CN113430843B - Method for dyeing cotton fabric by reactive dye - Google Patents

Abstract

The invention relates to the field of functional finishing of textiles and discloses a method for dyeing cotton fabrics by using reactive dyes. The method comprises the following steps: (1) completely immersing cotton fabrics in BTCA-sodium hypophosphite mixed solution, stirring for 10-15min, wherein the ratio of the cotton fabrics to the BTCA-sodium hypophosphite mixed solution is 3-5g/100mL, then removing redundant solution by rolling, controlling the rolling residue of the cotton fabrics to be 96-105 wt%, then drying the cotton fabrics, then solidifying for 4-12min at the temperature of 140-160 ℃, and then sequentially washing and drying to obtain anion modified cotton fabrics with the substitution degree of 0.4-0.5; (2) and (2) placing the modified cotton fabric obtained in the step (1) into reactive dye liquor with the pH value of 6-8 for dyeing, and then sequentially washing, soaping and drying. The method has simple process flow and good dye-resisting effect.

Description

Method for dyeing cotton fabric with reactive dyes

technical field

The invention relates to the field of textile functional finishing, in particular to a method for dyeing cotton fabrics with reactive dyes.

Background technique

Cotton fiber has a long history as a textile raw material. As early as thousands of years ago, people used cotton spinning and weaving to keep warm. So far, cotton is still one of the most important crops in China. Cotton fiber is very important in our daily life. still plays an important role. For a long time, cotton fiber has been widely used in medical supplies, clothing fabrics, daily production, etc. With the continuous growth of the industrial level, a variety of chemical fiber products have emerged one after another. These synthetic fibers have brought a certain impact to the cotton fiber industry by virtue of their excellent properties. However, with the continuous improvement of people's environmental protection awareness, people will gradually focus on Returning to the development and application of cotton fiber, cotton fiber has always been a natural fiber with its own firmness and wear resistance, washing resistance, high temperature ironing, moisture absorption and dehumidification, soft and non-irritating, comfortable and warm, and insect-resistant. Good quality is favored by people. In the process of industrial production, cotton fiber can be used not only for textile finishing, but also for fiber dyeing. As we all know, reactive dyes are one of the important dyes for cotton fiber dyeing, and the dyeing requirements in production are often varied, sometimes Then the fabric needs to be dyed to achieve the effect of different shades of color. At this time, a large part of the fabric is often selected to be cationized and then dyed to achieve the desired effect. However, this method has complicated and lengthy treatment processes and high costs. Defects, this problem is more pronounced when the content of colored fibers is high.

SUMMARY OF THE INVENTION

The object of the present invention is to overcome the problems of complicated process and higher cost in the prior art in order to obtain fabrics with different shades of color by using cationized dyeing, and to provide a method for dyeing cotton fabrics with reactive dyes. The dyeing method has a simple technological process and a good "dye-repelling" effect, so that the fabric can achieve the effect of different shades of color after dyeing.

In order to achieve the above object, the present invention provides a method for dyeing cotton fabric with reactive dyes, the method comprising the following steps:

(1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution and stirred for 10-15min. The ratio of the cotton fabric to the BTCA-sodium hypophosphite mixed solution is 3-5g/100mL, and then the excess solution is removed by rolling out and controlling The nip rate of the cotton fabric is 96-105% by weight, then the cotton fabric is dried, then cured at 140-160° C. for 4-12 min, and then washed and dried in sequence to obtain an anion modified with a degree of substitution of 0.4-0.5. Sexual cotton fabric;

(2) placing the modified cotton fabric obtained in step (1) in a reactive dye solution with a pH value of 6-8 for dyeing, the dyeing temperature is 60-80°C, the dyeing time is 25-30min, and then sequentially washing, soaping and drying;

Wherein, in step (1), the BTCA-sodium hypophosphite mixed solution contains 8-11% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 4-12% by weight of hypophosphite sodium;

In step (2), the amount of reactive dye in the reactive dye solution is 0.2-1.1% o.w.f.

Preferably, in step (1), the stirring temperature is 20-30° C., and the stirring speed is 20-180 r/min.

Preferably, in step (1), the drying temperature is 75-85° C., and the drying time is 10-15 min.

Preferably, in step (1), the cured cotton fabric is washed with an acetic acid-ethanol mixed solution.

Further preferably, the concentration of acetic acid in the acetic acid-ethanol mixed solution is 0.8-1.5 g/L, and the concentration of ethanol in the acetic acid-ethanol mixed solution is 0.8-1.5 g/L.

Further preferably, the washing times are 2-4 times.

Preferably, in step (1), the drying temperature is 75-85° C., and the drying time is 8-12 min.

Preferably, in step (2), the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100;

Further preferably, the reactive dye is reactive yellow X-R, reactive orange K-G or reactive brilliant blue KN-R.

Further preferably, the reactive dye is reactive orange K-G or reactive brilliant blue KN-R.

