CN103614927B - A kind of fiber textile containing cellulose antibiotic finishing method - Google Patents

Abstract

The invention relates to an antibacterial finishing method for textiles containing cellulose fibers. The method uses natural high polymer chitosan and sodium alginate as wall materials, Chinese medicine extracts as core materials, and adopts microcapsule technology to encapsulate the Chinese medicine extracts. ; Then use the post-finishing method to process the microcapsules on the partially carboxymethylated cellulose-containing fiber textiles, and impart antibacterial properties through the electrostatic attraction between the carboxyl groups on the cellulose fibers and chitosan, and the cross-linking effect of the cross-linking agent Good wash resistance. The raw materials used in the invention are environmentally friendly, safe and efficient, and the obtained textile has good antibacterial effect on common Staphylococcus aureus, Escherichia coli and Bacillus subtilis.

Description

A kind of antibacterial finishing method of textile containing cellulose fiber

technical field

The invention belongs to the technical field of textiles and relates to an antibacterial finishing method for textiles containing cellulose fibers.

Background technique

Textiles are easy to breed bacteria, molds and other microorganisms during use. Antibacterial textiles can not only effectively prevent textiles from being infringed by these harmful bacteria, but also protect the health of users, such as preventing underwear from producing odors and preventing socks from getting dirty. Growth and reproduction of fungi, prevention of erythema in infants and young children due to contact with diapers, etc.

Antibacterial agents used in textiles mainly include: organic antibacterial agents, inorganic antibacterial agents, and natural antibacterial agents. These antibacterial agents have their own characteristics, but it is difficult to meet the basic conditions of broad spectrum, high efficiency, safety, washability, and environmental protection at the same time. Using microcapsule technology to coat one or more antibacterial agents into antibacterial microcapsules, and then finishing them on textiles with a suitable crosslinking agent, can effectively overcome the above defects and obtain a good finishing effect.

Chitosan is the only alkaline polysaccharide existing in nature, and it is a non-toxic, biocompatible and biodegradable natural polymer material. The amino groups on the chitosan molecular chain are positively charged at low pH, and these amino groups can interact with the negatively charged groups on the surface of fungal cells, thereby changing the fluidity and permeability of the cell membrane of pathogenic bacteria, interfering with DNA replication and transcription, Blocks the metabolism of pathogenic bacteria and has good antibacterial activity. Sodium alginate is a kind of linear polysaccharide extracted from brown algae and seaweed plants, and its molecular chain contains a large number of carboxyl groups. Under certain conditions, the amino group on the chitosan molecular chain can form a polyelectrolyte membrane with the carboxyl group in the sodium alginate molecular chain through positive and negative charge attraction, and spontaneously form a capsule, which is widely used in drug sustained-release preparations. However, the use of sodium alginate/chitosan biomicrocapsules in the preparation of antibacterial textiles has not been reported so far.

Contents of the invention

The technical problem to be solved by the present invention is to provide an antibacterial finishing method for textiles containing cellulose fibers. In this method, chitosan and sodium alginate are used as wall materials, and microcapsule technology is used to encapsulate the antibacterial active ingredients. The resulting product is green, environmentally friendly, safe and efficient, and has broad-spectrum antibacterial properties; On textiles, capsules are firmly combined with textiles and have good washability.

The technical scheme to achieve the above purpose is: use the natural extract with antibacterial activity as the core material, and the natural high polymer chitosan and sodium alginate as the wall material, and prepare sodium alginate/chitosan biological antibacterial microbes by two-step method. Capsules; then soaked and baked to partially carboxymethylated cellulose-containing fiber textiles, the resulting antibacterial textiles have good broad-spectrum antibacterial properties and excellent washability.

