An anti-pilling layered composite fabric, a preparation method and application thereof

Abstract

The application relates to the technical field of multi-layer composite fabrics, and discloses an anti-pilling layered composite fabric, a preparation method and application. Quaternary ammonium organosilicon modified polyurethane and quaternary ammonium polyamide amine modified nano-silver are prepared, the two are finished on a polyester-cotton fabric through a light reaction with acrylic acid, the hydrophilicity of the quaternary ammonium polymer material is used to improve the moisture absorption and antistatic performance of the fabric, meanwhile, the functional components are crosslinked into a film through a light curing reaction and an esterification reaction, and are fixed on the polyester-cotton fabric, so that the movement of fibers is limited, and the anti-pilling performance of the fabric is improved.

Description

Technical Field

[0001] This invention relates to the field of multilayer composite fabric technology, specifically to an anti-pilling layered composite fabric, its preparation method, and its application. Background Technology

[0002] During use, textiles are constantly subjected to friction, causing the fiber ends to protrude from the fabric surface, creating numerous fuzzy fibers, a phenomenon known as "pilling." Under the continuous action of external force and static electricity, these fibers that fail to detach in time can become entangled, forming numerous small fuzz balls that adhere to the fabric surface and are difficult to remove, a phenomenon known as "pilling." Pilling occurs on both natural and synthetic fibers, but it is more pronounced and prominent in synthetic fibers. For example, in fabrics containing polyester fibers, due to the high tensile strength of polyester fibers, the resulting small balls are difficult to remove from the fabric surface, severely affecting the appearance and feel of the fabric.

[0003] Methods to prevent pilling in fabrics can be divided into two categories: physical methods and chemical methods. Physical methods mainly consider fiber properties, yarn, and fabric structure, while chemical methods involve treating the fabric with chemical reagents to improve its anti-pilling properties. Resin finishing is one of the effective methods for achieving anti-pilling properties in textiles; however, commercially available resin finishing agents can worsen the hand feel of the treated fabric, affecting its breathability and moisture absorption, thus impacting wearing comfort.

[0004] Polyester-cotton knitted fabrics are comfortable and elastic, but they are prone to snagging during use, causing pilling and fuzzing on the fabric surface, which affects the fabric's appearance and wearing comfort. Therefore, it is necessary to develop an anti-pilling finishing agent to treat polyester-cotton knitted fabrics, giving them anti-pilling properties without affecting their moisture absorption. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide an anti-pilling layered composite fabric, its preparation method, and its application. By preparing quaternized organosilicon-modified polyurethane and quaternized polyamide amine-modified nano-silver, these two materials are combined with acrylic acid and applied to a polyester-cotton fabric through a photo-irradiation reaction. The hydrophilicity of the quaternized polymer material improves the moisture absorption and antistatic properties of the fabric, while the functional components are cross-linked into a network film through photocuring and esterification reactions and fixed onto the polyester-cotton fabric, restricting fiber movement and thus improving the anti-pilling properties of the fabric.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing an anti-pilling layered composite fabric includes the following steps: Step (1): Mix hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether, add chloroplatinic acid in a nitrogen atmosphere, and react. After the reaction is completed, epoxy-terminated polyether silicone oil is obtained. The epoxy-terminated polyether silicone oil, dimethylallylamine, acetic acid, and isopropanol were mixed and the reaction continued. After the reaction was completed, the mixture was rotary evaporated to obtain the quaternized polyether silicone oil. Step (2): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react. After the reaction is complete, add quaternized polyether silicone oil and p-hydroxyanisole and continue the reaction. After the reaction is complete, the modified polyurethane is obtained. Step (3): Ultrasonically mix the modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water, and photoinitiator to obtain an anti-pilling finishing liquid; The quaternized polyamide amine modified silver nanoparticles are prepared by the following steps: S1. Mix N,N'-methylenebisacrylamide and water evenly, add 1-(2-aminoethyl)piperazine and aminated nano-silver, react, cool, filter, wash and dry to obtain polyamide amine modified nano-silver. S2. Mix polyamide-modified nano-silver with methanol, disperse by ultrasonication, add dimethyl diallyl ammonium chloride, react, filter, wash, and dry to obtain quaternized polyamide-modified nano-silver. Step (4): Impregnate the washed polyester-cotton fabric with anti-pilling finishing solution, bake, react, and dry to obtain anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer and inner layers, bonded together, aligned, and sewn to obtain an anti-pilling layered composite fabric.

[0007] Preferably, in step (1): the molar ratio of hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether is 1:2-2.2; the added mass of chloroplatinic acid is 0.03-0.05% of the total mass of hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether; the reaction conditions are: reaction at 60-90℃ for 4-6 hours.

[0008] Preferably, in step (1), the mass ratio of terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid, and isopropanol is 90:14-15:12:35-45; the reaction conditions are: to continue the reaction for 8-10 hours in a nitrogen atmosphere at a temperature of 60-80°C.

