Skin-friendly antibacterial spinning yarn and preparation method thereof

Abstract

The invention discloses a skin-friendly antibacterial spinning yarn and a preparation method thereof, and relates to the field of spinning yarns. When the skin-friendly antibacterial spinning yarn is prepared, 3-amino-1, 2, 4-triazine and vinyl phosphonyl chloride are subjected to a reaction, and a phosphorus-nitrogen flame-retardant monomer is obtained; activating bamboo nano-cellulose with ammonium ceric nitrate, grafting a phosphorus-nitrogen flame-retardant monomer, and performing electrostatic spinning to obtain modified bamboo nano-cellulose coated fibers; dipping polyester filament yarns in dopamine hydrochloride and sodium hypochlorite in sequence to obtain modified polyester core yarns; the modified bamboo nano-cellulose wrapping fiber and the modified polyester core yarn are twisted through a ring spinning frame and then react with 3, 3 ', 4, 4'-benzophenone tetracarboxylic dianhydride, and the skin-friendly antibacterial spinning yarn is obtained. The skin-friendly antibacterial spinning yarn prepared by the method has excellent skin-friendly antibacterial property, flame retardance, aging resistance and mechanical property.

Description

Technical Field

[0001] The invention relates to the field of spinning yarns, in particular to skin-friendly and antibacterial spinning yarns and a preparation method thereof. Background Art

[0002] Under the macro background of the rapid development of the global industrialization level, people's quality requirements for life such as food, clothing, housing and transportation are also increasing. In particular, "clothing" is ranked first in life needs. In addition to basic functions such as covering the body and keeping warm, its additional functions are also attracting much attention. Textile products with special functions such as antibacterial, radiation protection, sun protection, self-cleaning, moisture absorption and quick drying, anti-static, etc. are becoming more and more popular. In recent years, antibacterial textiles have been widely used in textiles, medicine, food and other fields, but traditional antibacterial technology is mainly used in the field of chemical fibers. In order to reduce dependence on petroleum resources and reduce our environmental pollution, natural fiber antibacterial products are urgently needed to be developed. Bamboo fiber is one of the main raw materials in the textile industry. It is a natural and environmentally friendly natural cellulose fiber with many excellent characteristics, such as soft hand feeling, good moisture absorption and breathability, good chemical stability, and easy processing. Therefore, it is widely used in people's underwear and medical dressings.

[0003] Bamboo fiber has certain biological activity, can release natural substances such as bamboo lactone and natural phenols, inhibit or reduce the growth of microorganisms such as bacteria and fungi, affect the metabolism of bacteria, and interfere with their normal reproduction and growth. Bamboo cellulose is cheap, has a wide range of natural sources, and is widely used in various fields. However, it is very easy to burn, and the flame spreads very quickly when burning, and it is easy to ignite other combustibles around. At the same time, due to its low ignition point, when the indoor temperature and combustible gas concentration are high in a fire, it will cause a flashover phenomenon, making the fire uncontrollable. Therefore, the present invention prepares a skin-friendly antibacterial spinning yarn with excellent flame retardant properties. Summary of the invention

[0004] The purpose of the present invention is to provide a skin-friendly antibacterial spun yarn and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A skin-friendly antibacterial spun yarn is obtained by twisting modified bamboo nano-cellulose outer fiber and modified polyester core yarn with a ring spinning machine and then reacting with 3,3',4,4'-benzophenonetetracarboxylic dianhydride.

[0007] As an optimization, the modified polyester core yarn is obtained by successively immersing polyester filaments in dopamine hydrochloride and sodium hypochlorite.

[0008] As an optimization, the polyester filament comes from Jiangsu Sanlian New Materials Co., Ltd.

[0009] As an optimization, the modified bamboo nanocellulose outer fiber is obtained by activating bamboo nanocellulose with ammonium cerium nitrate, grafting phosphorus and nitrogen flame retardant monomers, and then performing electrostatic spinning.

[0010] As an optimization, the bamboo nanocellulose comes from Suzhou Kaifa New Materials Technology Co., Ltd.

[0011] As an optimization, the phosphorus-nitrogen flame retardant monomer is obtained by reacting 3-amino-1,2,4-triazine and vinylphosphonic chloride.

[0012] A method for preparing skin-friendly antibacterial spinning yarn comprises the following preparation steps:

[0013] (1) 3-amino-1,2,4-triazine, vinylphosphonyl chloride, triethylamine and acetonitrile are mixed in a mass ratio of 1:(0.7-0.8):(1.5-1.7):(20-30), stirred at 20-30° C. and 100-200 rpm for 1-3 h, heated to 75-85° C. and refluxed for 7-9 h, naturally cooled to room temperature and filtered, washed with deionized water and anhydrous ethanol for 3-5 times respectively, and dried at 95-105° C. for 8-10 h to obtain a phosphorus-nitrogen flame retardant monomer;

[0014] (2) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1: (0.2-0.4): (95-105), ultrasonicate at 75-85° C. for 1-2 hours, add phosphorus-nitrogen flame retardant monomer in an amount of 1-2 times the mass of cotton cellulose, continue stirring for 2-4 hours, filter, wash with deionized water for 3-5 times, and dry at 75-85° C. for 11-13 hours to obtain modified bamboo nanocellulose; mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1: (2-4): (8-10), stir at 20-30° C. and 200-300 rpm for 47-49 hours to obtain a spinning solution; electrospin the spinning solution to obtain modified bamboo nanocellulose outer fiber;

