阅读说明：本技术 一种提高汉麻织物抗紫外线性能的方法 (Method for improving ultraviolet resistance of hemp fabric ) 是由 季萍 王潮霞 季国苗 殷允杰 于 2021-10-27 设计创作，主要内容包括：本发明公开了一种提高汉麻织物抗紫外线性能的方法,包括有机-无机复合溶胶液的制备、汉麻织物巯基偶联剂改性以及汉麻织物阳光下照射处理3个步骤。钛酸四正丁酯水解后会生产高紫外线屏蔽性能的纳米二氧化钛溶胶,邻羟基苯甲酸会催化钛酸四正丁酯和乙烯基三甲氧基硅烷的水解和缩合,同时还具有紫外线吸收性能。处理后的汉麻织物在紫外光的照射下,引起有机-无机复合溶胶液中的乙烯基与处理后汉麻织物中的巯基发生点击反应,使得汉麻织物具备良好的抗紫外线性能同时兼备可靠的耐洗性。(The invention discloses a method for improving the ultraviolet resistance of hemp fabrics, which comprises 3 steps of preparing organic-inorganic composite sol solution, modifying hemp fabric sulfydryl coupling agent and irradiating the hemp fabrics in the sun. After the tetrabutyl titanate is hydrolyzed, nano titanium dioxide sol with high ultraviolet shielding performance can be produced, and the o-hydroxybenzoic acid can catalyze the hydrolysis and condensation of the tetrabutyl titanate and the vinyl trimethoxy silane and also has ultraviolet absorption performance. Under the irradiation of ultraviolet light, the processed hemp fabric causes the vinyl in the organic-inorganic composite sol solution and the mercapto in the processed hemp fabric to have click reaction, so that the hemp fabric has good ultraviolet resistance and reliable washability.)

1. A method for improving the ultraviolet resistance of hemp fabrics comprises 3 steps of preparing an organic-inorganic composite sol solution, modifying a hemp fabric sulfydryl coupling agent and carrying out light irradiation treatment on the hemp fabrics:

(1) preparing an organic-inorganic composite sol solution: the method is implemented according to the following steps:

step 1, respectively weighing 15-25mL of organic solvent, 50-70mL of deionized water and 20-30mL of dispersant, mixing, and preparing hydrolysate; measuring 25-35mL of organic solvent, 10-12mL of tetra-n-butyl titanate, 8-12mL of vinyltrimethoxysilane and 6-8mL of o-hydroxybenzoic acid, and uniformly mixing to obtain a light yellow liquid, namely a precursor solution;

step 2, mixing the hydrolysate obtained in the step 1 with the precursor solution, stirring for 10-15 hours by using a constant-temperature magnetic stirrer, and carrying out an o-hydroxybenzoic acid catalytic reaction until a sol solution with blue transparent light appears; vacuum distilling and concentrating to 40% of original volume to obtain organic-inorganic composite sol solution;

(2) modification of hemp fabric by using a sulfhydryl coupling agent: soaking the hemp fabric in a sulfhydryl coupling agent solution for 30-80min at the soaking temperature of 30-45 ℃, and then carrying out mangling treatment;

(3) and (3) carrying out light irradiation treatment on the hemp fabric: adding 1% of photoinitiator benzoin dimethyl ether into the organic-inorganic composite sol solution prepared in the step (1), uniformly stirring, then placing the hemp fabric modified by the sulfhydryl coupling agent prepared in the step (2) into the organic-inorganic composite sol solution prepared in the step (1), and soaking for 10-18 min; then taking out the hemp fabric to be naturally dried in the sun, and then irradiating the hemp fabric under an ultraviolet lamp to obtain the hemp fabric with high ultraviolet resistance.

2. The method for improving the ultraviolet resistance of the hemp fabric as claimed in claim 1, wherein: the dispersant is one of sodium dodecyl benzene sulfonate and tween 80.

3. The method for improving the ultraviolet resistance of the hemp fabric as claimed in claim 1, wherein: the organic solvent is one of glycerol and glycol.

