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JP2707166B2 - Sponge gel and its manufacturing method - Google Patents
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JP2707166B2 - Sponge gel and its manufacturing method - Google Patents

Sponge gel and its manufacturing method

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Publication number
JP2707166B2
JP2707166B2 JP3162407A JP16240791A JP2707166B2 JP 2707166 B2 JP2707166 B2 JP 2707166B2 JP 3162407 A JP3162407 A JP 3162407A JP 16240791 A JP16240791 A JP 16240791A JP 2707166 B2 JP2707166 B2 JP 2707166B2
Authority
JP
Japan
Prior art keywords
chitosan
protein
gel
mixture
sponge
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.)
Expired - Fee Related
Application number
JP3162407A
Other languages
Japanese (ja)
Other versions
JPH05255596A (en
Inventor
尚之 塙
紹明 西谷
Original Assignee
雪印乳業 株式会社
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.)
Filing date
Publication date
Application filed by 雪印乳業 株式会社 filed Critical 雪印乳業 株式会社
Priority to JP3162407A priority Critical patent/JP2707166B2/en
Publication of JPH05255596A publication Critical patent/JPH05255596A/en
Application granted granted Critical
Publication of JP2707166B2 publication Critical patent/JP2707166B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Biological Depolymerization Polymers (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Jellies, Jams, And Syrups (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

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

【0001】[0001]

【産業上の利用分野】本発明は、スポンジ状ゲルに関
し、さらに詳しくは食品、ショック吸収材、吸水材など
広い分野に応用可能なスポンジ状多孔質体に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sponge-like gel, and more particularly to a sponge-like porous material applicable to a wide range of fields such as foods, shock absorbers, and water absorbing materials.

【0002】[0002]

【従来の技術】従来、蛋白質とキトサンを組み合わせた
技術としては、乳蛋白質とキトサンを水中に含有さ
せ、pH調整し、加熱処理する方法(特開昭63-169939)、
キトサンにコラーゲンを添加しスポンジ状に成形後、
アシル化する方法(特開昭62-238209)が知られている。
しかし、本発明のように、蛋白質とキトサンの複合体を
凍結処理によりゲル化させる技術は未だ報告されていな
い。
2. Description of the Related Art Conventionally, as a technique combining protein and chitosan, a method in which milk protein and chitosan are contained in water, pH is adjusted and heat treatment is carried out (JP-A-63-169939),
After adding collagen to chitosan and forming it into a sponge,
A method for acylation (JP-A-62-238209) is known.
However, a technique for gelling a complex of protein and chitosan by freeze treatment as in the present invention has not yet been reported.

【0003】すなわち、の方法は、加熱処理により得
られる沈澱物は、乳蛋白質とキトサンの複合体の凝集物
であり、また、これを噴霧乾燥または凍結乾燥により乾
燥しその部分的脱水物または粉末を得ることができる
が、本発明のようにスポンジ状ゲルを提供するものでは
ない。また、に用いられるコラーゲンは、蛋白質では
あるが、構成アミノ酸がグリシン、プロリン、ヒドロキ
シプロリン、アラニンに限られているためキトサンとの
反応性は殆どない。即ちの方法はキトサンをアシル化
することにより不溶性のスポンジ状物をつくる技術であ
り、コラーゲンはその補強剤として用いられているにす
ぎない。この方法では、キトサンの酸溶液にコラーゲン
を加え、これを凍結乾燥する等によってスポンジ状の成
形物を調製し、次いでアシル化を行う必要があるため、
多量のアシル化剤を用いる必要があり、化粧用材料とし
て好適であるが、食品用としては利用し難い、という問
題があった。
According to the method, the precipitate obtained by the heat treatment is an aggregate of a complex of milk protein and chitosan, and this is dried by spray drying or freeze drying to obtain a partially dehydrated product or powder thereof. Can be obtained, but does not provide a sponge-like gel as in the present invention. Collagen used is a protein, but has little reactivity with chitosan because its constituent amino acids are limited to glycine, proline, hydroxyproline and alanine. In other words, the method is a technique for producing an insoluble sponge-like material by acylating chitosan, and collagen is only used as a reinforcing agent. In this method, it is necessary to add a collagen to an acid solution of chitosan, prepare a sponge-like molded product by freeze-drying or the like, and then perform acylation.
It is necessary to use a large amount of an acylating agent, which is suitable as a cosmetic material, but has a problem that it is difficult to use it for food.

