JPH0455610B2 - - Google Patents
Info
- Publication number
- JPH0455610B2 JPH0455610B2 JP60203006A JP20300685A JPH0455610B2 JP H0455610 B2 JPH0455610 B2 JP H0455610B2 JP 60203006 A JP60203006 A JP 60203006A JP 20300685 A JP20300685 A JP 20300685A JP H0455610 B2 JPH0455610 B2 JP H0455610B2
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- spherical
- solution
- aqueous solution
- temperature atmosphere
- 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
- 229920001661 Chitosan Polymers 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003637 basic solution Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 239000000725 suspension Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 241000238557 Decapoda Species 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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 2
- 229920002101 Chitin Polymers 0.000 description 2
- 241000238424 Crustacea Species 0.000 description 2
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000850 deacetylating effect Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Peptides Or Proteins (AREA)
Description
本発明は、クロマトグラフイー用充填材、固定
化生理活性物質用坦体、化粧用素材、及び医薬用
助剤等に極めて好適な超微小球状キトサンの製造
方法に関するものである。
The present invention relates to a method for producing ultrafine spherical chitosan, which is extremely suitable for use as a filler for chromatography, a carrier for immobilized physiologically active substances, a cosmetic material, a pharmaceutical aid, and the like.
キトサンは海老、蟹等の甲殻類の外皮の構成物
質であるキチンから得られ、クロマトグラフイー
用充填材、各種物質用坦体として用いられる。超
微小粒状キトサンを得る方法として、キトサンフ
レークを機械的に粉砕する方法が知られている
が、この場合には、キトサンフレークは球状体と
なるものは少なく、多くは不規則な形状の微粒と
なり、この中から球状のものを選別することは不
可能に近い。又、得られた超微小キトサン粒子は
凝集してしまい、分散性のよいものを得ることは
出来ない欠点がある。
又、特公昭59−30722号公報に開示された方法
は、キトサンの酸性水溶液に乳化剤を含む疎水性
溶剤を入れ、撹拌してエマルジヨン化し、このも
のをアルカリ水溶液中で撹拌しながら凝固析出す
る方法であつて、この方法で得られるものは粒径
が２〜300μｍとかなり広い範囲に分布したもの
しか得られない欠点があり、製品の洗浄工程が煩
雑であつて工業的でない。
本発明者等は、先に特願昭59−16119号の発明
をなし、キトサンの酸性水溶液を塩基性溶液中に
落下させ凝固再生することによつて粒状化し、中
性になる迄充分に洗浄し、乾燥して粒状キトサン
を得る方法を提案した。該方法によつても超微小
球状キトサンを得ることは出来るが、この方法で
は、粒径が100μｍ以下のものの場合は、中和洗
浄等の操作が煩雑となる欠点があり、又、或る粒
径以下の超微小球状キトサンは個々に分離しにく
く、付着する傾向があり、個々の球状形態が失わ
れる欠点があつた。
Chitosan is obtained from chitin, which is a component of the outer skin of crustaceans such as shrimp and crabs, and is used as a filler for chromatography and as a carrier for various substances. A known method for obtaining ultrafine chitosan particles is to mechanically crush chitosan flakes, but in this case, the chitosan flakes are rarely spherical, and most are irregularly shaped fine particles. Therefore, it is almost impossible to select the spherical ones from among these. Furthermore, the resulting ultrafine chitosan particles tend to aggregate, making it impossible to obtain particles with good dispersibility. Furthermore, the method disclosed in Japanese Patent Publication No. 59-30722 is a method in which a hydrophobic solvent containing an emulsifier is added to an acidic aqueous solution of chitosan, the mixture is stirred to form an emulsion, and this is coagulated and precipitated in an alkaline aqueous solution while being stirred. However, the product obtained by this method has the disadvantage that only particles with particle sizes distributed over a fairly wide range of 2 to 300 μm can be obtained, and the washing process of the product is complicated, making it unsuitable for industrial use. The present inventors previously made the invention in Japanese Patent Application No. 59-16119, in which an acidic aqueous solution of chitosan is dropped into a basic solution, solidified and regenerated into granules, and thoroughly washed until it becomes neutral. We proposed a method to obtain granular chitosan by drying. Although it is possible to obtain ultrafine spherical chitosan by this method, this method has the disadvantage that operations such as neutralization and washing are complicated when the particle size is 100 μm or less, and there are certain Ultra-fine spherical chitosan having a particle size or smaller is difficult to separate into individual chitosan particles and tends to adhere to each other, which has the disadvantage that the individual spherical morphology is lost.
