TWI751552B - Manufacturing method of dyeing auxiliary - Google Patents

Abstract

The present invention provides a manufacturing method of dyeing auxiliaries. Using gelatin, tartaric acid, epichlorohydrin and sodium bisulfite as raw materials, the surfactant of hydrolyzed gelatin derivatives is synthesized by reaction, and the cohesive properties of the auxiliaries are used to make The dyes in the dyeing and finishing wastewater are caught and brought into the cellulose fabric, in order to increase the dyeing rate of the fabric during the dyeing process and reduce the residual rate of dyes in the subsequent wastewater.

Description

Manufacturing method of dyeing auxiliaries

The present invention belongs to the field of dyeing auxiliaries, and particularly relates to a method for manufacturing a dyeing auxiliaries which can improve the coloring rate during dyeing and reduce the residual rate of dyestuffs in subsequent waste water.

Press, in the textile industry, the dyeing and finishing process is a very important part, which will determine the performance of the finished product. With the progress of the times, the treatment technology and construction methods have been advancing with each passing day. The disposal is still one of the most thorny issues in today's generation that advocates environmental protection. The main pollutants in these dyeing and finishing wastewater are organic compounds of dyes. These substances are easily discharged into the river and cause a huge impact on the ecology. For the dyeing and finishing industry, in order to meet economic benefits, most of the treatment methods for dyeing and finishing wastewater are combined with biological Treatment and chemical coagulation procedures, there are currently about 10,000 different dyes used in industrial production grade, and 7x10 ⁵ kinds of auxiliaries, produced all over the world. However, even if the existing auxiliaries on the market are used to help the dyeing and finishing process, there are still about 20~25% of the dye compounds that cannot be attached to the fabric during the dyeing and finishing process and are discharged with the waste water. It is necessary to use more effective auxiliaries to reduce the harm of dyeing and finishing wastewater to the environment.

In view of this, the inventor of the present invention feels that it is not perfect and exhausts his mind and painstaking research, and based on his accumulated experience in the industry for many years, and further provides a manufacturing method of dyeing auxiliaries, in order to improve the above-mentioned conventional technology. missing.

One objective of the present invention is to provide a method for manufacturing dyeing auxiliaries, so as to increase the dyeing rate of fabrics during the dyeing process and reduce the residual rate of dyes in the subsequent waste water.

Moreover, the present invention also provides a method for preparing dyeing auxiliaries, comprising the following steps: (A) dissolving 0.2 moles of tartaric acid in water, then adding alcohol, placing it in a four-hole reaction tank and stirring for 30 minutes, and heating to 70 during the stirring process ℃, generate a first excess product and water; (B) add 50 ml of 20% gelatin to the first excess product and heat to 70°C, react for 1 to 2 hours, generate a second excess product; (C) This first excess product Second, after the excessive product is cooled down to room temperature, the mixed solution of epichlorohydrin and sodium bisulfite that has been adjusted to pH9 is added, and the dyeing auxiliary can be generated by stirring at a constant temperature of 50 ° C for 1 to 2 hours. The molar ratio of oxychloropropane and sodium bisulfite is 1:1.

Preferably, the present invention further comprises the following steps: (D) adding the dyeing auxiliaries to ethanol for dissolving, filtering, and then distillation under reduced pressure to remove the solvent, so as to obtain the dyeing auxiliaries with high purity.

In addition, the present invention provides a dyeing process using dyeing auxiliaries to improve the coloring rate. and (3) taking out the fibrous fabric, washing and soaping with water, and then drying it naturally.

Preferably, after the fiber fabric is put into a steel cylinder and sealed, it is heated and dyed at a rate of 2°C per minute from 30°C.

Preferably, the material of the fiber fabric is nylon fiber.

In this way, through the dyeing auxiliaries provided by the present invention, the content of dye compounds in the wastewater after dyeing can be greatly reduced, thereby reducing the pollution after the wastewater is discharged. It can not only improve the coloring rate of the fabric, but also reduce the ratio of dye compounds in the wastewater generated after the process.

Figure 1 is a graph of experimental data showing whether dyeing auxiliaries have the characteristics of auxiliaries.

