WO2014044011A1

WO2014044011A1 - Alginate woven fabrics and method for preparing the same

Info

Publication number: WO2014044011A1
Application number: PCT/CN2013/000237
Authority: WO
Inventors: 张平; 刘松林; 黄福龙; 李世普
Original assignee: 武汉百美特生物材料科技有限公司
Priority date: 2012-09-24
Filing date: 2013-03-06
Publication date: 2014-03-27
Also published as: CN102877204A

Abstract

Provided in the present invention is an alginate woven gauze; the alginate woven gauze is made from alginate composite yarns by a knitting machine or a loom; the alginate composite yarns are made by spinning from alginate composite fibres obtained by wet spinning after blending and/or crosslinking of the alginate with a polyvinyl alcohol. Also provided in the present invention is a method for preparing the alginate woven gauze. The alginate woven gauze and the preparation method provided in the present invention, during the blending and/or crosslinking, -OH in the polyvinyl alcohol chain of a fiber forms a strong hydrogen bond with -COO- and -OH of sodium alginate, increasing the strength and elasticity of the fibre. A hydrogel formed by sodium alginate and polyvinyl alcohol has excellent properties of very high blood compatibility, enabling an alginate fibre to obtain good service properties or processing properties by blending or crosslinking methods and being able to better promote healing of the wounds and skin regeneration and so on, solving the problem that the current alginate dressing can only be non-woven rather than being knitted or woven.

Description

海藻酸盐机织纱布及其制备方法 Alginate woven gauze and preparation method thereof

技术领域 Technical field

本发明涉及医用生物高分子材料领域，尤其涉及海藻酸盐纺织纱布及其制备方法。背景技术 The invention relates to the field of medical biopolymer materials, in particular to alginate textile gauze and a preparation method thereof. Background technique

医用纱布适用于创伤包扎使用，可以协助控制出血、防止感染并吸收分泌物。医用纱布一般为纯棉纱织成平纹原布，经脱脂、漂白而成，其具有吸水强、洁白、柔软的特性。随着我国医疗领域对高端医用敷料、功能性敷料的认知和需求的增强，高端敷料将成为推动敷料市场发展的驱动力。 Medical gauze is suitable for wound dressing and can help control bleeding, prevent infection and absorb secretions. Medical gauze is generally woven into plain plain cotton, which is degreased and bleached. It has the characteristics of strong water absorption, whiteness and softness. With the increasing awareness and demand for high-end medical dressings and functional dressings in China's medical field, high-end dressings will be the driving force behind the development of the dressing market.

海藻酸广泛存在于棕色海藻中，从化学结构看是一种高分子羧酸，由 β-D- 甘露糖醛酸（筒称 M单元）和 a-L-古罗糖醛酸（筒称 G单元）两种组分构成，因其为水溶性的线型高分子材料，可通过湿法纺丝成纤维。海藻酸应用于创面修复的历史较早，早在 1951 年， Blaine 等就探讨了使用海藻酸作为手术中的可吸收止血材料的可能性，同时发现海藻酸对细菌生长有抑制作用。海藻酸生物敷料从天然海藻中提取，加工过程中使用的材料没有任何毒性，因而海藻酸纤维生物敷料对人体无毒。海藻酸能够维持创面一个湿润的环境，有利于创面愈合和皮肤再生。海藻酸生物敷料止血性能良好，能 ^艮好地降低伤口的疼痛。 Alginic acid is widely present in brown algae. It is a high molecular weight carboxylic acid from the chemical structure, consisting of β-D-mannuronic acid (called M unit) and aL-guluronic acid (G unit). The two components are composed of a water-soluble linear polymer material which can be spun into a fiber by wet spinning. Alginic acid has been used in the repair of wounds earlier. As early as 1951, Blaine et al. explored the possibility of using alginic acid as an absorbable hemostatic material in surgery, and found that alginic acid inhibited bacterial growth. Alginic acid biological dressings are extracted from natural seaweed, and the materials used in the processing have no toxicity, so the alginate fiber biological dressing is not toxic to the human body. Alginic acid maintains a moist environment in the wound, which is good for wound healing and skin regeneration. The alginic acid biologic dressing has good hemostatic properties and can reduce the pain of the wound.

1980年以来，海藻酸盐纤维纱布海藻酸纤维一般应用湿法纺丝，广泛应用于西方医疗界，许多临床研究已证明了这种纱布的优越性能，制备过程主要为：将可溶性海藻酸盐（铵盐、钠盐、钾盐）溶于水中形成粘稠溶液，脱泡过滤后通过喷丝孔挤出到含有高价金属离子（镁离子除外，一般为钙离子）的凝固浴中，形成固态海藻酸 4丐纤维长丝。该长丝经过拉伸、水洗、干燥、卷曲形成纤维。目前市场上海藻酸钠纤维多是以无纺形式存在，几乎没有纺织的医用海藻酸钠纱布。造成这一现象的原因是海藻酸钠纤维强度太低，比较硬脆。 Since 1980, alginate fiber gauze alginic acid fiber has been widely used in wet spinning. It has been widely used in western medical circles. Many clinical studies have proved the superior performance of this gauze. The preparation process is mainly: Soluble alginate ( Ammonium salt, sodium salt, potassium salt) dissolved in water to form a viscous solution, which is defoamed and filtered and extruded through a spinning hole to contain high-valent metal ions (except magnesium ions, generally calcium ions) In the coagulation bath, solid alginic acid 4 丐 fiber filaments are formed. The filaments are drawn, washed, dried, and crimped to form fibers. At present, Shanghai alginate fibers are mostly in a non-woven form, and there is almost no medical medical alginate gauze. The reason for this phenomenon is that the strength of sodium alginate fiber is too low, relatively hard and brittle.

聚乙烯醇（Polyvinyl Alcohol, PVA )是一种无毒、无刺激性的亲水性高聚物，具有良好的生物亲和性、成纤性、成膜性、粘接性、生物降解性和环境友好性能，在纤维、薄膜、粘合剂和生物医学材料等领域具有广泛用途。 Polyvinyl Alcohol (PVA) is a non-toxic, non-irritating hydrophilic polymer with good bio-affinity, fiber-forming, film-forming, adhesion, biodegradability and Environmentally friendly, it has a wide range of applications in the fields of fibers, films, adhesives and biomedical materials.

PVA纤维的分子结构是（-CH2-CHOH- ) _n, 分子中含有大量的 -OH基团，可以吸收大量的水分并形成牢固的氢键结合，也可以与金属离子形成松散的络合。通过对 PVA纤维改性处理，使它获得必要的抗水性和离子交换性能，用来制造具有镇痛性能的药棉和各种纺织材料。 PVA 的针织材料弹性高，易于敷在突出伤口的表面。 The molecular structure of PVA fiber is (-CH2-CHOH-) _n , and the molecule contains a large amount of -OH groups, which can absorb a large amount of water and form a strong hydrogen bond, and can also form a loose complex with metal ions. By modifying the PVA fiber, it obtains the necessary water resistance and ion exchange properties, and is used to manufacture cotton wool with analgesic properties and various textile materials. PVA's knit material is highly elastic and easy to apply to the surface of the protruding wound.

中国发明专利申请公开第 1978718 A号中，公开了一种高强度海藻酸 /明胶共混纤维的制备方法及用途，将海藻酸钠和明胶的共混纺丝液通过与钙离子等二价金属离子交联及在酸性条件下二者聚电解质效应来制备海藻酸 /明胶共混纤维，可进一步提高纤维的交联度，提高纤维的断裂强度，从而改善海藻酸 /明胶共混纤维物理机械强度，其用途主要是用来制造无纺布。 Chinese Patent Application Publication No. 1978718 A discloses a preparation method and use of a high-strength alginic acid/gelatin blend fiber, and a blended spinning solution of sodium alginate and gelatin is passed through a divalent metal ion such as calcium ion. Cross-linking and polyelectrolyte effect under acidic conditions to prepare alginic acid/gelatin blend fiber can further improve the cross-linking degree of the fiber and increase the breaking strength of the fiber, thereby improving the physical and mechanical strength of the alginic acid/gelatin blend fiber. Its use is mainly used to make non-woven fabrics.