4. The method for improving the ultraviolet resistance of the hemp fabric as claimed in claim 1, wherein: the rotating speed of the magnetic stirring is 500-700 r/min.

5. The method for improving the ultraviolet resistance of the hemp fabric as claimed in claim 1, wherein: the mercapto coupling agent is modified into at least one of gamma-mercaptopropyltriethoxysilane and gamma-mercaptopropyltrimethoxysilane.

6. The method for improving the ultraviolet resistance of the hemp fabric as claimed in claim 1, wherein: the sulfhydryl coupling agent solution comprises the following components: 20-32 wt% of sulfydryl coupling agent, 25-35 wt% of ethanol, 15-41 wt% of water and 2-4 wt% of HCl solution with mass concentration of 10%.

7. The method for improving the ultraviolet resistance of the hemp fabric as claimed in claim 1, wherein: the mangle treatment is specifically carried out according to the following steps: and (3) soaking and rolling the soaked hemp fabric for two times, wherein the rolling residual rate is 90%, and then drying at 60 ℃.

8. The method for improving the ultraviolet resistance of the hemp fabric as claimed in claim 1, wherein: the irradiation treatment is carried out under an ultraviolet lamp, the ultraviolet dominant wavelength of the ultraviolet lamp is 360-365nm, the ultraviolet light intensity is 50-100mW cm < -2 >, and the irradiation time is 30-60 s.

Technical Field

The invention relates to a method for improving the ultraviolet resistance of hemp fabrics, belonging to the technical field of fabric after-finishing.

Background

In recent years, the development of a differentiated finishing technology to impart a specific function or multiple functionalities to hemp fabrics has been receiving more and more attention. China hemp fiber is widely applied to the manufacture of garment materials by virtue of excellent wearability, but the use of the China hemp fiber is limited to a certain extent due to the defects of poor light resistance and the like in the use process. Therefore, the improvement of the ultraviolet resistance of the hemp fabric has a vital significance. The invention takes the nano titanium dioxide sol as the ultraviolet-resistant finishing agent to modify the hemp fabric so as to improve the ultraviolet resistance of the hemp fabric. Meanwhile, the invention also adopts the o-hydroxybenzoic acid with good ultraviolet absorption performance, has good ultraviolet resistance performance, has catalytic effect on the hydrolysis of the tetra-n-butyl titanate and the vinyl trimethoxy silane, and is beneficial to the synthesis of the nano titanium dioxide sol with ultraviolet resistance performance. The invention modifies the sulfydryl of the hemp fabric by means of the click reaction generated by sulfydryl and vinyl under ultraviolet light, and the treated fabric can cause the vinyl in the organic-inorganic composite sol solution and the sulfydryl in the hemp fabric to generate click reaction under the irradiation of sunlight, so that the hemp fabric has good ultraviolet resistance and reliable washability, and the problem of washability is solved. Meanwhile, the sunlight can also play a role in anchoring the o-hydroxybenzoic acid in the organic-inorganic composite sol solution, namely TiO generated on the fabric₂And the anchoring o-hydroxybenzoic acid endows the fabric with high ultraviolet resistance.

Disclosure of Invention

The invention aims to provide a method for improving the ultraviolet resistance of hemp fabrics, which comprises 3 steps of preparing an organic-inorganic composite sol solution, modifying a hemp fabric sulfydryl coupling agent and carrying out sun irradiation treatment on the hemp fabrics, and can realize high ultraviolet resistance and water resistance of the hemp fabrics.

In order to achieve the purpose, the technical scheme of the invention is as follows:

(1) preparing an organic-inorganic composite sol solution: the method is implemented according to the following steps:

step 1, respectively weighing 15-25mL of organic solvent, 50-70mL of deionized water and 20-30mL of dispersant, mixing, and preparing hydrolysate; measuring 25-35mL of organic solvent, 10-12mL of tetra-n-butyl titanate, 8-12mL of vinyltrimethoxysilane and 6-8mL of o-hydroxybenzoic acid, and uniformly mixing to obtain a light yellow liquid, namely a precursor solution;

step 2, mixing the hydrolysate obtained in the step 1 with the precursor solution, stirring for 10-15 hours by using a constant-temperature magnetic stirrer, and carrying out an o-hydroxybenzoic acid catalytic reaction until a sol solution with blue transparent light appears; vacuum distilling and concentrating to 40% of original volume to obtain organic-inorganic composite sol solution.

