JP2009057327A - Fish-skin-derived collagen, cosmetic composition, and method for producing the fish-skin-derived collagen - Google Patents

Fish-skin-derived collagen, cosmetic composition, and method for producing the fish-skin-derived collagen Download PDF

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JP2009057327A
JP2009057327A JP2007226538A JP2007226538A JP2009057327A JP 2009057327 A JP2009057327 A JP 2009057327A JP 2007226538 A JP2007226538 A JP 2007226538A JP 2007226538 A JP2007226538 A JP 2007226538A JP 2009057327 A JP2009057327 A JP 2009057327A
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collagen
skin
fish
fish skin
derived
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Koji Nagatomi
功治 永冨
Masahiro Hizuka
正博 肥塚
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Nitta Gelatin Inc
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Nitta Gelatin Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a fish-skin-derived collagen satisfactorily usable also in a cosmetic for which colorless and transparent, odorless and high-quality collagen is required. <P>SOLUTION: Provided is a collagen extracted from fish skin, characterized in that the fish skin is sturgeon skin, has a fat-and-oil content of 0.3 wt.% or less and exhibits a light transmittance at 400 nm of 85% or higher. Due to these characteristics, various functions inherent in the collagen can be efficiently imparted to a cosmetic composition, and a high-quality and high-performance cosmetic composition can be provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、魚皮由来コラーゲン、化粧料組成物および魚皮由来コラーゲンの製造方法に関し、詳しくは、コラーゲンを豊富に含む魚の皮を利用して得られたコラーゲンと、このような魚皮由来コラーゲンを含む化粧料組成物と、このような魚皮由来コラーゲンを製造する方法とを対象にしている。   TECHNICAL FIELD The present invention relates to a fish skin-derived collagen, a cosmetic composition, and a method for producing a fish skin-derived collagen, and more specifically, a collagen obtained by using a fish skin rich in collagen, and such a fish skin-derived collagen. And a method for producing such fish skin-derived collagen.

コラーゲンは、各種医療材料、細胞培養用基質、化粧品、医薬部外品、医薬品添加物、食品などの用途に用いられており、特に、化粧品に配合することで保湿機能やシワ防止機能など優れた機能を発揮できることが知られている。
コラーゲンを工業的に製造するための原料として、従来良く知られていた牛や豚の皮に変えて、魚の皮を用いる技術が提案されている。BSE(牛海綿状脳症)の問題がなく、特性的にも豚皮コラーゲンなどとは少し異なる魚皮コラーゲンは、様々な分野における利用が求められている。例えば、化粧品の分野では、原料として豚皮コラーゲンや牛皮コラーゲンを配合する場合には、化粧品のしっとり感が高まるため、冬場に好んで用いられるものの、夏場には前記したしっとり感がベタツキとして感じられ、使用感が悪いという欠点があるのに対して、魚皮コラーゲンを配合すると、さっぱりとした使用感が得られるため、夏場においてもベタツキ感がなく、使用感が良いという利点がある。
Collagen is used for various medical materials, cell culture substrates, cosmetics, quasi-drugs, pharmaceutical additives, foods, etc., especially when blended into cosmetics, it has excellent moisture retention and wrinkle prevention functions. It is known that it can function.
As a raw material for industrially producing collagen, a technique using fish skin instead of the well-known cow or pig skin has been proposed. There is no problem of BSE (bovine spongiform encephalopathy), and fish skin collagen, which is slightly different from porcine skin collagen in terms of characteristics, is required to be used in various fields. For example, in the field of cosmetics, when pork skin collagen or cow skin collagen is blended as a raw material, the moist feeling of cosmetics increases, so it is preferred in winter, but the above moist feeling is felt as sticky in summer. On the other hand, there is a disadvantage that the feeling of use is bad, but when a fish skin collagen is blended, a refreshing feeling of use is obtained, so that there is no sticky feeling even in summer and there is an advantage that the feeling of use is good.

特許文献1には、ヨシキリザメなどのサメの皮からコラーゲンを得る技術が示されている(請求項2)。
特許文献2には、イズミダイなどのテラピア類の皮からコラーゲンを得る技術が示されている(請求項2)。
特開2003−92997号公報 特開2006−28138号公報
Patent Document 1 discloses a technique for obtaining collagen from shark skin such as blue shark (Claim 2).
Patent Document 2 discloses a technique for obtaining collagen from the skin of tilapia such as Izumidai (claim 2).
JP 2003-92997 A JP 2006-28138 A

