阅读说明：本技术 具有pH响应变色功能的织物传感器及其制备方法与应用 (Fabric sensor with pH response color change function and preparation method and application thereof ) 是由 张瑞萍 韦苏娟 孙荟云 朱楠 于 2020-06-27 设计创作，主要内容包括：本发明属于纺织品技术领域,公开了一种具有pH响应变色功能的织物传感器及其制备方法与应用。本发明采用柠檬提取液对茜草进行两次除杂色处理,后过滤去滤渣,得茜草提取液,调节茜草提取液的pH并对棉织物进行染色,再进行后处理,得到黄色和红色两种织物传感器。本发明提取的茜草提取液含杂色极少,棉织物上染的颜色饱和度很高,且属于天然染料,对环境无污染。本发明提供的织物传感器具有优异的pH响应变色性能和可逆变色灵敏性能,且耐摩擦牢度和耐洗牢度良好,可在环境酸碱监测中反复循环使用,如通过人体汗液pH改变提示人体健康状况；伤口纱布的颜色变化提示伤口的恢复与恶化；监控水质、土壤防护、制备指示酸性气体泄漏的防护服等。(The invention belongs to the technical field of textiles and discloses a fabric sensor with a pH response color change function and a preparation method and application thereof. According to the invention, the madder is subjected to impurity and color removal twice by using a lemon extract, filter residues are removed to obtain a madder extract, the pH of the madder extract is adjusted, cotton fabrics are dyed, and then post-treatment is carried out to obtain a yellow fabric sensor and a red fabric sensor. The madder root extracting solution extracted by the method disclosed by the invention is very little in variegated color, high in color saturation of cotton fabric dyeing, belongs to a natural dye and is free of pollution to the environment. The fabric sensor provided by the invention has excellent pH response color changing performance and reversible color changing sensitivity, has good rubbing fastness and washing fastness, and can be repeatedly recycled in environment acid-base monitoring, such as prompting the health condition of a human body through the change of the pH of human sweat; the color change of the wound gauze prompts the recovery and deterioration of the wound; monitoring water quality, soil protection, preparing protective clothing indicating acid gas leakage, and the like.)

1. A preparation method of a fabric sensor with a pH response color change function is characterized by comprising the following steps:

1) immersing madder into a lemon extracting solution with the concentration of 10-30g/L for 2-48 h, and filtering to obtain filter residues; the dosage ratio of the madder to the lemon extract is 10g (100-200) mL;

2) soaking the filter residue into a lemon extracting solution with the concentration of 10-30g/L, boiling for 5-60 min, filtering, and removing filtrate to obtain the madder except for variegated color; the dosage ratio of the filter residue to the lemon extract is 10g (100-200) mL;

3) immersing the madder subjected to impurity color removal into water at 40-50 ℃ for 30-60 min, then boiling for 5-60 min, cooling and filtering to obtain a filtrate; the dosage ratio of the madder subjected to impurity color removal to the water is 10g (100-200) mL;

4) and adjusting the pH value of the filtrate to 3-11, and then soaking the cotton fabric into the filtrate after the pH value is adjusted according to a bath ratio of 1 (20-50) for dyeing to obtain the fabric sensor.

2. The method of making a fabric sensor of claim 1, comprising the steps of:

1) immersing madder into a lemon extracting solution with the concentration of 15g/L for 12 hours, and filtering to obtain filter residue; the dosage ratio of the madder to the lemon extract is 10g to 100 mL;

2) soaking the filter residue into a lemon extracting solution with the concentration of 15g/L, boiling for 30min, filtering and removing filtrate to obtain the madder without impurity colors; the dosage ratio of the filter residue to the lemon extract is 10g:100 mL;

3) immersing the madder subjected to impurity color removal into water at 45 ℃ for 45min, then boiling for 30min, cooling and filtering to obtain filtrate; the dosage ratio of the madder subjected to impurity color removal to the water is 10g:100 mL;

4) and adjusting the pH of the filtrate to 3-11, and then soaking the cotton fabric into the filtrate after the pH is adjusted according to a bath ratio of 1:50 for dyeing to obtain the fabric sensor.

