JPS6390507A - Chitosan sponge - Google Patents
Chitosan spongeInfo
- Publication number
- JPS6390507A JPS6390507A JP61236622A JP23662286A JPS6390507A JP S6390507 A JPS6390507 A JP S6390507A JP 61236622 A JP61236622 A JP 61236622A JP 23662286 A JP23662286 A JP 23662286A JP S6390507 A JPS6390507 A JP S6390507A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- sponge
- wound
- acetic acid
- water
- 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.)
- Granted
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 77
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 abstract description 30
- 229920002101 Chitin Polymers 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 10
- 210000000416 exudates and transudate Anatomy 0.000 abstract description 9
- 230000002439 hemostatic effect Effects 0.000 abstract description 8
- 230000001112 coagulating effect Effects 0.000 abstract description 6
- 241000238557 Decapoda Species 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- 125000003047 N-acetyl group Chemical group 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 229940045110 chitosan Drugs 0.000 description 72
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 19
- 229960000583 acetic acid Drugs 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 208000027418 Wounds and injury Diseases 0.000 description 12
- 150000008065 acid anhydrides Chemical class 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 6
- -1 fatty acid salt Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 229960002442 glucosamine Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 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
- MBLBDJOUHNCFQT-LXGUWJNJSA-N N-acetylglucosamine Natural products CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229950006780 n-acetylglucosamine Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 208000028990 Skin injury Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical class O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000006265 aqueous foam Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- FLASNYPZGWUPSU-SICDJOISSA-N chitosan Chemical compound O([C@@H]1[C@@H](CO)O[C@H]([C@@H]([C@H]1O)N)O[C@@H]1[C@@H](CO)O[C@H]([C@@H]([C@H]1O)N)O[C@@H]1[C@@H](CO)O[C@H]([C@@H]([C@H]1O)N)O[C@@H]1[C@@H](CO)O[C@H]([C@@H]([C@H]1O)N)O[C@@H]1[C@@H](CO)O[C@H]([C@@H]([C@H]1O)N)O[C@H]1[C@H](O)[C@H]([C@@H](O[C@@H]1CO)O[C@@H]1[C@H](O[C@@H](O[C@@H]2[C@H](O[C@@H](O)[C@H](N)[C@H]2O)CO)[C@H](N)[C@H]1O)CO)NC(=O)OC)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1N FLASNYPZGWUPSU-SICDJOISSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 230000003544 deproteinization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- ILXYDRFJSVKZLV-UHFFFAOYSA-N oxosulfamic acid Chemical class OS(=O)(=O)N=O ILXYDRFJSVKZLV-UHFFFAOYSA-N 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規かつ有用なキトサンスポンジに関するも
のであり、さらに詳しくは、特に医用分野において、創
傷保護用あるいは外用止血用スポンジとして有用なキト
サンスポンジに関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a new and useful chitosan sponge, and more specifically, to a chitosan sponge useful as a sponge for wound protection or external hemostasis, particularly in the medical field. It's about sponges.
（従来の技術）（発明が解決しようとする問題点）外用
止血用スポンジとしては、ゼラチンスポンジが実用化さ
れている。ゼラチンは２本来水溶性であるため、血液や
体液などにより湿潤すると速やかに？８解する。そこで
、ホルムアルデヒドアセチル、グリオキザールなどのタ
ンパク変性剤を用いて改質されたゼラチンスポンジが市
販されている。(Prior Art) (Problems to be Solved by the Invention) Gelatin sponges have been put into practical use as external hemostatic sponges. 2 Gelatin is naturally water-soluble, so when it gets wet with blood or body fluids, it quickly dissolves. 8 Solve. Therefore, gelatin sponges modified with protein denaturants such as formaldehyde acetyl and glyoxal are commercially available.
しかしながら、このように改質されたゼラチンスポンジ
も，まだ湿潤時の強度が低いため，血液や体液などで湿
潤した場合には，創傷保護材としての機能を失うという
欠点があった。However, gelatin sponges modified in this manner still have low strength when wet, and therefore have the disadvantage that they lose their function as wound protection materials when they become wet with blood, body fluids, etc.
キチンスポンジとしては，例えば、第１回国際キチン・
キトサン会議記録集（ Ｐｒｏｃｅｅｄｉｎｇｓ ｏｆ
ｔｈｅ Ｆｉｒｓｔ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃ
ｏｎｆｅｒｅｎｃｅ ｏｎ Ｃｈｉｔｉｎ／Ｃｈｉｔｏ
ｓａｎ） ３ ０ ０ページ、１６ 〜２４行に，セル
ローズビスコース法と同様な工程により得られたキチン
溶液に硫酸ナトリウムを混合し，その溶液を凝固した後
，硫酸ナトリウムを溶出させるというスポンジの製造方
法が記載されている。また。As a chitin sponge, for example, the first international chitin
Proceedings of Chitosan Conference
the First International C
onference on Chitin/Chito
San) Page 300, lines 16 to 24, describes the manufacture of a sponge by mixing sodium sulfate with a chitin solution obtained by a process similar to the cellulose viscose method, coagulating the solution, and then eluting the sodium sulfate. The method is described. Also.
本発明者らは，キチン溶液に水溶性高分子物質を添加混
合し，その混合液を凝固して得られたキチン成形体から
水溶性高分子物質を溶出除去するという，湿潤強度の高
いキチンスポンジの製造方法を確立した（特開昭６１−
５３３３９号）。The present inventors have developed a chitin sponge with high wet strength, which involves adding and mixing a water-soluble polymer substance to a chitin solution, solidifying the mixture, and eluting and removing the water-soluble polymer substance from the obtained chitin molded body. Established a manufacturing method for
No. 53339).
しかしながら、このようにして得られたキチンスポンジ
は、止血効果が弱いという欠点があった。However, the chitin sponge obtained in this way had a drawback of having a weak hemostatic effect.
そこで、先に本発明者らは、水に不溶であり。Therefore, the present inventors first determined that the compound is insoluble in water.
希酢酸水溶液に溶解するキトサンスポンジを提案した（
特願昭６１−１）４２６号）。We proposed a chitosan sponge that dissolves in dilute acetic acid aqueous solution (
Patent Application No. 426).
しかしながら、このキトサンスポンジは、キチンスポン
ジと比較して止血効果の点では改良されていたが９例え
ば深度の皮膚欠損傷などのように創部の滲出液が多い場
合には融解してしまうという傾向があった。すなわち、
外用スポンジとしては、より湿潤時にも堅牢な構造を保
持するとともに止血効果を有し、さらに創部の滲出液に
融解しないという性質が望まれていた。However, although this chitosan sponge was improved in terms of hemostatic effect compared to chitin sponges,9 it has a tendency to melt when there is a lot of exudate from the wound, such as when there is a deep skin injury. there were. That is,
As a sponge for external use, it has been desired to have properties that maintain a robust structure even when wet, have a hemostatic effect, and not dissolve in exudate from a wound.
キトサンの成形技術に関しては９例えば、特開昭５９−
１）６４１８号公報にキトサン繊維及びフィルムの製造
法が、特公昭５９−３０７２２号公報には粉粒状多孔質
キトサンの製造方法が記載されている。しかしながら、
キトサンスポンジについては何も記載されていない。Regarding molding technology of chitosan, see 9, for example, JP-A-59-
1) Japanese Patent Publication No. 6418 describes a method for producing chitosan fibers and films, and Japanese Patent Publication No. 59-30722 describes a method for producing porous chitosan powder. however,
Nothing is written about chitosan sponge.
本発明の目的は、湿潤強度と止血作用と融解耐性を具備
した新規かつ有用な外用スポンジを提供することにある
。An object of the present invention is to provide a novel and useful external sponge having wet strength, hemostatic action, and resistance to melting.
（問題点を解決するための手段）
本発明者らは、上記のごとき目的を達成すべく鋭意検討
の結果、キトサンをスポンジ状に成形したのち、酸無水
物にて処理することにり、十分満足すべき外用スポンジ
が得られるという事実を見出し１本発明を完成した。(Means for Solving the Problems) As a result of intensive studies to achieve the above objectives, the present inventors have found that chitosan is formed into a sponge shape and then treated with an acid anhydride. The present invention was completed based on the discovery that a satisfactory external sponge could be obtained.
すなわち２本発明は、水及び２％酢酸水溶液に不溶であ
り、かつ９．気孔率が８０％以上であるキトサンスポン
ジを要旨とするものである。That is, 2. the present invention is insoluble in water and 2% acetic acid aqueous solution; and 9. The gist is a chitosan sponge with a porosity of 80% or more.
本発明におけるキトサンとは、グルコサミンからなるか
、あるいはグルコサミンと少量のＮ−アセチルグルコサ
ミンとからなる高分子化合物であり、水に不溶であって
、希酢酸水溶液には溶解するものをいう。希酢酸水溶液
の好ましい濃度は。Chitosan in the present invention is a polymer compound made of glucosamine or glucosamine and a small amount of N-acetylglucosamine, which is insoluble in water but soluble in a dilute acetic acid aqueous solution. What is the preferred concentration of dilute acetic acid aqueous solution?
０、１〜１０ｖ／ｖ％であり、特に２ ｖ／ｖ％が好ま
しい。本発明におけるキトサンは１例えばその０．５ｇ
を１００ｍ／の２ ｖ／ｖ％酢酸水溶液に添加し。0.1 to 10 v/v%, particularly preferably 2 v/v%. Chitosan in the present invention is 1, for example, 0.5g
was added to 100 m/m of 2 v/v% acetic acid aqueous solution.
室温で少なくとも３時間撹拌すると、均一で粘性のある
液体となるような性質をもっている。工業的には、主と
してカニ、エビなどの外骨格を脱灰。It has the property of becoming a homogeneous and viscous liquid when stirred at room temperature for at least 3 hours. Industrially, it mainly demineralizes the exoskeletons of crabs, shrimp, etc.
脱タンパクして得られるキチンを、さらに脱Ｎ−アセチ
ル処理することにより得られる。It is obtained by further subjecting the chitin obtained by deproteinization to a de-N-acetyl treatment.
本発明のキトサンスポンジは、以下の方法によって製造
することができる。The chitosan sponge of the present invention can be manufactured by the following method.
まず、キトサン粉末を希酢酸水溶液に溶解する。First, chitosan powder is dissolved in a dilute acetic acid aqueous solution.
キトサンは、グルコサミンからなるか、あるいはグルコ
サミンと少量のＮ−アセチルグルコサミンとからなる高
分子化合物であり、工業的には、主としてカニ、エビな
どの外骨格を脱灰、脱タンパクして得られるキチンを、
さらに脱Ｎ−アセチル処理することにより得られる。用
いる希酢酸水溶液の好ましい濃度は２０ｖ／ｖ％以下、
さらに好ましくは１０ｖ／ｖ％以下、最適には１〜５
ｖ／ｖ％の範囲である。上記希酢酸水溶液に溶解するキ
トサン濃度は、用いるキトサンの重合度により異なるが
、好ましくは３０％以下、さらに好ましくは２０％以下
、最適には１〜１０％の範囲である。溶解する際の具体
的方法は、水にキトサン粉末をよく分散させた後、攪拌
しながら所定量の酢酸を添加することにより、均一なキ
トサン溶液を得ることができる。不溶解骨がある場合に
は濾過により除去し、透明で均一なキトサン溶液を得る
ことができる。Chitosan is a polymeric compound consisting of glucosamine or glucosamine and a small amount of N-acetylglucosamine.Industrially, chitosan is mainly chitin obtained by decalcifying and deproteinizing the exoskeleton of crabs, shrimps, etc. of,
It can be obtained by further removing N-acetyl. The preferred concentration of the dilute acetic acid aqueous solution used is 20v/v% or less,
More preferably 10v/v% or less, optimally 1 to 5%
It is in the range of v/v%. The concentration of chitosan dissolved in the dilute acetic acid aqueous solution varies depending on the degree of polymerization of the chitosan used, but is preferably 30% or less, more preferably 20% or less, and optimally in the range of 1 to 10%. A specific method for dissolving the chitosan powder is to thoroughly disperse chitosan powder in water and then add a predetermined amount of acetic acid while stirring to obtain a uniform chitosan solution. If there is undissolved bone, it can be removed by filtration to obtain a transparent and uniform chitosan solution.
ついで、このようにして得られたキトサン溶液を凝固し
、多孔性にする。そのためには９例えば次の二つの方法
をあげることができる。一番目の方法は、キトサン溶液
を１例えば界面活性剤、化学的発泡剤、あるいは気体吹
込みなど、何らかの方法により発泡させたのち凝固する
方法であり。The chitosan solution thus obtained is then coagulated and rendered porous. For this purpose, the following two methods can be cited. The first method is to foam the chitosan solution using some method, such as a surfactant, a chemical foaming agent, or gas blowing, and then solidify it.
番目の方法は、キトサン溶液に粉末状固体物質を添加し
て、よ（分散させてから凝固し１次いで粉末状固体物質
を除去する方法である。The second method is to add a powdery solid material to a chitosan solution, disperse it, solidify it, and then remove the powdery solid material.
一番目の方法において、キトサン溶液を発泡するに際し
用いられる発泡剤としては９例えば石ケン（高級脂肪酸
塩、一般式： ＲＣＯＯ−Ｍａ、硫酸化物（高級脂肪列
アルコールの半硫酸エステル。In the first method, the foaming agents used when foaming the chitosan solution include 9, for example, soap (higher fatty acid salt, general formula: RCOO-Ma, sulfate (half-sulfate ester of higher fatty acid series alcohol).
一般式： ＲＣＨｚＯ５ＯｚＯ−Ｍ’、 ラウリル硫酸
ナトリウムなど）、スルホン化物（Ｒ３Ｏ，０−Ｍつ。General formula: RCHzO5OzO-M', sodium lauryl sulfate, etc.), sulfonated products (R3O, 0-M).
アルキルスルホン化物、アルキルアリルスルホン化物、
アミドスルホン化物、エステルスルホン化物およびニト
ロシルスルホン化物などのアニオン性界面活性剤や種々
のカチオン性界面活性剤、さらにスパン（商品名）系、
ツイーン（商品名）系、ショ糖の脂肪酸エステル、脂肪
酸の多価アルコールエステル、ポリエチレングリコール
の脂肪酸エステルなどの非イオン性、および両性の界面
活性剤などがあげられる。その他、酢酸水溶液と反応し
て発泡するような物質として１例えば炭酸カルシウムな
どを添加してもよく、さらに空気、チッ素。Alkyl sulfonated products, alkylaryl sulfonated products,
Anionic surfactants such as amide sulfonates, ester sulfonates, and nitrosyl sulfonates, as well as various cationic surfactants, as well as span (trade name) type surfactants,
Examples include nonionic and amphoteric surfactants such as Tween (trade name), fatty acid esters of sucrose, polyhydric alcohol esters of fatty acids, and fatty acid esters of polyethylene glycol. In addition, a substance that reacts with the acetic acid aqueous solution and foams, such as calcium carbonate, may be added, as well as air and nitrogen.
炭酸ガスなどの気体を直接キトサン溶液に吹込んで発泡
させてもよい。発泡剤の添加量は、キトサン溶液が発泡
する量であればよ（、好ましくは重量比でキトサン溶液
の５０％以下、さらに好ましくは１０％以下、最適には
０．０１〜５％の範囲である。Gas such as carbon dioxide gas may be directly blown into the chitosan solution to cause foaming. The amount of foaming agent to be added may be such that the chitosan solution foams (preferably 50% or less of the chitosan solution by weight, more preferably 10% or less, optimally in the range of 0.01 to 5%). be.
以上述べた方法、あるいはそれらの組合せの方法により
発泡させたキトサン溶液を凝固するには。To solidify the chitosan solution foamed by the method described above or a combination thereof.
凝固液と接触させればよい。凝固液としては、メタノー
ル、エタノール、イソプロパツールなどのアルコール溶
液や、アルカリ性溶液が好ましく用いられる。その具体
例としては、水酸化ナトリウム、水酸化カリウムあるい
はアンモニアを含んだ水またはアルコール溶液があげら
れる。凝固液として２例えば水酸化ナトリウム水溶液を
用いる場合、その好ましい濃度は４０ｅｖ／ｖ％以下、
さらに好ましくは２０ｗ／ｖ％以下、最適には１〜１０
ｗ／ｖ％の範囲である。凝固したのち、水あるいは各種
溶剤で洗浄し、湿潤したキトサンスポンジを得ることが
できる。It may be brought into contact with a coagulating liquid. As the coagulating liquid, an alcohol solution such as methanol, ethanol, isopropanol, or an alkaline solution is preferably used. Specific examples include water or alcohol solutions containing sodium hydroxide, potassium hydroxide, or ammonia. 2 For example, when using an aqueous sodium hydroxide solution as the coagulating liquid, the preferable concentration is 40 ev/v% or less,
More preferably 20w/v% or less, optimally 1 to 10%
The range is w/v%. After solidification, it can be washed with water or various solvents to obtain a wet chitosan sponge.
二番目にあげた方法では、キトサン溶液に粉末状固体物
質を添加するが、その物質は水溶性であることが好まし
く、さらに好ましくは、常温では水に不溶であるが、熱
水には溶解するという性質をもつものである。このよう
な物質の具体例としては、水溶性高分子物質があり２例
えばポリビニルアルコール、ポリエチレングリコール、
ポリプロピレングリコール、寒天粉末、可溶性デンプン
などがあげられる。これらの粉末を、キトサン溶液に対
して重量比で０．２〜５倍の割合に添加し。In the second method, a powdered solid substance is added to the chitosan solution, preferably water-soluble, more preferably insoluble in water at room temperature but soluble in hot water. It has this property. Specific examples of such substances include water-soluble polymer substances, such as polyvinyl alcohol, polyethylene glycol,
Examples include polypropylene glycol, agar powder, and soluble starch. These powders were added at a weight ratio of 0.2 to 5 times the weight of the chitosan solution.
均一に混合したのち、凝固液と接触させて凝固する。凝
固したのち、水溶性高分子物質を溶解除去するために、
好ましくは８０℃以上の熱水処理を繰り返して湿潤した
キトサンスポンジを得ることができる。この二番目の方
法は、前記一番目の方法と比較し、湿潤強度の高いキト
サンスポンジが得られるという点で有利である。After uniformly mixing, it is brought into contact with a coagulating liquid and coagulated. After solidification, in order to dissolve and remove water-soluble polymer substances,
Preferably, a wet chitosan sponge can be obtained by repeating hot water treatment at 80° C. or higher. This second method is advantageous over the first method in that a chitosan sponge with high wet strength can be obtained.
本発明のキトサンスポンジを得るには１以上述べたよう
な方法により得られたキトサンスポンジを、ついで酸無
水物にて処理すればよい。In order to obtain the chitosan sponge of the present invention, the chitosan sponge obtained by one or more of the methods described above may be then treated with an acid anhydride.
酸無水物処理は、キトサンの遊離アミノ基を部分的にア
シル化するための処理であり、酸無水物としては１例え
ば無水酢酸、無水プロピオン酸。The acid anhydride treatment is a treatment for partially acylating the free amino groups of chitosan, and examples of the acid anhydride include acetic anhydride and propionic anhydride.
無水ｎ−酪酸、無水１ｓｏ−酪酸、無水ｎ−カプロン酸
、無水へブタン酸、無水マレイン酸、無水グルタル酸、
無水安息香酸などがあげられる。n-butyric anhydride, 1so-butyric anhydride, n-caproic anhydride, hebutanoic anhydride, maleic anhydride, glutaric anhydride,
Examples include benzoic anhydride.
酸無水物による処理は、キトサンスポンジと酸無水物と
を接触させることによって行うことができる。例えば、
酸無水物を含む溶液にキトサンスポンジを浸漬すること
によって行うことができる。Treatment with an acid anhydride can be performed by bringing the chitosan sponge into contact with the acid anhydride. for example,
This can be done by immersing a chitosan sponge in a solution containing an acid anhydride.
その場合の好ましい溶剤としては１例えばメチルアルコ
ール、エチルアルコール、プロピルアルコール、メチル
アルコールなどのアルコール類、アセトン、メチルエチ
ルケトンなどのケトン類、ジメチルホルムアミド、ジメ
チルアセトアミド、Ｎ−メチルピロリドンなどのアミド
系有機溶剤があげられる。Preferred solvents in this case include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and methyl alcohol, ketones such as acetone and methyl ethyl ketone, and amide organic solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. can give.
酸無水物の使用量は、キトサンスポンジ１重量部（乾燥
重量）に対し、０．１〜１００重量部が好ましく、さら
に好ましくは０．２〜１０重量部である。処理温度は、
好ましくは２０〜８０℃であり。The amount of acid anhydride used is preferably 0.1 to 100 parts by weight, more preferably 0.2 to 10 parts by weight, per 1 part by weight (dry weight) of the chitosan sponge. The processing temperature is
Preferably it is 20-80°C.
処理時間は、好ましくは５分〜１０時間、さらに好まし
くは３０分〜６時間である。The treatment time is preferably 5 minutes to 10 hours, more preferably 30 minutes to 6 hours.
処理後はキトサンスポンジを有機溶剤あるいは水によっ
て洗浄し、ついで乾燥すればよい。乾燥方法としては、
その多孔性を損なわない点でとくに凍結乾燥法が好まし
い。After treatment, the chitosan sponge may be washed with an organic solvent or water, and then dried. The drying method is
A freeze-drying method is particularly preferred in that it does not impair its porosity.
以上述べた方法により得られる本発明のキトサンスポン
ジは、２％酢酸水溶液に不溶であり、かつ、気孔率が高
いという特徴をもっている。ここで２％酢酸水溶液とは
イオン交換水又は薄情水中に氷酢酸を２ ｖ ／ ｖ含
有する水溶液を意味し２本発明のキトサンスポンジは、
２５℃のこの２％酢酸水溶液に浸漬したとき、少なくと
も６時間経過後も溶解せずにその形態を保つという性能
を有する。また、ここで気孔率とは、キトサンスポンジ
の単位重量あたりに含まれる細孔容積の、スポンジ全体
の容積に対する割合を百分率で表示したものである。例
えば、スポンジの容積がＡｃｊで、そのスポンジ内部の
細孔容積がＢｅｄである場合には。The chitosan sponge of the present invention obtained by the method described above is characterized by being insoluble in a 2% acetic acid aqueous solution and having a high porosity. Here, the 2% aqueous acetic acid solution means an aqueous solution containing 2 v/v of glacial acetic acid in ion-exchanged water or light water.2 The chitosan sponge of the present invention is
When immersed in this 2% acetic acid aqueous solution at 25°C, it maintains its shape without dissolving even after at least 6 hours. Moreover, the porosity here refers to the ratio of the pore volume contained per unit weight of the chitosan sponge to the volume of the entire sponge, expressed as a percentage. For example, if the volume of the sponge is Acj and the pore volume inside the sponge is Bed.
気孔率はＢ／ＡＸ １００ｅ％）となる。本発明のキト
サンスポンジは、気孔率が、８０％以上、好ましくは９
０％以上、最適には９５％以上である。The porosity is B/AX 100e%). The chitosan sponge of the present invention has a porosity of 80% or more, preferably 9
0% or more, optimally 95% or more.
（実施例） 次に実施例をあげ１本発明をさらに具体的に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例１
キトサン粉末〔新日本化学０製〕１０ｇを９７０ｍ１ｌ
の薄情水に懸濁し、約３０分間室温で攪拌したのち、’
ｌＱｍ１の氷酢酸を加え、さらに２時間室温で攪拌した
。得られた粘性の高いキトサン溶液を１４８０メツシユ
のステンレスネットを用いて濾過し、透明なキトサン溶
液を得た。Example 1 Chitosan powder [manufactured by Shin Nihon Kagaku 0] 10g in 970ml
After suspending the suspension in water and stirring at room temperature for about 30 minutes,
1Qm1 of glacial acetic acid was added, and the mixture was further stirred at room temperature for 2 hours. The obtained highly viscous chitosan solution was filtered using a 1480 mesh stainless steel net to obtain a transparent chitosan solution.
キトサン？容液１００ｇをビーカーにとり、０．５ｇの
ドデシル硫酸ナトリウム粉末を加え、激しく攪拌してキ
トサン溶液を発泡させたのち、直径１．５１のシリンダ
ーから４ｗ／ｖ％の濃度に水酸化ナトリウムを含むメタ
ノール中に押し出し、キトサン溶液を円柱状に凝固させ
た。このものの水洗を繰り返し、ついでメタノールで洗
浄したのち、メタノール９５０ｇと無水酢酸５０ｇの混
合溶液中に浸漬し、６０℃で４時間ゆるやかに攪拌した
。ついでメタノールで洗浄し、さらに水洗したのち凍結
乾燥して１円柱状のキトサンスポンジを得た。Chitosan? Take 100 g of the solution in a beaker, add 0.5 g of sodium dodecyl sulfate powder, stir vigorously to foam the chitosan solution, and then add methanol containing sodium hydroxide to a concentration of 4 w/v % from a cylinder with a diameter of 1.51. The chitosan solution was extruded into a cylindrical shape. This product was repeatedly washed with water and then with methanol, and then immersed in a mixed solution of 950 g of methanol and 50 g of acetic anhydride, and gently stirred at 60° C. for 4 hours. Next, the mixture was washed with methanol, further washed with water, and then freeze-dried to obtain a cylindrical chitosan sponge.
このようにして得られたキトサンスポンジの気孔率は９
６％であり、湿潤強度は２．８ｇ／ｍｍ２であった。ま
た、このキトサンスポンジは水には溶解せず、２５℃の
２％酢酸水溶液に６時間浸漬してもわずかに膨潤するも
のの円柱状の形態を保ら溶解しなかった。The porosity of the chitosan sponge thus obtained was 9
6%, and the wet strength was 2.8 g/mm2. Further, this chitosan sponge did not dissolve in water, and even when immersed in a 2% acetic acid aqueous solution at 25° C. for 6 hours, it swelled slightly but maintained a cylindrical shape and did not dissolve.
実施例２
キトサン粉末２５ｇを９５５ｍ１ｌの薄情水に懸濁し、
約３０分間室温で攪拌したのち、’ｌＱｍｌの氷酢酸を
加え、さらに約３時間室温で攪拌した。Example 2 25g of chitosan powder was suspended in 955ml of light water,
After stirring at room temperature for about 30 minutes, 1Qml of glacial acetic acid was added, and the mixture was further stirred at room temperature for about 3 hours.
得られたキトサン溶液を１４８０メツシユのステンレス
ネットを用いて濾過し、透明なキトサン溶液を得た。The obtained chitosan solution was filtered using a 1480 mesh stainless steel net to obtain a transparent chitosan solution.
キトサン溶液１００ｇをビーカーにとり、５０ｇのポリ
ビニルアルコール〔ポバール０Ｆ−１７０ＧＳ、ユニチ
カケミカル■製：重合度１７０．ケン化度９５モル％以
上〕を添加して攪拌し、均一に分散させた。次いで、減
圧下で脱泡したのち。Take 100 g of chitosan solution in a beaker and add 50 g of polyvinyl alcohol [Poval 0F-170GS, manufactured by Unitika Chemical ■: degree of polymerization 170. Saponification degree of 95 mol% or more] was added and stirred to uniformly disperse. Then, after degassing under reduced pressure.
ガラス板上に約５鶴の厚みに流延し、４ｗ／ｖ％水酸化
ナトリウム水溶液に浸漬して凝固させた。ガラス板から
はがし、１）５℃の熱水処理を繰り返してポリビニルア
ルコールを溶出除去した。ついでメタノールで洗浄した
のち、メタノール１９００ｇと無水酢酸１００ｇとの混
合溶液中に浸漬し。It was cast onto a glass plate to a thickness of about 5 mm, and solidified by immersing it in a 4 w/v % aqueous sodium hydroxide solution. It was peeled off from the glass plate, and the polyvinyl alcohol was eluted and removed by repeating 1) hot water treatment at 5°C. Then, after washing with methanol, it was immersed in a mixed solution of 1900 g of methanol and 100 g of acetic anhydride.
６０℃で３時間ゆるやかに攪拌した。ついでメタノール
で洗浄し、さらに水洗したのち凍結乾燥して、シート状
のキトサンスポンジを得た。The mixture was gently stirred at 60°C for 3 hours. Next, the mixture was washed with methanol, further washed with water, and then freeze-dried to obtain a sheet-like chitosan sponge.
このようにして得られたキトサンスポンジの気孔率は９
７％であり、湿潤強度は３．０ｇ／ｍｓ”であった。ま
た、このキトサンスポンジは水には溶解せず、２５℃の
２％酢酸水溶液に６時間浸漬しても形態を保ち溶解しな
かった。The porosity of the chitosan sponge thus obtained was 9
7%, and the wet strength was 3.0 g/ms''.In addition, this chitosan sponge did not dissolve in water and retained its shape even when immersed in a 2% acetic acid aqueous solution at 25°C for 6 hours. There wasn't.
参考例１
酸無水物処理を行わなかったったキトサンスポンジと１
本発明のキトサンスポンジとの創傷保護材としての融解
耐性を比較した。Reference example 1 Chitosan sponge that was not treated with acid anhydride and 1
The melting resistance as a wound protection material was compared with the chitosan sponge of the present invention.
本発明のキトサンスポンジとしては、実施例２に記載の
方法で得られたシート状スポンジを用いた。比較のため
用いる酸無水物処理を行わなかったったキトサンスポン
ジとしては、実施例２に記載の方法において、酸無水物
処理のみを行わなかったものを用いた。すなわち、ポリ
ビニルアルコールを溶出除去したのち、水洗し、凍結乾
燥したものを用いた。As the chitosan sponge of the present invention, a sheet-like sponge obtained by the method described in Example 2 was used. As a chitosan sponge that was not subjected to acid anhydride treatment and used for comparison, a chitosan sponge that was not subjected to acid anhydride treatment was used in the method described in Example 2. That is, after polyvinyl alcohol was eluted and removed, it was washed with water and freeze-dried.
体重約２．５ｋｇ０家兎の背毛をそり、左右一対の剥皮
側（５ｃｍＸ５ｃｍ）を作った。右側に本発明のキトサ
ンスポンジを貼付し、左側に比較例の未処理のキトサン
スポンジを貼付したのち、木綿ガーゼをこれに当て、粘
着テープで固定した。創部からの滲出液によりガーゼが
汚れるため、ガーゼを毎日交換したが、貼付後２日目頃
から比較例のスポンジは融解が始まり、４日目では創部
の貯留液と区別できない状態となり、創傷保護材として
の機能を完全に失っていた。これに対し９本発明のスポ
ンジは、７日間経過後も目視により融解を認めず、構造
的にもしっかりとした多孔性を保ち。The back hair of a rabbit weighing approximately 2.5 kg was shaved, and a pair of left and right skinned sides (5 cm x 5 cm) were made. The chitosan sponge of the present invention was attached to the right side, and the untreated chitosan sponge of the comparative example was attached to the left side, and then cotton gauze was applied to this and fixed with adhesive tape. The gauze was soiled by exudate from the wound, so the gauze was replaced every day, but the sponge in the comparative example began to melt around the second day after application, and by the fourth day it was in a state that could not be distinguished from the fluid accumulated in the wound, making it difficult to protect the wound. It had completely lost its function as a material. On the other hand, the sponge of the present invention did not visually observe any melting even after 7 days had passed, and maintained a solid structure and porosity.
創部滲出液を遅滞なく上部のガーゼに吸収させるという
機能を保ち続けた。The function of absorbing wound exudate into the upper gauze without delay continued to be maintained.
（発明の効果）
本発明のキトサンスポンジは、高い湿潤強度と優れた止
血効果とを具備し、さらに創部滲出液に対する融解耐性
を有する。したがって、深度の皮膚欠損側など滲出液の
多い創部に使用した場合にも、長時間にわたってスポン
ジ状構造を維持できて、滲出液の貯留を防ぐという創傷
保護材として大きな利点を備えたものである。(Effects of the Invention) The chitosan sponge of the present invention has high wet strength and excellent hemostatic effect, and also has melting resistance against wound exudate. Therefore, even when used on a wound with a large amount of exudate, such as the side of a deep skin defect, it can maintain a spongy structure for a long time and has the great advantage of being a wound protection material in that it prevents exudate from accumulating. .
Claims (1)
率が８０％以上であるキトサンスポンジ。(1) A chitosan sponge that is insoluble in water and a 2% acetic acid aqueous solution and has a porosity of 80% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61236622A JPH0751603B2 (en) | 1986-10-03 | 1986-10-03 | Chitosan sponge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61236622A JPH0751603B2 (en) | 1986-10-03 | 1986-10-03 | Chitosan sponge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6390507A true JPS6390507A (en) | 1988-04-21 |
| JPH0751603B2 JPH0751603B2 (en) | 1995-06-05 |
Family
ID=17003362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61236622A Expired - Lifetime JPH0751603B2 (en) | 1986-10-03 | 1986-10-03 | Chitosan sponge |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0751603B2 (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05305129A (en) * | 1992-05-02 | 1993-11-19 | Nishikawa Rubber Co Ltd | Medical cover protective material |
| WO2001004187A1 (en) * | 1999-07-12 | 2001-01-18 | Cognis Deutschland Gmbh | Preparations that are devoid of cross-linking agents |
| WO2001004207A1 (en) * | 1999-07-12 | 2001-01-18 | Cognis Deutschland Gmbh | Preparations containing no cross-linking agents |
| WO2003094893A1 (en) * | 2002-05-08 | 2003-11-20 | Hee-Young Lee | Process for preparing an injection type solid chitosan powder |
| JP2005503197A (en) * | 2001-06-14 | 2005-02-03 | プロビデンス ヘルス システム−オレゴン | Wound dressing and method for controlling severe and life-threatening bleeding |
| JP2007236551A (en) * | 2006-03-07 | 2007-09-20 | National Institute For Materials Science | Chitin derivative composite material and medical material |
| US7371403B2 (en) | 2002-06-14 | 2008-05-13 | Providence Health System-Oregon | Wound dressing and method for controlling severe, life-threatening bleeding |
| JP2008220388A (en) * | 2006-02-14 | 2008-09-25 | Koyo Chemical Kk | Sponge hemostatic material made of amorphous partial deacetylated chitin salt, and method of manufacturing the same |
| JP2009513239A (en) * | 2005-10-28 | 2009-04-02 | ヘムコン， インコーポレイテッド | Hydrophilic polymer dental sponge |
| WO2015029892A1 (en) * | 2013-08-29 | 2015-03-05 | 大日精化工業株式会社 | Method for manufacturing water-insoluble molded article and water-insoluble molded article |
| US10086105B2 (en) | 2008-10-06 | 2018-10-02 | Providence Health System—Oregon | Chitosan foam medical devices and methods |
| US10398655B2 (en) * | 2016-02-18 | 2019-09-03 | Privo Technologies, Inc. | Two-stage microparticle-based therapeutic delivery system and method |
| CN112088184A (en) * | 2018-05-07 | 2020-12-15 | 克鲁兹泡沫有限公司 | Biodegradable foams |
| US11872319B2 (en) | 2017-05-03 | 2024-01-16 | Privo Technologies, Inc. | Intraoperative topically-applied non-implantable rapid release patch |
| US11938228B2 (en) | 2017-02-17 | 2024-03-26 | Privo Technologies, Inc. | Particle-based multi-layer therapeutic delivery device and method |
-
1986
- 1986-10-03 JP JP61236622A patent/JPH0751603B2/en not_active Expired - Lifetime
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05305129A (en) * | 1992-05-02 | 1993-11-19 | Nishikawa Rubber Co Ltd | Medical cover protective material |
| WO2001004187A1 (en) * | 1999-07-12 | 2001-01-18 | Cognis Deutschland Gmbh | Preparations that are devoid of cross-linking agents |
| WO2001004207A1 (en) * | 1999-07-12 | 2001-01-18 | Cognis Deutschland Gmbh | Preparations containing no cross-linking agents |
| JP2005503197A (en) * | 2001-06-14 | 2005-02-03 | プロビデンス ヘルス システム−オレゴン | Wound dressing and method for controlling severe and life-threatening bleeding |
| US7820872B2 (en) | 2001-06-14 | 2010-10-26 | Providence Health System-Oregon | Wound dressings, apparatus, and methods for controlling severe, life-threatening bleeding |
| WO2003094893A1 (en) * | 2002-05-08 | 2003-11-20 | Hee-Young Lee | Process for preparing an injection type solid chitosan powder |
| US7371403B2 (en) | 2002-06-14 | 2008-05-13 | Providence Health System-Oregon | Wound dressing and method for controlling severe, life-threatening bleeding |
| JP2009513239A (en) * | 2005-10-28 | 2009-04-02 | ヘムコン， インコーポレイテッド | Hydrophilic polymer dental sponge |
| JP2008220388A (en) * | 2006-02-14 | 2008-09-25 | Koyo Chemical Kk | Sponge hemostatic material made of amorphous partial deacetylated chitin salt, and method of manufacturing the same |
| JP2007236551A (en) * | 2006-03-07 | 2007-09-20 | National Institute For Materials Science | Chitin derivative composite material and medical material |
| US10086105B2 (en) | 2008-10-06 | 2018-10-02 | Providence Health System—Oregon | Chitosan foam medical devices and methods |
| WO2015029892A1 (en) * | 2013-08-29 | 2015-03-05 | 大日精化工業株式会社 | Method for manufacturing water-insoluble molded article and water-insoluble molded article |
| JP6077663B2 (en) * | 2013-08-29 | 2017-02-08 | 大日精化工業株式会社 | Method for producing water-insoluble molded body and water-insoluble molded body |
| US9879124B2 (en) | 2013-08-29 | 2018-01-30 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Method for manufacturing water-insoluble molded article and water-insoluble molded article |
| US10398655B2 (en) * | 2016-02-18 | 2019-09-03 | Privo Technologies, Inc. | Two-stage microparticle-based therapeutic delivery system and method |
| US11617722B2 (en) | 2016-02-18 | 2023-04-04 | Privo Technologies, Inc. | Two-stage microparticle-based therapeutic delivery system and method |
| US11938228B2 (en) | 2017-02-17 | 2024-03-26 | Privo Technologies, Inc. | Particle-based multi-layer therapeutic delivery device and method |
| US11872319B2 (en) | 2017-05-03 | 2024-01-16 | Privo Technologies, Inc. | Intraoperative topically-applied non-implantable rapid release patch |
| CN112088184A (en) * | 2018-05-07 | 2020-12-15 | 克鲁兹泡沫有限公司 | Biodegradable foams |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0751603B2 (en) | 1995-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6390507A (en) | Chitosan sponge | |
| US4501835A (en) | Polyacrylic acid/chitosan polyelectrolyte complex | |
| US7189667B1 (en) | Sponge towel based on cellulose and a method for producing the same | |
| JPS6145655B2 (en) | ||
| JPS6153339A (en) | Formed article of porous chitin, and its production | |
| US4062921A (en) | Solvents for and purification of chitin | |
| JPS62167331A (en) | Chitosan sponge | |
| JPS6176504A (en) | Production of porous granular chitosan | |
| JPS6059123A (en) | Production of chitosan fiber | |
| KR100912644B1 (en) | The preparing method of chemically transformed chitosan fiber | |
| JP2754162B2 (en) | Manufacturing method of chitin sponge, chitin paper and chitin film | |
| JPH02261838A (en) | Preparation of porous chitosan material | |
| JP2003292501A (en) | Chitosan sponge and method for producing the same | |
| JPH0442020B2 (en) | ||
| JPS6225168B2 (en) | ||
| KR100691869B1 (en) | A method for preparing chitosan/poly ?-glutamic acid polyelectrolyte complex | |
| JP4224775B2 (en) | Good quality chitosan sponge sheet | |
| JP2008094989A (en) | Method for dissolution of chitosan to water and resulting composition | |
| JPH0813746B2 (en) | Hemostatic agent | |
| JP3527582B2 (en) | Cellulose porous body and method for producing the same | |
| US3885054A (en) | Edible collagen casing cross-linked by bisulfite addition | |
| JPH0315464A (en) | Sheet for absorbing living body component | |
| JPS63186701A (en) | Chitin sponge | |
| JPS6253661A (en) | Chitin molded body | |
| JPH01308565A (en) | Chitosan type deodorant |