中国发明专利申请公开第 1858312 A号中，公开了一种纤维素 /海藻酸盐复合纤维及其制备方法，首先在一定工艺条件下制得海藻酸钠粘性溶液，然后将该溶液按照一定的比例与纤维素黄酸酯混合制得纺丝原液，再经过纺丝与精炼步骤制得纤维素 /海藻酸盐复合纤维。该复合纤维制得的织物，手感饱满，吸水性强，同时湿态下强度高，织物尺寸稳定性好，其用途适用于内衣、儿童服装等。 Chinese Patent Application Publication No. 1858312 A discloses a cellulose/alginate composite fiber and a preparation method thereof. First, a sodium alginate viscous solution is prepared under certain process conditions, and then the solution is proportioned according to a certain ratio. The spinning dope is prepared by mixing with cellulose flavanate, and then the cellulose/alginate composite fiber is obtained through a spinning and refining step. The fabric made of the composite fiber has a full feel, strong water absorption, high strength in a wet state, good dimensional stability of the fabric, and is suitable for use in underwear, children's clothing, and the like.

大连工业大学的王晓在《大连工业大学学报》上发表了一篇题名为《海藻酸钠 /聚乙烯醇 /羟基磷灰石复合纤维制备工艺及其性能》，指出了海藻酸钠 /聚乙烯醇共混复合纤维能很好的提高纤维的强度和弹性，其主要用途在于污水处理方面。 Wang Xiao of Dalian University of Technology published an article entitled "Preparation Process and Properties of Sodium Alginate/Polyvinyl Alcohol/Hydroxyapatite Composite Fiber" in "Journal of Dalian University of Technology", pointing out sodium alginate/polyethylene Alcohol blended composite fiber can improve the strength and elasticity of fiber, and its main purpose is Sewage treatment.

中国发明专利申请公开第 1986920A号中，公开了一种海藻酸盐 /聚乙烯醇复合纤维及其制备方法，先将海藻酸盐和聚乙烯醇物理混合之后，通过湿法纺丝机进行纺丝，进入第一凝固浴凝固牵伸，然后进入第二凝固浴中交联、牵伸。复合纤维经过集束牵伸、蒸汽烘干和热定型等工序制得海藻酸盐 /聚乙烯醇复合纤维。通过该方法制备复合纤维具有较好的强力、弹性以及生物相容性。 In Chinese Patent Application Publication No. 1986920A, a sea alginate/polyvinyl alcohol composite fiber and a preparation method thereof are disclosed. First, alginate and polyvinyl alcohol are physically mixed, and then spun by a wet spinning machine. , enter the first coagulation bath to solidify and draw, and then enter the second coagulation bath to crosslink and draw. The alginate/polyvinyl alcohol composite fiber is obtained by a process of bundle drawing, steam drying and heat setting. The composite fiber prepared by this method has good strength, elasticity and biocompatibility.

上述海藻酸盐 /聚乙烯醇复合纤维制备方法由于在第一凝固浴中复合纤维已经凝固了，在第二凝固浴中交联剂不能进入纤维内部，只能在表面交联，会造成内部与表面强力分布不均，导致纤维柔韧性变差、易脆，强度也不能满足纱布的纺织工艺要求。而且，其采用蒸汽烘干（80°C )和热定型等工序后也会导致纤维柔韧性更进一步变差，更易脆。最终制备得到的纤维强度文中记载为 4.0 cN/dtex左右，没有记载断裂伸长率数据。然而通过实验，按照这种方法所得到的实际纤维强度仅为 2.5~3.0 cN/dtex,根本不能满足纺织的强度要求。发明内容 The above alginate/polyvinyl alcohol composite fiber preparation method is because the composite fiber has solidified in the first coagulation bath, and the cross-linking agent cannot enter the fiber interior in the second coagulation bath, and can only crosslink on the surface, causing internal and external The surface is unevenly distributed, resulting in poor fiber flexibility and brittleness, and the strength cannot meet the textile process requirements of gauze. Moreover, its use in steam drying (80 ° C) and heat setting will lead to further deterioration of fiber flexibility and brittleness. The fiber strength finally prepared is described as about 4.0 cN/dtex, and the elongation at break data is not described. However, through experiments, the actual fiber strength obtained by this method is only 2.5~3.0 cN/dtex, which cannot meet the textile strength requirement at all. Summary of the invention

有鉴于此，本发明提供一种具有较高强度的海藻酸盐机织纱布。 In view of the above, the present invention provides an alginate woven gauze having a relatively high strength.

一种海藻酸盐机织纱布，所述海藻酸盐机织纱布由海藻酸盐复合纱线经针织机或织布机制成，所述海藻酸盐复合纱线由海藻酸盐与聚乙烯醇共混和 /或交联之后经湿法纺丝所得到的海藻酸盐复合纤维经纺纱制成。 A sea alginate woven gauze made of alginate composite yarn by a knitting machine or a looming machine, wherein the alginate composite yarn is composed of alginate and polyvinyl alcohol The alginate composite fiber obtained by wet spinning after the mixing/crosslinking is produced by spinning.

优选地，所述海藻酸盐机织纱布的干重量为 190~280g/m², 最小断裂率为 75~450N/50mm; 所述海藻酸盐复合纱线的单纱强度为 12~45 cN/dtex; 所述海藻酸盐复合纤维的干断裂强度为 4.2~15 cN/dtex, 纤维直径为 10~50μηι, 湿断裂强度为 4.0~12 cN/dtex, 干断裂伸长率为 12-25%。 Preferably, the alginate woven gauze has a dry weight of 190-280 g/m ² and a minimum rupture rate of 75-450 N/50 mm; and the single-yarn strength of the alginate composite yarn is 12-45 cN/ The alginate composite fiber has a dry rupture strength of 4.2 to 15 cN/dtex, a fiber diameter of 10 to 50 μm, a wet rupture strength of 4.0 to 12 cN/dtex, and a dry elongation at break of 12 to 25%.

本发明还提供一种具有较高强度的海藻酸盐机织纱布的制备方法。一种海藻酸盐机织纱布的制备方法，所述方法包括以下步骤：分别配制海藻酸盐溶液与聚乙烯醇溶液，按照海藻酸盐溶液的溶质与聚乙烯醇溶液的溶质的质量比例为 9: 1-1 : 1 ,将海藻酸盐溶液和聚乙烯醇溶液混合后搅拌均匀，真空脱泡 24h, 得到纺丝原液；控制纺丝原液在 25~45 °C进行湿法纺丝工序，得到海藻酸盐复合纤维；将海藻酸盐复合纤维经过纺纱工序生产海藻酸盐复合纱线；将海藻酸盐复合纱线经针织机或织布机制成藻酸盐纱布。 The invention also provides a preparation method of alginate woven gauze with higher strength. A method for preparing alginate woven gauze, the method comprising the steps of: separately preparing an alginate solution and a polyvinyl alcohol solution, wherein the mass ratio of the solute of the alginate solution to the solute of the polyvinyl alcohol solution is 9 : 1-1 : 1 , the alginate solution and the polyvinyl alcohol solution are mixed and stirred uniformly, and vacuum defoamed for 24 hours to obtain a spinning dope; the spinning dope is controlled at 25 to 45 ° C for wet spinning, and Alginate composite fiber; alginate composite fiber is subjected to a spinning process to produce alginate composite yarn; alginate composite yarn is made into alginate gauze through a knitting machine or a loom.