Figure 2 shows the experimental data of whether excessive foaming occurs after dyeing auxiliaries.

Figure 3 is a graph of the electrical conductivity data of dyeing auxiliaries under different auxiliaries concentrations.

Figure 4 is the experimental data diagram of the dyeing rate of dyeing auxiliaries on nylon fabrics under different auxiliaries concentrations.

Figure 5 is the experimental data diagram of the dyeing rate of nylon fabrics by dyeing auxiliaries under different dyeing times.

Figure 6 is the experimental data diagram of the dyeing rate of dyeing auxiliaries on nylon fabrics at different dyeing temperatures.

Fig. 7 is the experimental data graph of the dyeing rate of dyeing auxiliaries on nylon fabrics under different dye concentrations.

Figure 8 is the experimental data diagram of the dyeing rate of dyeing auxiliaries on nylon fabrics under different pH.

In order to enable those skilled in the art to clearly understand the content of the present invention, please refer to the following descriptions and drawings.

In this embodiment, a dyeing auxiliary provided by the present invention is made by the following method: first, dissolve 0.2 moles of tartaric acid in water, add alcohol and place it in a four-hole reaction tank to stir for 30 minutes, and stir During heating to 70°C, a first excess product and water are formed. Next, add 50 ml of 20% gelatin to the first excess product and heat to 70° C., and react for 1 to 2 hours to generate a second excess product. Finally, after the second excess product is cooled to room temperature, the mixed solution of epichlorohydrin and sodium bisulfite that has been adjusted to pH 9 is added, and the dyeing auxiliary can be generated by stirring at a constant temperature of 50 ° C for 1 to 2 hours. , wherein the molar ratio of epichlorohydrin and sodium bisulfite is 1:1.

After the process is completed, follow-up treatment can also be performed to purify the composite, dissolve the raw materials of the unfinished reaction with ethanol, filter, and then distill under reduced pressure to remove the solvent and excess water to obtain a higher-purity composite, and Different concentrations are prepared for different dyeing conditions.

Figure 1 shows the data analysis of the dyeing auxiliaries to confirm whether the dyeing auxiliaries have the characteristics of the auxiliaries. The X-axis is the concentration of the auxiliary, the Y-axis is the surface tension, and the Gelatin is Hydrolyzed gelatin, Gelatin-TA is the dyeing auxiliary of the present invention.

When pure water is at 25°C, the surface tension is about 72.4 dyne/cm. When the auxiliary agent is added, the surface tension will decrease with the increase of its concentration. It can be seen in Figure 1 that when the dyeing auxiliary agent is added, the surface tension decreases. The tension drops significantly, and as the concentration of the added auxiliaries increases, the surface tension also decreases slightly, so it can be determined that the dyeing auxiliaries have the characteristics of auxiliaries. The surface tension is reduced due to the way in which the part of the hydrophilic group of the surfactant remains in the liquid, while the part of the hydrophobic group protrudes from the water surface. Moreover, it can be seen from Figure 1 that the surface tension of the hydrolyzed gelatin derivative Gelatin-TA is lower than that of hydrolyzed gelatin, which helps the dye to enter the fiber, because the dyeing auxiliaries have multiple hydrophilic groups. It is difficult for the hydrophobic groups of the surfactant to be closely and regularly adsorbed on the water surface, so the reduction of the surface tension becomes smaller, and the surface tension appears to ease after reaching a low point when the concentration of the auxiliary agent is 0.2%. The dyeing auxiliaries are relatively stable.

Figure 2 is a schematic diagram of the results obtained after conducting experiments on whether excessive foaming will occur after adding the dyeing auxiliary. Gelatin is hydrolyzed gelatin, and Gelatin-TA is the dyeing auxiliary of the present invention.

Pure water does not foam, but when the solution contains surfactants, the solution is stirred, and air enters the solution to form bubbles. At this time, the additives will be adsorbed at the interface between the liquid and gas phases to form an elastic film. Therefore, If there is gas in the liquid, there will be foam. Derivatives can be seen from Figure 2 The hydrophilic groups and hydrophobic groups of Gelatin-TA are arranged in disorder, and it is not easy to arrange neatly and tightly around the bubbles, that is, it is not easy to form a stable elastic film at the interface, so when the bubbles are generated, they are quickly destroyed, so it can reduce the occurrence of bubbles. Foamy.

