Deodorizing skin-friendly fabric and preparation method thereof

Abstract

The invention discloses a deodorant skin-friendly fabric and a preparation method thereof, and relates to the field of fiber fabrics. When the deodorant skin-friendly fabric is prepared, microcrystalline cellulose sequentially reacts with ethylene (chloromethyl) dimethoxysilane and 1-amino-4-butylguanidine dihydrochloride, and modified cellulose is prepared; the preparation method comprises the following steps: polymerizing dimethyl terephthalate, 2-vinyl propane-1, 3-diol and ethylene glycol, and reacting with mercaptopropyl methyl dimethoxy silane to prepare modified polyester; the preparation method comprises the following steps: reacting anhydrous citric acid with cysteamine hydrochloride to prepare an ultraviolet absorbent; the preparation method comprises the following steps: reacting 3-[(2, 3)-epoxypropoxy] propyl methyl dimethoxy silane with DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) to prepare modified siloxane; and mixing the modified polyester and the modified cellulose, spinning, and sequentially carrying out surface treatment by using an ultraviolet absorbent and a silane mixed solution to obtain the deodorant skin-friendly fabric. The deodorant skin-friendly fabric prepared by the invention has flame-retardant and durable capabilities.

Description

TECHNICAL FIELD

[0001] The application relates to the field of fiber fabrics, in particular to a deodorizing skin-friendly fabric and a preparation method thereof. BACKGROUND

[0002] Natural fibers are the earliest textile materials used by human beings, and the moisture absorption and air permeability of cotton and hemp and the temperature control characteristics of mulberry silk lay a foundation for wearing requirements, but traditional materials have defects such as easy wrinkling and difficult care, which promotes the birth of artificial fibers, and polyester fabric is an artificial synthetic fabric made of polyester fiber, the fabric has the characteristics of strong wrinkle resistance, good shape retention, wear resistance and heat resistance due to the compact and symmetrical molecular chain structure, and is widely applied to garment fabrics.

[0003] Sweat itself has no smell, but the odor-causing bacteria (such as corynebacterium) on the surface of the skin can decompose organic matter (such as sebum and keratin) in sweat to produce volatile malodorous substances such as ammonia, acetic acid and isovaleric acid, and early addition of essence can cover up the odor, but the odor molecules are not actually eliminated, and the smell after mixing may be more irritating, therefore, the application introduces a deodorizing skin-friendly fabric and a preparation method thereof. SUMMARY

[0004] The application aims to provide a deodorizing skin-friendly fabric and a preparation method thereof to solve the problems in the prior art.

[0005] A deodorizing skin-friendly fabric is prepared by mixing modified polyester and modified cellulose, spinning, and then sequentially performing surface treatment with an ultraviolet absorber and a silane mixed solution.

[0006] The silane mixed solution is prepared by mixing modified siloxane, hydroxymethyl triethoxysilane, dimethoxydimethylsilane and deionized water.

[0007] The modified siloxane is prepared by reacting 3-[(2,3)-epoxypropoxy]propyl methyldimethoxysilane and DOPO.

[0008] The ultraviolet absorber is prepared by reacting anhydrous citric acid and cysteamine hydrochloride.

[0009] The modified polyester is prepared by polymerizing dimethyl terephthalate, 2-vinyl propane-1,3-diol and ethylene glycol, and then reacting with mercaptopropyl methyldimethoxysilane.

[0010] The modified cellulose is prepared by sequentially reacting microcrystalline cellulose with ethylene (chloromethyl) dimethoxysilane and 1-amino-4-butyl guanidine dihydrochloride.

[0011] A preparation method of a deodorizing skin-friendly fabric mainly includes the following preparation steps.

[0012] (1) mixing pre-modified cellulose, 1-amino-4-butyl guanidine dihydrochloride and ethanol according to the mass ratio of 4.8-5.2:1:24-26, stirring at 76-78℃ and 200-300r / min for 23.5-24.5h, filtering, washing with ethanol for 4-6 times, and vacuum drying at 60-70℃ for 11.5-12.5h to obtain modified cellulose;

[0013] (2) mixing pre-modified polyester, mercaptopropyl methyl dimethoxysilane, azobis isobutyronitrile and ethanol according to the mass ratio of 9-11:1.8-2.2:0.6-0.8:34-36, stirring at 200-300r / min for 3-4min, heating to 68-72℃, continuing to stir for 2.8-3.2h, adding 2,6-di-tert-butyl-4-methyl phenol solution of 0.2-0.3 times of the mass of pre-modified polyester, cooling to room temperature, filtering, washing with ethanol for 4-6 times, and vacuum drying at 40-50℃ for 13-14h to obtain modified polyester;

[0014] (3) soaking pre-modified composite fiber in silane mixed solution for 1-2min, taking out, until no liquid drops drop, standing at 78-82℃ for 2-2.4h, washing with deionized water for 6-8 times, vacuum drying at -10-0℃ for 23-25h to obtain modified composite fiber; spinning the modified composite fiber, weaving to obtain deodorant skin-friendly fabric.

[0015] As an optimization, the pre-modified cellulose in step (1) is prepared by mixing microcrystalline cellulose, dimethyl sulfoxide and ethylene (chloromethyl) dimethoxysilane according to the mass ratio of 1:32-34:0.94-0.96, stirring at 85-95℃ and 200-300r / min for 11.5-12.5h, pouring into deionized water, standing for 12-14min, filtering, washing with deionized water for 6-8 times, vacuum drying at 45-55℃ for 11.5-12.5h, and crushing to 8-10 mesh.

