JPH1192564A - Method for obtaining high-molecular-weight sericin by extraction - Google Patents

Method for obtaining high-molecular-weight sericin by extraction

Info

Publication number
JPH1192564A
JPH1192564A JP27806397A JP27806397A JPH1192564A JP H1192564 A JPH1192564 A JP H1192564A JP 27806397 A JP27806397 A JP 27806397A JP 27806397 A JP27806397 A JP 27806397A JP H1192564 A JPH1192564 A JP H1192564A
Authority
JP
Japan
Prior art keywords
sericin
molecular weight
extraction
raw silk
cocoons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP27806397A
Other languages
Japanese (ja)
Other versions
JP3516059B2 (en
Inventor
Kozo Tsubouchi
紘三 坪内
Hiroo Yamada
弘生 山田
Yoko Takasu
陽子 高須
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NAT INST OF SERICULTUAL AND EN
NATIONAL INSTITUTE OF SERICULTUAL AND ENTOMOLOGICAL SCIENCE
Original Assignee
NAT INST OF SERICULTUAL AND EN
NATIONAL INSTITUTE OF SERICULTUAL AND ENTOMOLOGICAL SCIENCE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority to JP27806397A priority Critical patent/JP3516059B2/en
Publication of JPH1192564A publication Critical patent/JPH1192564A/en
Application granted granted Critical
Publication of JP3516059B2 publication Critical patent/JP3516059B2/en
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Expired - Lifetime legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To obtain an extract having a mol.wt. as high as possible by extracting cocoons spun by silkworms, etc., threads obtd. from cocoons, raw silk, unscoured or semiscoured raw silk, fabrics prepd. from raw silk, and their residues with an aq. urea soln. at a specified temp. or higher. SOLUTION: All the protein fibers spun by silkworms, etc., including cocoons, threads obtd. from cocoons, raw silk, unscoured or incompletely scoured woven or knitted silk fabrics, and fibers, powder, films, etc., contg. sericin are used as the raw material. 1 g of such a raw material is immersed in 20-60 ml of an aq. urea soln. having a concn. of 2-8 mol/l and extracted at 100-130 deg.C for several min to several hr, pref. for 10 min or lower. After the completion of extraction, sericin having an average mol.wt. of 50,000 or higher is separated and recovered from the extractant e.g. by molecular-sieve chromatography, by using an ultrafiltration film, or by frational precipitation with an org. solvent.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、セリシンの取得方
法に関し、更に詳しくは、絹糸虫類が吐糸する繊維(繭
糸)からセリシンを、その分解を抑えながらできる限り
高分子量のままで抽出し、効率よく取得する方法に関す
る。
The present invention relates to a method for obtaining sericin, and more particularly, to extracting sericin from a fiber (cocoon thread) spun by silkworms while keeping its decomposition as high as possible while suppressing its decomposition. And how to get it efficiently.

【0002】[0002]

【従来の技術】絹糸虫類に吐糸する繊維、つまり繭糸
は、フィブロインとセリシンの蛋白質から構成されてお
り、セリシンはフィブロインをコーティングした状態で
存在している。従来から、繭糸は生糸に繰糸された後、
精練され絹織物へと加工されることによって利用されて
きた。繭糸を構成するセリシン自体は、セリシン分子の
会合や結晶化により熱水には難溶であるが、アルカリ性
の熱水には溶解することができる。そのため、通常、生
糸の精練としては、アルカリ水溶液に界面活性剤、例え
ば、マルセル石鹸等を加え、95℃以上で数時間処理す
る方法や、パパインやキモトリプシン等の蛋白質分解酵
素を用いる方法等が採られてきている。
2. Description of the Related Art Fibers spun by silkworms, that is, cocoons, are composed of proteins of fibroin and sericin, and sericin exists in a state coated with fibroin. Conventionally, after cocoon yarn is turned into raw silk,
It has been used by being refined and processed into silk fabric. Sericin itself, which constitutes the cocoon thread, is sparingly soluble in hot water due to association and crystallization of sericin molecules, but can be dissolved in alkaline hot water. For this reason, usually, scouring of raw silk is carried out by adding a surfactant such as Marcel soap to an aqueous alkali solution and treating the mixture at 95 ° C. or higher for several hours, or a method using a protease such as papain or chymotrypsin. Have been

