阅读说明：本技术 一种含百合活性成分的大生物粘胶纤维 (Lily active ingredient-containing macrobiotic viscose fiber ) 是由 黄效华 甄丽 张华� 于 2021-11-13 设计创作，主要内容包括：一种含百合活性成分的大生物粘胶纤维,包括壳聚糖包裹百合干粉微球的制备,壳聚糖包裹百合干粉微球分散液的制备,共混纺丝液的制备,纺丝和后处理。原粘胶纤维的干、湿断裂强度为2.72cN/dtex、1.89cN/dtex,断裂伸长率24.4%,本发明制备的含百合活性成分粘胶纤维干、湿断裂强度2.65～2.93cN/dtex、1.71～1.86cN/dtex,断裂伸长率22.9～24.8%；对金黄色葡萄球菌、大肠杆菌和白色念珠菌的抗菌率分别为93.5～96.6%、92.8～94.7%、91.8～92.3%,洗涤30次后相应抗菌率分别为90.8～94.3%、88.4～91.5%、87.9～89.6%。(A macrobiotic viscose fiber containing lily active ingredient comprises the preparation of chitosan-coated lily dry powder microspheres, the preparation of chitosan-coated lily dry powder microsphere dispersion, the preparation of blended spinning solution, spinning and post-treatment. The dry and wet breaking strength of the original viscose fiber is 2.72cN/dtex, 1.89cN/dtex, and the elongation at break is 24.4%, the dry and wet breaking strength of the viscose fiber containing the lily active ingredient prepared by the invention is 2.65-2.93 cN/dtex, 1.71-1.86 cN/dtex, and the elongation at break is 22.9-24.8%; the antibacterial rate of the antibacterial agent to staphylococcus aureus, escherichia coli and candida albicans is 93.5-96.6%, 92.8-94.7% and 91.8-92.3% respectively, and the corresponding antibacterial rate after washing for 30 times is 90.8-94.3%, 88.4-91.5% and 87.9-89.6% respectively.)

1. A large biological viscose fiber containing lily active ingredients is characterized in that: the preparation method comprises the steps of preparing chitosan-coated lily dry powder microspheres, preparing chitosan-coated lily dry powder microsphere dispersion liquid, preparing blended spinning solution, spinning and post-treatment.

2. The macrobioviscose fiber containing lily active ingredient according to claim 1, wherein: the preparation method comprises the steps of preparing the chitosan-coated lily dry powder microspheres, dropwise adding 0.1mol/L sodium hydroxide aqueous solution into a chitosan-coated lily dry powder microsphere solution at 1000-2000 rpm to adjust the pH to be 7.5-8.5, stirring for 10-20 minutes to generate flocculent precipitates in the solution, washing solids obtained by centrifugal separation of the solution with deionized water for three times, and freeze-drying at-30 to-40 ℃ to obtain the chitosan-coated lily dry powder microspheres with the particle size of 0.3-0.8 microns.

3. The macrobioviscose fiber containing lily active ingredient according to claim 2, wherein: the preparation method of the chitosan-coated lily dry powder microsphere solution comprises the steps of adding chitosan into 1wt% acetic acid solution, heating to 50-70 ℃, after the chitosan is fully dissolved, dropwise adding sodium hydroxide water solution to adjust the pH to be 4-5, adding lily dry powder with the mass of 0.5-0.7 times of that of the chitosan, stirring at 3000-4000 rpm for 40-80 minutes to obtain turbid liquid, dropwise adding sodium pyrophosphate water solution into the turbid liquid at the speed of 10 ml/min, and continuously stirring at 3000-4000 rpm for 20-40 minutes after the dropwise adding is finished to obtain the chitosan-coated lily dry powder microsphere solution.

4. The macrobioviscose fiber containing lily active ingredient according to claim 3, wherein: the addition amount of the chitosan is 6-10% of the mass of 1wt% acetic acid solution; the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L; the concentration of the sodium pyrophosphate aqueous solution is 0.6-0.8 g/L, and the addition amount is 12-15% of the mass of 1wt% acetic acid solution.

5. The macrobioviscose fiber containing lily active ingredient according to claim 3, wherein:

the preparation method of the lily dry powder comprises the steps of adding deionized water with the mass of 0.5-0.8 times of that of fresh lily into the fresh lily, beating the fresh lily into slurry at 10000-20000 rpm, drying the obtained slurry for 60-80 minutes at the temperature of 40-60 ℃, the pressure of-0.04-0.09 MPa and the thickness of the slurry of 0.5-1.5 cm to obtain solid with the water content of 0.5-1.3%, and dry-grinding the solid under the condition of 20000-35000 rpm to obtain the lily dry powder with the particle size of 0.1-0.5 micron.

6. The macrobioviscose fiber containing lily active ingredient according to claim 1, wherein: the preparation method of the dispersion liquid of the chitosan-coated lily dry powder microspheres comprises the steps of heating 30-50 g/L of sodium hydroxide aqueous solution to 40-60 ℃, adding aminopropylamine dioleate quaternary ammonium salt with the mass of 0.7-1.1% of the sodium hydroxide aqueous solution, 0.3-0.5% of DY-ET113 hydrophilic reactive polyether modified polysiloxane, 4-8% of THI S-S30 alkaline silica sol and 3-7% of chitosan-coated lily dry powder microspheres at 6000-9000 r/min in sequence, and stirring and dispersing for 2-4 hours to obtain the dispersion liquid of the chitosan-coated lily dry powder microspheres.