Further preferably, the reactive dye is reactive brilliant blue KN-R.

Preferably, in step (2), the reactive dye solution also contains sodium sulfate and sodium carbonate.

Further preferably, the concentration of sodium sulfate in the reactive dye solution is 8-12 g/L, and the concentration of sodium carbonate in the reactive dye solution is 8-12 g/L.

Preferably, in step (2), the washing times are 2-4 times.

Preferably, in step (2), the weight ratio of the modified cotton fabric obtained in the step (1) to the soaping solution is 1:100.

Preferably, in step (2), the soaping temperature is 70-80° C., and the soaping time is 15-20 min.

The dyeing method of the invention has simple technological process, low cost and good "dye repellent" effect.

Description of drawings

Fig. 1 is the infrared spectrogram of the modified cotton fabric obtained in Example 1 before dyeing of the present invention and the unmodified cotton fabric of Comparative Example 1;

Fig. 2 is the SEM photo of comparative example 1 unmodified cotton fabric before dyeing of the present invention;

Fig. 3 is the SEM photo of comparative example 1 unmodified cotton fabric before dyeing of the present invention;

Fig. 4 is the SEM photograph of the modified cotton fabric obtained in Example 1 before dyeing of the present invention;

Fig. 5 is the SEM photograph of the modified cotton fabric obtained in Example 1 before dyeing of the present invention;

Figure 6 is a comparison diagram of the zeta potential of the modified cotton fabric obtained in Example 1 and the unmodified cotton fabric of Comparative Example 1 at different pH values before dyeing of the present invention.

Detailed ways

The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, but not to limit the present invention.

The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.

The invention provides a method for dyeing cotton fabric with reactive dyes, which comprises the following steps:

(1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution and stirred for 10-15min. The ratio of the cotton fabric to the BTCA-sodium hypophosphite mixed solution is 3-5g/100mL, and then the excess solution is removed by rolling out and controlling The nip rate of the cotton fabric is 96-105% by weight, then the cotton fabric is dried, then cured at 140-160° C. for 4-12 min, and then washed and dried in sequence to obtain an anion modified with a degree of substitution of 0.4-0.5. Sexual cotton fabric;

(2) placing the modified cotton fabric obtained in step (1) in a reactive dye solution with a pH value of 6-8 for dyeing, the dyeing temperature is 60-80°C, the dyeing time is 25-30min, and then sequentially washing, soaping and drying;

Wherein, in step (1), the BTCA-sodium hypophosphite mixed solution contains 8-11% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 4-12% by weight of hypophosphite sodium;

In step (2), the amount of reactive dye in the reactive dye solution is 0.2-1.1% o.w.f.

In a specific embodiment, the content of BTCA in the BTCA (1,2,3,4-butanetetracarboxylic acid)-sodium hypophosphite mixed solution may be 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight % by weight, 10% by weight, 10.5% by weight or 11% by weight, the content of sodium hypophosphite in the BTCA-sodium hypophosphite mixed solution can be 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, or 12% by weight %.

Specifically, the ratio of the cotton fabric to the BTCA-sodium hypophosphite mixed solution can be 3g/100mL, 3.1g/100mL, 3.2g/100mL, 3.3g/100mL, 3.4g/100mL, 3.5g/100mL, 3.6 g/100mL, 3.7g/100mL, 3.8g/100mL, 3.9g/100mL, 4g/100mL, 4.1g/100mL, 4.2g/100mL, 4.3g/100mL, 4.4g/100mL, 4.5g/100mL, 4.6g /100mL, 4.7g/100mL, 4.8g/100mL, 4.9g/100mL or 5g/100mL.

In the present invention, the cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution, and the stirring time can be 10min, 10.5min, 11min, 11.5min, 12min, 12.5min, 13min, 13.5min, 14min, 14.25min , 14.5min, 14.75min or 15min.

In specific embodiments, the nip rate of the cotton fabric may be 96 wt%, 96.5 wt%, 97 wt%, 97.5 wt%, 98 wt%, 98.5 wt%, 99 wt%, 99.5 wt%, 100 wt%, 100.5%, 101%, 101.5%, 102%, 102.5%, 103%, 103.5%, 104%, 104.5%, or 105% by weight.

In the present invention, the nip rate refers to the percentage of the weight of the liquid on the fabric to the weight of the fabric itself.

In the present invention, the stirring temperature is 20-30°C. Specifically, the stirring temperature may be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C or 30°C.

In the present invention, the stirring speed is 20-180r/min. Specifically, the stirring speed can be 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min, 120r/min, 130r/min, 140r/min, 150r/min, 160r/min, 170r/min or 180r/min.

In the present invention, the drying temperature is 75-85° C., and the drying time is 10-15 min. In a specific embodiment, the drying temperature may be 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C or 85°C, and the dried The time can be 10min, 10.5min, 11min, 11.5min, 12min, 12.5min, 13min, 13.5min, 14min, 14.5min or 15min.