A method for antibacterial finishing of cellulose fiber textiles provided by the invention comprises the following steps:

(1) Preparation of sodium alginate/chitosan antimicrobial microcapsules: Add the extract of traditional Chinese medicine to 50-100mL sodium alginate solution with a mass fraction of 2%-4%, and stir well. At a height of 10cm from the liquid surface, use a No. 5 needle to mix sodium alginate and traditional Chinese medicine extracts, and under magnetic stirring, drop them into the _CaCl solution with a mass fraction of 1%-3% at a constant speed, and continue to stir for 0.5- After 1.5 hours, the gel microspheres were filtered out, washed 3-5 times with distilled water, and set aside. Dissolve chitosan in 0.5%-2% acetic acid solution by volume fraction to make a chitosan solution with mass fraction 1.5%-3%, then add the gel microspheres into the chitosan-acetic acid solution, and stir magnetically for 0.5- After 2 hours, the capsules were collected by suction filtration, washed 3-5 times with distilled water, and the surface water of the capsules was blotted dry with filter paper, and stored in a refrigerator at 4°C until use.

(2) Preparation of carboxymethylated cellulose fiber-containing textiles: immerse 5g of the fabric in a caustic soda solution with a mass fraction of 10%-30%, and soak for 15-45min at 20-35°C, then take out the fabric and put it in 100mL Put it in a certain concentration of chloroacetic acid aqueous solution, take it out after 30-45min, seal the fabric in a polyethylene plastic bag, put it in an oven at 30-80°C for 1-3h, and then use ethanol/water mixed solution (V/V=80/ 20) Wash 3-5 times and dry.

(3) Preparation of antibacterial textiles: Disperse sodium alginate/chitosan antibacterial microcapsules in distilled water to prepare a microcapsule finishing solution with a mass concentration of 5.0-10.0g/L; impregnate the above-mentioned carboxymethylated cellulose-containing fiber textiles In the microcapsule finishing solution, after soaking for 30-45 minutes, take it out, then soak it in a cross-linking agent solution with a mass fraction of 1%-5%, take it out after 0.5-1.5 hours, dry it at high temperature for 5-15 minutes, and wash it with water for 3-5 times , dry it.

Known by above-mentioned technical scheme: the present invention at first utilizes primary amino group on chitosan molecular chain and carboxyl group on sodium alginate molecular chain can form polyelectrolyte film by positive and negative charge attraction, spontaneously form the characteristic of capsule, will have antibacterial activity Microencapsulation of traditional Chinese medicine extracts; then partially carboxymethylate the textiles containing cellulose fibers, introduce an appropriate amount of carboxyl groups on the molecular chains of cellulose fibers, and use the carboxyl groups on the molecular chains of cellulose fibers to interact with the microcapsule wall material - chitosan molecules The electrostatic attraction between the amino groups on the chain, the sodium alginate/chitosan antibacterial microcapsules are treated on the cellulose fiber textiles, and the combination fastness of the microcapsules and textiles is improved through further crosslinking of the crosslinking agent to achieve antibacterial purpose of washing.

Preferably, the traditional Chinese medicine extract described in step (1) is one or more of honeysuckle extract, aloe extract, mugwort leaf extract, cortex phellodendron extract, scutellaria baicalensis extract, gallnut extract, and dandelion extract.

As a preference, the mass ratio of sodium alginate to traditional Chinese medicine extract in step (1) is 1:1-4:1.

Preferably, the molecular weight of the chitosan in step (1) is 0.5-3.5×10 ⁵ , and the degree of deacetylation is 60%-75%. If the degree of deacetylation of chitosan is too high, the adhesion of the microcapsules will be serious and cannot be formed. If the degree of deacetylation of chitosan is too low, the wall of the resulting microcapsules will be too thin.

Preferably, the cellulose-containing fiber textiles described in step (2) are cotton, linen, viscose fabrics, or interwoven fabrics of the two, or interwoven fabrics of these and other fibers.

Preferably, the concentration of chloroacetic acid in step (2) is 15%-30% relative to the weight of the fabric. If the concentration of chloroacetic acid is too low, the carboxymethyl content on the cellulose fiber will be less, which will affect the binding fastness of sodium alginate/chitosan antimicrobial microcapsules and textiles; but if the concentration of chloroacetic acid is too high, it will cause serious damage to the strength of the fabric .