[0009] Preferably, in step (2): the molar ratio of isophorone diisocyanate to polyethylene glycol is 2.5-3:1; the added mass of dibutyltin dilaurate is 0.1-0.5% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; the added mass of quaternized polyether silicone oil is equal to the added mass of polyethylene glycol; and the added mass of p-hydroxyanisole is 0.1-0.3% of the added mass of quaternized polyether silicone oil.

[0010] Preferably, in step (2), the reaction conditions are: reacting at 60-70℃ for 1-4 hours; and the conditions for continued reaction are: continuing the reaction at 60-70℃ for 1-3 hours.

[0011] Preferably, in step (3), the mass ratio of modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water, and photoinitiator is 10-15:3-5:8-10:100:2-3.

[0012] Preferably, in step (3), when preparing quaternized polyamide amine modified silver nanoparticles, the mass ratio of N,N'-methylenebisacrylamide, water, 1-(2-aminoethyl)piperazine, and aminated silver nanoparticles in S1 is 3:30-50:2-2.5:0.5-1.5; the reaction conditions are: reacting at 20-30℃ for 60-72h.

[0013] Preferably, in step (3), when preparing quaternized polyamide amine modified nano-silver, the mass ratio of polyamide amine modified nano-silver, dimethyl diallyl ammonium chloride, and methanol in S2 is 1:8-10:30; the addition conditions of dimethyl diallyl ammonium chloride are: added in a nitrogen atmosphere at a temperature of 0-5℃; the reaction conditions are: reacted in a nitrogen atmosphere at 30-40℃ for 10-20h.

[0014] Preferably, in step (4): the washed polyester-cotton fabric is prepared by immersing the polyester-cotton fabric in a 1wt% sodium dodecyl sulfonate aqueous solution with a bath ratio of 1:30, ultrasonically cleaning for 30 min, taking it out, washing it again with ethanol and water in sequence, and drying it.

[0015] Preferably, in step (4): the ratio of the washed polyester-cotton fabric to the anti-pilling finishing liquid is 1:10-50; the padding operation includes: immersing the washed polyester-cotton fabric in the anti-pilling finishing liquid for 5-10 minutes, then taking it out, and performing two dips and two paddings with a padding rate of 60-80%; the baking conditions are: baking at 180℃ for 3-5 minutes; the reaction conditions are: reacting under ultraviolet light with a wavelength of 365nm for 60-90 seconds.

[0016] Preferably, an anti-pilling layered composite fabric is prepared using the method described above for preparing anti-pilling layered composite fabric.

[0017] Preferably, an application of the anti-pilling layered composite fabric as described above on a fabric.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention prepares quaternized organosilicon-modified polyurethane and quaternized polyamide amine-modified nano-silver, and then applies them to polyester-cotton fabric via photo-irradiation reaction with acrylic acid. By utilizing the hydrophilicity of the quaternized polymer materials to improve the fabric's moisture absorption and antistatic properties, the functional components are cross-linked into a network film through photocuring and esterification reactions, and then fixed onto the polyester-cotton fabric, restricting fiber movement and thus improving the fabric's anti-pilling properties.

[0019] This invention introduces epoxy groups into hydrogen-terminated silicone oil via hydrosilylation, and then introduces dimethylallylamine to produce a quaternized polyether silicone oil with a quaternary ammonium salt structure, hydroxyl groups, and carbon-carbon double bonds. The quaternized polyether silicone oil is introduced into polyurethane by reacting hydroxyl groups with isocyanate groups. The resulting modified polyurethane has improved hydrophilicity due to the presence of polyether segments and a quaternary ammonium salt structure, and can be further crosslinked through carbon-carbon double bonds.

[0020] In this invention, N,N'-methylenebisacrylamide, 1-(2-aminoethyl)piperazine, and aminated nano-silver undergo a Michael addition reaction to produce polyamide amine modified nano-silver. Dimethyl diallyl ammonium chloride is then introduced to perform surface grafting, resulting in quaternized polyamide amine modified nano-silver containing carbon-carbon double bonds. This nano-silver is then mixed with modified polyurethane, acrylic acid, a photoinitiator, and water to prepare an anti-pilling finishing solution. When finishing polyester-cotton fabrics, the carboxyl groups of acrylic acid can undergo esterification with the hydroxyl groups of cotton fibers. The photo-irradiation reaction causes the functional components to cross-link and form a network film, which is then deposited on the fabric surface. This improves the anti-pilling and anti-wrinkle properties of the fabric while also enhancing its moisture absorption and antistatic properties. Attached Figure Description

[0021] Figure 1 This is a bar chart showing the moisture absorption performance of the anti-pilling layered composite fabrics prepared in Examples 1-5 and Comparative Examples 1-2 of this invention during performance testing. Figure 2 This is a line graph showing the electrostatic voltage half-life of the anti-pilling layered composite fabrics prepared in Examples 1-5 and Comparative Examples 1-2 of this invention during performance testing. Figure 3 This is a schematic diagram of the structure of the anti-pilling layered composite fabric prepared in this invention; In the picture, Figure 3 In the diagram, 1 represents the outer fabric and 2 represents the inner fabric. Detailed Implementation

[0022] The present invention will be further illustrated below through specific embodiments. The following embodiments are specific implementations of the present invention, but the implementation of the present invention is not limited to the following embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and are included within the protection scope of the present invention.

