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(1. College of Textile and Garment, Yancheng Institute of Technology, Yancheng, Jiangsu 224051, China; 2. Wuxi Changtai Textile Co., Ltd., Wuxi 214101, China)
Abstract: The dyeing properties of Remazol RR series reactive dyes on soy protein composite fibers, including dye uptake, fixation rate and SERF, were studied. The results show that this series of dye-dyed soy protein composite fiber has high dye uptake and fixation rate, and has good reproducibility; yellow Y-RR dyed soy protein composite fiber and cotton fiber in Remazol RR series The comparison shows that the soy protein composite fiber and the cotton fiber have different dyeing behaviors, that is, before the alkali is added, the reactive dye and the soy protein composite fiber will have a certain degree of fixation, and the adsorption and fixation of the dye are simultaneously performed, which is supposed to be Reactive dyes are involved in the reaction of basic amino acids in soy protein composite fibers. It is also pointed out that the dyeing of soy protein composite fiber should pay attention to the control of the process to ensure the dyeing leveling property. At the same time, the dyeing characteristics of the soy protein composite fiber reactive dye should not be characterized by the SERF characteristic value dyed by cotton fiber reactive dye. Adjust according to the actual situation.
Key words: Remazol RR reactive dye; soy protein composite fiber; dyeing performance; SERF value; dye uptake rate; fixation rate CLC number: TS 193.63+2 Document code: AArticle ID:1000-4033(2012)03 -0025-04
With the continuous improvement of living standards, people's awareness of environmental protection has gradually strengthened, and there is a growing need for new types of fibers that are economical and have less environmental pollution during production. Soy protein composite fibers fit this demand.
Soy protein composite fiber (referred to as soybean fiber) is a kind of soybean protein modified from soybean meal after soybean oil extraction, and then grafted, copolymerized and blended with a polymer such as polyethylene. synthetic fiber. The fiber monofilament has low linear density, low density, light weight, high strength, soft handfeel like cashmere, soft luster like silk, good moisture absorption, comfortable wearing and warmth [1].
Remazol RR series reactive dyes are produced by DyStar. This series of reactive dyes has excellent water solubility, high fixing rate and excellent fastness properties. Since the reactive group is a vinyl sulfone group and the dye precursor is a ruthenium structure, the bond between the dye and the fiber formed is very stable [2].
The research group studied the dyeing characteristic value of Remazol RR series reactive dyes on soy protein composite fiber under certain process conditions, and provided reference for the practical application of such dyes in industrial production.
1. Experimental part 1.1 Materials and reagent materials: Soy protein composite fiber (14.6tex) and spandex (2.2 tex) blended elastic knitted fabric (provided by Wuxi Hengtian Textile Co., Ltd.), whiteness before boiling About 59%, its whiteness after bleaching is about 78%; pure cotton knitwear.
Reagents: Remazol RR series reactive dyes; sodium carbonate, sodium sulfate, citric acid, disodium hydrogen phosphate, etc. (all analytical reagents); flat plus O, neutral soaping agent (industrial grade).
1.2 Instruments and equipment Oscillating dyeing machine, 722S visible light spectrophotometer, Color-eye 7000A computer color matching instrument.
1.3 SERF value research experiment Dyeing conditions:
Dye 2%
Yuanming powder 40 g/L
Soda ash 3 g/L
Flat plus O 0.5 g/L
Bath ratio 1:30
Soaping conditions:
Neutral soaping agent 2 g/L
Temperature 90 ° C
Time 15 min
Specific steps: adding dye, Yuanming powder, flattening O and fabric, dyeing at a certain dyeing temperature for 40 min, adding alkali agent, continuing dyeing for 60 min, and finally washing with water and soaping.
Dyeing temperature selection: using constant temperature dyeing method, the temperature of cotton fabric dyeing is 60 °C; the temperature of soybean protein composite fiber fabric is 70 °C.
1.4 Determination of SERF value The dye uptake rate was determined by the residue liquid colorimetric method, in which the absorbance was measured on a 722S visible light spectrophotometer using a 1 cm thick cuvette.
The S value is the dye uptake rate before dyeing for 40 min.
E value is the dye uptake rate at the end of dyeing.
The R value is the ratio of the fixing rate of the dye at the end of the dyeing at 5 min. The F value is the dye fixing rate after the fabric is washed away from the floating color at the end of the dyeing.
The S value, E value, R value, and F value are calculated according to formulas (1) to (4) [3-4]: 
Where: A0 is the absorbance of the dye solution before dyeing, A1 is the absorbance of the dye solution when dyeing for 40 min, A2 is the absorbance of the dye solution at the end of dyeing, and A3 is the absorbance of the soap washing liquid after the dyeing is washed off. F1 is the fixing rate of the dye when the base is added for 5 minutes (the F1 calculation method is similar to the F calculation method).
