吐出し、当該シャーレ内で約１分間に亘って変性・固化させた。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表１に示す。
[Example 15]
The keratin-containing substance was changed from wool top to waste human hair, and about 1500 ml (about 1580 g) of reduced keratin extract was obtained by the same method as in Example 1. While stirring about 100 ml (about 105 g) of the reduced keratin extract with a stirrer, a 20% sodium sulfate solution was added in a volume ratio of 3 times the reduced keratin extract to precipitate reduced salting out keratin. The reduced salting out keratin was separated from the reaction solution with the reaction solution at a rotational speed of 3500 rpm for 10 minutes, and about 10 ml of reduced salting out keratin was recovered from the reaction solution. Thereafter, the reduced salting out keratin solution is put into a syringe that can be pressurized, and 30% sulfuric acid adjusted to about 17 ° C. from a spinning nozzle (one hole) having a pore diameter of about 1.0 mm while being pressurized to 0.3 MPa. It was discharged into a petri dish filled with a coagulating liquid consisting of a solution, and denatured and solidified in the petri dish for about 1 minute. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 1 together with the spinning conditions.
［実施例１６］
還元塩析ケラチン繊維を変性させる際の凝固液を１０％のＴＣＡ溶液に変更した以外は、実施例１５と同様にして還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表１に示す。
[Example 16]
Reduced salting-out keratin fibers were obtained in the same manner as in Example 15 except that the coagulation liquid for modifying the reduced salting-out keratin fibers was changed to a 10% TCA solution. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 1 together with the spinning conditions.
［実施例１７］
実施例１５と同様な方法によって得られた還元塩析ケラチン液をシリンジに入れ、そのシリンジを約０．３ＭＰａに加圧しながら、先端の孔径約１．０ｍｍの紡糸ノズル（１孔）から、約１７℃に調節された５％のＴＣＡ溶液からなる凝固液を満たしたシャーレ内に吐出し、当該シャーレ内で約１８時間に亘って変性・固化させた。しかる後、その変性後の還元塩析ケラチン繊維をＧＡ水溶液に１分浸漬し架橋させた後に、室温中で十分に乾燥させた。そして、還元塩析ケラチン繊維（変性・架橋したもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表１に示す。表１から長時間に亘って変性させ架橋した還元塩析ケラチン繊維は、そのような処理を施さなかった還元塩析ケラチン繊維に比べて高い強度を有していることが分かる。
[Example 17]
The reduced salting-out keratin solution obtained by the same method as in Example 15 was put into a syringe, and while the syringe was pressurized to about 0.3 MPa, from a spinning nozzle (one hole) having a hole diameter of about 1.0 mm at the tip, about It was discharged into a petri dish filled with a coagulating liquid consisting of a 5% TCA solution adjusted to 17 ° C., and denatured and solidified in the petri dish for about 18 hours. Thereafter, the reduced salted-out keratin fibers after the modification were immersed in an aqueous GA solution for 1 minute to crosslink, and then sufficiently dried at room temperature. Then, the strength of the reduced salting out keratin fibers (modified and crosslinked) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 1 together with the spinning conditions. It can be seen from Table 1 that reduced salted-out keratin fibers that have been modified and crosslinked for a long time have higher strength than reduced salted-out keratin fibers that have not been subjected to such treatment.
［実施例１８〜２３］
実施例１と同様な方法で得られた還元塩析ケラチンをシリンジに入れ、そのシリンジを約０．３ＭＰａに加圧しながら、先端の孔径０．６ｍｍの紡糸ノズル（１孔）を、約１７℃の液温で０．５％，１％，５％，１０％，２０％，３０％の各濃度に調整した硫酸溶液からなる凝固液を満たしたシャーレ内に挿入した状態で、シリンジ内の還元塩析ケラチンを凝固液中に吐出させた。しかる後、１分間に亘って変性・固化させ、気中で約２倍に延伸した後、１％アンモニア水で中和し、風乾することによって、実施例１８〜２３の還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表２に示す。
[Examples 18 to 23]
The reduced salting-out keratin obtained by the same method as in Example 1 was put into a syringe, and while the syringe was pressurized to about 0.3 MPa, a spinning nozzle (one hole) with a hole diameter of 0.6 mm at the tip was placed at about 17 ° C. Reduction in the syringe while inserted in a petri dish filled with a coagulation liquid consisting of sulfuric acid solution adjusted to 0.5%, 1%, 5%, 10%, 20%, 30% concentration at the liquid temperature of Salting-out keratin was discharged into the coagulation liquid. Thereafter, the reduced salting-out keratin fibers of Examples 18 to 23 were denatured and solidified for 1 minute, stretched about twice in the air, neutralized with 1% aqueous ammonia, and air-dried. Obtained. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 2 together with the spinning conditions.