[0023] Example 1 This embodiment discloses a method for preparing an anti-pilling layered composite fabric, including the following steps: Step (1): Hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether are mixed, and chloroplatinic acid catalyst is added in a nitrogen atmosphere. The mixture is reacted at 80°C for 4 hours. After the reaction is completed, epoxy-terminated polyether silicone oil is obtained. The molar ratio of hydrogen-terminated silicone oil to allyl polyoxyethylene polyoxypropylene glycidyl ether is 1:2; the added mass of chloroplatinic acid is 0.03% of the sum of the masses of hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether. Terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid and isopropanol were mixed in a mass ratio of 90:14:12:35 and reacted at 70°C for 8 hours under a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation to obtain quaternized polyether silicone oil. Step (2): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react at 60°C for 2.5 h. After the reaction is complete, add quaternized polyether silicone oil and p-hydroxyanisole and continue to react at 60°C for 1 h. After the reaction is complete, the modified polyurethane is obtained. The molar ratio of isophorone diisocyanate to polyethylene glycol is 3:1; the added mass of dibutyltin dilaurate is 0.3% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; the added mass of quaternized polyether silicone oil is equal to the added mass of polyethylene glycol; and the added mass of p-hydroxyanisole is 0.1% of the added mass of quaternized polyether silicone oil. Step (3): The modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water and photoinitiator are ultrasonically mixed at a mass ratio of 10:3:8:100:2 to obtain an anti-pilling finishing liquid. The quaternized polyamide amine modified silver nanoparticles are prepared by the following steps: S1. N,N'-methylenebisacrylamide and water were mixed evenly, and 1-(2-aminoethyl)piperazine and aminated nano-silver were added. The mixture was reacted at 30°C for 60 h. After the reaction was completed, the mixture was cooled to room temperature, filtered with acetone and washed, and dried at 40°C for 48 h to obtain polyamide-amine modified nano-silver. The mass ratio of N,N'-methylenebisacrylamide, water, 1-(2-aminoethyl)piperazine, and amino-modified nanosilver is 3:30:2:1. S2. Mix polyamide-modified nano-silver with methanol and ultrasonically disperse for 20 min. Add dimethyl diallyl ammonium chloride in a nitrogen atmosphere at 0 °C and heat to 35 °C for 12 h. After the reaction is complete, filter with acetone and wash. Dry at 40 °C for 12 h to obtain quaternized polyamide-modified nano-silver. The mass ratio of polyamide-modified nano-silver, dimethyl diallyl ammonium chloride, and methanol is 1:8:30. Step (4): Immerse the polyester-cotton fabric in a 1wt% sodium dodecyl sulfonate aqueous solution with a bath ratio of 1:30, ultrasonically clean for 30 min, take it out, wash it again with ethanol and water in sequence, and dry it at 80℃ for 1 h to obtain the washed polyester-cotton fabric. The washed polyester-cotton fabric was immersed in an anti-pilling finishing solution with a liquor ratio of 1:30 for 5-10 minutes. After immersion, it was taken out and subjected to two dips and two nips with a nips ratio of 70%. It was then baked at 180°C for 3 minutes, reacted under ultraviolet light at a wavelength of 365nm for 60 seconds, and dried at 60°C for 24 hours to obtain an anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer and inner layers, bonded together, aligned, and sewn to obtain an anti-pilling layered composite fabric.