[0015] (3) Polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water are mixed in a mass ratio of 1:(0.05-0.15):(0.05-0.07):(45-55), sodium hydroxide is added to adjust the pH value of the solution to 8-9, ultrasonically treated at 20-30°C for 23-25 ​​hours, taken out, washed with deionized water for 3-5 times, and dried at 100-110°C for 11-13 hours to obtain a pre-modified polyester core yarn; the pre-modified polyester core yarn is immersed in a sodium hypochlorite solution with a pH value of 4-6, ultrasonically treated at 20-30°C for 15-25 minutes, taken out, washed with deionized water for 3-5 times, and dried at 65-75°C for 8-10 hours to obtain a modified polyester core yarn;

[0016] (4) The modified bamboo nanocellulose outer fiber and the modified polyester core yarn are twisted by a ring spinning machine to obtain skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber is immersed in a cross-linking treatment solution for 1 to 3 hours and then taken out, pre-baked at 90 to 100° C. for 4 to 6 minutes, heated to 160 to 170° C. and baked for 2 to 4 minutes, washed with deionized water for 3 to 5 times, and dried at 50 to 60° C. for 7 to 9 hours to obtain skin-friendly antibacterial spun yarn.

[0017] As an optimization, the reaction equation of the phosphorus-nitrogen flame retardant monomer in step (1) is:

[0018]

[0019] As an optimization, the reaction equation for modifying the bamboo nanocellulose in step (2) is:

[0020]

[0021] As an optimization, the electrospinning process parameters of step (2) are: injection pump flow rate 6.7-6.9 μL / min, spinning voltage 16-18 kV, distance between spinneret and drum 16-18 cm, moving distance on the drum 14-16 cm, spinneret inner diameter 0.5-0.7 mm.

[0022] As an optimization, the reaction equation of the modified polyester core yarn in step (3) is:

[0023]

[0024] As an optimization, the cross-linking treatment liquid in step (4) is obtained by mixing 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water in a mass ratio of 1:(0.32-0.34):(15-25), and stirring at 50-60°C and 200-300 rpm for 20-30 min.

[0025] As an optimization, the reaction equation of the skin-friendly antibacterial spinning yarn in step (4) is:

[0026]

[0027] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0028] When preparing the skin-friendly antibacterial spun yarn, the present invention comprises the following steps: reacting 3-amino-1,2,4-triazine and vinylphosphonyl chloride to obtain a phosphorus-nitrogen flame-retardant monomer; activating bamboo nano-cellulose with ammonium cerium nitrate, grafting the phosphorus-nitrogen flame-retardant monomer, and then electrospinning to obtain modified bamboo nano-cellulose sheath fibers; soaking polyester filaments in dopamine hydrochloride and sodium hypochlorite in sequence to obtain modified polyester core yarns; twisting the modified bamboo nano-cellulose sheath fibers and the modified polyester core yarns with a ring spinning machine, and then reacting the modified bamboo nano-cellulose sheath fibers with 3,3',4,4'-benzophenonetetracarboxylic dianhydride to obtain the skin-friendly antibacterial spun yarn.

[0029] Firstly, 3-amino-1,2,4-triazine and vinylphosphonyl chloride are reacted to obtain phosphorus-nitrogen flame retardant monomers; then, bamboo nanocellulose is activated by ammonium cerium nitrate and then grafted with phosphorus-nitrogen flame retardant monomers, and then electrospinning is performed to obtain modified bamboo nanocellulose outer fiber; natural and environmentally friendly green bamboo nanocellulose is used as the outer layer of the spinning line, and the natural components in the bamboo cellulose have good compatibility with human skin, thereby improving the skin-friendliness of the skin-friendly and antibacterial spinning line; ammonium cerium nitrate is used as an initiator to oxidize the hydroxyl groups on the bamboo nanocellulose, and phosphorus-nitrogen flame retardant monomers based on vinylphosphonyl chloride are grafted, which can release phosphorus-containing free radicals during combustion to capture and quench the free radicals in the combustion, and at the same time promote the dehydration of the matrix into carbon, forming a dense carbon layer that is oxygen-insulated and heat-insulated, cutting off the heat exchange in the combustion, and the triazine nitrogen heterocycle can also release non-flammable gas during the pyrolysis process, further increasing the gas phase flame retardant effect, and improving the flame retardant properties of the skin-friendly and antibacterial spinning line.