7. The macrobioviscose fiber containing lily active ingredient according to claim 1, wherein: preparing a blending spinning solution, namely taking cellulose pulp as a raw material, carrying out the steps of dipping, squeezing, crushing, ageing and yellowing to obtain a yellowing product, and dissolving the yellowing product in a chitosan-coated lily dry powder microsphere dispersion solution according to the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion solution of 1: 2-4 to obtain the blending spinning solution; the blended spinning solution contains 8.8wt% of alpha-cellulose, 53s viscosity and 18mL of ripening degree (9.9% NH)₄Cl）。

8. The macrobioviscose fiber containing lily active ingredient according to claim 1, wherein: and in the spinning and post-treatment, the blended spinning solution is filtered, defoamed and then sent into a nozzle of a spinning machine to spray fine flow, the fine flow is sprayed out to form tows through one bath, the tows are sent into two baths by a first drafting machine, the tows after the two baths are sent into three baths by two drafting machines, the tows after the three baths are sent to post-treatment by the three drafting machines, and the post-treatment is to desulfurize, float and oil the tows after the drafting.

9. The macrobioviscose fiber containing lily active ingredient according to claim 8, wherein: the coagulating bath used in the first bath is 100-125 g/L sulfuric acid, 200-260 g/L sodium sulfate and 12-16 g/L zinc sulfate, the temperature of the first bath is 45-55 ℃, and the drafting rate of a primary drafting machine is 55-75%; the coagulating bath used in the second bath is 16-24 g/L sulfuric acid, the temperature of the second bath is 75-90 ℃, and the drafting rate of the second drafting machine is 35-45%;

the coagulation bath used in the three baths is sulfuric acid with the pH = 1.5-2.5, the temperature of the three baths is 80-90 ℃, and the drafting rate of the three drafting machines is 6-12%.

10. The macrobioviscose fiber containing lily active ingredient according to claim 8, wherein: the desulfurizing agent used in the desulfurization consists of sodium sulfide with the concentration of 3-7 g/L and sodium carbonate with the concentration of 2-5 g/L; bleaching, wherein the used bleaching agent is hydrogen peroxide with the concentration of 0.2-0.4 g/L; and oiling, wherein the adding amount of the used oiling agent is 5-8 g/L.

Technical Field

The invention relates to a large biological viscose fiber containing lily active ingredients, belonging to the technical field of viscose fibers.

Background

Viscose fiber is particularly suitable for being used as close-fitting clothing fabric due to the characteristics of good hygroscopicity, good air permeability, easiness in dyeing, soft and bright hand feeling, super-strong antistatic performance, good wearing comfort and the like, and viscose fiber textile is converted from practical type to functional type along with the improvement of technological progress and living standard, so that viscose fiber with antibacterial property, skin care property or other medical care functions is more and more favored by the market.

The lily contains various bioactive substances such as natural plant protein, polysaccharide, steroid saponin, phenolic compounds, flavonoid compounds, alkaloid and the like, and has very excellent antibacterial function. In the aspect of nervous system, the product has the effects of tranquilizing and allaying excitement, helping sleep, resisting melancholy and relieving psychological pressure; in the aspect of skin care, the lily bioactive substance has the effects of conditioning greasy skin, eliminating body odor, moisturizing, increasing skin elasticity, conditioning skin metabolism, moistening and smoothing skin and repairing skin tissues. Therefore, the lily bioactive substance is mixed into the viscose fiber to develop fiber textiles with excellent antibacterial and skin care functions.

Chinese patent CN103741245A discloses a viscose fiber with ginkgo leaf antibacterial function and its preparation method, adding water solution of natural ginkgo leaf extract powder into viscose spinning solution, forming by wet spinning and spinning process to obtain the viscose fiber with ginkgo leaf antibacterial function, the main antibacterial component natural ginkgo leaf extract powder in the patent is doped into the viscose fiber in a physical blending mode, the antibacterial powder will continuously fall off and run off in the using process of the fiber, and the antibacterial effect is difficult to last.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a large biological viscose fiber containing lily active ingredients, which realizes the following purposes: the viscose fiber containing chitosan coated lily active ingredient particles is prepared, the mechanical property of the fiber is not influenced by the doping of the particles, and the particles have lasting antibacterial and skin-care functions, the lily active ingredient is coated by chitosan and then chemically bonded to the molecular structure of the viscose fiber, and the loss speed of the chitosan and the lily active ingredient in the fiber washing process is reduced.

In order to realize the purpose, the invention adopts the following technical scheme:

a macrobiotic viscose fiber containing lily active ingredient comprises the preparation of chitosan-coated lily dry powder microspheres, the preparation of chitosan-coated lily dry powder microsphere dispersion, the preparation of blended spinning solution, spinning and post-treatment.

The following is a further improvement of the above technical solution:

step (1) preparation of chitosan-coated lily dry powder microspheres

1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the mass being 0.5-0.8 times of the total mass of the fresh lily, placing the fresh lily into a high-speed beater, beating the fresh lily into slurry at 10000-20000 rpm, drying the slurry in a vacuum microwave dryer to obtain dry solid with the water content of 0.5-1.3%, and carrying out dry grinding in a high-speed ball mill at 20000-35000 rpm to obtain lily dry powder with the particle size of 0.1-0.5 microns.