[0024] Example 2 This embodiment discloses a method for preparing an anti-pilling layered composite fabric, including the following steps: Step (1): Hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether are mixed, and chloroplatinic acid catalyst is added in a nitrogen atmosphere. The mixture is reacted at 80°C for 4 hours. After the reaction is completed, epoxy-terminated polyether silicone oil is obtained. The molar ratio of hydrogen-terminated silicone oil to allyl polyoxyethylene polyoxypropylene glycidyl ether is 1:2.1; the added mass of chloroplatinic acid is 0.03% of the sum of the masses of hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether. Terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid and isopropanol were mixed in a mass ratio of 90:14.3:12:40 and reacted at 70°C for 9 hours under a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation to obtain quaternized polyether silicone oil. Step (2): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react at 60°C for 2.5 h. After the reaction is complete, add quaternized polyether silicone oil and p-hydroxyanisole and continue to react at 60°C for 1 h. After the reaction is complete, the modified polyurethane is obtained. The molar ratio of isophorone diisocyanate to polyethylene glycol is 3:1; the added mass of dibutyltin dilaurate is 0.3% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; the added mass of quaternized polyether silicone oil is equal to the added mass of polyethylene glycol; and the added mass of p-hydroxyanisole is 0.1% of the added mass of quaternized polyether silicone oil. Step (3): The modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water and photoinitiator are ultrasonically mixed in a mass ratio of 12:3.5:8.5:100:2.5 to obtain an anti-pilling finishing liquid; The quaternized polyamide amine modified silver nanoparticles are prepared by the following steps: S1. N,N'-methylenebisacrylamide and water were mixed evenly, and 1-(2-aminoethyl)piperazine and aminated nano-silver were added. The mixture was reacted at 30°C for 60 h. After the reaction was completed, the mixture was cooled to room temperature, filtered with acetone and washed, and dried at 40°C for 48 h to obtain polyamide-amine modified nano-silver. The mass ratio of N,N'-methylenebisacrylamide, water, 1-(2-aminoethyl)piperazine, and amino-modified nanosilver is 3:30:2:1. S2. Mix polyamide-modified nano-silver with methanol and ultrasonically disperse for 20 min. Add dimethyl diallyl ammonium chloride in a nitrogen atmosphere at 0 °C and heat to 35 °C for 12 h. After the reaction is complete, filter with acetone and wash. Dry at 40 °C for 12 h to obtain quaternized polyamide-modified nano-silver. The mass ratio of polyamide-modified nano-silver, dimethyl diallyl ammonium chloride, and methanol is 1:8.5:30. Step (4): Immerse the polyester-cotton fabric in a 1wt% sodium dodecyl sulfonate aqueous solution with a bath ratio of 1:30, ultrasonically clean for 30 min, take it out, wash it again with ethanol and water in sequence, and dry it at 80℃ for 1 h to obtain the washed polyester-cotton fabric. The washed polyester-cotton fabric was immersed in an anti-pilling finishing solution with a liquor ratio of 1:30 for 5-10 minutes. After immersion, it was taken out and subjected to two dips and two nips with a nips ratio of 70%. It was then baked at 180°C for 4 minutes, reacted under ultraviolet light at a wavelength of 365nm for 60 seconds, and dried at 60°C for 24 hours to obtain an anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer and inner layers, bonded together, aligned, and sewn to obtain an anti-pilling layered composite fabric.

[0025] Example 3 This embodiment discloses a method for preparing an anti-pilling layered composite fabric, including the following steps: Step (1): Hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether are mixed, and chloroplatinic acid catalyst is added in a nitrogen atmosphere. The mixture is reacted at 80°C for 4 hours. After the reaction is completed, epoxy-terminated polyether silicone oil is obtained. The molar ratio of hydrogen-terminated silicone oil to allyl polyoxyethylene polyoxypropylene glycidyl ether is 1:2.1; the added mass of chloroplatinic acid is 0.03% of the sum of the masses of hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether. Terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid and isopropanol were mixed in a mass ratio of 90:14.5:12:40 and reacted at 70°C for 9 hours under a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation to obtain quaternized polyether silicone oil. Step (2): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react at 60°C for 2.5 h. After the reaction is complete, add quaternized polyether silicone oil and p-hydroxyanisole and continue to react at 60°C for 1 h. After the reaction is complete, the modified polyurethane is obtained. The molar ratio of isophorone diisocyanate to polyethylene glycol is 3:1; the added mass of dibutyltin dilaurate is 0.3% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; the added mass of quaternized polyether silicone oil is equal to the added mass of polyethylene glycol; and the added mass of p-hydroxyanisole is 0.1% of the added mass of quaternized polyether silicone oil. Step (3): The modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water and photoinitiator are ultrasonically mixed at a mass ratio of 13:4:9:100:2.5 to obtain an anti-pilling finishing liquid; The quaternized polyamide amine modified silver nanoparticles are prepared by the following steps: S1. N,N'-methylenebisacrylamide and water were mixed evenly, and 1-(2-aminoethyl)piperazine and aminated nano-silver were added. The mixture was reacted at 30°C for 60 h. After the reaction was completed, the mixture was cooled to room temperature, filtered with acetone and washed, and dried at 40°C for 48 h to obtain polyamide-amine modified nano-silver. The mass ratio of N,N'-methylenebisacrylamide, water, 1-(2-aminoethyl)piperazine, and amino-modified nanosilver is 3:30:2:1. S2. Mix polyamide-modified nano-silver with methanol and ultrasonically disperse for 20 min. Add dimethyl diallyl ammonium chloride in a nitrogen atmosphere at 0 °C and heat to 35 °C for 12 h. After the reaction is complete, filter with acetone and wash. Dry at 40 °C for 12 h to obtain quaternized polyamide-modified nano-silver. The mass ratio of polyamide-modified nano-silver, dimethyl diallyl ammonium chloride, and methanol is 1:9:30. Step (4): Immerse the polyester-cotton fabric in a 1wt% sodium dodecyl sulfonate aqueous solution with a bath ratio of 1:30, ultrasonically clean for 30 min, take it out, wash it again with ethanol and water in sequence, and dry it at 80℃ for 1 h to obtain the washed polyester-cotton fabric. The washed polyester-cotton fabric was immersed in an anti-pilling finishing solution with a liquor ratio of 1:30 for 5-10 minutes. After immersion, it was taken out and subjected to two dips and two nips with a nips ratio of 70%. It was then baked at 180°C for 4 minutes, reacted under ultraviolet light at a wavelength of 365nm for 60 seconds, and dried at 60°C for 24 hours to obtain an anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer and inner layers, bonded together, aligned, and sewn to obtain an anti-pilling layered composite fabric.