1.5 Determination of transfer dyeing index MI Two equal-quality fabrics A and B were simultaneously placed in the same dye bath, dyed for 40 min without alkali, then taken out, washed with water, and air-dried.
The staining prescription is:
Dye 2%
Yuanming powder 40 g/L
Next, take a piece of the same kind of white fabric C with the quality of the dyed fabric B, and place the fabric C and the dyed fabric B in a dye bath similar to the above dyeing conditions (just without dye), transfer treatment for 60 min, and then Take out, wash and dry.
Determine the apparent color depth K/S value of the sample and calculate according to formula (5): 
Where: (K/S)A and (K/S)B are the K/S value of the fabric A and the K/S value after the dyeing treatment of the dyeing sample B, respectively.
1.6 Determination of leveling factor LDF The determination of LDF is calculated according to (6): 
2. Results and discussion 2.1 Dyeing and fixing rate of reactive dyes on soy protein composite fibers The dyeing and fixing experiments of soy protein composite fiber elastic knitted fabrics were carried out using Remazol RR series reactive dyes. The results are shown in Figure 1. Show.
Figure 1 is a graph showing the dye uptake and fixation rates of three dyes on soy protein composite fibers. It can be seen from Fig. 1 that no matter which kind of dye, the dyeing process shows the same rule, that is, the dye-to-soy protein composite fiber starts to dye faster, and then gradually slows down, after dyeing for 40 minutes, adding alkali agent, dyeing The rate is accelerated and then gradually slows down to reach a new balance.
Generally speaking, the dyeing of reactive dyes is divided into two stages of dyeing and fixing. The dye uptake curve and the fixing rate curve of Fig. 1 basically reflect these two stages.
In the dyeing stage, in the neutral dyeing solution in the presence of electrolyte, the dye overcomes the Coulomb repulsion of the negative charge generated by the ionization of the water-soluble group of the dye on the surface of the soy protein composite fiber, and transfers from the dye solution to the fiber. Adsorbed by the surface of the fiber, and then diffused into the fiber under the concentration gradient of the fiber surface and the inside, until the dye concentration reaches equilibrium between the dye solution and the fiber, and the dye concentration on the fiber surface is close to the inside [5]. This process is called the first adsorption stage, as shown in the uptake rate curve in Figure 1 from 0 to 40 min. 
In the fixation phase, the pH of the dye liquor rises due to the addition of the alkaline agent, and the equilibrium formed during the adsorption phase is destroyed. Β-ethyl sulfone sulfate will undergo β-elimination reaction to form vinyl sulfone, which is easy to undergo nucleophilic addition reaction with soy protein composite fiber [6]; water molecules gradually dissociate into hydroxide anion and undergo hydrolysis reaction with active groups. It can be seen from the upper dyeing rate curve in Fig. 1. After the alkali agent is added, the dye and the soybean protein composite fiber undergo a bonding reaction, which changes the properties of the dye, and the fiber-bonded dye can no longer be transferred to the dyeing liquid, thereby reducing the fiber. The concentration of the reactive dye, thereby destroying the original dye concentration balance between the dye liquor and the fiber. The new balance shifts the dye in the solution upwards in the direction of the dyed fiber, and a new dyeing process occurs, which continues to increase the dye uptake rate. This process is called the second adsorption stage.
In addition, as can be seen from Fig. 1, before the alkali addition, the three Remazol RR reactive dyes have a dye uptake rate of about 30% on the soy protein composite fiber, and the fixation rate reaches 10% or more. This may be due to the reaction of the reactive dye with the basic amino acids in the soy protein composite fiber before the addition of the base [4].
2.2 Reactive dyes The SERF value of the soy protein composite fiber dyed SERF value comprehensively reflects the dyeing performance of reactive dyes, and expresses these properties in numerical form, so it is more scientific and has important guidance for the application of reactive dyes. Significance [7]. The SERF values ​​of the soy protein composite fiber reactive dye staining are shown in Table 1. 
The dyeing level of reactive dyes is related to the S and E values. The S and E values ​​indicate the affinity of the reactive dyes to the fibers. They are related to the molecular structure of the dye precursor, the nature and quantity of the hydrophilic groups, and the dyeing. Neutral salt type and quantity, dyeing temperature, bath ratio, dye bath pH, ​​dye concentration and fabric type. In the case of the dye itself, when the S value is <30%, the leveling property and reproducibility of the dye are not good, and the hydrolysis tendency of the reactive dye is increased; when the S value is >70%, the dye is not easily leveled; when the S value = (1/3~2/3)/E, it has good leveling property [8].
