JPH06220103A - Water-solubilization treatment of chitosan - Google Patents
Water-solubilization treatment of chitosanInfo
- Publication number
- JPH06220103A JPH06220103A JP809093A JP809093A JPH06220103A JP H06220103 A JPH06220103 A JP H06220103A JP 809093 A JP809093 A JP 809093A JP 809093 A JP809093 A JP 809093A JP H06220103 A JPH06220103 A JP H06220103A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- water
- ion
- aqueous solution
- soluble
- 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.)
- Pending
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 68
- 238000005063 solubilization Methods 0.000 title abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 5
- 239000001110 calcium chloride Substances 0.000 abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 5
- 239000001103 potassium chloride Substances 0.000 abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 230000006196 deacetylation Effects 0.000 description 8
- 238000003381 deacetylation reaction Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000850 deacetylating effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 230000003779 hair growth Effects 0.000 description 1
- 230000003699 hair surface Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 210000004761 scalp Anatomy 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明はキトサンの水溶化処理
方法および化粧料、整髪剤、医料用素材、食品等に汎用
される水溶性キトサンの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for water-solubilizing chitosan and a method for producing water-soluble chitosan generally used for cosmetics, hair styling agents, medical materials, foods and the like.
【０００２】[0002]
【従来の技術】一般に、キトサンは、精製キチンを原料
として、３０〜６０％の水酸化カリウム、水酸化ナトリ
ウムなどの濃アルカリ溶液中で加熱することによって脱
アセチル化して調製されたものであり、上記調製に際し
て均一系で減圧、中和熱の管理、副生成物の除去を行な
い、脱アセチル化度を４０〜６０％としたキトサンは、
水に可溶であることが知られている。一方、上記所定の
調製を行わずに不均一系で調製されたキトサンは、同様
に脱アセチル化度を４０〜６０％としても水に不溶であ
り、塩酸や硫酸などの無機酸、または酢酸、乳酸、リン
ゴ酸、フマール酸などの有機酸には溶解する。2. Description of the Related Art In general, chitosan is prepared by deacetylating purified chitin as a raw material by heating it in a concentrated alkaline solution such as 30 to 60% potassium hydroxide or sodium hydroxide. Chitosan having a deacetylation degree of 40 to 60% under uniform pressure reduction, control of neutralization heat, and removal of by-products during the above preparation is
It is known to be soluble in water. On the other hand, chitosan prepared in a heterogeneous system without performing the above-mentioned predetermined preparation is similarly insoluble in water even when the deacetylation degree is 40 to 60%, and an inorganic acid such as hydrochloric acid or sulfuric acid, or acetic acid, It is soluble in organic acids such as lactic acid, malic acid and fumaric acid.
【０００３】そして、前記した水溶性のキトサンは、優
れた保湿力を有し、肌への浸透性も優れていることか
ら、肌や頭皮を活性化する化粧料もしくは育毛剤の成分
として用いられ、また毛髪に対しても保湿力、浸透性お
よび帯電防止効果を発揮するので、ブラシや櫛のとおり
を良くし、毛髪表面を保護する整髪剤として適用される
ことが期待できる。Since the above-mentioned water-soluble chitosan has excellent moisturizing power and excellent permeability to the skin, it is used as a component of cosmetics or hair-growth agents that activate the skin and scalp. Also, since it exerts a moisturizing power, a penetrating property and an antistatic effect on hair, it can be expected to be applied as a hair styling agent which improves the smoothness of brushes and combs and protects the hair surface.
【０００４】[0004]
【発明が解決しようとする課題】しかし、前記した水溶
性のキトサンを製造するには、減圧、中和熱の除去、副
生成物の処理などに煩雑な操作を要するので、生産効率
が劣る。However, in order to produce the above-mentioned water-soluble chitosan, the production efficiency is poor because it requires complicated operations such as depressurization, removal of the heat of neutralization, and treatment of by-products.