[0026] Example 4 This embodiment discloses a method for preparing an anti-pilling layered composite fabric, including the following steps: Step (1): Hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether are mixed, and chloroplatinic acid catalyst is added in a nitrogen atmosphere. The mixture is reacted at 80°C for 4 hours. After the reaction is completed, epoxy-terminated polyether silicone oil is obtained. The molar ratio of hydrogen-terminated silicone oil to allyl polyoxyethylene polyoxypropylene glycidyl ether is 1:2.1; the added mass of chloroplatinic acid is 0.03% of the sum of the masses of hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether. Terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid and isopropanol were mixed in a mass ratio of 90:14.8:12:40 and reacted at 70°C for 9 hours under a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation to obtain quaternized polyether silicone oil. Step (2): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react at 60°C for 2.5 h. After the reaction is complete, add quaternized polyether silicone oil and p-hydroxyanisole and continue to react at 60°C for 1 h. After the reaction is complete, the modified polyurethane is obtained. The molar ratio of isophorone diisocyanate to polyethylene glycol is 3:1; the added mass of dibutyltin dilaurate is 0.3% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; the added mass of quaternized polyether silicone oil is equal to the added mass of polyethylene glycol; and the added mass of p-hydroxyanisole is 0.1% of the added mass of quaternized polyether silicone oil. Step (3): Modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water, and photoinitiator are ultrasonically mixed at a mass ratio of 14:4.5:9.5:100:2.5 to obtain an anti-pilling finishing liquid; The quaternized polyamide amine modified silver nanoparticles are prepared by the following steps: S1. N,N'-methylenebisacrylamide and water were mixed evenly, and 1-(2-aminoethyl)piperazine and aminated nano-silver were added. The mixture was reacted at 30°C for 60 h. After the reaction was completed, the mixture was cooled to room temperature, filtered with acetone and washed, and dried at 40°C for 48 h to obtain polyamide-amine modified nano-silver. The mass ratio of N,N'-methylenebisacrylamide, water, 1-(2-aminoethyl)piperazine, and amino-modified nanosilver is 3:30:2:1. S2. Mix polyamide-modified nano-silver with methanol and ultrasonically disperse for 20 min. Add dimethyl diallyl ammonium chloride in a nitrogen atmosphere at 0 °C and heat to 35 °C for 12 h. After the reaction is complete, filter with acetone and wash. Dry at 40 °C for 12 h to obtain quaternized polyamide-modified nano-silver. The mass ratio of polyamide-modified nano-silver, dimethyl diallyl ammonium chloride, and methanol is 1:9.5:30. Step (4): Immerse the polyester-cotton fabric in a 1wt% sodium dodecyl sulfonate aqueous solution with a bath ratio of 1:30, ultrasonically clean for 30 min, take it out, wash it again with ethanol and water in sequence, and dry it at 80℃ for 1 h to obtain the washed polyester-cotton fabric. The washed polyester-cotton fabric was immersed in an anti-pilling finishing solution with a liquor ratio of 1:30 for 5-10 minutes. After immersion, it was taken out and subjected to two dips and two nips with a nips ratio of 70%. It was then baked at 180°C for 4 minutes, reacted under ultraviolet light at a wavelength of 365nm for 60 seconds, and dried at 60°C for 24 hours to obtain an anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer and inner layers, bonded together, aligned, and sewn to obtain an anti-pilling layered composite fabric.