(2) Modification of hemp fabric by using a sulfhydryl coupling agent: soaking the hemp fabric in a sulfhydryl coupling agent solution for 30-80min at the soaking temperature of 30-45 ℃, and then carrying out mangling treatment;

(3) and (3) carrying out light irradiation treatment on the hemp fabric: adding 1% of photoinitiator benzoin dimethyl ether into the organic-inorganic composite sol solution prepared in the step (1), uniformly stirring, then placing the hemp fabric modified by the sulfhydryl coupling agent prepared in the step (2) into the organic-inorganic composite sol solution prepared in the step (1), and soaking for 10-18 min; then taking out the hemp fabric to be naturally dried in the sun, and then irradiating the hemp fabric under an ultraviolet lamp to obtain the hemp fabric with high ultraviolet resistance.

Further, a method for improving the ultraviolet resistance of hemp fabrics, wherein the dispersant is one of sodium dodecyl benzene sulfonate and tween 80.

Further, a method for improving the ultraviolet resistance of hemp fabric, wherein the organic solvent is one of glycerol and glycol.

Further, a method for improving the ultraviolet resistance of the hemp fabric, wherein the rotating speed of the magnetic stirring is one of 500-700 r/min.

Further, the method for improving the ultraviolet resistance of the hemp fabric is characterized in that the mercapto-coupling agent is modified into at least one of gamma-mercaptopropyltriethoxysilane and gamma-mercaptopropyltrimethoxysilane.

Further, a method for improving the ultraviolet resistance of hemp fabrics, wherein the sulfhydryl coupling agent solution comprises the following components: 20-32 wt% of sulfydryl coupling agent, 25-35 wt% of ethanol, 15-41 wt% of water and 2-4 wt% of HCl solution with mass concentration of 10%.

Further, the mangle fabric ultraviolet resistance improving method comprises the following steps: and (3) soaking and rolling the soaked hemp fabric for two times, wherein the rolling residual rate is 90%, and then drying at 60 ℃.

Further, a method for improving the ultraviolet resistance of the hemp fabric, wherein the hemp fabric is irradiated under an ultraviolet lamp, the ultraviolet dominant wavelength of the ultraviolet lamp is 360-365nm, and the ultraviolet light intensity is 50-100mW cm^-2The irradiation time is 30-60 s.

Has the advantages that:

the nano titanium dioxide sol with high ultraviolet shielding performance can be produced after the tetra-n-butyl titanate in the precursor solution prepared by the invention is hydrolyzed, the o-hydroxybenzoic acid can catalyze the hydrolysis of the tetra-n-butyl titanate and the vinyl trimethoxy silane, and the o-hydroxybenzoic acid has stronger ultraviolet absorption performance. Therefore, the hemp fabric prepared by the method has two layers of effects on ultraviolet rays, namely TiO₂The ultraviolet screening effect of (1) and the ultraviolet absorption effect of the o-hydroxybenzoic acid.

TiO in the organic-inorganic composite sol solution₂Inorganic components, a mercapto-containing chain and an o-hydroxybenzoic acid organic component, so that the cross-linked product has certain mechanical strength and excellent flexibility. The film generated by the sulfydryl reaction can further anchor the o-hydroxybenzoic acid material, and the durability of the o-hydroxybenzoic acid on the surface of the fiber is improved.

Irradiating the treated hemp fabric in the sun, wherein except for removing moisture, the ultraviolet ray in the sun can cause the vinyl in the organic-inorganic composite sol solution and the sulfydryl in the hemp fabric to generate click reaction; in order to further improve the reaction rate, the ultraviolet lamp is used for continuous irradiation, so that the vinyl in the organic-inorganic composite sol solution and the sulfydryl in the hemp fabric generate click reaction to the maximum extent, and the hemp fabric has good ultraviolet resistance and reliable washability.