前記した従来技術で得られる魚皮コラーゲンには、原料として用いた魚種に特有の問題があり、特に化粧品などには使用し難いことが多い。
特許文献1のサメ皮から得られた魚皮コラーゲンは、サメ類に特有の臭いが強く残っており、化粧品に用いることは難しい。特許文献2のテラピア類の皮から得られた魚皮コラーゲンも、サメ皮ほどではないが、やはり、臭いが残ってしまう。配合成分にできるだけ臭いのない材料を使用することが求められる化粧品には使用し難いものであった。
その他にも、種々の魚種材料を使って、魚皮コラーゲンの製造が試みられているが、前記同様に魚特有の臭いがあったり、にごりがついてしまったりする問題があるため、化粧品に使用するには、問題が多かった。
The fish skin collagen obtained by the above-described prior art has a problem peculiar to the fish species used as a raw material, and is often difficult to use especially for cosmetics.
The fish skin collagen obtained from the shark skin of Patent Document 1 has a strong odor peculiar to sharks and is difficult to use in cosmetics. The fish skin collagen obtained from the tilapia skin of Patent Document 2 also has a odor remaining, although not as much as shark skin. It has been difficult to use in cosmetics that require the use of materials with as little odor as possible for the ingredients.
In addition to this, attempts have been made to produce fish skin collagen using various fish species materials. However, as mentioned above, there are problems with fish-like odors and stagnation. There were many problems to do.

本発明の課題は、無色透明・無臭であって、各種用途、特に高品質のコラーゲンが求められる化粧品などにも十分に利用できる魚皮由来コラーゲンを提供することである。   An object of the present invention is to provide a fish skin-derived collagen that is colorless and transparent and odorless and can be sufficiently used for various uses, particularly for cosmetics that require high-quality collagen.

本発明にかかる魚皮由来コラーゲンは、魚皮から抽出されてなるコラーゲンであって、前記魚皮がチョウザメの皮であり、油脂分が0.3重量%以下であり、波長400nmにおける光線透過率が85%以上である。   The fish skin-derived collagen according to the present invention is collagen extracted from fish skin, wherein the fish skin is sturgeon skin, the fat and oil content is 0.3% by weight or less, and the light transmittance at a wavelength of 400 nm. Is 85% or more.

本発明にかかる魚皮由来コラーゲンは、抽出原料として、チョウザメの皮を用いることによって、無色透明で臭いがほとんどなく、各種特性にも優れた高品質の魚皮由来コラーゲンとなる。特に、にごりおよび臭いを嫌う化粧料に利用するのに好適となる。   The fish skin-derived collagen according to the present invention becomes a high-quality fish skin-derived collagen that is colorless and transparent, has almost no odor, and is excellent in various properties by using sturgeon skin as an extraction raw material. In particular, it is suitable for use in cosmetics that dislike dust and odor.

以下、本発明にかかる魚皮由来コラーゲンについて詳しく説明するが、本発明の範囲はこれらの説明に拘束されることなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更実施し得る。
〔チョウザメの皮〕
チョウザメは、硬骨魚類に属する淡水魚であり、学術的にはチョウザメ類「Acipenseriformes」に属する魚の総称である。具体的には、チョウザメ「Acipenser」やヘラチョウザメ「Polyodon」、シロチョウザメ「Acipenser transmontanus」、オオチョウザメ(ベルーガ)「huso」などが含まれる。なお、一般的に知られるヨシキリザメなどのサメは、軟骨魚類であり板鰓類に属している。チョウザメは、学術的にサメとは全く異なる魚である。
Hereinafter, the fish skin-derived collagen according to the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and modifications other than the following examples are made as appropriate without departing from the spirit of the present invention. Can do.
[Sturgeon skin]
Sturgeon is a freshwater fish belonging to teleosts, and is scientifically a collective term for fish belonging to the sturgeon "Acipenseriformes". Specifically, sturgeon “Acipenser”, spatula shark “Polyodon”, white sturgeon “Acipenser transmontanus”, giant sturgeon (beluga) “huso” and the like are included. In addition, generally known sharks such as blue sharks are cartilaginous fishes and belong to the shark species. Sturgeon is an academically different fish from sharks.

チョウザメは、自然界ではロシア・中国・北米などの河川や湖に生息している。また、近年、我が国において、チョウザメの養殖が産業化されている。魚皮由来コラーゲンの原料としては、養殖チョウザメが有効に利用できる。
チョウザメの皮は、チョウザメの魚体から卵(キャビア)を採取したり、魚肉などの可食部分を取り出したりしたあと、廃棄物として残った皮を利用することができる。チョウザメの皮には鱗もついているが、鱗については除去して利用すればよい。
〔コラーゲンの抽出〕
基本的には、通常の魚皮コラーゲン製造技術と同様の方法が適用できる。
Sturgeon inhabits rivers and lakes in Russia, China and North America in nature. In recent years, the cultivation of sturgeon has been industrialized in Japan. Cultured sturgeon can be used effectively as a raw material for fish skin-derived collagen.
For the skin of sturgeon, after collecting eggs (caviar) from the fish body of sturgeon or taking out edible parts such as fish meat, the skin remaining as waste can be used. Sturgeon skin has scales, but scales can be removed and used.
[Collagen extraction]
Basically, a method similar to a normal fish skin collagen production technique can be applied.