The drying is carried out under the specific conditions that: the drying temperature is 40-60 ℃, the thickness of the slurry is 0.5-1.5 cm, the drying time is 60-80 minutes, and the pressure is-0.04 to-0.09 MPa.

2) Adding a certain amount of chitosan into 1wt% of acetic acid solution, heating to 50-70 ℃, stirring to fully dissolve the chitosan, dropwise adding sodium hydroxide aqueous solution to adjust the pH to be = 4-5, adding dried lily powder with the mass of 0.5-0.7 times that of the chitosan, stirring at the stirring speed of 3000-4000 rpm for 40-80 minutes to obtain uniform and stable suspension, dropwise adding sodium pyrophosphate aqueous solution into the suspension at the speed of 10 ml/min, continuously stirring at 3000-4000 rpm for 20-40 minutes after dropwise adding is finished to obtain chitosan-coated dried lily powder microsphere solution, dropping the stirring speed to 1000-2000 rpm, then adding sodium hydroxide aqueous solution to adjust the pH to be = 7.5-8.5, stirring for 10-20 minutes to generate flocculent precipitates, centrifuging the obtained solution after stirring is stopped, removing supernatant, washing the obtained solid with deionized water for three times, and freeze-drying at the temperature of-30 ℃ to-40 ℃ to obtain chitosan-coated dried lily powder with the particle size of 0.3-0.8 micrometers Microspheres;

the addition amount of the chitosan is 6-10% of the mass of 1wt% acetic acid solution;

the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L;

the concentration of the sodium pyrophosphate aqueous solution is 0.6-0.8 g/L, and the addition amount is 12-15% of the mass of 1wt% acetic acid solution.

Step (2) preparation of chitosan-coated lily dry powder microsphere dispersion liquid

Heating to 40-60 ℃ in a sodium hydroxide aqueous solution with a certain concentration, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI S-S30 alkaline silica sol and chitosan-coated lily dry powder microspheres at 6000-9000 r/min, stirring and dispersing for 2-4 hours to obtain a chitosan-coated lily dry powder microsphere dispersion liquid;

the THI S-S30 alkaline silica sol has the silicon dioxide content of 30wt% and the particle size of the colloidal particles of 20 nm;

the concentration of the sodium hydroxide aqueous solution is 30-50 g/L;

the adding amount of the aminopropylamine dioleate quaternary ammonium salt is 0.7-1.1% of that of the sodium hydroxide aqueous solution;

the addition amount of the DY-ET113 hydrophilic reactive polyether modified polysiloxane is 0.3-0.5% of that of the sodium hydroxide aqueous solution;

the THI S-S30 alkaline silica sol is added in an amount of 4-8% of the sodium hydroxide aqueous solution;

the addition amount of the chitosan-coated lily dry powder microspheres is 3-7% of the sodium hydroxide aqueous solution.

Step (3) preparation of blended spinning solution

Cellulose pulp is used as a raw material, and a yellowing product is obtained through the steps of dipping, squeezing, crushing, ageing and yellowing, and is dissolved in chitosan-coated lily dry powder microsphere dispersion liquid to obtain blended spinning liquid;

the yellowing product is dissolved in the chitosan-coated lily dry powder microsphere dispersion liquid, and the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion liquid is 1: 2-4;

the blended spinning solution contains 8.8wt% of alpha-cellulose, 53s viscosity and 18mL of ripening degree (9.9% NH)₄Cl）。

Step (4) spinning and post-treatment

Filtering and defoaming the blended spinning solution, sending the blended spinning solution into a nozzle of a spinning machine to spray fine flow, forming filament bundles through a first bath, sending the filament bundles into a second bath through a first drafting machine, sending the filament bundles into a third bath through a second drafting machine after the second bath, and sending the filament bundles after the third bath to post-treatment through the third drafting machine;

the coagulating bath used in the first bath is 100-125 g/L sulfuric acid, 200-260 g/L sodium sulfate and 12-16 g/L zinc sulfate, the temperature of the first bath is 45-55 ℃, and the drafting rate of a primary drafting machine is 55-75%;

the coagulating bath used in the second bath is 16-24 g/L sulfuric acid, the temperature of the second bath is 75-90 ℃, and the drafting rate of the second drafting machine is 35-45%;

the coagulation bath used in the three baths is sulfuric acid with the pH = 1.5-2.5, the temperature of the three baths is 80-90 ℃, and the drafting rate of the three drafting machines is 6-12%;

the post-treatment comprises the steps of desulfurizing, bleaching and oiling the drafted tows, wherein a desulfurizing agent used for desulfurization consists of sodium sulfide with the concentration of 3-7 g/L and sodium carbonate with the concentration of 2-5 g/L; the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.2-0.4 g/L; the adding amount of the oiling agent used for oiling is 5-8 g/L.

The preferable technical scheme is as follows:

the preparation of the chitosan-coated lily dry powder microspheres in the step (1)

1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the mass of 0.6 times of the total mass of the fresh lily, placing the fresh lily into a high-speed beater, beating into slurry at 15000 r/min, drying to obtain dry solid with the water content of 0.8, and dry-grinding in a high-speed ball mill at 30000 r/min to obtain lily dry powder with the particle size of 0.3 micron.