【0003】[0003]

【発明が解決しようとする課題】従来法のアルカリ水溶
液による精練工程を採用した場合には、セリシンが加水
分解による分子鎖の切断のために低分子量化する傾向が
あった。したがって、精練工程からの廃液から抽出して
得られるセリシンは、ほとんど平均分子量50,000
以下のものである(特開平1−168906号公報、特
開平4−202435号公報等参照)。本来、繭糸ある
いは生糸を構成しているセリシンは、平均分子量が6
0,000〜300,000(SDS電気泳動による測
定)とされているにもかかわらず、現実に利用されてい
る精練工程の廃液から抽出して得られるセリシンは、上
記のように平均分子量が50,000以下のものでしか
ない。このようなセリシンは、主として繊維改質材とし
て利用されている。
When the conventional scouring step using an aqueous alkaline solution is employed, sericin tends to be reduced in molecular weight due to cleavage of a molecular chain by hydrolysis. Therefore, sericin obtained by extracting from the waste liquid from the scouring process has an average molecular weight of almost 50,000.
These are as follows (see JP-A-1-168906, JP-A-4-202435, etc.). Sericin, which originally constitutes cocoon or raw silk, has an average molecular weight of 6
Despite being between 000 and 300,000 (measured by SDS electrophoresis), sericin obtained by extraction from the waste liquid of the actually used scouring process has an average molecular weight of 50 as described above. Less than 2,000. Such sericin is mainly used as a fiber modifying material.

【0004】ところが、近年、セリシンにおいて生体防
御性を有することが注目され、そのセリシンの特有の性
質を利用した新素材の開発が盛んに行われるようになっ
た。本発明者等の知見によると、平均分子量が50,0
00以下の低分子量のセリシンは、水に溶け易く、強度
が低く脆いものであって、フィルム形成性を有しないも
のであり、人体と馴染み難いことが分かった。更にま
た、反対に、平均分子量が50,000を超える高分子
量のセリシンの場合には、物理的強度等が、それを超え
るに従って次第に大きくなり、そのためフィルム形成性
の優れた水不溶性の物質となることから、人体への適用
性が良くなることが分かった。
[0004] In recent years, however, attention has been paid to sericin having a biological defense property, and development of new materials utilizing the specific properties of sericin has been actively carried out. According to the findings of the present inventors, the average molecular weight is 50,0.
It was found that low molecular weight sericin having a molecular weight of 00 or less was easily soluble in water, had low strength and was brittle, had no film-forming property, and was hardly compatible with the human body. Furthermore, in contrast, in the case of sericin having a high molecular weight having an average molecular weight exceeding 50,000, the physical strength and the like gradually increases as the average molecular weight exceeds the value, and therefore, a water-insoluble substance having excellent film-forming properties is obtained. From this, it was found that the applicability to the human body was improved.

【0005】上述の点から、セリシンにおいて生体防御
性を有効に利用するには、平均分子量が50,000を
超える高分子量のセリシンを抽出取得することが必要で
ある。本発明は、以上の技術的背景をもとになされたも
のである。すなわち、本発明は、新しい素材、例えば、
創傷被覆材、化粧用添加剤等としての利用可能性が期待
できる高分子量のセリシンを得る方法を提供することを
目的とする。詳しくは、繭糸あるいは生糸等からセリシ
ンを、その分解を抑えながら可能な限り高分子量のまま
で抽出し、効率よく取得する方法を提供することを目的
とする。
[0005] In view of the above, in order to effectively utilize the biological defense properties of sericin, it is necessary to extract and obtain high molecular weight sericin having an average molecular weight exceeding 50,000. The present invention has been made based on the above technical background. That is, the present invention provides a new material, for example,
It is an object of the present invention to provide a method for obtaining high-molecular-weight sericin which can be expected to be used as a wound dressing, a cosmetic additive, and the like. More specifically, an object of the present invention is to provide a method for efficiently extracting sericin from cocoon or raw silk while keeping its molecular weight as high as possible while suppressing its decomposition.