【０００５】また、水に不溶なキトサンを、無機酸また
は有機酸で溶解した液状化キトサンは、キトサンの水溶
液と同様に、液状化されたことによって有効に利用でき
るものではあるが、その溶液には通常、酸が含まれてい
るために、化学的にも不安定であり、またこのままでは
化粧料などの材料として安全に利用できない。Further, liquefied chitosan obtained by dissolving water-insoluble chitosan in an inorganic acid or an organic acid can be effectively used by being liquefied as in the case of an aqueous solution of chitosan. Usually, it is chemically unstable because it contains an acid, and as it is, it cannot be safely used as a material for cosmetics and the like.
【０００６】そこで、この発明は上記した問題点を解決
し、量産可能な非水溶性のキトサンを利用して生産効率
の高いキトサンの水溶化処理方法とすると共に、化学的
に安定した生理的安全性の高いキトサン水溶液が得られ
る水溶化処理方法とし、またこの処理方法を利用して安
全性の高い固体状の水溶性キトサンを提供することを課
題としている。Therefore, the present invention solves the above-mentioned problems and provides a water-soluble treatment method for chitosan having high production efficiency by utilizing mass-producible non-water-soluble chitosan, and chemically stable physiological safety. It is an object of the present invention to provide a water-solubilization treatment method capable of obtaining an aqueous chitosan solution having high properties, and to provide a highly safe solid water-soluble chitosan using this treatment method.
【０００７】[0007]
【課題を解決するための手段】上記の課題を解決するた
め、この発明においては、カリウムイオン、マグネシウ
ムイオンおよびカルシウムイオンからなる群から選ばれ
る一種以上のアルカリ金属またはアルカリ土類金属イオ
ンを総量で０．９〜１．１グラムイオン／リットル含有
する塩類の水溶液に、キトサンを溶解する手段を採用し
たのである。In order to solve the above problems, in the present invention, the total amount of one or more alkali metal or alkaline earth metal ions selected from the group consisting of potassium ion, magnesium ion and calcium ion is used. A means for dissolving chitosan in an aqueous solution of salts containing 0.9 to 1.1 gram ion / liter was adopted.
【０００８】また、ナトリウムイオン、カリウムイオ
ン、マグネシウムイオンおよびカルシウムイオンからな
る群から選ばれる二種以上のアルカリ金属またはアルカ
リ土類金属イオンを総量で０．５〜１．１グラムイオン
／リットル含有する塩類の水溶液に、キトサンを溶解す
る手段を採用することもできる。Further, it contains 0.5 to 1.1 gram ion / liter in total of two or more kinds of alkali metal or alkaline earth metal ions selected from the group consisting of sodium ion, potassium ion, magnesium ion and calcium ion. Means for dissolving chitosan in an aqueous salt solution can also be adopted.
【０００９】固体状の水溶性キトサンを得る手段として
は、上記したキトサンの水溶化処理方法によって得られ
た水溶液を、乾燥し固形化してキトサンを分取する方法
を採用することができる。As a means for obtaining solid water-soluble chitosan, a method in which an aqueous solution obtained by the above-described method for water-solubilizing chitosan is dried and solidified to fractionate chitosan can be adopted.
【００１０】[0010]
【作用】この発明のキトサンの水溶化処理方法では、非
水溶性キトサンを原材料として用い、これに所定種類か
つ所定濃度の塩類水溶液を混合するだけでキトサンを溶
解できるので、水溶化の処理効率が高く、しかも塩酸や
硫酸などの酸を用いず、化学的に安定した低濃度の塩類
水溶液を溶媒とする処理方法であるから、生理的安全性
の高いキトサン水溶液が得られる。また、このキトサン
水溶液を乾燥して得られる固形状のキトサン化合物は、
粉体やシートなどにも成形可能な水溶性キトサンとな
る。In the method for water-solubilizing chitosan of the present invention, non-water-soluble chitosan is used as a raw material, and chitosan can be dissolved by simply mixing it with an aqueous salt solution of a predetermined type and a predetermined concentration. This is a treatment method which uses a chemically stable, low-concentration salt aqueous solution as a solvent without using an acid such as hydrochloric acid or sulfuric acid, so that a chitosan aqueous solution having high physiological safety can be obtained. Further, the solid chitosan compound obtained by drying this chitosan aqueous solution,
It becomes a water-soluble chitosan that can be formed into powder and sheets.