具体的には、脱脂処理、酸漬処理、アルカリ漬処理、粉砕処理などのあと、抽出処理を行なう。なお、従来、魚鱗コラーゲンの製造において、魚鱗に含まれる灰分を取り除くために必要とされていた脱灰処理は不要であり、製造工程が削減できる。
抽出処理によって得られた抽出液に、不純物の除去処理、濾過処理、濃縮処理、精製処理などを行って、各種用途に利用できる魚皮由来コラーゲンが得られる。
〔脱脂処理〕
脱脂処理は、抽出原料に含まれる油脂分を除去する。通常の豚皮などに対する脱脂処理と共通する技術が適用できる。
Specifically, extraction processing is performed after degreasing, pickling, alkali pickling, pulverization, and the like. Conventionally, in the production of fish scale collagen, the decalcification treatment that has been required to remove the ash contained in the fish scale is unnecessary, and the production process can be reduced.
A fish skin-derived collagen that can be used for various purposes is obtained by performing an impurity removal process, a filtration process, a concentration process, a purification process, and the like on the extract obtained by the extraction process.
[Degreasing]
A degreasing process removes the fats and oils contained in an extraction raw material. A technique common to the degreasing treatment for normal pork skin and the like can be applied.

例えば、エタノールやアセトン等の有機溶剤処理液、水酸化ナトリウムや水酸化カリウム等のアルカリ処理液、非イオン性界面活性剤等の界面活性剤処理液を用いて行なうことができる。処理時間は、目的とする脱脂が十分に達成されれば十分である。通常、24〜72時間に設定できる。処理温度は、4〜10℃の範囲に設定できる。
その後、処理液から抽出原料を取り出したり水洗したり、水洗後に乾燥させたりすることができる。これらの処理も、通常のゼラチン製造技術における脱脂処理と共通する技術が適用できる。
脱脂処理を終えたチョウザメの皮が、油脂分0.3重量%以下になるようにしておくことが好ましい。より好ましくは、油脂分0.15重量%以下である。油脂分が十分に低減された抽出原料から得られる魚皮由来コラーゲンは、透明性が高く無臭性にも優れたものとなる。
For example, it can be performed using an organic solvent treatment solution such as ethanol or acetone, an alkali treatment solution such as sodium hydroxide or potassium hydroxide, or a surfactant treatment solution such as a nonionic surfactant. The treatment time is sufficient if the desired degreasing is sufficiently achieved. Usually, it can be set to 24 to 72 hours. The treatment temperature can be set in the range of 4 to 10 ° C.
Thereafter, the extraction raw material can be taken out from the treatment liquid, washed with water, or dried after washing with water. For these treatments, a technique common to a degreasing treatment in a normal gelatin production technique can be applied.
It is preferable that the sturgeon skin that has been degreased has a fat content of 0.3% by weight or less. More preferably, the oil content is 0.15% by weight or less. Fish skin-derived collagen obtained from an extraction raw material with a sufficiently reduced oil and fat is highly transparent and excellent in odorlessness.

〔抽出処理〕
基本的に、通常の豚皮や魚皮からのコラーゲン抽出処理と同様の技術が適用できる。
脱脂処理を終えたチョウザメの皮は、そのままで抽出処理に供しても良いし、細かく粉砕しておくこともできる。粉砕処理には、高速ホモジナイザーによる粉砕や凍結乾燥粉砕などが適用できる。粉砕後の粒径を、平均粒径0.1〜1mmの範囲に設定できる。
抽出処理は、酵素による可溶化に基づき行なうことが好ましい。
<酵素処理>
酵素処理は、抽出原料に、タンパク質分解酵素などの酵素を加えて、抽出原料の組織を分解し、コラーゲンが抽出され易くする。酵素として、ペプシン、プロクターゼ、パパインなどが使用できる。酵素処理は、温度4〜10℃で24〜72時間かけて行なうことができる。
[Extraction process]
Basically, the same technique as that for collagen extraction from normal pig skin or fish skin can be applied.
The sturgeon skin that has been degreased may be subjected to an extraction process as it is, or may be finely pulverized. For the pulverization treatment, pulverization with a high-speed homogenizer, freeze-drying pulverization, or the like can be applied. The particle size after pulverization can be set in the range of an average particle size of 0.1 to 1 mm.
The extraction treatment is preferably performed based on solubilization with an enzyme.
<Enzyme treatment>
In the enzyme treatment, an enzyme such as a proteolytic enzyme is added to the extraction raw material to decompose the tissue of the extraction raw material so that collagen is easily extracted. As the enzyme, pepsin, proctase, papain and the like can be used. The enzyme treatment can be performed at a temperature of 4 to 10 ° C. for 24 to 72 hours.

