阅读说明：本技术 一种抗褐变茶多酚改性粘胶纤维 (Anti-browning tea polyphenol modified viscose fiber ) 是由 黄效华 郑来久 郑天勇 伏广伟 姜义军 黄效龙 王丙伟 刘彦明 于 2020-04-01 设计创作，主要内容包括：本发明提供一种抗褐变茶多酚改性粘胶纤维,其特征在于：所述抗褐变茶多酚改性粘胶纤维,茶多酚含量1-5%；所述抗褐变茶多酚改性粘胶纤维吸湿率11.3-12.2%。本发明制备的抗褐变茶多酚改性粘胶纤维具有较低的色差、染色稳定性及保暖性能；由于采用抗褐变茶多酚改性剂制备前处理的方法,本发明制备的抗褐变茶多酚改性粘胶纤维可以防止制备的纤维发生褐变,同批次纤维间色差较小。(The invention provides an anti-browning tea polyphenol modified viscose fiber, which is characterized in that: the browning resistant tea polyphenol modified viscose fiber has a tea polyphenol content of 1-5%; the moisture absorption rate of the anti-browning tea polyphenol modified viscose fiber is 11.3-12.2%. The brown stain resistant tea polyphenol modified viscose fiber prepared by the invention has lower color difference, dyeing stability and heat retention performance; due to the adoption of the preparation pretreatment method of the anti-browning tea polyphenol modifier, the anti-browning tea polyphenol modified viscose fiber prepared by the invention can prevent the prepared fiber from browning, and the color difference between fibers in the same batch is small.)

1. An anti-browning tea polyphenol modified viscose fiber is characterized in that: the browning resistant tea polyphenol modified viscose fiber has a tea polyphenol content of 1-5%; the moisture absorption rate of the anti-browning tea polyphenol modified viscose fiber is 11.3-12.2%.

2. The anti-browning tea polyphenol modified viscose fiber according to claim 1, wherein: the preparation method of the fiber comprises the following steps: preparing an anti-browning tea polyphenol modifier, preparing a tea polyphenol functional complexing agent, preparing a spinning solution, spinning and post-treating.

3. The anti-browning tea polyphenol modified viscose fiber according to claim 2, wherein: the preparation method of the anti-browning tea polyphenol modifier comprises the following steps:

introducing tea polyphenols micropowder and dispersant into pulverizer, pulverizing to below 5 μm to obtain A microparticle; adding the prepared A particles into a low-concentration sodium hydroxide solution, heating to 60-80 ℃, stirring, and then preserving heat for activation treatment for 20-30min to obtain a solution B;

when the temperature of the liquid B is naturally reduced to room temperature, adding an activation auxiliary agent into the liquid B, raising the temperature to 40-50 ℃ at the speed of 0.5-1 ℃, and then stirring for 10-15 minutes at the speed of 600-800r/min to form a liquid C;

and grinding the liquid C by a ball mill until a stable and uniform solution appears, evaporating water to obtain solid particles, drying to obtain powder, and grinding the powder into powder with the particle size of less than 1 mu m to obtain the anti-browning tea polyphenol modifier.

4. The anti-browning tea polyphenol modified viscose fiber according to claim 3, wherein the concentration of the sodium hydroxide solution is 20-35 g/L, the activating auxiliary agents are polyvinyl alcohol, sodium caseinate and potassium polyacrylate, the adding amount of the activating auxiliary agents is 3-5% of the mass of the tea polyphenol powder, and the mass ratio of the polyvinyl alcohol to the sodium caseinate to the potassium polyacrylate in the activating auxiliary agents is 1-3:10-15: 0.5-1.5.

5. The anti-browning tea polyphenol modified viscose fiber according to claim 3, wherein: the preparation method of the tea polyphenol functional compound agent comprises the following steps: the following raw materials: anti-browning tea polyphenol modifier, montmorillonite, zeolite powder, aerogel and porous nano TiO 2/SiO 2 microspheres.

6. The anti-browning tea polyphenol modified viscose fiber according to claim 5, wherein:

the tea polyphenol functional complexing agent is prepared from the following raw materials in parts by weight: 0.5-1 part of anti-browning modifier, 1-2 parts of montmorillonite, 0.5-0.9 part of zeolite powder, 0.4-0.6 part of aerogel and 0.1-0.3 part of porous nano TiO 2/SiO 2 microsphere.

7. The anti-browning tea polyphenol modified viscose fiber according to claim 5, wherein:

the average particle size of the montmorillonite is 1-1.5 mu m, and the swelling degree is more than or equal to 13.5%; the zeolite powder is 50-80 meshes; the aerogel is silicon dioxide powder with the specific surface area of 1000-²The porosity is more than or equal to 90 percent; the porous nano TiO₂/ SiO₂The microsphere specification is 100-500 nm.