Preferably, the crosslinking agent described in step (3) is one of isophorone diisocyanate and 1,6-hexamethylene diisocyanate.

Preferably, the high-temperature drying temperature in step (3) is 80-100°C.

A kind of method for antibacterial finishing of cellulose fiber textiles of the present invention has the advantages of:

(1) Chinese medicine extracts are used as antibacterial components, and natural high polymer chitosan and sodium alginate are used as wall materials of microcapsules, which is green and environmentally friendly.

(2) The Chinese medicine extract is encapsulated by microcapsule technology, which improves the stability of the Chinese medicine extract, prolongs the action time of the active ingredients, and reduces the irritation of the Chinese medicine extract.

(3) By carboxymethylating the electrostatic attraction between the carboxyl group and hydroxyl group on the cellulose-containing fiber fabric and the amino group on chitosan, with the help of the cross-linking effect of the cross-linking agent, the bonding fastness between the microcapsules and the textile is improved, and the antibacterial Persistence of effect.

Detailed ways

The terms used in the present invention, unless otherwise specified, generally have the meanings commonly understood by those skilled in the art.

The present invention will be described in further detail below in conjunction with specific embodiments. It should be understood that these examples are only for illustration of the present invention, but not to limit the scope of the present invention in any way.

Example 1

(1) Add 1g of honeysuckle extract to 50mL sodium alginate solution with a mass fraction of 2%, and stir well. At a height of 10 cm from the liquid surface, use a No. 5 needle to mix sodium alginate and honeysuckle extract, and under magnetic stirring, drop it into _the CaCl solution with a mass fraction of 1% at a constant speed, and continue stirring for 0.5 hours. The gel microspheres were filtered out, washed 3 times with distilled water, and set aside. Dissolve chitosan (molecular weight 0.5×10 ⁵ , degree of deacetylation is 75%) in 0.5% acetic acid solution by volume fraction to make chitosan solution with mass fraction 1.5%, then add gel microspheres to chitosan After magnetically stirring for 0.5 h in the acetic acid solution, suction filter, collect the capsules, wash 3 times with distilled water, blot the water on the surface of the capsules with filter paper, and store them in a refrigerator at 4°C until use.

(2) Soak 5g of pure cotton fabric in a caustic soda solution with a mass fraction of 10%, and soak it for 15 minutes at 35°C, then take out the fabric, put it in 100mL of 15% aqueous solution of chloroacetic acid relative to the weight of the fabric, take it out after 30 minutes, and put the fabric Seal it in a polyethylene plastic bag, place it in an oven at 30°C for 3 hours, wash it with ethanol/water mixed solution (V/V=80/20) for 3 times, and dry it.

(3) Disperse sodium alginate/chitosan antibacterial microcapsules in distilled water to prepare a microcapsule finishing solution with a mass concentration of 5.0 g/L; soak the above-mentioned carboxymethylated cotton fabric in the microcapsule finishing solution for 30 minutes , take it out, and then soak it in 1% isophorone diisocyanate solution by mass fraction, take it out after 0.5h, dry it at 80°C for 15min, wash it with water three times, and dry it.

Comparative example 1

Adopt the same method as Example 1 to prepare sodium alginate/chitosan antibacterial microcapsules and carboxymethylated cotton fabric, then sodium alginate/chitosan antibacterial microcapsules are dispersed in distilled water, prepare mass concentration 5.0g/ L microcapsule finishing solution: soak the cotton fabric in the microcapsule finishing solution for 30 minutes, take it out, dry it at 80°C for 15 minutes, wash it with water three times, and dry it.