[0016] As an optimization, the pre-modified polyester in step (2) is prepared by mixing dimethyl terephthalate, 2-vinyl propane-1,3-diol, ethylene glycol and sodium acetate according to the molar ratio of 9-11:2-3:7-8:0.1-0.2, stirring at 250-260℃ and 200-300r / min under nitrogen protection for 11.5-12.5h, cooling to room temperature, and crushing to 8-10 mesh.

[0017] As optimization, the silane mixed solution in step (3) is prepared by mixing modified siloxane, hydroxymethyl triethoxysilane, dimethoxydimethylsilane and deionized water in a mass ratio of 1:3-4:6-7:28-32, adjusting pH to 4.6-5.4 with 0.1 mol / L hydrochloric acid aqueous solution, stirring at room temperature at 200-300 r / min for 5-7 min, and preparing.

[0018] As optimization, the modified siloxane is prepared by taking 3-[(2,3)-epoxypropoxy] propyl methyldimethoxysilane 1 part, DOPO 1 part and triphenylphosphine 0.04-0.06 parts in mole fraction, heating DOPO to 128-132℃, standing for 9-11 min, adding 3-[(2,3)-epoxypropoxy] propyl methyldimethoxysilane and triphenylphosphine, stirring at 200-300 r / min under nitrogen protection for 9.5-10.5 h, and cooling to room temperature.

[0019] As optimization, the pre-modified composite fiber in step (3) is prepared by uniformly mixing ultraviolet absorber and dichloromethane in a mass ratio of 1:12-14 to prepare an ultraviolet absorber solution, immersing the composite fiber in the ultraviolet absorber solution for 1-2 min, taking it out until no liquid drops fall, and standing at 250-260℃ for 40-50 min.

[0020] As optimization, the composite fiber is prepared by stirring modified polyester at 258-262℃ and 200-240 r / min for 12-16 min, adding modified cellulose in an amount of 0.3-0.4 times the mass of the modified polyester, continuing to stir for 18-22 min, melt spinning, spinning temperature 260-264℃, extrusion rate 36-40 r / min, winding speed 15-17 r / min, drawing at room temperature to 3-5 times, drawing at 126-128℃ to 8-10 times, and finally setting at 136-138℃ for 100-110 s.

[0021] As optimization, the ultraviolet absorber is prepared by mixing anhydrous citric acid, cysteamine hydrochloride and deionized water in a mass ratio of 1.8-2:1.1-1.2:9-11, stirring at 200-300 r / min for 5-7 min, standing at 125-135℃ for 11.5-12.5 h, cooling to room temperature, washing with deionized water for 8-10 times, and vacuum drying at 78-82℃ for 23-25 h.

[0022] As optimization, the spinning in step (3) refers to spinning by using FA320A high-speed drawing frame, THC2015 type full-automatic doffer roving frame, TH598 type spinning frame and GMR001 type small-sized winding frame in sequence, and the drawing process is: 6 ends are adopted for doubling, and the draft ratio is 1.4-1.6 times; the roving process is: the draft ratio in the rear zone is 1.2-1.24 times, the roving twist factor is 118-122, and the roving weight is 6g / (10m); the spinning process is: the draft ratio in the rear zone is 1.15-1.17 times, the gauge block specification is 3.0mm, and the spindle rotating speed is 10000-12000rpm.

[0023] Compared with the prior art, the present application has the following beneficial effects:

[0024] In the preparation of the deodorizing skin-friendly fabric, the microcrystalline cellulose is sequentially reacted with ethylene (chloromethyl) dimethoxysilane and 1-amino-4-butyl guanidine dihydrochloride to prepare modified cellulose; dimethyl terephthalate, 2-vinyl propane-1,3-diol and ethylene glycol are polymerized and then reacted with mercaptopropyl methyl dimethoxysilane to prepare modified polyester; anhydrous citric acid and cysteamine hydrochloride are reacted to prepare an ultraviolet absorber; 3-[(2,3)-epoxypropoxy] propyl methyl dimethoxysilane is reacted with DOPO to prepare modified siloxane; the modified polyester and the modified cellulose are mixed, spun, and then surface treated with the ultraviolet absorber and the silane mixture in sequence to prepare the deodorizing skin-friendly fabric.

[0025] First, the microcrystalline cellulose is sequentially reacted with ethylene (chloromethyl) dimethoxysilane and 1-amino-4-butyl guanidine dihydrochloride to prepare modified cellulose; the microcrystalline cellulose is sequentially reacted with ethylene (chloromethyl) dimethoxysilane to provide a site for siloxane polymerization, facilitating the formation of polysiloxane on the material surface; and then reacted with 1-amino-4-butyl guanidine dihydrochloride, introducing guanidine on the material surface through the reaction of amino and alkene, which can destroy the structure and stability of the cell membrane by electrostatic interaction with the phospholipid molecules on the cell membrane of bacteria, increase the permeability of the cell membrane, and cause the leakage of intracellular substances, and can also combine with the polysaccharide components in the bacterial cell wall to hinder the synthesis and repair of the cell wall, so that the integrity of the bacterial cell wall is destroyed, and the normal morphology and function of the cell cannot be maintained, thereby achieving the antibacterial effect; the organic matter in the sweat will be decomposed by the odor-causing bacteria on the skin surface to produce volatile malodorous substances such as ammonia, acetic acid and isovaleric acid, and the guanidine introduced plays a role in killing bacteria to achieve the purpose of deodorization.