Figure 3 is a schematic diagram of the results obtained after conducting experiments to measure the electrical conductivity of dyeing auxiliaries under different auxiliaries concentrations. Gelatin is hydrolyzed gelatin, and Gelatin-TA is the dyeing auxiliary of the present invention.

It can be observed from Figure 3 that with the increase of concentration, the conductivity of Gelatin-TA derivatives will gradually increase, while the hydrolyzed gelatin gradually increases and is close to gentle. The higher the conductivity, the higher the degree of ion dissociation or the more ions in the solution, so the use of Gelatin-TA derivatives helps to increase the dyeing rate of nylon fabrics.

In the dyeing process, the most ideal situation is to make the dyed fabric fully absorb the dye, so that the finished product can be close to the original color of the dye, and the problem of excessively high color of the discharged wastewater is solved, but it is often difficult to operate on site achieved. Therefore, in this embodiment, the present invention provides a dyeing process that utilizes the above-mentioned dyeing auxiliaries to improve the coloring rate and reduce the residual rate of dyes in wastewater, which includes the following steps: (1) adding dyes and a Auxiliary agent for dyeing; (2) put a fiber fabric into a steel cylinder and seal it for dyeing; and (3) take out the fiber fabric, wash it with water and soap, and then dry it naturally. In this embodiment, nylon fibers are used for the dyed fabric. Among them, after the fiber fabric is placed in a steel cylinder and sealed, it is heated and dyed from 30°C at a rate of 2°C per minute. Through this heating rate, the dyeing process can be more stable and the coloring rate can be improved.

Figures 4 to 8 show the results of detecting the dyeing rate of nylon fabrics after the dyeing process is completed under different auxiliaries concentration, dyeing time, dyeing temperature, dye concentration and pH. Intentionally, Gelatin is hydrolyzed gelatin, Gelatin-TA is the dyeing auxiliary of the present invention, and Blank is a control group without adding auxiliary.

From Figure 4, it can be observed that when the concentration of the auxiliary agent increases, the coloring rate also increases. When the concentration of its derivative Gelatin-TA reaches 15 (g/L), a higher coloring rate can be obtained. When the concentration increases When the coloring rate decreases, the concentration of the derivative Gelatin-TA is 15 (g/L) in order to obtain a high coloring rate. It can also be seen from Figure-5 that when dyeing nylon fabrics, Gelatin-TA derivatives can help dye nylon fabrics more than hydrolyzed gelatin, so Gelatin-TA derivatives can improve the dyeing rate of nylon fabrics.

Time is a necessary condition for fiber dyeing, and dyeing is a complex process. The dyeing process generally includes three stages: adsorption, diffusion and fixation. All three stages require a certain amount of time to complete the staining procedure. From Figure 5, it can be observed that the dyeing rate of hydrolyzed gelatin and its derivative Gelatin-TA increases when the dyeing time increases. When the time reaches 60 minutes, the derivative Gelatin-TA has the highest coloring rate, and the coloring rate decreases when the time is longer. Therefore, it can be seen that the best holding time is 60 minutes. Excessive holding time will only increase the dyeing cost. And cause a waste of power.

Generally, dyeing and finishing plants and setting equipment use boilers for heating by steam or electric heat. Therefore, knowing the optimal coloring temperature of fibers and dyes by auxiliaries can help reduce the use of energy. It can be seen from Figure 6 that with the increase of the dyeing temperature, the dyeing rate also increases. When the dyeing temperature of hydrolyzed gelatin and its derivative Gelatin-TA reaches 90 °C, the highest dyeing rate can be obtained, and The coloring rate of the derivative Gelatin-TA is higher than that of hydrolyzed gelatin. When the temperature increases to 100 and 110 °C, the coloring rate decreases. Therefore, the optimal temperature for nylon fabrics to achieve high coloring rate is 90 °C. Too much temperature will only Increase energy consumption.