［実施例２４］
還元塩析ケラチン繊維を変性させる際の凝固液を１０％のＴＣＡ溶液に変更した以外は、実施例１８と同様にして還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表２に示す。
[Example 24]
Reduced salting-out keratin fibers were obtained in the same manner as in Example 18 except that the coagulating liquid for modifying the reduced salting-out keratin fibers was changed to a 10% TCA solution. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 2 together with the spinning conditions.
［実施例２５］
実施例１と同様な方法で得られた還元塩析ケラチンをシリンジに入れ、そのシリンジを約０．２ＭＰａに加圧しながら、内部の還元塩析ケラチンを先端の孔径０．６ｍｍの紡糸ノズル（１孔）から気中に吐出させた。しかる後、吐出させた還元塩析ケラチンを、約２０℃に調節した５％のＴＣＡ溶液を満たしたシャーレ中に投入した。なお、その際の紡糸ノズルの先端からのエアギップは、約１０ｍｍに調整した。しかる後、シャーレ中に投入された還元塩析ケラチンを、そのシャーレ中で1分間に亘って変性させた後、１％ＧＡ溶液に室温で１分間に亘って浸漬させて架橋させた後に、２４時間以上に亘って十分に風乾させることによって、還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表２に示す。
[Example 25]
The reduced salting-out keratin obtained by the same method as in Example 1 was put in a syringe, and while the syringe was pressurized to about 0.2 MPa, the internal reduced salting-out keratin was fed with a spinning nozzle (1 From the hole). Thereafter, the discharged reduced salting out keratin was put into a petri dish filled with 5% TCA solution adjusted to about 20 ° C. The air gap from the tip of the spinning nozzle at that time was adjusted to about 10 mm. Thereafter, the reduced salting-out keratin introduced into the petri dish was denatured in the petri dish for 1 minute, and then immersed in a 1% GA solution at room temperature for 1 minute to crosslink. Reduced salting-out keratin fibers were obtained by sufficiently air-drying over a period of time. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 2 together with the spinning conditions.
［実施例２６〜２９］
還元塩析ケラチン繊維を変性させる際のＴＣＡ溶液の濃度を、それぞれ、１０％，２０％，３０％，４０％に変更した以外は、実施例２５と同様にして、実施例２６〜２９の還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表２に示す。
[Examples 26 to 29]
Reduction of Examples 26 to 29 was carried out in the same manner as in Example 25 except that the concentration of the TCA solution when modifying the reduced salting out keratin fibers was changed to 10%, 20%, 30%, and 40%, respectively. Salted-out keratin fibers were obtained. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 2 together with the spinning conditions.
［実施例３０，３１］
吐出させた還元塩析ケラチン繊維を変性させる際のＴＣＡ溶液の温度を、それぞれ４０℃，６０℃に変更した以外は、実施例２５と同様にして、実施例３０，３１の還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表２に示す。
[Examples 30 and 31]
The reduced salting-out keratin fibers of Examples 30 and 31 were the same as Example 25 except that the temperature of the TCA solution when modifying the discharged reduced salting-out keratin fibers was changed to 40 ° C. and 60 ° C., respectively. Got. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 2 together with the spinning conditions.
［実施例３２〜３５］
吐出させた還元塩析ケラチン繊維を５％のＴＣＡ溶液内で変性・凝固させる際の変性時間を、それぞれ、２分、１０分、３０分、６０分に変更した以外は、実施例２５と同様にして、実施例３２〜３５の還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表２に示す。
[Examples 32-35]
The same as Example 25, except that the denaturation time when denaturing and coagulating the discharged salted-out keratin fibers in a 5% TCA solution was changed to 2 min, 10 min, 30 min, and 60 min, respectively. Thus, reduced salting out keratin fibers of Examples 32-35 were obtained. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 2 together with the spinning conditions.