【００１１】[0011]
【実施例】この発明に用いるキトサンは、特にその製造
方法を限定したものでなく、キチンを濃アルカリ溶液中
で加熱することにより、脱アセチル化して得られる周知
の非水溶性のキトサンを用いることができる。利用可能
な市販のキトサンとしては、甲陽ケミカル社製：ＳＫ−
１０（脱アセチル化度８５％以上）などが挙げられる。[Examples] The chitosan used in the present invention is not particularly limited in its production method, and a well-known water-insoluble chitosan obtained by deacetylating chitin by heating it in a concentrated alkaline solution may be used. You can Commercially available chitosan is available from Koyo Chemical Co., Ltd .: SK-
10 (degree of deacetylation of 85% or more) and the like.
【００１２】また、この発明で用いるカリウムイオン
（以下、Ｋ+ と記す) 、マグネシウムイオン（以下、Ｍ
ｇ2+と記す) およびカルシウムイオン（以下、Ｃａ2+と
記す)からなる群から選ばれる一種以上、またはナトリ
ウムイオン（以下、Ｎａ+ と記す) 、Ｋ+ 、Ｍｇ2+およ
びＣａ2+からなる群から選ばれる二種以上のアルカリ金
属またはアルカリ土類金属イオンは、それぞれ１価また
は２価のイオンであり、これらを総量で０．９〜１．１
グラムイオン／リットル（前記一種以上の場合）または
０．５〜１．１グラムイオン／リットル（前記二種以上
の場合）含有する塩類の水溶液を用いる。なぜなら、上
記所定濃度範囲外のイオン濃度の塩類水溶液では、前記
したキトサンが溶解しないからである。The potassium ion (hereinafter referred to as K + ) and magnesium ion (hereinafter referred to as M
g 2+ ) and one or more selected from the group consisting of calcium ions (hereinafter referred to as Ca 2+ ) or sodium ions (hereinafter referred to as Na + ), K + , Mg 2+ and Ca 2+ Two or more kinds of alkali metal or alkaline earth metal ions selected from the group are monovalent or divalent ions, respectively, and their total amount is 0.9 to 1.1.
An aqueous solution of salts containing gram ion / liter (in the case of one or more kinds) or 0.5 to 1.1 gram ion / liter (in the case of two or more kinds) is used. This is because the above-mentioned chitosan does not dissolve in an aqueous salt solution having an ion concentration outside the above-mentioned predetermined concentration range.
【００１３】上記したイオンを水溶液中に供給する塩類
は、特に限定されるものではなく、このような塩を得る
ための具体的な酸成分としては、酢酸、塩酸、炭酸、ホ
ウ酸、リン酸、蟻酸、乳酸、リンゴ酸、アジピン酸、ス
テアリン酸などを挙げることができる。The salts for supplying the above-mentioned ions into the aqueous solution are not particularly limited, and specific acid components for obtaining such salts include acetic acid, hydrochloric acid, carbonic acid, boric acid and phosphoric acid. , Formic acid, lactic acid, malic acid, adipic acid, stearic acid and the like.
【００１４】一方、塩基としては、水酸化ナトリウム、
水酸化カリウム、水酸化マグネシウム、水酸化カルシウ
ムなどを挙げることができる。On the other hand, as the base, sodium hydroxide,
Examples thereof include potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like.
【００１５】〔実施例１〜７、比較例１〜４〕Ｋ+ 、Ｍ
ｇ2+またはＣａ2+、Ｎａ+ を供給する塩類としてそれぞ
れ塩化カリウム、塩化マグネシウム、塩化カルシウム、
塩化ナトリウムを用い、これらを表１で示す配合割合
（イオン濃度）となるように塩類水溶液を調製し、その
１リットルに非水溶性キトサン（甲陽ケミカル社製：Ｓ
Ｋ−１０（脱アセチル化度８５％以上））を１重量％添
加して室温で放置し、溶解しない場合にはホモミキサー
（ホモジナイザー）またはガラス棒などで攪拌して非水
溶性キトサンの溶解性を調べた。溶解性の結果は、☆印
は完全溶解、〇印はほぼ溶解、△印は残留物残るがほぼ
溶解、×印は不溶解とする４段階に評価し、表１中に併
記した。[Examples 1 to 7, Comparative Examples 1 to 4] K + , M
g 2+ or Ca 2+ , Na + as salts for supplying potassium chloride, magnesium chloride, calcium chloride,
An aqueous salt solution was prepared using sodium chloride so as to have the blending ratio (ion concentration) shown in Table 1, and water-insoluble chitosan (manufactured by Koyo Chemical Co .: S
Add 1% by weight of K-10 (deacetylation degree of 85% or more) and leave it at room temperature. If it does not dissolve, stir it with a homomixer (homogenizer) or glass rod to dissolve the water-insoluble chitosan. I checked. The results of solubility were evaluated in four stages, in which star marks are completely dissolved, ◯ marks are almost dissolved, Δ marks are almost dissolved, and X marks are almost dissolved, and the results are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１の結果から明らかなように、塩類溶液
中のＫ+ 、Ｍｇ2+、Ｃａ2+が所定のイオン濃度（０．９
〜１．１グラムイオン／リットル）範囲外である比較例
１〜６では、キトサンは塩類水溶液に溶解しなかった。
また、Ｎａ+ を含有する塩類溶液である比較例７は、所
定濃度範囲であるにも拘わらずキトサンは溶解しなかっ
た。しかし、所定のイオンを所定の濃度範囲内に配合し
た実施例１〜７では、ホモミキサーで攪拌するかまたは
放置するだけでキトサンは溶解した。As is clear from the results shown in Table 1, K + , Mg 2+ and Ca 2+ in the salt solution have predetermined ion concentrations (0.9
In the comparative examples 1 to 6, which are out of the range (.about.1.1 gram ion / liter), chitosan did not dissolve in the salt solution.
Further, in Comparative Example 7 which is a salt solution containing Na + , chitosan was not dissolved even though the concentration range was within the predetermined range. However, in Examples 1 to 7 in which predetermined ions were blended within a predetermined concentration range, chitosan dissolved only by stirring with a homomixer or leaving it to stand.
【００１８】〔実施例８〜１２〕Ｋ+ 、Ｍｇ2+、Ｃ
ａ2+、Ｎａ+ を供給する塩類としてそれぞれ塩化カリウ
ム、塩化マグネシウム、塩化カルシウム、塩化ナトリウ
ム（それぞれが１グラムイオン／リットルの濃度であ
る）を用い、これらを２種類組み合わせて表２で示す配
合割合（容量比）となるように塩類水溶液を調製し、そ
の１リットルに非水溶性キトサン（甲陽ケミカル社製：
ＳＫ−１０（脱アセチル化度８５％以上））を１重量％
添加して室温で放置し、溶解しない場合にはホモミキサ
ー（ホモジナイザー）またはガラス棒などで攪拌して非
水溶性キトサンの溶解性を調べ、実施例１〜７の場合と
同様の基準で評価して結果を表２中に併記した。[Examples 8 to 12] K + , Mg 2+ , C
As salts for supplying a 2+ and Na + , potassium chloride, magnesium chloride, calcium chloride, and sodium chloride (each having a concentration of 1 gram ion / liter) are used, and a combination of these two types is shown in Table 2. An aqueous salt solution was prepared so as to have a ratio (volume ratio), and 1 liter of the water-insoluble chitosan (manufactured by Koyo Chemical Co., Ltd .:
1% by weight of SK-10 (deacetylation degree of 85% or more))
After the addition, the mixture is allowed to stand at room temperature, and if it does not dissolve, it is stirred with a homomixer (homogenizer) or a glass rod to check the solubility of the water-insoluble chitosan, and evaluated according to the same criteria as in Examples 1 to 7. The results are also shown in Table 2.