[0027] Example 5 This embodiment discloses a method for preparing an anti-pilling layered composite fabric, including the following steps: Step (1): Hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether are mixed, and chloroplatinic acid catalyst is added in a nitrogen atmosphere. The mixture is reacted at 80°C for 4 hours. After the reaction is completed, epoxy-terminated polyether silicone oil is obtained. The molar ratio of hydrogen-terminated silicone oil to allyl polyoxyethylene polyoxypropylene glycidyl ether is 1:2.2; the added mass of chloroplatinic acid is 0.03% of the sum of the masses of hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether. Terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid and isopropanol were mixed in a mass ratio of 90:15:12:45 and reacted at 70°C for 10 h in a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation to obtain quaternized polyether silicone oil. Step (2): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react at 60°C for 2.5 h. After the reaction is complete, add quaternized polyether silicone oil and p-hydroxyanisole and continue to react at 60°C for 1 h. After the reaction is complete, the modified polyurethane is obtained. The molar ratio of isophorone diisocyanate to polyethylene glycol is 3:1; the added mass of dibutyltin dilaurate is 0.3% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; the added mass of quaternized polyether silicone oil is equal to the added mass of polyethylene glycol; and the added mass of p-hydroxyanisole is 0.1% of the added mass of quaternized polyether silicone oil. Step (3): The modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water and photoinitiator are ultrasonically mixed in a mass ratio of 15:5:10:100:3 to obtain an anti-pilling finishing liquid. The quaternized polyamide amine modified silver nanoparticles are prepared by the following steps: S1. N,N'-methylenebisacrylamide and water were mixed evenly, and 1-(2-aminoethyl)piperazine and aminated nano-silver were added. The mixture was reacted at 30°C for 60 h. After the reaction was completed, the mixture was cooled to room temperature, filtered with acetone and washed, and dried at 40°C for 48 h to obtain polyamide-amine modified nano-silver. The mass ratio of N,N'-methylenebisacrylamide, water, 1-(2-aminoethyl)piperazine, and amino-modified nanosilver is 3:30:2:1. S2. Mix polyamide-modified nano-silver with methanol and ultrasonically disperse for 20 min. Add dimethyl diallyl ammonium chloride in a nitrogen atmosphere at 0 °C and heat to 35 °C for 12 h. After the reaction is complete, filter with acetone and wash. Dry at 40 °C for 12 h to obtain quaternized polyamide-modified nano-silver. The mass ratio of polyamide-modified nano-silver, dimethyl diallyl ammonium chloride, and methanol is 1:10:30. Step (4): Immerse the polyester-cotton fabric in a 1wt% sodium dodecyl sulfonate aqueous solution with a bath ratio of 1:30, ultrasonically clean for 30 min, take it out, wash it again with ethanol and water in sequence, and dry it at 80℃ for 1 h to obtain the washed polyester-cotton fabric. The washed polyester-cotton fabric was immersed in an anti-pilling finishing solution with a liquor ratio of 1:30 for 5-10 minutes. After immersion, it was taken out and subjected to two dips and two nips with a nips ratio of 70%. It was then baked at 180°C for 5 minutes, reacted under ultraviolet light at a wavelength of 365nm for 60 seconds, and dried at 60°C for 24 hours to obtain an anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer and inner layers, bonded together, aligned, and sewn to obtain an anti-pilling layered composite fabric.

[0028] Comparative Example 1 This comparative example discloses a method for preparing an anti-pilling layered composite fabric, comprising the following steps: Step (1): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react at 60°C for 2.5 h. After the reaction is complete, add hydroxyl-terminated polydimethylsiloxane and continue the reaction at 60°C for 1 h. After the reaction is complete, the modified polyurethane is obtained. The molar ratio of isophorone diisocyanate to polyethylene glycol is 3:1; the added mass of dibutyltin dilaurate is 0.3% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; and the added mass of dihydroxyl-terminated polydimethylsiloxane is equal to the added mass of polyethylene glycol. Step (2): The modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water and photoinitiator are ultrasonically mixed at a mass ratio of 10:3:8:100:2 to obtain an anti-pilling finishing liquid. The quaternized polyamide amine modified silver nanoparticles are prepared by the following steps: S1. N,N'-methylenebisacrylamide and water were mixed evenly, and 1-(2-aminoethyl)piperazine and aminated nano-silver were added. The mixture was reacted at 30°C for 60 h. After the reaction was completed, the mixture was cooled to room temperature, filtered with acetone and washed, and dried at 40°C for 48 h to obtain polyamide-amine modified nano-silver. The mass ratio of N,N'-methylenebisacrylamide, water, 1-(2-aminoethyl)piperazine, and amino-modified nanosilver is 3:30:2:1. S2. Mix polyamide-modified nano-silver with methanol and ultrasonically disperse for 20 min. Add dimethyl diallyl ammonium chloride in a nitrogen atmosphere at 0 °C and heat to 35 °C for 12 h. After the reaction is complete, filter with acetone and wash. Dry at 40 °C for 12 h to obtain quaternized polyamide-modified nano-silver. The mass ratio of polyamide-modified nano-silver, dimethyl diallyl ammonium chloride, and methanol is 1:8:30. Step (3): Immerse the polyester-cotton fabric in a 1wt% sodium dodecyl sulfonate aqueous solution with a bath ratio of 1:30, ultrasonically clean for 30 min, take it out, wash it again with ethanol and water in sequence, and dry it at 80℃ for 1 h to obtain the washed polyester-cotton fabric. The washed polyester-cotton fabric was immersed in an anti-pilling finishing solution with a liquor ratio of 1:30 for 5-10 minutes. After immersion, it was taken out and subjected to two dips and two nips with a nips ratio of 70%. It was then baked at 180°C for 3 minutes, reacted under ultraviolet light at a wavelength of 365nm for 60 seconds, and dried at 60°C for 24 hours to obtain an anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer and inner layers, bonded together, aligned, and sewn to obtain an anti-pilling layered composite fabric.