优选地，在制备所述纺丝原液的步骤中，在将海藻酸盐溶液和聚乙烯醇溶液混合步骤之后和搅拌均匀步骤之前进一步包括加入交联剂的步骤。 Preferably, in the step of preparing the spinning dope, the step of adding a crosslinking agent is further included after the step of mixing the alginate solution and the polyvinyl alcohol solution and before the step of stirring the homogenization.

优选地，所述交联剂为氧化海藻酸钠、京尼平、戊二醛中的一种或任意两种以上按任意配比的混合物，所述交联剂的加入量为所述海藻酸盐质量的 0~5%。 Preferably, the crosslinking agent is one of oxidized sodium alginate, genipin, glutaraldehyde or a mixture of any two or more thereof, and the crosslinking agent is added in an amount of the alginic acid. The salt quality is 0~5%.

优选地，所述制备纺丝原液的海藻酸盐为海藻酸钠、海藻酸钾、海藻酸铵中的一种或任意两种以上按任意配比的混合物，所述海藻酸盐溶液中海藻酸盐的质量百分数浓度为 0.5%~20% , 所述海藻酸盐的数均分子量为 4000-500000 Preferably, the alginate for preparing the spinning dope is one of sodium alginate, potassium alginate, ammonium alginate or a mixture of any two or more of any ratio, and the alginic acid in the alginate solution The mass percentage concentration of the salt is 0.5% to 20%, and the number average molecular weight of the alginate is 4000-500000

优选地，所述聚乙烯醇溶液中聚乙烯醇的质量百分数浓度为 0.5%~2.5%, 所述聚乙烯醇的数均分子量为 10000~300000。 Preferably, the polyvinyl alcohol solution has a mass percentage concentration of polyvinyl alcohol of 0.5% to 2.5%, and the polyvinyl alcohol has a number average molecular weight of 10,000 to 300,000.

优选地，在所述制备海藻酸盐复合纤维的步骤中，所述海藻酸盐复合纤维采用分步凝固方式，先采用浓度为 0~5 wt%的凝固液进行预凝固，然后再用 0~ 10wt%的凝固液进行边拉伸边凝固。 Preferably, in the step of preparing the alginate composite fiber, the alginate composite fiber adopts a stepwise solidification method, and firstly uses a coagulation liquid having a concentration of 0 to 5 wt% for pre-solidification, and then uses 0~ 10% by weight of the coagulating liquid was solidified while stretching.

优选地，所述凝固液为氯化钙、氯化辞水溶液中的一种或任意两种以上按任意配比的混合物。 Preferably, the coagulating liquid is one of calcium chloride, aqueous chlorinated solution or a mixture of any two or more of any ratio.

优选地，在制备海藻酸盐复合纤维的步骤中，所述湿法纺丝的温度为 40 Preferably, in the step of preparing the alginate composite fiber, the wet spinning temperature is 40

°C。 °C.

本发明所提供的海藻酸盐机织纱布和制备方法由海藻酸盐与聚乙烯醇共混和 /或交联之后得到纤维，再经纺纱制成纱线、经针织机或织布机制成机织纱布。在共混和 /或交联过程中，纤维中的聚乙烯醇链上的 -OH和海藻酸钠的 -COO-、 -OH形成了强烈的氢键，提高纤维的强力和弹性。由海藻酸钠与聚乙烯醇形成的水凝胶有艮高的血液相溶性，所以借助聚乙烯醇的良好性能，通过共混或交联的方法可使海藻酸纤维获得良好的使用性能或加工性能，具有高吸湿成胶性、整体易去除性、高透氧性、生物相容性、生物降解吸收性，能 4艮好的促进创面愈合和皮肤再生等优异性能，解决了目前海藻酸盐敷料只能是无纺而不能针织或机织的问题。具体实施方式 The alginate woven gauze provided by the invention and the preparation method are obtained by blending and/or cross-linking alginate with polyvinyl alcohol to obtain fibers, which are then spun into yarns, and are machined by a knitting machine or a loom machine. Weaving Gauze. During the blending and/or cross-linking process, -OH on the polyvinyl alcohol chain in the fiber and -COO-, -OH of sodium alginate form strong hydrogen bonds, increasing the strength and elasticity of the fiber. The hydrogel formed by sodium alginate and polyvinyl alcohol has high blood compatibility, so that the alginic acid fiber can be used for good performance or processing by blending or cross-linking by virtue of the good properties of polyvinyl alcohol. Performance, high hygroscopicity, overall easy to remove, high oxygen permeability, biocompatibility, biodegradable absorption, excellent performance in promoting wound healing and skin regeneration, solving the current alginate Dressings can only be non-woven and not knitted or woven. detailed description

为了更好地理解本发明，以下将结合实施例进一步阐明本发明的技术内容，但本发明的技术内容不仅^限于下面的实施例。 In order to better understand the present invention, the technical content of the present invention will be further clarified below with reference to the embodiments, but the technical content of the present invention is not limited to the following embodiments.

现有技术表明，按照传统方法制备的海藻酸纤维都存在力学性能不高的缺陷，使得海藻酸纤维的可纺性与可编织性能差。为了得到力学性能 4艮好的海藻酸盐针织或有纺纱布（即海藻酸复合纤维），从而解决藻酸盐纤维的可纺性与可编织性能，本发明提供一种海藻酸盐机织纱布和制备方法，其具体实施方式陈述如下。实施例 1 : The prior art shows that alginic acid fibers prepared according to the conventional method have defects in which the mechanical properties are not high, so that the spinnability and the woven property of the alginic acid fibers are poor. In order to obtain an alginate knitted or woven fabric (ie, alginic acid composite fiber) having a good mechanical properties, thereby solving the spinnability and woven properties of the alginate fiber, the present invention provides an alginate woven fabric. The gauze and the preparation method are as follows. Example 1

一种海藻酸盐机织纱布的制备方法，包括以下几个步骤： A method for preparing alginate woven gauze comprises the following steps:

1 )配制质量百分数为 2.5%的海藻酸钠溶液（SA )与质量百分数为 8%的聚乙烯醇（PVA )溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 3: 1 , 将海藻酸钠溶液和聚乙烯醇溶液混合，搅拌均匀，真空脱泡 24h, 得到纺丝原液，备用。所述的海藻酸钠的数均分子量为 200000。所述的聚乙烯醇的数均分子量为 80000。 1) Prepare a 2.5% by mass sodium alginate solution (SA) and a mass percentage of 8% in a polyvinyl alcohol (PVA) solution, according to the solute of the sodium alginate solution and the polyvinyl alcohol solution (ie, sodium alginate and poly The mass ratio of vinyl alcohol is 3:1. The sodium alginate solution and the polyvinyl alcohol solution are mixed, stirred uniformly, and degassed under vacuum for 24 hours to obtain a spinning dope, which is ready for use. The sodium alginate has a number average molecular weight of 200,000. The polyvinyl alcohol has a number average molecular weight of 80,000.

2 )控制纺丝原液在 40 °C下进行纺丝，将步骤 1 )得到的纺丝原液经过湿法纺丝，得到海藻酸盐复合纤维（凝固液为 2 wt%的氯化钙水溶液，拉伸浴中氯化钙浓度为 5%)。 2) Control the spinning dope to be spun at 40 °C, and wet-spin the spinning dope obtained in step 1) to obtain alginate composite fiber (the coagulating solution is a 2 wt% aqueous solution of calcium chloride, pull Stretching in the bath The calcium chloride concentration is 5%).

3)将步骤 2)得到的海藻酸盐复合纤维经过纺纱以及后加工等生产纱线 (即海藻酸盐复合纱线）。 3) The alginate composite fiber obtained in the step 2) is subjected to spinning and post-processing to produce a yarn (i.e., alginate composite yarn).