[0026] Secondly, dimethyl terephthalate, 2-vinyl propane-1, 3-diol, ethylene glycol are polymerized and then reacted with mercaptopropyl methyl dimethoxysilane to prepare a modified polyester; anhydrous citric acid and cysteamine hydrochloride are reacted to prepare a UV absorber; 3-[(2,3)-epoxy propoxy] propyl methyl dimethoxysilane and DOPO are reacted to prepare a modified siloxane; the modified polyester is mixed with modified cellulose, spun, and then surface treated with a UV absorber and a silane mixture in sequence to prepare a deodorizing skin-friendly fabric; anhydrous citric acid and cysteamine hydrochloride are reacted to form a pyridone structure, and the pyridone molecular structure contains a pyridone ring conjugated system, which can absorb UV light energy and convert it into heat energy under UV irradiation, thereby achieving the purpose of resisting photoaging; 3-[(2,3)-epoxy propoxy] propyl methyl dimethoxysilane and DOPO are reacted to introduce an organic phosphorus flame retardant, which can produce phosphoric acid, metaphosphoric acid, poly-metaphosphoric acid and other substances when decomposed, and these compounds have strong dehydration properties, which can promote the dehydration and carbonization of the polymer surface to form a protective layer to isolate oxygen and heat transfer and inhibit the continuous combustion reaction, and the free radicals generated by decomposition can capture hydrogen radicals in the gas phase, thereby interrupting the combustion chain reaction to achieve the flame retardation effect; the surface of the fabric is surface treated with a silane mixture to form a polysiloxane on the surface of the material, the polysiloxane molecular backbone is composed of siloxane bonds, which belongs to a non-polar molecular structure and has low solubility with polar substances such as oil and moisture on the surface of human skin, and can form a stable protective layer on the skin surface, and this structural characteristic can reduce the direct contact area with the skin, reduce the friction feeling and improve the smoothness of the skin; at the same time, the siloxane radicals released by the decomposition of polysiloxane can capture active radicals in the combustion chain reaction, thereby interrupting the combustion chain reaction, and a dense silicon-containing carbon layer can be formed on the surface of the material to isolate heat and oxygen and inhibit the escape of flammable gas, thereby playing a physical barrier role and achieving the flame retardation effect together with the organic phosphorus. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0028] The spinning in the following examples and comparative examples refers to the yarns made by using FA320A high-speed drawing frame, THC2015 type automatic doffer roving frame, TH598 type spinning frame and GMR001 type small-sized winding frame in sequence, and the drawing process: 6 ends of doubling, draft ratio 1.5 times; the roving process: draft ratio 1.22 times in the back zone, roving twist factor 120, roving weight 6 g / (10 m); the spinning process: draft ratio 1.16 times in the back zone, gauge block specification 3.0 mm, spindle speed 11000 rpm.

[0029] Example 1:

[0030] A preparation method of a deodorant skin-friendly fabric mainly comprises the following preparation steps:

[0031] (1) Microcrystalline cellulose, dimethyl sulfoxide and ethylene (chloromethyl) dimethoxysilane are mixed in a mass ratio of 1:32:0.94, stirred at 85°C and 200 r / min for 11.5 h, poured into deionized water, left for 12 min, filtered, washed with deionized water for 6 times, vacuum dried at 45°C for 11.5 h, and crushed to 8 mesh to obtain pre-modified cellulose; the pre-modified cellulose, 1-amino-4-butyl guanidine dihydrochloride and ethanol are mixed in a mass ratio of 4.8:1:24, stirred at 76°C and 200 r / min for 23.5 h, filtered, washed with ethanol for 4 times, and vacuum dried at 60°C for 11.5 h to obtain modified cellulose;

[0032] (2) Dimethyl terephthalate, 2-vinyl propane-1,3-diol, ethylene glycol and sodium acetate are mixed in a molar ratio of 9:2:7:0.1, stirred at 250°C and 200 r / min under nitrogen protection for 11.5 h, cooled to room temperature, and crushed to 8 mesh to obtain pre-modified polyester; the pre-modified polyester, mercaptopropyl methyl dimethoxysilane, azobisisobutyronitrile and ethanol are mixed in a mass ratio of 9:1.8:0.6:34, stirred at 200 r / min for 3 min, heated to 68°C, and continuously stirred for 2.8 h, 0.2 times of 2,6-di-tert-butyl-4-methylphenol solution of the mass of the pre-modified polyester is added, cooled to room temperature, filtered, washed with ethanol for 4 times, and vacuum dried at 40°C for 13 h to obtain modified polyester;