【００１９】[0019]
【表２】 [Table 2]
【００２０】表２の結果から明らかなように、全ての組
合せ（Ｍｇ−Ｃａの組合せを除く）でキトサンは溶解し
た。As is clear from the results in Table 2, chitosan was dissolved in all combinations (except the Mg-Ca combination).
【００２１】〔実施例１３〕Ｍｇ2+、Ｃａ2+を供給する
塩類として塩化マグネシウム、塩化カルシウムをそれぞ
れが０．５グラムイオン／リットルの濃度として、両者
を容量比で１：９から９：１の範囲で配合した塩類溶液
に、実施例８〜１２と全く同じ条件でキトサンを混合
し、溶解性を調べた。この結果、Ｍｇ−Ｃａが０．５グ
ラムイオン／リットルの条件の全ての場合に前記した実
施例１〜７と同じ評価基準における〇印の溶解性が得ら
れた。[Embodiment 13] Magnesium chloride and calcium chloride as salts for supplying Mg 2+ and Ca 2+ , respectively, have a concentration of 0.5 g ion / liter, and both are in a volume ratio of 1: 9 to 9: 9. Chitosan was mixed with the salt solution formulated in the range of 1 under the same conditions as in Examples 8 to 12, and the solubility was examined. As a result, in all cases where the Mg-Ca content was 0.5 g ion / liter, the solubility of O was obtained under the same evaluation criteria as in Examples 1 to 7.
【００２２】〔実施例１４〜５３〕Ｋ+ 、Ｍｇ2+、Ｃａ
2+、Ｎａ+ を供給する塩類としてそれぞれ塩化カリウ
ム、塩化マグネシウム、塩化カルシウム、塩化ナトリウ
ム（それぞれが１グラムイオン／リットルの濃度であ
る）を用い、これらを３種類組み合わせて表３で示す配
合割合（容量比）となるように塩類水溶液を調製する以
外は、実施例１〜７と全く同様にしてキトサンの溶解性
を調べ、同様の評価を行った結果を表３中に併記した。[Examples 14 to 53] K + , Mg 2+ , Ca
Potassium chloride, magnesium chloride, calcium chloride, and sodium chloride (each having a concentration of 1 gram ion / liter) are used as salts for supplying 2+ and Na + , respectively, and the combination ratios shown in Table 3 are obtained by combining these three types. The solubility of chitosan was examined in the same manner as in Examples 1 to 7 except that the aqueous salt solution was prepared so as to have a (volume ratio), and the same evaluation results were also shown in Table 3.
【００２３】[0023]
【表３】 [Table 3]
【００２４】表３の結果から明らかなように、全ての組
合わせの場合に前記評価の☆印または〇印の溶解性が得
られた。As is clear from the results in Table 3, the solubility marked with ∘ or ∘ in the above evaluation was obtained in all combinations.