Example 2

(1) Add 1g of aloe vera extract to 100mL of sodium alginate solution with a mass fraction of 4%, and stir well. At a height of 10cm from the liquid surface, use a No. 5 needle to mix sodium alginate and traditional Chinese medicine extracts. Under magnetic stirring, drop by drop into _the CaCl solution with a mass fraction of 3% at a constant speed, and continue stirring for 1.5 hours. The gel microspheres were filtered out, washed 5 times with distilled water, and set aside. Dissolve chitosan (molecular weight 3.5×10 ⁵ , degree of deacetylation is 70%) in 2% acetic acid solution by volume fraction to prepare chitosan solution with 3% mass fraction, and then add gel microspheres to chitosan In the acetic acid solution, after magnetic stirring for 2 hours, the capsules were collected by suction filtration, washed 5 times with distilled water, and the surface water of the capsules was blotted dry with filter paper, and stored in a refrigerator at 4°C until use.

(2) Soak 5g of ramie fabric in caustic soda solution with a mass fraction of 30%, and soak it for 45 minutes at 20°C, then take out the fabric, put it in 100mL of 30% chloroacetic acid aqueous solution relative to the weight of the fabric, take it out after 45 minutes, and seal the fabric In a polyethylene plastic bag, place it in an oven at 80°C for 1 hour, then wash it with ethanol/water mixed solution (V/V=80/20) for 5 times, and dry it.

(3) Disperse sodium alginate/chitosan antibacterial microcapsules in distilled water to prepare a microcapsule finishing solution with a mass concentration of 10.0 g/L; soak the above-mentioned carboxymethylated ramie fabric in the microcapsule finishing solution for 45 minutes , take it out, and then soak it in 1,6-hexamethylene diisocyanate solution with a mass fraction of 5%, take it out after 1.5 hours, dry it at 100°C for 5 minutes, wash it with water 5 times, and dry it.

Comparative example 2

Adopt the same method as Example 2 to prepare sodium alginate/chitosan antibacterial microcapsules and carboxymethylated ramie fabrics, then sodium alginate/chitosan antibacterial microcapsules are dispersed in distilled water, and the preparation mass concentration 10.0g/ L microcapsule finishing solution: soak the ramie fabric in the microcapsule finishing solution for 45 minutes, take it out and dry it at 100°C for 5 minutes, wash it with water for 5 times, and dry it.

Example 3

(1) Add 1g of mugwort leaf extract to 80mL of sodium alginate solution with a mass fraction of 2.5%, and stir well. At a height of 10cm from the liquid surface, use a No. 5 needle to mix the sodium alginate and Artemisia argyi extract, drop by drop into the CaCl solution with a mass fraction of ₂ % at a constant speed under magnetic stirring, and continue stirring for 1 hour. The gel microspheres were filtered out, washed 4 times with distilled water, and set aside. Dissolve chitosan (molecular weight: 1.5×10 ⁵ , deacetylation degree: 65%) in 1% acetic acid solution by volume fraction to prepare chitosan solution with mass fraction of 2.5%, then add gel microspheres to chitosan In the acetic acid solution, after magnetic stirring for 1 h, suction filtration, the capsules were collected, washed 4 times with distilled water, the surface water of the capsules was blotted dry with filter paper, and stored in a refrigerator at 4°C until use.

(2) Soak 5g of viscose fabric in a caustic soda solution with a mass fraction of 20%, and soak it for 30 minutes at 30°C, then take out the fabric, put it in 100mL of 20% chloroacetic acid aqueous solution relative to the weight of the fabric, take it out after 40 minutes, and put the fabric Seal it in a polyethylene plastic bag, place it in an oven at 60°C for 2 hours, wash it with ethanol/water mixed solution (V/V=80/20) 4 times, and dry it.

(3) Disperse sodium alginate/chitosan antibacterial microcapsules in distilled water to prepare a microcapsule finishing solution with a mass concentration of 8.0 g/L; soak the above-mentioned carboxymethylated viscose fabric in the microcapsule finishing solution for 40 minutes Finally, take it out, and then dip it in a 3% isophorone diisocyanate solution, take it out after 1 hour, dry it at 90°C for 10 minutes, wash it with water 4 times, and dry it.