[0030] Secondly, the polyester filaments are successively immersed in dopamine hydrochloride and sodium hypochlorite to obtain modified polyester core yarns; the modified bamboo nanocellulose outer fiber and the modified polyester core yarn are twisted by a ring spinning machine and then reacted with 3,3',4,4'-benzophenonetetracarboxylic dianhydride to obtain skin-friendly and antibacterial spinning yarns; dopamine is oxidized and self-polymerized under weak alkaline conditions to form adhesive polydopamine, which is attached to the surface of the polyester filaments, and then chlorinated with sodium hypochlorite to form a halamine structure that can release oxidized chloride ions, destroy or prevent normal cell metabolism, and promote bacterial death, thereby improving the antibacterial property of the skin-friendly and antibacterial spinning yarns; 3,3',4,4'-diphenylmethane is used to synthesize the polydopamine with adhesive properties under weak alkaline conditions. The yarn is impregnated with ketone tetracarboxylic dianhydride. After 3,3',4,4'-benzophenone tetracarboxylic dianhydride is dissolved in hot water, the anhydride forms a carboxyl group. Under high-temperature baking, an esterification reaction can occur between the hydroxyl groups on the modified bamboo nanocellulose outer fiber and the hydroxyl groups on the polydopamine layer on the modified polyester core yarn to form a cross-linked network, thereby improving the mechanical properties of the skin-friendly and antibacterial yarn. At the same time, the π-π and n-π electron transitions in the 3,3',4,4'-benzophenone tetracarboxylic dianhydride molecules, the electronic interaction between the transitions and the conjugation effect show a strong absorption effect in the ultraviolet light region, thereby further improving the anti-ultraviolet aging performance of the skin-friendly and antibacterial yarn. DETAILED DESCRIPTION

[0031] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0032] Embodiment 1:

[0033] A method for preparing skin-friendly antibacterial spun yarn, the method for preparing skin-friendly antibacterial spun yarn comprising the following preparation steps:

[0034] (1) 3-amino-1,2,4-triazine, vinylphosphonyl chloride, triethylamine and acetonitrile were mixed in a mass ratio of 1:0.7:1.5:20, stirred at 20° C. and 100 rpm for 3 h, heated to 75° C. and refluxed for 9 h, naturally cooled to room temperature and filtered, washed with deionized water and anhydrous ethanol for 3 times respectively, and dried at 95° C. for 10 h to obtain a phosphorus-nitrogen flame retardant monomer;

[0035] (2) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1:0.2:95, ultrasonicate at 75°C for 2h, add phosphorus nitrogen flame retardant monomer with a mass of 1 times that of cotton cellulose, continue stirring for 4h, filter, wash with deionized water 3 times, and dry at 75°C for 13h to obtain modified bamboo nanocellulose; Mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1:2:8, stir at 20°C and 200rpm for 49h to obtain spinning solution, and perform electrostatic spinning under the conditions of injection pump flow rate of 6.7μL / min, spinning voltage of 16kV, distance between spinneret and drum of 16cm, moving distance on drum of 14cm, and inner diameter of spinneret of 0.5mm to obtain modified bamboo nanocellulose outer fiber;

[0036] (3) The polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water were mixed in a mass ratio of 1:0.05:0.05:45, sodium hydroxide was added to adjust the pH value of the solution to 8, the solution was taken out after ultrasonic treatment at 20°C for 25 hours, washed with deionized water for 3 times, and dried at 100°C for 13 hours to obtain a pre-modified polyester core yarn; the pre-modified polyester core yarn was immersed in a sodium hypochlorite solution with a pH value of 4, ultrasonic treatment at 20°C for 25 minutes, the solution was taken out after ultrasonic treatment, washed with deionized water for 3 times, and dried at 65°C for 10 hours to obtain a modified polyester core yarn;

[0037] (4) 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water were mixed in a mass ratio of 1:0.32:15, and stirred at 50°C and 200 rpm for 30 min to obtain a cross-linking treatment solution; the modified bamboo nanocellulose outer fiber and the modified polyester core yarn were twisted by a ring spinning machine to obtain a skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber was immersed in the cross-linking treatment solution for 1 hour and then taken out, pre-dried at 90°C for 6 minutes, heated to 160°C and baked for 4 minutes, washed with deionized water 3 times, and dried at 50°C for 9 hours to obtain a skin-friendly antibacterial yarn.

[0038] Embodiment 2:

[0039] A method for preparing skin-friendly antibacterial spun yarn, the method for preparing skin-friendly antibacterial spun yarn comprising the following preparation steps:

[0040] (1) 3-amino-1,2,4-triazine, vinylphosphonyl chloride, triethylamine and acetonitrile were mixed in a mass ratio of 1:0.75:1.6):25, stirred at 25°C and 150 rpm for 2 hours, heated to 80°C and refluxed for 8 hours, naturally cooled to room temperature and filtered, washed with deionized water and anhydrous ethanol for 4 times respectively, and dried at 100°C for 9 hours to obtain a phosphorus-nitrogen flame retardant monomer;

[0041] (2) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1:0.3:100, ultrasonicate at 80°C for 1.5 hours, add phosphorus nitrogen flame retardant monomer 1.5 times the mass of cotton cellulose, continue stirring for 3 hours, filter, wash with deionized water 4 times, and dry at 80°C for 12 hours to obtain modified bamboo nanocellulose; Mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1:3:9, stir at 25°C and 250rpm for 48 hours to obtain spinning solution, and perform electrostatic spinning under the conditions of injection pump flow rate of 6.8μL / min, spinning voltage of 17kV, distance between spinneret and drum of 17cm, moving distance on the drum of 15cm, and inner diameter of spinneret of 0.6mm to obtain modified bamboo nanocellulose outer fiber;