[0033] (3) Anhydrous citric acid, cysteamine hydrochloride and deionized water were mixed in a mass ratio of 1.8:1.1:9, stirred at 200 r / min for 5 min, allowed to stand at 125°C for 11.5 h, cooled to room temperature, washed 8 times with deionized water, and vacuum dried at 78°C for 23 h to prepare a UV absorber; 1 part of 3-[(2,3)-epoxypropoxy]propylmethyldimethoxysilane, 1 part of DOPO and 0.04 parts of triphenylphosphine were taken in molar proportions, and DOPO was heated to 128°C. , let it stand for 9 minutes, add 3-[(2,3)-epoxypropyloxy]propylmethyldimethoxysilane and triphenylphosphine, stir at 200r / min, under nitrogen protection for 9.5h, cool to room temperature to obtain modified siloxane; stir the modified polyester at 258℃ and 200r / min for 12min, add modified cellulose with a mass of 0.3 times that of the modified polyester, continue stirring for 18min, melt spinning, spinning temperature 260℃, extrusion rate 36r / min, winding rate 15r / min, stretched to 3 times at room temperature, then drawn to 8 times at 126℃, and finally fixed at 136℃ for 100s to obtain a composite fiber; the ultraviolet absorber and dichloromethane were mixed evenly in a mass ratio of 1:12 to obtain an ultraviolet absorber solution, the composite fiber was immersed in the ultraviolet absorber solution for 1 minute, taken out, and allowed to stand at 250℃ for 40 minutes to obtain a pre-modified composite fiber; modified siloxane, hydroxymethyltriethoxysilane, dimethoxydimethylsilane and deoxysilane were added. Deionized water was mixed in a mass ratio of 1:3:6:28, the pH was adjusted to 4.6 with a 0.1 mol / L hydrochloric acid aqueous solution, and the mixture was stirred at 200 r / min at room temperature for 5 min to obtain a silane mixture; the pre-modified composite fiber was immersed in the silane mixture for 1 min, taken out until no liquid dripped, and allowed to stand at 78°C for 2 h, washed with deionized water 6 times, and vacuum dried at -10°C for 23 h to obtain a modified composite fiber; the modified composite fiber was spun and woven to obtain a deodorizing skin-friendly fabric.

[0034] Example 2:

[0035] A method for preparing a deodorizing skin-friendly fabric mainly comprises the following preparation steps:

[0036] (1) Microcrystalline cellulose, dimethyl sulfoxide and ethylene (chloromethyl) dimethoxysilane were mixed in a mass ratio of 1:33:0.95, stirred at 90°C and 250 r / min for 12 h, poured into deionized water, allowed to stand for 13 min, filtered, washed with deionized water 7 times, vacuum dried at 50°C for 12 h, and crushed to 9 mesh to obtain pre-modified cellulose; pre-modified cellulose, 1-amino-4-butylguanidine dihydrochloride and ethanol were mixed in a mass ratio of 5:1:25, stirred at 77°C and 250 r / min for 24 h, filtered, washed with ethanol 5 times, and vacuum dried at 65°C for 12 h to obtain modified cellulose;

[0037] (2) Dimethyl terephthalate, 2-vinyl propane-1, 3-diol, ethylene glycol and sodium acetate were mixed in a molar ratio of 10:2.5:7.5:0.15, stirred at 255℃, 250r / min under nitrogen protection for 12h, cooled to room temperature, crushed to 9 mesh, and a pre-modified polyester was prepared; the pre-modified polyester, mercaptopropyl methyl dimethoxysilane, azobisdimethyl valeronitrile and ethanol were mixed in a mass ratio of 10:2:0.7:35, stirred at 250r / min for 3.5min, heated to 70℃, and continued to stir for 3h; a solution of 2, 6-di-tert-butyl-4-methyl phenol with a mass of 0.25 times that of the pre-modified polyester was added, cooled to room temperature, filtered, washed with ethanol for 5 times, and vacuum dried at 45℃ for 13.5h to prepare a modified polyester;

[0038] (3) Anhydrous citric acid, cysteamine hydrochloride and deionized water were mixed in a mass ratio of 1.9:1.15:10, stirred at 250r / min for 6min, and left at 130℃ for 12h; cooled to room temperature, washed with deionized water for 9 times, and vacuum dried at 80℃ for 24h to prepare a UV absorber; 3-[(2,3)-epoxypropoxy] propyl methyl dimethoxysilane, DOPO and triphenylphosphine were taken in a molar fraction of 1 part, 1 part and 0.05 part respectively, DOPO was heated to 130℃, and left for 10min; 3-[(2,3)-epoxypropoxy] propyl methyl dimethoxysilane and triphenylphosphine were added, stirred at 250r / min under nitrogen protection for 10h, and cooled to room temperature to prepare a modified siloxane; the modified polyester was stirred at 260℃, 220r / min for 14min, and the modified cellulose with a mass of 0.35 times that of the modified polyester was added, and continued to stir for 20min; melt spinning was performed with a spinning temperature of 262℃, an extrusion rate of 38r / min, a winding rate of 16r / min, drawing at room temperature to 4 times, drawing at 127℃ to 9 times, and finally setting at 137℃ for 105s to prepare a composite fiber; the UV absorber and dichloromethane were mixed in a mass ratio of 1:13 to prepare a UV absorber solution; the composite fiber was soaked in the UV absorber solution for 1.5min, taken out, and dripped until no liquid drops were observed; the pre-modified composite fiber was left at 255℃ for 45min to prepare a pre-modified composite fiber; the modified siloxane, hydroxymethyl triethoxysilane, dimethoxy dimethyl silane and deionized water were mixed in a mass ratio of 1:3.5:6.5:30, and the pH was adjusted to 5 with 0.1mol / L hydrochloric acid solution; stirred at room temperature, 250r / min for 6min to prepare a silane mixture; the pre-modified composite fiber was soaked in the silane mixture for 1.5min, taken out, and dripped until no liquid drops were observed; left at 80℃ for 2.2h, washed with deionized water for 7 times, and vacuum dried at-5℃ for 24h to prepare a modified composite fiber; the modified composite fiber was spun and woven to prepare a deodorant skin-friendly fabric.