［実施例３６〜３９］
吐出させた還元塩析ケラチン繊維を５％のＴＣＡ溶液内で変性・凝固させる際のＴＣＡ溶液の温度を４０℃に変更し、変性時間を、それぞれ、２分、１０分、３０分、６０分に変更した以外は、実施例２５と同様にして、実施例３６〜３９の還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表２に示す。
[Examples 36 to 39]
The temperature of the TCA solution when denaturing and coagulating the discharged reduced salting out keratin fibers in a 5% TCA solution was changed to 40 ° C., and the denaturation times were 2 minutes, 10 minutes, 30 minutes, and 60 minutes, respectively. Except having changed into, it carried out similarly to Example 25, and obtained the reduction salting-out keratin fiber of Examples 36-39. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 2 together with the spinning conditions.
［実施例４０〜４３］
吐出させた還元塩析ケラチン繊維を５％のＴＣＡ溶液内で変性・凝固させる際のＴＣＡ溶液の温度を６０℃に変更し、変性時間を、それぞれ、２分、１０分、３０分、６０分に変更した以外は、実施例２５と同様にして、実施例４０〜４３の還元塩析ケラチン繊維を得た。そして、還元塩析ケラチン繊維（変性させたもの）の強度を測定した。還元塩析ケラチン繊維の強度の測定結果を、製糸条件とともに表２に示す。
[Examples 40 to 43]
The temperature of the TCA solution when denaturing and coagulating the discharged reduced salting out keratin fibers in a 5% TCA solution was changed to 60 ° C., and the denaturation times were 2 minutes, 10 minutes, 30 minutes, and 60 minutes, respectively. Except having changed into, it carried out similarly to Example 25, and obtained the reduction | restoration salting-out keratin fiber of Examples 40-43. Then, the strength of the reduced salting out keratin fiber (modified one) was measured. The measurement results of the strength of the reduced salting out keratin fibers are shown in Table 2 together with the spinning conditions.
［比較例１］
還元ケラチン抽出液を用いて還元塩析ケラチンを析出させる際に添加する２０％硫酸ナトリウム溶液の量を、還元ケラチン抽出液に対する容量比で１倍に変更した以外は、実施例２と同様にして還元塩析ケラチンを得た。そして、実施例２と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。また、実施例１と同様に、曳糸性を評価した後に全ての還元塩析ケラチンを乾燥させて重量を測定し、還元ケラチン抽出液に添加した硫酸ナトリウムの量が、ケラチン１０ｇに対して何ｍｏｌに相当するものであったのかを算出した。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から比較例１の方法で製糸した場合の曳糸性が不良であることが分かる。
[Comparative Example 1]
Except that the amount of 20% sodium sulfate solution added when the reduced salting-out keratin was precipitated using the reduced keratin extract was changed to 1 by the volume ratio with respect to the reduced keratin extract, the same as in Example 2. Reduced salting out keratin was obtained. Then, in the same manner as in Example 2, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Further, as in Example 1, after evaluating spinnability, all reduced salted-out keratins were dried and weighed, and the amount of sodium sulfate added to the reduced keratin extract was determined with respect to 10 g of keratin. It was calculated whether it was equivalent to mol. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Comparative Example 1 is poor.
［比較例２］
還元ケラチン抽出液を得る際に用いる界面活性剤（ＳＤＳ）の量を２５％に変更した以外は、実施例１と同様にして還元塩析ケラチンを得た。そして、実施例１と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から比較例２の方法で製糸した場合の曳糸性が不良であることが分かる。
[Comparative Example 2]
Reduced salting-out keratin was obtained in the same manner as in Example 1 except that the amount of surfactant (SDS) used in obtaining the reduced keratin extract was changed to 25%. In the same manner as in Example 1, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Comparative Example 2 is poor.
［比較例３］
還元ケラチン抽出液を得る際に用いる界面活性剤（ＳＤＳ）の量を５０％に変更した以外は、実施例７と同様にして還元塩析ケラチンを得た。そして、実施例７と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から比較例３の方法で製糸した場合の曳糸性が不良であることが分かる。
[Comparative Example 3]
Reduced salting-out keratin was obtained in the same manner as in Example 7 except that the amount of surfactant (SDS) used for obtaining the reduced keratin extract was changed to 50%. In the same manner as in Example 7, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Comparative Example 3 is poor.