〔後処理〕
抽出されたコラーゲンは、例えば、従来から哺乳動物由来のコラーゲンの製造で行なわれている通常の物理的分離手段によって回収すればよく、その方法は特に限定されない。
具体的には、例えば、前記酵素処理後に遠心分離や濾過などを行なうことによりコラーゲンを含む上澄み液を分離し、前記コラーゲンを含む上澄み液に塩化ナトリウムなどを加えて塩濃度を上昇させるか、または、水酸化ナトリウムなどを加えてpHを中性付近に調整することにより、コラーゲンを線維化し、該線維化したコラーゲンを遠心分離などにより回収することができる。
[Post-processing]
The extracted collagen may be recovered, for example, by a conventional physical separation means conventionally used in the production of mammal-derived collagen, and the method is not particularly limited.
Specifically, for example, the supernatant containing collagen is separated by performing centrifugation or filtration after the enzyme treatment, and sodium chloride or the like is added to the supernatant containing collagen to increase the salt concentration, or By adding sodium hydroxide or the like to adjust the pH to near neutrality, collagen can be fibrillated, and the fibrillated collagen can be recovered by centrifugation or the like.

その後、必要に応じて、回収した前記線維化したコラーゲンを精製水などに再度溶解し、前記と同様の方法で線維化と回収を行なうことにより、精製することもできる。また、前記精製操作は複数回繰り返し行ってもよい。
〔チョウザメ皮コラーゲン〕
このようにして得られた魚皮由来コラーゲンすなわちチョウザメ皮コラーゲンは、コラーゲンとしての各種機能を十分に有しているとともに、無色透明・無臭である。
具体的には、油脂分が0.3重量%以下である。好ましくは0.15重量%以下である。
Thereafter, if necessary, the recovered fibrillated collagen can be dissolved again in purified water and purified by fibrillation and recovery in the same manner as described above. The purification operation may be repeated a plurality of times.
[Sturgeon skin collagen]
The fish skin-derived collagen thus obtained, that is, sturgeon skin collagen, has sufficient functions as collagen and is colorless and transparent and odorless.
Specifically, the fat and oil content is 0.3% by weight or less. Preferably it is 0.15 weight% or less.

波長400nmにおける光線透過率が85%以上である。好ましくは90〜100%である。
このような魚皮由来コラーゲンは、通常の魚ゼラチンあるいは牛骨ゼラチンなどと同様にして、各種用途に利用することができる。具体的には、食品用のほか、化粧品用、写真用などが挙げられる。
魚皮由来コラーゲンは、水溶液の状態で供給することもできるし、乾燥させた固形分からなる粉粒の状態で供給することもできる。魚皮由来コラーゲンからコラーゲンスポンジを製造して、各種用途に提供することもできる。
The light transmittance at a wavelength of 400 nm is 85% or more. Preferably it is 90 to 100%.
Such fish skin-derived collagen can be used in various applications in the same manner as normal fish gelatin or beef bone gelatin. Specific examples include foods, cosmetics, and photographs.
The fish skin-derived collagen can be supplied in the form of an aqueous solution, or can be supplied in the form of powder particles comprising a dried solid content. Collagen sponges can be produced from fish skin-derived collagen and provided for various uses.

魚皮由来コラーゲンを原料にして、コラーゲンペプチドを製造することもできる。コラーゲンペプチドは、魚皮由来コラーゲンを蛋白質分解酵素で分解処理することで得られる。得られたコラーゲンペプチドは、透明性が高く、臭いもないので、飲食品、化粧品、医薬品などに有効に利用できる。
〔化学修飾〕
魚皮由来コラーゲンに、化学修飾を施すことができる。化学修飾の具体的手段や処理条件は、通常の化学修飾コラーゲンの製造技術が適用される。
化学修飾の具体例として、コハク化、フタル化、メチルエステル化等が挙げられ、特公昭62−44522号公報や特公平5−79046号公報等に記載の化学修飾技術が適用できる。化学修飾を施すことにより、弱酸性から中性で溶解可能にできる。ヒアルロン酸やエタノール等の各種化粧品原料との相溶性も改善できる。化学修飾された魚皮由来コラーゲンは、化粧品用途等に特に好適に用いることができる。
Collagen peptides can also be produced using fish skin-derived collagen as a raw material. The collagen peptide is obtained by decomposing fish skin-derived collagen with a proteolytic enzyme. The obtained collagen peptide is highly transparent and has no odor, so that it can be effectively used for foods, drinks, cosmetics, pharmaceuticals and the like.
[Chemical modification]
Chemical modification can be applied to fish skin-derived collagen. As a specific means of chemical modification and processing conditions, a normal technology for producing chemically modified collagen is applied.
Specific examples of the chemical modification include succination, phthalation, methyl esterification and the like, and the chemical modification techniques described in JP-B-62-44522 and JP-B-5-79046 can be applied. By applying chemical modification, it can be dissolved from weakly acidic to neutral. Compatibility with various cosmetic raw materials such as hyaluronic acid and ethanol can also be improved. Chemically modified fish skin-derived collagen can be particularly suitably used for cosmetic applications and the like.

