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

Alginate woven gauze and preparation method thereof

Technical field

The invention relates to the field of medical biopolymer materials, in particular to alginate textile gauze and a preparation method thereof. Background technique

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.

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.

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.

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.

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.

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.

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.

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.

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.

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

In view of the above, the present invention provides an alginate woven gauze having a relatively high strength.

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.

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%.

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.

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.

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%.

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

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.

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.

Preferably, the coagulating liquid is one of calcium chloride, aqueous chlorinated solution or a mixture of any two or more of any ratio.

Preferably, in the step of preparing the alginate composite fiber, the wet spinning temperature is 40

°C.

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

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.

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

A method for preparing alginate woven gauze comprises the following steps:

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) 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) 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 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:

A method for preparing alginate woven gauze comprises the following steps:

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) 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) 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:

A method for preparing alginate woven gauze, comprising the following steps:

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) 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.

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:

A method for preparing alginate woven gauze comprises the following steps:

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) 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) 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:

A method for preparing alginate woven gauze comprises the following steps:

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) 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

A method for preparing alginate woven gauze comprises the following steps:

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) 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) 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) 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) 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) 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) 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

A method for preparing alginate woven gauze comprises the following steps:

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) 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

A method for preparing alginate woven gauze comprises the following steps:

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) 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) 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.

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.

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.

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.

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%.

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%.

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.

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.

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.

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.

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

claims

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. 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. 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;

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;

Alginate composite yarn is processed into alginate gauze through a knitting machine or loom.

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. 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. 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. 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. 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. 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. 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.