TWI628192B - Dyeing auxiliary agent, its manufacturing method and applied dyeing process - Google Patents

Abstract

The invention provides a dyeing auxiliary agent, a manufacturing method thereof and a dyeing process applied thereto, and the agglutination property of the auxiliary agent is utilized by grafting a natural material chitosan with a fatty acid to form a chitosan derivative type auxiliary agent. The dye in the dyeing and finishing wastewater is grasped and brought into the cellulose fabric in order to increase the dyeing rate of the cloth in the dyeing process and to lower the dye residual rate of the wastewater generated subsequently.

Description

Dyeing auxiliary agent, its manufacturing method and applied dyeing process

The present invention relates to the field of dyeing auxiliaries, and more particularly to a dyeing auxiliary which can improve the coloring rate at the time of dyeing and reduce the dye residual ratio of the wastewater generated subsequently, a method for producing the same, and a dyeing process applied thereto.

According to the textile industry, the dyeing and finishing process is a very important part, which will determine the performance of the finished product. With the advancement of the times, the processing technology and engineering methods have been advancing with each passing day, but the dyed and finished high-color wastewater The handling of this is still the most difficult issue in the current generation of environmental protection. The main pollutants in these dyeing and finishing wastewaters are organic compounds of dyes, which are easily affected by the discharge of the substances in the river. For the dyeing and finishing industry, in order to meet the economic benefits, most of the dyeing and finishing treatment methods use biological treatment and chemical coagulation procedures. Currently, there are about 10,000 different dyes produced and used in the industry, and there are 7x10 ⁵ different kinds of assistance. The agents are used in the dyeing process individually or in combination. However, even if the existing additives on the market are used to help the dyeing process, about 20~25% of the dye compounds can not be attached to the fabric during the dyeing and finishing process, and as the wastewater is discharged, it is needed in the process. Use more effective additives to reduce the environmental damage caused by dyeing and finishing wastewater.

In view of this, the inventors feel that they have not perfected their efforts and painstakingly studied it, and based on their accumulated experience in the industry for many years, they provide a dyeing auxiliary, its manufacturing method and the applied dyeing process, with a view to The lack of the above-mentioned prior art can be improved.

In view of the above, an object of the present invention is to provide an auxiliary agent for dyeing, a method for producing the same, and a dyeing process applied to increase the dyeing rate of the cloth in the dyeing process and to lower the dye residual rate of the wastewater generated subsequently. .

In order to achieve the above object, the dyeing auxiliary agent of the present invention is provided for improving the coloring ratio at the time of dyeing and reducing the dye residual ratio of the wastewater generated later, characterized in that the dyeing aid has a general formula of

Wherein R represents an alkyl group having 12 to 16 carbon atoms, and n is 1000 to 3,000.

Moreover, the present invention also provides a method for preparing an auxiliary for dyeing, comprising the steps of: (A) dissolving chitosan in an aqueous acid solution and stirring to a uniform state; (B) stirring the chitosan with uniformity and The epichlorohydrin was mixed and stirred at a constant temperature of 70 ° C for 2 hours; (C) additionally, the monoacid was mixed with sodium hydrogen sulfite and stirred at a temperature of 80 ° C to 90 ° C for 2 hours; (D) the step The product of C is mixed with thiophosphorus chloride to produce a chlorosulfonation reaction; and (E) the product of step B and the product of step D are subjected to a synthesis reaction at a temperature of 100 ° C for 2 hours to remove water, thereby obtaining a dyeing Use additives. Wherein, the general formula of the dyeing auxiliary agent is

Wherein R represents an alkyl group having 12 to 16 carbon atoms, and n is 1000 to 3,000.

Preferably, the aqueous acid solution is an aqueous acetic acid solution.

Preferably, the acid is one of myristic acid, palmitic acid or stearic acid.

In addition, the present invention further provides a dyeing process for improving the coloring rate by using a dyeing auxiliary agent, comprising the steps of: (1) adding a dye and a dyeing auxiliary agent to the steel cylinder; and (2) placing a fiber fabric into the steel bottle. After the medium is closed, the dyeing is carried out; and (3) the fiber fabric is taken out, washed with water and soaped, and then naturally dried. Wherein, the general formula of the dyeing auxiliary agent is

Wherein R represents an alkyl group having 12 to 16 carbon atoms, and n is 1000 to 3,000.

Further, the material of the fiber fabric is a natural fiber.

In this way, the dyeing auxiliary provided by the invention can greatly reduce the dyeing The content of the dye compound in the waste water, thereby reducing the pollution after the discharge of the waste water, and the dyeing process described above can also increase the coloring rate of the fabric and reduce the wastewater generated after the process by adding the auxiliary agent for the dyeing. The ratio of medium dye compounds.