The drying conditions are as follows: the drying temperature is 50 ℃, the thickness of the slurry is 1.0 cm, the drying time is 70 minutes, and the pressure is-0.08 MPa.

2) Adding chitosan into 1wt% acetic acid solution, heating to 60 ℃, stirring for dissolving, dropwise adding sodium hydroxide aqueous solution to adjust the pH to be 4.5, adding 0.6 time of lily dry powder of chitosan quality, stirring for 60 minutes at a stirring speed of 3500 rpm to obtain uniform and stable suspension, after the dropwise adding of sodium pyrophosphate aqueous solution is finished, continuously stirring for 30 minutes at 3500 rpm to obtain chitosan-coated lily dry powder microsphere solution, reducing the stirring speed to be 1500 rpm, dropwise adding sodium hydroxide aqueous solution to adjust the pH to be 8.0, stirring for 15 minutes to generate flocculent precipitate, washing the solid obtained by centrifugation, and freeze-drying at-35 ℃ to obtain chitosan-coated lily dry powder microspheres with the particle size of 0.5 micron;

the addition amount of the chitosan is 8 percent of the mass of 1 weight percent of acetic acid solution;

the concentration of the sodium pyrophosphate aqueous solution is 0.7g/L, and the adding amount is 13.5 percent of the mass of 1 weight percent of acetic acid solution.

Heating the sodium hydroxide aqueous solution with a certain concentration obtained in the step (2) to 50 ℃, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI S-S30 alkaline silica sol and chitosan-coated lily dry powder microspheres at 7500 r/min, stirring and dispersing for 3 hours to obtain a chitosan-coated lily dry powder microsphere dispersion liquid;

the concentration of the sodium hydroxide aqueous solution is 40 g/L;

the adding amount of the aminopropylamine dioleate quaternary ammonium salt is 0.9 percent of that of the sodium hydroxide aqueous solution;

the addition amount of the DY-ET113 hydrophilic reactive polyether modified polysiloxane is 0.4 percent of the sodium hydroxide aqueous solution;

the THI S-S30 alkaline silica sol is added in an amount of 6 percent of the sodium hydroxide aqueous solution;

the addition amount of the chitosan-coated lily dry powder microspheres is 5 percent of that of the sodium hydroxide aqueous solution.

Dissolving the yellowing product in the step (3) in the chitosan-coated lily dry powder microsphere dispersion, wherein the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion is 1: 3;

the coagulating bath used in the first bath in the step (4) is 115g/L sulfuric acid, 240g/L sodium sulfate and 14g/L zinc sulfate, the temperature of the first bath is 50 ℃, and the drafting rate of a single drafting machine is 65%;

the coagulating bath used in the second bath is 20g/L sulfuric acid, the temperature of the second bath is 80 ℃, and the drafting rate of the second drafting machine is 40%;

the coagulation bath used by the three baths is sulfuric acid with pH =2, the temperature of the three baths is 85 ℃, and the drafting rate of the three drafting machines is 8%; the desulfurizer used for desulfurization consists of sodium sulfide with the concentration of 5g/L and sodium carbonate with the concentration of 3.6 g/L;

the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.3 g/L;

the adding amount of the oiling agent used for oiling is 7 g/L.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the viscose fiber containing the chitosan-coated lily active ingredient particles, the lily active ingredient is coated by the chitosan and then chemically bonded to the molecular structure of the viscose fiber, so that the viscose fiber has the dual effects of antibiosis and skin care, the fiber strength is not affected, the dry breaking strength of the viscose fiber containing the chitosan-coated lily active ingredient particles is 2.72cN/dtex, the wet breaking strength is 1.89cN/dtex, the elongation at break is 24.4%, the dry breaking strength of the viscose fiber containing the chitosan-coated lily active ingredient particles is 2.65-2.93 cN/dtex, the wet breaking strength is 1.71-1.86 cN/dtex, and the elongation at break is 22.9-24.8%;

2. the viscose fiber containing chitosan-coated lily active ingredient particles prepared by the invention has good and durable antibacterial effect, the antibacterial rate to staphylococcus aureus, escherichia coli and candida albicans is 93.5-96.6%, 92.8-94.7% and 91.8-92.3%, and the corresponding antibacterial rate after washing for 30 times is 90.8-94.3%, 88.4-91.5% and 87.9-89.6%.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.

Example 1: lily active ingredient-containing macrobiotic viscose fiber

The method comprises the following steps:

1. preparation of chitosan coated lily dry powder microsphere

1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the mass of 0.6 times of the total mass of the fresh lily, placing the fresh lily into a high-speed beater, beating into slurry at 15000 r/min, sending the obtained slurry into a vacuum microwave dryer for drying to obtain dried solid with the water content of 0.8%, and carrying out dry grinding in a high-speed ball mill at 30000 r/min to obtain lily dry powder with the particle size of 0.3 micron.