The dye concentration must be increased in order to obtain a dark color in the fabric, so it is very important to know the maximum absorption value of the dye by the fabric. From Figure 7, it can be observed that when the dye concentration is increased, the nylon fabric is colored The dyeing ratio also increases, but when the dye concentration reaches 1.5%, the dyeing ratio is only slightly increased, so the optimal dye concentration of nylon fabric is 1.5%, and the dyeing ratio of nylon fabric is obtained by using the derivative Gelatin-TA as dyeing auxiliaries. All are higher than hydrolyzed gelatin and nylon fabric without additives.

In order to improve the dyeing rate of the fabric during dyeing, acid and alkali chemicals are added to the dye bath to change the pH value of the dye bath, so it is very important whether the auxiliaries can also help the fabric dye under the change of the pH value of the dye bath. From Figure 8, it can be observed that the nylon fabric has a higher coloring rate when the pH value is weak acid or weak base. It may be that the auxiliaries are acidic, which makes the pH value of the original dyeing bath more acidic, and the negatively charged dyes will be affected by nylon. The surface of the fiber molecule [H ⁺ ] is adsorbed, thereby increasing the number of protons on the surface of the nylon fiber molecule, and promoting the electrostatic potential and positive charge on the surface of the nylon fiber molecule, thereby increasing the force on the acid dye anion and improving the nylon fiber. For the adsorption effect of acid dyes, when the pH value of the dye bath is 3, hydrolyzed gelatin and its derivative Gelatin-TA will be restrained by anions in the dye bath, so that the dyeing rate of nylon fabrics is slightly lower.

To sum up, the above experimental data show that adding the dyeing auxiliary provided by the present invention during dyeing will increase the dyeing rate of nylon fabrics to direct dyes. And has the following advantages or effects:

1. The dyeing auxiliaries of hydrolyzed gelatin derivatives have good foam defoaming, almost no foam, and will not cause defects in the dyeing process, so it is very suitable for dyeing and finishing auxiliaries.

2. The dyeing auxiliaries of hydrolyzed gelatin derivatives are added to the dyeing bath of acid dyes to dye nylon fabrics, which can improve the dyeing rate of nylon fabrics.

3. The dyeing auxiliaries of hydrolyzed gelatin derivatives are used to dye nylon fabrics, and the pH value is changed in the dyeing bath. The dyeing rate of the hydrolyzed gelatin derivative Gelatin-TA is higher than that of hydrolyzed gelatin.

4. The dyeing auxiliaries of hydrolyzed gelatin and its derivatives are used for dyeing nylon fabrics, and the conditions for obtaining high dyeing rate are: auxiliaries concentration of 1.5%, dyeing temperature of 90°C, dyeing holding time of 60 minutes and dye concentration of 1.5% .

5. The dyeing auxiliaries of hydrolyzed gelatin derivatives can improve the dyeing rate of nylon fabrics and effectively reduce the dye content in wastewater.

Therefore, the dyeing auxiliaries can indeed improve the dyeing rate of the fabric, and at the same time, it can reduce the residual dye content in the waste water produced later, so as to avoid further pollution to the environment.

However, the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of implementation of the present invention; therefore, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be included in the within the scope of the patent of the present invention.

Claims (2)

A method for preparing dyeing auxiliaries, comprising the following steps: (A) dissolving 0.2 moles of tartaric acid in water, then adding alcohol, placing it in a four-hole reaction tank and stirring for 30 minutes, and heating to 70° C. during the stirring process to generate a first an excess product and water; (B) add 50 ml of 20% gelatin to the first excess product and heat to 70° C., and react for 1 to 2 hours to generate a second excess product; (C) cool the second excess product to reduce After reaching room temperature, add the mixed solution of epichlorohydrin and sodium bisulfite that has been adjusted to pH 9, and stir at a constant temperature of 50 ° C for 1 to 2 hours to generate the dyeing auxiliaries. The molar ratio of sodium bisulfate is 1:1. The method of claim 1 further comprises the following steps: (D) adding the dyeing auxiliary to ethanol to dissolve, filtering, and then vacuum distillation to remove the solvent, so as to obtain the dyeing auxiliary with high purity.

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