[0042] (3) The polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water were mixed in a mass ratio of 1:0.1:0.06:50, sodium hydroxide was added to adjust the pH value of the solution to 8.5, and the solution was taken out after ultrasonic treatment at 25°C for 24 hours, washed with deionized water for 4 times, and dried at 105°C for 12 hours to obtain a pre-modified polyester core yarn; the pre-modified polyester core yarn was immersed in a sodium hypochlorite solution with a pH value of 5, and the solution was taken out after ultrasonic treatment at 25°C for 20 minutes, washed with deionized water for 4 times, and dried at 70°C for 9 hours to obtain a modified polyester core yarn;

[0043] (4) 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water were mixed in a mass ratio of 1:0.33:20, and stirred at 55°C and 250 rpm for 25 min to obtain a cross-linking treatment solution; the modified bamboo nanocellulose outer fiber and the modified polyester core yarn were twisted by a ring spinning machine to obtain a skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber was immersed in the cross-linking treatment solution for 2 h and then taken out, pre-baked at 95°C for 5 min, heated to 165°C and baked for 3 min, washed with deionized water 4 times, and dried at 55°C for 8 h to obtain a skin-friendly antibacterial spun yarn.

[0044] Embodiment 3:

[0045] A method for preparing skin-friendly antibacterial spun yarn, the method for preparing skin-friendly antibacterial spun yarn comprising the following preparation steps:

[0046] (1) 3-amino-1,2,4-triazine, vinylphosphonyl chloride, triethylamine and acetonitrile were mixed in a mass ratio of 1:0.8:1.7:30, stirred at 30° C. and 200 rpm for 1 hour, heated to 85° C. and refluxed for 7 hours, naturally cooled to room temperature and filtered, washed with deionized water and anhydrous ethanol for 5 times respectively, and dried at 105° C. for 8 hours to obtain a phosphorus-nitrogen flame retardant monomer;

[0047] (2) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1:0.4:105, ultrasonicate at 85°C for 1 hour, add phosphorus nitrogen flame retardant monomer twice the mass of cotton cellulose, continue stirring for 2 hours, filter, wash with deionized water 5 times, and dry at 85°C for 11 hours to obtain modified bamboo nanocellulose; Mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1:4:10, stir at 30°C and 300rpm for 47 hours to obtain spinning solution, and perform electrostatic spinning under the conditions of injection pump flow rate of 6.9μL / min, spinning voltage of 18kV, distance between spinneret and drum of 18cm, moving distance on the drum of 16cm, and inner diameter of spinneret of 0.7mm to obtain modified bamboo nanocellulose outer fiber;

[0048] (3) The polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water were mixed in a mass ratio of 1:0.15:0.07:55, sodium hydroxide was added to adjust the pH value of the solution to 9, the solution was ultrasonically treated at 30°C for 23 hours, the solution was taken out, the solution was washed with deionized water for 5 times, and the solution was dried at 110°C for 11 hours to obtain a pre-modified polyester core yarn; the pre-modified polyester core yarn was immersed in a sodium hypochlorite solution with a pH value of 6, the solution was ultrasonically treated at 30°C for 15 minutes, the solution was taken out, the solution was washed with deionized water for 5 times, and the solution was dried at 75°C for 8 hours to obtain a modified polyester core yarn;

[0049] (4) 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water were mixed in a mass ratio of 1:0.34:25, and stirred at 60°C and 300 rpm for 20 min to obtain a cross-linking treatment solution; the modified bamboo nanocellulose outer fiber and the modified polyester core yarn were twisted by a ring spinning machine to obtain a skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber was immersed in the cross-linking treatment solution for 3 h and then taken out, pre-dried at 100°C for 4 min, heated to 170°C and baked for 2 min, washed with deionized water 5 times, and dried at 60°C for 7 h to obtain a skin-friendly antibacterial spun yarn.

[0050] Comparative Example 1:

[0051] A method for preparing skin-friendly antibacterial spun yarn, the method for preparing skin-friendly antibacterial spun yarn comprising the following preparation steps:

[0052] (1) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1:0.3:100, ultrasonicate at 80°C for 1.5 hours, add vinylphosphonyl chloride in an amount 1.5 times the mass of cotton cellulose, continue stirring for 3 hours, filter, wash with deionized water 4 times, and dry at 80°C for 12 hours to obtain modified bamboo nanocellulose; Mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1:3:9, stir at 25°C and 250 rpm for 48 hours to obtain a spinning solution, and perform electrostatic spinning under the conditions of a syringe pump flow rate of 6.8 μL / min, a spinning voltage of 17 kV, a distance between the spinneret and the drum of 17 cm, a moving distance on the drum of 15 cm, and an inner diameter of the spinneret of 0.6 mm to obtain modified bamboo nanocellulose outer fiber;

[0053] (2) Polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water were mixed in a mass ratio of 1:0.1:0.06:50, sodium hydroxide was added to adjust the pH value of the solution to 8.5, the solution was ultrasonically treated at 25°C for 24 hours, the solution was taken out, the solution was washed with deionized water for 4 times, and the solution was dried at 105°C for 12 hours to obtain a pre-modified polyester core yarn; the pre-modified polyester core yarn was immersed in a sodium hypochlorite solution with a pH value of 5, the solution was ultrasonically treated at 25°C for 20 minutes, the solution was taken out, the solution was washed with deionized water for 4 times, and the solution was dried at 70°C for 9 hours to obtain a modified polyester core yarn;

[0054] (3) 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water were mixed in a mass ratio of 1:0.33:20, and stirred at 55°C and 250 rpm for 25 min to obtain a cross-linking treatment solution; the modified bamboo nanocellulose outer fiber and the modified polyester core yarn were twisted using a ring spinning machine to obtain a skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber was immersed in the cross-linking treatment solution for 2 h and then taken out, pre-baked at 95°C for 5 min, heated to 165°C and baked for 3 min, washed with deionized water 4 times, and dried at 55°C for 8 h to obtain a skin-friendly antibacterial spun yarn.