【0006】[0006]

【課題を解決するための手段】本発明者等は、セリシン
の抽出条件(抽出剤と温度)と得られるセリシンの分子
量との関係を綿密に検討して、高分子量セリシンを得る
方法を確立した。
Means for Solving the Problems The present inventors have carefully examined the relationship between the sericin extraction conditions (extractant and temperature) and the obtained sericin molecular weight, and established a method for obtaining high molecular weight sericin. .

【0007】即ち、本発明は、(1)絹糸虫類の吐糸し
た繭、該繭から得られる繭糸、生糸、未精練もしくは半
精練の生糸、該生糸から調製された布、およびそれらの
残糸を、100℃を超える温度において尿素水溶液で抽
出することからなる平均分子量50,000以上のセリ
シンを取得する方法に存する。
That is, the present invention relates to (1) a cocoon spun by a silkworm, a cocoon thread obtained from the cocoon, a raw silk, an unrefined or semi-refined raw silk, a cloth prepared from the raw silk, and a residue thereof. A method for obtaining sericin having an average molecular weight of 50,000 or more, comprising extracting a yarn with an aqueous urea solution at a temperature exceeding 100 ° C.

【0008】そしてまた、(2)100℃を越え130
℃以下の温度において尿素水溶液で抽出する上記1のセ
リシンを取得する方法に存する。
Also, (2) exceeding 100 ° C. and 130
The present invention resides in a method for obtaining the above-mentioned sericin which is extracted with an aqueous urea solution at a temperature of not more than ℃.

【0009】[0009]

【発明の実施の形態】本発明でセリシンを取得するため
の原料としては、基本的には、家蚕および野蚕の絹糸虫
類が吐糸したすべての蛋白質繊維が対象となり、これら
蛋白質繊維由来のフィブロインとセリシンを含有する物
質を原料とする。また、フィブロインを含まずセリシン
のみを吐糸するセリシン蚕の繭も原料にすることができ
る。これらの原料の形態は繭、繭糸、生糸、絹織編物の
未精練物また未完全精練物およびセリシンを含有する繊
維、粉末、フィルム等があるが、これらすべてを原料と
して使用できる。
BEST MODE FOR CARRYING OUT THE INVENTION As a raw material for obtaining sericin in the present invention, basically, all protein fibers spliced by silkworms of silkworms and wild silkworms are targeted, and fibroin derived from these protein fibers is used. And a substance containing sericin. In addition, a cocoon of sericin silkworm which spins only sericin without fibroin can be used as a raw material. Examples of the form of these raw materials include cocoon, cocoon thread, raw silk, unscrutinized and unsmelted knitted fabrics, fibers containing sericin, powders, films and the like, all of which can be used as the raw material.

【0010】セリシンの抽出は、原料1g当たり2〜8
モル/l濃度の尿素水溶液20〜60ml中に浸漬し、
100℃を超え約130℃以下の温度で数分ないし数時
間かけて行う。抽出温度が100℃以下だとセリシンの
抽出効率の観点で劣り、一方、抽出温度が130℃を超
えると尿素の分解が起こり易く好ましくない。ここで、
より高収率で高分子量のセリシンを抽出するには、でき
る限り高温で短時間で抽出することが好ましい。高温、
例えば120℃においては、10分以下で抽出を完了す
るのが望ましく、それ以上抽出時間を長くするとセリシ
ンの分解が起こるようになるから注意する必要がある。
[0010] Sericin is extracted in an amount of 2 to 8 per gram of raw material.
Immersed in 20-60 ml of a urea aqueous solution of mol / l concentration,
It is performed at a temperature of more than 100 ° C. and about 130 ° C. for several minutes to several hours. If the extraction temperature is 100 ° C. or lower, the extraction efficiency of sericin is poor. On the other hand, if the extraction temperature exceeds 130 ° C., urea is likely to be decomposed, which is not preferable. here,
In order to extract high molecular weight sericin in higher yield, it is preferable to extract at a temperature as high as possible and in a short time. high temperature,
For example, at 120 ° C., it is desirable to complete the extraction in 10 minutes or less, and it should be noted that if the extraction time is longer, sericin will be decomposed.

