JPH0651724B2 - Process for producing activated chitin and chitosan - Google Patents
Process for producing activated chitin and chitosanInfo
- Publication number
- JPH0651724B2 JPH0651724B2 JP60096681A JP9668185A JPH0651724B2 JP H0651724 B2 JPH0651724 B2 JP H0651724B2 JP 60096681 A JP60096681 A JP 60096681A JP 9668185 A JP9668185 A JP 9668185A JP H0651724 B2 JPH0651724 B2 JP H0651724B2
- Authority
- JP
- Japan
- Prior art keywords
- chitin
- chitosan
- pressure
- chitins
- softening treatment
- 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 - Lifetime
Links
- 229920002101 Chitin Polymers 0.000 title claims description 70
- 229920001661 Chitosan Polymers 0.000 title claims description 48
- 238000000034 method Methods 0.000 title description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000006835 compression Effects 0.000 description 14
- 238000007906 compression Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 238000010025 steaming Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 241000238421 Arthropoda Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000239366 Euphausiacea Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- -1 acetic acid Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-QZABAPFNSA-N beta-D-glucosamine Chemical compound N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-QZABAPFNSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、キチン及びキトサンに膨軟化処理を施すこと
により、化学薬品等との反応性に優れた活性化したキチ
ン及びキトサンを製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing activated chitin and chitosan excellent in reactivity with chemicals and the like by subjecting chitin and chitosan to a softening treatment.
従来の技術及び発明が解決しようとする問題点 キチンは、下記一般式(1) で表わされるＮ−アセチル化Ｄ−グルコサミンがβ−
１，４で結合したもので、節足動物、軟体動物などの有
機骨格物質として天然に存在し、また植物ではカビの菌
系や胞子に存在し、これから得ることができるものであ
る。例えば、カニ、エビ、オキアミなどの甲殻を原料と
する場合には、甲殻を塩酸で処理して炭酸カルシウムを
除き、さらに苛性ソーダで処理して蛋白質その他の夾雑
物を除去してから水洗、乾燥することによりキチンを得
ることができる。また、キチンから誘導されるキトサン
はキチンの脱アセチル化物であり、たとえばキチンをア
ルカリ処理することにより得ることができるものであ
る。Problems to be Solved by the Related Art and Invention Chitin is represented by the following general formula (1) The N-acetylated D-glucosamine represented by
It is a bond of 1, 4 and naturally exists as an organic skeletal substance of arthropods, molluscs and the like, and also exists in fungal strains and spores of plants, and can be obtained therefrom. For example, when the shell of crab, shrimp, krill, etc. is used as a raw material, the shell is treated with hydrochloric acid to remove calcium carbonate, further treated with caustic soda to remove proteins and other contaminants, and then washed and dried. By doing so, chitin can be obtained. Further, chitosan derived from chitin is a deacetylated product of chitin, and can be obtained, for example, by treating chitin with an alkali.
しかし、キチン及びキトサンはセルロースに類似した化
学構造を有し、天然界で生合成される量もセルロースに
匹敵する多糖類であるにもかかわらず、セルロースやそ
の他の多糖類に比べて化学工業的な利用度が極端に低い
のが実情である。これは、キチン及びキトサンは分子内
にそれぞれ存在するアミノアセチル基及びアミノ基の窒
素原子に由来する極めて強固な分子間力による結晶構造
を有するため、化学薬品に対する抵抗性がセルロース等
に比べてはるかに大きく、化学薬品との反応活性が著し
く低いことが大きな原因である。However, although chitin and chitosan have a chemical structure similar to that of cellulose and the amount of biosynthesized in the natural world is also a polysaccharide comparable to that of cellulose, it is more industrially chemical than cellulose and other polysaccharides. The reality is that such usage is extremely low. This is because chitin and chitosan have a very strong intermolecular force derived from the amino acetyl group and the nitrogen atom of the amino group existing in the molecule, respectively. The reason is that the reaction activity with chemicals is extremely low.