[0039] Example 3

[0040] A preparation method of a deodorant skin-friendly fabric, mainly comprising the following preparation steps:

[0041] (1) Microcrystalline cellulose, dimethyl sulfoxide and ethylene (chloromethyl) dimethoxysilane are mixed in a mass ratio of 1:34:0.96, stirred at 95℃ and 300r / min for 12.5h, poured into deionized water, and then placed for 14min. After filtration, the product is washed with deionized water for 8 times, vacuum dried at 55℃ for 12.5h, and then crushed to 10 mesh to obtain a pre-modified cellulose; the pre-modified cellulose, 1-amino-4-butyl guanidine dihydrochloride and ethanol are mixed in a mass ratio of 5.2:1:26, stirred at 78℃ and 300r / min for 24.5h, filtered, washed with ethanol for 6 times, and then vacuum dried at 70℃ for 12.5h to obtain a modified cellulose;

[0042] (2) Dimethyl terephthalate, 2-vinyl propane-1,3-diol, ethylene glycol and sodium acetate are mixed in a molar ratio of 11:3:8:0.2, stirred at 260℃ and 300r / min under nitrogen protection for 12.5h, cooled to room temperature, and then crushed to 10 mesh to obtain a pre-modified polyester; the pre-modified polyester, mercaptopropyl methyl dimethoxysilane, azobis isobutyronitrile and ethanol are mixed in a mass ratio of 11:2.2:0.8:36, stirred at 300r / min for 4min, heated to 72℃, and then continuously stirred for 3.2h. A 2,6-di-tert-butyl-4-methyl phenol solution with a mass of 0.3 times that of the pre-modified polyester is added, and then the mixture is cooled to room temperature, filtered, washed with ethanol for 6 times, and then vacuum dried at 50℃ for 14h to obtain a modified polyester;

[0043] (3) anhydrous citric acid, cysteamine hydrochloride and deionized water were mixed in a mass ratio of 2:1.2:11, stirred at 300 r / min for 7 min, and then left to stand at 135℃ for 12.5 h. After cooling to room temperature, the mixture was washed with deionized water for 10 times and vacuum dried at 82℃ for 25 h to obtain an ultraviolet absorber. 3-[(2,3)-epoxypropoxy]propyl methyl dimethoxysilane, DOPO and triphenylphosphine were taken in a molar ratio of 1:1:0.06. The DOPO was heated to 132℃ and left to stand for 11 min. Then 3-[(2,3)-epoxypropoxy]propyl methyl dimethoxysilane and triphenylphosphine were added. The mixture was stirred at 300 r / min under nitrogen protection for 10.5 h and then cooled to room temperature to obtain a modified siloxane. The modified polyester was stirred at 262℃ and 240 r / min for 16 min. Then the modified cellulose was added in an amount of 0.4 times the mass of the modified polyester. The mixture was continuously stirred for 22 min and then melt spun. The spinning temperature was 264℃, the extrusion rate was 40 r / min, the winding rate was 17 r / min, the drawing ratio was 5 times at room temperature, the drawing ratio was 10 times at 128℃, and finally the setting temperature was 138℃ for 110 s to obtain a composite fiber. The ultraviolet absorber and dichloromethane were mixed in a mass ratio of 1:14 to obtain an ultraviolet absorber solution. The composite fiber was soaked in the ultraviolet absorber solution for 2 min, taken out, and left to stand at 260℃ for 50 min to obtain a pre-modified composite fiber. The modified siloxane, hydroxymethyl triethoxysilane, dimethoxydimethylsilane and deionized water were mixed in a mass ratio of 1:4:7:32. The pH was adjusted to 5.4 with 0.1 mol / L hydrochloric acid solution. The mixture was stirred at room temperature and 300 r / min for 7 min to obtain a silane mixture. The pre-modified composite fiber was soaked in the silane mixture for 2 min, taken out, and left to stand at 82℃ for 2.4 h. The fiber was washed with deionized water for 8 times and vacuum dried at 0℃ for 25 h to obtain a modified composite fiber. The modified composite fiber was spun and woven to obtain a deodorizing skin-friendly fabric.

[0044] Comparative Example 1

[0045] The preparation method of the deodorizing skin-friendly fabric of Comparative Example 1 is different from that of Example 2 in that the microcrystalline cellulose is not modified. The other steps are the same as those of Example 2.

[0046] Comparative Example 2

[0047] The preparation method of the deodorizing skin-friendly fabric of Comparative Example 2 is different from that of Example 2 in that step (3) is changed to: mixing anhydrous citric acid, cysteamine hydrochloride and deionized water in a mass ratio of 2:1.2:11, stirring at 300 r / min for 7 min, standing at 135℃ for 12.5 h, cooling to room temperature, washing 10 times with deionized water, and vacuum drying at 82℃ for 25 h to obtain an ultraviolet absorber; mixing the modified polyester at 262℃ and stirring at 240 r / min for 16 min, adding 0.4 times the mass of the modified cellulose to the modified polyester, continuing to stir for 22 min, melt spinning, spinning temperature 264℃, extrusion rate 40 r / min, winding speed 17 r / min, drawing to 5 times at room temperature, drawing to 10 times at 128℃, and finally setting at 138℃ for 110 s to obtain a composite fiber; mixing the ultraviolet absorber and dichloromethane in a mass ratio of 1:14 to obtain an ultraviolet absorber solution, immersing the composite fiber in the ultraviolet absorber solution for 2 min, taking it out until no liquid drops fall, standing at 260℃ for 50 min to obtain a pre-modified composite fiber; mixing hydroxymethyl triethoxysilane, dimethoxydimethylsilane and deionized water in a mass ratio of 4:7:32, adjusting the pH to 5.4 with 0.1 mol / L hydrochloric acid aqueous solution, stirring at room temperature and 300 r / min for 7 min to obtain a silane mixture; immersing the pre-modified composite fiber in the silane mixture for 2 min, taking it out until no liquid drops fall, standing at 82℃ for 2.4 h, washing 8 times with deionized water, and vacuum drying at 0℃ for 25 h to obtain a modified composite fiber; spinning the modified composite fiber, weaving, and obtaining a deodorizing skin-friendly fabric. The remaining steps are the same as those of Example 2.