【0011】抽出終了後、抽出液からのセリシンの分
離、回収は、例えば、以下の方法を採用して行う。 1)分子ふるいクロマトを用いる方法;分画分子量が
5,000〜600,000程度のセファデックス等を
用いるカラムクロマトグラフィー法によって、分子量が
50,000より大きい画分を集める。
After completion of the extraction, the separation and recovery of sericin from the extract is performed, for example, by the following method. 1) Method using molecular sieve chromatography: A fraction having a molecular weight of more than 50,000 is collected by column chromatography using Sephadex having a molecular weight cutoff of about 5,000 to 600,000.

【0012】2)限外ろ過膜を用いる方法;分画分子量
が50,000以上の限外ろ過膜を用いて、ろ過を行
い、高分子画分を集めて濃縮する。
2) Method using ultrafiltration membrane: Filtration is performed using an ultrafiltration membrane having a molecular weight cut-off of 50,000 or more, and a high molecular fraction is collected and concentrated.

【0013】3)有機溶媒で分別沈澱をおこなう方法;
抽出する高分子量セリシンの分子量に応じてメチルアル
コール、エチルアルコール、プロピルアルコール、アセ
トン等の親水性有機溶媒を50〜80%(重量比)にな
るように添加して高分子量セリシンを選択的に沈澱させ
る。
3) a method of performing fractional precipitation with an organic solvent;
Depending on the molecular weight of the high molecular weight sericin to be extracted, a hydrophilic organic solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, acetone or the like is added so as to be 50 to 80% (weight ratio) to selectively precipitate high molecular weight sericin. Let it.

【0014】ここで、本発明により取得された高分子量
のセリシン(通常、これらの高分子量のセリシンの分子
量は液体クロマトグラフィー及び又はSDS電気泳動装
置で分析する)は、分子量が高いため、フィルムに成形
して腰のある新しい素材として利用できる他、粉末とし
て或いは溶液としても当然利用することができる。ま
た、本発明により取得された高分子量セリシンは、吸湿
性に富み、強靱で、かつ熱水に溶けにくいものである。
そのため、創傷被覆材などの医療用材料や化粧用添加剤
等としても有用であり、また繊維製品の着用時の快適性
を向上させるための繊維改良材、処理剤、コーティング
剤等としても有用である。以下、実施例及び比較例を挙
げて本発明を説明するが、本発明は、それらに限定され
るものではない。
Here, the high molecular weight sericin obtained by the present invention (the molecular weight of these high molecular weight sericins is usually analyzed by liquid chromatography and / or SDS electrophoresis) has a high molecular weight, so In addition to being molded and used as a new material with a firm shape, it can be naturally used as a powder or as a solution. The high-molecular-weight sericin obtained by the present invention is rich in hygroscopicity, tough, and hardly soluble in hot water.
Therefore, it is also useful as a medical material such as a wound dressing material, a cosmetic additive, and the like, and is also useful as a fiber improving material, a treating agent, a coating agent, and the like for improving comfort when wearing textile products. is there. Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

【0015】[0015]