【0004】[0004]

【発明が解決しようとする課題】本発明はアシル化など
の化学合成を行うことなく、食品分野を始め広い分野に
応用できるキトサンのスポンジ状ゲルを提供することを
課題とする。
SUMMARY OF THE INVENTION An object of the present invention is to provide a chitosan sponge-like gel which can be applied to a wide range of fields including the food field without performing chemical synthesis such as acylation.

【0005】[0005]

【課題を解決するための手段】本発明は、大豆蛋白質、
ホエー蛋白質またはカゼインから選択される蛋白質、キ
トサン、および水を酸性下に混合し、次いで中和するこ
とにより均一に混合し、得られた粘稠な混合物を、さら
に凍結処理して得られるスポンジ状ゲルである。また本
発明は、前記原料を酸性下に混合し、次いで中和するこ
とにより均一に混合し、得られた粘稠な混合物を、さら
に凍結処理するスポンジ状ゲルの製造法である。
The present invention provides a soy protein,
A protein selected from whey protein or casein , chitosan, and water are mixed under acidic conditions, then neutralized and uniformly mixed, and the resulting viscous mixture is further sponge-formed by freezing. It is a gel. The present invention is also a method for producing a sponge-like gel in which the raw materials are mixed under acidic conditions and then neutralized to uniformly mix the resulting viscous mixture, followed by freezing.

【0006】本発明に用いる蛋白質は、キトサンとの反
応性の高いものであれば全て用いることができるが、大
豆蛋白質、ホエー蛋白質、カゼインが好ましいものとし
て挙げられる。これらの蛋白質を予め加熱変性させ、補
助的にゲル強度を上げることもできる。ここでいうカゼ
インとは、牛乳、脱脂粉乳、カゼインソーダ等の乳製品
を含む。キトサンとの反応性の低いコラーゲン、卵白ア
ルブミンは本発明に用いることはできない。反応性の高
い蛋白質は、1種又は2種以上を用いることができる。
As the protein used in the present invention, any protein having high reactivity with chitosan can be used, but soy protein, whey protein and casein are preferred. These proteins can be denatured by heating in advance to increase the gel strength. Here, casein includes dairy products such as milk, skim milk powder, and casein soda. Collagen with low reactivity with chitosan, ovalbumin, cannot be used in the present invention. One or more of the highly reactive proteins can be used.

【0007】本発明では、キトサンと蛋白質を水に均一
に混合し、複合体とすることが肝要である。そのために
は、キトサンを酸に溶解し、蛋白質と酸性下に混合し、
次いで中和を行うことが望ましい。中和を行わないと凍
結処理してもゲル化を起こすことがなく、予め中和剤を
キトサンと蛋白質に加えると部分的な凝集物が生じ、均
一に混合することが困難となる。用いる酸としてはキト
サンを溶解し得るものであれば全て用いることができる
が、好ましいものとして、酢酸、乳酸、クエン酸、塩酸
などが挙げられる。pHはキトサンを溶解できる程度に調
整する。蛋白質を混合する際のpHは5.5 以下、好ましく
は4.8 以下が望ましい。pHが5.5 を超えるとキトサンの
溶解が充分に行われず、蛋白質とキトサンを均一に混合
することが困難となる。
In the present invention, it is important to mix chitosan and protein uniformly in water to form a complex. To do this, chitosan is dissolved in acid, mixed with protein under acidic conditions,
Next, it is desirable to perform neutralization. If the neutralization is not performed, gelation does not occur even by a freezing treatment, and if a neutralizing agent is added to chitosan and protein in advance, partial aggregates will be generated, making it difficult to mix uniformly. Any acid can be used as long as it can dissolve chitosan, but preferred examples include acetic acid, lactic acid, citric acid, and hydrochloric acid. Adjust the pH to such an extent that the chitosan can be dissolved. The pH at the time of mixing the proteins is desirably 5.5 or lower, preferably 4.8 or lower. If the pH exceeds 5.5, the chitosan is not sufficiently dissolved, and it becomes difficult to uniformly mix the protein and chitosan.