[0048] Comparative Example 3:

[0049] The preparation method of the deodorizing skin-friendly fabric of Comparative Example 3 is different from that of Example 2 in that step (3) is different. Step (3) is modified as follows: 3-[(2,3)-epoxypropoxy]propyl methyldimethoxysilane 1 part, DOPO 1 part, and triphenylphosphine 0.06 part are taken by mole fraction, DOPO is warmed to 132℃, and is left standing for 11 min. 3-[(2,3)-epoxypropoxy]propyl methyldimethoxysilane and triphenylphosphine are added, stirring is carried out at 300 r / min under nitrogen protection for 10.5 h, and cooling is carried out to room temperature to prepare modified siloxane. The modified polyester is stirred at 262℃ and 240 r / min for 16 min, 0.4 times the mass of the modified polyester of modified cellulose is added, stirring is continued for 22 min, melt spinning is carried out, the spinning temperature is 264℃, the extrusion rate is 40 r / min, the winding rate is 17 r / min, drawing is carried out to 5 times at room temperature, drawing is carried out to 10 times at 128℃, and finally setting is carried out at 138℃ for 110 s to prepare composite fibers. The modified siloxane, hydroxymethyl triethoxysilane, dimethoxydimethylsilane, and deionized water are mixed in a mass ratio of 1:4:7:32, 0.1 mol / L hydrochloric acid aqueous solution is used to adjust the pH to 5.4, stirring is carried out at room temperature and 300 r / min for 7 min to prepare a silane mixture. The composite fibers are soaked in the silane mixture for 2 min, taken out, until no liquid drops fall, left standing at 82℃ for 2.4 h, washed with deionized water for 8 times, and vacuum dried at 0℃ for 25 h to prepare modified composite fibers. The modified composite fibers are spun and woven to prepare the deodorizing skin-friendly fabric. The remaining steps are the same as those of Example 2.

[0050] Comparative Example 4:

[0051] The preparation method of the deodorizing skin-friendly fabric of Comparative Example 4 is different from that of Example 2 in that step (3) is different. Step (3) is modified as follows: anhydrous citric acid, cysteamine hydrochloride, and deionized water are mixed in a mass ratio of 2:1.2:11, stirring is carried out at 300 r / min for 7 min, left standing at 135℃ for 12.5 h, cooled to room temperature, washed with deionized water for 10 times, and vacuum dried at 82℃ for 25 h to prepare an ultraviolet absorber. The modified polyester is stirred at 262℃ and 240 r / min for 16 min, 0.4 times the mass of the modified polyester of modified cellulose is added, stirring is continued for 22 min, melt spinning is carried out, the spinning temperature is 264℃, the extrusion rate is 40 r / min, the winding rate is 17 r / min, drawing is carried out to 5 times at room temperature, drawing is carried out to 10 times at 128℃, and finally setting is carried out at 138℃ for 110 s to prepare composite fibers. The ultraviolet absorber and dichloromethane are mixed in a mass ratio of 1:14 to prepare an ultraviolet absorber solution. The composite fibers are soaked in the ultraviolet absorber solution for 2 min, taken out, until no liquid drops fall, left standing at 260℃ for 50 min to prepare the deodorizing skin-friendly fabric. The remaining steps are the same as those of Example 2.

[0052] Test Example 1

[0053] Antibacterial and deodorizing test:

[0054] Test method: Test according to GB / T20944.3-2008, and the selected bacteria is Propionibacterium acnes. The results are shown in Table 1.

[0055] Table 1

[0056]

[0057]

[0058] From the experimental data in Table 1, it can be found that the deodorizing skin-friendly fabric prepared by the application has good antibacterial and deodorizing ability.

[0059] From the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 1, it can be found that the bacteriostatic rates of Examples 1, 2 and 3 are high. The difference between Comparative Example 1 and the examples is that guanidine is not introduced on the surface of the material by the reaction of amino and olefin. It shows that the guanidine group can destroy the structure and stability of the cell membrane by electrostatic interaction with the phospholipid molecules on the cell membrane, increase the permeability of the cell membrane, lead to the leakage of intracellular substances, and also can combine with the polysaccharide components in the bacterial cell wall, hinder the synthesis and repair of the cell wall, destroy the integrity of the bacterial cell wall, and cannot maintain the normal morphology and function of the cell, so as to achieve the antibacterial effect. The organic matter in sweat will be decomposed by the odor-causing bacteria on the skin surface to produce volatile malodorous substances such as ammonia, acetic acid and isovaleric acid. By introducing guanidine, the bactericidal effect is achieved, and then the deodorizing purpose is achieved.