4)将步骤 3)所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2)中所得到的海藻酸盐复合纤维的干断裂强度为 6cN/dtex, 湿断裂强度为 5.5 cN/dtex, 干断裂伸长率为 14.3%。上述步骤 3)所得到的纱线 (即海藻酸盐复合纱线）单纱强度为 25 cN/dtex。上述步骤 4 )所得到的海藻酸盐针织或有纺纱布（织物）干重量为 210 g/m², 最小断裂率为 220 N/50mm。实施例 2: 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) had a dry rupture strength of 6 cN/dtex, a wet rupture strength of 5.5 cN/dtex, and a dry elongation at break of 14.3%. The yarn obtained in the above step 3) (i.e., the alginate composite yarn) has a single yarn strength of 25 cN/dtex. The alginate knitted or woven gauze (fabric) obtained in the above step 4) had a dry weight of 210 g/m ² and a minimum breaking rate of 220 N/50 mm. Example 2:

1 ) 配制质量百分数为 2%的海藻酸钠 (SA)溶液与质量百分数为 10%的聚乙烯醇（PVA)溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 4: 1, 将海藻酸钠溶液和聚乙烯醇溶液混合，搅拌均匀，真空脱泡 24h, 得到纺丝原液，备用。所述的海藻酸钠的数均分子量为 200000。所述的聚乙烯醇的数均分子量为 80000。 1) Prepare 2% by mass of sodium alginate (SA) solution and 10% by mass of polyvinyl alcohol (PVA) solution, according to the solute of sodium alginate solution and polyvinyl alcohol solution (ie, sodium alginate and poly The mass ratio of vinyl alcohol is 4: 1, the sodium alginate solution and the polyvinyl alcohol solution are mixed, stirred uniformly, and degassed under vacuum for 24 hours to obtain a spinning dope, which is ready for use. The sodium alginate has a number average molecular weight of 200,000. The polyvinyl alcohol has a number average molecular weight of 80,000.

2 )控制纺丝原液在 40 °C进行纺丝，将步骤 1 )得到的纺丝原液经过湿法纺丝，得到海藻酸盐复合纤维（凝固液为 1 wt%的氯化钙水溶液，拉伸浴为 2.5 wt%的氯化钙水溶液和 2.5 wt%的氯化辞水溶液）。 2) Control the spinning dope to be spun at 40 °C, and wet-spin the spinning dope obtained in step 1) to obtain alginate composite fiber (the coagulating solution is 1 wt% calcium chloride aqueous solution, stretching The bath was a 2.5 wt% aqueous solution of calcium chloride and a 2.5 wt% aqueous solution of chloride.

4)将步骤 3)所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2)得到的海藻酸盐复合纤维的干断裂强度为 12cN/dtex,湿断裂强度为 10.5cN/dtex, 干断裂伸长率为 22%。上述步骤 3)得到的纱线（即海藻酸盐复合纱线）单纱强度为 40 cN/dtex。上述步骤 4)得到的海藻酸盐针织或有纺纱布（织物）干重量为 220 g/m², 最小断裂率为 420N/50mm。实施例 3: 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) had a dry rupture strength of 12 cN/dtex, a wet rupture strength of 10.5 cN/dtex, and a dry elongation at break of 22%. The yarn obtained in the above step 3) (i.e., the alginate composite yarn) has a single yarn strength of 40 cN/dtex. The alginate knitted or woven gauze (fabric) obtained in the above step 4) had a dry weight of 220 g/m ² and a minimum breaking rate of 420 N/50 mm. Example 3:

一种海藻酸盐机织纱布的制备方法，它包括以下几个步骤： A method for preparing alginate woven gauze, comprising the following steps:

1 )配制质量百分数为 2.5%海藻酸钠 ( SA )溶液与质量百分数为 8%的聚乙烯醇（PVA )溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 3: 1 , 将海藻酸钠溶液和聚乙烯醇溶液混合，在混合后加入氧化海藻酸钠交联剂，其质量为海藻酸钠质量的 0.5%,搅拌均匀，真空脱泡 24h,得到纺丝原液，备用。所述的海藻酸钠的数均分子量为 200000。所述的聚乙烯醇的数均分子量为 80000。 1) Prepare a 2.5% mass% sodium alginate (SA) solution and a mass percentage of 8% polyvinyl alcohol (PVA) solution, according to the solute of sodium alginate solution and polyvinyl alcohol solution (ie sodium alginate and polyethylene) The mass ratio of alcohol) is 3:1, the sodium alginate solution and the polyvinyl alcohol solution are mixed, and after mixing, the oxidized sodium alginate cross-linking agent is added, the mass of which is 0.5% of the mass of sodium alginate, the mixture is evenly stirred, and the vacuum is removed. After soaking for 24 hours, a spinning dope was obtained and used. The sodium alginate has a number average molecular weight of 200,000. The polyvinyl alcohol has a number average molecular weight of 80,000.

2 )控制纺丝原液在 40 °C下进行纺丝，将步骤 1 )得到的纺丝原液经过湿法纺丝，得到海藻酸盐复合纤维（凝固液为 2 wt%的氯化钙水溶液，拉伸浴为 2.5 wt%的氯化钙水溶液和 2.5 wt%的氯化辞水溶液）。 2) Control the spinning dope to be spun at 40 °C, and wet-spin the spinning dope obtained in step 1) to obtain alginate composite fiber (the coagulating solution is a 2 wt% aqueous solution of calcium chloride, pull The stretching bath was a 2.5 wt% aqueous solution of calcium chloride and a 2.5 wt% aqueous solution of chlorinated water.

3 )将步骤 2 )得到的海藻酸盐复合纤维经过纺纱以及后加工等生产纱线 (即海藻酸盐复合纱线）。 3) The alginate composite fiber obtained in the step 2) is subjected to spinning and post-processing to produce a yarn (i.e., alginate composite yarn).

4 )将步骤 3 )所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2 )得到的海藻酸盐复合纤维的干断裂强度为 7.3cN/dtex, 湿断裂强度为 6.5 cN/dtex, 干断裂伸长率为 12%。上述步骤 3 )得到的纱线（即海藻酸盐复合纱线）单纱强度为 27.1 cN/dtex₀ 上述步骤 4 )得到的海藻酸盐针织或有纺纱布（织物 )干重量为 215 g/m², 最小断裂率为 280 N/50mm。实施例 4: 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) had a dry rupture strength of 7.3 cN/dtex, a wet rupture strength of 6.5 cN/dtex, and a dry elongation at break of 12%. The yarn obtained in the above step 3) (ie, alginate composite yarn) has a single yarn strength of 27.1 cN/dtex. ₀ The alginate knitted or woven fabric (fabric) obtained in the above step 4) has a dry weight of 215 g/ m ² , the minimum fracture rate is 280 N/50 mm. Example 4:

1 ) 配制质量百分数为 2%海藻酸钠 ( SA )溶液与质量百分数为 10%的聚乙烯醇（PVA )溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 4: 1 , 将海藻酸钠溶液和聚乙烯醇溶液混合，在混合后加入氧化海藻酸钠交联剂，其质量为海藻酸钠质量的 1%, 搅拌均匀，真空脱泡 24h,得到纺丝原液，备用。所述的海藻酸钠的数均分子量为 200000。所述的聚乙烯醇的数均分子量为 80000。 1) Prepare a 2% by mass sodium alginate (SA) solution and a 10% by mass solution of polyvinyl alcohol (PVA), according to the solute of sodium alginate solution and polyvinyl alcohol solution (ie sodium alginate and polyethylene) The mass ratio of the alcohol is 4:1, the sodium alginate solution and the polyvinyl alcohol solution are mixed, and after mixing, the oxidized sodium alginate cross-linking agent is added, the mass of which is 1% of the mass of sodium alginate, and the mixture is evenly stirred. The mixture was degassed under vacuum for 24 h to obtain a spinning dope and set aside. The sodium alginate has a number average molecular weight of 200,000. The polyvinyl alcohol has a number average molecular weight of 80,000.