In the present invention, there is no special requirement for the drying equipment, which can be a conventional choice in the field. Preferably, an electric heating blast drying oven is used to dry the cotton fabric.

In the present invention, in step (1), the cured cotton fabric is washed with an acetic acid-ethanol mixed solution.

Preferably, the concentration of acetic acid in the acetic acid-ethanol mixed solution is 0.8-1.5 g/L, and the concentration of ethanol in the acetic acid-ethanol mixed solution is 0.8-1.5 g/L. Specifically, the concentration of acetic acid in the acetic acid-ethanol mixed solution may be 0.8g/L, 0.9g/L, 1g/L, 1.1g/L, 1.2g/L, 1.3g/L, 1.4g/L or 1.5g/L, the concentration of ethanol in the acetic acid-ethanol mixed solution can be 0.8g/L, 0.9g/L, 1g/L, 1.1g/L, 1.2g/L, 1.3g/L, 1.4g/L L or 1.5g/L.

In a preferred case, the number of times of the washing is 2-4 times. Specifically, the number of washings may be 2, 3 or 4 times.

In the present invention, the drying temperature is 75-85° C., and the drying time is 8-12 min. Specifically, the drying temperature may be 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C or 85°C, and the drying time Can be 8min, 8.5min, 9min, 9.5min, 10min, 10.5min, 11min, 11.5min or 12min.

In the present invention, the degree of substitution of the modified cotton fabric obtained in step (1) may be 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49 or 0.5.

In the present invention, the cotton fabric after polycarboxylation modification treatment has carboxyl groups in its structure, so the degree of substitution of the modified cotton fabric can be determined by calculating the carboxyl group content therein. The larger the degree of substitution, the higher the degree of modification reaction. bigger;

The test method for carboxyl content (degree of substitution) DS is:

(1) Preparation of 100mmol/L NaOH solution

Weigh 1.0 g of solid sodium hydroxide, dissolve it in 50 mL of deionized water, stir well, dilute to 250 mL, and save for later use.

(2) Preparation of 100mmol/L HCl solution

Measure 8.3ml of concentrated hydrochloric acid solution with a pipette and pour it into a volumetric flask, then add deionized water to the volumetric flask, make the volume to 1L, shake well and seal it for later use.

(3) Determination of carboxylic acid group content on modified cotton fabrics

A 5cm x 5cm sample of modified cotton fabric was immersed in 100 mL of 0.5% HCl solution for 16 hours, then the fabric was rinsed with deionized water until the HCl was completely removed from the sample, using a silver nitrate drip test to ensure that the fabric surface was free of chlorine chemical residues. After rinsing, the samples were dried at room temperature. Weigh about 0.25 g of the sample, and soak it in 50 mL of 100 mmol/L NaOH solution for 4 hours at room temperature, seal the container to ensure that NaOH will not react with _CO in the air, and take another 50 mL of 100 mmol/L NaOH solution as a blank control. After 4 hours, the solution was titrated with 100 mmol/L HCl solution. Phenolphthalein was used to determine the end point. In order to improve the accuracy of the method, the amount of titrant was determined by weighing the remaining titrant and calculating the amount used, recording the amount of titrant reacted, performing three experiments and taking the average value,

Its calculation formula is shown in formula (2.1) and formula (2.2):

Q _COOH = (V ₁ C ₁ -V ₂ C ₂ )/m (2.1)

Wherein V ₁ and C ₁ are the volume and concentration of the sodium hydroxide solution used, V ₂ and C ₂ are the concentration and remaining volume of the hydrochloric acid used, and m is the weight of the measured cotton fabric.

In a specific embodiment, in step (2), the pH value of the reactive dye solution can be 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9 or 8.

In the process of experimental research, the inventor found that the modified cotton fabric obtained by this method will hydrolyze the ester bond under acidic or alkaline conditions, and the hydrolysis ability of the ester bond is stronger under alkaline conditions, which will make the hydrolysis of the ester bond stronger. In the solution, the repulsion between the surface of the cotton fiber and the dye anions decreases, resulting in a decrease in the "dye repellency" performance. The stronger the acidity or alkalinity, the worse the "dye repellency" performance. The pH value is set to 6-8, which is beneficial to further improve the "dye repellency" performance.

In a specific embodiment, in step (2), the amount of reactive dye in the reactive dye solution can be 0.2% o.w.f, 0.3% o.w.f, 0.4% o.w.f, 0.5% o.w.f, 0.6% o.w.f, 0.7% o.w.f, 0.8% o.w.f, 0.9% o.w.f, 1% o.w.f or 1.1% o.w.f.

In the present invention, in step (2), the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100.

In the present invention, the reactive dye is reactive yellow X-R, reactive orange K-G or reactive brilliant blue KN-R.