〔化粧料組成物〕
コラーゲンが有する特性や機能が必要とされる各種化粧品あるいは化粧品を製造するための中間製品となる化粧料組成物に、魚皮由来コラーゲンを配合しておくことができる。
化粧料として、皮膚化粧料、毛髪化粧料、口紅などが挙げられる。
魚皮由来コラーゲン以外に化粧料組成物に添加される成分の具体例として、ツバキ油などの油脂類、ラウリン酸などの脂肪酸類、エタノールなどのアルコール類、ビタミンCなどのビタミン類、システインなどのアミノ酸類、アロエなどの植物生薬類、シルク蛋白などの動物系成分、海洋深層水などの海洋成分、顔料、紫外線吸収/遮断剤、抗炎症剤、グリセリンなどの保湿剤、香料などが挙げられる。
[Cosmetic composition]
Collagen derived from fish skin can be added to various cosmetics that require the properties and functions of collagen or cosmetic compositions that are intermediate products for producing cosmetics.
Examples of cosmetics include skin cosmetics, hair cosmetics, and lipsticks.
Specific examples of ingredients added to the cosmetic composition other than collagen derived from fish skin include fats and oils such as camellia oil, fatty acids such as lauric acid, alcohols such as ethanol, vitamins such as vitamin C, cysteine, etc. Examples include herbal medicines such as amino acids, aloe, animal components such as silk protein, marine components such as deep sea water, pigments, ultraviolet absorption / blocking agents, anti-inflammatory agents, humectants such as glycerin, and fragrances.

公知の化粧品処方(例えば、特開2003−327599号公報に記載されている化粧品処方)において、そこに配合されているコラーゲンの代わり、あるいは、それに加えて、本発明の魚皮由来コラーゲンを配合しておくことが有効である。   In a known cosmetic formulation (for example, a cosmetic formulation described in Japanese Patent Application Laid-Open No. 2003-327599), the fish skin-derived collagen of the present invention is blended in place of or in addition to the collagen blended therein. It is effective to keep it.

以下、実施例および比較例によって本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。以下では、便宜上、「重量部」を単に「部」、「重量%」を単に「%」、「リットル」を単に「L」と記すことがある。
〔実施例〕
湿重量で10kgの新鮮なチョウザメの魚皮を15℃以下の水で3回水洗し、次いで、10%塩化ナトリウム水溶液50L中で24時間撹拌した後に魚皮を分離するという操作を3回繰り返すことにより、血液などの夾雑物を除去した。
血液などの夾雑物を除去後、水洗を行ない、5℃のエタノール20L中で48時間撹拌した後に魚皮を分離、水洗することにより脱脂処理を行い、前処理済み魚皮を得た。脱脂処理後の魚皮に残存する油脂分含有量は0.12%であった。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to these Examples. Hereinafter, for convenience, “parts by weight” may be simply referred to as “parts”, “weight%” may be simply referred to as “%”, and “liter” may be simply referred to as “L”.
〔Example〕
Repeat the operation of washing 10 kg of fresh sturgeon fish skin in wet weight 3 times with water below 15 ° C., then stirring the mixture in 50 L of 10% aqueous sodium chloride solution for 24 hours and then separating the fish skin 3 times. Thus, contaminants such as blood were removed.
After removing contaminants such as blood, washing with water was performed in 20 L of ethanol at 5 ° C. for 48 hours, and then the fish skin was separated and washed with water to obtain a pretreated fish skin. The fat content remaining in the fish skin after the degreasing treatment was 0.12%.