The drying is carried out under the specific conditions that: the drying temperature is 50 ℃, the thickness of the slurry is 1.0 cm, the drying time is 70 minutes, the pressure is-0.08 MPa,

2) adding a certain amount of chitosan into 1wt% acetic acid solution, heating to 60 deg.C, stirring to dissolve chitosan sufficiently, adding sodium hydroxide aqueous solution dropwise to adjust pH =4.5, adding 0.6 times of Bulbus Lilii dry powder, stirring at 3500 rpm for 60 min to obtain uniform and stable suspension, dripping sodium pyrophosphate aqueous solution into the suspension at the speed of 10 ml/min, continuously stirring for 30 minutes at 3500 rpm after dripping to obtain chitosan-coated lily dry powder microsphere solution, reducing the stirring speed to 1500 rpm, dropwise adding sodium hydroxide aqueous solution to adjust the pH =8.0, stirring for 15 minutes to generate flocculent precipitate, stopping stirring, centrifuging the obtained solution, removing supernatant, washing the obtained solid with deionized water for three times, freeze-drying at-35 deg.C to obtain dried powder microsphere with particle size of 0.5 μm;

the addition amount of the chitosan is 8 percent of the mass of 1 weight percent of acetic acid solution;

the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L;

the concentration of the sodium pyrophosphate aqueous solution is 0.7g/L, and the adding amount is 13.5 percent of the mass of 1 weight percent of acetic acid solution.

2. Preparation of chitosan-coated lily dry powder microsphere dispersion

Heating a sodium hydroxide aqueous solution with a certain concentration to 50 ℃, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI S-S30 alkaline silica sol and chitosan-coated lily dry powder microspheres at 7500 r/min, stirring and dispersing for 3 hours to obtain a chitosan-coated lily dry powder microsphere dispersion liquid;

the THI S-S30 alkaline silica sol has the silicon dioxide content of 30wt% and the particle size of the colloidal particles of 20 nm;

the concentration of the sodium hydroxide aqueous solution is 40 g/L;

the adding amount of the aminopropylamine dioleate quaternary ammonium salt is 0.9 percent of the mass of the sodium hydroxide aqueous solution;

the addition amount of the DY-ET113 hydrophilic reactive polyether modified polysiloxane is 0.4 percent of the sodium hydroxide aqueous solution;

the THI S-S30 alkaline silica sol is added in an amount of 6 percent of the sodium hydroxide aqueous solution;

the addition amount of the chitosan-coated lily dry powder microspheres is 5 percent of that of the sodium hydroxide aqueous solution;

in the step, aminopropylamine dioleate quaternary ammonium salt is used as a dispersing agent, so that the chitosan-coated lily dry powder microspheres can be uniformly dispersed in an alkaline solution, and both DY-ET113 hydrophilic reactive polyether modified polysiloxane and THI S-S30 alkaline silica sol have a large number of silicon hydroxyl groups with strong reactivity, and can be chemically bonded with hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres, so that the number of the surface active hydroxyl groups of the chitosan-coated lily dry powder microspheres is increased, and the chitosan-coated lily dry powder microspheres have high reactivity.

3. Preparation of blended spinning solution

Cellulose pulp is used as a raw material, and a yellowing product is obtained through the steps of dipping, squeezing, crushing, ageing and yellowing, and is dissolved in chitosan-coated lily dry powder microsphere dispersion liquid to obtain blended spinning liquid;

dissolving the yellowing product in chitosan-coated lily dry powder microsphere dispersion, wherein the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion is 1: 3;

the blended spinning solution contains 8.8wt% of alpha-cellulose, 53s viscosity and 18mL of ripening degree (9.9% NH)₄Cl）；

4. Spinning and aftertreatment

Filtering and defoaming the blended spinning solution, sending the blended spinning solution into a nozzle of a spinning machine to spray fine flow, forming filament bundles through a first bath, sending the filament bundles into a second bath through a first drafting machine, sending the filament bundles into a third bath through a second drafting machine after the second bath, and sending the filament bundles after the third bath to post-treatment through the third drafting machine;

the coagulating bath used in the first bath is 115g/L sulfuric acid, 240g/L sodium sulfate and 14g/L zinc sulfate, the temperature of the first bath is 50 ℃, and the drafting rate of a single-pass drafting machine is 65%;

the coagulating bath used in the second bath is 20g/L sulfuric acid, the temperature of the second bath is 80 ℃, and the drafting rate of the second drafting machine is 40%;

the coagulation bath used by the three baths is sulfuric acid with pH =2, the temperature of the three baths is 85 ℃, and the drafting rate of the three drafting machines is 8%;

the post-treatment comprises the steps of desulfurizing, bleaching and oiling the drafted tows, wherein a desulfurizing agent used for desulfurizing consists of sodium sulfide with the concentration of 5g/L and sodium carbonate with the concentration of 3.6 g/L; the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.3 g/L; the adding amount of the oiling agent used for oiling is 7 g/L.

The antibacterial capacity evaluation refers to GB/T20944-2007, and the antibacterial rate of the obtained viscose fiber on staphylococcus aureus, escherichia coli and candida albicans is tested;

and (3) testing the washing resistance of the antibacterial effect: at room temperature, the detergent is a commercially available common washing powder with the mass concentration of 0.3 percent, the procedure of washing once is washing for 15 minutes, rinsing twice with clear water for 5 minutes each time, and naturally airing at room temperature.

The fiber obtained in example 1 had a dry breaking strength of 2.93cN/dtex, a wet breaking strength of 1.86cN/dtex, an elongation at break of 24.8%, an antibacterial rate against Staphylococcus aureus, Escherichia coli and Candida albicans of 96.6%, 94.7% and 92.3%, respectively, and an antibacterial rate after 30 washing of 94.3%, 91.5% and 89.6%, respectively.