このため、キチン、キトサンを充分に溶解、分散或いは
膨潤させる溶剤や、反応条件の研究が遅れ、セルロース
その他の多糖類に比べてキチン、キトサンの利用度が極
めて低い原因となっていた。For this reason, research on a solvent for sufficiently dissolving, dispersing or swelling chitin and chitosan and reaction conditions has been delayed, which has been a cause of extremely low utilization of chitin and chitosan as compared with cellulose and other polysaccharides.
本発明は上記事情に鑑みなされたもので、化学薬品との
反応活性が高く、このためキチン及びキトサンを種々の
用途に有効に利用することができる活性化したキチン及
びキトサンの製造方法を提供することを目的とする。The present invention has been made in view of the above circumstances, and provides a method for producing activated chitin and chitosan, which has high reaction activity with chemicals and therefore can effectively utilize chitin and chitosan for various purposes. The purpose is to
問題点を解決するための手段及び作用 本発明者らは上記目的を達成するため鋭意研究を行った
結果、キチン若しくはキトサン又はこれらの混合物の含
水率を１０〜６０重量％に調整すると共に、これを１７
０℃以上の温度で８〜87.6kg／cm2の圧力において圧縮
蒸煮し、その後圧縮を急速に解除することにより、分子
間に存在する水分子の急激な膨張でキチン，キトサンの
分子間結合を部分的に切断して結晶構造を部分的に膨軟
破壊し、窒素原子に由来するキチン，キトサンの高結晶
性を物質内部から破壊してその反応活性を確実に高める
ことができ、キチン又はキトサンが膨軟化処理されて活
性化されることを知見し、本発明をなすに至ったもので
ある。Means and Actions for Solving Problems The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, while adjusting the water content of chitin or chitosan or a mixture thereof to 10 to 60% by weight, To 17
By compressing and steaming at a temperature of 0 ° C or higher at a pressure of 8 to 87.6 kg / cm 2 , and then rapidly releasing the compression, the intermolecular bonds of chitin and chitosan are caused by the rapid expansion of water molecules existing between the molecules. Chitin or chitosan can be cut to partially swell and soften the crystal structure, destroy the high crystallinity of chitin and chitosan derived from the nitrogen atom from inside the substance, and reliably enhance the reaction activity. The present inventors have made the present invention by finding that they are activated by being softened.
従って、本発明は、キチン若しくはキトサン又はこれら
の混合物の含水率を１０〜６０重量％に調整すると共
に、これを１７０℃以上の温度で８〜87.6kg／cm2の圧
力において圧縮蒸煮し、その後圧縮を急速に解除するこ
とにより、キチン又はキトサンを膨軟化処理して活性化
することを特徴とする活性化したキチン又はキトサンの
製造方法を提供する。Therefore, the present invention adjusts the water content of chitin or chitosan or a mixture thereof to 10 to 60% by weight, compresses and steams it at a temperature of 170 ° C. or higher at a pressure of 8 to 87.6 kg / cm 2 , and then Disclosed is a method for producing activated chitin or chitosan, which comprises activating the softening treatment of chitin or chitosan by rapidly releasing the compression.
以下、本発明につき更に詳しく説明する。Hereinafter, the present invention will be described in more detail.
本発明においては、キチン及びキトサンに膨軟化処理を
施すものであるが、この場合キチン及びキトサンの形状
は特に制限されない。例えば、粒径が数cmオーダーから
数mmオーダーのフレーク状であってもよく、また微粉砕
したパウダー状であってもよく、本発明によればどのよ
うな形状のキチン，キトサンをも良好に活性化すること
ができる。In the present invention, chitin and chitosan are subjected to softening treatment, but in this case, the shapes of chitin and chitosan are not particularly limited. For example, it may be in the form of flakes having a particle size of several cm to several mm, or may be in the form of finely pulverized powder. According to the present invention, any shape of chitin or chitosan can be satisfactorily used. Can be activated.
キチン，キトサンはエビやカニの甲殻等からハックマン
の方法に準じて得られるものを用いることができ、また
市販品を用いることもできる。ここで、市販のキチンと
しては南陽化成（株）製の「REGITEX-FX」等を、キトサ
ンとしては共和油脂工業（株）製の「フローナック−
Ｎ」等を挙げることができる。As chitin and chitosan, those obtained from shrimp or crab shells according to the Hackman method can be used, and commercially available products can also be used. Here, as commercially available chitin, "REGITEX-FX" manufactured by Nanyo Kasei Co., Ltd., and as chitosan, "Flownac-
N ”and the like.
また、膨軟化処理の方法としては、キチン若しくはキト
サン又はこれらの混合物（以下単に「キチン類」とい
う。）の含水率を１０〜６０％（重量％、以下同じ）に
調整すると共に、これを加圧状態で１７０℃以上の温度
に加熱して圧縮蒸煮した後、圧力を急激に低下させる
（圧縮を急速に解除する）方法が採用される。即ち、こ
のように加圧状態で加熱した後圧力を急激に低下させた
場合、原料物質の外側の圧力は急激に低下するが、物質
内部の圧力（主に水分に起因する水蒸気圧）はそのまま
残るので、原料物質の内部と外部との間に大きな圧力差
が生じ、その結果原料物質が内部より膨張して爆砕し、
その結晶構造が部分的に破壊されてキチン，キトサンが
活性化されるものである。In addition, as a method for the softening treatment, while adjusting the water content of chitin or chitosan or a mixture thereof (hereinafter simply referred to as “chitins”) to 10 to 60% (weight%, the same applies hereinafter), this is added. A method is employed in which, after heating in a pressure state to a temperature of 170 ° C. or higher and compression boiling, the pressure is rapidly reduced (compression is rapidly released). That is, when the pressure is drastically decreased after heating in a pressurized state in this way, the pressure outside the raw material is drastically decreased, but the pressure inside the material (mainly water vapor pressure due to water) remains unchanged. Since it remains, a large pressure difference occurs between the inside and outside of the raw material, and as a result the raw material expands from the inside and explodes,
The crystal structure is partially destroyed and chitin and chitosan are activated.
具体的には、まずキチン類に必要により水を添加してそ
の含水率を１０〜６０％、好ましくは３０〜５０％に調
整する。この場合、膨軟化処理において水は必須成分で
ある。膨軟化処理においては通常被処理物の含水率が５
〜９０％であることが必要であるが、本発明においては
１０〜６０％、特に３０〜５０％の含水率とすることが
好適である。含水率が１０％より低いと圧縮時のキチン
類の蒸煮が不充分となって圧縮蒸煮時にキチン類の炭化
等が生じ易いと共に、圧縮を急激に解除した後の膨軟破
壊が不充分になることがあり、また６０％より高いとキ
チン類の温度をコントロールすることが困難となり、適
正な膨軟破壊がなされないことがある。なお、キチン，
キトサンには通常５〜１５％の自由水が含まれているの
で場合によってはそのまま膨軟化処理することもできる
が、水を添加して含水率を上記好適範囲に調整してから
膨軟化処理を行うことが製造効率の点で好ましい。含水
率の調整は圧縮蒸煮工程の前に行なってもよく、また圧
縮蒸煮工程において系外から水分を導入することにより
行なってもよい。次に、キチン類をその含水率を上記範
囲（１０〜６０％）に保持した状態で１７０℃以上に加
熱すると共に圧縮してキチン類を蒸煮した後、圧縮を急
激に解除することにより、キチン，キトサンの組織を膨
軟破壊して活性化したキチン，キトサンを得るものであ
る。Specifically, first, if necessary, water is added to chitins to adjust the water content to 10 to 60%, preferably 30 to 50%. In this case, water is an essential component in the softening treatment. In the softening treatment, the water content of the object to be treated is usually 5
It is necessary to be 90%, but in the present invention, a water content of 10 to 60%, particularly 30 to 50% is preferable. If the water content is less than 10%, the chitins are insufficiently steamed during compression, carbonization of the chitins is likely to occur during compression steaming, and the expansion and contraction after the rapid release of compression is insufficient. If it is higher than 60%, it becomes difficult to control the temperature of chitins, and proper expansion, softening and fracture may not be achieved. In addition, chitin,
Since chitosan usually contains 5 to 15% of free water, it may be subjected to the softening treatment as it is depending on the case, but water is added to adjust the water content to the above-mentioned preferable range, and then the softening treatment is carried out. It is preferable to carry out in terms of production efficiency. The water content may be adjusted before the compression steaming step, or by introducing water from the outside of the system in the compression steaming step. Next, the chitins are heated to 170 ° C. or higher while keeping the water content in the above range (10 to 60%) and compressed to steam the chitins, and then the compression is rapidly released to obtain chitin. , Chitosan tissue is swelled and destroyed to obtain activated chitin and chitosan.
なお、圧縮蒸煮は適当な圧縮設備を有する気密に密閉さ
れた容器内で行なうが、この場合圧縮圧力は８〜８７．
６kg／cm2とする。また、キチン類の加熱は容器を加熱
することにより間接的に行なってもよく、また外部から
容器内に熱源を導入してこの熱源でキチン類を直接加熱
するようにしてもよく、後者の場合には含水率調整を兼
ねて容器内に水蒸気を導入してこの水蒸気でキチン類を
加熱することができる。更に、圧縮時に発生する機械的
摩擦熱で加熱することも可能である。ここで、上述した
ようにキチン類は170℃以上に加熱するもので、含水率
１０〜６０％の範囲でキチン類を170℃以上に加熱して
圧縮蒸煮することによりキチン，キトサンの組織を確実
に膨軟破壊することができるが、170℃未満、特に150℃
未満では充分な加圧ができないので組織の膨軟破壊が良
好に行われない。また、加熱温度の上限は３００℃（こ
の温度に相当する水蒸気圧は８７．６kg／cm2）であ
り、この温度を越えるとキチン類が変質するおそれがあ
り、また経済的メリットがない。The compression steaming is carried out in an airtightly sealed container equipped with an appropriate compression facility. In this case, the compression pressure is 8 to 87.
6 kg / cm 2 The heating of the chitins may be performed indirectly by heating the container, or a heat source may be introduced into the container from the outside to directly heat the chitins with the heat source. In the latter case For the purpose of adjusting the water content, steam can be introduced into the container to heat the chitins with the steam. Furthermore, it is also possible to heat with the mechanical frictional heat generated at the time of compression. Here, as described above, the chitins are heated to 170 ° C. or higher, and the chitin and chitosan tissues are surely heated by heating the chitins to 170 ° C. or higher and compressively steaming them in a water content range of 10 to 60%. Can be swelled and broken into less than 170 ℃, especially 150 ℃
If it is less than the above range, sufficient pressurization cannot be performed, so that the tissue does not swell and soften properly. Moreover, the upper limit of the heating temperature is 300 ° C. (the steam pressure corresponding to this temperature is 87.6 kg / cm 2 ), and if this temperature is exceeded, the chitins may be altered and there is no economic merit.
また、本発明における膨軟化処理方法としては、圧力容
器の中に含水率を１０〜６０％に調整したキチン類を入
れ、容器に蓋をして密閉した後、容器内のキチン類を加
熱し、加熱によって容器内の圧力が所定値（通常８〜２
０kg／cm2）に高まった時に蓋を開き、これにより原料
物質の外側の圧力を急激に低下させてキチン，キトサン
を膨軟化する方法も好適に採用される。Further, as the softening treatment method in the present invention, chitins having a water content adjusted to 10 to 60% are put in a pressure vessel, the vessel is covered and sealed, and then the chitins in the vessel are heated. , The pressure in the container is heated to a specified value (usually 8 to 2
A method in which the lid is opened when the pressure rises to 0 kg / cm 2 ) and thereby the pressure on the outer side of the raw material is drastically reduced to soften chitin or chitosan is also suitably adopted.
なお、上記方法により膨軟化処理を行なう場合、その装
置としては鶴見曹達（株）製の膨軟処理装置「プレスパ
ンダ」や、爆弾あられ製造機、ぽんせんべい製造機等を
用いことができる。When the softening treatment is carried out by the above-mentioned method, a softening treatment device “presspanda” manufactured by Tsurumi Soda Co., Ltd., a bomb hail maker, a ponsenbei maker, etc. can be used as the device.
本発明製造方法によって得られた活性化したキチン及び
キトサンは、種々の化学薬品に対する反応性が高く、種
々の用途に有効に使用される。例えば、水酸化ナトリウ
ム，水酸化カリウム等の塩基や、塩酸等の鉱酸，酢酸等
の有機酸などと容易に反応するため、これらとの反応化
合物を簡単に得ることができる。The activated chitin and chitosan obtained by the production method of the present invention have high reactivity to various chemical agents and are effectively used for various purposes. For example, since it easily reacts with a base such as sodium hydroxide and potassium hydroxide, a mineral acid such as hydrochloric acid, an organic acid such as acetic acid, a reaction compound therewith can be easily obtained.
発明の効果 以上説明したように、本発明製造方法によれば、種々の
化学薬品との反応性に優れた活性化したキチン及びキト
サンを簡単かつ確実に製造することができるものであ
る。EFFECTS OF THE INVENTION As described above, according to the production method of the present invention, activated chitin and chitosan having excellent reactivity with various chemicals can be easily and reliably produced.
次に実施例を示し、本発明を具体的に説明するが、本発
明は下記の実施例に限定されるものではない。Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.
〔実施例１〕 鶴見曹達（株）製の膨軟処理装置プレスパンダＰ−３０
Ｂを使用し、第１表に示す条件下でキチン及びキトサン
を膨軟化処理してＡ〜Ｄのサンプルをそれぞれ得た。な
お、原料キチンとしては南陽化成（株）のREGITEX-FA
（サンプルＥ）、原料キトサンとしては片倉チッカリン
（株）製キトサン（サンプルＦ）をそれぞれ用いた。[Example 1] Pressurizing and softening apparatus Press Panda P-30 manufactured by Tsurumi Soda Co., Ltd.
Using B, chitin and chitosan were softened under the conditions shown in Table 1 to obtain samples A to D, respectively. In addition, as raw material chitin, Nanyo Kasei's REGITEX-FA
(Sample E) and chitosan (Sample F) manufactured by Katakura Chikkarin Co., Ltd. were used as the raw material chitosan.
次いで、膨軟化処理前のキチン（サンプルＥ）及び処理
後のシチン（サンプルＡ）の組織を走査型電子顕微鏡で
調べた。この場合、サンプルを水、水−エタノール、エ
タノール、酢酸イソアミルで臨界点乾燥し、Auスパッタ
リング法を用いて写真撮影した。サンプルＥの写真を参
考図１に、サンプルＡの写真を参考図２に示す。なお、
倍率1000倍であり、写真左下の白線の横長が１μを表わ
す。 Then, the tissues of chitin (sample E) before the softening treatment and cytin (sample A) after the treatment were examined by a scanning electron microscope. In this case, the sample was critical point dried with water, water-ethanol, ethanol, isoamyl acetate and photographed using the Au sputtering method. A photograph of Sample E is shown in Reference Figure 1, and a photograph of Sample A is shown in Reference Figure 2. In addition,
The magnification is 1000 times, and the horizontal length of the white line in the lower left of the photograph represents 1 μ.
この結果、サンプルＡの組織はサンプルＥの組織と比較
すると太さ約０．１μの細い糸状物質が多数生じてお
り、本発明によればキチン、キトサンの結晶構造が破壊
され、従ってキチン、キトサンが活性化されることが認
められた。As a result, the structure of sample A has a large number of fine thread-like substances having a thickness of about 0.1 μ as compared with the structure of sample E, and according to the present invention, the crystal structure of chitin and chitosan is destroyed, and thus chitin and chitosan. Were found to be activated.
次に、上記各サンプルの化学薬品との反応性を調べるた
め、下記実験を行なった。Next, the following experiment was conducted in order to investigate the reactivity of each of the above samples with a chemical agent.
実験 ４０％濃度の水酸化ナトリウム水溶液にサンプルＡ〜Ｄ
及び膨軟化処理前のキチン（サンプルＥ）とキトサン
（サンプルＦ）をそれぞれ浸漬し、−２０℃で第２表に
示す時間凍結した後、又は凍結せずにそのまま０℃付近
でニーディングし、生成物の粘稠化状態を調べた。即
ち、キチンやキトサンのＮａ化においては、通常高濃度
水酸化ナトリウム溶液にキチン或いはキトサンを浸漬
し、これを−２０℃で１〜２昼夜以上凍結して分子間結
合を凍結破壊した後、０℃付近でニーディングすること
によりビスコース状のＮａ化合物を得ているが、膨軟化
処理を行なうことによりキチン、キトサンが活性化さ
れ、Ｎａ化反応が容易になることを実証するのが本実験
の目的である。結果を第２表に示す。なお、評価基準は
下記の通りである。Experiment Samples A to D were added to a 40% aqueous sodium hydroxide solution.
And chitin (Sample E) and chitosan (Sample F) before the softening treatment were each immersed, and after freezing at -20 ° C for the time shown in Table 2, or by kneading at around 0 ° C without freezing, The thickening state of the product was investigated. That is, in the conversion of chitin or chitosan to Na, usually, chitin or chitosan is immersed in a high-concentration sodium hydroxide solution and frozen at -20 ° C for 1 to 2 days or more to freeze and break the intermolecular bond, and then We obtained a viscose-like Na compound by kneading at around ℃, but this experiment proves that the chitin and chitosan are activated by the softening treatment to facilitate the Na-forming reaction. Is the purpose of. The results are shown in Table 2. The evaluation criteria are as follows.
評価基準 ◎：非常に均一に粘稠化している。Evaluation Criteria ⊚: Very uniformly thickened.
○：均一に粘稠化している。◯: Uniformly thickened.
△：一部未反応物があるが、粘稠化している。Δ: There is some unreacted material, but it is thickened.
×：反応しておらず、粘稠化していない。X: Not reacted and not thickened.
キチンのＮａ化物は従来からアルカリ凍結法で比較的簡
単に得られているが、第２表の結果より、膨軟化処理し
たキチンは凍結しなくてもビスコース状Ｎａ化物が得ら
れ、従って本発明の膨軟化処理を施したキチンは高い反
応活性を有することが認められた。 Conventionally, sodium chloride of chitin has been obtained relatively easily by the alkali freezing method. From the results shown in Table 2, it is possible to obtain the viscose-like sodium chloride of chitin which has been subjected to the softening treatment without freezing. It was found that chitin subjected to the softening treatment of the invention has high reaction activity.
また、キトサンはアミノ基の影響で水酸化ナトリウムが
排斥され、Ｎａ化が困難であるため、従来凍結法を繰り
返し行なって強引にＮａ化しており、またその収率も著
しく低いものであった。これに対し、第２表の結果よ
り、膨軟化処理したキトサンは２時間の凍結でもかなり
粘稠化し、更に４８時間の凍結ではほぼ満足できる均一
なビスコース状Ｎａ化キトサンが得られることが認めら
れ、本発明の膨軟化処理を施したキトサンは反応活性に
優れていることが認められた。Further, in chitosan, sodium hydroxide is rejected due to the influence of amino groups and it is difficult to convert it into Na. Therefore, the conventional freezing method was repeatedly carried out to forcibly convert it into Na, and the yield thereof was remarkably low. On the other hand, from the results in Table 2, it was confirmed that the chitosan which had been subjected to the softening treatment became considerably viscous even after being frozen for 2 hours, and further, when it was frozen for 48 hours, a substantially viscous Na-modified chitosan was obtained. It was confirmed that the chitosan subjected to the softening treatment of the present invention has excellent reaction activity.
〔実施例２〕 キチン１ｋｇを容積３リットルの蒸煮・爆砕装置に入れ
た。これに第３表に示した所定の温度の水蒸気を入れ、
所定時間保持した後、弁を全開して急激に圧力を解除し
た。この解除処理の時間は２秒以内と極めて短時間であ
り、そのため爆発音を生じた。なお、処理後の処理物の
温度は４０℃とした。[Example 2] 1 kg of chitin was placed in a steaming / blasting device having a volume of 3 liters. Put the steam of the specified temperature shown in Table 3 into this,
After holding for a predetermined time, the valve was fully opened to suddenly release the pressure. The time for this release processing was extremely short, within 2 seconds, and therefore an explosion sound occurred. The temperature of the treated product after the treatment was 40 ° C.
比較のため、５０ｇのキチンに１リットルの水を加え、
圧力釜中で１．３kg／cm2、125℃において３０分煮沸し
た。処理後、この加圧系を２０分かけて徐々に減圧して
常圧に戻した後、さらに冷却して処理物の温度を４０℃
に調整した（サンプルＩ）。 For comparison, add 1 liter of water to 50 g of chitin,
It was boiled for 30 minutes at 125 ° C. at 1.3 kg / cm 2 in a pressure cooker. After the treatment, the pressure system was gradually decompressed over 20 minutes to return to normal pressure, and then cooled to 40 ° C.
(Sample I).
次に、実施例１と同様の実験を行い、上記処理後のキチ
ンの状態を評価した。結果を第４表に示す。Next, the same experiment as in Example 1 was performed to evaluate the state of chitin after the above treatment. The results are shown in Table 4.
比較例の条件で処理したキチンは、本発明の処理物より
も十分にほぐれていないので、アルカキチン溶液を得る
には、再度凍結処理を行うという結晶構造をほぐすため
のプロセスが必要となるものであった。 Since the chitin treated under the conditions of the comparative example is not sufficiently loosened as compared with the treated product of the present invention, in order to obtain the alkachitin solution, a process for loosening the crystal structure of performing freezing treatment again is required. there were.
Claims (1)
物の含水率を１０〜６０重量％に調整すると共に、これ
を１７０℃以上の温度で８〜87.6kg／cm2の圧力におい
て圧縮蒸煮し、その後圧縮を急速に解除することによ
り、キチン又はキトサンを膨軟化処理して活性化するこ
とを特徴とする活性化したキチン又はキトサンの製造方
法。1. A chitin or chitosan or a mixture thereof is adjusted to a water content of 10 to 60% by weight, and this is steam-compressed at a temperature of 170 ° C. or higher at a pressure of 8-87.6 kg / cm 2 , and then compressed. The method for producing activated chitin or chitosan is characterized in that chitin or chitosan is activated by subjecting it to a softening treatment by rapidly releasing the chitin or chitosan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096681A JPH0651724B2 (en) | 1985-05-09 | 1985-05-09 | Process for producing activated chitin and chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096681A JPH0651724B2 (en) | 1985-05-09 | 1985-05-09 | Process for producing activated chitin and chitosan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61255902A JPS61255902A (en) | 1986-11-13 |
| JPH0651724B2 true JPH0651724B2 (en) | 1994-07-06 |
Family
ID=14171532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60096681A Expired - Lifetime JPH0651724B2 (en) | 1985-05-09 | 1985-05-09 | Process for producing activated chitin and chitosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0651724B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1229754B (en) * | 1989-05-17 | 1991-09-10 | Farmhispania | PROCEDURE FOR THE PREPARATION OF THE CHITOSAN AND ITS DERIVATIVES CONTAINING GROUPS OF QUATERNARY AMMONIUM |
| JP2009068014A (en) * | 2008-09-19 | 2009-04-02 | Toppan Printing Co Ltd | Water-soluble oxidized chitin and its producing method |
| CN103145873B (en) * | 2011-12-06 | 2015-12-09 | 蔡敏郎 | Chitin deacetylation method |
| TWI740312B (en) * | 2019-12-18 | 2021-09-21 | 國立臺灣海洋大學 | Chitin aqueous solution and its obtaining method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55152703A (en) * | 1979-05-18 | 1980-11-28 | Mitsubishi Rayon Co Ltd | Preparation of water-soluble alkali chitin |
-
1985
- 1985-05-09 JP JP60096681A patent/JPH0651724B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61255902A (en) | 1986-11-13 |
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