[0029] Comparative Example 2 This comparative example discloses a method for preparing an anti-pilling layered composite fabric, comprising the following steps: Step (1): Hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether are mixed, and chloroplatinic acid catalyst is added in a nitrogen atmosphere. The mixture is reacted at 80°C for 4 hours. After the reaction is completed, epoxy-terminated polyether silicone oil is obtained. The molar ratio of hydrogen-terminated silicone oil to allyl polyoxyethylene polyoxypropylene glycidyl ether is 1:2; the added mass of chloroplatinic acid is 0.03% of the sum of the masses of hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether. Terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid and isopropanol were mixed in a mass ratio of 90:14:12:35 and reacted at 70°C for 8 hours under a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation to obtain quaternized polyether silicone oil. Step (2): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react at 60°C for 2.5 h. After the reaction is complete, add quaternized polyether silicone oil and p-hydroxyanisole and continue to react at 60°C for 1 h. After the reaction is complete, the modified polyurethane is obtained. The molar ratio of isophorone diisocyanate to polyethylene glycol is 3:1; the added mass of dibutyltin dilaurate is 0.3% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; the added mass of quaternized polyether silicone oil is equal to the added mass of polyethylene glycol; and the added mass of p-hydroxyanisole is 0.1% of the added mass of quaternized polyether silicone oil. Step (3): The modified polyurethane, nano silver, acrylic acid, water and photoinitiator are ultrasonically mixed in a mass ratio of 10:3:8:100:2 to obtain an anti-pilling finishing liquid. Step (4): Immerse the polyester-cotton fabric in a 1wt% sodium dodecyl sulfonate aqueous solution with a bath ratio of 1:30, ultrasonically clean for 30 min, take it out, wash it again with ethanol and water in sequence, and dry it at 80℃ for 1 h to obtain the washed polyester-cotton fabric. The washed polyester-cotton fabric was immersed in an anti-pilling finishing solution with a liquor ratio of 1:30 for 5-10 minutes. After immersion, it was taken out and subjected to two dips and two nips with a nips ratio of 70%. It was then baked at 180°C for 3 minutes, reacted under ultraviolet light at a wavelength of 365nm for 60 seconds, and dried at 60°C for 24 hours to obtain an anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer and inner layers, bonded together, aligned, and sewn to obtain an anti-pilling layered composite fabric.

[0030] In the above examples and comparative examples: the hydrogen-terminated silicone oil was a double-terminated silicone oil with a Mw of 880; the aminated nano-silver was from Xi'an Qiyue Biotechnology Co., Ltd., with a particle size of 20-40nm and product number Q-0087007; the polyethylene glycol was PEG2000; the polyester-cotton fabric was a polyester-cotton blended knitted fabric with a weight of 130-150g / m2; and the double-terminated hydroxyl polydimethylsiloxane had a Mw of 1000.

[0031] Test case The anti-pilling layered composite fabrics prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests. The specific test results are shown in Table 1. Table 1

[0032] The tests for each indicator in Table 1 were conducted according to the following standards: anti-pilling properties were determined according to GB / T 4802.3 "Textiles - Determination of Pilling Properties - Part 3: Pilling Box Method"; moisture absorption properties were determined according to GB / T12704.1-2009 "Textiles - Test Method for Moisture Permeability - Part 1: Moisture Absorption Method"; and antistatic properties were expressed by the electrostatic voltage half-life and determined according to GB / T12703 "Evaluation of Electrostatic Properties of Textiles".

[0033] As can be seen from the test results in Table 1, the layered composite fabric prepared by this invention has good moisture absorption and antistatic properties, as well as excellent anti-pilling properties. This is because the anti-pilling finishing liquid containing quaternized organosilicon-modified polyurethane, quaternized polyamide amine-modified nano-silver, and acrylic acid is applied to the polyester-cotton fabric through a photo-irradiation reaction. The hydrophilicity of the quaternized polymer material improves the moisture absorption and antistatic properties of the fabric, while the functional components are cross-linked into a network film through photocuring and esterification reactions and fixed on the polyester-cotton fabric, restricting fiber movement and thus improving the anti-pilling properties of the fabric. Among them, the modified polyurethane has polyether segments and quaternary ammonium salt structure, and the quaternized polyamide amine-modified nano-silver has a quaternary ammonium salt structure. Therefore, the hydrophilic and moisture absorption properties of the fabric are improved after finishing, and the antistatic properties are also improved.

[0034] In Comparative Example 1, replacing the quaternized polyether silicone oil with hydroxyl-terminated polydimethylsiloxane resulted in a decrease in the hydrophilicity of the modified polyurethane, and it could not crosslink with other functional components to form a film through photocuring, thus affecting the anti-pilling properties of the fabric. Therefore, the anti-pilling, moisture absorption, and antistatic properties of Comparative Example 1 were inferior to those of the Example.

[0035] In Comparative Example 2, the quaternized polyamide amine modified nano-silver was replaced with nano-silver. Nano-silver is prone to agglomeration, and since the quaternized polyamide amine lacks the effect of improving hydrophilic and antistatic properties, the moisture absorption and antistatic properties of Comparative Example 2 are not as good as those of the Example.

[0036] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing an anti-pilling layered composite fabric, characterized in that, Includes the following steps: Step (1): Mix isophorone diisocyanate, polyethylene glycol and dibutyltin dilaurate and react. After the reaction is complete, add quaternized polyether silicone oil and p-hydroxyanisole and continue the reaction. After the reaction is complete, the modified polyurethane is obtained. The quaternized polyether silicone oil is prepared by the following steps: S1. Hydrogen-terminated silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether are mixed, and chloroplatinic acid is added in a nitrogen atmosphere. After the reaction is completed, epoxy-terminated polyether silicone oil is obtained. S2. Mix terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid, and isopropanol, and continue the reaction. After the reaction is completed, rotary evaporate to obtain quaternized polyether silicone oil. Step (2): Ultrasonically mix modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water, and photoinitiator to obtain an anti-pilling finishing liquid; The quaternized polyamide amine modified silver nanoparticles are prepared by the following steps: S1. Mix N,N'-methylenebisacrylamide and water evenly, add 1-(2-aminoethyl)piperazine and aminated nano-silver, react, cool, filter, wash and dry to obtain polyamide amine modified nano-silver. S2. Mix polyamide-modified nano-silver with methanol, disperse by ultrasonication, add dimethyl diallyl ammonium chloride, react, filter, wash, and dry to obtain quaternized polyamide-modified nano-silver. Step (3): Impregnate the washed polyester-cotton fabric with anti-pilling finishing solution, bake, react under ultraviolet light with a wavelength of 365nm for 60-90s, and dry to obtain anti-pilling polyester-cotton single-layer fabric. Anti-pilling polyester-cotton single-layer fabric is used as the outer layer and combined with the inner layer to obtain an anti-pilling layered composite fabric.

2. The method for preparing an anti-pilling layered composite fabric according to claim 1, characterized in that, In step (1), when preparing quaternized polyether silicone oil, in S1: the molar ratio of terminal hydrogen-containing silicone oil to allyl polyoxyethylene polyoxypropylene glycidyl ether is 1:2-2.2; the added mass of chloroplatinic acid is 0.03-0.05% of the total mass of terminal hydrogen-containing silicone oil and allyl polyoxyethylene polyoxypropylene glycidyl ether; the reaction conditions are: reaction at 60-90℃ for 4-6 hours; in S2: the mass ratio of terminal epoxy polyether silicone oil, dimethylallylamine, acetic acid, and isopropanol is 90:14-15:12:35-45; the continued reaction conditions are: continued reaction at 60-80℃ in a nitrogen atmosphere for 8-10 hours.

3. The method for preparing an anti-pilling layered composite fabric according to claim 1, characterized in that, In step (1): the molar ratio of isophorone diisocyanate to polyethylene glycol is 2.5-3:1; the added mass of dibutyltin dilaurate is 0.1-0.5% of the sum of the masses of isophorone diisocyanate and polyethylene glycol; the added mass of quaternized polyether silicone oil is equal to the added mass of polyethylene glycol; the added mass of p-hydroxyanisole is 0.1-0.3% of the added mass of quaternized polyether silicone oil; the reaction conditions are: reacting at 60-70℃ for 1-4 hours; the continued reaction conditions are: continuing the reaction at 60-70℃ for 1-3 hours.

4. The method for preparing an anti-pilling layered composite fabric according to claim 1, characterized in that, In step (2), the mass ratio of modified polyurethane, quaternized polyamide amine modified nano silver, acrylic acid, water, and photoinitiator is 10-15:3-5:8-10:100:2-3.

5. The method for preparing an anti-pilling layered composite fabric according to claim 1, characterized in that, In step (2), when preparing quaternized polyamide amine modified nano-silver, in S1, the mass ratio of N,N'-methylenebisacrylamide, water, 1-(2-aminoethyl)piperazine, and aminated nano-silver is 3:30-50:2-2.5:0.5-1.5; the reaction conditions are: reacting at 20-30℃ for 60-72h; in S2, the mass ratio of polyamide amine modified nano-silver, dimethyl diallyl ammonium chloride, and methanol is 1:8-10:30; the addition conditions of dimethyl diallyl ammonium chloride are: added in a nitrogen atmosphere at 0-5℃; the reaction conditions are: reacting in a nitrogen atmosphere at 30-40℃ for 10-20h.

6. The method for preparing an anti-pilling layered composite fabric according to claim 1, characterized in that, In step (3): the ratio of the washed polyester-cotton fabric to the anti-pilling finishing liquid is 1:10-50; the padding operation includes: immersing the washed polyester-cotton fabric in the anti-pilling finishing liquid for 5-10 minutes, then taking it out, and performing two dips and two paddings with a padding rate of 60-80%; the baking conditions are: baking at 180℃ for 3-5 minutes.

7. An anti-pilling layered composite fabric prepared by the preparation method of the anti-pilling layered composite fabric as described in any one of claims 1-6.

8. An application of the anti-pilling layered composite fabric as described in claim 7 on a fabric.

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