In a preferred case, the reactive dye is reactive orange K-G or reactive brilliant blue KN-R.

Further preferably, the reactive dye is reactive brilliant blue KN-R.

In the present invention, in step (2), the reactive dye solution also contains sodium sulfate and sodium carbonate.

In a preferred case, the concentration of sodium sulfate in the reactive dye solution is 8-12 g/L, and the concentration of sodium carbonate in the reactive dye solution is 8-12 g/L. Specifically, the concentration of sodium sulfate in the reactive dye solution can be 8g/L, 8.25g/L, 8.5g/L, 8.75g/L, 9g/L, 9.25g/L, 9.5g/L, 9.75g/L g/L, 10g/L, 10.25g/L, 10.5g/L, 10.75g/L, 11g/L, 11.25g/L, 11.5g/L, 11.75g/L or 12g/L, the reactive dye The concentration of sodium carbonate in the dye liquor can be 8g/L, 8.25g/L, 8.5g/L, 8.75g/L, 9g/L, 9.25g/L, 9.5g/L, 9.75g/L, 10g/L , 10.25g/L, 10.5g/L, 10.75g/L, 11g/L, 11.25g/L, 11.5g/L, 11.75g/L or 12g/L.

In a specific embodiment, the dyeing temperature can be 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C ℃, 73℃, 74℃, 75℃, 76℃, 77℃, 78℃, 79℃ or 80℃, the dyeing time can be 25min, 25.5min, 26min, 26.5min, 27min, 27.5min, 28min, 28.5min, 29min, 29.5min or 30min.

In the process of experimental research, the inventor found that the modified cotton fabric obtained by the present invention has poor "dye repellency" performance at high temperature. Therefore, in the present invention, in order to achieve a better "dye repellency" effect, the dyeing temperature is set. 60-80℃.

In the present invention, in step (2), the washing times are 2-4 times. Specifically, the number of washings may be 2, 3 or 4 times.

In the present invention, in step (2), the weight ratio of the modified cotton fabric obtained in the step (1) to the soaping solution is 1:100.

In the present invention, in step (2), the temperature of the soaping is 70-80° C., and the time of the soaping is 15-20 min. Specifically, the soaping temperature can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, and the soaping time Can be 15min, 15.5min, 16min, 16.5min, 17min, 17.5min, 18min, 18.5min, 19min, 19.5min or 20min.

The method of the invention has a simple technical process. The cotton fabric is modified and then matched with a suitable dyeing process. The modified cotton fabric can show greater negative charge in the solution. If the dye anion needs to be dyed and modified Cotton fabrics need to overcome greater repulsion, which will make the cotton fabric lighter in color. In addition, the primary hydroxyl sites of the modified cotton fibers become smaller, and the dye anions mainly react with the primary hydroxyl groups on the cotton fibers. , which will also make it difficult to dye the dye, and with the appropriate dyeing process, the K/S value of the dyed cotton fabric will be smaller, the "dye-rejection" effect will be better, and the color depth after dyeing will be lighter, with better application prospects.

The present invention will be described in detail below by means of examples. However, the method described in the present invention is not limited to this. The reactive brilliant blue KN-R used in the examples and comparative examples is C.I. reactive blue 19, which was purchased from Shanghai Aladdin Biotechnology Co., Ltd.

Example 1

(1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution (the BTCA-sodium hypophosphite mixed solution contains 10% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 10% by weight of Sodium phosphite), the ratio of cotton fabric and BTCA-sodium hypophosphite mixed solution is 4g/100mL, stir at 25 ° C for 15min, the stirring speed is 100r/min, then remove excess solution, control cotton fabric The ratio was 100% by weight, then the cotton fabric was put into an electric heating blast drying oven to be dried at 80°C for 10min, then cured at 150°C for 10min, and then the cured cotton fabric was washed 3 times with an acetic acid-ethanol mixed solution. -The concentration of acetic acid in the ethanol mixed solution is 1g/L, and the concentration of ethanol in the acetic acid-ethanol mixed solution is 1g/L, and then placed in an oven at 80°C for 10min to obtain an anion-modified cotton with a degree of substitution DS of 0.451 fabric;

(2) place the modified cotton fabric obtained in step (1) in a reactive dye (reactive brilliant blue KN-R) dye liquor with a pH value of 7 for dyeing (the concentration of sodium sulfate in the reactive dye liquor is 10 g/L) , the concentration of sodium carbonate in the reactive dye solution is 10g/L), the amount of reactive dye in the reactive dye solution is 1% o.w.f, the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100, and the dyeing temperature be 70 ℃, the time of dyeing is 30min, then wash 3 times, then carry out soaping in the soaping solution of 0.1g/L, the weight ratio of the modified cotton fabric obtained in step (1) and the soaping solution is 1 : 100, the temperature of soaping was 70°C, the time of soaping was 15min, and finally dried to obtain the dyed cotton fabric A1.

