CN1162665A - Chitin medical fiber paper and its manufacturing method - Google Patents
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- 239000000835 fiber Substances 0.000 title claims abstract description 43
- 229920002101 Chitin Polymers 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003599 detergent Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 206010052428 Wound Diseases 0.000 abstract description 15
- 208000027418 Wounds and injury Diseases 0.000 abstract description 15
- 230000029663 wound healing Effects 0.000 abstract description 4
- 230000035699 permeability Effects 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 abstract 2
- 230000001070 adhesive effect Effects 0.000 abstract 1
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- 238000009987 spinning Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 230000015271 coagulation Effects 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000036407 pain Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 208000032544 Cicatrix Diseases 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000003110 anti-inflammatory effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
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- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 102000016943 Muramidase Human genes 0.000 description 1
- 108010014251 Muramidase Proteins 0.000 description 1
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
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- 239000004325 lysozyme Substances 0.000 description 1
- 235000010335 lysozyme Nutrition 0.000 description 1
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- 230000007721 medicinal effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
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Abstract
Description
本发明有关一种医用甲壳素纤维的制造方法及由该纤维制得的甲壳素纤维纸型伤口贴剂及伤口敷料。The invention relates to a manufacturing method of medical chitin fiber and chitin fiber paper wound patch and wound dressing prepared from the fiber.
目前,医学上手术患者大量使用的传统棉纱敷料,在使用中易引起皮肤发炎,用于渗液、渗血较多的地方时会造成积液,易与伤口粘结等不良现象,且需经常性换药,既增加患者痛苦,更会给愈合中的伤口造成新创伤,令伤口愈合缓慢,疤痕大。故,寻求使用效果更优良的医用敷料乃为目前医药界努力的方向。At present, traditional cotton gauze dressings, which are widely used by surgical patients in medicine, can easily cause skin inflammation during use. Sexual dressing changes not only increase the pain of the patient, but also cause new wounds to the healing wound, resulting in slow wound healing and large scars. Therefore, it is the direction of the present medical circle to seek the medical dressing with better use effect.
甲壳素系广泛存在于暇、蟹、昆虫外壳和菌类、藻类细胞壁中一种带正电的天然多糖高聚物。在自然界中,甲壳素的贮藏量仅次于纤维素,为一种极具潜在实用价值又尚待开发的自然资源。甲壳素的化学名称是聚乙酰氨基葡萄糖,其化学结构与天然纤维素的结构相近,甲壳素对人体无毒、无刺激过敏反应,与人体具有良好的生物相容性,无抗体反应,并可被人体内的溶菌酶分解而被人体吸收,另具有消炎、止血、镇痛和促进人体组织生长等独特的医药特性。Chitin is a kind of positively charged natural polysaccharide polymer widely present in crabs, crabs, insect shells, fungi, and algae cell walls. In nature, the storage capacity of chitin is second only to cellulose, and it is a natural resource with great potential practical value and yet to be developed. The chemical name of chitin is polyacetylglucosamine, its chemical structure is similar to that of natural cellulose, chitin is non-toxic to human body, has no irritation and allergic reaction, has good biocompatibility with human body, has no antibody reaction, and can It is decomposed by lysozyme in the human body and absorbed by the human body. It also has unique medicinal properties such as anti-inflammatory, hemostatic, analgesic and promotion of human tissue growth.
目前世界各国用于制造甲壳素纺丝浆液的溶剂有三氯乙酸与氯化烃的混合物,二氯乙酸与氯化烃的混合物,二甲基乙酰胺(D M Ac)与氯化锂混合溶剂,N-甲基吡咯烷酮(NMP)与氯化锂的混合溶剂等;在已发表的文献里,以采用前二种溶剂较多。At present, the solvents used in the manufacture of chitin spinning slurry in various countries in the world include a mixture of trichloroacetic acid and chlorinated hydrocarbons, a mixture of dichloroacetic acid and chlorinated hydrocarbons, a mixed solvent of dimethylacetamide (DM Ac) and lithium chloride, Mixed solvents of N-methylpyrrolidone (NMP) and lithium chloride, etc.; in the published literature, the first two solvents are used more.