2 )控制纺丝原液在 40 °C下进行纺丝，将步骤 1 )得到的纺丝原液经过湿法纺丝，得到海藻酸盐复合纤维（凝固液为 1 wt%的氯化辞水溶液）。 2) The spinning dope is controlled to be spun at 40 ° C, and the spinning dope obtained in the step 1) is subjected to wet spinning to obtain an alginate composite fiber (the coagulating liquid is a 1 wt% aqueous solution).

4 )将步骤 3 )所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2 )得到的海藻酸盐复合纤维的干断裂强度为 15 cN/dtex, 湿断裂强度为 12 cN/dtex , 干断裂伸长率为 25%。所述步骤 3 )得到的纱线（即海藻酸盐复合纱线）单纱强度为 45cN/dtex。所述步骤 4 )得到的海藻酸盐针织或有纺纱布（织物 )干重量为 280 g/m² , 最小断裂率为 450 N/50mm。实施例 5: 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) has a dry breaking strength of 15 cN/dtex, a wet breaking strength of 12 cN/dtex, and a dry elongation at break of 25%. The yarn obtained in the step 3) (i.e., the alginate composite yarn) has a single yarn strength of 45 cN/dtex. The alginate knitted or woven gauze (fabric) obtained in the step 4) has a dry weight of 280 g/m ² and a minimum breaking rate of 450 N/50 mm. Example 5:

1 )配制质量百分数为 2.5%海藻酸钠 ( SA )溶液与质量百分数为 8%的聚乙烯醇（PVA )溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 4: 1 , 将海藻酸钠溶液和聚乙烯醇溶液混合，在混合后加入质量百分数为 8%的羟乙基壳聚糖水溶液，搅拌均勾，真空脱泡 24h, 得到纺丝原液，备用。其中羟乙基壳聚糖占所述纺丝原液溶质的质量比例为 10% , 所述的海藻酸钠的数均分子量为 200000 , 所述的聚乙烯醇的数均分子量为 80000。 1) Prepare a 2.5% mass% sodium alginate (SA) solution and a mass percentage of 8% polyvinyl alcohol (PVA) solution, according to the solute of sodium alginate solution and polyvinyl alcohol solution (ie sodium alginate and polyethylene) The mass ratio of the alcohol is 4:1. The sodium alginate solution and the polyvinyl alcohol solution are mixed. After mixing, an aqueous solution of hydroxyethyl chitosan having a mass percentage of 8% is added, stirred and hooked, and vacuum degassed for 24 hours. Spinning stock solution, spare. The hydroxyethyl chitosan accounts for 10% by mass of the spinning solution solute, the sodium alginate has a number average molecular weight of 200,000, and the polyvinyl alcohol has a number average molecular weight of 80,000.

3 )将步骤 2 )得到的海藻酸盐复合纤维经过纺纱以及后加工等生产纱线 (即海藻酸盐复合纱线）。 4 )将步骤 3 )所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2 )得到的海藻酸盐复合纤维的干断裂强度为 6.3 cN/dtex, 湿断裂强度为 5.9 cN/dtex, 干断裂伸长率为 12.2%。上述步骤 3 )得到的纱线（即海藻酸盐复合纱线）单纱强度为 26.3 cN/dtex₀ 上述步骤 4 )得到的海藻酸盐针织或有纺纱布（织物 )干重量为 212 g/m², 最小断裂率为 215 N/50mm。实施例 6: 3) The alginate composite fiber obtained in the step 2) is subjected to spinning and post-processing to produce a yarn (i.e., alginate composite yarn). 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) had a dry rupture strength of 6.3 cN/dtex, a wet rupture strength of 5.9 cN/dtex, and a dry elongation at break of 12.2%. The yarn obtained in the above step 3) (ie, the alginate composite yarn) has a single yarn strength of 26.3 cN/dtex. ₀ The alginate knitted or woven fabric (fabric) obtained in the above step 4) has a dry weight of 212 g/ m ² , the minimum fracture rate is 215 N/50 mm. Example 6

1 ) 配制质量百分数为 2%海藻酸钠 ( SA )溶液与质量百分数为 10%的聚乙烯醇（PVA )溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 1 : 1 , 将海藻酸钠溶液和聚乙烯醇溶液混合，在混合后加入京尼平交联剂，其质量为海藻酸钠质量的 0.1%, 搅拌均匀，真空脱泡 24h, 得到纺丝原液，备用。所述的海藻酸钠的数均分子量为 200000。所述的聚乙烯醇的数均分子量为 80000。 1) Prepare a 2% by mass sodium alginate (SA) solution and a 10% by mass solution of polyvinyl alcohol (PVA), according to the solute of sodium alginate solution and polyvinyl alcohol solution (ie sodium alginate and polyethylene) The mass ratio of alcohol) is 1:1, the sodium alginate solution and the polyvinyl alcohol solution are mixed, and after mixing, the genipin cross-linking agent is added, the mass of which is 0.1% of the mass of sodium alginate, evenly stirred, vacuum defoaming At 24h, the spinning dope was obtained and used. The sodium alginate has a number average molecular weight of 200,000. The polyvinyl alcohol has a number average molecular weight of 80,000.

2 )控制纺丝原液在 25 °C下进行纺丝，将步骤 1 )得到的纺丝原液经过湿法纺丝，得到海藻酸盐复合纤维（凝固液为 l wt%的氯化钙水溶液，拉伸浴为 2.5 wt%的氯化钙水溶液和 2.5 wt%的氯化辞水溶液）。 2) Control the spinning dope to be spun at 25 °C, and wet-spin the spinning dope obtained in step 1) to obtain alginate composite fiber (the coagulating solution is a lwt% aqueous solution of calcium chloride, pull The stretching bath was a 2.5 wt% aqueous solution of calcium chloride and a 2.5 wt% aqueous solution of chlorinated water.

3 )将步骤 2 )得到的海藻酸盐复合纤维经过纺纱以及后加工等生产纱线 (即海藻酸盐复合纱线）； 3) the alginate composite fiber obtained in the step 2) is subjected to spinning and post-processing to produce a yarn (ie, alginate composite yarn);

4 )将步骤 3 )所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2 )得到的海藻酸盐复合纤维的干断裂强度为 8.5 cN/dtex, 湿断裂强度为 7.3 cN/dtex, 干断裂伸长率为 12.1%。上述步骤 3 )得到的纱线（即海藻酸盐复合纱线）单纱强度为 26 cN/dtex。上述步骤 4 )得到的海藻酸盐针织或有纺纱布（织物）干重量为 211 g/m², 最小断裂率为 235 N/50mm。实施例 7: 一种海藻酸盐机织纱布的制备方法，包括以下几个步骤： 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) had a dry rupture strength of 8.5 cN/dtex, a wet rupture strength of 7.3 cN/dtex, and a dry elongation at break of 12.1%. The yarn obtained in the above step 3) (i.e., the alginate composite yarn) has a single yarn strength of 26 cN/dtex. The alginate knitted or woven gauze (fabric) obtained in the above step 4) had a dry weight of 211 g/m ² and a minimum breaking rate of 235 N/50 mm. Example 7 A method for preparing alginate woven gauze comprises the following steps:

1 )配制质量百分数为 0.5%海藻酸钠 ( SA )溶液与质量百分数为 1%的聚乙烯醇（PVA )溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 9: 1 , 将海藻酸钠溶液和聚乙烯醇溶液混合，在混合后加入氧化海藻酸钠交联剂，其质量为海藻酸钠质量的 5%, 搅拌均匀，真空脱泡 24h,得到纺丝原液，备用。所述的海藻酸钠的数均分子量为 500000, 所述的聚乙烯醇的数均分子量为 300000。 1) Prepare a solution of 0.5% sodium alginate (SA) solution and 1% by mass of polyvinyl alcohol (PVA), according to the solute of sodium alginate solution and polyvinyl alcohol solution (ie sodium alginate and polyethylene) The mass ratio of alcohol) is 9:1. The sodium alginate solution and the polyvinyl alcohol solution are mixed. After mixing, the oxidized sodium alginate cross-linking agent is added, the mass of which is 5% of the mass of sodium alginate, and the mixture is evenly stirred. After soaking for 24 hours, a spinning dope was obtained and used. The sodium alginate has a number average molecular weight of 500,000, and the polyvinyl alcohol has a number average molecular weight of 300,000.