[0060] Test Example 2

[0061] Aging resistance and flame retardant test:

[0062] Aging resistance test Test method: The single yarn of the fabric prepared in each example and comparative example is tested. The breaking strength is tested according to GB / T9997-1988, which is recorded as A0. The sample is irradiated by fluorescent ultraviolet lamp UV-A340 for 20 days according to ISO4892-3, and the breaking strength is tested again, which is recorded as A1. The breaking strength retention rate is calculated, wherein the breaking strength retention rate = A1 / A0 x 100%.

[0063] Flame retardant test Test method: The limiting oxygen index is tested according to GB / T5454-1997 test standard. The results are shown in Table 2.

[0064] Table 2

[0065]

[0066]

[0067] From the comparison of the experimental data in Table 2, it can be found that the deodorizing skin-friendly fabric prepared by the application has good aging resistance and flame retardance.

[0068] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3 in Table 2, it can be found that the breaking strength retention rates of Examples 1, 2 and 3 are large, and the difference between Comparative Example 3 and the examples is that no pyridone structure is formed by the reaction of anhydrous citric acid and cysteamine hydrochloride, which indicates that the pyridone ring conjugated system is contained in the pyridone-based molecular structure, and under ultraviolet irradiation, the conjugated system can absorb ultraviolet light energy and convert it into heat energy, thereby achieving the purpose of anti-photoaging.

[0069] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2, it can be found that the limiting oxygen indices of Examples 1, 2 and 3 are large, and the difference between Comparative Example 2 and the examples is that no organic phosphorus is introduced by the reaction of 3-[(2,3)-epoxypropoxy]propyl methyl dimethoxysilane and DOPO, which indicates that the organic phosphorus can produce phosphoric acid, metaphosphoric acid, poly-metaphosphoric acid and other substances when decomposed by heat, and these compounds have strong dehydration property, which promotes the dehydration and carbonization of the polymer surface to form a protective layer, insulates oxygen and heat transfer, and inhibits the continuous combustion reaction, and the free radicals generated by decomposition can capture hydrogen radicals in the gas phase, thereby interrupting the combustion chain reaction to achieve the effect of flame retardation.

[0070] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4, it can be found that the limiting oxygen indices of Examples 1, 2 and 3 are large, and the difference between Comparative Example 4 and the examples is that no polysiloxane is formed on the surface of the fabric by using the silane mixed solution for surface treatment, which indicates that the silicon-oxygen free radicals released by the decomposition of polysiloxane can capture active free radicals in the combustion chain reaction, thereby interrupting the combustion chain reaction, and a dense silicon-containing carbon layer can also be formed on the surface of the material to insulate heat and oxygen, while inhibiting the escape of flammable gas, thereby playing a physical barrier role to achieve the effect of flame retardation.

[0071] Test Example 3:

[0072] Skin-friendly test:

[0073] Test method: The fabrics prepared in each example and comparative example are made into samples of 40 cm x 20 cm, and 600 people are selected, including 200 people aged 11-30, 200 people aged 31-50, and 200 people aged 51-70, who are asked to touch the samples in turn and record the number of people who think the skin-friendliness is good. The results are shown in Table 3.

[0074] Table 3

[0075] Number of persons Example 1 568 Example 2 570 Example 3 571 Comparative Example 1 565 Comparative Example 2 569 Comparative Example 3 566 Comparative Example 4 405

[0076] From the comparison of the experimental data in Table 3, it can be found that the deodorizing skin-friendly fabric prepared by the application has good skin-friendliness.

[0077] From the experimental data of Example 1, 2, 3 and Comparative Example 4 in Table 3, it can be found that the skin friendliness of Example 1, 2, 3 is good. The difference between Comparative Example 4 and the examples is that the surface of the fabric is not treated with the silane mixed solution, and polysiloxane is formed on the surface of the material, which shows that the polysiloxane molecular backbone is composed of siloxane bonds, which belongs to a non-polar molecular structure, and has low compatibility with polar substances such as oil and moisture on the surface of human skin, and can form a stable protective layer on the skin surface. This structural characteristic can reduce the direct contact area with the skin, reduce the friction feeling, and improve the smoothness of the skin.

[0078] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A deodorizing skin-friendly fabric, characterized in that, The deodorizing skin-friendly fabric is prepared by mixing modified polyester and modified cellulose, spinning, and then sequentially performing surface treatment with a UV absorber and a silane mixed solution. The silane mixed solution is prepared by mixing modified siloxane, hydroxymethyl triethoxysilane, dimethoxydimethylsilane and deionized water. The modified siloxane is prepared by reacting 3-[(2,3)-epoxypropoxy]propyl methyldimethoxysilane and DOPO. The UV absorber is prepared by reacting anhydrous citric acid and cysteamine hydrochloride. The modified polyester is prepared by polymerizing dimethyl terephthalate, 2-vinyl propane-1,3-diol and ethylene glycol, and then reacting with mercaptopropyl methyldimethoxysilane. The modified cellulose is prepared by sequentially reacting microcrystalline cellulose with ethylene(chloromethyl)dimethoxysilane and 1-amino-4-butyl guanidine dihydrochloride.