Comparative example 3

Adopt the same method as embodiment 3 to prepare sodium alginate/chitosan antibacterial microcapsules and carboxymethylated viscose fabric, then sodium alginate/chitosan antibacterial microcapsules are dispersed in distilled water, preparation mass concentration 8.0g /L microcapsule finishing solution; soak the viscose fabric in the microcapsule finishing solution for 40 minutes, take it out, dry it at 90°C for 10 minutes, wash it with water 4 times, and dry it.

Example 4

(1) Add 0.6g Phellodendron Phellodendri extract to 60mL sodium alginate solution with a mass fraction of 3%, and stir well. At a height of 10cm from the liquid surface, use a No. 5 needle to mix the sodium alginate and Phellodendron Phellodendri extract, drop by drop into the CaCl2 solution with a mass fraction of 1.5% at a constant speed under magnetic stirring, and continue stirring for 1 hour. The microspheres were filtered out, washed 3 times with distilled water, and set aside. Dissolve chitosan (molecular weight: 2.0×10 ⁵ , deacetylation degree: 68%) in 1.5% acetic acid solution by volume fraction to make a 2% chitosan solution by mass fraction, then add gel microspheres to chitosan After magnetically stirring for 1.5 h in the acetic acid solution, suction filter, collect the capsules, wash 3 times with distilled water, dry the surface water of the capsules with filter paper, and store them in a refrigerator at 4°C until use.

(2) Soak 5g of polyester/cotton blended fabric in a caustic soda solution with a mass fraction of 25%, and soak it for 40 minutes at 25°C, then take out the fabric and put it in 100mL of 25% chloroacetic acid aqueous solution relative to the weight of the fabric, and take it out after 35 minutes. Seal the fabric in a polyethylene plastic bag, place it in an oven at 40°C for 2.5 hours, and then wash it three times with a mixed solution of ethanol/water (V/V=80/20) and dry it.

(3) Disperse sodium alginate/chitosan antibacterial microcapsules in distilled water to prepare a microcapsule finishing solution with a mass concentration of 6.0 g/L; soak the above carboxymethylated polyester/cotton blended fabric in the microcapsule finishing solution, After soaking for 30 minutes, take it out, then soak it in 2% 1,6-hexamethylene diisocyanate solution, take it out after 0.5 hours, dry it at 85°C for 15 minutes, wash it with water three times, and dry it.

Comparative example 4

Adopt the same method as embodiment 4 to prepare sodium alginate/chitosan antibacterial microcapsules and carboxymethylated polyester/cotton blended fabric, then sodium alginate/chitosan antibacterial microcapsules are dispersed in distilled water, prepare mass concentration 6.0g/L microcapsule finishing solution; soak the polyester/cotton blended fabric in the microcapsule finishing solution for 30 minutes, take it out, dry at 85°C for 15 minutes, wash 3 times with water, and dry.

Example 5

Antibacterial performance test: Refer to FZ/T01021-1992 "Test Method for Antibacterial Performance of Fabrics" to measure the antibacterial performance of the finished fabric, and calculate the antibacterial rate according to the following formula:

In the formula: A - the average number of colonies on the fabric without antibacterial treatment; B - the average number of colonies on the fabric with antibacterial treatment.

Antibacterial effect washability test: fabric antibacterial effect washability test is completed in the washing fastness test machine, the washing procedure is as follows (this washing procedure is equivalent to 5 times of washing): room temperature, detergent concentration 0.2%, 150mL solution, 10 steel balls, wash for 45 minutes. After washing, take out the sample and wash it twice in 100mL water, each time for 1min.

The results of fabric antibacterial test are as follows:

Table 1 fabric antibacterial performance test

As can be seen from the above table, the obtained sodium alginate/chitosan antibacterial microcapsules have good antibacterial properties, and the fabrics treated by it have good antibacterial effects on Staphylococcus aureus, Escherichia coli, and Bacillus subtilis, and the microcapsules Combined with textiles firmly, antibacterial effect has good washing resistance. Because the fabric is not treated with carboxymethylation and no cross-linking agent is added in the comparative example, the amount of microcapsules processed on the fabric is less, and the combination of the microcapsule and the fabric is weaker. Therefore, compared with the embodiment, no matter It is antibacterial or washable performance is poor.