乾燥重量で2kgの前記前処理済み魚皮をpH2.2の塩酸溶液100L中に3時間浸漬し、魚皮を膨張させた。その後、高速ホモジナイザー(日本特殊機化製)を用いて7000rpm×60分間の条件で前記魚皮を破砕し、これに、ペプシン(天野エンザイム製)20gを加え、撹拌機にて撹拌しながら48時間反応させることにより、酵素処理を行なった。次いで、前記酵素処理で得られた溶液を6000rpm×2L/分の条件で連続遠心し、可溶性コラーゲンを含む上澄み液を回収した。
得られた上澄み液に、水酸化ナトリウムを加えてpHを7.4に調整した後、6000rpm×2L/分の条件で連続遠心して、粗製コラーゲン線維を回収した。前記粗製コラーゲン線維を、精製水100Lに溶解させ、pHを7.4に調整した後、6000rpm×2L/分の条件で連続遠心する操作を3回繰り返すことにより、油脂分0.09重量%の精製コラーゲン線維を得た。得られた精製コラーゲン線維を濃度0.3%の塩酸溶液に調製し、ソジウムドデシルサルフェイト―ポリアクリルアミドゲル電気泳動(以下、「SDS−page」と略記する)、アミノ酸分析、比旋光度を測定したところ、コラーゲン特有の電気泳動パターンおよびアミノ酸分析値を示し、比旋光度は−398.3°、変性温度は24.6℃であり、得られた精製コラーゲン線維がコラーゲンへリックス構造を保持していることが確認された。
2 kg of the pretreated fish skin by dry weight was immersed in 100 L of hydrochloric acid solution of pH 2.2 for 3 hours to expand the fish skin. Thereafter, the fish skin was crushed using a high-speed homogenizer (manufactured by Nippon Koki Co., Ltd.) under the conditions of 7000 rpm × 60 minutes, 20 g of pepsin (manufactured by Amano Enzyme) was added thereto, and the mixture was stirred with a stirrer for 48 hours. Enzyme treatment was performed by reacting. Next, the solution obtained by the enzyme treatment was continuously centrifuged under conditions of 6000 rpm × 2 L / min, and a supernatant containing soluble collagen was collected.
After adding sodium hydroxide to the obtained supernatant liquid and adjusting pH to 7.4, it centrifuged continuously on the conditions of 6000 rpm x 2 L / min, and collect | recovered crude collagen fibers. The crude collagen fibers were dissolved in 100 L of purified water, adjusted to pH 7.4, and then continuously centrifuged three times under the condition of 6000 rpm × 2 L / min, whereby the fat and oil content was 0.09 wt%. Purified collagen fibers were obtained. The obtained purified collagen fibers were prepared in a hydrochloric acid solution having a concentration of 0.3%, and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (hereinafter abbreviated as “SDS-page”), amino acid analysis, and specific rotation were performed. As a result of measurement, it showed an electrophoresis pattern and amino acid analysis value peculiar to collagen, specific rotation was -398.3 °, denaturation temperature was 24.6 ° C, and the obtained purified collagen fiber retained the collagen helix structure. It was confirmed that

〔比較例〕
湿重量で10kgの新鮮なチョウザメの魚皮を15℃以下の水で3回水洗し、次いで、10%塩化ナトリウム水溶液50L中で24時間撹拌した後に魚皮を分離するという操作を3回繰り返すことにより、血液などの夾雑物を除去した。
血液などの夾雑物を除去後、水洗を行ない、5℃のエタノール20L中で4時間撹拌した後に魚皮を分離、水洗することにより脱脂処理を行い、前処理済み魚皮を得た。脱脂処理後の魚皮に残存する油脂分含有量は3.2%であった。
乾燥重量で2kgの前記前処理済み魚皮をpH2.2の塩酸溶液100L中に3時間浸漬し、魚皮を膨張させた。その後、高速ホモジナイザー(日本特殊機化製)を用いて7000rpm×60分間の条件で前記魚皮を破砕し、これに、ペプシン(天野エンザイム製)20gを加え、撹拌機にて撹拌しながら48時間反応させることにより、酵素処理を行なった。次いで、前記酵素処理で得られた溶液を6000rpm×2L/分の条件で連続遠心し、可溶性コラーゲンを含む上澄み液を回収した。
[Comparative example]
Repeat the operation of washing 10 kg of fresh sturgeon fish skin in wet weight 3 times with water below 15 ° C., then stirring the mixture in 50 L of 10% aqueous sodium chloride solution for 24 hours and then separating the fish skin 3 times. Thus, contaminants such as blood were removed.
After removing contaminants such as blood, washing with water was performed in 20 L of ethanol at 5 ° C. for 4 hours, and then the fish skin was separated and washed with water to obtain a pretreated fish skin. The fat content remaining in the fish skin after the degreasing treatment was 3.2%.
2 kg of the pretreated fish skin by dry weight was immersed in 100 L of hydrochloric acid solution of pH 2.2 for 3 hours to expand the fish skin. Thereafter, the fish skin was crushed using a high-speed homogenizer (manufactured by Nippon Koki Co., Ltd.) under the conditions of 7000 rpm × 60 minutes, 20 g of pepsin (manufactured by Amano Enzyme) was added thereto, and the mixture was stirred with a stirrer for 48 hours. Enzyme treatment was performed by reacting. Next, the solution obtained by the enzyme treatment was continuously centrifuged under conditions of 6000 rpm × 2 L / min, and a supernatant containing soluble collagen was collected.