2. A process for the preparation of a deodorizing skin-friendly fabric, characterized in that, The preparation method of the deodorizing skin-friendly fabric mainly comprises the following steps: (1) mixing pre-modified cellulose, 1-amino-4-butyl guanidine dihydrochloride and ethanol according to a mass ratio of 4.8-5.2:1:24-26, stirring at 76-78℃ and 200-300r / min for 23.5-24.5h, filtering, washing with ethanol for 4-6 times, and vacuum drying at 60-70℃ for 11.5-12.5h to obtain modified cellulose; (2) mixing pre-modified polyester, mercaptopropyl methyldimethoxysilane, azobisisobutyronitrile and ethanol according to a mass ratio of 9-11:1.8-2.2:0.6-0.8:34-36, stirring at 200-300r / min for 3-4min, heating to 68-72℃, continuing to stir for 2.8-3.2h, adding 0.2-0.3 times of 2,6-di-tert-butyl-4-methylphenol solution based on the mass of pre-modified polyester, cooling to room temperature, filtering, washing with ethanol for 4-6 times, and vacuum drying at 40-50℃ for 13-14h to obtain modified polyester; (3) soaking pre-modified composite fiber in the silane mixed solution for 1-2min, taking out, until no liquid drops drop, standing at 78-82℃ for 2-2.4h, washing with deionized water for 6-8 times, and vacuum drying at-10-0℃ for 23-25h to obtain modified composite fiber; spinning the modified composite fiber, weaving, and obtaining the deodorizing skin-friendly fabric.

3. A method of making a deodorizing skin-friendly fabric according to claim 2, characterized in that, In step (1), the pre-modified cellulose is prepared by mixing microcrystalline cellulose, dimethyl sulfoxide and ethylene(chloromethyl)dimethoxysilane according to a mass ratio of 1:32-34:0.94-0.96, stirring at 85-95℃ and 200-300r / min for 11.5-12.5h, pouring into deionized water, standing for 12-14min, filtering, washing with deionized water for 6-8 times, vacuum drying at 45-55℃ for 11.5-12.5h, and crushing to 8-10 mesh.

4. A method of making a deodorizing skin-friendly fabric according to claim 2, characterized in that, The pre-modified polyester in step (2) is prepared by mixing dimethyl terephthalate, 2-vinyl propane-1, 3-diol, ethylene glycol and sodium acetate in a molar ratio of 9-11:2-3:7-8:0.1-0.2, stirring at 250-260℃ and 200-300r / min under nitrogen protection for 11.5-12.5h, cooling to room temperature, crushing to 8-10 mesh, and obtaining.

5. The method of making a deodorizing skin-friendly fabric according to claim 2, wherein, The silane mixture in step (3) is prepared by mixing modified siloxane, hydroxymethyl triethoxysilane, dimethoxy dimethyl silane and deionized water in a mass ratio of 1:3-4:6-7:28-32, adjusting pH to 4.6-5.4 with 0.1mol / L hydrochloric acid aqueous solution, stirring at room temperature and 200-300r / min for 5-7min, and obtaining.

6. A method of making a deodorizing skin-friendly fabric according to claim 5, characterized in that, The modified siloxane is prepared by taking 3-[(2,3)-epoxy propoxy] propyl methyl dimethoxysilane 1 part, DOPO 1 part and triphenyl phosphine 0.04-0.06 parts, heating DOPO to 128-132℃, standing for 9-11min, adding 3-[(2,3)-epoxy propoxy] propyl methyl dimethoxysilane and triphenyl phosphine, stirring at 200-300r / min under nitrogen protection for 9.5-10.5h, and cooling to room temperature.

7. The method of making a deodorizing skin-friendly fabric according to claim 2, wherein, The pre-modified composite fiber in step (3) is prepared by mixing ultraviolet absorber and dichloromethane in a mass ratio of 1:12-14 to obtain an ultraviolet absorber solution, immersing the composite fiber in the ultraviolet absorber solution for 1-2min, taking out the fiber without liquid drops, standing at 250-260℃ for 40-50min, and obtaining.

8. A method of making a deodorizing skin-friendly fabric according to claim 7, characterized in that, The composite fiber is prepared by stirring the modified polyester at 258-262℃ and 200-240r / min for 12-16min, adding modified cellulose in an amount of 0.3-0.4 times the mass of the modified polyester, continuing to stir for 18-22min, melt spinning, spinning temperature 260-264℃, extrusion rate 36-40r / min, winding rate 15-17r / min, drawing at room temperature to 3-5 times, drawing at 126-128℃ to 8-10 times, and finally setting at 136-138℃ for 100-110s.

9. The method of making a deodorizing skin-friendly fabric according to claim 7, wherein, The ultraviolet absorber is prepared by mixing anhydrous citric acid, cysteamine hydrochloride and deionized water in a mass ratio of 1.8-2:1.1-1.2:9-11, stirring at 200-300r / min for 5-7min, standing at 125-135℃ for 11.5-12.5h, cooling to room temperature, washing with deionized water for 8-10 times, and vacuum drying at 78-82℃ for 23-25h.

10. A method of making a deodorizing skin-friendly fabric according to claim 2, characterized in that, The spinning in step (3) refers to spinning yarns by using FA320A high-speed drawing frame, THC2015 type automatic doffer roving frame, TH598 type spinning frame and GMR001 type small winding frame in sequence, the drawing process adopts 6 ends of blending, the draft ratio is 1.4-1.6 times; the roving process: the draft ratio in the rear zone is 1.2-1.24 times, the roving twist factor is 118-122, and the roving weight is 6 g / (10 m); the spinning process: the draft ratio in the rear zone is 1.15-1.17 times, the gauge block specification is 3.0 mm, and the spindle speed is 10000-12000 rpm.

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