【0008】蛋白質の濃度としては1〜30重量%程度が
望ましく、1重量%よりも小さいとゲル化が不充分であ
り、30重量%を超えると蛋白質の溶解やキトサンとの混
合が困難となる。蛋白質100 重量部に対するキトサンの
割合は、蛋白質の種類や共存物によっても異なるが、10
〜300 重量部、好ましくは30〜200 重量部が望ましい。
10重量部よりも小さいとゲル化が起こらず、300 重量部
を超えるとキトサンを添加してもゲル強度は変化しな
い。
[0008] The concentration of the protein is preferably about 1 to 30% by weight, and if it is less than 1% by weight, gelation is insufficient, and if it exceeds 30% by weight, it becomes difficult to dissolve the protein or mix it with chitosan. . The ratio of chitosan to 100 parts by weight of protein varies depending on the type of protein and its coexisting substances.
It is desirable that the amount be from 300 to 300 parts by weight, preferably from 30 to 200 parts by weight.
If it is less than 10 parts by weight, gelling does not occur, and if it exceeds 300 parts by weight, the gel strength does not change even if chitosan is added.

【0009】中和剤としては適当なアルカリ化剤を用い
れば良いが、水酸化ナトリウム、重曹、炭酸カルシウ
ム、水酸化カルシウム等が例示できる。本発明では上記
中和後の粘調な混合物を凍結処理する。凍結を行う前は
混合物はゾル状であり、形を持たないのに対し、凍結・
解凍後では、非常に弾力性のあるスポンジ状ゲル化物と
なる。凍結によりゲル化する理由としては、不明な部分
が多いが、キトサンと蛋白質との反応による複合体が凍
結による変性を受け、氷晶による凍結濃縮と結合部位の
固定化が起こり、不溶性の多孔質体が形成するためと推
察される。
As the neutralizing agent, an appropriate alkalizing agent may be used, and examples thereof include sodium hydroxide, sodium bicarbonate, calcium carbonate, calcium hydroxide and the like. In the present invention, the viscous mixture after the neutralization is frozen. Before freezing, the mixture is in the form of a sol and has no shape.
After thawing, it becomes a very elastic spongy gel. There are many unknown reasons for gelation due to freezing, but the complex due to the reaction between chitosan and protein undergoes denaturation due to freezing, freeze concentration by ice crystals and immobilization of the binding site occur, and insoluble porous It is presumed that the body forms.

【0010】このゲル化物はそのまま調理し、高野豆腐
のように食品として用いたり、乾燥して衝撃吸収材や吸
水材として用いることが出来る。乾燥方法としては、熱
風乾燥、凍結乾燥、マイクロウェーブ乾燥などが例示で
き、特に限定はされない。
This gelled product can be cooked as it is and used as food like Takano tofu, or dried and used as a shock absorbing material or water absorbing material. Examples of the drying method include hot air drying, freeze drying, and microwave drying, and are not particularly limited.

【0011】[0011]

【発明の効果】本発明によれば、蛋白質とキトサンを混
合し凍結処理することにより、アシル化等の化学処理を
することなく不溶性のスポンジ状ゲルが得られるので、
食品や衝撃吸収材など幅広い分野に応用することができ
る。また、天然物のみを用い、特殊な化学合成を行わな
いので安全性が高く、生分解性が良く公害とならず、さ
らに可燃性にも優れる素材を提供することができる。
According to the present invention, an insoluble sponge-like gel can be obtained by mixing a protein with chitosan and subjecting the mixture to a freezing treatment without performing a chemical treatment such as acylation.
It can be applied to a wide range of fields such as foods and shock absorbers. Further, since only natural products are used and no special chemical synthesis is performed, a material having high safety, good biodegradability, no pollution, and excellent flammability can be provided.

【0012】[0012]

【実施例】次に実施例を用い、本発明を具体的に説明す
る。 〔原料蛋白質の違いによるゲル強度の違い〕ISP(分
離大豆蛋白質)2.5g、水95.1g、キトサン(脱アセチル
化度75%)1.2g、乳酸1.2gをホモゲナイザーで均一に混
合した。次いで重曹0.8gを添加し、さらに混合し粘調な
混合物を得た。この時のpHは6.4 であった。この混合物
を−20℃で一夜静置し凍結処理を行った。
Next, the present invention will be specifically described with reference to examples. [Difference in gel strength due to difference in raw protein] 2.5 g of ISP (isolated soybean protein), 95.1 g of water, 1.2 g of chitosan (75% deacetylation degree), and 1.2 g of lactic acid were uniformly mixed with a homogenizer. Next, 0.8 g of sodium bicarbonate was added and further mixed to obtain a viscous mixture. At this time, the pH was 6.4. This mixture was allowed to stand at −20 ° C. overnight to perform a freezing treatment.

【0013】比較のためWPC(ホエー蛋白質濃縮物)
および卵白アルブミンをISPの代わりに用い、同様に
操作した。得られたゲルは25℃に解凍後、レオメーター
によりゲル強度の測定を行った。測定は直径5mmの円盤
型プランジャーを6cm/minで突入させた時の応力を測る
ことにより行った。
For comparison, WPC (whey protein concentrate)
And ovalbumin were used in place of the ISP, and operated in the same manner. After the obtained gel was thawed at 25 ° C., the gel strength was measured with a rheometer. The measurement was performed by measuring the stress when a disk-type plunger having a diameter of 5 mm was inserted at 6 cm / min.

【0014】下表に示すように、ISP、WPC、カゼ
インを用いたものが、ゲル強度を有し、ISPを用いた
ものが最もゲル強度が高かった。
As shown in the table below, those using ISP, WPC and casein had gel strength, and those using ISP had the highest gel strength.

【0015】[0015]

【表1】 得られたISPのゲルはスポンジ状のゲルとなり、マイ
クロウェーブにより乾燥すると気孔率の極めて高いクッ
ション状の多孔質体となった。 〔蛋白質−キトサン複合体ゲルの必須条件の検討〕下記
表に示したように、蛋白質を使用せずに、キトサン、乳
酸、重曹のうち、1つ以上を除いた全ての組み合わせで
サンプルを調製し、凍結解凍後ゲル化の有無を調べた。
なお、キトサン、乳酸、重曹については添加順序の影響
も併せて検討した。用いた原料の割合は重量%で示す。
[Table 1] The obtained ISP gel became a sponge-like gel, and when dried by microwave, became a cushion-like porous body having extremely high porosity. [Examination of essential conditions for protein-chitosan complex gel] As shown in the table below, samples were prepared in all combinations except for one or more of chitosan, lactic acid and baking soda without using proteins. After freezing and thawing, the presence or absence of gelation was examined.
The effects of the order of addition of chitosan, lactic acid, and baking soda were also examined. The proportions of the raw materials used are shown in% by weight.

【0016】[0016]

【表2】 *は最後に添
加したことを示す 表から明らかなように、蛋白質を使用しない場合、キト
サン、乳酸、重曹をいかに組み合わせても、全てゲル化
しなかった。
* Indicates that it was added last As is clear from the table, when no protein was used, no combination of chitosan, lactic acid and baking soda resulted in any gelling.