【実施例】【Example】

〔実施例1〕家蚕の繭糸5gを、30倍量の尿素水溶液
(2モル/l濃度)中に浸漬し、120℃(2気圧)で
5分間かけて抽出処理した。この抽出液をファルマシア
社製ハイロードQのカラム(内径2.6cm×長さ10
cm)に通過させてセリシンを吸着させた。次いで、カ
ラムを0.2モル硫酸ナトリウムで溶出し蛋白の分画を
集め、アミコン社製限外ろ過膜セントリフロー50でろ
過脱塩したのち凍結乾燥し、1gの粉末状セリシンを得
た。この方法で得たセリシンの平均分子量は,クロマト
法(セファクリルS−500)による測定で約180,
000であった。
[Example 1] 5 g of cocoon thread of silkworm was immersed in a 30-fold amount of urea aqueous solution (2 mol / l concentration) and extracted at 120 ° C (2 atm) for 5 minutes. This extract was applied to a column of High Load Q manufactured by Pharmacia (inner diameter 2.6 cm × length 10).
cm) to adsorb sericin. Then, the column was eluted with 0.2M sodium sulfate, and the protein fraction was collected, filtered and desalted with an ultrafiltration membrane Centriflow 50 manufactured by Amicon, and lyophilized to obtain 1 g of powdered sericin. The average molecular weight of sericin obtained by this method was about 180, as measured by a chromatographic method (Sephacryl S-500).
000.

【0016】〔実施例2〕抽出温度を110℃(1.4
気圧)とした以外は上記実施例1と同様な条件で家蚕の
繭糸を抽出処理し、平均分子量約200,000のセリ
シン0.75gを得た。
Example 2 The extraction temperature was set to 110 ° C. (1.4
The cocoon thread of the silkworm, Bombyx mori, was extracted under the same conditions as in Example 1 except that the pressure was changed to 0.75 g of sericin having an average molecular weight of about 200,000.

【0017】〔実施例3〕抽出温度を105℃(1.2
気圧)とした以外は上記実施例1と同様な条件で家蚕の
繭糸を抽出処理し、平均分子量約220,000のセリ
シン0.65gを得た。
Example 3 The extraction temperature was set to 105 ° C. (1.2
The cocoon thread of the silkworm, Bombyx mori, was extracted under the same conditions as in Example 1 except that the pressure was changed to (atmospheric pressure) to obtain 0.65 g of sericin having an average molecular weight of about 220,000.

【0018】〔実施例4〕抽出温度を100℃(1気
圧)とした以外は上記実施例1と同様な条件で家蚕の繭
糸を抽出処理し、平均分子量約220,000のセリシ
ン0.25gを得た。
Example 4 A cocoon thread of a silkworm, Bombyx mori, was extracted under the same conditions as in Example 1 except that the extraction temperature was changed to 100 ° C. (1 atm), and 0.25 g of sericin having an average molecular weight of about 220,000 was obtained. Obtained.

【0019】〔実施例5〕抽出温度を80℃(1気圧)
とした以外は上記実施例1と同様な条件で家蚕の繭糸を
抽出処理したが、セリシンは殆ど抽出できなかった。
Example 5 The extraction temperature was 80 ° C. (1 atm)
The cocoon thread of Bombyx mori was extracted under the same conditions as in Example 1 except that no sericin was extracted.

【0020】[0020]

【比較例】[Comparative example]

〔比較例1〕家蚕の繭糸5gを、30倍量の水に浸漬
し、120℃(2気圧)で5分間かけて抽出処理した。
この抽出液を濾過した後、4倍容量のエチルアルコール
を加えて生成した沈澱を遠心分離して集めた。これをエ
チルアルコールで洗浄脱水し、エチルエーテルで洗浄、
乾燥し、0.55gの粉末状セリシンを得た。この方法
で得たセリシンの平均分子量は,クロマト法(セファク
リルS−500)による測定で約180,000であっ
た。
[Comparative Example 1] 5 g of a silkworm cocoon thread was immersed in 30 times the volume of water and extracted at 120 ° C (2 atm) for 5 minutes.
After the extract was filtered, a precipitate formed by adding 4 volumes of ethyl alcohol was collected by centrifugation. This is washed with ethyl alcohol, dehydrated, washed with ethyl ether,
After drying, 0.55 g of sericin powder was obtained. The average molecular weight of sericin obtained by this method was about 180,000 as measured by a chromatographic method (Sephacryl S-500).