Claims (8)

1. A method for antibacterial finishing of cellulose fiber textiles, comprising the following steps: (1) Preparation of sodium alginate/chitosan antibacterial microcapsules: adding the Chinese medicine extract to 50-100mL of sodium alginate solution with a mass fraction of 2%-4%, fully stirring and mixing; At a high place, use a No. 5 needle to mix sodium alginate and traditional Chinese medicine extract, under magnetic stirring, drop by drop into the CaCl ₂ solution with a mass fraction of 1%-3% at a constant speed, and continue stirring for 0.5-1.5h, then put The gel microspheres are filtered out, washed 3-5 times with distilled water, and set aside; chitosan is dissolved in 0.5%-2% acetic acid solution by volume fraction to prepare a mass fraction 1.5%-3% chitosan solution, and then Add the gel microspheres to the chitosan acetic acid solution, stir magnetically for 0.5-2 hours, filter with suction, collect the capsules, wash with distilled water for 3-5 times, dry the surface water of the capsules with filter paper, and place them in a refrigerator at 4°C Save for later use; (2) Preparation of carboxymethylated cellulose fiber-containing textiles: immerse 5g of the fabric in a caustic soda solution with a mass fraction of 10%-30%, and after soaking for 15-45min at 20-35°C, take out the fabric and put it in 100mL Put it in a certain concentration of chloroacetic acid aqueous solution, take it out after 30-45min, seal the fabric in a polyethylene plastic bag, put it in an oven at 30-80°C for 1-3h, and then use a mixture of ethanol and water with a volume ratio of 80:20 The solution is washed 3-5 times and dried; (3) Preparation of antibacterial textiles: Disperse sodium alginate/chitosan antibacterial microcapsules in distilled water, prepare a microcapsule finishing solution with a mass concentration of 5.0-10.0g/L; impregnate the above-mentioned carboxymethylated cellulose-containing fiber textiles In the microcapsule finishing solution, after soaking for 30-45 minutes, take it out, then soak it in a cross-linking agent solution with a mass fraction of 1%-5%, take it out after 0.5-1.5 hours, dry it at high temperature for 5-15 minutes, and wash it with water for 3-5 times , dry it. 2. A kind of cellulose-containing fiber textile antibacterial finishing method described in claim 1 is characterized in that: the Chinese medicine extract is honeysuckle extract, aloe extract, Artemisia argyi extract, Cortex Phellodendri extract, Scutellaria baicalensis extract, gallnut extract , one or more of dandelion extracts. 3. A method for antibacterial finishing of cellulose fiber textiles according to claim 1, characterized in that the mass ratio of sodium alginate to Chinese medicine extract is 1:1-4:1. 4. An antibacterial finishing method for cellulose fiber-containing textiles as claimed in claim 1, characterized in that the molecular weight of chitosan is 0.5-3.5×10 ⁵ , and the degree of deacetylation is 60%-75%. 5. A kind of method for antibacterial finishing of cellulose-containing fiber textiles described in claim 1 is characterized in that: the cellulose-containing fiber textiles are cotton, hemp, viscose fabrics, or both interwoven fabrics, or they and other fibers Interwoven fabric. 6. A method for antibacterial finishing of cellulose fiber textiles according to claim 1, characterized in that the concentration of chloroacetic acid is 15%-30% relative to the weight of the fabric. 7. A method for antibacterial finishing of cellulose fiber-containing textiles according to claim 1, characterized in that: the crosslinking agent is one of isophorone diisocyanate and 1,6-hexamethylene diisocyanate. 8. The method for antibacterial finishing of cellulose fiber-containing textiles according to claim 1, characterized in that: the high-temperature drying temperature is 80-100°C.