In the following description, the same components are denoted by the same reference numerals for the sake of understanding.

In the present embodiment, one of the dyeing aids provided by the present invention is produced by the following method: First, the chitosan is dissolved in an aqueous acid solution and stirred to a uniform state, where the aqueous acid solution is It is made of acetic acid. Next, the uniformly stirred chitosan was mixed with epichlorohydrin and stirred at a constant temperature of 70 ° C for 2 hours, at which time a first intermediate product was produced by the reaction. Further, a monoacid was mixed with sodium hydrogen sulfite, and the acid was myristic acid, and the mixture was stirred at a temperature of 80 ° C to 90 ° C for 2 hours. Next, the product obtained by mixing myristic acid and sodium hydrogen sulfite is mixed with thiopurine chlorine to produce a chlorosulfonation reaction, and a second intermediate product is produced. Finally, the first intermediate product and the second intermediate product are subjected to a synthesis reaction at a temperature of 100 ° C for 2 hours, and then the water is removed to obtain the dyeing auxiliary. At this time, the chemical structure of the dyeing auxiliary agent is

The n series is 1000-3000. After the process is completed, a subsequent treatment may be performed to purify the composition, and the raw materials of the unreacted reaction are dissolved in ethanol, and then filtered, and the solvent and excess water are distilled off under reduced pressure to obtain a composition of higher purity, and Different concentrations are modulated for different dyeing conditions.

Fig. 1 is a graph showing the data analysis of the dyeing auxiliary agent, and further confirming whether or not the dyeing auxiliary agent has an auxiliary property.

When the pure water is at 25 ° C, the surface tension is about 72.4 dyne / cm. When the additive is added, the surface tension will decrease as the concentration increases. It can be seen in Figure 1 that when the dyeing auxiliary is added, The concentration of the additive added is increased, and the surface tension is decreased accordingly, thereby determining the auxiliary agent for dyeing Has the characteristics of additives.

Fig. 2 is a schematic diagram showing the results obtained after an experiment was conducted on whether or not excessive foaming occurred after the addition of the dyeing auxiliary.

Since excessive foam hinders the contact between the dye and the cloth fibers, uneven dyeing problems occur, and if the foam is difficult to remove, the discharge into the river will result in no oxidation and a burden on the environment. In Fig. 2, it can be seen that the addition of the dyeing auxiliary agent has low foaming property, good foam stability and environmental protection requirements, and therefore is an auxiliary agent which is good and less polluting.

In the dyeing process, the most ideal condition is to enable the dyed fabric to completely absorb the dye, which not only allows the finished product to approach the primary color of the dye, but also solves the problem of excessive chromaticity of the discharged wastewater, but it is often difficult to operate in the field. Achieved. Therefore, in the present embodiment, the present invention provides a dyeing process using the above-mentioned dyeing auxiliary agent to increase the coloring rate and reduce the dye residual ratio in the waste water, comprising the following steps: (1) adding a dye and a cylinder to the cylinder (2) A fiber fabric is placed in a steel bottle and sealed for dyeing; and (3) the fiber fabric is taken out, washed with water and soaped, and then naturally dried. In the present embodiment, the fiber fabric is dyed. Use natural fiber.

FIG. 3 and FIG. 4 below are schematic diagrams showing the results of detecting the coloring rate of the cloth and the dye residual rate in the wastewater after the completion of the process, after adding the dyeing auxiliary agents at different concentrations.

It can be seen from Fig. 3 and Fig. 4 that the dyeing auxiliary has a significant difference in the dye residual ratio and 0.2% in the concentration of 0.4%, and in terms of the color intensity, that is, the coloring ratio, 0.4% is six kinds. The strongest interval in the test concentration, after the above analysis, the concentration of the dyeing auxiliary is 0.4% as the optimum condition.

Regarding the dyeing auxiliary at a concentration of 0.4%, the color intensity tends to gradually decrease, and the reason The dyeing aid is a zwitterionic surfactant. The structure has a positively charged amine group which is attracted to the anion of the direct dye. When the concentration exceeds a hypothetical critical value, such as 0.4%, The dyeing auxiliary agent competes with the natural fiber to affect the dyeing, thereby affecting the dye entering the fiber interior, so that the dyeing residual rate and the color strength are reduced together. Therefore, if the concentration of the dyeing auxiliary agent exceeds 0.4%, although The content of the dye in the wastewater is slightly decreased, but the efficiency of dyeing is deteriorated, which is less than the expectation of the user.

Figure 5 and Figure 6 below show the experimental results of how the dyeing time of the fabric and the dye residue rate in the wastewater after the completion of the process are affected by the length of dyeing after the addition of the dyeing aid.