3. The method according to claim 2, wherein the step 4) is: and adjusting the pH of the filtrate to 3-6, and then soaking the cotton fabric into the filtrate after the pH is adjusted according to a bath ratio of 1:50 for dyeing to obtain a yellow fabric sensor.

4. The method of claim 3, further comprising the post-treatment steps of:

uniformly mixing absolute ethyl alcohol and distilled water, slowly dropwise adding tetraethyl orthosilicate, uniformly stirring, dropwise adding a hydrochloric acid solution with the concentration of 0.01mol/L, stirring for 4 hours at 60 ℃, adding a chitosan solution with the concentration of 50g/L, aging for 24 hours, putting a yellow fabric sensor into the aged solution, treating for 30 minutes, taking out, soaking for 10 minutes by using a plant ash solution with the concentration of 20g/L according to a bath ratio of 1:50, taking out, dehydrating, drying at 80 ℃, and baking at 130-150 ℃, wherein the volume ratio of the absolute ethyl alcohol to the distilled water to the tetraethyl orthosilicate to the hydrochloric acid solution to the chitosan solution is 60:3:20:7: 10.

5. The method for preparing a composite material according to claim 1 or 2, wherein the step 4) is: and adjusting the pH value of the filtrate to 7-11, and then soaking the cotton fabric into the filtrate after the pH value is adjusted according to a bath ratio of 1:50 for dyeing to obtain the red fabric sensor.

6. The method of claim 5, further comprising the post-treatment steps of:

under the stirring condition, adding ammonia water and distilled water into absolute ethyl alcohol, continuously stirring uniformly, then dropwise adding tetraethyl orthosilicate, continuously stirring for 90min at 25 ℃, adding a sodium alginate solution with the concentration of 20g/L, aging for 24h, then placing a red fabric sensor into the aged solution, treating for 30min, taking out, soaking for 10min by using a plant ash solution with the concentration of 20g/L according to the bath ratio of 1:50, taking out, dehydrating, drying at 80 ℃, and baking at 130-150 ℃, wherein the volume ratio of the ammonia water to the distilled water to the absolute ethyl alcohol to the tetraethyl orthosilicate to the sodium alginate is 7:3:60:20: 10.

7. The fabric sensor prepared by the preparation method according to claim 4 or 6.

8. Use of the fabric sensor of claim 7 in environmental acid-base monitoring.

9. The application according to claim 8, wherein the application comprises: the health condition of the human body is prompted through the change of the pH value of the sweat of the human body, and the recovery and the deterioration of the wound are prompted through the color change of the wound gauze.

10. The application according to claim 8, wherein the application comprises: monitoring water quality, protecting soil and preparing protective clothing indicating acid gas leakage.

Technical Field

The invention relates to the technical field of textiles, in particular to a fabric sensor with a pH response color change function and a preparation method and application thereof.

Background

The color of the color-changing textile is changed along with external stimulation such as illumination, temperature, humidity or pressure, and the like, so that the pattern of the textile presents the effect of changing from 'static color' to 'dynamic color'. The color-changing textile is divided into photochromic, thermochromic, electrochromic, wet-photochromic and the like according to the conditions required by the color change of the color-changing textile, and is considered as a novel intelligent textile material with great potential due to the advantages of good flexibility, reusability, mechanical stability, air permeability, light weight and the like.

In recent years, researchers have attracted extensive attention to the development of pH-sensitive color-changing textile flexible sensors, and when the pH value changes, the electronic arrangement changes due to ring opening or isomerization of dye molecules and proton transfer, so that reversible change of color occurs. The scholars of Mohrg.J. found that the color of textiles such as lycra, terylene and chinlon dyed with bromocresol purple dye changes gradually from yellow to red purple in the pH range of 4-10, and the change of the pH of sweat in dressing suggests the health condition of human body (Mohrg.J., Muller.H, Bussemer.B, et al.design of ascorbic acids for fasciation of pH sensor layers [ J ]. Analytical and biochemical chemistry, 2008, 392(7-8): 1411-1418); in China, Hoodipine and the like dye cotton fabrics by bromothymol blue, and when the pH value is changed between 5 and 8.5, the cotton fabrics show reversible change of yellow-green blue (Hoodipine, Vaihui. preparation of novel acid-base color-changing textiles and color change research [ J ] printing and dyeing auxiliary agents 2015, 32 (2): 22-28).