Example 2

(1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution (the BTCA-sodium hypophosphite mixed solution contains 10% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 10% by weight of Sodium phosphite), the ratio of cotton fabric and BTCA-sodium hypophosphite mixed solution is 3g/100mL, stirred at 20 ° C for 15min, the stirring speed is 80r/min, and then the excess solution is removed, and the cotton fabric is controlled. The ratio was 102% by weight, then the cotton fabric was placed in an electric heating blast drying oven to dry at 75°C for 15min, then cured at 160°C for 5min, and then the cured cotton fabric was washed 3 times with acetic acid-ethanol mixed solution, acetic acid -The concentration of acetic acid in the ethanol mixed solution is 1g/L, the concentration of ethanol in the acetic acid-ethanol mixed solution is 1g/L, and then placed in an oven at 75°C for 11min to obtain an anion-modified cotton with a degree of substitution DS of 0.441 fabric;

(2) place the modified cotton fabric obtained in step (1) in a reactive dye (reactive brilliant blue KN-R) dye solution with a pH value of 6.5 for dyeing (the concentration of sodium sulfate in the reactive dye dye solution is 9 g/L , the concentration of sodium carbonate in the reactive dye solution is 10g/L), the amount of reactive dye in the reactive dye solution is 0.5% o.w.f, the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100, and the dyeing temperature be 60 ℃, the time of dyeing is 30min, then wash 3 times, then carry out soaping in the soaping solution of 0.1g/L, the weight ratio of the modified cotton fabric obtained in step (1) and the soaping solution is 1 : 100, the temperature of soaping is 73 ℃, the time of soaping is 19min, and finally drying obtains the cotton fabric A2 after dyeing.

Example 3

(1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution (the BTCA-sodium hypophosphite mixed solution contains 10% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 5% by weight of Sodium phosphite), the ratio of cotton fabric and BTCA-sodium hypophosphite mixed solution is 4g/100mL, stir at 30 ° C for 15min, the stirring speed is 50r/min, then remove the excess solution, control the cotton fabric The ratio was 98% by weight, and then the cotton fabric was placed in an electric heating blast drying oven to dry at 75 ° C for 11 min, then cured at 145 ° C for 10 min, and then the cured cotton fabric was washed twice with an acetic acid-ethanol mixed solution. -The concentration of acetic acid in the ethanol mixed solution is 1.5g/L, and the concentration of ethanol in the acetic acid-ethanol mixed solution is 1.5g/L, and then placed in an oven at 85 ° C and dried for 10min to obtain an anion modified with a degree of substitution DS of 0.425. Sexual cotton fabric;

(2) The modified cotton fabric obtained in step (1) is placed in a reactive dye (reactive brilliant blue KN-R) dye solution with a pH value of 8 and dyed (the concentration of sodium sulfate in the reactive dye dye solution is 11 g/L) , the concentration of sodium carbonate in the reactive dye solution is 10g/L), the amount of reactive dye in the reactive dye solution is 1.1% o.w.f, the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100, and the dyeing temperature be 78 ℃, the time of dyeing is 25min, then wash 2 times, then carry out soaping in the soaping solution of 0.1g/L, the weight ratio of the modified cotton fabric obtained in step (1) and the soaping solution is 1 : 100, the temperature of soaping was 75°C, the time of soaping was 18min, and finally dried to obtain the dyed cotton fabric A3.

Example 4

(1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution (the BTCA-sodium hypophosphite mixed solution contains 8% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 10% by weight of Sodium phosphite), the ratio of cotton fabric and BTCA-sodium hypophosphite mixed solution is 5g/100mL, stir at 28 ° C for 10min, the stirring speed is 120r/min, then remove the excess solution, control the cotton fabric The ratio was 96% by weight, then the cotton fabric was placed in an electric heating blast drying oven to dry at 85°C for 10min, then cured at 148°C for 10min, and then the cured cotton fabric was washed twice with an acetic acid-ethanol mixed solution, acetic acid - The concentration of acetic acid in the ethanol mixed solution is 1.1 g/L, and the concentration of ethanol in the acetic acid-ethanol mixed solution is 1.1 g/L, and then placed in an oven at 80 ° C and dried for 9 minutes to obtain an anion modified with a degree of substitution DS of 0.423. Sexual cotton fabric;

(2) The modified cotton fabric obtained in step (1) is placed in a reactive dye (reactive brilliant blue KN-R) dye liquor with a pH value of 6 and dyed (the concentration of sodium sulfate in the reactive dye liquor is 10 g/L) , the concentration of sodium carbonate in the reactive dye solution is 9g/L), the amount of reactive dye in the reactive dye solution is 0.8% o.w.f, the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100, and the dyeing temperature be 70 ℃, the time of dyeing is 30min, then wash 4 times, then carry out soaping in the soaping solution of 0.1g/L, the weight ratio of the modified cotton fabric obtained in step (1) and the soaping solution is 1 : 100, the temperature of soaping was 78°C, the time of soaping was 15min, and finally dried to obtain the dyed cotton fabric A4.