【0021】〔比較例2〕抽出温度を110℃(1.4
気圧)とした以外は上記比較例1と同様な条件で家蚕の
繭糸を抽出処理し、平均分子量約180,000のセリ
シン0.45gを得た。
Comparative Example 2 An extraction temperature of 110 ° C. (1.4
The cocoon thread of the silkworm, Bombyx mori, was extracted under the same conditions as in Comparative Example 1 except that the pressure was changed to (atmospheric pressure) to obtain 0.45 g of sericin having an average molecular weight of about 180,000.

【0022】〔比較例3〕抽出温度を105℃(1.2
気圧)とした以外は上記比較例1と同様な条件で家蚕の
繭糸を抽出処理し、平均分子量約200,000のセリ
シン0.25gを得た。
Comparative Example 3 The extraction temperature was set to 105 ° C. (1.2
The cocoon thread of the silkworm, Bombyx mori, was extracted under the same conditions as in Comparative Example 1 except that the pressure was changed to 0.25 g of sericin having an average molecular weight of about 200,000.

【0023】〔比較例4〕抽出温度を100℃(1気
圧)とした以外は上記比較例1と同様な条件で家蚕の繭
糸を抽出処理し、平均分子量約200,000のセリシ
ン0.15gを得た。
Comparative Example 4 A cocoon thread of a silkworm was extracted under the same conditions as in Comparative Example 1 except that the extraction temperature was changed to 100 ° C. (1 atm), and 0.15 g of sericin having an average molecular weight of about 200,000 was obtained. Obtained.

【0024】〔比較例5〕抽出温度を80℃(1気圧)
とした以外は上記比較例1と同様な条件で家蚕の繭糸を
抽出処理したがセリシンは殆ど抽出できなかった。
[Comparative Example 5] Extraction temperature was 80 ° C (1 atm)
The cocoon thread of Bombyx mori was extracted under the same conditions as in Comparative Example 1 except that no sericin was extracted.

【0025】以上の〔実施例〕及び〔比較例〕の結果
を、まとめて〔表1〕に示す。表1から明らかなよう
に、尿素水溶液を用いた場合には、尿素を含まない熱水
を用いた場合に比較して、ほぼ2倍程度抽出率が上が
り、特に、実施例1においては原料繭糸中含まれるセリ
シンの80%以上が抽出されていることが理解されよ
う。また、尿素水溶液を用いた場合には、抽出温度が1
00℃を越えると抽出率が大きく高まることが分かる。
The results of [Example] and [Comparative Example] are collectively shown in [Table 1]. As is clear from Table 1, when the urea aqueous solution is used, the extraction rate is increased by about twice as compared with the case where the hot water not containing urea is used. It will be understood that more than 80% of the sericin contained therein was extracted. When an aqueous urea solution is used, the extraction temperature is 1
It is found that when the temperature exceeds 00 ° C., the extraction rate is greatly increased.

【0026】[0026]

【参考例】[Reference example]

〔参考例1〕実施例3で得られた平均分子量約220,
000のセリシンを水溶液とした(試料1)。また、実
施例3で得られた平均分子量約220,000のセリシ
ンを炭酸ソーダ0.1重量%溶液にして、5分間煮沸し
た後、透析して炭酸ソーダを除去したセリシン水溶液と
した(試料2)。また同様に30分間煮沸した後、透析
して炭酸ソーダを除去したセリシン水溶液とした(試料
3)。また同様に2時間煮沸した後、透析して炭酸ソー
ダを除去したセリシン水溶液とした(試料4)。以上の
4つの試料を室温に静置してゲル化するまでの時間を調
査した。その結果とクロマト法(セファクリルS−50
0)で求めた分子量とを〔表2〕に示す。
[Reference Example 1] The average molecular weight of about 220 obtained in Example 3,
000 sericin was used as an aqueous solution (sample 1). Further, the sericin having an average molecular weight of about 220,000 obtained in Example 3 was made into a 0.1% by weight solution of sodium carbonate, boiled for 5 minutes, and dialyzed to obtain a sericin aqueous solution from which sodium carbonate was removed (sample 2). ). Similarly, after boiling for 30 minutes, a sericin aqueous solution from which sodium carbonate was removed by dialysis was used (sample 3). Similarly, after boiling for 2 hours, a sericin aqueous solution from which sodium carbonate was removed by dialysis was used (sample 4). The time until the above four samples were allowed to stand at room temperature and gelled was investigated. The results and the chromatographic method (Sephacryl S-50)
Table 2 shows the molecular weight determined in step (0).