Most of dyes used for developing pH sensitive color-changing fabrics at present are chemical dyes such as pH indicators, and some dyes are unsafe and even carcinogenic. The traditional Chinese medicine madder is safe and harmless, and the current research reports about madder pigment mainly focus on the aspects of pigment extraction and dyeing processes. The reversible color change characteristics of the madder dyed cotton fabric in different pH environments are analyzed, and the fabric sensor with the pH response color change function is developed, so that the fabric sensor has great market application value.

Disclosure of Invention

The invention aims to provide a fabric sensor with a pH response color change function, a preparation method and application thereof.

In order to solve the technical problem, the invention provides a preparation method of a fabric sensor with a pH response color change function, which comprises the following steps:

1) immersing madder into a lemon extracting solution with the concentration of 10-30g/L for 2-48 h, and filtering to obtain filter residues; the dosage ratio of the madder to the lemon extract is 10g (100-200) mL;

2) soaking the filter residue into a lemon extracting solution with the concentration of 10-30g/L, boiling for 5-60 min, filtering, and removing filtrate to obtain the madder except for variegated color; the dosage ratio of the filter residue to the lemon extract is 10g (100-200) mL;

3) immersing the madder subjected to impurity color removal into water at 40-50 ℃ for 30-60 min, then boiling for 5-60 min, cooling and filtering to obtain a filtrate; the dosage ratio of the madder subjected to impurity color removal to the water is 10g (100-200) mL;

4) and adjusting the pH value of the filtrate to 3-11, and then soaking the cotton fabric into the filtrate after the pH value is adjusted according to a bath ratio of 1 (20-50) for dyeing to obtain the fabric sensor.

Further, the invention provides a preparation method of the fabric sensor with the pH response color change function, which comprises the following steps:

1) immersing madder into a lemon extracting solution with the concentration of 15g/L for 12 hours, and filtering to obtain filter residue; the dosage ratio of the madder to the lemon extract is 10g to 100 mL;

2) soaking the filter residue into a lemon extracting solution with the concentration of 15g/L, boiling for 30min, filtering and removing filtrate to obtain the madder without impurity colors; the dosage ratio of the filter residue to the lemon extract is 10g:100 mL;

3) immersing the madder subjected to impurity color removal into water at 45 ℃ for 45min, then boiling for 30min, cooling and filtering to obtain filtrate; the dosage ratio of the madder subjected to impurity color removal to the water is 10g:100 mL;

4) and adjusting the pH of the filtrate to 3-11, and then soaking the cotton fabric into the filtrate after the pH is adjusted according to a bath ratio of 1:50 for dyeing to obtain the fabric sensor.

Further, the step 4) is as follows: and adjusting the pH of the filtrate to 3-6, and then soaking the cotton fabric into the filtrate after the pH is adjusted according to a bath ratio of 1:50 for dyeing to obtain a yellow fabric sensor.

Further, the yellow fabric sensor can be post-processed, and the specific steps are as follows: uniformly mixing absolute ethyl alcohol and distilled water, slowly adding tetraethyl orthosilicate dropwise, uniformly stirring, then adding a hydrochloric acid solution dropwise, stirring for 4 hours at 60 ℃, adding a chitosan solution with the concentration of 50g/L, aging for 24 hours, then placing the color fabric sensor into the aged solution, treating for 30 minutes, taking out, soaking for 10 minutes by using a plant ash solution with the concentration of 20g/L according to a bath ratio of 1:50, taking out, dehydrating, drying at 80 ℃, and baking at 130-150 ℃, wherein the volume ratio of the absolute ethyl alcohol to the distilled water to the tetraethyl orthosilicate to the hydrochloric acid solution to the chitosan solution is 60:3:20:7: 10. This step increases the rub and wash fastness of the fabric sensor, which appears yellow, ensuring its repeated recycling.