Example 2: lily active ingredient-containing macrobiotic viscose fiber

The method comprises the following steps:

1. preparation of chitosan coated lily dry powder microsphere

1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the mass of 0.5 time of that of the fresh lily, placing the fresh lily into a high-speed beater, beating the fresh lily into slurry at 10000 r/min, drying the slurry in a vacuum microwave dryer to obtain dry solid with the water content of 0.5%, and dry-grinding the dry lily in a high-speed ball mill at 20000 r/min to obtain the lily dry powder with the particle size of 0.1 micron.

The drying is carried out under the specific conditions that: drying at 40 deg.C for 60 min to obtain slurry with thickness of 0.5 cm and pressure of-0.04 MPa;

2) adding a certain amount of chitosan into 1wt% acetic acid solution, heating to 50 deg.C, stirring to dissolve chitosan sufficiently, adding dropwise sodium hydroxide aqueous solution to adjust pH =4, adding 0.5 times of Bulbus Lilii dry powder, stirring at 3000 rpm for 40 min to obtain uniform and stable suspension, dripping sodium pyrophosphate aqueous solution into the suspension at the speed of 10 ml/min, continuously stirring for 20 minutes at 3000 r/min after finishing dripping to obtain chitosan-coated lily dry powder microsphere solution, reducing the stirring speed to 1000 r/min, dropwise adding sodium hydroxide aqueous solution to adjust the pH =7.5, stirring for 10 minutes to generate flocculent precipitate, stopping stirring, centrifuging the obtained solution, removing supernatant, washing the obtained solid with deionized water for three times, freeze-drying at-30 deg.C to obtain dried powder microsphere with particle size of 0.3 μm;

the addition amount of the chitosan is 6 percent of the mass of 1 weight percent of acetic acid solution;

the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L;

the concentration of the sodium pyrophosphate aqueous solution is 0.6g/L, and the adding amount is 12 percent of the mass of 1 weight percent of acetic acid solution.

2. Preparation of chitosan-coated lily dry powder microsphere dispersion

Heating to 40 ℃ in a sodium hydroxide aqueous solution with a certain concentration, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI S-S30 alkaline silica sol and chitosan-coated lily dry powder microspheres into the aqueous solution at 6000 rpm, and stirring and dispersing for 2 hours to obtain a chitosan-coated lily dry powder microsphere dispersion liquid;

the THI S-S30 alkaline silica sol has the silicon dioxide content of 30wt% and the particle size of the colloidal particles of 20 nm;

the concentration of the sodium hydroxide aqueous solution is 30 g/L;

the adding amount of the aminopropylamine dioleate quaternary ammonium salt is 0.7 percent of the mass of the sodium hydroxide aqueous solution;

the addition amount of the DY-ET113 hydrophilic reactive polyether modified polysiloxane is 0.3 percent of the sodium hydroxide aqueous solution;

the THI S-S30 alkaline silica sol is added in an amount of 4 percent of the sodium hydroxide aqueous solution;

the addition amount of the chitosan-coated lily dry powder microspheres is 3 percent of that of the sodium hydroxide aqueous solution;

in the step, aminopropylamine dioleate quaternary ammonium salt is used as a dispersing agent, so that the chitosan-coated lily dry powder microspheres can be uniformly dispersed in an alkaline solution, and both DY-ET113 hydrophilic reactive polyether modified polysiloxane and THI S-S30 alkaline silica sol have a large number of silicon hydroxyl groups with strong reactivity, and can be chemically bonded with hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres, so that the number of the surface active hydroxyl groups of the chitosan-coated lily dry powder microspheres is increased, and the chitosan-coated lily dry powder microspheres have high reactivity.

3. Preparation of blended spinning solution

Cellulose pulp is used as a raw material, and a yellowing product is obtained through the steps of dipping, squeezing, crushing, ageing and yellowing, and is dissolved in chitosan-coated lily dry powder microsphere dispersion liquid to obtain blended spinning liquid;

dissolving the yellowing product in chitosan-coated lily dry powder microsphere dispersion, wherein the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion is 1: 2;

the blended spinning solution contains 8.8wt% of alpha-cellulose, 53s viscosity and 18mL of ripening degree (9.9% NH)₄Cl）；

4. Spinning and aftertreatment

Filtering and defoaming the blended spinning solution, sending the blended spinning solution into a nozzle of a spinning machine to spray fine flow, forming filament bundles through a first bath, sending the filament bundles into a second bath through a first drafting machine, sending the filament bundles into a third bath through a second drafting machine after the second bath, and sending the filament bundles after the third bath to post-treatment through the third drafting machine;

the coagulating bath used in the first bath is 100g/L sulfuric acid, 200g/L sodium sulfate and 12g/L zinc sulfate, the temperature of the first bath is 45 ℃, and the drafting rate of the first drafting machine is 55%;

the coagulating bath used in the second bath is 16g/L sulfuric acid, the temperature of the second bath is 75 ℃, and the drafting rate of the second drafting machine is 35 percent;

the coagulation bath used by the three baths is sulfuric acid with pH =1.5, the temperature of the three baths is 80 ℃, and the drafting rate of the three drafting machines is 6%;

the post-treatment comprises the steps of desulfurizing, bleaching and oiling the drafted tows, wherein a desulfurizing agent used for desulfurizing consists of sodium sulfide with the concentration of 3g/L and sodium carbonate with the concentration of 2 g/L; the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.2 g/L; the adding amount of the oiling agent is 5 g/L.