In the dyeing process, the control of time is related to the difference of the color ratio and the uniformity of dyeing, etc., and the dyeing time is the intangible cost in the dyeing and finishing, which is a very important part of the output efficiency, in Fig. 5 and Fig. 6 It can be found that at 75 minutes, the dyeing residual ratio of the dyeing auxiliary agent reaches the lowest value, and the color intensity reaches a peak. Compared with 90 minutes, not only the time-saving effect is more outstanding, so it can be inferred that the dyeing aid is added. After the agent, the optimum dyeing time was 75 minutes.

Figure 7 and Figure 8 below show the experimental results of how the dyeing temperature of the fabric and the dye residue in the wastewater after the completion of the process are affected by the dyeing temperature after the addition of the dyeing aid.

In the dyeing process, the dyeing temperature will affect the shade of the fabric and the dye residue in the wastewater. Factors such as retention rate. It can be seen from Fig. 7 and Fig. 8 that the dyeing temperature is not necessarily proportional to the coloring rate. In the control group to which no auxiliary agent is added, the excessive temperature does not help the coloring rate to increase, and to join the In the process of dyeing with an auxiliary agent, the dye residual ratio is nearly the same under the dyeing conditions of 90 degrees and 100 degrees, and the color intensity is the maximum at 100 degrees, so that 100 degrees is considered as the optimum dyeing temperature.

Figure 9 and Figure 10 below are schematic diagrams showing how the dyeing rate of the fabric and the dye residue in the wastewater after the completion of the process are affected by dyeing at different pH values after adding the dyeing aid.

In the dyeing process, in order to improve the fabric coloring rate, an acid or alkali solution is added to adjust the pH value of the dyeing bath, so whether the auxiliary agent can have a color-assisting effect in different pH environments is essential. It can be found from Fig. 9 and Fig. 10 that in the control group to which no auxiliary agent is added, the dyeing residual ratio has a significant drop depending on the pH value, and the dyeing auxiliary agent is in acid, medium or alkaline. Under the environment, the improvement of the coloring effect is still good, and it can be seen that the dyeing auxiliary has excellent stability, and is not affected by the dyeing environment, and can still have a good coloring rate and a low dye residual rate.

In summary, the above experimental data shows that the dyeing auxiliary provided by the present invention can make the fabric in the dyeing process in comparison with the process of adding no auxiliary agent and the process of adding a general commercial additive. The coloring rate is increased, and at the same time, the amount of dye remaining in the wastewater generated later can be reduced to avoid deepening the pollution to the environment.

However, the above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the practice of the present invention, so that it is common knowledge in the art or equivalent or easy to be familiar with the technology. Variations and modifications made by those skilled in the art without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (7)

An auxiliary agent for dyeing, which is used for improving the coloring rate during dyeing and reducing the dye residual rate of the wastewater generated subsequently, characterized in that the general formula of the dyeing auxiliary agent is Wherein R represents an alkyl group having 12 to 16 carbon atoms, and n is 1000 to 3,000. A method for preparing an auxiliary for dyeing, comprising the steps of: (A) dissolving chitosan in an aqueous acid solution and stirring to a uniform state; (B) mixing the chitosan uniformly mixed with epichlorohydrin And stirring at a constant temperature of 70 ° C for 2 hours; (C) additionally, mixing the acid with sodium hydrogen sulfite and stirring at a temperature of 80 ° C to 90 ° C for 2 hours; (D) the product of step C and sulfur The chlorosulfonation reaction is carried out by mixing ruthenium chloride; and (E) the product of the step B and the product of the step D are subjected to a synthesis reaction at a temperature of 100 ° C for 2 hours, and then water is removed to obtain an auxiliary for dyeing. The method of claim 2, wherein the dyeing auxiliary has the formula Wherein R represents an alkyl group having 12 to 16 carbon atoms, and n is 1000 to 3,000. The method of claim 3, wherein the aqueous acid solution is an aqueous acetic acid solution. The method of claim 3, wherein the acid is one of myristic acid, palmitic acid or stearic acid. A dyeing process for improving the coloring rate by using a dyeing auxiliary agent, comprising the steps of: (1) adding a dye and a dyeing auxiliary agent to a steel cylinder; and (2) placing a fiber fabric in a steel cylinder and sealing it for dyeing. And (3) taking out the fiber fabric, washing it with water and soaping, and then drying it naturally; wherein the dyeing aid has the formula Wherein R represents an alkyl group having 12 to 16 carbon atoms, and n is 1000 to 3,000. The dyeing process of claim 6, wherein the fiber fabric is made of natural fibers.