2 )控制纺丝原液在 40 °C下进行纺丝，将步骤 1 )得到的纺丝原液经过湿法纺丝，得到海藻酸盐复合纤维（凝固液为 l wt%的氯化钙水溶液，拉伸浴为 2.5 wt%的氯化钙水溶液和 2.5wt%的氯化辞水溶液，洗涤浴为 3 wt%银系抗菌剂溶液）。 2) Control the spinning dope to be spun at 40 °C, and wet-spin the spinning dope obtained in step 1) to obtain alginate composite fiber (the coagulating solution is a lwt% aqueous solution of calcium chloride, pull The stretching bath was a 2.5 wt% aqueous solution of calcium chloride and a 2.5 wt% aqueous solution of chlorinated water, and the washing bath was a 3 wt% silver-based antibacterial agent solution).

4 )将步骤 3 )所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2)得到的海藻酸盐复合纤维的干断裂强度为 4.3 cN/dtex,湿断裂强度为 4.0 cN/dtex, 干断裂伸长率为 13.1%。上述步骤 3 )得到的纱线（即海藻酸盐复合纱线）单纱强度为 19 cN/dtex。上述述步骤 4 )得到的海藻酸盐针织或有纺纱布（织物 )干重量为 203 g/m², 最小断裂率为 135 N/50mm。实施例 8: 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) had a dry rupture strength of 4.3 cN/dtex, a wet rupture strength of 4.0 cN/dtex, and a dry elongation at break of 13.1%. The yarn obtained in the above step 3) (i.e., the alginate composite yarn) has a single yarn strength of 19 cN/dtex. The alginate knitted or woven gauze (fabric) obtained in the above step 4) had a dry weight of 203 g/m ² and a minimum breaking rate of 135 N/50 mm. Example 8

1 )配制质量百分数为 0.5%海藻酸钠 ( SA )溶液与质量百分数为 1%的聚乙烯醇（PVA )溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 9: 1 , 将海藻酸钠溶液和聚乙烯醇溶液混合，搅拌均匀，真空脱泡 24h, 得到纺丝原液，备用。所述的海藻酸钠的数均分子量为 4000, 所述的聚乙烯醇的数均分子量为 10000。 2 )控制纺丝原液在 40 °C下进行纺丝，将步骤 1 )得到的纺丝原液经过湿法纺丝，得到海藻酸盐复合纤维（凝固液为 lwt%的氯化辞水溶液，拉伸浴为 2.5wt%的氯化钙水溶液和 2.5wt%的氯化辞水溶液）。 1) Prepare a solution of 0.5% sodium alginate (SA) solution and 1% by mass of polyvinyl alcohol (PVA), according to the solute of sodium alginate solution and polyvinyl alcohol solution (ie sodium alginate and polyethylene) The mass ratio of the alcohol is 9:1. The sodium alginate solution and the polyvinyl alcohol solution are mixed, stirred uniformly, and degassed under vacuum for 24 hours to obtain a spinning dope, which is ready for use. The sodium alginate has a number average molecular weight of 4,000, and the polyvinyl alcohol has a number average molecular weight of 10,000. 2) The spinning dope is controlled to be spun at 40 ° C, and the spinning dope obtained in step 1) is subjected to wet spinning to obtain alginate composite fiber (the coagulating solution is a lwt% aqueous solution of chlorination, stretching) The bath was a 2.5 wt% aqueous solution of calcium chloride and a 2.5 wt% aqueous solution of chlorinated water.

4 )将步骤 3 )所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2)得到的海藻酸盐复合纤维的干断裂强度为 4.5 cN/dtex,湿断裂强度为 4.2 cN/dtex, 干断裂伸长率为 13%。所述步骤 3 )得到的纱线（即海藻酸盐复合纱线）单纱强度为 12 cN/dtex。上述步骤 4 )得到的海藻酸盐针织或有纺纱布（织物）干重量为 190 g/m², 最小断裂率为 75 N/50mm。实施例 9: 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) had a dry rupture strength of 4.5 cN/dtex, a wet rupture strength of 4.2 cN/dtex, and a dry elongation at break of 13%. The yarn obtained in the step 3) (i.e., the alginate composite yarn) has a single yarn strength of 12 cN/dtex. The alginate knitted or woven gauze (fabric) obtained in the above step 4) had a dry weight of 190 g/m ² and a minimum breaking rate of 75 N/50 mm. Example 9

1 ) 配制质量百分数为 2%海藻酸钠 ( SA )溶液与质量百分数为 10%的聚乙烯醇（PVA )溶液，按照海藻酸钠溶液与聚乙烯醇溶液的溶质 (即海藻酸钠与聚乙烯醇）的质量比例为 4: 1 , 将海藻酸钠溶液和聚乙烯醇溶液混合，在混合后加入戊二醛交联剂，其质量为海藻酸钠质量的 1%, 搅拌均勾，真空脱泡 24h, 得到纺丝原液，备用。所述的海藻酸钠的数均分子量为 200000。所述的聚乙烯醇的数均分子量为 80000。 1) Prepare a 2% by mass sodium alginate (SA) solution and a 10% by mass solution of polyvinyl alcohol (PVA), according to the solute of sodium alginate solution and polyvinyl alcohol solution (ie sodium alginate and polyethylene) The mass ratio of alcohol) is 4:1. The sodium alginate solution and the polyvinyl alcohol solution are mixed. After mixing, the glutaraldehyde cross-linking agent is added, the mass of which is 1% of the mass of sodium alginate, and the mixture is stirred and vacuumed. After soaking for 24 hours, the spinning dope was obtained and used. The sodium alginate has a number average molecular weight of 200,000. The polyvinyl alcohol has a number average molecular weight of 80,000.

2 )控制纺丝原液在 40 °C下进行纺丝，将步骤 1 )得到的纺丝原液经过湿法纺丝，得到海藻酸盐复合纤维（凝固液为 l wt%的氯化钙水溶液，拉伸浴为 2.5 wt%的氯化钙水溶液和 2.5 wt%的氯化辞水溶液）。 2) Control the spinning dope to be spun at 40 °C, and wet-spin the spinning dope obtained in step 1) to obtain alginate composite fiber (the coagulating solution is a lwt% aqueous solution of calcium chloride, pull The stretching bath was a 2.5 wt% aqueous solution of calcium chloride and a 2.5 wt% aqueous solution of chlorinated water.