The antibacterial capacity evaluation refers to GB/T20944-2007, and the antibacterial rate of the obtained viscose fiber on staphylococcus aureus, escherichia coli and candida albicans is tested;

and (3) testing the washing resistance of the antibacterial effect: at room temperature, the detergent is a commercially available common washing powder with the mass concentration of 0.3 percent, the procedure of washing once is washing for 15 minutes, rinsing twice with clear water for 5 minutes each time, and naturally airing at room temperature.

The fiber obtained in example 2 had a dry breaking strength of 2.77cN/dtex, a wet breaking strength of 1.71cN/dtex, an elongation at break of 23.5%, an antibacterial rate against Staphylococcus aureus, Escherichia coli and Candida albicans of 94.9%, 93.6% and 91.8%, respectively, and an antibacterial rate after 30 washing of 90.8%, 90.2% and 87.9%, respectively.

Example 3: lily active ingredient-containing macrobiotic viscose fiber

The method comprises the following steps:

1. preparation of chitosan coated lily dry powder microsphere

1) Removing roots of fresh lily, cleaning, draining, adding deionized water with the mass of 0.8 time of the fresh lily, placing the fresh lily in a high-speed beater, beating into slurry at 20000 revolutions per minute, sending the obtained slurry into a vacuum microwave dryer for drying to obtain dry solid with the water content of 1.3%, and carrying out dry grinding in a high-speed ball mill at 35000 revolutions per minute to obtain lily dry powder with the particle size of 0.5 micron.

The drying is carried out under the specific conditions that: the drying temperature is 60 ℃, the thickness of the slurry is 1.5 cm, the drying time is 80 minutes, the pressure is-0.09 MPa,

2) adding a certain amount of chitosan into 1wt% acetic acid solution, heating to 70 deg.C, stirring to dissolve chitosan sufficiently, adding dropwise sodium hydroxide aqueous solution to adjust pH =5, adding 0.7 times of Bulbus Lilii dry powder of chitosan quality, stirring at 4000 rpm for 80 minutes to obtain uniform and stable suspension, dripping sodium pyrophosphate aqueous solution into the suspension at the speed of 10 ml/min, continuously stirring for 40 minutes at 4000 rpm after finishing dripping to obtain chitosan-coated lily dry powder microsphere solution, reducing the stirring speed to 2000 rpm, dropwise adding sodium hydroxide aqueous solution to adjust the pH =8.5, stirring for 20 minutes to generate flocculent precipitate, stopping stirring, centrifuging the obtained solution, removing supernatant, washing the obtained solid with deionized water for three times, freeze-drying at-40 deg.C to obtain dried powder microsphere of Bulbus Lilii coated with chitosan with particle size of 0.8 micrometer;

the addition amount of the chitosan is 10 percent of the mass of 1 weight percent of acetic acid solution;

the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L;

the concentration of the sodium pyrophosphate aqueous solution is 0.8g/L, and the addition amount is 15 percent of the mass of 1 weight percent of acetic acid solution.

2. Preparation of chitosan-coated lily dry powder microsphere dispersion

Heating to 60 ℃ in a sodium hydroxide aqueous solution with a certain concentration, adding aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane, THI S-S30 alkaline silica sol and chitosan-coated lily dry powder microspheres at 9000 r/min, stirring and dispersing for 4 hours to obtain a chitosan-coated lily dry powder microsphere dispersion liquid;

the THI S-S30 alkaline silica sol has the silicon dioxide content of 30wt% and the particle size of the colloidal particles of 20 nm;

the concentration of the sodium hydroxide aqueous solution is 50 g/L;

the adding amount of the aminopropylamine dioleate quaternary ammonium salt is 1.1 percent of the mass of the sodium hydroxide aqueous solution;

the addition amount of the DY-ET113 hydrophilic reactive polyether modified polysiloxane is 0.5 percent of the sodium hydroxide aqueous solution;

the THI S-S30 alkaline silica sol is added in an amount of 8 percent of the sodium hydroxide aqueous solution;

the addition amount of the chitosan-coated lily dry powder microspheres is 7 percent of that of the sodium hydroxide aqueous solution;

in the step, aminopropylamine dioleate quaternary ammonium salt is used as a dispersing agent, so that the chitosan-coated lily dry powder microspheres can be uniformly dispersed in an alkaline solution, and both DY-ET113 hydrophilic reactive polyether modified polysiloxane and THI S-S30 alkaline silica sol have a large number of silicon hydroxyl groups with strong reactivity, and can be chemically bonded with hydroxyl groups on the surfaces of the chitosan-coated lily dry powder microspheres, so that the number of the surface active hydroxyl groups of the chitosan-coated lily dry powder microspheres is increased, and the chitosan-coated lily dry powder microspheres have high reactivity.