Example 5

(1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution (the BTCA-sodium hypophosphite mixed solution contains 8% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 10% by weight of Sodium phosphite), the ratio of cotton fabric and BTCA-sodium hypophosphite mixed solution is 3g/100mL, stir at 30 ° C for 10min, the stirring speed is 150r/min, then remove excess solution, control cotton fabric The ratio was 105% by weight, then the cotton fabric was put into an electric heating blast drying oven to be dried at 80 ° C for 11 min, then cured at 158 ° C for 5 min, and then the cured cotton fabric was washed 4 times with acetic acid-ethanol mixed solution, acetic acid -The concentration of acetic acid in the ethanol mixed solution is 1.2g/L, and the concentration of ethanol in the acetic acid-ethanol mixed solution is 1.2g/L, and then placed in a drying oven at 77°C for 10min to obtain an anion modified with a degree of substitution DS of 0.419. Sexual cotton fabric;

(2) place the modified cotton fabric obtained in step (1) in a reactive dye (reactive brilliant blue KN-R) dye liquor with a pH value of 7 for dyeing (the concentration of sodium sulfate in the reactive dye liquor is 10 g/L) , the concentration of sodium carbonate in the reactive dye solution is 8g/L), the amount of reactive dye in the reactive dye solution is 0.2% o.w.f, the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100, and the dyeing temperature It is 80 DEG C, the time of dyeing is 25min, then washed 4 times, then soaped in the soaping solution of 0.1g/L, and the weight ratio of the modified cotton fabric obtained in step (1) to the soaping solution is 1 : 100, the temperature of soaping was 71°C, the time of soaping was 15min, and finally dried to obtain the dyed cotton fabric A5.

Example 6

(1) The cotton fabric is completely immersed in the mixed solution of BTCA-sodium hypophosphite (the mixed solution of BTCA-sodium hypophosphite contains 11% by weight of BTCA, and the mixed solution of BTCA-sodium hypophosphite contains 4% by weight of Sodium phosphite), the ratio of cotton fabric and BTCA-sodium hypophosphite mixed solution is 5g/100mL, stir at 23 ° C for 15min, the stirring speed is 120r/min, then remove the excess solution, control the cotton fabric The ratio was 100% by weight, and then the cotton fabric was placed in an electric heating blast drying oven to dry at 83 ° C for 10 min, then cured at 140 ° C for 12 min, and then the cured cotton fabric was washed 3 times with an acetic acid-ethanol mixed solution, acetic acid -The concentration of acetic acid in the ethanol mixed solution is 1.5g/L, and the concentration of ethanol in the acetic acid-ethanol mixed solution is 1.5g/L, and then placed in an oven at 83 ° C and dried for 8min to obtain an anion modified with a degree of substitution DS of 0.433. Sexual cotton fabric;

(2) place the modified cotton fabric obtained in step (1) in a reactive dye (reactive brilliant blue KN-R) dye liquor with a pH value of 7 for dyeing (the concentration of sodium sulfate in the reactive dye liquor is 10 g/L) , the concentration of sodium carbonate in the reactive dye solution is 9g/L), the amount of reactive dye in the reactive dye solution is 1% o.w.f, the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100, and the dyeing temperature be 65 ℃, the time of dyeing is 30min, then wash 2 times, then carry out soaping in the soaping solution of 0.1g/L, the weight ratio of the modified cotton fabric obtained in step (1) and the soaping solution is 1 : 100, the temperature of soaping is 70 ℃, the time of soaping is 20min, and finally drying obtains the cotton fabric A6 after dyeing.

Example 7

(1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution (the BTCA-sodium hypophosphite mixed solution contains 9% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 12% by weight of Sodium phosphite), the ratio of cotton fabric and BTCA-sodium hypophosphite mixed solution is 4g/100mL, stirred at 22 ° C for 15min, the stirring speed is 125r/min, and then the excess solution is removed, and the cotton fabric is controlled. The ratio was 103% by weight, then the cotton fabric was placed in an electric heating blast drying oven to be dried at 76 ° C for 12 min, then cured at 157 ° C for 4 min, and then the cured cotton fabric was washed twice with acetic acid-ethanol mixed solution, acetic acid -The concentration of acetic acid in the ethanol mixed solution is 1.2g/L, and the concentration of ethanol in the acetic acid-ethanol mixed solution is 1.2g/L, and then placed in a drying oven at 75°C for 12min to obtain an anion modified with a degree of substitution DS of 0.437. Sexual cotton fabric;

(2) place the modified cotton fabric obtained in step (1) in a reactive dye (reactive brilliant blue KN-R) dye solution with a pH value of 7 and dye it (the concentration of sodium sulfate in the reactive dye dye solution is 9 g/L) , the concentration of sodium carbonate in the reactive dye solution is 11g/L), the amount of reactive dye in the reactive dye solution is 0.9% o.w.f, the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100, and the dyeing temperature be 70 ℃, the time of dyeing is 30min, then wash 2 times, then carry out soaping in the soaping solution of 0.1g/L, the weight ratio of the modified cotton fabric obtained in step (1) and the soaping solution is 1 : 100, the soaping temperature was 80°C, the soaping time was 15 min, and finally the dyed cotton fabric A7 was obtained by drying.