本発明は、上記した従来法における諸欠点を解
決し、平均球径が20μｍ以下であつて、しかも粒
度分布の小さな微小球状キトサンを得ることを目
的とする。本発明方法は、更に製造工程における
作業性を改善し、得られた超微小球状キトサンの
分散性が高い超微小球状キトサンを製造する方法
を提供することを目的とする。
The present invention aims to solve the various drawbacks of the conventional methods described above and to obtain microspherical chitosan having an average spherical diameter of 20 μm or less and a small particle size distribution. The method of the present invention further aims to improve the workability in the production process and to provide a method for producing ultrafine spherical chitosan with high dispersibility.
本発明方法は、キトサンを酸性水溶液中に溶解
し、該酸性溶液を塩基性溶液中に加えて凝固再生
し、生成した凝固物を中性になる迄充分に洗浄後
洗浄に用いた液を分散媒としてキトサンを粉砕分
散せしめて懸濁液とし、該懸濁液を高温雰囲気中
に加圧空気と共に吐出し、乾燥させることにより
超微小球状キトサンを得るものである。
キトサンは、天然に存在する蟹、海老等の甲殻
類から得たキチンを脱アセチル化して得ることが
出来る。キトサンは通常のフレーク状キトサンも
使用することが出来るが、平均分子量が10000〜
230000の低分子量キトサンを用いると、添加剤等
を加えずに高濃度の酸性水溶液が得られるので、
低分子化して使用することが好ましい。キトサン
は、酢酸、ジクロル酢酸、蟻酸の単独、若しくは
混合物の水溶液に溶解して該溶解液を落下等の手
段により塩基性水溶液中に加えて凝固再生させ
る。キトサン酸性水溶液を凝固再生させる塩基性
水溶液の組成は、凝固したキトサンを粉砕する際
に懸濁し、乳状液となり易い状態、即ち、脆い状
態のキトサン凝固物が得られるようなものが好ま
しく、アンモニア、エチレンジアミン、苛性ソー
ダ等の水溶液、又は、これら塩基性物質にメタノ
ール、エタノール等の極性を有するアルコールを
添加したものであつても良い。キトサン酸性溶液
を塩基性溶液中で凝固析出させて得る凝固物の大
きさは、特に制限されるべきものではないが、粒
状のものである場合は、中和洗浄等の作業性から
粒径が１〜２mmのものが好ましい。
上記のようにして得られたキトサン凝固物は水
で中性になる迄充分洗浄し、洗浄後、水中で粉
砕、分散せしめて乳状の懸濁液を得る。粉砕には
ホモジナイザーを使用することができる。粉砕後
の懸濁液は、ノズル周辺から吐出される加圧空気
と共に高温雰囲気中に吐出乾燥される。高温雰囲
気の温度は、超微小球状キトサンが乾燥されるに
充分な温度で100〜180℃の範囲で自由に選択出来
る。吐出は、懸濁液の分散性を保持しながら行う
ことが必要で、例えば、ホモジナイザーで分散を
行いながら吐出することも可能である。吐出され
たキトサン懸濁液は、分散媒である水の表面張力
等によつて高温雰囲気中で乾燥される際に、微小
な球状体に成形される。得られる球状体の球径
は、高温雰囲気中に吐出する際の吐出量と加えた
空気圧力とを適宜調節することによつて任意に選
択することが出来る。
The method of the present invention involves dissolving chitosan in an acidic aqueous solution, adding the acidic solution to a basic solution to coagulate and regenerate, thoroughly washing the resulting coagulate until it becomes neutral, and then dispersing the liquid used for washing. Chitosan is pulverized and dispersed as a medium to form a suspension, and the suspension is discharged into a high temperature atmosphere together with pressurized air and dried to obtain ultrafine spherical chitosan. Chitosan can be obtained by deacetylating naturally occurring chitin obtained from crustaceans such as crabs and shrimps. Ordinary flaky chitosan can also be used, but the average molecular weight is 10,000~
By using low molecular weight chitosan of 230,000, a highly concentrated acidic aqueous solution can be obtained without adding any additives.