【0017】次に、表3、表4に示したように蛋白質
(ISP、WPC)を使用した他は、前記と同様にキト
サン、乳酸、重曹のうち、1つ以上を除いた全ての組み
合わせでサンプルを調製し、凍結解凍後、ゲル化の有無
を調べた。なお、同様に、キトサン、乳酸、重曹につい
て、添加順序の影響も検討した。
Next, as shown in Tables 3 and 4, all combinations except for one or more of chitosan, lactic acid and baking soda were used except that proteins (ISP, WPC) were used. Samples were prepared, freeze-thawed, and examined for gelation. Similarly, the influence of the order of addition on chitosan, lactic acid, and sodium bicarbonate was also examined.

【0018】[0018]

【表3】 *は最後に添加
したことを示す
* Indicates that it was added last

【0019】[0019]

【表4】 *は最後に添加
したことを示す 表3、表4より明らかなように、キトサン、乳酸、重曹
を全て用い、しかも重曹を最後に加えたもののみが、硬
いゲルとなった。
Table 4 * indicates last addition As is clear from Tables 3 and 4, only those using all of chitosan, lactic acid and baking soda and adding baking soda at the end gave a hard gel.

【0020】蛋白質としてカゼイン 2.5重量%を用いた
場合も上表と同様の結果であった。以上の結果より、蛋
白質、キトサン、乳酸を水と共に混合し、次いで重曹に
より中和することが複合体ゲルの調製に必須であるとい
える。
The same results as in the above table were obtained when 2.5% by weight of casein was used as the protein. From the above results, it can be said that mixing protein, chitosan, and lactic acid with water and then neutralizing with sodium bicarbonate is essential for preparing the composite gel.

フロントページの続き (56)参考文献 特開 昭56−131639(JP,A) 特開 昭63−287447(JP,A) 特公 昭46−10022(JP,B1)Continuation of the front page (56) References JP-A-56-131639 (JP, A) JP-A-62-287447 (JP, A) JP-B-46-10022 (JP, B1)

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 大豆蛋白質、ホエー蛋白質またはカゼイ
ンから選択される蛋白質、キトサン、および水を酸性下
に混合し、次いで中和することにより均一に混合し、得
られた粘稠な混合物を、さらに凍結処理して得られるス
ポンジ状ゲル。
1. A soybean protein, whey protein or casey
A sponge-like gel obtained by mixing a protein selected from the group , chitosan, and water under acidic conditions, and then neutralizing the mixture to uniformly mix the mixture, and then subjecting the resulting viscous mixture to a further freeze treatment.
【請求項2】 大豆蛋白質、ホエー蛋白質またはカゼイ
ンから選択される蛋白質、キトサン、および水を酸性下
に混合し、次いで中和することにより均一に混合し、得
られた粘稠な混合物を、さらに凍結処理するスポンジ状
ゲルの製造法。
2. Soy protein, whey protein or casey
A method for producing a sponge-like gel, comprising mixing a protein selected from the group , chitosan, and water under acidic conditions, and then neutralizing the mixture to uniformly mix the resulting mixture, followed by further freezing the resulting viscous mixture.
JP3162407A 1991-06-07 1991-06-07 Sponge gel and its manufacturing method Expired - Fee Related JP2707166B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3162407A JP2707166B2 (en) 1991-06-07 1991-06-07 Sponge gel and its manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3162407A JP2707166B2 (en) 1991-06-07 1991-06-07 Sponge gel and its manufacturing method

Publications (2)

Publication Number Publication Date
JPH05255596A JPH05255596A (en) 1993-10-05
JP2707166B2 true JP2707166B2 (en) 1998-01-28

Family

ID=15754022

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3162407A Expired - Fee Related JP2707166B2 (en) 1991-06-07 1991-06-07 Sponge gel and its manufacturing method

Country Status (1)

Country Link
JP (1) JP2707166B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3967731A1 (en) * 2020-09-09 2022-03-16 Xampla Limited Protein dispersions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56131639A (en) * 1980-03-21 1981-10-15 Kureha Chem Ind Co Ltd Protein-chitosan composition
JPH0648955B2 (en) * 1987-05-20 1994-06-29 南日本酪農協同株式会社 Milk protein complex manufacturing method

Also Published As

Publication number Publication date
JPH05255596A (en) 1993-10-05

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