得られた上澄み液に、水酸化ナトリウムを加えてpHを7.4に調整した後、6000rpm×2L/分の条件で連続遠心して、粗製コラーゲン線維を回収した。前記粗製コラーゲン線維を、精製水100Lに溶解させ、pHを7.4に調整した後、6000rpm×2L/分の条件で連続遠心する操作を3回繰り返すことにより、油脂分2.6重量%の精製コラーゲン線維を得た。得られた精製コラーゲン線維を濃度0.3%の塩酸溶液に調製し、ソジウムドデシルサルフェイト―ポリアクリルアミドゲル電気泳動(以下、「SDS−page」と略記する)、アミノ酸分析、比旋光度を測定したところ、コラーゲン特有の電気泳動パターンおよびアミノ酸分析値を示し、比旋光度は−364.3°、変性温度は24.8℃であり、得られた精製コラーゲン線維がコラーゲンへリックス構造を保持していることが確認された。   After adding sodium hydroxide to the obtained supernatant liquid and adjusting pH to 7.4, it centrifuged continuously on the conditions of 6000 rpm x 2 L / min, and collect | recovered crude collagen fibers. The crude collagen fiber was dissolved in 100 L of purified water, pH was adjusted to 7.4, and then continuously centrifuged at 6000 rpm × 2 L / min three times to obtain 2.6% by weight of fat and oil. Purified collagen fibers were obtained. The obtained purified collagen fibers were prepared in a hydrochloric acid solution having a concentration of 0.3%, and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (hereinafter abbreviated as “SDS-page”), amino acid analysis, and specific rotation were performed. As a result of measurement, it showed an electrophoresis pattern and amino acid analysis value peculiar to collagen, specific rotation was −364.3 °, denaturation temperature was 24.8 ° C., and the resulting purified collagen fiber retained the collagen helix structure. It was confirmed that

〔性能評価試験〕
光線透過率:0.3%コラーゲン溶液を調製し、波長400nmの光線に対する透過率を、分光光度計を用いて測定した。
臭い:0.3%コラーゲン溶液を調製し、5名のモニターが臭いを嗅いで、5段階で評価した。数値が大きいほど、臭いが強いことを表す。
〔測定結果〕
表1に試験結果を示す。
[Performance evaluation test]
Light transmittance: A 0.3% collagen solution was prepared, and the transmittance for light having a wavelength of 400 nm was measured using a spectrophotometer.
Odor: A 0.3% collagen solution was prepared, and five monitors sniffed the odor and evaluated it in five stages. The larger the value, the stronger the odor.
〔Measurement result〕
Table 1 shows the test results.

Figure 2009057327
Figure 2009057327

〔評価〕
表1を見ると、本発明にかかる方法により製造した実施例の魚皮由来コラーゲンは波長400nmにおける光線透過率が85%以上であって、本発明にかかる魚皮由来コラーゲンが満たすべき条件を具備しており、無色透明・無臭であるので、後述の化粧料組成物に好適に使用することができる。
一方、脱脂が十分に行なわれていない比較例の魚皮由来コラーゲンは、波長400nmにおける光線透過率が85%未満でにごりがあり、また、魚特有の臭いがあるため、化粧料組成物に使用し難いものである。
[Evaluation]
When Table 1 is seen, the fish skin origin collagen of the Example manufactured by the method concerning this invention has the light transmittance in wavelength 400nm or more 85%, Comprising: The conditions which the fish skin origin collagen concerning this invention should satisfy | fill Since it is colorless and transparent and odorless, it can be suitably used in a cosmetic composition described later.
On the other hand, the collagen derived from the fish skin of the comparative example, which has not been sufficiently degreased, has a light transmittance at a wavelength of 400 nm of less than 85%, and has a smell peculiar to fish, so it is used in a cosmetic composition. It is difficult to do.