Description of the drawings:

fig. 1 is a particle size diagram of an organic-inorganic composite sol solution.

FIG. 2 is an electron microscope image of the organic-inorganic composite sol solution.

Detailed Description

Example 1: a method for improving the ultraviolet resistance of hemp fabric comprises the following steps of (1) respectively weighing 15mL of organic solvent, 50mL of deionized water and 20mL of sodium dodecyl benzene sulfonate, mixing, and preparing hydrolysate; measuring 25mL of glycerol organic solvent, 10mL of tetra-n-butyl titanate, 8mL of vinyl trimethoxy silane and 6mL of o-hydroxybenzoic acid, and uniformly mixing to obtain a light yellow liquid, namely a precursor solution; mixing the hydrolysate obtained in the step 1 with the precursor solution, stirring for 10 hours by a constant-temperature magnetic stirrer with 500 revolutions per minute, and carrying out an o-hydroxybenzoic acid catalytic reaction until a sol solution with blue transparent light appears; vacuum distilling and concentrating to 40% of original volume to obtain organic-inorganic composite sol solution. (2) The hemp fabric is soaked in a gamma-mercaptopropyltriethoxysilane coupling agent solution for 30min, and the composition of the mercapto coupling agent solution is as follows: 20% of sulfhydryl coupling agent, 35% of ethanol, 41% of water, 4% of 10% HCl solution, and 30 ℃ of dipping, then dipping and rolling for two times, wherein the rolling residual rate is 90%, and then drying at 60 ℃; (3) adding 1% of photoinitiator benzoin dimethyl ether into the organic-inorganic composite sol solution prepared in the step (1), then placing the hemp fabric modified by the sulfhydryl coupling agent prepared in the step (2) into the organic-inorganic composite sol solution prepared in the step (1), and dipping for 10 min; then taking out, naturally drying in the sun, and irradiating under ultraviolet lamp with ultraviolet dominant wavelength of 360nm and ultraviolet light intensity of 50mW cm^-2And the irradiation time is 60s, so that the hemp fabric with high ultraviolet resistance is obtained.

The method for testing the ultraviolet resistance comprises the following steps: the absorption capacity of hemp before and after treatment on ultraviolet rays is tested by adopting an American LAMBDA35 type integrating sphere visible ultraviolet spectrophotometer. The test conditions were: the scanning range is 200-500nm, and the scanning speed is 200 nm/min. After the test is finished, calculating corresponding UPF value and T (UVA) value, and simultaneously testing the water washing resistance of the fabric.

As can be seen from figure 1, the particle size of the composite sol solution is 127.1nm, the PDI value is small, which indicates that the particle size distribution of the emulsion is uniform, so that the organic-inorganic composite sol solution can better permeate into hemp fabric fibers in the impregnation process.

Fig. 2 can further prove that the organic-inorganic composite sol liquid has smaller particles and is uniformly dispersed.

Example 2: a method for improving the ultraviolet resistance of hemp fabrics comprises the following steps of (1) respectively measuring 25mL of organic solvent, 70mL of deionized water and 30mL of Tween 80 dispersant, mixing, and preparing hydrolysate; weighing 35mL of ethylene glycol organic solvent, 12mL of tetra-n-butyl titanate, 12mL of vinyl trimethoxy silane and 8mL of o-hydroxybenzoic acid, and uniformly mixing to obtain a light yellow liquid, namely a precursor solution; mixing the hydrolysate obtained in the step 1 with the precursor solution, stirring for 15 hours by a constant-temperature magnetic stirrer at 700 revolutions per minute, and carrying out an o-hydroxybenzoic acid catalytic reaction until a sol solution with blue transparent light appears; vacuum distilling and concentrating to 40% of original volume to obtain organic-inorganic composite sol solution. (2) The hemp fabric is soaked in a gamma-mercaptopropyltrimethoxysilane mercapto coupling agent solution for 80min, and the mercapto coupling agent solution comprises the following components: 32% of sulfydryl coupling agent, 35% of ethanol, 31% of water, 2% of 10% HCl solution and 45 ℃ of dipping temperature, then dipping and rolling twice, wherein the rolling residual rate is 90%, and then drying at 60 ℃; (3) adding 1% of photoinitiator benzoin dimethyl ether into the organic-inorganic composite sol solution prepared in the step (1), then placing the hemp fabric modified by the sulfhydryl coupling agent prepared in the step (2) into the organic-inorganic composite sol solution prepared in the step (1), and dipping for 18 min; then taking out, naturally drying in the sun, and irradiating under ultraviolet lamp with ultraviolet dominant wavelength of 365nm and ultraviolet light intensity of 100mW cm^-2And the irradiation time is 30s, so that the hemp fabric with high ultraviolet resistance is obtained. The test procedure was the same as in example 1.