Further, the step 4) is as follows: and adjusting the pH value of the filtrate to 7-11, and then soaking the cotton fabric into the filtrate after the pH value is adjusted according to a bath ratio of 1:50 for dyeing to obtain the red fabric sensor.

Furthermore, a red fabric sensor can be used for post-treatment, and the method comprises the following specific steps: under the stirring condition, adding ammonia water and distilled water into absolute ethyl alcohol, continuously stirring uniformly, then dropwise adding tetraethyl orthosilicate, continuously stirring for 90min at 25 ℃, adding a sodium alginate solution with the concentration of 20g/L, aging for 24h, then placing a fabric sensor with the red color into the aged solution, treating for 30min, taking out, soaking for 10min by using a plant ash solution with the concentration of 20g/L, taking out, dehydrating, drying at 80 ℃, and baking at 130-150 ℃, wherein the volume ratio of the ammonia water to the distilled water to the absolute ethyl alcohol to the tetraethyl orthosilicate to the sodium alginate is 7:3:60:20: 10. This step increases the rub and wash fastness of the fabric sensor appearing red, ensuring repeated recycling of the fabric sensor.

The invention also provides the fabric sensor prepared by the preparation method.

The invention also provides application of the fabric sensor in environmental acid-base monitoring as a flexible pH response color change sensor.

Particularly, the method can be applied to prompting the health condition of a human body through the change of the pH value of human sweat; the recovery and deterioration of the wound are prompted through the color change of the wound gauze; monitoring water quality, soil protection, preparing protective clothing indicating acid gas leakage, and the like.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the method, the lemon extract is used as the impurity removal coloring agent to carry out impurity color removal treatment on the madder twice, so that the obtained madder extract is extremely low in impurity color and very high in color saturation for dyeing cotton fabrics. And the madder root extracting solution belongs to natural dye, and has no pollution to the environment.

2. According to the method, cotton fabrics are dyed in different colors according to different pH values of the madder extract, and the cotton fabrics are gradually deepened along with the increase of the pH value within the range of 3-11 of the madder extract, so that the cotton fabrics show acid yellow alkali red, and have excellent pH response color changing performance. In addition, the color change phenomenon of the acid yellow alkali red is reversible, when yellow cotton fabrics prepared under the acidic condition are placed in an alkaline environment, the color of the cotton fabrics is changed from yellow to red, and when red cotton fabrics prepared under the alkaline condition are placed in the acidic environment, the color of the cotton fabrics is changed from red to yellow, and the color change phenomenon can tend to be stable within 30s, which shows that the reversible color change sensitivity of the fabric sensor is high, and the fabric sensor can be repeatedly recycled.

3. The invention obviously improves the rubbing fastness and washing fastness of the fabric sensor with the pH response color change function through the post-treatment process, and ensures the repeated recycling of the fabric sensor.

Drawings

FIG. 1 is a graph showing the color of an extract of Rubia cordifolia as a function of pH;

fig. 2 is a graph comparing ultraviolet spectra of alizarin standard and rubia cordifolia extract (pH 5 and pH 10);

fig. 3 is an HPLC profile of alizarin standards and rubia cordifolia extracts (pH 5 and pH 10);

FIG. 4 is a graph showing the change of color parameters a and b of cotton fabric under different dyeing pH conditions of the madder extract;

FIG. 5 is a graph of K/S as a function of wavelength for fabric sensors provided in examples 2, 4, 6, 8 and 10;

FIG. 6 is a graph showing the variation trend of the color parameters a and b of the yellow fabric sensor provided in example 4 under different pH environments;

fig. 7 is a graph showing the variation trend of the color parameters a and b of the red fabric sensor provided in example 9 under different pH environments.

Detailed Description

For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow.

All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.