[0055] Comparative Example 2:

[0056] A method for preparing skin-friendly antibacterial spun yarn, the method for preparing skin-friendly antibacterial spun yarn comprising the following preparation steps:

[0057] (1) Bamboo nanocellulose, dichloromethane and dimethyl sulfoxide were mixed in a mass ratio of 1:3:9, stirred at 25°C and 250 rpm for 48 h to obtain a spinning solution, and electrospinning was performed under the conditions of a syringe pump flow rate of 6.8 μL / min, a spinning voltage of 17 kV, a distance between the spinneret and the drum of 17 cm, a moving distance on the drum of 15 cm, and an inner diameter of the spinneret of 0.6 mm to obtain bamboo nanocellulose outer fibers;

[0058] (2) Polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water were mixed in a mass ratio of 1:0.1:0.06:50, sodium hydroxide was added to adjust the pH value of the solution to 8.5, the solution was ultrasonically treated at 25°C for 24 hours, the solution was taken out, the solution was washed with deionized water for 4 times, and the solution was dried at 105°C for 12 hours to obtain a pre-modified polyester core yarn; the pre-modified polyester core yarn was immersed in a sodium hypochlorite solution with a pH value of 5, the solution was ultrasonically treated at 25°C for 20 minutes, the solution was taken out, the solution was washed with deionized water for 4 times, and the solution was dried at 70°C for 9 hours to obtain a modified polyester core yarn;

[0059] (3) 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water were mixed in a mass ratio of 1:0.33:20, and stirred at 55°C and 250 rpm for 25 min to obtain a cross-linking treatment solution; the bamboo nanocellulose outer fiber and the modified polyester core yarn were twisted using a ring spinning machine to obtain a skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber was immersed in the cross-linking treatment solution for 2 h and then taken out, pre-baked at 95°C for 5 min, heated to 165°C and baked for 3 min, washed with deionized water 4 times, and dried at 55°C for 8 h to obtain a skin-friendly antibacterial yarn.

[0060] Comparative Example 3:

[0061] A method for preparing skin-friendly antibacterial spun yarn, the method for preparing skin-friendly antibacterial spun yarn comprising the following preparation steps:

[0062] (1) 3-amino-1,2,4-triazine, vinylphosphonyl chloride, triethylamine and acetonitrile were mixed in a mass ratio of 1:0.75:1.6):25, stirred at 25°C and 150 rpm for 2 hours, heated to 80°C and refluxed for 8 hours, naturally cooled to room temperature and filtered, washed with deionized water and anhydrous ethanol for 4 times respectively, and dried at 100°C for 9 hours to obtain a phosphorus-nitrogen flame retardant monomer;

[0063] (2) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1:0.3:100, ultrasonicate at 80°C for 1.5 hours, add phosphorus nitrogen flame retardant monomer 1.5 times the mass of cotton cellulose, continue stirring for 3 hours, filter, wash with deionized water 4 times, and dry at 80°C for 12 hours to obtain modified bamboo nanocellulose; Mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1:3:9, stir at 25°C and 250rpm for 48 hours to obtain spinning solution, and perform electrostatic spinning under the conditions of injection pump flow rate of 6.8μL / min, spinning voltage of 17kV, distance between spinneret and drum of 17cm, moving distance on the drum of 15cm, and inner diameter of spinneret of 0.6mm to obtain modified bamboo nanocellulose outer fiber;

[0064] (3) The polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water were mixed in a mass ratio of 1:0.1:0.06:50, sodium hydroxide was added to adjust the pH value of the solution to 8.5, and the solution was taken out after ultrasonic treatment at 25°C for 24 hours, washed with deionized water for 4 times, and dried at 105°C for 12 hours to obtain a pre-modified polyester core yarn;

[0065] (4) 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water were mixed in a mass ratio of 1:0.33:20, and stirred at 55°C and 250 rpm for 25 min to obtain a cross-linking treatment solution; the modified bamboo nanocellulose outer fiber and the pre-modified polyester core yarn were twisted using a ring spinning machine to obtain a skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber was immersed in the cross-linking treatment solution for 2 h and then taken out, pre-baked at 95°C for 5 min, heated to 165°C and baked for 3 min, washed with deionized water 4 times, and dried at 55°C for 8 h to obtain a skin-friendly antibacterial spun yarn.

[0066] Comparative Example 4:

[0067] A method for preparing skin-friendly antibacterial spun yarn, the method for preparing skin-friendly antibacterial spun yarn comprising the following preparation steps:

[0068] (1) 3-amino-1,2,4-triazine, vinylphosphonyl chloride, triethylamine and acetonitrile were mixed in a mass ratio of 1:0.75:1.6):25, stirred at 25°C and 150 rpm for 2 hours, heated to 80°C and refluxed for 8 hours, naturally cooled to room temperature and filtered, washed with deionized water and anhydrous ethanol for 4 times respectively, and dried at 100°C for 9 hours to obtain a phosphorus-nitrogen flame retardant monomer;

[0069] (2) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1:0.3:100, ultrasonicate at 80°C for 1.5 hours, add phosphorus nitrogen flame retardant monomer 1.5 times the mass of cotton cellulose, continue stirring for 3 hours, filter, wash with deionized water 4 times, and dry at 80°C for 12 hours to obtain modified bamboo nanocellulose; Mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1:3:9, stir at 25°C and 250rpm for 48 hours to obtain spinning solution, and perform electrostatic spinning under the conditions of injection pump flow rate of 6.8μL / min, spinning voltage of 17kV, distance between spinneret and drum of 17cm, moving distance on the drum of 15cm, and inner diameter of spinneret of 0.6mm to obtain modified bamboo nanocellulose outer fiber;

[0070] (3) 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water were mixed in a mass ratio of 1:0.33:20, and stirred at 55°C and 250 rpm for 25 min to obtain a cross-linking treatment solution; the modified bamboo nanocellulose outer fiber and the polyester filament core yarn were twisted using a ring spinning machine to obtain a skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber was immersed in the cross-linking treatment solution for 2 h and then taken out, pre-baked at 95°C for 5 min, heated to 165°C and baked for 3 min, washed with deionized water 4 times, and dried at 55°C for 8 h to obtain a skin-friendly antibacterial yarn.

[0071] Comparative Example 5:

[0072] A method for preparing skin-friendly antibacterial spun yarn, the method for preparing skin-friendly antibacterial spun yarn comprising the following preparation steps:

[0073] (1) 3-amino-1,2,4-triazine, vinylphosphonyl chloride, triethylamine and acetonitrile were mixed in a mass ratio of 1:0.75:1.6):25, stirred at 25°C and 150 rpm for 2 hours, heated to 80°C and refluxed for 8 hours, naturally cooled to room temperature and filtered, washed with deionized water and anhydrous ethanol for 4 times respectively, and dried at 100°C for 9 hours to obtain a phosphorus-nitrogen flame retardant monomer;

[0074] (2) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1:0.3:100, ultrasonicate at 80°C for 1.5 hours, add phosphorus nitrogen flame retardant monomer 1.5 times the mass of cotton cellulose, continue stirring for 3 hours, filter, wash with deionized water 4 times, and dry at 80°C for 12 hours to obtain modified bamboo nanocellulose; Mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1:3:9, stir at 25°C and 250rpm for 48 hours to obtain spinning solution, and perform electrostatic spinning under the conditions of injection pump flow rate of 6.8μL / min, spinning voltage of 17kV, distance between spinneret and drum of 17cm, moving distance on the drum of 15cm, and inner diameter of spinneret of 0.6mm to obtain modified bamboo nanocellulose outer fiber;

[0075] (3) The polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water were mixed in a mass ratio of 1:0.1:0.06:50, sodium hydroxide was added to adjust the pH value of the solution to 8.5, and the solution was taken out after ultrasonic treatment at 25°C for 24 hours, washed with deionized water for 4 times, and dried at 105°C for 12 hours to obtain a pre-modified polyester core yarn; the pre-modified polyester core yarn was immersed in a sodium hypochlorite solution with a pH value of 5, and the solution was taken out after ultrasonic treatment at 25°C for 20 minutes, washed with deionized water for 4 times, and dried at 70°C for 9 hours to obtain a modified polyester core yarn;

[0076] (4) The modified bamboo nanocellulose outer fiber and the modified polyester core yarn are twisted using a ring spinning machine to obtain skin-friendly and antibacterial spun yarn.

[0077] Test Example 1:

[0078] 1. Skin-friendly

[0079] Test method: The skin-friendly antibacterial spun yarns obtained in each embodiment and the comparative example were woven into fabrics, and the transverse bending stiffness was tested using an electronic stiffness tester LLY-01B according to GB / T18318.

[0080] 2. Antibacterial

[0081] Test method: Take 0.75g of the skin-friendly antibacterial spun yarn obtained in each embodiment and the comparative example, cut them into pieces as the test sample, and select Gram-negative Escherichia coli to culture at 37°C for 18h according to the GB / T20944 oscillation method to obtain a single isolated colony. On the solid culture medium, select a typical colony, transfer it to 20mL of liquid culture medium using an inoculation loop, and culture it at 37°C and an oscillation speed of 120r / min for 20h to obtain a bacterial solution with a specific number of viable bacteria; the test sample Put it into a flask (no sample is added as the control group), add 70mL PBS buffer and 5mL diluted bacterial solution with a specific number of viable bacteria, then shake on a shaker at 37°C and 120rpm for 18h, take 100μL of the bacterial suspension diluted to an appropriate multiple, evenly apply it on the surface of the solid culture medium, and culture it in a sterile environment at a constant temperature of 37°C for 24h, count the single colonies on the solid culture medium W1 (the viable bacteria concentration of the control group W0), and calculate the inhibition rate = (W0-W1) / W0*100%.

[0082] Table 1 below shows the analysis results of the skin-friendly and antibacterial properties of the skin-friendly and antibacterial spun yarns of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0083] Table 1

[0084]

[0085] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 1, it can be found that the skin-friendly and antibacterial spun yarn prepared by the present invention has good skin-friendly and antibacterial properties.

[0086] By comparison, the lateral bending stiffness data of Examples 1, 2, and 3 compared with Comparative Examples 1 to 5 are not much different, indicating that by using natural, environmentally friendly green bamboo nanocellulose as the outer layer of the spinning thread, the natural components in the bamboo cellulose have good compatibility with human skin, thereby improving the skin-friendly and antibacterial spinning thread.

[0087] By comparison, the antibacterial rates of Examples 1, 2, and 3 are higher than those of Comparative Example 3, which illustrates that dopamine is oxidized and self-polymerized under weakly alkaline conditions to form adhesive polydopamine, which is attached to the surface of the polyester filament and then chlorinated with sodium hypochlorite to form a halamine structure that can release oxidized chloride ions, destroy or prevent the normal metabolism of cells, and promote the death of bacteria, thereby improving the antibacterial properties of the skin-friendly and antibacterial yarn.

[0088] Test Example 2:

[0089] 1. Flame retardancy

[0090] Test method: The skin-friendly antibacterial spun yarn obtained in each embodiment and the comparative example were tested for limiting oxygen index according to GB / T2046.

[0091] 2. Mechanical properties

[0092] Test method: The skin-friendly and antibacterial spun yarns obtained in each embodiment and the comparative example were tested for breaking strength σ0 according to GB / T3916, using a constant speed stretching method and a YG068C fully automatic single yarn strength tester at a gauge of 500 mm and a stretching speed of 500 mm / min.

[0093] 3. Anti-aging

[0094] Test method: The skin-friendly antibacterial spun yarns obtained in each embodiment and the comparative example were respectively subjected to a textile ultraviolet accelerated aging tester (Q-LAB, USA) at an ultraviolet wavelength of 315-400nm and a power of 0.89W / m 2 , irradiated at 60℃ for 24h, in accordance with GB / T3916, using constant speed stretching method, using YG068C fully automatic single yarn strength tester, at a gauge of 500mm and a stretching speed of 500mm / min, tested the breaking strength σ1, and calculated the strength retention rate = σ1 / σ0*100%.

[0095] Table 2 below shows the analysis results of the flame retardancy, aging resistance and mechanical properties of the skin-friendly antibacterial spun yarns of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0096] Table 2

[0097] Limiting oxygen index % Breaking strength CN / dtex Strength retention rate % Example 1 33.6 11.83 84.1 Example 2 33.9 11.87 84.6 Example 3 33.2 11.86 83.8 Comparative Example 1 29.4 11.82 82.5 Comparative Example 2 22.6 11.79 83.2 Comparative Example 3 32.8 11.75 82.7 Comparative Example 4 33.0 8.62 83.4 Comparative Example 5 33.2 6.19 59.6

[0098] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 5 in Table 2, it can be found that the skin-friendly antibacterial spun yarn prepared by the present invention has good flame retardancy, aging resistance and mechanical properties.

[0099] By comparison, the limiting oxygen index of Examples 1, 2, and 3 is higher than that of Comparative Example 1, which indicates that grafting triazine nitrogen heterocycle onto vinylphosphonyl chloride can release non-flammable gas during pyrolysis, increase the gas phase flame retardant effect, and improve the flame retardant properties of skin-friendly and antibacterial spinning yarn.

[0100] By comparison, the limiting oxygen index of Examples 1, 2, and 3 is higher than that of Comparative Example 2, which indicates that the use of ammonium cerium nitrate as an initiator to oxidize the hydroxyl-grafted phosphorus-nitrogen flame-retardant monomer based on vinylphosphonyl chloride on bamboo nanocellulose can release phosphorus-containing free radicals to capture and quench the free radicals in the combustion, while promoting the dehydration of the matrix into carbon, forming a dense carbon layer that is oxygen-insulated and heat-insulating, cutting off the heat exchange in the combustion, and improving the flame retardant properties of the skin-friendly and antibacterial spinning yarn.

[0101] By comparison, the breaking strength of Examples 1, 2, and 3 is higher than that of Comparative Example 4, which indicates that the spun yarn is impregnated and finished by 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and the anhydride forms a carboxyl group after 3,3',4,4'-benzophenonetetracarboxylic dianhydride is dissolved in hot water. Under high-temperature baking, it can undergo esterification reaction with the hydroxyl group of the polydopamine layer on the modified polyester core yarn to form a cross-linked network, thereby improving the mechanical properties of the skin-friendly and antibacterial spun yarn.

[0102] By comparison, the breaking strength and strength retention rate of Examples 1, 2, and 3 are higher than those of Comparative Example 5, which indicates that after 3,3',4,4'-benzophenonetetracarboxylic dianhydride is dissolved in hot water, the anhydride forms a carboxyl group, which can react with the hydroxyl groups on the modified bamboo nanocellulose outer fiber and the hydroxyl groups on the polydopamine layer on the modified polyester core yarn under high-temperature baking to form a cross-linked network, thereby improving the mechanical properties of the skin-friendly antibacterial spinning yarn; at the same time, the π-π and n-π electron transitions in the 3,3',4,4'-benzophenonetetracarboxylic dianhydride molecules, the electronic interaction between the transitions and the conjugation effect show a strong absorption effect in the ultraviolet light region, thereby improving the anti-ultraviolet aging performance of the skin-friendly antibacterial spinning yarn.

[0103] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A skin-friendly antibacterial spinning yarn, characterized in that: The skin-friendly antibacterial spun yarn is obtained by twisting modified bamboo nanocellulose outer fiber and modified polyester core yarn with a ring spinning machine and then reacting with 3,3',4,4'-benzophenone tetracarboxylic dianhydride; The modified polyester core yarn is obtained by successively dipping polyester filaments in dopamine hydrochloride and sodium hypochlorite; The modified bamboo nanocellulose outer fiber is obtained by activating bamboo nanocellulose with ammonium cerium nitrate, grafting phosphorus and nitrogen flame retardant monomers, and then performing electrostatic spinning; The phosphorus-nitrogen flame retardant monomer is obtained by reacting 3-amino-1,2,4-triazine with vinylphosphonyl chloride.

2. A method for preparing skin-friendly antibacterial spinning yarn, characterized in that: The method comprises the following preparation steps: (1) 3-amino-1,2,4-triazine, vinylphosphonyl chloride, triethylamine and acetonitrile are mixed in a mass ratio of 1:(0.7-0.8):(1.5-1.7):(20-30), stirred at 20-30° C. and 100-200 rpm for 1-3 h, heated to 75-85° C. and refluxed for 7-9 h, naturally cooled to room temperature and filtered, washed with deionized water and anhydrous ethanol for 3-5 times respectively, and dried at 95-105° C. for 8-10 h to obtain a phosphorus-nitrogen flame retardant monomer; (2) Mix bamboo nanocellulose, ammonium cerium nitrate and deionized water in a mass ratio of 1: (0.2-0.4): (95-105), ultrasonicate at 75-85° C. for 1-2 hours, add phosphorus-nitrogen flame retardant monomer in an amount of 1-2 times the mass of cotton cellulose, continue stirring for 2-4 hours, filter, wash with deionized water for 3-5 times, and dry at 75-85° C. for 11-13 hours to obtain modified bamboo nanocellulose; mix modified bamboo nanocellulose, dichloromethane and dimethyl sulfoxide in a mass ratio of 1: (2-4): (8-10), stir at 20-30° C. and 200-300 rpm for 47-49 hours to obtain a spinning solution; electrospin the spinning solution to obtain modified bamboo nanocellulose outer fiber; (3) Polyester filament, dopamine hydrochloride, tris(hydroxymethyl)aminomethane) and deionized water are mixed in a mass ratio of 1:(0.05-0.15):(0.05-0.07):(45-55), sodium hydroxide is added to adjust the pH value of the solution to 8-9, ultrasonically treated at 20-30°C for 23-25 ​​hours, taken out, washed with deionized water for 3-5 times, and dried at 100-110°C for 11-13 hours to obtain a pre-modified polyester core yarn; the pre-modified polyester core yarn is immersed in a sodium hypochlorite solution with a pH value of 4-6, ultrasonically treated at 20-30°C for 15-25 minutes, taken out, washed with deionized water for 3-5 times, and dried at 65-75°C for 8-10 hours to obtain a modified polyester core yarn; (4) The modified bamboo nanocellulose outer fiber and the modified polyester core yarn are twisted by a ring spinning machine to obtain skin-friendly antibacterial fiber; the skin-friendly antibacterial fiber is immersed in a cross-linking treatment solution for 1 to 3 hours and then taken out, pre-baked at 90 to 100° C. for 4 to 6 minutes, heated to 160 to 170° C. and baked for 2 to 4 minutes, washed with deionized water for 3 to 5 times, and dried at 50 to 60° C. for 7 to 9 hours to obtain skin-friendly antibacterial spun yarn.

3. The method for preparing a skin-friendly antibacterial spinning yarn according to claim 2, characterized in that: The reaction equation of the phosphorus-nitrogen flame retardant monomer in step (1) is:

4. The method for preparing a skin-friendly antibacterial spinning yarn according to claim 2, characterized in that: The reaction equation for modifying the bamboo nanocellulose in step (2) is:

5. The method for preparing a skin-friendly antibacterial spinning yarn according to claim 2, characterized in that: The electrospinning process parameters of step (2) are: injection pump flow rate 6.7-6.9 μL / min, spinning voltage 16-18 kV, distance between spinneret and drum 16-18 cm, moving distance on the drum 14-16 cm, spinneret inner diameter 0.5-0.7 mm.

6. The method for preparing a skin-friendly antibacterial spinning yarn according to claim 2, characterized in that: The cross-linking treatment solution in step (4) is obtained by mixing 3,3',4,4'-benzophenonetetracarboxylic dianhydride, sodium hypophosphite and deionized water in a mass ratio of 1:(0.32-0.34):(15-25), and stirring at 50-60° C. and 200-300 rpm for 20-30 min.

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