It is preferable to reduce the molecular weight and use it. Chitosan is dissolved in an aqueous solution of acetic acid, dichloroacetic acid, or formic acid alone or in a mixture, and the dissolved solution is added to a basic aqueous solution by means such as dropping to solidify and regenerate. The composition of the basic aqueous solution for coagulating and regenerating the chitosan acidic aqueous solution is preferably such that when the coagulated chitosan is crushed, it is suspended and easily becomes an emulsion, that is, a brittle chitosan coagulated product is obtained. It may be an aqueous solution of ethylenediamine, caustic soda, etc., or a product obtained by adding a polar alcohol such as methanol or ethanol to these basic substances. The size of the coagulated product obtained by coagulating and precipitating a chitosan acidic solution in a basic solution should not be particularly limited, but if it is granular, the particle size may be limited due to workability such as neutralization washing. A thickness of 1 to 2 mm is preferable. The chitosan coagulate obtained as described above is thoroughly washed with water until it becomes neutral, and after washing, it is crushed and dispersed in water to obtain a milky suspension. A homogenizer can be used for grinding. The pulverized suspension is dried by being discharged into a high-temperature atmosphere together with pressurized air discharged from around the nozzle. The temperature of the high temperature atmosphere can be freely selected within the range of 100 to 180°C, which is sufficient to dry the ultrafine spherical chitosan. Discharging must be performed while maintaining the dispersibility of the suspension; for example, it is also possible to discharge while dispersing with a homogenizer. The discharged chitosan suspension is formed into minute spherical bodies when dried in a high temperature atmosphere due to the surface tension of water, which is a dispersion medium. The spherical diameter of the obtained spherical body can be arbitrarily selected by appropriately adjusting the discharge amount and the applied air pressure when discharging into the high-temperature atmosphere.
次に、本発明の方法を実施例を挙げて説明す
る。尚、実施例中に記載の部は全て重量部とす
る。
◇実施例 １
脱アセチル化度77％、平均分子量142000のキト
サン25ｇを酢酸12.5ｇを含む水975ｇを加えて溶
解し、キトサン酸性溶液を得た。この溶液の20℃
における粘度は、回転粘度計で測定したところ
2100cpであつた。このキトサン酸性溶液を５％
のアンモニア水溶液中に落下させて細状にキトサ
ンを凝集再生させた。この凝固物を中性になるま
で充分水で洗浄した後、水中でホモジナイザー
（日本精機株式会社製、AM−３型）を用いて
15000rpmの回転数で７分間粉砕して分散させ、
乳状の懸濁液とした。これを120メツシユのフル
イで粗大片を濾別し、濾液を4.0mg／cm2の加圧空
気と共に毎分17.6mlの液量で170〜175℃の高温雰
囲気中に吐出して乾燥し、乾燥物をサイクロンコ
レクターに捕集した。捕集した粒状物の粒径を走
査型電子顕微鏡で測定したところ、平均球径5μ
ｍ、球径分布１〜10μｍの超微小球状キトサン19
ｇを得た。
◇実施例 ２
脱アセチル化度95％、平均分子量46000のキト
サン60ｇを30ｇの蟻酸を含む水940ｇに溶解して
キトサン酸性溶液を得た。この溶液の20℃におけ
る粘度は、回転粘度計で測定したところ2800cp
であつた。このキトサン酸性溶液を10％苛性ソー
ダと30％メチルアルコール及び水60％から成る塩
基性水溶液中に孔径0.25ｍ／ｍのノズルより落下
させてキトサンを凝固再生し、中性になるまで充
分水で洗浄して粒径0.7〜2.0ｍ／ｍの粒状物を得
た。該粒状物600mlをとり、実施例１と同様にホ
モジナイザーを用いて15000rpmの回転数で７分
間撹拌して乳状の懸濁液とし、更に水を加えて１
〓とした。これを100メツシユのフルイで濾過後、
濾液をホモジナイザーで撹拌しながら分散状態を
保ちつつ、3.0Kg／cm2の加圧空気と共に毎分17.6
mlの液量で175℃の高温雰囲気中に吐出して乾燥
し、乾燥物をサイクロンコレクターで捕集した。
この捕集した球状物の球径を走査型電子顕微鏡で
測定したところ、平均球径10μｍ、球径分布５〜
15μｍの超微小球状キトサン25.5ｇを得た。
Next, the method of the present invention will be explained by giving examples. In addition, all parts described in the examples are parts by weight. ◇Example 1 25 g of chitosan having a degree of deacetylation of 77% and an average molecular weight of 142,000 was dissolved in 975 g of water containing 12.5 g of acetic acid to obtain an acidic chitosan solution. 20℃ of this solution
The viscosity was measured using a rotational viscometer.