4 )将步骤 3 )所得到的纱线经针织机或织布机制成机织纱布（绷带）。上述步骤 2 )得到的海藻酸盐复合纤维的干断裂强度为 14.5 cN/dtex, 湿断裂强度为 11.6 cN/dtex, 干断裂伸长率为 23.9%。上述步骤 3 )得到的纱线 (即海藻酸盐复合纱线）单纱强度为 42.8 cN/dtex₀ 上述步骤 4 )得到的海藻酸盐针织或有纺纱布（织物）干重量为 249 g/m², 最小断裂率为 415 N/50mm。在上述几个实施例中，制备纺丝原液的海藻酸钠中可加入海藻酸钾、海藻酸铵或其混合物，海藻酸钠也可由海藻酸钾、海藻酸铵或其混合物替代。换言之，制备纺丝原液的海藻酸盐为海藻酸钠、海藻酸钾、海藻酸铵中的一种或任意两种以上按任意配比的混合物。 4) The yarn obtained in the step 3) is made into a woven gauze (bandage) by a knitting machine or a weaving machine. The alginate composite fiber obtained in the above step 2) has a dry rupture strength of 14.5 cN/dtex, wet The breaking strength was 11.6 cN/dtex and the dry elongation at break was 23.9%. The single yarn of the yarn obtained in the above step 3) (ie, alginate composite yarn) has a strength of 42.8 cN/dtex. ₀ The alginate knitted or woven fabric (fabric) obtained in the above step 4) has a dry weight of 249 g/ m ² , the minimum fracture rate is 415 N/50 mm. In the above several embodiments, potassium alginate, ammonium alginate or a mixture thereof may be added to the sodium alginate for preparing the spinning dope, and the sodium alginate may also be replaced by potassium alginate, ammonium alginate or a mixture thereof. In other words, the alginate to prepare the spinning dope is one of sodium alginate, potassium alginate, ammonium alginate or a mixture of any two or more thereof in any ratio.

在上述几个实施例中，湿法纺丝的温度控制在 40°C , 其为最佳条件。在其它实施例中，湿法纺丝的温度控制在 25~45 °C即可。 In the above several embodiments, the temperature of the wet spinning was controlled at 40 ° C, which was an optimum condition. In other embodiments, the temperature of the wet spinning is controlled at 25 to 45 °C.

在上述几个实施例中，海藻酸盐的数均分子量为 4000~500000, 优选数均分子量为 50000~500000的海藻酸盐，进一步优选 200000~500000的海藻酸盐。 In the above several embodiments, the alginate has a number average molecular weight of 4,000 to 500,000, preferably a alginate having a number average molecular weight of 50,000 to 500,000, and further preferably an alginate of 200,000 to 500,000.

在上述几个实施例中，聚乙烯醇的数均分子量为 10000~300000 , 优选 50000-250000, 进一步优选 70000~150000的聚乙烯醇。 In the above several embodiments, the polyvinyl alcohol has a number average molecular weight of 10,000 to 300,000, preferably 50,000 to 250,000, more preferably 70,000 to 150,000.

在上述几个实施例中，海藻酸盐溶液中海藻酸盐的质量百分数浓度为 0.5%~20%, 优选 3%~8%。 In the above several embodiments, the mass percentage of the alginate in the alginate solution is from 0.5% to 20%, preferably from 3% to 8%.

在上述几个实施例中，聚乙烯醇溶液中聚乙烯醇的质量百分数浓度为 0.5%~25%, 优选 5%~15%。 In the above several embodiments, the mass percentage concentration of the polyvinyl alcohol in the polyvinyl alcohol solution is from 0.5% to 25%, preferably from 5% to 15%.

在上述几个实施例中，所采用的交联剂为氧化海藻酸钠、京尼平、戊二醛中的一种或任意两种以上（含任意两种）按任意配比的混合物，优选氧化海藻酸钠和 /或京尼平，进一步优选氧化海藻酸钠。 In the above several embodiments, the crosslinking agent used is one of oxidized sodium alginate, genipin, glutaraldehyde or a mixture of any two or more (including any two) in any ratio, preferably Oxidized sodium alginate and/or genipin, and further preferably oxidized sodium alginate.

在上述几个实施例中，海藻酸盐复合纤维的凝固方法为分步凝固，先采用浓度为 0~5 wt%的凝固液进行预凝固，然后再用 0~10\¥1%的凝固液进行边拉伸边凝固。 In the above several embodiments, the solidification method of the alginate composite fiber is a stepwise solidification, first pre-solidification using a coagulating liquid having a concentration of 0 to 5 wt%, and then using 0 to 10% of the coagulating liquid. It is solidified while stretching.

本发明的海藻酸盐机织纱布，由海藻酸盐与聚乙烯醇共混和 /或交联之后，经湿法纺丝得到纤维，再经纺纱制成纱线，该纱线经针织机或织布机制成机织纱布（绷带）。海藻酸钠与聚乙烯醇共混纤维有良好的机械性能，因为在共混纤维中聚乙烯醇链上的 -OH和海藻酸钠的 -COO-、 -OH形成了强烈的氢键，提高纤维的强力和弹性。由海藻酸钠与聚乙烯醇形成的水凝胶有很高的血液相溶性，所以借助聚乙烯醇的良好性能，通过共混或交联的方法可使海藻酸纤维获得良好的使用性能或加工性能。通过本发明的方法制得的海藻酸盐复合纤维的干断裂强度为 4.2~15 cN/dtex, 纤维直径为 10~50μηι, 湿断裂强度为 4.0-12 cN/dtex, 干断裂伸长率为 12-25%, 从而解决了藻酸盐纤维的可纺性与可编织性能。再通过专业的纺纱技术，得到力学性能优异的纱线，海藻酸盐复合纱线的单纱强度为 12~45 cN/dtex。进一步加工可生产得到医用纱布或医用绷带，海藻酸盐机织纱布的干重量为 190~280g/m² , 最小断裂率为 75~450N/50mm。 The alginate woven gauze of the present invention, after being blended and/or crosslinked by alginate and polyvinyl alcohol, is subjected to wet spinning to obtain fibers, which are then spun into yarns, which are passed through a knitting machine or Loom machine Weaving gauze (bandage). Sodium alginate and polyvinyl alcohol blend fibers have good mechanical properties because -OH on the polyvinyl alcohol chain and -COO-, -OH of sodium alginate form strong hydrogen bonds in the blended fibers, and the fibers are increased. Strong and flexible. The hydrogel formed by sodium alginate and polyvinyl alcohol has high blood compatibility, so the alginic acid fiber can be used for good performance or processing by blending or cross-linking by virtue of the good properties of polyvinyl alcohol. performance. The alginate composite fiber obtained by the method of the invention has a dry breaking strength of 4.2 to 15 cN/dtex, a fiber diameter of 10 to 50 μm, a wet breaking strength of 4.0 to 12 cN/dtex, and a dry elongation at break of 12 -25%, thereby solving the spinnability and woven properties of alginate fibers. Through the professional spinning technology, the yarn with excellent mechanical properties is obtained. The single yarn strength of the alginate composite yarn is 12~45 cN/dtex. Further processing can produce medical gauze or medical bandage. The dry weight of alginate woven gauze is 190~280g/m ² , and the minimum breaking rate is 75~450N/50mm.

按照本发明的制备方法得到了力学性能很好的海藻酸盐机织纱布（即海藻酸复合纤维），从而解决了藻酸盐纤维的可纺性与可编织性能。并且通过对普通棉纱布和海藻酸复合纱布的吸湿性、扩散性、透湿性等性能进行研究，结果显示海藻酸复合纱布作为医用敷料比传统的棉纱布具有明显的优越性。单位质量海藻酸复合纱布的吸液率是棉纱布的 3 倍以上，其阻止液体扩散的性能更明显地体现了海藻酸复合纱布作为一种高科技医用敷料的性能优势。 According to the preparation method of the present invention, alginate woven gauze (i.e., alginate composite fiber) having excellent mechanical properties is obtained, thereby solving the spinnability and the woven property of the alginate fiber. Moreover, by studying the hygroscopicity, diffusibility, moisture permeability and the like of ordinary cotton gauze and alginic acid composite gauze, the results show that alginic acid composite gauze has obvious superiority as a medical dressing than conventional cotton gauze. The unit mass of alginic acid composite gauze has a liquid absorption rate more than three times that of cotton gauze. Its ability to prevent liquid diffusion more clearly reflects the performance advantages of alginic acid composite gauze as a high-tech medical dressing.