【0027】〔参考例2〕上記参考例1の試料1〜試料
4の水溶液からフィルム(厚さ50μm±5μm)を作
成し、各フィルムの強度を〔表3〕に示す。強度は、2
0℃、65%RHにおけるフィルムの引張り強度(把持
巾7mm、把持間隔2cm、引張り速度約100/mi
n)で示した。これらの各フィルムを110℃±5℃の
スチームで1時間処理してセリシンを結晶化させた。こ
れらの各フイルムのセリシンの熱水(100℃±3℃,
1時間)における溶解性を測定したところ〔表4〕の結
果となった。
Reference Example 2 Films (thickness: 50 μm ± 5 μm) were prepared from the aqueous solutions of Samples 1 to 4 of Reference Example 1, and the strength of each film is shown in Table 3. Strength is 2
Tensile strength of film at 0 ° C. and 65% RH (gripping width: 7 mm, holding distance: 2 cm, pulling speed: about 100 / mi
n). Each of these films was treated with steam at 110 ° C. ± 5 ° C. for 1 hour to crystallize sericin. Sericin hot water of each of these films (100 ° C ± 3 ° C,
(1 hour) was measured, and the results are shown in [Table 4].

【0028】ここで、溶解性は元の重量(A)と1時間
後の熱水中の沈澱物を遠心分離(2000G)して回収
し、乾燥後の重量(B)から次の式(1)で計算した。 (1)熱水溶解性(%)=(A−B/A)×100
Here, the solubility was determined from the original weight (A) and the precipitate in hot water after 1 hour by centrifugation (2000 G) and recovered, and from the weight after drying (B), the following formula (1) was obtained. ). (1) Hot water solubility (%) = (AB / A) × 100

【0029】〔参考例3〕上記参考例1の試料1〜試料
4のセリシン水溶液にCgのナイロン編物を1時間浸漬
し、乾燥後の重量の測定値をDgとした。次にこれらを
110℃±5℃でスチーム処理を1時間行い、乾燥した
後、熱水処理(100℃±3℃,1時間)し、再び乾燥
した後の重量の測定値をEgとした。その結果を〔表
5〕に示す。
REFERENCE EXAMPLE 3 A Cg nylon knit was immersed in the sericin aqueous solution of each of Samples 1 to 4 of Reference Example 1 for 1 hour, and the measured value of the weight after drying was Dg. Next, these were subjected to a steam treatment at 110 ° C. ± 5 ° C. for 1 hour, dried, subjected to a hot water treatment (100 ° C. ± 3 ° C., 1 hour), and dried again. The results are shown in [Table 5].

【0030】ここで、「セリシンの付着量」及び「熱水
処理後のセリシン付着量」は下記の式(1)及び式
(2)で計算した。 (1)セリシンの付着量(%)=(D−C)/C×10
0 (2)熱水処理後のセリシンの付着量(%)=(E−
C)/C×100
Here, the “adhered amount of sericin” and “adhered amount of sericin after hot water treatment” were calculated by the following equations (1) and (2). (1) Sericin adhesion amount (%) = (D−C) / C × 10
0 (2) Sericin adhesion amount (%) after hot water treatment = (E−
C) / C × 100

【0031】[0031]

【発明の効果】以上の結果から、本願発明の抽出方法に
より得られたセリシンは、精練液から抽出して得られる
従来の低分子量化(加水分解)されたセリシンとは異な
り、分子量が大きいため、強度が増しフィルム形成能が
高まる上、更に熱水不溶性を有する。また本来の吸湿性
や肌触性の良い特性を合わせ持つ利点がある。セリシン
が有する特有の性質である生体防御性を生かした創傷被
覆材等の医療用材料や化粧用添加剤等に極めて有用であ
From the above results, sericin obtained by the extraction method of the present invention has a large molecular weight, unlike conventional low molecular weight (hydrolyzed) sericin obtained by extraction from a scouring solution. In addition, the strength is increased and the ability to form a film is enhanced. In addition, there is an advantage in that it has characteristics of good moisture absorption and good touch. It is extremely useful for medical materials such as wound dressing materials and cosmetic additives that make use of the unique properties of sericin.