日本公开特许公报第57-16999号专利,提出一种甲壳素纤维纸的制造方法,将甲壳素与甲酸的混合物反复冻融,然后加入二氯乙酸配制成均匀的纺丝浆液,将浆液挤出到乙酸乙脂的第一凝固浴中,经过甲醇第二凝固浴,最后用乙醇进行洗涤。其所得纤维单丝纤度为3.0袋(即3.3dte×),强度为1.0g/d(即0.89CM/DTE×)。将这利纤维切成约5mm长,依通常的造纸工艺抄纸,其所得纸的定量为65g/m,耐破因子为1.11。Japanese Patent Publication No. 57-16999 patent proposes a manufacturing method of chitin fiber paper, the mixture of chitin and formic acid is repeatedly frozen and thawed, then dichloroacetic acid is added to prepare a uniform spinning slurry, and the slurry is extruded In the first coagulation bath of ethyl acetate, through the second coagulation bath of methanol, and finally washed with ethanol. The monofilament fineness of the obtained fiber is 3.0 bags (ie 3.3dte×), and the strength is 1.0g/d (ie 0.89CM/DTE×). Cut the fiber into about 5mm long, and make paper according to the usual papermaking process. The weight of the obtained paper is 65g/m, and the burst resistance factor is 1.11.
本发明的目的在于提出一种采用DMAC-LICL或NMP-LICL为溶剂,经湿法纺丝和适当拉伸的工艺,以制取符合加工医用纸要求的甲壳素纤维。该纤维的纤度为0.56-11.1dte×即(0.5-10d),干强度1.34-1.78CM/dte×即(1.5-2.0g/d),伸长4-8%,用这种纤维造纸即可开发多种用途的医用甲壳素纤维纸型敷料。采用DMAc-LICL或NMP-LICL配制的甲壳素,浆液其优点是对设备腐蚀性低,浆液的稳定性极好,配制的浆液可放置一年以上时间仍可正常纺丝。The purpose of the present invention is to propose a process using DMAC-LICL or NMP-LICL as a solvent, wet spinning and proper stretching to produce chitin fibers that meet the requirements for processing medical paper. The fineness of the fiber is 0.56-11.1dte×(0.5-10d), the dry strength is 1.34-1.78CM/dte×(1.5-2.0g/d), and the elongation is 4-8%. It is enough to make paper with this fiber Development of multi-purpose medical chitin fiber paper dressing. Chitin prepared with DMAc-LICL or NMP-LICL has the advantages of low corrosion to equipment and excellent stability of the slurry. The prepared slurry can still be spun normally after being placed for more than one year.
本发明所称的甲壳素,也包括脱乙酰甲壳素(又称壳聚糖、甲壳胺),乃市售从暇、蟹壳中提取制备所得的产品。且,原料甲壳素的主要质量指标,如色泽、水份、灰份、粘度、溶解性能等,对甲壳素浆液的配制、纤维的纺制及成品纤维的质量有密切关连,故,本发明对原料甲壳素质量指标的要求是含水率≤10%,灰份≤0.3%,比浓对数粘度在4.5-5.5,并要求它溶解性良好;该法配制的甲壳素浆液中甲壳素浓度(又称浆液浓度)一般为1-10%,较理想的浓度为1-6%。The chitin referred to in the present invention also includes deacetylated chitin (also known as chitosan, chitosan), which is a commercially available product extracted and prepared from crab shells. Moreover, the main quality indicators of raw chitin, such as color, moisture, ash, viscosity, solubility, etc., are closely related to the preparation of chitin slurry, the spinning of fibers and the quality of finished fibers. The requirement of raw material chitin quality index is water content≤10%, ash content≤0.3%, inherent viscosity is at 4.5-5.5, and requires its good solubility; Chitin concentration (also Called slurry concentration) is generally 1-10%, more ideal concentration is 1-6%.
本发明制造甲壳素纤维纸的过程如下:The process that the present invention makes chitin fiber paper is as follows:
用DMAc-LICL或NMP-LICL为溶剂,在室温或低于室温的温度下搅拌溶解一定的时间后,配制成甲壳素纺丝浆液。该浆液经过滤和真空脱泡处理后用计量泵输送到纺丝帽,将纺丝浆喷丝液从帽孔中挤出到凝固浴中,凝固成纤维。所采用的纺丝帽规格是40-120孔,孔径为0.04-0.08mm,凝固浴的凝固剂可用丙酮、甲醇、乙醇等较为理想。凝固浴中凝固剂的浓度视纺丝孔多少、喷丝速度大小等因素而调整,一般凝固浴浓度控制在50%以上,温度在100-300℃。为保证纤维有足够强度,在纺丝过程中须给以适当拉伸,拉伸的倍数可在0.5-2倍之间选择。凝固后的纤维必须彻底洗涤干净,冼涤剂最好用无水乙醇,洗净的甲壳素纤维直接切成5mm长的短纤维,将其均匀地分散在水中,依常规造纸工艺抄纸,并根据产品需要,制成不同重量和不同尺寸的医用纸。Using DMAc-LICL or NMP-LICL as a solvent, stirring and dissolving at room temperature or lower than room temperature for a certain period of time, the chitin spinning slurry is prepared. After the slurry is filtered and vacuum defoamed, it is transported to the spinning cap by a metering pump, and the spinning slurry is extruded from the cap hole into the coagulation bath to be solidified into fibers. The specification of the spinning cap used is 40-120 holes, the hole diameter is 0.04-0.08mm, and the coagulant of the coagulation bath can be preferably acetone, methanol, ethanol, etc. The concentration of the coagulant in the coagulation bath is adjusted depending on the number of spinning holes, the size of the spinning speed and other factors. Generally, the concentration of the coagulation bath is controlled at more than 50%, and the temperature is 100-300°C. In order to ensure that the fiber has sufficient strength, it must be properly stretched during the spinning process, and the stretching ratio can be selected between 0.5 and 2 times. The coagulated fibers must be thoroughly washed. The best detergent is absolute ethanol. The washed chitin fibers are directly cut into short fibers with a length of 5mm, dispersed evenly in water, and made into paper according to the conventional papermaking process. According to the needs of the product, it can be made into medical paper of different weights and different sizes.
作为医用纤维纸原料的甲壳素纤维,必须控制其单丝直径和长度在一定范围内,纤维太粗,抄纸时纤维间的自粘性下降;纤维太长,在水中分散性差,都不利于抄纸,所以纤维的纤度宜控制在11.1dte×以下,纤维长度不能超过20mm。As the raw material of medical fiber paper, the chitin fiber must be controlled within a certain range in diameter and length. If the fiber is too thick, the self-adhesiveness between the fibers will decrease during papermaking; if the fiber is too long, the dispersion in water will be poor, which is not conducive to papermaking. Paper, so the fineness of the fiber should be controlled below 11.1dte×, and the fiber length should not exceed 20mm.
本发明制造甲壳素纤维纸的实际过程如下:The actual process that the present invention makes chitin fiber paper is as follows:
把粘度为1pas的甲壳素粉3份(DMAc),置入含6%LICL的DMAc混合溶剂中,在20℃时搅拌三小时,制成透明的甲壳素纺丝浆液。将这些浆液在0.4Mpa的压力下用300目的不锈钢网过滤,而后在真空下进行脱泡。过滤脱泡后的甲壳素浆液再用0.2Mpa的压力通过计量泵,纺丝帽规格是100孔,孔径为0.8mm,纺丝用计量泵的规格是0.8ml/转,以14ml/min的喷出量进行纺丝,纺丝速度控制在15m/min左右,凝固浴采用含有70%无水乙醇的DMAc混合液,提出凝固浴的甲壳素纤维继续用无水乙醇洗涤并给以适当的拉伸,拉伸的倍数控制在0.5-2倍之间,经洗净的甲壳素纤维单丝纤度2.5dtex,干强度1.5cN/dtex,断裂伸长为7-8%。将甲壳素纤维集束后切成5mm长的短纤维,使其均匀的分散在水中,用常规抄纸方法制成甲壳素纤维纸。再按照所需要的尺寸切割成各种不同规格的纸,并粘贴在涂有不干胶的弹性无纺布基材上,制成各种创伤愈合贴布及小尺寸的伤口贴布或不同规格的医用或家庭用伤口贴合敷料后,在N的环境保证下,装入备妥的包装袋中,再以常规消毒即为成品。Put 3 parts of chitin powder (DMAc) with a viscosity of 1pas into a DMAc mixed solvent containing 6% LICL, and stir for three hours at 20°C to prepare a transparent chitin spinning slurry. These slurries were filtered through a 300-mesh stainless steel mesh under a pressure of 0.4 MPa, and then degassed under vacuum. The chitin slurry after filtering and defoaming is passed through the metering pump with a pressure of 0.2Mpa. The specification of the spinning cap is 100 holes, and the aperture is 0.8mm. Spinning is carried out, the spinning speed is controlled at about 15m/min, the coagulation bath adopts DMAc mixed solution containing 70% absolute ethanol, and the chitin fiber taken out of the coagulation bath is continued to be washed with absolute ethanol and properly stretched , the stretching ratio is controlled between 0.5-2 times, the chitin fiber monofilament fineness after washing is 2.5dtex, the dry strength is 1.5cN/dtex, and the elongation at break is 7-8%. The chitin fibers are bundled and cut into short fibers of 5 mm in length, dispersed evenly in water, and chitin fiber paper is made by conventional papermaking methods. Then cut into various papers of different specifications according to the required size, and paste them on the elastic non-woven fabric substrate coated with self-adhesive to make various wound healing patches and small-sized wound patches or different specifications After the medical or household wound dressing is applied, it is packed into a prepared packaging bag under the guarantee of N environment, and then the finished product is finished by routine disinfection.
用上述方法制成的甲壳素纤维纸型创伤敷料,与棉质纤维等天然高聚物和各种合成高聚的医用敷料相比,具有下列特性:Compared with natural polymers such as cotton fibers and various synthetic polymeric medical dressings, the chitin fiber paper-type wound dressing made by the above method has the following characteristics:
一、敷贴性好,可直接敷贴在创伤面,可作覆盖创面用,对创伤面有消炎、止血、止痛,促进伤口组织生长等作用,能促使伤口愈合,甚至使疤痕消失。1. Good applicability, can be applied directly on the wound surface, can be used to cover the wound surface, has anti-inflammatory, hemostasis, pain relief, and promotes the growth of wound tissue on the wound surface, can promote wound healing, and even make scars disappear.
二、治疗期间不必更换敷料,亦可多层重复敷贴,以减少患者的痛苦。2. There is no need to change the dressing during the treatment, and it can also be applied repeatedly in multiple layers to reduce the pain of the patient.
三、透气性好,透湿性佳,在敷料下无积液,使伤口面保持干燥,伤口愈合快。3. Good air permeability, good moisture permeability, no fluid accumulation under the dressing, keep the wound surface dry, and the wound heals quickly.
四、对烧伤、烫伤、体表溃烂等有显著疗效,可适用于各医院的外科、整形外科等手术后的贴布;亦可供战地救护使用,也可作为家庭与旅行时的常备药品。4. It has significant curative effect on burns, scalds, body surface ulcers, etc. It can be used as a patch after surgery and plastic surgery in various hospitals; it can also be used for field rescue, and it can also be used as a standing medicine for family and travel.
五、可用常规方法消毒,使用及携带非常方便。5. It can be sterilized by conventional methods, and it is very convenient to use and carry.
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CN101748499B (en) * | 2008-12-05 | 2011-10-05 | 中国纺织科学研究院 | A kind of chitin fiber and preparation method thereof |
CN109701065A (en) * | 2019-01-03 | 2019-05-03 | 中国人民解放军总医院 | A kind of preparation process for the chitin biodressing being coated with small molecule lithium chloride |
CN111434816A (en) * | 2019-01-15 | 2020-07-21 | 青岛大学 | A kind of anti-scattering chitin fiber fabric and preparation method thereof |
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1996
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101748499B (en) * | 2008-12-05 | 2011-10-05 | 中国纺织科学研究院 | A kind of chitin fiber and preparation method thereof |
CN101649574B (en) * | 2009-08-31 | 2010-12-08 | 四川大学 | A kind of waste cellophane recycling method |
CN109701065A (en) * | 2019-01-03 | 2019-05-03 | 中国人民解放军总医院 | A kind of preparation process for the chitin biodressing being coated with small molecule lithium chloride |
CN109701065B (en) * | 2019-01-03 | 2020-07-17 | 中国人民解放军总医院 | Preparation process of chitosan biological dressing coated with micromolecular lithium chloride |
CN111434816A (en) * | 2019-01-15 | 2020-07-21 | 青岛大学 | A kind of anti-scattering chitin fiber fabric and preparation method thereof |
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