经过检测，本发明的海藻酸盐复合纱线和织物的各项指标均达到国家医药行业标准（YY 0311-2006、 YY 0594-2006 ), 具有高吸湿成胶性、整体易去除性、高透氧性、生物相容性、生物降解吸收性，能 ^艮好的促进创面愈合和皮肤再生，解决了目前海藻酸盐敷料只能是无纺而不能针织或有纺的问题。细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。 After testing, the indicators of the alginate composite yarn and fabric of the invention all meet the national pharmaceutical industry standards (YY 0311-2006, YY 0594-2006), have high moisture absorption gelation, overall easy to remove, high permeability Oxygen, biocompatibility, biodegradability and absorption, can promote wound healing and skin regeneration, and solve the problem that alginate dressing can only be non-woven and not knitted or spun. It is not to be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the spirit and scope of the invention. Therefore, the scope of the invention is to be determined by the appended claims.

Claims

权利要求书 claims

1、一种海藻酸盐机织纱布，其特征在于：所述海藻酸盐机织纱布由海藻酸盐复合纱线经针织机或织布机制成，所述海藻酸盐复合纱线由海藻酸盐与聚乙烯醇共混和 /或交联之后经湿法纺丝所得到的海藻酸盐复合纤维经纺纱制成。 1. An alginate woven gauze, characterized in that: the alginate woven gauze is made of alginate composite yarn through a knitting machine or a loom, and the alginate composite yarn is made of alginate The alginate composite fiber obtained by wet spinning after salt and polyvinyl alcohol is blended and/or cross-linked is spun.

2、根据权利要求 1所述的海藻酸盐机织纱布，其特征在于：所述海藻酸盐机织纱布的干重量为 190~280g/m², 最小断裂率为 75~450N/50mm; 所述海藻酸盐复合纱线的单纱强度为 12~45 cN/dtex; 所述海藻酸盐复合纤维的干断裂强度为 4.2~15 cN/dtex, 纤维直径为 10~50μηι, 湿断裂强度为 4.0~12 cN/dtex, 干断裂伸长率为 12-25%。 2. The alginate woven gauze according to claim 1, characterized in that: the dry weight of the alginate woven gauze is 190~280g/ ^m2 , and the minimum breakage rate is 75~450N/50mm; so The single yarn strength of the alginate composite yarn is 12~45 cN/dtex; the dry breaking strength of the alginate composite fiber is 4.2~15 cN/dtex, the fiber diameter is 10~50 μm, and the wet breaking strength is 4.0 ~12 cN/dtex, dry elongation at break 12-25%.

3、一种海藻酸盐机织纱布的制备方法，所述方法包括以下步骤：分别配制海藻酸盐溶液与聚乙烯醇溶液,按照海藻酸盐溶液的溶质与聚乙烯醇溶液的溶质的质量比例为 9: 1-1 : 1 , 将海藻酸盐溶液和聚乙烯醇溶液混合后搅拌均匀，真空脱泡 24h, 得到纺丝原液； 3. A method for preparing alginate woven gauze. The method includes the following steps: Prepare an alginate solution and a polyvinyl alcohol solution respectively, according to the mass ratio of the solute of the alginate solution and the solute of the polyvinyl alcohol solution. The ratio is 9: 1-1: 1. Mix the alginate solution and the polyvinyl alcohol solution, stir evenly, and vacuum degas for 24 hours to obtain the spinning stock solution;

控制纺丝原液在 25~45 °C进行湿法纺丝工序，得到海藻酸盐复合纤维；将海藻酸盐复合纤维经过纺纱工序生产海藻酸盐复合纱线； Control the spinning solution to perform a wet spinning process at 25~45 °C to obtain alginate composite fibers; pass the alginate composite fibers through the spinning process to produce alginate composite yarns;

将海藻酸盐复合纱线经针织机或织布机制成藻酸盐纱布。 Alginate composite yarn is processed into alginate gauze through a knitting machine or loom.

4、根据权利要求 3所述的海藻酸盐机织纱布的制备方法，其特征在于：在制备所述纺丝原液的步骤中，在将海藻酸盐溶液和聚乙烯醇溶液混合步骤之后和搅拌均匀步骤之前进一步包括加入交联剂的步骤。 4. The preparation method of alginate woven gauze according to claim 3, characterized in that: in the step of preparing the spinning stock solution, after the step of mixing the alginate solution and the polyvinyl alcohol solution and stirring The homogenizing step further includes a step of adding a cross-linking agent.

5、根据权利要求 4所述的海藻酸盐机织纱布的制备方法，其特征在于：所述交联剂为氧化海藻酸钠、京尼平、戊二醛中的一种或任意两种以上按任意配比的混合物，所述交联剂的加入量为所述海藻酸盐质量的 0~5%。 5. The preparation method of alginate woven gauze according to claim 4, characterized in that: the cross-linking agent is one or any two or more of oxidized sodium alginate, genipin, and glutaraldehyde. According to the mixture in any proportion, the added amount of the cross-linking agent is 0 to 5% of the mass of the alginate.

6、根据权利要求 3至 5中任一项所述的海藻酸盐机织纱布的制备方法，其特征在于：所述制备纺丝原液的海藻酸盐为海藻酸钠、海藻酸钾、海藻酸铵中的一种或任意两种以上按任意配比的混合物，所述海藻酸盐溶液中海藻酸盐的质量百分数浓度为 0.5%~20% , 所述海藻酸盐的数均分子量为 4000-500000 6. The method for preparing alginate woven gauze according to any one of claims 3 to 5, characterized in that: the alginate used to prepare the spinning stock solution is sodium alginate, potassium alginate, or alginic acid. One kind of ammonium or a mixture of any two or more in any proportion, the mass percentage concentration of alginate in the alginate solution is 0.5%~20%, and the number average molecular weight of the alginate is 4000- 500000

7、根据权利要求 3至 5中任一项所述的海藻酸盐机织纱布的制备方法，其特征在于：所述聚乙烯醇溶液中聚乙烯醇的质量百分数浓度为 0.5%~2.5%, 所述聚乙烯醇的数均分子量为 10000~300000。 7. The preparation method of alginate woven gauze according to any one of claims 3 to 5, characterized in that: the mass percentage concentration of polyvinyl alcohol in the polyvinyl alcohol solution is 0.5% to 2.5%, The number average molecular weight of the polyvinyl alcohol is 10,000~300,000.

8、根据权利要求 3至 5中任一项所述的海藻酸盐机织纱布的制备方法，其特征在于：在所述制备海藻酸盐复合纤维的步骤中，所述海藻酸盐复合纤维采用分步凝固方式，先采用浓度为 0~5wt%的凝固液进行预凝固，然后再用 0~ 10wt%的凝固液进行边拉伸边凝固。 8. The method for preparing alginate woven gauze according to any one of claims 3 to 5, characterized in that: in the step of preparing alginate composite fiber, the alginate composite fiber adopts In the step-by-step coagulation method, a coagulation liquid with a concentration of 0~5wt% is first used for pre-coagulation, and then a coagulation liquid with a concentration of 0~10wt% is used for solidification while stretching.

9、根据权利要求 8所述的海藻酸盐机织纱布的制备方法，其特征在于：所述凝固液为氯化钙、氯化辞水溶液中的一种或任意两种以上按任意配比的混合物。 9. The preparation method of alginate woven gauze according to claim 8, characterized in that: the coagulation liquid is one of calcium chloride, aqueous chloride solution or any two or more in any proportion. mixture.

10、根据权利要求 3至 5中任一项所述的海藻酸盐机织纱布的制备方法，其特征在于：在制备海藻酸盐复合纤维的步骤中，所述湿法纺丝的温度为 40 10. The method for preparing alginate woven gauze according to any one of claims 3 to 5, characterized in that: in the step of preparing alginate composite fibers, the wet spinning temperature is 40

°C。 °C.