JPH02274257A - Laminate type porous chitin material and its manufacture - Google Patents
Laminate type porous chitin material and its manufactureInfo
- Publication number
- JPH02274257A JPH02274257A JP1095352A JP9535289A JPH02274257A JP H02274257 A JPH02274257 A JP H02274257A JP 1095352 A JP1095352 A JP 1095352A JP 9535289 A JP9535289 A JP 9535289A JP H02274257 A JPH02274257 A JP H02274257A
- Authority
- JP
- Japan
- Prior art keywords
- chitin
- porous
- layer
- aqueous solution
- sheet
- 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
- 229920002101 Chitin Polymers 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000010409 thin film Substances 0.000 claims abstract description 21
- 238000006640 acetylation reaction Methods 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 230000002378 acidificating effect Effects 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 230000010933 acylation Effects 0.000 claims description 11
- 238000005917 acylation reaction Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 230000021736 acetylation Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 206010052428 Wound Diseases 0.000 description 17
- 208000027418 Wounds and injury Diseases 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000012528 membrane Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241000700199 Cavia porcellus Species 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 208000005422 Foreign-Body reaction Diseases 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 206010040047 Sepsis Diseases 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 230000009450 sialylation Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 230000008736 traumatic injury Effects 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はラミネート型多孔質キチン材料、およびその製
造方法に関するものである。更に詳しく述べるならば、
本発明は保水材、或は創傷被覆材等として有用な、ラミ
ネート型多孔質キチン材料、および、それを効率よく製
造する方法に係るものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a laminated porous chitin material and a method for producing the same. To explain in more detail,
The present invention relates to a laminated porous chitin material useful as a water-retaining material, a wound dressing, etc., and a method for efficiently producing the same.
キチンは、Ｎ−アセチル−Ｄ−グルコサミンの１．４−
β結合体からなる高分子物質であり、自然界には、セル
ロースに匹敵する量で存在している。しかしながら、キ
チンは、極めて結晶性が高く、かつその分子内でアミノ
アセチル基が、極めて強固な結合を形成しているので、
これを溶媒中に溶解、分散、或いは膨潤させることが極
めて困難であり、このため、キチン資源の有効利用法の
開発が、著しく遅れている。Chitin is a 1,4-
It is a polymeric substance consisting of β-conjugates, and exists in nature in an amount comparable to that of cellulose. However, chitin has extremely high crystallinity and aminoacetyl groups form extremely strong bonds within its molecules.
It is extremely difficult to dissolve, disperse, or swell chitin in a solvent, and for this reason, the development of effective utilization methods for chitin resources has been significantly delayed.
従って、キチン資源の有効利用を促進するためには、キ
チン材料の溶解および凝固を自由に行うことができ、そ
れによって、キチン材料を所望の形状、構造に変換する
技術の開発が強く望まれている。Therefore, in order to promote the effective use of chitin resources, it is strongly desired to develop a technology that can freely melt and solidify chitin materials and thereby convert them into desired shapes and structures. There is.
一方、悲傷及び物理的、外科的な皮膚欠損部の創傷面を
一定期間安全に被覆保護する目的で創傷被覆材が使用さ
れている。On the other hand, wound dressings are used for the purpose of safely covering and protecting the wound surfaces of traumatic injuries, physical and surgical skin defects for a certain period of time.
例えば熱傷の治療に、現在各種の創傷被覆材が使用され
ているが、広範囲熱傷において効果的に感染を防止でき
る創傷被覆材はいまだ開発されていない。For example, various wound dressings are currently used to treat burns, but a wound dressing that can effectively prevent infection in extensive burns has not yet been developed.
悲傷による死亡の最も多い原因は、細菌感染による敗血
症である。それゆえ、外部からの細菌の侵入を阻止し、
創傷面に既に存在する細菌の増殖を抑制できる創傷被覆
材の開発は、臨床医療により強く望まれている。The most common cause of death from trauma is sepsis caused by bacterial infection. Therefore, it prevents the invasion of bacteria from the outside,
The development of wound dressings that can suppress the growth of bacteria already present on the wound surface is strongly desired by clinical medicine.
このような要求に答えるためには、創傷被覆材はつぎの
ような性質を具備することが重要である。In order to meet these demands, it is important for the wound dressing to have the following properties.
すなわち、創傷面において著しい異物反応を起こさない
非刺激性の材料であること、および、創傷面との密着性
が良好であることなどである。良好な密着が得られなけ
れば浸出液の貯留を生じ、細菌の増殖を促進する結果と
なる。創傷面との確実な密着を得るためには、多孔質構
造体を用いることが好ましい。しかし、一方、外部から
の細菌の侵入を阻止するためには、均一非多孔質膜が適
していると思われる。That is, it must be a non-irritating material that does not cause a significant foreign body reaction on the wound surface, and it must have good adhesion to the wound surface. If good adhesion is not achieved, exudate will accumulate and the growth of bacteria will be promoted. In order to obtain reliable contact with the wound surface, it is preferable to use a porous structure. However, on the other hand, a uniform non-porous membrane seems to be suitable for preventing the invasion of bacteria from the outside.
このような創傷被覆材として、キチンを利用しようとす
る試みが知られているが、このような用途に適合した、
組織構造を有するキチン誘導体材料およびその製造方法
が知られていなかった。Attempts to use chitin as such a wound dressing material are known, but there are
A chitin derivative material having a tissue structure and a method for producing the same have not been known.
本発明は、保水材および創傷被覆材などの用途に適した
組織および構造を有するラミネート型多孔質キチン材料
、および、その製造方法を提供しようとするものである
。The present invention aims to provide a laminated porous chitin material having a structure and structure suitable for uses such as water-retaining materials and wound dressings, and a method for producing the same.
本発明のラミネート型キチン多孔質積層材料は、キチン
からなり、かつ、三次元網状の連続空孔を有する三次元
網状構造体から構成された多孔質層と、この多孔質層の
少なくとも一面上に形成され、かつキチンからなる非多
孔質簿膜層と、からなることを特徴とするものである。The laminated chitin porous laminate material of the present invention includes a porous layer made of chitin and a three-dimensional network structure having three-dimensional continuous pores, and a porous layer on at least one surface of the porous layer. and a non-porous membrane layer made of chitin.
上記多孔質材料を製造するための本発明方法は、キチン
の脱Ｎ−アセチル化生成物を酸水溶液に溶解して、酸性
水溶液を調製し、
前記キチンの脱Ｎ−アセチル化生成物酸性水溶液の一部
分をシート状に展延し、これを凍結乾燥して、キチンの
脱Ｎ−アセチル化生成物からなる多孔質シートを形成し
、
別に、前記酸性水溶液の他の一部分を薄膜状に展延し、
これを蒸発乾燥して、キチンの脱Ｎ−アセチル化生成物
からなる非多孔質薄膜を作成し、前記キチンの脱Ｎ−ア
セチル化生成物非多孔質薄膜を、それが完全に乾燥しな
いうちに、又は、その乾燥体の一面を水で湿潤して、こ
れを、前記キチンの脱Ｎ−アセチル化生成物多孔質シー
トの一面に積層貼着し、
前記積層体に、有機酸無水物を含むアシル化剤によるア
シル化処理を施して、前記キチンの脱Ｎ−アセチル化生
成物をキチン化し、
得られたキチン積層体を乾燥する、
ことを特徴とするものである。The method of the present invention for producing the above-mentioned porous material includes dissolving the de-N-acetylation product of chitin in an acid aqueous solution to prepare an acidic aqueous solution, and dissolving the de-N-acetylation product of chitin in the acidic aqueous solution. A portion of the acidic aqueous solution is spread into a sheet and freeze-dried to form a porous sheet made of the de-N-acetylated chitin product. Separately, the other portion of the acidic aqueous solution is spread into a thin film. ,
This is evaporated to dryness to create a non-porous thin film of the de-N-acetylated chitin product, and the non-porous thin film of the de-N-acetylated chitin product is removed before it is completely dried. or, one side of the dried product is moistened with water and laminated and pasted on one side of the chitin de-N-acetylation product porous sheet, and the laminate contains an organic acid anhydride. The method is characterized in that the chitin de-N-acetylated product is chitinated by performing an acylation treatment using an acylating agent, and the obtained chitin laminate is dried.
また、上記多孔質材料を製造するための他の本発明方法
は、キチンの脱Ｎ−アセチル化生成物を酸水溶液に溶解
して、酸性水溶液を調製し、このキチンの脱Ｎ−アセチ
ル化生成物酸性水溶液をシート状に展延し、
このシート状層の表面に塩基性物質のガス流、又は噴霧
流を接触させて、このシート状層の表面部分を中和・凝
固させてキチンの脱Ｎ−アセチル化生成物からなる非多
孔質薄膜を形成し、かつ、シート状層を凍結乾燥して、
残余のキチンの脱Ｎ−アセチル化生成物の酸性水溶液か
ら多孔質シートを形成し、キチンの脱Ｎ−アセチル化生
成物からなる、非多孔質簿膜層と多孔質シート層との積
層体を形成し、
この積層体に、有機酸無水物を含むアシル化剤によるア
シル化処理を施して、キチンの脱Ｎ−アセチル化生成物
をキチン化し、
得られたキチン積層体を乾燥する、
ことを特徴とするものである。Another method of the present invention for producing the above-mentioned porous material includes dissolving the de-N-acetylated product of chitin in an acid aqueous solution to prepare an acidic aqueous solution, and producing the de-N-acetylated chitin. The acidic aqueous solution is spread in the form of a sheet, and the surface of this sheet-like layer is brought into contact with a gas stream or a spray stream of a basic substance to neutralize and solidify the surface portion of this sheet-like layer, thereby removing chitin. forming a non-porous thin film of the N-acetylated product and freeze-drying the sheet-like layer;
A porous sheet is formed from an acidic aqueous solution of the remaining chitin de-N-acetylated product, and a laminate of a non-porous film layer and a porous sheet layer made of the chitin de-N-acetylated product is formed. forming the laminate, subjecting the laminate to an acylation treatment with an acylating agent containing an organic acid anhydride to chitinate the de-N-acetylation product of chitin, and drying the obtained chitin laminate. This is a characteristic feature.
本発明の創傷被覆材は、上記のラミネート型キチン多孔
譬材料を有効主要素とするものである。The wound dressing of the present invention has the above-mentioned laminated chitin porous material as an effective main element.
本発明者らは、上述の状況に鑑み、キチン材料の利用開
発に関して鋭意研究の結果、キチンの脱Ｎ−アセチル化
生成物であるキトサンは、酸水溶液に溶解し、この酸性
水溶液は、アルカリで中和すると凝固して皮膜を形成す
ること、またこのキトサン酸性水溶液を凍結乾燥すると
容易に多孔質化し、これを風乾すると容易に薄膜化する
ことができること、湿潤状態において両者はたやすく接
着、一体化してラミネート化することができること、お
よびキトサン材料をアシル化剤で処理するとキチン化し
て酸、アルカリ、−Ｉｎの有機溶媒に不７容となること
などを見い出し、本発明に到達したのである。In view of the above-mentioned situation, the present inventors have conducted intensive research on the development of the use of chitin materials. As a result, chitosan, which is a de-N-acetylation product of chitin, is dissolved in an acid aqueous solution, and this acidic aqueous solution is alkali-based. When neutralized, it coagulates to form a film; when this acidic aqueous chitosan solution is freeze-dried, it easily becomes porous; when air-dried, it can easily be made into a thin film; and when wet, the two easily adhere and form a single body. The present invention was achieved by discovering that the chitosan material can be oxidized and laminated, and that when chitosan material is treated with an acylating agent, it becomes chitinized and becomes insoluble in organic solvents such as acids, alkalis, and -In.
本発明のラミネート型多孔質キチン材料は、多孔質キチ
ン層と、その少なくとも１面上に形成・結着しているキ
チン非多孔質簿膜層とからなるものである。The laminated porous chitin material of the present invention consists of a porous chitin layer and a non-porous chitin film layer formed and bound on at least one surface of the porous chitin layer.
上記キチン多孔質層は、三次元網状の連続空孔を有する
ものであり、このような複雑な形状の連続空孔をとりか
こむ、キチンからなる実体部分（マトリフクス）も三次
元網状の複雑な連続構造を有するものである。また、キ
チンからなる非多孔質簿膜層は、実質的に連続空孔を有
しない、又は少ない均質層であり、多孔質層よりも高い
密度を有するものである。The chitin porous layer has three-dimensional network-like continuous pores, and the substantial part (matrix) made of chitin that surrounds these complex-shaped continuous pores also has a three-dimensional network-like continuous pore. It has a structure. Further, the non-porous membrane layer made of chitin is a homogeneous layer having substantially no or few continuous pores, and has a higher density than the porous layer.
多孔質層および、非多孔質薄ＩＩ！ｉＩ層の厚さは、キ
チン材料の用途や必要性能に応じて適宜定められるもの
であって、格別の限定はない。しかし、般に、多孔質層
は０．１〜５０ｍｍの厚さ、およびｏ、ｏｏｓ〜０．１
５ｇ／Ｃ１ｊの密度を有するものであることが好ましく
、また、非多孔質層は、０．３〜１００−の厚さ、およ
び０．８〜１．３ ｇ ／ｃ４の密度を有するものであ
ることが好ましい。Porous layer and non-porous thin II! The thickness of the iI layer is appropriately determined depending on the use and required performance of the chitin material, and is not particularly limited. However, in general, the porous layer has a thickness of 0.1 to 50 mm, and o, oos to 0.1
Preferably, the non-porous layer has a density of 5 g/c, and the non-porous layer has a thickness of 0.3 to 100 and a density of 0.8 to 1.3 g/c. It is preferable.
本発明のラミネート型多孔質キチン材料は、上記の本発
明方法により製造することができる。The laminated porous chitin material of the present invention can be produced by the method of the present invention described above.
本発明方法に用いられるキチンの脱Ｎ−アセチル化生成
物は、市販品から入手したものでもよく、或は、カニ、
エビなどの甲かく類の殻から常法により分離精製して得
られたキチンを濃アルカリとともに加熱して脱Ｎ−アセ
チル化反応を行わせて得られたものであってもよい。一
般に、本発明に用いられるキチンの脱Ｎ−アセチル化生
成物は、それが酸水溶液に可溶である限り、その脱Ｎ−
アセチル化度に格別の限定はない、しかし、一般に、脱
Ｎ−アセチル化度は、５０〜１００％であることが好ま
しく、５０〜９９％であることがより好ましい。The chitin de-N-acetylation product used in the method of the present invention may be obtained from a commercially available product, or may be obtained from crab, crab, etc.
Chitin obtained by separating and purifying the shells of shellfish such as shrimp by conventional methods may be heated with concentrated alkali to perform a de-N-acetylation reaction. In general, the de-N-acetylation product of chitin used in the present invention can be used as long as it is soluble in an aqueous acid solution.
There is no particular limitation on the degree of acetylation, but in general, the degree of de-N-acetylation is preferably from 50 to 100%, more preferably from 50 to 99%.
本発明方法において、キチンの脱Ｎ−アセチル化生成物
を酸の水溶液に溶解し、酸性水溶液を調製する。この工
程に用いられる酸には、それがキチンの脱Ｎ−アセチル
化生成物を分解或は変質させない限り、格別の限定はな
いが、例えば酢酸、乳酸、および塩酸から選ばれる。こ
のとき用いられる酸水溶液の酸濃度には、キチンの脱Ｎ
−アセチル化生成物を溶解し得る限り格別の限定はない
が、一般に、０．５〜１５％酢酸水溶液、１〜２０％乳
酸水溶液、および０．５〜８％塩酸水溶液を用いること
が好ましい。また、このような酸水溶液に溶解されるキ
チンの脱Ｎ−アセチル化生成物の濃度は、それから得ら
れる溶液が、所望の流動性を有する限り、任意に設定す
ることができるが、一般には、０．５〜１５％（重量）
の範囲にあることが好ましい。In the method of the present invention, the de-N-acetylation product of chitin is dissolved in an aqueous acid solution to prepare an acidic aqueous solution. The acid used in this step is not particularly limited as long as it does not degrade or alter the de-N-acetylation product of chitin, but is selected from, for example, acetic acid, lactic acid, and hydrochloric acid. The acid concentration of the acid aqueous solution used at this time includes chitin deN removal.
- Although there are no particular limitations as long as they can dissolve the acetylated product, it is generally preferable to use 0.5-15% acetic acid aqueous solution, 1-20% lactic acid aqueous solution, and 0.5-8% hydrochloric acid aqueous solution. Further, the concentration of the de-N-acetylation product of chitin dissolved in such an acid aqueous solution can be arbitrarily set as long as the solution obtained therefrom has the desired fluidity, but in general, 0.5-15% (weight)
It is preferable that it is in the range of .
本発明方法において上記キチンの脱Ｎ−アセチル化生成
物酸性水溶液の一部分を、所定容器中、又は基台（ガラ
ス板、又はポリテトラフルオロエチレン板など）の上で
シート状に展延し、これを例えば−１Ｏ〜−８０°Ｃで
予備凍結した後、凍結乾燥する。すると、キチンの脱Ｎ
−アセチル化生成物は、析出凝固して、三次元網状の連
続構造体を形成し、その中に形成された三次元網状の連
続空孔内に含浸された酸水溶液凍結体は昇華連敗し、従
って、多孔質シートが得られる。In the method of the present invention, a portion of the acidic aqueous solution of the de-N-acetylation product of chitin is spread in a sheet shape in a predetermined container or on a base (glass plate, polytetrafluoroethylene plate, etc.). For example, after pre-freezing at -10 to -80°C, the sample is freeze-dried. Then, chitin de-N
- The acetylation product precipitates and solidifies to form a three-dimensional network continuous structure, and the frozen acid aqueous solution impregnated into the three-dimensional network continuous pores formed therein undergoes continuous sublimation and failure, A porous sheet is thus obtained.
上記凍結乾燥は、通常の凍結乾燥機を用いて容易に行う
ことができる。キチンの脱Ｎ−アセチル化生成物の酸性
水溶液には、その粘度を低下又は調整するために、メタ
ノール、エタノール、Ｎ −プロパツール、およびイソ
プロパツールの少なくとも１種を含む粘度調節剤を、例
えば、０．５〜５０％添加配合されていてもよい。The above freeze-drying can be easily performed using a normal freeze dryer. The acidic aqueous solution of the de-N-acetylation product of chitin is treated with a viscosity modifier containing at least one of methanol, ethanol, N-propanol, and isopropanol, for example, in order to reduce or adjust its viscosity. , 0.5 to 50% may be added.
別に、上記酸性水溶液の他の一部分を容器中、又は基台
上に薄膜状に展延し、これを蒸発乾燥法により乾燥すれ
ば、キチンの脱Ｎ−アセチル化生成物の非多孔質薄膜が
得られる。このときの蒸発乾燥条件に格別の制限はなく
、一般に５〜１１０°Ｃの温度で、徐々に蒸発乾燥させ
ればよい。Separately, by spreading the other part of the above acidic aqueous solution into a thin film in a container or on a base and drying this by evaporation drying, a non-porous thin film of the de-N-acetylation product of chitin can be formed. can get. There are no particular restrictions on the evaporative drying conditions at this time, and it is generally sufficient to gradually evaporate and dry at a temperature of 5 to 110°C.
上記のキチンの脱Ｎ−アセチル化生成物の非多孔質薄膜
を、それが完全に乾燥しないうち（若干湿潤しているう
ち）に、又は、その乾燥体の一面を水（例えば液体水、
水蒸気、又は湯気など）で湿潤し、これを、前記キチン
の脱Ｎ−アセチル化生成物の多孔質シートの一面に積層
貼着して前駆積層体を形成する。A non-porous thin film of the chitin de-N-acetylation product described above is coated with water (e.g. liquid water) before it is completely dry (while still slightly wet) or one side of the dried film is soaked with water (e.g. liquid water, etc.).
(water vapor, steam, etc.), and this is laminated and adhered to one surface of the porous sheet of the chitin de-N-acetylation product to form a precursor laminate.
本発明方法において、上記前駆積層体は、下記のように
して作成してもよい。すなわち、キチンの脱Ｎ−アセチ
ル化生成物の酸性水溶液を容器中、又は基台上にシート
状に展延し、このシート状層の表面に塩基性物質のガス
流、又は噴霧流を接触させる。すると、シート状層の表
面部分は中和される。このため、この表面部分に存在す
るキチンの脱Ｎ−アセチル化生成物は、析出凝固して、
シート伏層表面にキチンの脱Ｎ−アセチル化生成物から
なる非多孔質薄膜を形成する。In the method of the present invention, the precursor laminate may be created as follows. That is, an acidic aqueous solution of a de-N-acetylation product of chitin is spread in a sheet shape in a container or on a base, and a gas stream or a spray stream of a basic substance is brought into contact with the surface of this sheet layer. . Then, the surface portion of the sheet-like layer is neutralized. Therefore, the de-N-acetylation products of chitin present on this surface part precipitate and solidify.
A non-porous thin film made of a de-N-acetylation product of chitin is formed on the surface of the sheet underlying layer.
この工程に用いられる中和剤は、例えば気体アンモニア
を含むガス流、又は、アンモニア或は、他のアルカリ物
質（例えば、水酸化ナトリウム、水酸化カリウム、炭酸
ナトリウム、および炭酸カリウムなど）の水溶液の微細
噴霧粒子を含むガス流などから選ぶことができる。The neutralizing agent used in this step can be, for example, a gas stream containing gaseous ammonia or an aqueous solution of ammonia or other alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. You can choose from gas streams containing fine atomized particles, etc.
次に、このシート状層を凍結乾燥して、非多孔質化して
いない残余のキチンの脱Ｎ−アセル化生成物をその酸性
水溶液から析出凝固させ多孔質シート層を形成する。こ
の多孔質シート層は、前述のように、三次元網状の連続
空孔を有する。このようにしてキチンの脱Ｎ−アセチル
化生成物からなる非多孔質簿膜層と、それに連続する多
孔質シート層とからなる前駆積層体が得られる。Next, this sheet-like layer is freeze-dried to form a porous sheet layer by precipitating and solidifying the remaining non-porous chitin de-N-acetylated product from the acidic aqueous solution. As described above, this porous sheet layer has a three-dimensional network of continuous pores. In this way, a precursor laminate consisting of a non-porous membrane layer made of a de-N-acetylation product of chitin and a porous sheet layer continuous thereto is obtained.
上記非多孔質簿膜層の形成工程と、前記凍結乾燥による
多孔質シート層形成工程とを、上記順序に別個に行って
もよいが、非多孔質薄膜形成工程が、前記凍結乾燥操作
の初期段階に重複するように行ってもよい。The step of forming a non-porous thin film layer and the step of forming a porous sheet layer by freeze-drying may be performed separately in the above order; The steps may overlap.
上記のようにして得られた前駆積層体にをＪＲ，酸無水
物を含むアシル化剤によるアシル化処理を施して、キチ
ンの脱Ｎ−アセチル化生成物をキチン化し、得られたキ
チン複合体を乾燥する。The precursor laminate obtained as described above was subjected to an acylation treatment using an acylating agent containing an acid anhydride to chitinate the de-N-acetylation product of chitin, and the resulting chitin complex was obtained. Dry.
上記アシル化剤に含まれる有機酸無水物は、例えば酢酸
、プロピオン酸、酪酸、吉草酸などの脂肪族酸の無水物
から選ばれた少なくとも１種を含むことが好ましい。ア
シル化剤は、上記のような有機酸無水物を水、メタノー
ル、又は水／メタノール混合物からなる溶媒に溶解して
調製される。The organic acid anhydride contained in the acylating agent preferably contains at least one selected from aliphatic acid anhydrides such as acetic acid, propionic acid, butyric acid, and valeric acid. The acylating agent is prepared by dissolving the organic acid anhydride as described above in a solvent consisting of water, methanol, or a water/methanol mixture.
溶剤は、アシル化工程において、前駆積層体を溶解した
り、或は過度に膨潤させることのないものであることが
必要であって、好ましくは水とメタノールとのＯ−１：
１の混合物が用いられる。アシル化剤の使用量は、有機
酸無水物の量で、キチンの脱Ｎ−アセチル化生成物の脱
Ｎ−アセチル化度に応じて、その１〜１００倍モルにす
ることが好ましく、５〜２０倍モルにすることが好まし
い。The solvent needs to be one that does not dissolve or excessively swell the precursor laminate in the acylation step, and preferably O-1 of water and methanol:
A mixture of 1 is used. The amount of the acylating agent to be used is preferably 1 to 100 times the amount of organic acid anhydride, and 5 to 100 times the amount of the organic acid anhydride, depending on the degree of de-N-acetylation of the chitin de-N-acetylation product. It is preferable to use 20 times the molar amount.
アシル化工程は、前駆積層体を５〜６０°Ｃにおいてア
シル化剤中に浸漬するだけでよいが、必要に応じ、真空
脱気、或は、超音波振動による脱気を行うことにより、
シアル化反応を均一に促進することができる。In the acylation step, it is sufficient to simply immerse the precursor laminate in an acylating agent at 5 to 60°C, but if necessary, by performing vacuum degassing or degassing by ultrasonic vibration,
The sialylation reaction can be uniformly promoted.
アシル化工程が完了したならば、積層体を十分に水洗し
、その後これを乾燥する。乾燥方法に格別の制限はなく
、一般に５°Ｃ〜１１０“Ｃにおける熱風乾燥、親水性
有機溶媒による脱水、又は凍結乾燥などを用いることが
できる。Once the acylation step is complete, the laminate is thoroughly washed with water and then dried. There are no particular restrictions on the drying method, and generally hot air drying at 5°C to 110"C, dehydration with a hydrophilic organic solvent, freeze drying, etc. can be used.
本発明を実施例により更に説明する。 The present invention will be further explained by examples.
尖施血上
脱Ｎ−アセチル化度８０％のキチンの脱Ｎ−アセチル化
生成物を２％酢酸水溶液に常温で溶解して、濃度２重量
％のキチンの脱Ｎ−アセチル化生成物酸性水溶液を調製
した。The de-N-acetylation product of chitin with a degree of de-N-acetylation of 80% was dissolved in a 2% acetic acid aqueous solution at room temperature to obtain an acidic aqueous solution of the de-N-acetylation product of chitin with a concentration of 2% by weight. was prepared.
上記酸性水溶液の一部分を、縦・横寸法が、５Ｘ５ＣＴ
１１、厚さ１ ＋ｎｍの正方形型枠に流延し、これに凍
結乾燥を施して、多孔質シートを作製した。A part of the above acidic aqueous solution has vertical and horizontal dimensions of 5X5CT.
11. A porous sheet was prepared by casting into a square mold with a thickness of 1 + nm and freeze-drying the resultant.
別に、上記酸性水溶液の残余分を、エタノールと等溶量
で混合し、この混合液をガラス板上に、厚さ２００卿の
液層を形成するように、展延し、これを徐々に風乾して
、非多孔質薄膜を形成した。Separately, the remaining amount of the above acidic aqueous solution was mixed with ethanol in an equidiscretion amount, the mixed solution was spread on a glass plate to form a liquid layer with a thickness of 200 mm, and this was gradually air-dried. A non-porous thin film was formed.
この非多孔質３膜の一表面を、湯浴上にかざして水草気
によりこれを湿潤した。この湿潤面が接着するように、
この非多孔質薄膜を多孔質シートに積層し、これを水２
０緘とメタノール６０戚との混合溶液中に浸漬し、真空
脱気を施し、この混合液中にＩｄの無水酢酸を添加し、
振盪しながら９０分間のアシル化処理を施した。One surface of this non-porous 3 membrane was held over a hot water bath and moistened with water plants. In order for this wet surface to adhere,
This non-porous thin film is laminated on a porous sheet, and then water
It was immersed in a mixed solution of 0.0 and methanol 60, subjected to vacuum deaeration, and acetic anhydride of Id was added to this mixed solution,
Acylation treatment was performed for 90 minutes while shaking.
得られたラミネート型多孔質キチン材料を十分に水洗し
た後、その一部分を採取して凍結乾燥し、この試料を走
査型電子顕微鏡で観察した。得られたラミネート型多孔
質キチン材料は、厚さ約１１１ＩＩｌのキチン多孔質層
と、厚さ約３μのキチン非多孔質７ｉｔ膜とを有し、多
孔質層の連続空孔は５０〜１１０μの不均一なサイズを
有するものであった。After thoroughly washing the obtained laminated porous chitin material with water, a portion thereof was collected and freeze-dried, and this sample was observed with a scanning electron microscope. The obtained laminated porous chitin material has a chitin porous layer with a thickness of about 111 IIl and a chitin non-porous 7it membrane with a thickness of about 3μ, and the continuous pores of the porous layer are 50 to 110μ thick. They were of non-uniform size.
側１例１
実施例１と同様の操作を行った。但し、キチンの脱Ｎ−
アセチル化生成物の酢酸水溶液中２重世％）８液を、前
記型枠にシート状に流延し、その表面上をアンモニアガ
ス流に２分間曝露した。すると、シート状体の表面部分
は中和凝固して非多孔質薄膜を形成した。このシート状
体を一３０°Ｃで予備凍結後、凍結乾燥したところ非多
孔質簿膜層と多孔質シート層とからなる前駆積層体が得
られた。この前駆積層体に、実施例１記載と同様のアシ
ル化処理を施した。Side 1 Example 1 The same operation as in Example 1 was performed. However, de-N-
A solution of the acetylated product (8%) in acetic acid aqueous solution was cast in the form of a sheet onto the mold, and the surface thereof was exposed to a stream of ammonia gas for 2 minutes. Then, the surface portion of the sheet-like body was neutralized and solidified to form a non-porous thin film. This sheet-like body was pre-frozen at -30°C and then freeze-dried to obtain a precursor laminate consisting of a non-porous membrane layer and a porous sheet layer. This precursor laminate was subjected to the same acylation treatment as described in Example 1.
得られたキチン積層体は、厚さ約１０卿の非多孔質簿膜
層と、それに連続している厚さ約１ ｍｍの多孔質層と
からなり、多孔質中には不均一な孔径を有する三次元網
状の連続空孔が形成されていた。The obtained chitin laminate consists of a non-porous film layer with a thickness of about 10 cm and a porous layer with a thickness of about 1 mm, which is continuous with the non-porous film layer, with non-uniform pore sizes in the porosity. A three-dimensional network of continuous pores was formed.
実施Ｍユ
実施例１と同様の操作を行った。但し、アシル化工程を
、前駆積層体を、水１５％、メタノール８５％の混合溶
液１００戚に浸漬し、これに真空脱気を施した後、１
ｍｌの無水酢酸を添加することによって行った。Implementation The same operations as in Example 1 were performed. However, the acylation step was carried out by immersing the precursor laminate in a mixed solution of 15% water and 85% methanol and vacuum degassing it.
This was done by adding ml of acetic anhydride.
得られたキチン材料を、エチレンオキサイドガスで滅菌
し、これを、モルモットｔｙ＞溝；造＝はぼ２ Ｘ ３
ｃｍ、深さ１ ｍｍの大きさの創傷面に貼りつけ、ガ
ーゼ、包帯を用いて固定した。手術後２週間目に、ガー
ゼ、包帯を取り除いたところ、創傷部は、径約５ｍｍの
かさぶたを残して、治癒していた。The obtained chitin material was sterilized with ethylene oxide gas, and then sterilized into a guinea pig ty>groove;
It was attached to the wound surface with a size of 1 cm and a depth of 1 mm, and fixed using gauze and a bandage. Two weeks after the surgery, the gauze and bandage were removed, and the wound had healed, leaving behind a scab with a diameter of approximately 5 mm.
本発明のラミネート型多孔質キチン材料は、極めて薄い
非多孔質簿膜層と、それに結着、又は連続している多孔
質シート状層とからなるものであって、保水材、創傷被
覆材および濾過材等として有用なものである。また、本
発明方法によりこのような多孔質キチン材料を効率よく
製造することが可能になった。The laminated porous chitin material of the present invention is composed of an extremely thin non-porous membrane layer and a porous sheet-like layer attached to or continuous with the extremely thin non-porous membrane layer, and is useful as a water-retaining material, a wound dressing material, and a porous sheet-like layer. It is useful as a filter material, etc. Furthermore, the method of the present invention makes it possible to efficiently produce such a porous chitin material.
Claims (4)
する三次元網状構造体から構成された多孔質層と、この
多孔質層の少なくとも一面上に形成され、かつキチンか
らなる非多孔質薄膜層と、からなるラミネート型キチン
多孔質材料。1. A porous layer made of chitin and composed of a three-dimensional network structure having continuous pores in the form of a three-dimensional network, and a non-porous thin film layer formed on at least one surface of this porous layer and made of chitin. A laminated chitin porous material consisting of.
して、酸性水溶液を調製し、 前記キチンの脱Ｎ−アセチル化生成物酸性水溶液の一部
分をシート状に展延し、これを凍結乾燥して、キチンの
脱Ｎ−アセチル化生成物からなる多孔質シートを形成し
、 別に、前記酸性水溶液の他の一部分を薄膜状に展延し、
これを蒸発乾燥して、キチンの脱Ｎ−アセチル化生成物
からなる非多孔質薄膜を作成し、前記キチンの脱Ｎ−ア
セチル化生成物非多孔質薄膜を、それが完全に乾燥しな
いうちに、又は、その乾燥体の一面を水で湿潤して、こ
れを、前記キチンの脱Ｎ−アセチル化生成物多孔質シー
トの一面に積層貼着し、 前記積層体に、有機酸無水物を含むアシル化剤によるア
シル化処理を施して、前記キチンの脱Ｎ−アセチル化生
成物をキチン化し、 得られたキチン積層体を乾燥する、 ことを特徴とする、ラミネート型キチン多孔質材料の製
造方法。2. A de-N-acetylation product of chitin is dissolved in an acid aqueous solution to prepare an acidic aqueous solution, a portion of the acidic aqueous solution of the de-N-acetylation product of chitin is spread into a sheet, and this is freeze-dried. to form a porous sheet made of the de-N-acetylation product of chitin, and separately, spread another part of the acidic aqueous solution into a thin film,
This is evaporated to dryness to create a non-porous thin film of the de-N-acetylated chitin product, and the non-porous thin film of the de-N-acetylated chitin product is removed before it is completely dried. or, one side of the dried product is moistened with water and laminated and pasted on one side of the chitin de-N-acetylation product porous sheet, and the laminate contains an organic acid anhydride. A method for producing a laminated porous chitin material, comprising: performing an acylation treatment with an acylating agent to chitinize the de-N-acetylation product of chitin, and drying the obtained chitin laminate. .
して、酸性水溶液を調製し、 このキチンの脱Ｎ−アセチル化生成物酸性水溶液をシー
ト状に展延し、 このシート状層の表面に塩基性物質のガス流、又は噴霧
流を接触させて、このシート状層の表面部分を中和・凝
固させてキチンの脱Ｎ−アセチル化生成物からなる非多
孔質薄膜を形成し、 かつ、シート状層を凍結乾燥して、残余のキチンの脱Ｎ
−アセチル化生成物の酸性水溶液から多孔質シートを形
成し、キチンの脱Ｎ−アセチル化生成物からなる、非多
孔質簿膜層と多孔質シート層との積層体を形成し、 この積層体に、有機酸無水物を含むアシル化剤によるア
シル化処理を施して、キチンの脱Ｎ−アセチル化生成物
をキチン化し、 得られたキチン積層体を乾燥する、 ことを特徴とするラミネート型キチン多孔質材料の製造
方法。3. The de-N-acetylation product of chitin is dissolved in an acid aqueous solution to prepare an acidic aqueous solution, and the acidic aqueous solution of the de-N-acetylation product of chitin is spread in a sheet form, and the acidic aqueous solution of the de-N-acetylation product of chitin is spread on the surface of this sheet-like layer. Contact with a gas stream or a spray stream of a basic substance to neutralize and solidify the surface portion of this sheet-like layer to form a non-porous thin film consisting of a de-N-acetylation product of chitin, and Freeze-dry the sheet-like layer to remove nitrogen from the remaining chitin.
- forming a porous sheet from an acidic aqueous solution of an acetylation product, and forming a laminate of a non-porous film layer and a porous sheet layer made of the de-N-acetylation product of chitin; this laminate; is subjected to an acylation treatment with an acylating agent containing an organic acid anhydride to chitinize the de-N-acetylation product of chitin, and the obtained chitin laminate is dried. Method for manufacturing porous materials.
効主要素とする創傷被覆材。4. A wound dressing comprising the laminated chitin porous material according to claim 1 as an effective main element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1095352A JPH02274257A (en) | 1989-04-17 | 1989-04-17 | Laminate type porous chitin material and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1095352A JPH02274257A (en) | 1989-04-17 | 1989-04-17 | Laminate type porous chitin material and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02274257A true JPH02274257A (en) | 1990-11-08 |
Family
ID=14135273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1095352A Pending JPH02274257A (en) | 1989-04-17 | 1989-04-17 | Laminate type porous chitin material and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02274257A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405314A (en) * | 1992-11-02 | 1995-04-11 | Sunfive Company Ltd. | Wound protecting member including chitin |
| JP2015526189A (en) * | 2012-08-24 | 2015-09-10 | ツェルテル ポルスカ エスペー・ゾオＣｅｌｔｈｅｒ Ｐｏｌｓｋａ Ｓｐ． Ｚ Ｏ．Ｏ． | Active polymer layer comprising chitin derivative especially for bandage and use thereof |
-
1989
- 1989-04-17 JP JP1095352A patent/JPH02274257A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405314A (en) * | 1992-11-02 | 1995-04-11 | Sunfive Company Ltd. | Wound protecting member including chitin |
| JP2015526189A (en) * | 2012-08-24 | 2015-09-10 | ツェルテル ポルスカ エスペー・ゾオＣｅｌｔｈｅｒ Ｐｏｌｓｋａ Ｓｐ． Ｚ Ｏ．Ｏ． | Active polymer layer comprising chitin derivative especially for bandage and use thereof |
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