【００２５】なお、以上述べた実施例における塩類水溶
液への非水溶性キトサンの溶解度（重量％）は、非水溶
性キトサンの分子量が脱アセチル化度によって変化する
ため、一様な基準で評価できるものではない。しかしな
がら、三種イオンの配合された塩類水溶液に対する最大
溶解率は、脱アセチル化度が７５％以上のキトサン（甲
陽ケミカル社製：ＳＫ−４００）で最高８重量％であ
り、脱アセチル化度が８５％以上のキトサン（甲陽ケミ
カル社製：ＳＫ−２０）で最高１８重量％であった。The solubility (% by weight) of the water-insoluble chitosan in the aqueous salt solution in the above-mentioned examples can be evaluated on a uniform basis because the molecular weight of the water-insoluble chitosan changes depending on the degree of deacetylation. Not a thing. However, the maximum dissolution rate in a salt aqueous solution containing three kinds of ions is up to 8% by weight for chitosan (SK-400 manufactured by Koyo Chemical Co., Ltd.) having a deacetylation degree of 75% or more, and a deacetylation degree of 85. % Of chitosan (SK-20 manufactured by Koyo Chemical Co., Ltd.) was up to 18% by weight.
【００２６】次に、水溶性キトサンの製造方法について
説明する。Next, a method for producing water-soluble chitosan will be described.
【００２７】以上の実施例で得られたキトサン溶解の塩
類水溶液を、乾燥して固体状のキトサンを得、これが水
に溶解する水溶性キトサンであることを確認した。この
場合の乾燥方法としては、常温（自然）乾燥でもよい
が、キトサン水溶液に４〜５％のデキストリンを加え、
エアーガンと熱風で処理するスプレードライ法、その他
周知の乾燥方法を採用できる。水溶性キトサンの原液と
しては５〜１３重量％のキトサン水溶液が好ましく、こ
の原液の被加熱温度は最高７０〜８０℃で３秒以内とす
ることが好ましい。The chitosan-dissolved salt aqueous solution obtained in the above Examples was dried to obtain solid chitosan, which was confirmed to be water-soluble chitosan. The drying method in this case may be room temperature (natural) drying, but 4 to 5% of dextrin is added to the chitosan aqueous solution,
A spray dry method of treating with an air gun and hot air, and other known drying methods can be adopted. The stock solution of water-soluble chitosan is preferably a 5 to 13 wt% chitosan aqueous solution, and the temperature to be heated of this stock solution is preferably 70 to 80 ° C. at maximum and within 3 seconds.
【００２８】このようにして得られた固形状の水溶性キ
トサンは、粉体またはシート状などの取り扱いの簡便な
形態に成形してもよく、その際に香料やＰＨ調製剤、水
溶性ビタミン、水溶性防腐剤、水溶性高分子その他の水
溶性成分を添加してもよいのは勿論である。The solid water-soluble chitosan thus obtained may be molded into a convenient form such as a powder or a sheet, and at that time, a fragrance, a pH adjusting agent, a water-soluble vitamin, Of course, a water-soluble preservative, a water-soluble polymer and other water-soluble components may be added.
【００２９】[0029]
【効果】この発明は、以上説明したように、塩酸や硫酸
などの酸を用いることなく、化学的にも安定した比較的
低濃度の塩類水溶液を用いた処理方法であるから、生理
的安全性の高いキトサンの水溶化処理方法であり、しか
も非水溶性キトサンを原材料として用い、これに所定の
塩類水溶液を所定濃度で混合するだけで溶解させるよう
にしたので、水溶化の処理効率が高く、またこの処理方
法を利用してキトサン水溶液を乾燥させるだけで、有用
性が高く高品質かつ安全な固体状の水溶性キトサンを製
造できるという利点がある。[Effects] As described above, the present invention is a treatment method using a salt solution having a relatively low concentration that is chemically stable without using an acid such as hydrochloric acid or sulfuric acid. It is a highly water-soluble treatment method for chitosan, and moreover, non-water-soluble chitosan is used as a raw material, and a predetermined salt aqueous solution is mixed therein at a predetermined concentration to dissolve it, so that the treatment efficiency of water solubilization is high, In addition, there is an advantage that a highly useful and high-quality and safe solid water-soluble chitosan can be produced only by drying the chitosan aqueous solution using this treatment method.