It was 2100 cp. Add this chitosan acidic solution to 5%
The chitosan was dropped into an aqueous ammonia solution to regenerate the finely aggregated chitosan. After washing the coagulated material with water sufficiently until it becomes neutral, it was washed in water using a homogenizer (manufactured by Nippon Seiki Co., Ltd., model AM-3).
Grind and disperse for 7 minutes at a rotation speed of 15000 rpm,
A milky suspension was obtained. This is filtered to remove coarse particles using a 120-mesh sieve, and the filtrate is discharged into a high-temperature atmosphere of 170 to 175°C at a rate of 17.6 ml per minute along with 4.0 mg/cm 2 of pressurized air to dry it. The material was collected in a cyclone collector. When the particle size of the collected particles was measured using a scanning electron microscope, the average spherical diameter was 5μ.
m, ultrafine spherical chitosan with a spherical diameter distribution of 1 to 10 μm19
I got g. ◇Example 2 60 g of chitosan having a degree of deacetylation of 95% and an average molecular weight of 46,000 was dissolved in 940 g of water containing 30 g of formic acid to obtain an acidic chitosan solution. The viscosity of this solution at 20℃ was 2800 cp as measured by a rotational viscometer.
It was hot. This acidic chitosan solution is dropped into a basic aqueous solution consisting of 10% caustic soda, 30% methyl alcohol, and 60% water through a nozzle with a pore size of 0.25 m/m to solidify and regenerate chitosan, and then rinse thoroughly with water until it becomes neutral. A granular material having a particle size of 0.7 to 2.0 m/m was obtained. Take 600 ml of the granular material and stir it for 7 minutes at 15,000 rpm using a homogenizer in the same manner as in Example 1 to obtain a milky suspension, and then add water to make a milky suspension.
〓. After filtering this through a 100 mesh sieve,
While stirring the filtrate with a homogenizer to maintain a dispersed state, the filtrate is heated at 17.6 per minute with pressurized air of 3.0Kg/ cm2 .
A liquid volume of 1 ml was discharged into a high temperature atmosphere of 175°C to dry, and the dried material was collected with a cyclone collector.
When the spherical diameter of this collected spherical material was measured using a scanning electron microscope, the average spherical diameter was 10 μm, and the spherical diameter distribution was 5 to 5 μm.
25.5 g of ultrafine spherical chitosan of 15 μm was obtained.