［比較例４］
還元ケラチン抽出液を用いて還元塩析ケラチンを析出させる際に還元ケラチン抽出液に加える界面活性剤（ＳＤＳ）の量を１１０％に変更した以外は、実施例７と同様にして還元塩析ケラチンを得た。そして、実施例７と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から比較例４の方法で製糸した場合の曳糸性が不良であることが分かる。
[Comparative Example 4]
Reduced salting out keratin in the same manner as in Example 7 except that the amount of surfactant (SDS) added to the reduced keratin extract was changed to 110% when reducing salted out keratin was precipitated using the reduced keratin extract. Got. In the same manner as in Example 7, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Comparative Example 4 is poor.
［比較例５］
還元ケラチン抽出液を得る際に用いる界面活性剤（ＳＤＳ）の量を１５０％に変更した以外は、実施例７と同様にして還元塩析ケラチンを得た。そして、実施例７と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から比較例５の方法で製糸した場合の曳糸性が不良であることが分かる。
[Comparative Example 5]
Reduced salting-out keratin was obtained in the same manner as in Example 7 except that the amount of the surfactant (SDS) used for obtaining the reduced keratin extract was changed to 150%. In the same manner as in Example 7, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Comparative Example 5 is poor.
［比較例６］
還元ケラチン抽出液を得る際に用いる第三級ホスフィン化合物をメタ重亜硫酸ナトリウムに変更した以外は、実施例１と同様にして還元塩析ケラチンを得た。そして、実施例１と同様に、２０℃の条件下で粘度測定開始から３０分後の還元塩析ケラチンの粘度および曳糸性を調べた。還元塩析ケラチンの粘度・曳糸性の評価結果を、製糸条件とともに表１に示す。表１から比較例６の方法で製糸した場合の曳糸性が不良であることが分かる。
[Comparative Example 6]
Reduced salting-out keratin was obtained in the same manner as in Example 1 except that the tertiary phosphine compound used for obtaining the reduced keratin extract was changed to sodium metabisulfite. In the same manner as in Example 1, the viscosity and spinnability of reduced salting-out keratin 30 minutes after the start of viscosity measurement under the condition of 20 ° C. were examined. Table 1 shows the evaluation results of the viscosity and spinnability of the reduced salting-out keratin together with the spinning conditions. It can be seen from Table 1 that the spinnability when the yarn is produced by the method of Comparative Example 6 is poor.
［比較例７，８］
凝固液として用いる硫酸溶液の濃度を、それぞれ、０．１％，０．２％に変更した以外は、実施例１８と同様にして還元塩析ケラチン繊維を得ようと試みたが、吐出された還元塩析ケラチンが十分に固化せず、凝固液中に溶解した状態になってしまい、還元塩析ケラチン繊維を得ることができなかった。
[Comparative Examples 7 and 8]
An attempt was made to obtain reduced salting-out keratin fibers in the same manner as in Example 18 except that the concentration of the sulfuric acid solution used as the coagulation liquid was changed to 0.1% and 0.2%, respectively. The reduced salting-out keratin did not sufficiently solidify and became dissolved in the coagulation liquid, and reduced salting-out keratin fibers could not be obtained.
［比較例９，１０］
還元塩析ケラチン繊維を変性させる際のＴＣＡ溶液の濃度を、それぞれ、１％，２％に変更した以外は、実施例２５と同様にして還元塩析ケラチン繊維を得ようと試みたが、還元塩析ケラチンが十分に固化せず、凝固液中に溶解した状態になってしまい、還元塩析ケラチン繊維を得ることができなかった。
[Comparative Examples 9 and 10]
An attempt was made to obtain reduced salting-out keratin fibers in the same manner as in Example 25 except that the concentration of the TCA solution when modifying the reduced salting-out keratin fibers was changed to 1% and 2%, respectively. The salted-out keratin did not solidify sufficiently and became dissolved in the coagulation liquid, and reduced salted-out keratin fibers could not be obtained.
［実施例の還元塩析ケラチン繊維の効果］
表１、表２から、実施例の方法によって得られる還元塩析ケラチンは、曳糸性が良好であり、繊維状に形成された還元塩析ケラチン繊維が実用に耐え得る強度を発現させることが分かる。これに対して、還元ケラチン抽出液を得る際の界面活性剤の量が少なすぎたり多すぎたりした場合、還元ケラチン抽出液を得る際の第三級ホスフィン化合物が不適切なものである場合や、還元ケラチン抽出液を用いて塩析処理する際の無機塩の濃度が低かったりした場合には、得られる還元塩析ケラチンの曳糸性が不良となり、還元塩析ケラチン繊維が得られないことが分かる。
[Effects of reduced salting out keratin fibers in Examples]
From Tables 1 and 2, the reduced salting-out keratin obtained by the method of the examples has good spinnability, and the reduced salting-out keratin fiber formed into a fiber shape can develop a strength that can be practically used. I understand. On the other hand, if the amount of surfactant in obtaining the reduced keratin extract is too small or too large, the tertiary phosphine compound in obtaining the reduced keratin extract may be inappropriate or If the inorganic salt concentration is low when salting out using the reduced keratin extract, the spinnability of the resulting reduced salting out keratin will be poor, and reduced salting out keratin fibers will not be obtained. I understand.
Claims (3)
（ａ）タンパク質変性剤、第三級ホスフィン化合物、および、ケラチン含有物質の質量に対して６０質量％以上１００質量％以下の界面活性剤を加えた水溶液中でケラチン含有物質を還元処理する工程
（ｂ）前記還元処理工程で得られた還元ケラチンを含む水溶液に、０．９Ｍ以上飽和濃度未満に相当する量の無機塩あるいは無機塩の水溶液を添加して、水溶液中のケラチン成分を塩析させることによって還元塩析ケラチンを得る工程
（ｃ）還元塩析ケラチンを繊維状に形成して気中に吐出あるいは所定の濃度に調整した酸性凝固液中に浸漬する工程 A method for producing reduced salting-out keratin fibers using reduced salting-out keratin obtained by salting out the obtained reduced keratin after reducing the keratin-containing substance, wherein the following (a) to (c) A process for producing reduced salting-out keratin fibers, comprising the step of
(A) A step of reducing the keratin-containing substance in an aqueous solution to which 60% by mass to 100% by mass of a surfactant is added with respect to the mass of the protein denaturant, the tertiary phosphine compound, and the keratin-containing substance ( b) Adding an inorganic salt or an aqueous solution of an inorganic salt in an amount corresponding to 0.9 M or more and less than a saturated concentration to the aqueous solution containing the reduced keratin obtained in the reduction treatment step to salt out the keratin component in the aqueous solution. (C) A step of forming reduced salting-out keratin in a fibrous form and discharging it into the air or immersing it in an acidic coagulating liquid adjusted to a predetermined concentration
前記塩析時に用いる無機塩が、硫酸アンモニウムあるいは硫酸ナトリウムであることを特徴とする請求項１に記載の還元塩析ケラチン繊維の製造方法。 The protein denaturant, surfactant, and tertiary phosphine compound used during the reduction treatment are urea or thiourea, sodium dodecyl sulfate, and trialkylphosphine, respectively.
The method for producing reduced salting-out keratin fibers according to claim 1, wherein the inorganic salt used during salting-out is ammonium sulfate or sodium sulfate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018207827A1 (en) | 2017-05-10 | 2018-11-15 | Ｓｐｉｂｅｒ株式会社 | Polypeptide solution, production method for polypeptide fibre, and artificial polypeptide |
| WO2020067572A1 (en) * | 2018-09-28 | 2020-04-02 | Ｓｐｉｂｅｒ株式会社 | Protein composition production method |
| CN114213683A (en) * | 2021-12-30 | 2022-03-22 | 江南大学 | Preparation method of high-concentration keratin eutectic system solution |
| EP4093366A4 (en) * | 2020-01-21 | 2024-04-24 | NUtech Ventures | Continuous production of keratin fibers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018207827A1 (en) | 2017-05-10 | 2018-11-15 | Ｓｐｉｂｅｒ株式会社 | Polypeptide solution, production method for polypeptide fibre, and artificial polypeptide |
| CN110546264A (en) * | 2017-05-10 | 2019-12-06 | 丝芭博株式会社 | Method for producing polypeptide solution and polypeptide fiber, and artificial polypeptide |
| WO2020067572A1 (en) * | 2018-09-28 | 2020-04-02 | Ｓｐｉｂｅｒ株式会社 | Protein composition production method |
| JPWO2020067572A1 (en) * | 2018-09-28 | 2021-03-18 | Ｓｐｉｂｅｒ株式会社 | Method for producing protein composition |
| EP4093366A4 (en) * | 2020-01-21 | 2024-04-24 | NUtech Ventures | Continuous production of keratin fibers |
| CN114213683A (en) * | 2021-12-30 | 2022-03-22 | 江南大学 | Preparation method of high-concentration keratin eutectic system solution |
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