Claims (3)
よびカルシウムイオンからなる群から選ばれる一種以上
のアルカリ金属またはアルカリ土類金属イオンを総量で
０．９〜１．１グラムイオン／リットル含有する塩類の
水溶液に、キトサンを溶解することからなるキトサンの
水溶化処理方法。1. An aqueous salt solution containing one or more alkali metal or alkaline earth metal ions selected from the group consisting of potassium ion, magnesium ion and calcium ion in a total amount of 0.9 to 1.1 gram ion / liter. , A method for water-solubilizing chitosan, which comprises dissolving chitosan.
グネシウムイオンおよびカルシウムイオンからなる群か
ら選ばれる二種以上のアルカリ金属またはアルカリ土類
金属イオンを総量で０．５〜１．１グラムイオン／リッ
トル含有する塩類の水溶液に、キトサンを溶解すること
からなるキトサンの水溶化処理方法。2. A total amount of 0.5 to 1.1 gram ion / liter of two or more kinds of alkali metal or alkaline earth metal ions selected from the group consisting of sodium ion, potassium ion, magnesium ion and calcium ion. A method for water-solubilizing chitosan, which comprises dissolving chitosan in an aqueous salt solution.
の水溶化処理方法によって得られた水溶液を、乾燥し固
形化したキトサンを分取することからなる水溶性キトサ
ンの製造方法。3. A method for producing water-soluble chitosan, which comprises separating an aqueous solution obtained by the method for water-solubilizing chitosan according to claim 1 or 2 and drying and solidifying chitosan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP809093A JPH06220103A (en) | 1993-01-21 | 1993-01-21 | Water-solubilization treatment of chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP809093A JPH06220103A (en) | 1993-01-21 | 1993-01-21 | Water-solubilization treatment of chitosan |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06220103A true JPH06220103A (en) | 1994-08-09 |
Family
ID=11683631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP809093A Pending JPH06220103A (en) | 1993-01-21 | 1993-01-21 | Water-solubilization treatment of chitosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06220103A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003035700A1 (en) * | 2001-09-25 | 2003-05-01 | Jae Woon Nah | Method for preparing water-soluble free amine chitosan |
| KR100381387B1 (en) * | 1998-12-30 | 2003-08-19 | 주식회사 효성 | Manufacturing method of chitosan derivative |
| KR100546484B1 (en) * | 1999-01-28 | 2006-01-26 | 주식회사 효성 | Method for producing chitosan polymer coagulant |
| JP2008094989A (en) * | 2006-10-13 | 2008-04-24 | Hyogo Prefecture | Method for dissolving chitosan in water and composition thereof |
-
1993
- 1993-01-21 JP JP809093A patent/JPH06220103A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100381387B1 (en) * | 1998-12-30 | 2003-08-19 | 주식회사 효성 | Manufacturing method of chitosan derivative |
| KR100546484B1 (en) * | 1999-01-28 | 2006-01-26 | 주식회사 효성 | Method for producing chitosan polymer coagulant |
| WO2003035700A1 (en) * | 2001-09-25 | 2003-05-01 | Jae Woon Nah | Method for preparing water-soluble free amine chitosan |
| GB2397304A (en) * | 2001-09-25 | 2004-07-21 | Jae Woon Nah | Method for preparing water-soluble free amine chitosan |
| GB2397304B (en) * | 2001-09-25 | 2005-07-20 | Jae Woon Nah | Method for preparing water-soluble free amine chitosan |
| US7345165B2 (en) | 2001-09-25 | 2008-03-18 | Jae Woon Nah | Method for preparing water-soluble free amine chitosan |
| JP2008094989A (en) * | 2006-10-13 | 2008-04-24 | Hyogo Prefecture | Method for dissolving chitosan in water and composition thereof |
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