Example 3: a method for improving the ultraviolet resistance of hemp fabric comprises (1) measuring 20mL of organic solvent, 60mL of deionized water and 25mL of dodecylbenzene sulfonic acid respectivelyMixing sodium dispersing agents to prepare hydrolysate; measuring 30mL of glycerol, 11mL of tetra-n-butyl titanate, 10mL of vinyl trimethoxy silane and 7mL of ortho-hydroxybenzoic acid, and uniformly mixing to obtain a light yellow liquid, namely a precursor solution; mixing the hydrolysate obtained in the step 1 with the precursor solution, stirring for 12 hours by a constant-temperature magnetic stirrer at 600 revolutions per minute, and carrying out an o-hydroxybenzoic acid catalytic reaction until a sol solution with blue transparent light appears; vacuum distilling and concentrating to 40% of original volume to obtain organic-inorganic composite sol solution. (2) The hemp fabric is soaked in a gamma-mercaptopropyltriethoxysilane coupling agent solution for 55min, and the composition of the mercapto coupling agent solution is as follows: 28 percent of sulfhydryl coupling agent, 30 percent of ethanol, 28 percent of water, 4 percent of 10 percent of HCl solution, 40 ℃ of dipping temperature, then dipping and rolling twice, the rolling residual rate is 90 percent, and then drying at 60 ℃; (3) adding 1% of photoinitiator benzoin dimethyl ether into the organic-inorganic composite sol solution prepared in the step (1), then placing the hemp fabric modified by the sulfhydryl coupling agent prepared in the step (2) into the organic-inorganic composite sol solution prepared in the step (1), and soaking for 14 min; then taking out, naturally drying in the sun, and irradiating under ultraviolet lamp with ultraviolet dominant wavelength of 360nm and ultraviolet light intensity of 50mW cm^-2And the irradiation time is 60s, so that the hemp fabric with high ultraviolet resistance is obtained. The test procedure was the same as in example 1.

Example 4: a method for improving the ultraviolet resistance of hemp fabrics comprises the following steps of (1) respectively measuring 22mL of organic solvent, 62mL of deionized water and 23mL of Tween 80 dispersant, mixing, and preparing hydrolysate; measuring 30mL of ethylene glycol organic solvent, 11mL of tetra-n-butyl titanate, 10mL of vinyl trimethoxy silane and 7mL of o-hydroxybenzoic acid, and uniformly mixing to obtain a light yellow liquid, namely a precursor solution; mixing the hydrolysate obtained in the step (1) with the precursor solution, stirring for 13 hours by a constant-temperature magnetic stirrer at the speed of 600 revolutions per minute, and carrying out catalytic reaction on the o-hydroxybenzoic acid until a sol solution with blue transparent light appears; vacuum distilling and concentrating to 40% of original volume to obtain organic-inorganic composite sol solution. (2) The hemp fabric is soaked in a gamma-mercaptopropyltrimethoxysilane coupling agent solution for 55min, and the mercapto coupling agent solution comprises the following components: the dosage of the sulfhydryl coupling agent is 28 percent30% of ethanol, 28% of water and 4% of 10% HCl solution, and the dipping temperature is 40 ℃, then the mixture is dipped for two rolls, the rolling residual rate is 90%, and then the mixture is dried at 60 ℃; (3) adding 1% of photoinitiator benzoin dimethyl ether into the organic-inorganic composite sol solution prepared in the step (1), then placing the hemp fabric modified by the sulfhydryl coupling agent prepared in the step (2) into the organic-inorganic composite sol solution prepared in the step (1), and soaking for 14 min; then taking out, naturally drying in the sun, and irradiating under ultraviolet lamp with ultraviolet dominant wavelength of 365nm and ultraviolet light intensity of 100mW cm^-2And the irradiation time is 60s, the hemp fabric with high ultraviolet resistance is obtained, and the testing steps are the same as example 1.

Control case 1: a method for improving the ultraviolet resistance of hemp fabrics comprises the following steps of (1) respectively measuring 22mL of organic solvent, 62mL of deionized water and 23mL of Tween 80 dispersant, mixing, and preparing hydrolysate; measuring 30mL of ethylene glycol organic solvent, 11mL of tetra-n-butyl titanate, 10mL of vinyl trimethoxy silane and 7mL of concentrated nitric acid, and uniformly mixing to obtain a light yellow liquid, namely a precursor solution; mixing the hydrolysate obtained in the step (1) with the precursor solution, stirring for 13 hours by a constant-temperature magnetic stirrer at the speed of 600 revolutions per minute, and carrying out catalytic reaction on the o-hydroxybenzoic acid until a sol solution with blue transparent light appears; vacuum distilling and concentrating to 40% of original volume to obtain organic-inorganic composite sol solution. (2) The hemp fabric is soaked in a gamma-mercaptopropyltrimethoxysilane coupling agent solution for 55min, and the mercapto coupling agent solution comprises the following components: 28 percent of sulfhydryl coupling agent, 30 percent of ethanol, 28 percent of water, 4 percent of 10 percent of HCl solution, 40 ℃ of dipping temperature, then dipping and rolling twice, the rolling residual rate is 90 percent, and then drying at 60 ℃; (3) adding 1% of photoinitiator benzoin dimethyl ether into the organic-inorganic composite sol solution prepared in the step (1), then placing the hemp fabric modified by the sulfhydryl coupling agent prepared in the step (2) into the organic-inorganic composite sol solution prepared in the step (1), and soaking for 14 min; then taking out, naturally drying in the sun, and irradiating under ultraviolet lamp with ultraviolet dominant wavelength of 365nm and ultraviolet light intensity of 100mW cm^-2And the irradiation time is 60s, the hemp fabric with high ultraviolet resistance is obtained, and the testing steps are the same as example 1.

Control case 2: hemp fabric was treated directly with 7mL of o-hydroxybenzoic acid using the same procedure as in example 1. And (3) evaluating the ultraviolet resistance of the hemp fabric:

table 1: test condition of ultraviolet resistance of hemp fabric

As can be seen from examples 1-4 in Table 1, compared with untreated fabrics, the ultraviolet-resistant hemp fabric prepared by the invention has high UPF value, reaches the highest requirement of ultraviolet resistance of 50+, and the ultraviolet transmittance is lower than 5%; as can be seen from example 4 and comparative examples 1 and 2, TiO₂And the o-hydroxybenzoic acid have the ultraviolet resistance, which shows that the ultraviolet linearity of the hemp fabric prepared by the invention is caused by TiO₂And the o-hydroxybenzoic acid.

It can be seen from example 4 and comparative example 2 that the hemp fabric treated with only o-hydroxybenzoic acid has very poor water resistance, while the fabric treated with the organic-inorganic composite sol solution has better ultraviolet resistance and washing resistance, and the main reason is that the treated hemp fabric is irradiated under the sun, the ultraviolet rays in the sun and the ultraviolet rays of the ultraviolet lamp can cause the vinyl in the organic-inorganic composite sol solution and the mercapto in the hemp fabric to have click reaction, so that the hemp fabric has good ultraviolet resistance and simultaneously has reliable washing resistance.

The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered by the claims of the present invention as long as they do not depart from the scope of the technical solutions of the present invention.