【0032】[0032]

【表1】 [Table 1]

【0033】[0033]

【表2】 [Table 2]

【0034】[0034]

【表3】 [Table 3]

【0035】[0035]

【表4】 [Table 4]

【0036】[0036]

【表5】 [Table 5]

フロントページの続き (71)出願人 597143731 高須 陽子 茨城県つくば市並木2丁目14−301−504 (72)発明者 坪内 紘三 茨城県北相馬郡守谷町松前台6丁目15−8 (72)発明者 山田 弘生 茨城県つくば市二の宮1丁目8−10 時計 台ハイツA107 (72)発明者 高須 陽子 茨城県つくば市並木2丁目14−301−504Continuation of the front page (71) Applicant 597143731 Yoko Takasu 2- 14-301-504 Namiki, Tsukuba City, Ibaraki Prefecture (72) Inventor Kozo Tsubouchi 6-15-8 Matsumaedai, Moriyacho, Kitasoma-gun, Ibaraki Prefecture (72) Inventor Hiroo Yamada 1-8-10 Ninomiya, Tsukuba, Ibaraki Pref. Clock Tower Heights A107 (72) Inventor Yoko Takasu 2-301-304-504 Namiki, Tsukuba, Ibaraki Prefecture

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 絹糸虫類の吐糸した繭、該繭から得られ
る繭糸、生糸、未精練もしくは半精練の生糸、該生糸か
ら調製された布、およびそれらの残糸を、100℃を超
える温度において尿素水溶液で抽出することからなる平
均分子量50,000以上のセリシンを取得する方法。
Claims 1. A cocoon that has been spun from a silkworm, a cocoon thread obtained from the cocoon, a raw silk, an unrefined or semi-refined raw silk, a cloth prepared from the raw silk, and a residual thread thereof are heated at a temperature exceeding 100 ° C. A method for obtaining sericin having an average molecular weight of 50,000 or more by extracting with an aqueous urea solution at a temperature.
【請求項2】 100℃を越え130℃以下の温度にお
いて尿素水溶液で抽出することを特徴とする請求項1記
載のセリシンを取得する方法。
2. The method for obtaining sericin according to claim 1, wherein the extraction is carried out with an aqueous urea solution at a temperature higher than 100 ° C. and lower than 130 ° C.
JP27806397A 1997-09-24 1997-09-24 How to extract and obtain high molecular weight sericin Expired - Lifetime JP3516059B2 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002034885A1 (en) * 2000-10-24 2002-05-02 National Institute Of Agrobiological Sciences Sericin-containing material, process for producing the same and method of using the same
JP2018075832A (en) * 2016-11-01 2018-05-17 エーアイシルク株式会社 Manufacturing method of electroconductive polymer conductor and manufacturing method of substrate
CN112515980A (en) * 2019-09-18 2021-03-19 株式会社Lg生活健康 Cosmetic composition comprising high molecular weight sericin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002034885A1 (en) * 2000-10-24 2002-05-02 National Institute Of Agrobiological Sciences Sericin-containing material, process for producing the same and method of using the same
US6815427B2 (en) 2000-10-24 2004-11-09 National Institute Of Agrobiological Sciences Sericin-containing material, process for producing the same method of using the same
JP2018075832A (en) * 2016-11-01 2018-05-17 エーアイシルク株式会社 Manufacturing method of electroconductive polymer conductor and manufacturing method of substrate
CN112515980A (en) * 2019-09-18 2021-03-19 株式会社Lg生活健康 Cosmetic composition comprising high molecular weight sericin

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