〔化粧料組成物〕
上記実施例で得られた本発明の魚皮由来コラーゲンを用い、以下に示す配合で化粧料組成物を得た。なお、配合割合を示す各数値は、重量%を表す。
<配合例>
スクワラン 8.0
ホホバ油 7.0
セチルアルコール 1.5
グリセリンモノステアレート 2.0
ポリオキシエチレン(20)セチルエーテル 3.0
ポリオキシエチレン(20)ソオルビタンモノオレート 2.0
1,3-ブチレングリコール 1.0
グリセリン 2.0
コラーゲン液 10.0
防腐剤(パラオキシ安息香酸エステル) 適量
精製水 各成分の合計量を100としたときの残余
[Cosmetic composition]
Using the fish skin-derived collagen of the present invention obtained in the above examples, a cosmetic composition was obtained with the formulation shown below. In addition, each numerical value which shows a compounding ratio represents weight%.
<Formulation example>
Squalane 8.0
Jojoba oil 7.0
Cetyl alcohol 1.5
Glycerol monostearate 2.0
Polyoxyethylene (20) cetyl ether 3.0
Polyoxyethylene (20) soorbitan monooleate 2.0
1,3-butylene glycol 1.0
Glycerin 2.0
Collagen fluid 10.0
Preservative (paraoxybenzoic acid ester) Appropriate amount Purified water Residue when the total amount of each component is 100

本発明の魚皮由来コラーゲンは、例えば、化粧料組成物に配合し、皮膚用化粧品に利用することで、保湿機能やシワ防止機能、老化防止機能などを良好に発揮できるとともに、従来における魚皮由来コラーゲンの欠点であった、にごりや臭いなど化粧品にとって好ましくないとされる問題も解消できる。   The fish skin-derived collagen of the present invention can be used in skin cosmetics, for example, by blending it in a cosmetic composition, and thereby exhibiting a moisturizing function, an anti-wrinkle function, an anti-aging function, etc. It is possible to solve problems that are undesirable for cosmetics, such as dust and odor, which are disadvantages of the collagen derived from the collagen.

Claims (4)

魚皮から抽出されてなるコラーゲンであって、
前記魚皮がチョウザメの皮であり、
油脂分が0.3重量%以下であり、
波長400nmにおける光線透過率が85%以上である、
魚皮由来コラーゲン。
Collagen extracted from fish skin,
The fish skin is sturgeon skin,
The fat and oil content is 0.3% by weight or less,
The light transmittance at a wavelength of 400 nm is 85% or more.
Collagen derived from fish skin.
化学修飾が施されてなる、請求項1に記載の魚皮由来コラーゲン。   The fish skin-derived collagen according to claim 1, which is chemically modified. 請求項1または2に記載の魚皮由来コラーゲンを、全体量の0.001〜100重量%含む、化粧料組成物。   A cosmetic composition comprising 0.001 to 100% by weight of the whole amount of the collagen derived from the fish skin according to claim 1 or 2. 請求項1または2に記載の魚皮由来コラーゲンを得る方法であって、
前記魚皮としてチョウザメの皮を用い、油脂分0.3重量%以下に脱脂する工程(a)と、
前記脱脂後のチョウザメの皮に対して、酵素による可溶化に基づく抽出処理を行なって、水溶性コラーゲンを含む抽出液を得る工程(b)と、
を含む魚皮由来コラーゲンの製造方法。
A method for obtaining fish skin-derived collagen according to claim 1 or 2,
Using the skin of sturgeon as the fish skin, degreasing the fat and oil to 0.3% by weight or less (a);
A step (b) of obtaining an extract containing water-soluble collagen by performing an extraction treatment based on solubilization with an enzyme on the skin of the sturgeon after defatting;
A method for producing fish skin-derived collagen, comprising:
JP2007226538A 2007-08-31 2007-08-31 Fish-skin-derived collagen, cosmetic composition, and method for producing the fish-skin-derived collagen Pending JP2009057327A (en)

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JP2013014529A (en) * 2011-07-01 2013-01-24 Hokkaido Univ Type ii collagen obtained from notochord of sturgeons by simple extraction method
KR101339423B1 (en) 2011-12-12 2013-12-10 유은경 cosmetic composition having collagen derived from fishes and manufacturing method thereof
JP2014136676A (en) * 2013-01-15 2014-07-28 Tokyo Institute Of Technology Collagen-containing composition
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CN110128530A (en) * 2019-05-31 2019-08-16 湖北清江鲟龙渔业有限公司 The technique for extracting collagen using sturgeon raw material
CN113528602A (en) * 2021-06-03 2021-10-22 山东农业大学 Salmon skin polypeptide extraction method and application

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CN102242172A (en) * 2010-05-10 2011-11-16 上海海健堂生物科技有限公司 Method for extracting fish collagen from fish skin
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CN113528602A (en) * 2021-06-03 2021-10-22 山东农业大学 Salmon skin polypeptide extraction method and application

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