8. The anti-browning tea polyphenol modified viscose fiber according to claim 5, wherein:

the tea polyphenol functional complexing agent is prepared by the following preparation method: weighing montmorillonite, zeolite powder, aerogel and porous nano TiO 2/SiO 2 microspheres, adding an anti-browning modifier, adding into a crusher, uniformly stirring at the speed of 20-30rad/s, and then sieving by a 10000-mesh sieve to obtain uniform particles; adding deionized water into the uniform particles for ultrasonic dispersion, wherein the ultrasonic dispersion frequency is 60-65kHZ, and the dispersion time is 20-120 min; and adding fatty amine polyoxyethylene ether and glycerol into the dispersion liquid subjected to ultrasonic dispersion, and emulsifying and dispersing for 20-120min at 55-65 ℃ after the emulsifying temperature to obtain the tea polyphenol functional complexing agent.

9. The anti-browning tea polyphenol modified viscose fiber according to claim 2, wherein: adding a stabilizer into the spinning solution in the spinning solution preparation step, wherein the stabilizer comprises polyoxyethylene, hydroxypropyl methyl cellulose and citric acid fatty glyceride; the mass ratio of polyoxyethylene, hydroxypropyl methylcellulose and citric acid fatty glyceride in the stabilizer is 3-5:1-2: 10-15.

10. The anti-browning tea polyphenol modified viscose fiber as claimed in claim 2, wherein in the spinning and post-treatment steps, the concentration of tea polyphenol in the spinning solution is 2-5 g/L.

Technical Field

The invention relates to a tea polyphenol modified viscose fiber, in particular to an anti-browning tea polyphenol modified viscose fiber, belonging to the field of cellulose fiber preparation.

Background

Functional and differential fibers are the main development direction of fibers in recent years, for example, graphene fibers, protein fibers, wormwood fibers and the like, and the prepared fibers have different characteristics by adopting a mixing or post-treatment method and adding functional substance components in the fiber preparation process or a post-treatment process after the fibers are prepared so as to meet the requirements of different customers.

For example, chinese patent nos.: CN201810553400.3 discloses a preparation process of a tea polyphenol modified viscose fiber, which comprises the steps of taking commercially available tea polyphenol and viscose fiber as raw materials, pretreating the viscose fiber by preparing a surfactant, preparing cellulose hydrolyzed viscose fiber, preparing adsorbed tea polyphenol viscose fiber, and preparing grafted tea polyphenol viscose fiber, so that the viscose fiber with the tea polyphenol grafting rate of 8-10% is prepared. Before the preparation of the grafted tea polyphenol viscose fiber, the cellulose is hydrolyzed, so that the viscose fiber is degraded to a certain degree, active hydroxyl groups on the viscose fiber are fully exposed, and the grafting rate of tea polyphenol is conveniently improved; the method adopts the diglycidyl ether with a diepoxy functional group as a reaction cross-linking agent, so that the viscose fiber and the tea polyphenol are stably connected through a chemical covalent bond, the tea polyphenol grafting rate is high, the stability is enhanced, and the functions of oxidation resistance, radiation resistance, antibiosis, metal ion chelation and the like of the product are obviously improved. The patent mainly adopts a fiber reprocessing method, and the prepared viscose fiber is modified to further adsorb tea polyphenol, so that the prepared viscose fiber has the functionality of tea polyphenol finally, but the tea polyphenol is adsorbed on the surface of the fiber prepared by the method, so that in the application process, the tea polyphenol on the surface of the fiber is less and less, and the durability of the fiber function is poor.

For example, chinese patent application No. CN200610069129.3 discloses a viscose fiber with tea antibacterial and deodorant functions and a preparation method thereof, the viscose fiber comprises viscose fiber and antibacterial agent contained therein, and is characterized in that: the antibacterial agent is at least one of natural tea pigment, tea polyphenol and catechin, fine powder particles of the natural tea pigment or the tea polyphenol or the catechin or a solution thereof is added into the viscose spinning solution, and the addition amount of the fine powder particles of the natural tea pigment or the tea polyphenol or the catechin is 1-10% of the mass of the viscose spinning solution. The natural tea pigment, tea polyphenol and catechin are used as antibacterial agents, and the antibacterial agents are uniformly distributed in the fibers, so that the antibacterial and deodorant functions are lasting. The tea polyphenol fiber prepared by the method is prepared by directly adding the tea polyphenol into viscose spinning solution, and the tea polyphenol is aqueous solution, powdery solid or crystal with light yellow to dark brown and slight tea aroma, has astringent taste, is easy to dissolve in water, ethanol and ethyl acetate, and is slightly soluble in grease. The heat resistance and the acid resistance are good, the stability is very high in the range of pH2-7, and the browning reaction is easy to oxidize under the alkaline condition; because the spinning solution contains a large amount of sodium hydroxide in the production process of the viscose, and most of the early stage of the process is an alkaline environment, the viscose prepared by the preparation process of directly adding tea polyphenol into the spinning solution can generate large color change and large color difference, particularly when the concentration content of the sodium hydroxide generates slight change, the color difference of the fiber can continuously change, and the same batch can generate different color difference problems, so that the quality of the prepared tea polyphenol fiber is extremely unstable.

Of course, in addition to the above technical problems, the large shrinkage of viscose fiber is also one of the important technical problems that are difficult to solve in the field of cellulose fiber preparation at present.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides an anti-browning tea polyphenol modified viscose fiber, which aims to solve the following technical problems:

in order to solve the technical problems, the invention adopts the technical scheme that:

the browning resistant tea polyphenol modified viscose fiber has a tea polyphenol content of 1-5%; the dry breaking strength is more than or equal to 3.55CN/dtex, the wet breaking strength is more than or equal to 2.65CN/dtex, the dry elongation is 18-25 percent, and the wet elongation is 12-15 percent;

the heat conductivity coefficient (lambda) of the anti-browning tea polyphenol modified viscose fiber is 0.032-0.035, and the color difference △ E is less than 0.12;

furthermore, the antibacterial rate of the anti-browning tea polyphenol modified viscose fiber to staphylococcus aureus is more than or equal to 99%, and the antibacterial rate to dysentery bacillus is more than or equal to 99%; the moisture absorption rate of the anti-browning tea polyphenol modified viscose fiber is 11.3-12.2%.

The preparation method of the browning resistant tea polyphenol modified viscose fiber comprises the following preparation processes:

1. preparation of brown stain resistant tea polyphenol modifier

(1) Introducing commercially available tea polyphenols micropowder and dispersant into pulverizer, pulverizing to below 5 μm to obtain A microparticle; adding the prepared A particles into a low-concentration sodium hydroxide solution, heating to 60-80 ℃, stirring, and then preserving heat for activation treatment for 20-30min to obtain a solution B;

(2) when the temperature of the liquid B is naturally reduced to room temperature, adding an activation auxiliary agent into the liquid B, raising the temperature to 40-50 ℃ at the speed of 0.5-1 ℃, and then stirring for 10-15 minutes at the speed of 600-800r/min to form a liquid C;

(3) and grinding the liquid C by a ball mill until a stable and uniform solution appears, evaporating water to obtain solid particles, drying to obtain powder, and grinding the powder into powder with the particle size of less than 1 mu m to obtain the anti-browning tea polyphenol modifier.

The tea polyphenol is a general name of polyphenol substances in tea and is white amorphous powder, and the tea polyphenol comprises the following main components: flavanones, anthocyanidins, flavonols and anthocyanins, phenolic acids and depside 6 compounds;

furthermore, the concentration of the sodium hydroxide solution is 20-35 g/L, the activation auxiliary agents are polyvinyl alcohol, sodium caseinate and potassium polyacrylate, the addition amount of the activation auxiliary agents is 3-5% of the weight of the tea polyphenol powder, the mass ratio of the polyvinyl alcohol to the sodium caseinate to the potassium polyacrylate in the activation auxiliary agents is 1-3:10-15:0.5-1.5, the activation auxiliary agents can greatly delay the alkalization degree of the tea polyphenol powder and prolong the functional duration of fibers, compared with the prior art, the addition of the activation auxiliary agents can prolong the antibacterial time of the fibers by at least 2 times, and the dispersing agent is a conventional dispersing agent.

Preparation of tea polyphenol functional compound agent

The preparation of the tea polyphenol functional complexing agent comprises the following steps: the method comprises the following raw materials: anti-browning tea polyphenol modifier, montmorillonite, zeolite powder, aerogel and porous nano-microsphere;

as an improvement, the tea polyphenol functional compound agent is prepared from the following raw materials in parts by weight: 0.5-1 part of anti-browning modifier, 1-2 parts of montmorillonite, 0.5-0.9 part of zeolite powder, 0.4-0.6 part of aerogel and 0.1-0.3 part of porous nano microsphere;

the porous nano-microspheres are one or more of TiO 2/SiO 2 porous nano-microspheres;

the average particle size of the montmorillonite is 1-1.5 mu m, and the swelling degree is more than or equal to 13.5%; the zeolite powder is 50-80 meshes; the aerogel is silicon dioxide powder with the specific surface area of 1000-²The porosity is more than or equal to 90 percent; the porous nano TiO₂/ SiO₂The specification of the microsphere is 100-500 nm; the raw materials are all purchased in the market, and the raw materials with the specifications are more favorable for the production of the invention;

as an improvement, the tea polyphenol functional complexing agent is prepared by adopting the following preparation method: weighing montmorillonite, zeolite powder, aerogel and porous nano TiO 2/SiO 2 microspheres, adding an anti-browning modifier, adding into a crusher, uniformly stirring at the speed of 20-30rad/s, and then sieving by a 10000-mesh sieve to obtain uniform particles; adding deionized water into the uniform particles for ultrasonic dispersion, wherein the ultrasonic dispersion frequency is 60-65kHZ, and the dispersion time is 20-120 min; and adding fatty amine polyoxyethylene ether and glycerol into the dispersion liquid subjected to ultrasonic dispersion, and emulsifying and dispersing for 20-120min at 55-65 ℃ after the emulsifying temperature to obtain the tea polyphenol functional complexing agent. The prepared tea polyphenol functional complexing agent can not foam through the steps of sieving, then carrying out ultrasonic dispersion and finally carrying out emulsification dispersion, and can be directly added into spinning solution.

Preparation of spinning solution

Injecting the prepared tea polyphenol functional complexing agent into spinning solution through a pre-spinning injection system to form modified spinning glue; the content of tea polyphenol (calculated by the content of tea polyphenol) in the modified spinning glue is 1-5%, and the content of the stabilizer is 0.5-1.5%; the content of the spinning glue A cellulose is 7.2-8.0%, the ripening degree (10% ammonium chloride) is 20-25ml, and the esterification degree is 45-50; the alkali content is 3.5-4.5%, and the viscosity is 35-45 s;

preferably, a stabilizing agent is preferably added into the spinning solution, and the stabilizing agent comprises polyoxyethylene, hydroxypropyl methyl cellulose and citric acid fatty glyceride; the mass ratio of polyoxyethylene, hydroxypropyl methyl cellulose and citric acid fatty glyceride in the stabilizer is 3-5:1-2: 10-15; because the maximum moisture absorption rate of the viscose fibers can reach between 13 and 16 percent, the fibers are easy to swell, the most important performance is that the shrinkage is serious after washing, and the main function of adding the stabilizer is to reduce the moisture absorption rate of the fibers and further reduce the shrinkage rate of the fiber fabric.

Spinning and post-treatment

The anti-browning tea polyphenol modified viscose fiber is prepared by the steps of carrying out drawing, refining, oiling and drying on the cellulose fiber in a spinning bath, wherein the concentration of sulfuric acid is 100-120 g/L, the concentration of zinc sulfate is 50-65 g/L, the concentration of sodium sulfate is 150-180 g/L, the concentration of tea polyphenol is 2-5 g/L, and the temperature of the spinning bath is 20-55 ℃.

Due to the adoption of the technical scheme, the invention achieves the technical effects that:

1. the anti-browning tea polyphenol modified viscose fiber prepared by the invention has the dry breaking strength of more than or equal to 3.55CN/dtex, the wet breaking strength of more than or equal to 2.65CN/dtex, the dry elongation of 18-25 percent and the wet elongation of 12-15 percent, and has no browning phenomenon in appearance.

2. Due to the adoption of the processing technology of the anti-browning tea polyphenol modifier, the anti-browning tea polyphenol modified viscose fiber prepared by the invention can prevent the prepared fiber from browning, and the color difference (△ E) of the same batch is less than or equal to 0.12.

3. The anti-browning tea polyphenol modified viscose fiber prepared by the invention has good heat preservation and insulation effects because a large amount of honeycomb structures are formed in the fiber due to the tea polyphenol functional complexing agent, wherein the heat conductivity coefficient (lambda) is 0.32-0.35.

4. In the preparation step of the spinning solution, the addition of the stabilizer has great influence on the shrinkage of the prepared fiber, and after the stabilizer is added, the moisture absorption rate and the shrinkage of the fiber are respectively reduced from 14.3-15.2% and 6.6-7.2% to 11.3-12.2% and 2.5-2.8%, so that the shrinkage of the fiber is obviously reduced.

5. The brown stain resistant tea polyphenol modified viscose fiber prepared by the invention has good antibacterial property, and the antibacterial rate to staphylococcus aureus is more than or equal to 99.9%, and the antibacterial rate to dysentery bacillus is more than or equal to 99.9%.

Detailed Description

The invention is further illustrated by the following specific examples. The use and purpose of these exemplary embodiments are to illustrate the present invention, not to limit the actual scope of the present invention in any way, and not to limit the scope of the present invention in any way.