3. Preparation of blended spinning solution

Cellulose pulp is used as a raw material, and a yellowing product is obtained through the steps of dipping, squeezing, crushing, ageing and yellowing, and is dissolved in chitosan-coated lily dry powder microsphere dispersion liquid to obtain blended spinning liquid;

dissolving the yellowing product in chitosan-coated lily dry powder microsphere dispersion, wherein the mass ratio of the yellowing product to the chitosan-coated lily dry powder microsphere dispersion is 1: 4;

the blended spinning solution contains 8.8wt% of alpha-cellulose, 53s viscosity and 18mL of ripening degree (9.9% NH)₄Cl）；

4. Spinning and aftertreatment

Filtering and defoaming the blended spinning solution, sending the blended spinning solution into a nozzle of a spinning machine to spray fine flow, forming filament bundles through a first bath, sending the filament bundles into a second bath through a first drafting machine, sending the filament bundles into a third bath through a second drafting machine after the second bath, and sending the filament bundles after the third bath to post-treatment through the third drafting machine;

the coagulating bath used in the first bath is 125g/L sulfuric acid, 260g/L sodium sulfate and 16g/L zinc sulfate, the temperature of the first bath is 55 ℃, and the drafting rate of the single-pass drafting machine is 75 percent;

the coagulating bath used in the second bath is 24g/L sulfuric acid, the temperature of the second bath is 90 ℃, and the drafting rate of the second drafting machine is 45%;

the coagulation bath used by the three baths is sulfuric acid with pH =2.5, the temperature of the three baths is 90 ℃, and the drafting rate of the three drafting machines is 12%;

the post-treatment comprises the steps of desulfurizing, bleaching and oiling the drafted tows, wherein a desulfurizing agent used for desulfurizing consists of sodium sulfide with the concentration of 7g/L and sodium carbonate with the concentration of 5 g/L; the bleaching agent used for bleaching is hydrogen peroxide with the concentration of 0.4 g/L; the adding amount of the oiling agent used for oiling is 8 g/L.

The antibacterial capacity evaluation refers to GB/T20944-2007, and the antibacterial rate of the obtained viscose fiber on staphylococcus aureus, escherichia coli and candida albicans is tested;

and (3) testing the washing resistance of the antibacterial effect: at room temperature, the detergent is a commercially available common washing powder with the mass concentration of 0.3 percent, the procedure of washing once is washing for 15 minutes, rinsing twice with clear water for 5 minutes each time, and naturally airing at room temperature.

The fiber obtained in example 3 had a dry breaking strength of 2.65cN/dtex, a wet breaking strength of 1.81cN/dtex, an elongation at break of 22.9%, an antibacterial rate against Staphylococcus aureus, Escherichia coli and Candida albicans of 93.5%, 92.8% and 92.0%, respectively, and an antibacterial rate against Staphylococcus aureus, Escherichia coli and Candida albicans of 92.7%, 88.4% and 89.3%, respectively, after washing 30 times.

Comparative example 1: during the preparation of the chitosan-coated lily dry powder microsphere dispersion, aminopropylamine dioleate quaternary ammonium salt, DY-ET113 hydrophilic reactive polyether modified polysiloxane and THI S-S30 alkaline silica sol are not added

1. The preparation of the chitosan-coated lily dry powder microspheres is the same as that in the example 1;

2. preparation of chitosan-coated lily dry powder microsphere dispersion

Heating sodium hydroxide aqueous solution with certain concentration to 50 ℃, adding the chitosan-coated lily dry powder microspheres at 7500 r/min, stirring and dispersing for 3 hours to obtain chitosan-coated lily dry powder microsphere dispersion liquid;

the concentration of the sodium hydroxide aqueous solution is 40 g/L;

the addition amount of the chitosan-coated lily dry powder microspheres is 5 percent of that of the sodium hydroxide aqueous solution;

3. preparation of the blended dope was the same as in example 1

4. Spinning and working up were the same as in example 1

The antibacterial capacity evaluation refers to GB/T20944-2007, and the antibacterial rate of the obtained viscose fiber on staphylococcus aureus, escherichia coli and candida albicans is tested;

and (3) testing the washing resistance of the antibacterial effect: at room temperature, the detergent is a commercially available common washing powder with the mass concentration of 0.3 percent, the procedure of washing once is washing for 15 minutes, rinsing twice with clear water for 5 minutes each time, and naturally airing at room temperature;

the dry breaking strength of the fiber obtained in comparative example 1 is 2.84cN/dtex, the wet breaking strength is 1.91cN/dtex, the elongation at break is 25.6%, the antibacterial rate to staphylococcus aureus, escherichia coli and candida albicans is 95.9%, 95.4% and 91.1%, respectively, and the corresponding antibacterial rate after 30 times of washing is 51.7%, 48.9% and 60.2%, respectively.

Comparative example 2: the viscose fiber is not added with chitosan to wrap dry lily powder microspheres

1. Preparation of the spinning dope

Cellulose pulp is taken as a raw material, and is subjected to the steps of dipping, squeezing, crushing, ageing and yellowing to obtain a yellowing product, and the yellowing product is dissolved in 40g/L sodium hydroxide aqueous solution to obtain spinning solution;

dissolving the yellowing product in 40g/L sodium hydroxide aqueous solution, wherein the mass ratio of the yellowing product to the 40g/L sodium hydroxide aqueous solution is 1: 3;

the dope contains 8.8wt% of alpha-cellulose, 53s viscosity and 18mL of ripening degree (9.9% NH)₄Cl）；

2. Spinning and post-treatment were the same as in example 1;

the fiber obtained in comparative example 2 had a dry breaking strength of 2.72cN/dtex, a wet breaking strength of 2.13cN/dtex, and an elongation at break of 24.4%.