Comparative Example 1

According to the method described in Example 1, the difference is that the cotton fabric is directly dyed without modification treatment to obtain the dyed cotton fabric D1.

Comparative Example 2

According to the method described in Example 4, the difference is that in step (1), the BTCA-sodium hypophosphite mixed solution contains 5% by weight of BTCA to obtain a modified cotton fabric with a degree of substitution DS of 0.373 , and then dyed to obtain the dyed cotton fabric D2.

Comparative Example 3

According to the method described in Example 6, the difference is that in step (1), the BTCA-sodium hypophosphite mixed solution contains 14% by weight of BTCA to obtain a modified cotton fabric with a degree of substitution DS of 0.343 , and then dyed to obtain the dyed cotton fabric D3.

Comparative Example 4

According to the method described in Example 6, the difference is that, in step (1), the BTCA-sodium hypophosphite mixed solution contains 2% by weight of sodium hypophosphite to obtain a modified DS with a degree of substitution of 0.313. The dyed cotton fabric is then dyed to obtain the dyed cotton fabric D4.

Comparative Example 5

According to the method described in Example 7, the difference is that in step (1), the BTCA-sodium hypophosphite mixed solution contains 16% by weight of sodium hypophosphite, to obtain a modified DS with a degree of substitution of 0.339. The dyed cotton fabric is then dyed to obtain the dyed cotton fabric D5.

Comparative Example 6

According to the method described in Example 6, the difference is that in step (1), the curing time is 17min to obtain a modified cotton fabric with a degree of substitution DS of 0.335, and then dyed to obtain a dyed cotton fabric Fabric D6.

Comparative Example 7

According to the method described in Example 7, the difference is that in step (1), the curing time is 2min to obtain a modified cotton fabric with a degree of substitution DS of 0.327, and then dyed to obtain a dyed cotton fabric Fabric D7.

Comparative Example 8

According to the method described in Example 3, the difference is that in step (2), the pH of the reactive dye solution is 8.5, and the dyed cotton fabric D8 is obtained.

Comparative Example 9

According to the method described in Example 4, the difference is that in step (2), the pH of the reactive dye solution is 5, and the dyed cotton fabric D9 is obtained.

Comparative Example 10

According to the method described in Example 2, the difference is that in step (2), the dyeing temperature is 50° C. to obtain the dyed cotton fabric D10.

Comparative Example 11

According to the method described in Example 5, the difference is that in step (2), the dyeing temperature is 90° C. to obtain the dyed cotton fabric D11.

Test Example 1

Fourier transform infrared spectrometer (Bruker TENSOR-II) was used to conduct infrared analysis on the modified cotton fabric of Example 1 before dyeing and the unmodified cotton fabric of Comparative Example 1 (in order to reduce the influence of bound water, the The unmodified cotton fabric powder and the modified cotton fabric powder were dried at 100°C for 2h), the spectral scanning range of the samples to be tested was 400-4000cm ^-1 , the number of scans: 32 times, the resolution: 4cm ^-1 .

The results are shown in Figure 1. The stretching vibration peak of the ester carbonyl group at 1732 cm ^-1 corresponds to the stretching vibration peak of CO in the COC group at 1022 cm ^-1 . The peak at 1596 cm ^-1 is the carboxyl group reaction that is not involved in the conversion. It becomes the stretching vibration peak of the carbonyl group in the carboxylate, the peak at 2900cm ^-1 is the stretching vibration peak of the methylene carbon-hydrogen bond in cellulose, and as shown in the figure, the blank cotton fabric does not have a peak near 1732cm ^-1 . The corresponding stretching vibration peak was found, and the corresponding stretching vibration peak was found in the modified cotton fabric near 1732cm ^-1 , which indicated that the polycarboxylic acid molecule (BTCA) had undergone esterification reaction with the hydroxyl group in cellulose after modification and formed ester bond.

Test case 2

The microstructures of the modified cotton fabric of Example 1 and the unmodified cotton fabric of Comparative Example 1 before dyeing were photographed by scanning electron microscope. The SEM photos of the unmodified cotton fabric are shown in Figures 2-3. The photo is shown in Figure 4-5,

As shown in the figure, the modified cotton fibers swelled, and there were cross-links between the fibers. The surface of the fibers became rough and wrinkled and deposited deposits. This is because the acidity of the BTCA solution will damage the cotton fiber structure. And due to the tetracarboxyl structure of BTCA, it will undergo an esterification reaction with multiple cotton fiber molecules during the modification process to form multiple crosslinks.