本発明の方法は、キトサン酸性水溶液を塩基性
溶液中で分散に望ましい脆い状態のキトサンとし
て凝固再生し、このものを充分に洗浄後粉砕分散
せしめ、該分散液を高温雰囲気中に加圧空気と共
に吐出乾燥するものであつて、キトサンは微細片
に破砕され、乳状の懸濁液として高温雰囲気中に
噴出され、乾燥される際に、ほぼ球状の平均球径
が20μｍ以下の超微小球を形成する。このように
して得られた超微小球状キトサンは、実施例に記
載のように球状で粒度が揃つた粒径分布の小さい
ものであり、しかも各超微小球体が凝集、接着す
ることがないので、クロマトグラフイー用充填
材、固定化生理活性物質用坦体、化粧用素材、医
薬用助剤等の各種用途に極めて好適なものであ
る。
更に、本発明方法においては、従来法における
ように製造工程において各種の添加剤を加える必
要がなく、特にキトサンを微小球状体とした後
に、これを洗浄する必要がないので製造時間を短
縮することが出来、工業的に極めて有利である。
The method of the present invention involves coagulating and regenerating an acidic chitosan aqueous solution as chitosan in a brittle state that is desirable for dispersion in a basic solution, thoroughly washing and pulverizing the dispersion, and placing the dispersion in a high-temperature atmosphere together with pressurized air. Chitosan is crushed into fine pieces and sprayed into a high-temperature atmosphere as a milky suspension, and when dried, it produces almost spherical ultra-microspheres with an average diameter of 20 μm or less. Form. The ultrafine spherical chitosan thus obtained is spherical, uniform in particle size, and has a small particle size distribution, as described in the examples, and furthermore, the ultrafine spheres do not aggregate or adhere to each other. Therefore, it is extremely suitable for various uses such as a filler for chromatography, a carrier for immobilized physiologically active substances, a cosmetic material, and a pharmaceutical aid. Furthermore, in the method of the present invention, unlike conventional methods, there is no need to add various additives during the production process, and in particular, there is no need to wash the chitosan after it is made into microspheres, so the production time can be shortened. This is extremely advantageous industrially.
Claims (1)
液を塩基性溶液中で凝固再成し、生成した凝固物
を洗浄後粉砕分散せしめ、該分散液を高温雰囲気
中に加圧空気と共に吐出乾燥することを特徴とす
る超微小球状キトサンの製造方法。1. A solution obtained by dissolving chitosan in an acidic aqueous solution is coagulated and reconstituted in a basic solution, the resulting coagulated product is washed, pulverized and dispersed, and the dispersion is discharged into a high temperature atmosphere with pressurized air and dried. A method for producing ultrafine spherical chitosan, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60203006A JPS6262827A (en) | 1985-09-12 | 1985-09-12 | Method for producing ultrafine spherical chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60203006A JPS6262827A (en) | 1985-09-12 | 1985-09-12 | Method for producing ultrafine spherical chitosan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6262827A JPS6262827A (en) | 1987-03-19 |
| JPH0455610B2 true JPH0455610B2 (en) | 1992-09-03 |
Family
ID=16466770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60203006A Granted JPS6262827A (en) | 1985-09-12 | 1985-09-12 | Method for producing ultrafine spherical chitosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6262827A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6320301A (en) * | 1986-07-11 | 1988-01-28 | Dainichi Color & Chem Mfg Co Ltd | chitosan microparticles |
| JPH0768648B2 (en) * | 1991-02-20 | 1995-07-26 | 富士紡績株式会社 | Modified cellulose regenerated fiber |
| JPH05345834A (en) * | 1992-06-15 | 1993-12-27 | Fuji Spinning Co Ltd | Antibacterial and antifungal porous polyurethane sheet |
| US6252003B1 (en) | 1998-06-04 | 2001-06-26 | Kao Corporation | Polymer emulsion and process for producing the same |
| US6130321A (en) * | 1998-07-10 | 2000-10-10 | Vanson, Inc. | High tap density chitosan, and methods of production |
| ATE275392T1 (en) * | 1999-04-12 | 2004-09-15 | Shionogi & Co | METHOD FOR PRODUCING MEDICINAL PRODUCTS OF A BASIC HYDROPHOBIC ACTIVE SUBSTANCE |
| GB0126923D0 (en) * | 2001-11-09 | 2002-01-02 | Procter & Gamble | Chitosan compositions |
| US6749748B1 (en) | 2001-12-28 | 2004-06-15 | Vanson Halosource, Inc. | Methods for reducing the amount of contaminants in water |
| CN105797697A (en) * | 2016-05-24 | 2016-07-27 | 夏百庆 | Biocompatible high-purity chromatographic material and preparation method thereof |
-
1985
- 1985-09-12 JP JP60203006A patent/JPS6262827A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6262827A (en) | 1987-03-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |