CN109505028B - Long-acting broad-spectrum antibacterial Tiancha fiber and preparation method thereof - Google Patents
Long-acting broad-spectrum antibacterial Tiancha fiber and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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Abstract
The invention provides a long-acting broad-spectrum antibacterial Tiancha fiber, and belongs to the field of cellulose fibers. The fiber consists of an inner layer and an outer layer; micro-cavities and carbon nanotubes are distributed on the inner layer; the inner layer accounts for 65-75% of the dry total weight of the fiber; the outer layer accounts for 25-35% of the total weight of the fiber. The invention also provides a preparation method of the long-acting broad-spectrum antibacterial Tiancha fiber, which comprises the preparation step of the viscose spinning solution; the preparation step of the viscose spinning solution comprises the steps of adding modified auxiliary agent slurry in a dissolving process; the inner layer of the long-acting broad-spectrum antibacterial Tiancha fiber prepared by the invention adopts a traditional sulfonate method glue making process, a coagulating bath process without a skin core layer is adopted, the outer layer is uniformly coated, coagulated and regenerated by a creative solvent method, and the prepared fiber has higher strength, good antibacterial persistence and higher wet modulus, and particularly has higher dry breaking strength than that of a common viscose fiber.
Description
Technical Field
The invention provides an antibacterial fiber and a preparation method thereof, in particular to a long-acting broad-spectrum antibacterial Tiancha fiber and a preparation method thereof, belonging to the field of cellulose fiber.
Background
The strategic problems of resources, environment and sustainable development become global hot problems facing human society, and the great trend of current social development is that the biological resources are required to be utilized finely and efficiently. With the gradual depletion of petroleum resources, the development of natural products produced by photosynthesis is becoming popular nowadays, and specifically includes primary development mainly aiming at the development of high-quality and high-yield raw materials, secondary development aiming at the development of raw material processing, and tertiary development aiming at the deep development of raw materials and applications thereof.
The existing regenerated cellulose fiber products have the characteristics of good moisture absorption and air permeability and comfortable wearing, are always well favored by people, but along with the improvement of living standard and the change of living concept, people pay more and more attention to the health care function of textiles, hope that the existing cellulose fiber textiles are improved in the aspects of antibacterial performance, fabric wrinkle resistance, other functions and the like, at present, the domestic dye for textile industry is almost all synthetic dye, has large side effect and is not beneficial to human health. With the rapid development of economy in China, the health consciousness of people is gradually enhanced, the use of synthetic dyes is gradually forbidden, and safe and high-quality natural dyes are developed and utilized. Tea not only contains rich pigment and can be used for dyeing natural plant dyes, but also contains a plurality of effective biological active ingredients such as catechin, cholestenone, caffeine, inositol, folic acid, pantothenic acid, amino acid and the like, and the great revolution of the functional textile field is realized by organically combining most ingredients of the tea with cellulose which is also a photosynthesis product.
The Chinese patent with the application number of 201711092932.3 discloses a method for dyeing cellulose fiber by using natural tea pigment, which comprises the steps of firstly extracting the natural tea pigment in tea, and then carrying out plant dyeing on the cellulose, thereby realizing environment-friendly dyeing and pure naturalization of garment materials; the Chinese patent with the application number of 201611163439.1 discloses a method for preparing tea polyphenol cellulose fiber by grafting tea polyphenol in viscose spinning solution through a silane coupling agent and then carrying out processes such as spinning and the like, thereby realizing functionalization. Chinese patent No. 201610347050.6 discloses a tea polyphenol cellulose fiber spunlace nonwoven fabric and a production process thereof. The tea polyphenol fiber is applied to spunlace non-woven fabrics.
According to the production technology of tea modified cellulose fiber or plant dyed fiber by taking tea polyphenol as natural pigment disclosed in China at present, only the plant pigment such as tea polyphenol in tea is extracted, and other components such as protein, amino acid, caffeine, polyphenol, carbohydrate, lipid, mineral substances, a part of plant pigment, vitamin and organic acid (the specific tea components are shown in table 1) can not be dissolved in tea soup through the steaming process, so that the effective bioactive components and the cellulose of tea leaves are not effectively utilized, and in addition, the tea polyphenol is aqueous solution, powdery solid or crystal which is light yellow to tea brown and slightly fragrant, has astringent taste, is easily soluble in water, ethanol and ethyl acetate, and is soluble in oil and fat. Has good heat resistance and acid resistance, and is relatively stable in the pH range of 2-7. The viscose fiber is easy to oxidize and brown stain under alkaline conditions, and as known knowledge, the strong alkaline viscose spinning solution of the production process of the viscose fiber by the common sulfonate method is sprayed into a strong acid bath environment for forming, so that the damage and the loss of effective components are easily caused.
TABLE 1A summary of specific ingredients in tea
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a long-acting broad-spectrum antibacterial Tiancha fiber and a preparation method thereof, so as to realize the following purposes:
1. the invention provides a long-acting broad-spectrum antibacterial Tiancha fiber and a preparation method thereof, which fully utilizes cellulose and tea which are products of photosynthesis to achieve the purpose of efficiently and comprehensively utilizing biological resources;
2. according to the long-acting broad-spectrum antibacterial Tiancha fiber prepared by the invention, the inner layer adopts a traditional sulfonate method glue making process, a coagulating bath process without a skin core layer is adopted, and the outer layer adopts a creative solvent method to be uniformly coated, coagulated and regenerated, so that all components of tea are uniformly dispersed in the outer layer of the fiber, and the antibacterial performance and the health-care function generated by contact of the prepared fiber are greatly improved;
3. the invention provides a long-acting broad-spectrum antibacterial Tiancha fiber and a preparation method thereof, which simultaneously adopts unique glue making and forming processes to ensure that an inner layer and an outer layer are in staggered close combination, and the phenomenon of delamination caused by stretching and twisting of two materials in different forming processes is avoided;
4. the invention provides a long-acting broad-spectrum antibacterial Tiancha fiber, wherein a certain amount of micro-cavities and carbon nano tube conductive particles are stored in an inner layer, and a pure-spun fabric has high hygroscopicity, high fabric conductivity and prominent anti-wrinkle effect in an environment with relative humidity of 65% at room temperature and is suitable for intelligent wearable textiles with micro-current;
5. the inner-layer and outer-layer two-phase coagulating bath regeneration process adopted by the invention avoids the decomposition and oxidation damage of strong acid and strong alkali to effective substances in tea, so that the effective components in the tea are retained in the outer layer of the fiber to the maximum extent, and the prepared plant has good antibacterial performance, especially good antibacterial performance to Klebsiella pneumoniae.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a long-acting broad-spectrum antibacterial Tiancha fiber is composed of an inner layer and an outer layer, wherein the inner layer is a fiber spun by a sulfonate method, micro-cavities and carbon nano tubes are distributed on the inner layer, and the outer layer is a fiber cortex formed by uniform coating by a LiCl/DMAc solvent method; the outer fiber layer contains cellulose and tea components; wherein the inner layer accounts for 65-75% of the dry total weight of the fiber, and the outer layer accounts for 25-35% of the total weight of the fiber. The inner layer and the outer layer are distributed in a proper proportion, so that the prepared fiber has both functional and physical properties, namely, the fiber has good antibacterial, bacteriostatic persistence and moisture absorption properties, and also has good wet modulus and dry and wet strength; the proportion of the outer layer is too large, so that the difficulty of large-line production is increased, the proportion of the outer layer is too small, and the functionality of the prepared fiber is influenced; the proportion and size distribution of the inner layer and the outer layer of the fiber is the result of extensive research and summary by the inventor.
Furthermore, the color of the fiber is light coffee, the dry strength is 3.8-4.2cN/dtex, the dry elongation is 16-18.5%, the wet modulus is 0.80-0.92 cN/dtex, and the whiteness is 45 +/-3%.
After the long-acting broad-spectrum antibacterial Tiancha fiber prepared by the invention is washed by water for 100 times, the long-acting broad-spectrum antibacterial Tiancha fiber still reaches more than 99% to Klebsiella pneumoniae, more than 98.5% to Candida albicans, and more than 99.0 to Bacillus subtilis and Escherichia coli; the hydroscopic property of the pure textile fabric made of the fiber reaches more than 16.4 percent in the environment with the relative humidity of 65 percent at normal temperature, and the conductivity of the fabric is 1.8 multiplied by 104The color fastness to washing reaches 4-5 grades.
A preparation method of long-acting broad-spectrum antibacterial Tiancha fiber comprises the following steps:
preparation of viscose spinning solution
1. Soaking, squeezing, crushing, aging and yellowing pulp, adding modified auxiliary agent slurry in a dissolving process, filtering, defoaming and aging to prepare conventional sulfonate viscose spinning solution; the indexes of the viscose spinning solution are as follows: containing alkali: 2.5 ± 0.2%, alpha-cellulose: 6.6 +/-0.2%, maturity: 12-16ml (15% ammonium chloride), viscosity 50-60S;
further, the preparation method of the modification auxiliary agent slurry comprises the following steps: mixing sodium bicarbonate: sodium carbonate: mixing the carbon nanotubes according to a proportion, adding 6 times of water by weight, adding a dispersing agent, and stirring for 2 hours at the temperature of 60 +/-3 ℃;
further, the sodium bicarbonate: sodium carbonate: the mass ratio of the carbon nano tube is 2: 1: 1;
furthermore, the addition amount of the modification auxiliary agent slurry is 3.5-5.5% of the weight of the methyl fiber in the viscose spinning solution. The ratio and the addition of the components of the modified auxiliary agent slurry directly influence the formation of inner layer micro-cavities of the prepared broad-spectrum antibacterial Tiancha fiber, and further influence the bonding force of the inner layer and the outer layer of the fiber and the fiber strength.
Second, preparation of plant source bath lotion
1. Dry tea A preparation method
Crushing fresh tea leaves to 6-8mm, spreading on a chain plate with the thickness of 10-15mm, spraying an aqueous solution of cobalt chloride, irradiating for 2-3 hours at room temperature by adopting ultraviolet rays, and drying to obtain dry tea leaves A with the water content of 0.3-0.8%; because the natural tea has higher polymerization degree, the cobalt chloride aqueous solution can accelerate the cellulose degradation and prepare for the next dissolution.
Further, the concentration of the aqueous solution of the cobalt chloride is 0.2-0.3g/l, and the addition amount of the cobalt chloride is 0.02-0.03 percent of the weight of the dry tea A;
the wavelength of the ultraviolet ray is 3100-3400A, and the energy is 135-140 kcal.
2. Preparation of flaky tea B
Crushing the dry tea A by ultrasonic for 2-3 hours to obtain 3-4mm flaky tea B; and when the ultrasonic wave is broken, the output frequency is 33-38 KHz. The ultrasonic pulverization aims at pulverization and further degrading the polymerization degree of cellulose in the natural tea.
3. Preparation of bath lotion C of plant origin
Adding the flaky tea slices B into a DMAC solvent, adding a small amount of catalyst, heating at the ambient temperature of 150 +/-2 ℃ for 1-2 hours for activation, cooling to 95 +/-2 ℃, and supplementing DMAC and LiCl to prepare an activation solution; adding negative electricity modifier into the activating solution, continuously stirring for 2-3 hr to obtain gel, standing at 25 + -2 deg.C to obtain transparent solution with solid content of 6.6 + -0.2%, and adding into the tank as plant source bath solution C;
the concentration of DMAC in the activating solution is controlled to be 94 +/-1%, the concentration of LiCl is controlled to be 6 +/-1%, and the moisture content is controlled to be 0.5-1%; the concentration and the moisture content of each component in the activation solution are properly adjusted for a mixed dissolved substance of the natural tea, so that the influence caused by large polymerization degree and uneven distribution of the natural tea is reduced, and beneficial functional components in the natural tea are protected from being damaged.
The catalyst is a mixture consisting of cobalt chloride and potassium permanganate, and the ratio is 1: 1.2; the addition amount of the catalytic additive is 0.01-0.02% of the flaky tea slice B; the catalyst can further rapidly reduce the polymerization degree of each component in the tea.
The negative electricity modifier is a mixture of BTCA salt and cyclodextrin, wherein the weight ratio of the BTCA salt to the cyclodextrin is 3: 1;
the weight of the negative electricity modifier is 0.3-0.5% of the weight of the flaky tea pieces B.
Three, two-forming spinning
Introducing the viscose spinning solution into a coagulating bath I for forming, and then obtaining nascent fiber tows after nozzle drafting, disc-to-disc drafting and two-bath drafting; then the nascent tows respectively pass through a desulfurization tank and a rinsing tank I, are drawn to a microwave dryer to be dried to be absolutely dry, enter a bath tank C, pass through a plant source bath liquid C, and are retained for a certain time; uniformly coating the plant source bath lotion C on the surface of the nascent fiber tow; finally, performing bidirectional regeneration through a coagulating bath II, and performing three-bath drafting, oiling, cutting and drying to obtain finished fibers;
further, the residence time of the nascent fiber tows in the C bath tank is 5-8 s; the retention time has great relation with the distribution of the inner layer and the outer layer of the prepared fiber and the strength of the fiber; the retention time is too long, the nascent fiber tows are easily dissolved by the plant source bath liquid, and the strength of the prepared fiber is relatively low; the retention time is short, and the proportion of the outer layer of the prepared camellia japonica fiber is small, so that the aim of the invention cannot be achieved.
The coagulation bath I comprises the following components: h3PO4 ：60±2g/l，NaH2PO4 70 +/-2 g/l, cationic cellulose JR-400 (sold by Guangzhou Nanjia chemical technology Co., Ltd.) 18 +/-2 g/l, temperature: 60 +/-3 ℃; by using
The draft of the spray head is 20-30%, and the draft between discs is as follows: 25 to 35 percent;
the two-bath draft is 15-20%, the temperature is 95 +/-3 ℃, and H3PO4The concentration is 5-8 g/l; the proper concentration of phosphoric acid can avoid the damage of the following oxidation to the functional components of the tea.
Phosphoric acid with relatively weak acidity is adopted as forming acid in the coagulating bath I and the two-bath drafting, when the modifying auxiliary agent slurry meets the phosphoric acid, micro-cavities are slowly formed in the fibers, particularly the weak acid is more beneficial to forming the micro-cavities in the nascent fiber tows, the formed micro-cavities are smaller, the strength of the fibers is not influenced, the combining fastness of the inner layer and the outer layer, the cationic modification of the nascent fiber tows and the improvement of the moisture absorption performance of the prepared fibers are further facilitated.
The drying temperature of the microwave dryer is 100 +/-3 ℃; the back traction draft is 3-5%;
the ethanol content in the coagulation bath II is 1-2%, and the balance is deionized water; the temperature of the coagulation bath II is 40 +/-3 ℃;
the three-bath drafting is 10-12%, and the temperature is 80 +/-3 ℃.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
1. according to the long-acting broad-spectrum antibacterial Tiancha fiber prepared by the invention, the inner layer adopts a traditional sulfonate method glue making process, a coagulating bath process without a skin core layer is adopted, the outer layer is uniformly coated, coagulated and regenerated by a creative solvent method, and all components of tea are uniformly dispersed in the outer layer, so that the antibacterial performance and the health-care function generated by contact are greatly improved;
2. the long-acting broad-spectrum antibacterial Tiancha fiber prepared by the invention adopts an internal and external double-forming spinning process, so that the prepared fiber has higher strength and higher wet modulus, and particularly the dry breaking strength exceeds that of a common viscose fiber;
3. according to the invention, the prepared nascent fiber tow is subjected to positive charge treatment by a traditional sulfonate method to enable the tow to have positive charges, then the negative charges of the outer layer of the plant source bath liquid C are modified, and finally the inner layer and the outer layer of the prepared broad-spectrum antibacterial Tiancha fiber are tightly combined together by a double-forming spinning process, so that the antibacterial persistence of the prepared Tiancha fiber is improved, and the practicability is strong; the inner layer and the outer layer are combined in a staggered and tight manner by adopting a unique glue making and forming process, so that the phenomenon of delamination and peeling caused by stretching and twisting of two materials in different forming processes in the using process is avoided;
4. the long-acting broad-spectrum antibacterial Tiancha fiber and the preparation method thereof completely utilize the cellulose and the tea which are the products of photosynthesis, achieve the aim of efficiently utilizing biological resources and avoid the waste of resources;
5. the long-acting broad-spectrum antibacterial Tiancha fiber prepared by the invention is characterized in that a certain amount of micro-cavities and carbon nano tube conductive particles are stored in the inner layer of the fiber by adding the modified auxiliary agent slurry, the hygroscopicity of pure textile fabric is more than 16.4% in the environment with the relative humidity of 65% at room temperature, and the conductivity of the textile fabric is 1.8 multiplied by 104The anti-wrinkle effect is prominent over S/m, and the fabric is very suitable for intelligent wearable textiles with micro-current;
6. the inner-outer layer two-phase coagulating bath regenerating process avoids the decomposition and oxidation damage of strong acid and strong alkali to effective matter in tea, makes the effective component in tea retained in the outer layer of fiber to the maximum, and makes the fiber woven fabric reach 99% to Klebsiella pneumoniae, 98.5% to Candida albicans and 99.0 to Bacillus subtilis and colibacillus after 100 times water washing.
Detailed Description
Embodiment 1 a method for preparing long-acting broad-spectrum natural tea fiber, comprising the following steps:
preparation of viscose spinning solution
1. Soaking, squeezing, crushing, aging and yellowing pulp, adding modified auxiliary agent slurry in a dissolving process, filtering, defoaming and aging to prepare conventional sulfonate viscose spinning solution; the indexes of the viscose spinning solution are as follows: containing alkali: 2.5 ± 0.2%, alpha-cellulose: 6.6 +/-0.2%, maturity: 12ml (15% ammonium chloride), viscosity 50S;
the preparation method of the modified auxiliary agent slurry comprises the following steps: mixing sodium bicarbonate: sodium carbonate: mixing the carbon nanotubes according to a proportion, adding 6 times of water by weight, adding a dispersing agent, and stirring for 2 hours at the temperature of 60 +/-3 ℃; sodium bicarbonate: sodium carbonate: the mass ratio of the carbon nano tube is 2: 1: 1; the addition amount of the modified auxiliary agent slurry is 3.5 percent of the weight of the methyl fiber in the viscose spinning solution.
Second, preparation of plant source bath lotion
1. Dry tea A preparation method
Crushing fresh tea leaves to 6-8mm, spreading on a chain plate with the thickness of 10-15mm, spraying an aqueous solution of cobalt chloride, irradiating for 2 hours at room temperature by adopting ultraviolet rays, and drying to obtain dry tea leaves A with the water content of 0.3%;
the concentration of the cobalt chloride aqueous solution is 0.2g/l, and the addition amount of the cobalt chloride is 0.02 percent of the weight of the dry tea A; the wavelength of the ultraviolet light is 3100-3400A, and the energy is 135-140 kcal.
2. Preparation of flaky tea B
Crushing the dry tea A by ultrasonic for 2-3 hours to obtain 3-4mm flaky tea B; when the ultrasonic wave is broken, the output frequency is 33-38 KHz.
3. Preparation of bath lotion C of plant origin
Adding the flaky tea pieces B into a DMAC solvent, adding a small amount of catalyst, heating for 1 hour at the ambient temperature of 150 +/-2 ℃, cooling to 95 +/-2 ℃, and supplementing DMAC and LiCl to prepare an activation solution; adding negative electricity modifier into the activating solution, stirring for 2 hr until it is gelatinous, standing at 25 + -2 deg.C to obtain transparent solution with solid content of 6.6 + -0.2%, and adding into the tank as plant source bath solution C;
the concentration of DMAC in the activating solution is controlled to be 94 +/-1%, the concentration of LiCl is controlled to be 6 +/-1%, and the moisture content is controlled to be 0.5%; the catalyst is a mixture of cobalt chloride and potassium permanganate, and the proportion is 1: 1.2; the addition amount of the catalyst is 0.01 percent of the flake tea B; the negative electricity modifier is a mixture of BTCA salt and cyclodextrin, wherein the weight ratio of the BTCA salt to the cyclodextrin is 3: 1; the weight of the added negative electricity modifier is 0.3 percent of the weight of the flaky tea pieces B.
Three, two-forming spinning
Introducing the viscose spinning solution into a coagulating bath I for forming, and then obtaining nascent fiber tows after nozzle drafting, disc-to-disc drafting and two-bath drafting; then the nascent tows respectively pass through a desulfurization tank and a rinsing tank I, are drawn to a microwave dryer to be dried to be absolutely dry, enter a bath tank C, pass through a plant source bath liquid C, and are retained for a certain time; uniformly coating the plant source bath lotion C on the surface of the nascent fiber tow; finally, performing bidirectional regeneration through a coagulating bath II, and performing three-bath drafting, oiling, cutting and drying to obtain finished fibers;
the detention time of the nascent fiber tows in the C bath tank is 5 s; the coagulation bath I had the composition: h3PO4 ：60±2g/l，NaH2PO4 70 +/-2 g/l, cationic cellulose JR-400 (sold by Guangzhou Nanjia chemical technology Co., Ltd.) 18 +/-2 g/l, temperature: 60 +/-3 ℃; the draft of the nozzle is 20%, and the draft between discs is: 25 percent; the two-bath draft is 15%, the temperature is 95 +/-3 ℃, and the temperature is H3PO4The concentration is 5 g/l; the drying temperature of the microwave dryer is 100 +/-3 ℃; the back draft is 3%; the ethanol content in the coagulation bath II is 1 percent, and the balance is deionized water; the temperature of the coagulation bath II is 40 +/-3 ℃; the three bath draft is 10% and the temperature is 80 + -3 deg.C.
Embodiment 2 a method for preparing long-acting broad-spectrum natural tea fibers, comprising the following steps:
preparation of viscose spinning solution
1. Soaking, squeezing, crushing, aging and yellowing pulp, adding modified auxiliary agent slurry in a dissolving process, filtering, defoaming and aging to prepare conventional sulfonate viscose spinning solution; the indexes of the viscose spinning solution are as follows: containing alkali: 2.5 ± 0.2%, alpha-cellulose: 6.6 +/-0.2%, maturity: 14ml (15% ammonium chloride), viscosity 55S;
the preparation method of the modified auxiliary agent slurry comprises the following steps: mixing sodium bicarbonate: sodium carbonate: mixing the carbon nanotubes according to a proportion, adding 6 times of water by weight, adding a dispersing agent, and stirring for 2 hours at the temperature of 60 +/-3 ℃; sodium bicarbonate: sodium carbonate: the mass ratio of the carbon nano tube is 2: 1: 1; the addition amount of the modifying additive slurry is 4.7 percent of the weight of the methyl fiber in the viscose spinning solution.
Second, preparation of plant source bath lotion
1. Dry tea A preparation method
Crushing fresh tea leaves to 6-8mm, spreading on a chain plate with the thickness of 10-15mm, spraying an aqueous solution of cobalt chloride, irradiating for 2.5 hours at room temperature by adopting ultraviolet rays, and drying to obtain dry tea leaves A with the water content of 0.6%;
the concentration of the cobalt chloride aqueous solution is 0.3g/l, and the addition amount of the cobalt chloride is 0.03 percent of the weight of the dry tea A; the wavelength of the ultraviolet light is 3100-3400A, and the energy is 135-140 kcal.
2. Preparation of flaky tea B
Crushing the dry tea A by ultrasonic for 2-3 hours to obtain 3-4mm flaky tea B; and when the ultrasonic wave is broken, the output frequency is 33-38 KHz.
3. Preparation of bath lotion C of plant origin
Adding the prepared flaky tea slices B into a DMAC solvent, then adding a small amount of catalyst, heating for 1-2 hours at the ambient temperature of 150 +/-2 ℃, cooling to 95 +/-2 ℃, and then supplementing DMAC and LiCl to prepare an activation solution; adding negative electricity modifier into the activating solution, continuously stirring for 2.5 hr to obtain gel, standing at 25 + -2 deg.C to obtain transparent solution with solid content of 6.6 + -0.2%, and adding into the tank as plant source bath solution C;
the concentration of DMAC in the activating solution is controlled to be 94 +/-1%, the concentration of LiCl is controlled to be 6 +/-1%, and the moisture content is controlled to be 0.8%; the catalyst is a mixture of cobalt chloride and potassium permanganate, and the proportion is 1: 1.2; the addition amount of the catalyst is 0.02 percent of the flaky tea piece B; the negative electricity modifier is a mixture of BTCA salt and cyclodextrin, wherein the weight ratio of the BTCA salt to the cyclodextrin is 3: 1; the weight of the added negative electricity modifier is 0.4 percent of the weight of the flaky tea pieces B.
Three, two-forming spinning
Introducing the viscose spinning solution into a coagulating bath I for forming, and then obtaining nascent fiber tows after nozzle drafting, disc-to-disc drafting and two-bath drafting; then the nascent tows respectively pass through a desulfurization tank and a rinsing tank I, are drawn to a microwave dryer to be dried to be absolutely dry, enter a bath tank C, pass through a plant source bath liquid C, and are retained for a certain time; uniformly coating the plant source bath lotion C on the surface of the nascent fiber tow; finally, performing bidirectional regeneration through a coagulating bath II, and performing three-bath drafting, oiling, cutting and drying to obtain finished fibers;
the detention time of the nascent fiber tows in the bath tank C is 6 s; the coagulation bath I had the composition: h3PO4 ：60±2g/l，NaH2PO4 70 +/-2 g/l, cationic cellulose JR-400 (sold by Guangzhou Nanjia chemical technology Co., Ltd.) 18 +/-2 g/l, temperature: 60 +/-3 ℃; the draft of the nozzle is 25%, and the draft between discs is: 35 percent; the two-bath draft is 117 percent, the temperature is 95 +/-3 ℃, and H3PO4The concentration is 6 g/l; a microwave dryer, wherein the drying temperature is 100 +/-3 ℃; the back traction draft is 4 percent; the ethanol content in the coagulation bath II is 2 percent, and the balance is deionized water; the temperature of the coagulation bath II is 40 +/-3 ℃; the three bath draft is 11% and the temperature is 80 + -3 deg.C.
Embodiment 3 a method for preparing long-acting broad-spectrum natural tea fibers, comprising the following steps:
preparation of viscose spinning solution
1. Soaking, squeezing, crushing, aging and yellowing pulp, adding modified auxiliary agent slurry in a dissolving process, filtering, defoaming and aging to prepare conventional sulfonate viscose spinning solution; the indexes of the viscose spinning solution are as follows: containing alkali: 2.5 ± 0.2%, alpha-cellulose: 6.6 +/-0.2%, maturity: 16ml (15% ammonium chloride), viscosity 60S;
the preparation method of the modified auxiliary agent slurry comprises the following steps: mixing sodium bicarbonate: sodium carbonate: mixing the carbon nanotubes according to a proportion, adding 6 times of water by weight, adding a dispersing agent, and stirring for 2 hours at the temperature of 60 +/-3 ℃; sodium bicarbonate: sodium carbonate: the mass ratio of the carbon nano tube is 2: 1: 1; the addition amount of the modified auxiliary agent slurry is 5.5 percent of the weight of the methyl fiber in the viscose spinning solution.
Second, preparation of plant source bath lotion
1. Dry tea A preparation method
Crushing fresh tea leaves to 6-8mm, spreading on a chain plate with the thickness of 10-15mm, spraying an aqueous solution of cobalt chloride, irradiating for 3 hours at room temperature by adopting ultraviolet rays, and drying to obtain dry tea leaves A with the water content of 0.8%;
the concentration of the cobalt chloride aqueous solution is 0.3g/l, and the addition amount of the cobalt chloride is 0.03 percent of the weight of the dry tea A; the wavelength of the ultraviolet light is 3100-3400A, and the energy is 135-140 kcal.
2. Preparation of flaky tea B
Crushing the dry tea A by ultrasonic for 2-3 hours to obtain 3-4mm flaky tea B; and when the ultrasonic wave is broken, the output frequency is 33-38 KHz.
3. Preparation of bath lotion C of plant origin
Adding the flaky tea pieces B into a DMAC solvent, adding a small amount of catalyst, heating for 2 hours at the ambient temperature of 150 +/-2 ℃, cooling to 95 +/-2 ℃, and supplementing DMAC and LiCl to prepare an activation solution; adding negative electricity modifier into the activating solution, stirring for 3 hr until it is gelatinous, standing at 25 + -2 deg.C to obtain transparent solution with solid content of 6.6 + -0.2%, and adding into the tank as plant source bath solution C;
the concentration of DMAC in the activating solution is controlled to be 94 +/-1%, the concentration of LiCl is controlled to be 6 +/-1%, and the moisture content is controlled to be 1%; the catalyst is a mixture of cobalt chloride and potassium permanganate, and the proportion is 1: 1.2; the addition amount of the catalytic additive is 0.02 percent of that of the flaky tea slices B; the negative electricity modifier is a mixture of BTCA salt and cyclodextrin, wherein the weight ratio of the BTCA salt to the cyclodextrin is 3: 1; the weight of the added negative electricity modifier is 0.5 percent of the weight of the flaky tea pieces B.
Three, two-forming spinning
Introducing the viscose spinning solution into a coagulating bath I for forming, and then obtaining nascent fiber tows after nozzle drafting, disc-to-disc drafting and two-bath drafting; then the nascent tows respectively pass through a desulfurization tank and a rinsing tank I, are drawn to a microwave dryer to be dried to be absolutely dry, enter a bath tank C, pass through a plant source bath liquid C, and are retained for a certain time; uniformly coating the plant source bath lotion C on the surface of the nascent fiber tow; finally, performing bidirectional regeneration through a coagulating bath II, and performing three-bath drafting, oiling, cutting and drying to obtain finished fibers;
the detention time of the nascent fiber tows in the bath tank C is 8 s; the coagulation bath I had the composition: h3PO4 ：60±2g/l，NaH2PO4 70 +/-2 g/l, cationic cellulose JR-400 (sold by Guangzhou Nanjia chemical technology Co., Ltd.) 18 +/-2 g/l, temperature: 60 +/-3 ℃;
the draft of the nozzle is 30%, and the draft between discs is: 32 percent; the two-bath draft is 20 percent, the temperature is 95 +/-3 ℃, and the temperature is H3PO4The concentration is 8 g/l; a microwave dryer, wherein the drying temperature is 100 +/-3 ℃; the back draft is 5%; the ethanol content in the coagulation bath II is 2 percent, and the balance is deionized water; the temperature of the coagulation bath II is 40 +/-3 ℃; the three bath draft is 12% and the temperature is 80 + -3 deg.C.
The long-acting broad-spectrum Tiancha fiber prepared by the invention has good physical properties and good functionality, and the detection results of related indexes are shown in Table 2
TABLE 2
The broad-spectrum antibacterial Tiancha fiber prepared by the invention adopts an internal and external double-forming spinning process in the preparation process, so that the prepared fiber has higher strength and higher wet modulus, and particularly the dry breaking strength exceeds that of a common viscose fiber; the broad-spectrum antibacterial Tiancha fiber prepared by the invention is light coffee overall; as can be seen from Table 2, the dry strength of the broad-spectrum antibacterial native tea fiber prepared by the invention is 3.8-4.2cN/dtex, the dry elongation is 16-18.5%, the wet modulus is 0.80-0.92 cN/dtex, and the whiteness is 45 +/-3%.
In addition, the broad-spectrum antibacterial Tiancha fiber prepared by the invention has good antibacterial property, and particularly has excellent antibacterial persistence; meanwhile, the inner layer of the fiber contains a large number of micro-cavities, so the moisture absorption of the fiber is excellent; due to the addition of the carbon nano tube, the prepared broad-spectrum antibacterial Tiancha fiber has good fabric conductivity; according to the invention, the prepared nascent fiber tow is subjected to positive charge treatment by a traditional sulfonate method to enable the tow to have positive charges, then the negative charges of the outer layer of the plant source bath liquid C are modified, and finally the inner layer and the outer layer of the prepared broad-spectrum antibacterial Tiancha fiber are tightly combined together by a double-forming spinning process, so that the antibacterial persistence and the washing color fastness of the prepared Tiancha fiber are improved.
The broad-spectrum antibacterial Tiancha fiber prepared by the invention has the antibacterial detection indexes shown in Table 3
TABLE 3
The antibacterial detection indexes of the broad-spectrum antibacterial Tiancha fiber prepared by the invention after being washed by water for 100 times are shown in Table 4
TABLE 4
As can be seen from the comparison of tables 3 and 4, after the long-acting broad-spectrum antibacterial Tiancha fiber prepared by the invention is washed by water for 100 times, the antibacterial rate to Klebsiella pneumoniae still reaches more than 99%, the antibacterial rate to Candida albicans reaches more than 98.5%, and the antibacterial rate to Bacillus subtilis and Escherichia coli reaches more than 99.0%; in particular, the long-acting broad-spectrum antibacterial Tiancha fiber prepared in example 2 has an antibacterial rate against klebsiella pneumoniae and an antibacterial rate against bacillus subtilis still reaching more than 99.9% after being washed with water for 100 times, which is beneficial to almost completely dissolving the flaky tea B and eliminating the large particle state of the flaky tea B due to the preparation of the plant source bath liquid C in the process of the invention; meanwhile, the prepared nascent fiber tows are subjected to positive charge treatment by a traditional sulfonate method to form fiber tow bands with positive charges, then the negative charges of the outer layer of the plant source bath liquid C are modified, and finally the inner layer and the outer layer of the prepared broad-spectrum antibacterial native tea fibers are tightly combined together by a double-forming spinning process to prevent the loss of tea components caused by the conventional method, so that the prepared broad-spectrum antibacterial native tea fibers are very excellent in antibacterial persistence.
The broad-spectrum antibacterial Tiancha fiber prepared by the invention has good moisture absorption performance, conductivity and washing color fastness, and the table 5 shows the detection indexes of the broad-spectrum antibacterial Tiancha fiber prepared by the invention:
TABLE 5
Detection standard:
washing color fastness: color fastness to chlorinated water of GB/T8433 and 2013 textile color fastness test in swimming pool water;
from the table 5, it can be concluded that the broad-spectrum antibacterial Tiancha fiber prepared by the invention has good moisture absorption performance, conductivity, washing fastness and continuity of over 16.4% in an environment with relative humidity of 65%, and the fabric conductivity is 1.8 × 104 The anti-wrinkle effect is outstanding when the ratio of S/m is more than that of the standard, and the fabric is very suitable for manufacturing intelligent wearable textiles with micro-current; the unique washing color fastness is more than 5 grade based on the invention.
Comparative example 4
The inventor finds out through a large number of experiments that in the double-forming spinning step, the retention time of the nascent fiber tows in the C bath tank has an important influence on the strength of the long-acting broad-spectrum antibacterial Tiancha fiber prepared by the invention and the weight ratio distribution of the inner layer and the outer layer, and further influences the overall performance of the fiber, the inventor adopts the method of example 2, and only changes the retention time of the nascent fiber tows in the C bath tank in the double-forming spinning step under the condition that other processes are not changed, and respectively detects the prepared fiber, and concretely, the method is shown in Table 6
TABLE 6
As can be seen from Table 6, when the residence time of the nascent fiber tow in the C bath tank is less than or equal to 5s, the dry breaking strength of the prepared fiber is obviously reduced, the change of the wet modulus is small, the color fastness of the fabric to washing is greatly changed, and the ratio of the inner layer and the outer layer of the fiber to the total weight of the fiber is also greatly changed.
It is noted that, according to conventional understanding, the strength of the fiber produced by the conventional method should be greater than that of the fiber produced by the solvent spinning process, that is, the strength of the fiber produced should be linearly increased as the specific gravity of the inner layer in the total weight of the fiber is increased, and it is apparent from table 6 that, as compared with comparative examples 5 and 6, the dry breaking strength of the fiber produced is rather greatly reduced as the inner layer in the total weight of the fiber is increased, which was not thought by the inventors, because the improvement of the smaller strength of the cellulose fiber, particularly the fiber produced by the additional solvent spinning process, is difficult, the invention enables the dry breaking strength of the long-lasting broad-spectrum antibacterial Tiancha fiber produced to be greatly improved by an innovative combination of a series of processes, and overcomes the technical prejudice.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A long-acting broad-spectrum antibacterial Tiancha fiber is characterized in that: the fiber consists of an inner layer and an outer layer; micro-cavities and carbon nanotubes are distributed on the inner layer; the outer layer is a fiber skin layer formed by a LiCl/DMAc solvent method in a coating mode; the fiber skin layer contains cellulose and tea components; the inner layer accounts for 65-75% of the dry total weight of the fiber; the outer layer accounts for 25-35% of the total weight of the fiber; the preparation method of the Tiancha fiber comprises the steps of preparing viscose spinning solution; the preparation step of the viscose spinning solution comprises the steps of adding modified auxiliary agent slurry in a dissolving process; the preparation method of the modified auxiliary agent slurry comprises the following steps: mixing sodium bicarbonate: sodium carbonate: mixing the carbon nanotubes according to a proportion, adding 6 times of water by weight, adding a dispersing agent, and stirring for 2 hours at the temperature of 60 +/-3 ℃; the sodium bicarbonate: sodium carbonate: the mass ratio of the carbon nano tube is 2: 1: 1;
the addition amount of the modified auxiliary agent slurry is 3.5-5.5% of the weight of the methyl fiber in the viscose spinning solution;
the method also comprises a preparation step of the plant source bath lotion; the preparation steps of the plant source bath lotion comprise a dry tea A preparation step, a flaky tea B preparation step and a plant source bath lotion C preparation step; the preparation method of the dry tea A comprises the following steps: pulverizing fresh folium Camelliae sinensis to 6-8mm, spreading to 10-15mm thickness, spraying cobalt chloride water solution, irradiating with ultraviolet at room temperature for 2-3 hr, and oven drying; the concentration of the aqueous solution of the cobalt chloride is 0.2-0.3 g/L; the addition amount of the cobalt chloride is 0.02-0.03% of the weight of the dry tea A;
preparing the flaky tea B: crushing the dry tea A by ultrasonic for 2-3 hours to obtain 3-4mm flaky tea B; when the ultrasonic wave is broken, the output frequency is 33-38 KHz;
the preparation step of the plant source bath lotion C is as follows: adding the prepared flaky tea B into a DMAC solvent, then adding a small amount of catalyst, heating for 1-2 hours at the ambient temperature of 150 +/-2 ℃ for activation, cooling to 95 +/-2 ℃, and then supplementing DMAC and LiCl to prepare an activation solution; adding negative electricity modifier into the activating solution, stirring for 2-3 hr until it is gelatinous, standing at 25 + -2 deg.C to obtain plant bath lotion C with solid content of 6.6 + -0.2%; the catalyst is a mixture consisting of cobalt chloride and potassium permanganate; the negative electricity modifier is a mixture of BTCA salt and cyclodextrin;
the method further comprises a double profile spinning step: introducing the viscose spinning solution into a coagulating bath I for forming, and then obtaining nascent fiber tows after nozzle drafting, disc-to-disc drafting and two-bath drafting; then, the nascent fiber tows respectively pass through a desulfurization tank, a rinsing tank I and then are stretched to a microwave dryer to be dried to be absolutely dry, then enter a bath tank C, pass through a plant source bath liquid C and are retained for a certain time, and the plant source bath liquid C is uniformly coated on the surfaces of the nascent fiber tows; finally, performing bidirectional regeneration through a coagulating bath II, and performing three-bath drafting, oiling, cutting and drying to obtain finished fibers;
the retention time of the nascent fiber tows in the bath tank C is 5-8 s; the coagulation bath I comprises the following components: h3PO4 ：60±2g/L，NaH2PO4 70 +/-2 g/L, cationic cellulose JR-40018 +/-2 g/L, temperature: 60 +/-3 ℃; the two-bath draft is 15-20%, the temperature is 95 +/-3 ℃, and H3PO4The concentration is 5-8 g/L; the ethanol content in the coagulation bath II is 1-2%, and the balance is deionized water; the temperature of the coagulation bath II is 40 +/-3 ℃; the three-bath drafting is 10-12%, and the temperature is 80 +/-3 ℃.
2. The long-acting broad-spectrum antibacterial Tiancha fiber according to claim 1, wherein: the dry strength of the fiber is 3.8-4.2cN/dtex, and the wet modulus is 0.80-0.92 cN/dtex.
3. The long-acting broad-spectrum antibacterial Tiancha fiber according to claim 1, wherein: the concentration of DMAC in the activating solution is controlled to be 94 +/-1%, and the concentration of LiCl is controlled to be 6 +/-1%; the water content of the activating solution is 0.5-1%.
4. The long-acting broad-spectrum antibacterial Tiancha fiber according to claim 1, wherein: the mass ratio of cobalt chloride to potassium permanganate in the catalyst is 1: 1.2; the addition amount of the catalyst is 0.01-0.02% of the flaky tea B.
5. The long-acting broad-spectrum antibacterial Tiancha fiber according to claim 1, wherein: the mass ratio of BTCA salt to cyclodextrin in the negative electricity modifier is 3: 1; the weight of the negative electricity modifier is 0.3-0.5% of the weight of the flaky tea B.
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