Test case 3

The electric solid surface analyzer SurPASS 3 was used to measure the zeta potential of the modified cotton fabric of Example 1 before dyeing and the unmodified cotton fabric of Comparative Example 1 at different pH values by the slit method, and the temperature parameter was set to 20 °C;

The results are shown in Figure 6. When the pH value is 10, the absolute value of the surface zeta potential of the BTCA-modified cotton fabric is the largest. At this time, the zeta potential value is -32.09mV. This is because the cotton fabric treated with BTCA has a More carboxyl structure, so its surface has more negative charge, which is more negatively charged.

Test Example 4

Determine the K/S value of A1-A7, D1-D11 and the color difference ΔE between A1-A7, D2-D11 and D1;

The dyed cotton fabric was tested with a color matching instrument, and the L, a, b and K/S values of the dyed cotton fabric were obtained, compared with the blank cotton fabric, and calculated by formula (1.1) ΔE.

The results are shown in Table 1.

Table 1

It can be seen from the results in Table 1 that the dyed cotton fabric obtained by the method of the present invention has a small K/S value and a good "dye repellent" effect.

The preferred embodiments of the present invention have been described above in detail, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, a variety of simple modifications can be made to the technical solutions of the present invention, including combining various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the content disclosed in the present invention. All belong to the protection scope of the present invention.

Claims (16)

1. a reactive dyestuff is to the dyeing method of cotton fabric, it is characterised in that the method comprises the following steps: (1) The cotton fabric is completely immersed in the BTCA-sodium hypophosphite mixed solution and stirred for 10-15min. The ratio of the cotton fabric to the BTCA-sodium hypophosphite mixed solution is 3-5g/100mL, and then the excess solution is removed by rolling out and controlling The nip rate of the cotton fabric is 96-105% by weight, then the cotton fabric is dried, then cured at 140-160° C. for 4-12 min, and then washed and dried in sequence to obtain an anion modified with a degree of substitution of 0.4-0.5. Sexual cotton fabric; (2) placing the modified cotton fabric obtained in step (1) in a reactive dye solution with a pH value of 6-8 for dyeing, the dyeing temperature is 60-80°C, the dyeing time is 25-30min, and then sequentially washing, soaping and drying; Wherein, in step (1), the BTCA-sodium hypophosphite mixed solution contains 8-11% by weight of BTCA, and the BTCA-sodium hypophosphite mixed solution contains 4-12% by weight of hypophosphite sodium; In step (2), the amount of reactive dye in the reactive dye solution is 0.2-1.1% o.w.f. 2 . The method according to claim 1 , wherein, in step (1), the temperature of the stirring is 20-30° C., and the speed of the stirring is 20-180 r/min. 3 . 3 . The method according to claim 1 , wherein, in step (1), the drying temperature is 75-85° C., and the drying time is 10-15 min. 4 . 4. The method according to claim 1, characterized in that, in step (1), the cured cotton fabric is washed with an acetic acid-ethanol mixed solution. 5. method according to claim 4, is characterized in that, in described acetic acid-ethanol mixed solution, the concentration of acetic acid is 0.8-1.5g/L, and in described acetic acid-ethanol mixed solution, the concentration of ethanol is 0.8-1.5g /L. 6. The method according to claim 4, wherein the washing times are 2-4 times. 7. The method according to claim 1, wherein in step (1), the drying temperature is 75-85°C, and the drying time is 8-12 min. 8. The method according to claim 1, wherein in step (2), the weight ratio of the modified cotton fabric to the reactive dye solution is 1:100. 9. The method according to claim 8, wherein the reactive dye is reactive yellow X-R, reactive orange K-G or reactive brilliant blue KN-R. 10. The method according to claim 8, wherein the reactive dye is reactive orange K-G or reactive brilliant blue KN-R. 11. The method according to claim 8, wherein the reactive dye is reactive brilliant blue KN-R. 12. The method according to claim 1 or 8, characterized in that, in step (2), the reactive dye solution also contains sodium sulfate and sodium carbonate. 13. method according to claim 12, is characterized in that, the concentration of sodium sulfate in described reactive dye liquor is 8-12g/L, and the concentration of sodium carbonate in described reactive dye liquor is 8-12g/L . 14. The method according to claim 1, characterized in that, in step (2), the washing times are 2-4 times. 15. The method according to claim 1 or 14, characterized in that, in step (2), the weight ratio of the modified cotton fabric obtained in step (1) to the soaping solution is 1:100. 16. The method according to claim 15, wherein in step (2), the temperature of the soaping is 70-80°C, and the time of the soaping is 15-20 min.

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