For dyeing of reactive dyes, adsorption is the premise of fixation, so the greater the directness (S value) of the dye, the more the amount of dye dyed on the fiber, the easier it is to be fixed by the fiber, and the higher the dye fixing rate; On the other hand, the adhesion of the hydrolyzed dye to the fiber is correspondingly increased, and the removal of the floating color is more difficult. Therefore, it is disadvantageous that the S value of the dye is too high or too low.
At the same time, it was found that the levelness of dye dyeing is largely related to the difference in E-S. The difference between the different dyes is different. When color matching, dyes with similar differences should be used, because the closer the difference, the better the compatibility of the dye and the better the dye reproducibility.
The R value of the reactive dye is too large, such as more than 65%, indicating that the reaction ability with the fiber is strong, but on the other hand, it is easy to hydrolyze, so its F value is not high; at the same time, the dye is not easy because the fixing speed is too fast. Infiltration, it is easy to form surface deposits, and the washing property is deteriorated. If the R value is too small, such as less than 25%, it will increase the chance of dye hydrolysis, and the dye fixing rate F value will not be high [8]. Therefore, the ideal R value should be in the range of 35% to 60%, which is very advantageous for the leveling and fixing of the dye.
As can be seen from Table 1, the R value of the Remazol RR series dyes to the soy protein composite fibers is relatively high, both being close to 60%, but also in the range of 35% to 60%. This indicates that the reactive dyes of the series and the soy protein composite fibers have better reactivity, which is beneficial to the leveling and fixing of the dyes. It also shows that the reactive dyes have been fixed to the soybean protein composite fibers before the alkali addition. .
It can be seen from Table 1 that the E-S difference of the three primary colors of the Remazol RR series dyes is relatively close, both <30%, the R value is also less than 60%, and the S value is also large, so it can be concluded that the Remazol RR type dye has a very large Good reproducibility, the color of the soy protein composite fiber can be color-coded by using the three primary colors of the series.
It can be seen from the transfer dye value MI that only the Remazol RR yellow has a transfection index of more than 35% among the three dyes, and the other two dyes have lower transfection indexes. This indicates that the dyes reacted with the fibers and covalently bonded in the dyeing process of the soy protein composite fiber have no room for transfer dyeing. Therefore, it is necessary to properly control the dyeing conditions and improve the dye in the first dyeing stage. Transferability, improve dye leveling effect. However, in general, for reactive dyes, dye transferability has less effect on leveling.
In terms of leveling factor LDF, the leveling factor of RemazolRR series reactive dyes for soy protein composite fibers is only about 20%, which is difficult to dye and use. Therefore, corresponding measures should be taken according to the actual situation: such as using the law of the dyeing and fixing rate of each dye, formulating a suitable heating process, prolonging the dyeing and holding time, using salt and alkali in batches, paying attention to the dyeing process. Stirring and other methods to achieve the purpose of leveling.
2.3 Dyeing comparison of soy protein composite fiber and cotton fiber The dyeing of the soy protein composite fiber elastic knitted fabric and the pure cotton knitted fabric were respectively dyed with reactive dye yellow Y-RR, and the contrast curves of dyeing rate and fixing rate are shown in Fig. 2. Shown. The pair of SERF values ​​is shown in Table 2. 
It can be seen from Fig. 2 that the soy protein composite fiber exhibits a different dyeing behavior than the cotton fiber before the alkali is added, that is, the adsorption and fixation are simultaneously performed, which should be combined with the pre-alkali reactive dye and the soy protein composite fiber. Basic amino acid reaction is related.
After adding alkali, the fixing speed of the reactive dyes is accelerated regardless of the fiber, which indicates that the dyeing behavior of the soy protein composite fiber and the cotton fiber after alkali addition is consistent. However, it is worth noting that the dyes have a large difference in the dyeing curve and fixing curve of the two fibers. Due to the difference in the structure of the two kinds of fibers, the basic amino acid is present in the soy protein composite fiber, and may also be fixed to the dye before the alkali is added. Therefore, the fixing rate of the soy protein composite fiber before alkali addition is higher than that of the cotton fiber. Fixing rate.
Tang Rencheng, Fang Xuejuan et al. [9-10] believe that the fixing mechanism of reactive dyes on soy protein composite fibers and cotton fibers is different. The reactive dyes can be combined with the basic, hydroxyl and sulfur-containing amino acids in the protein component of soy protein composite fibers. The reaction can also be reacted with residual hydroxyl groups on the polyvinyl alcohol component. Due to the different reactive groups of different reactive dyes, they differ from the fixing rate of soy protein composite fibers. Therefore, when dyeing soybean protein composite fiber with reactive dyes, corresponding measures should be taken according to the different fixing rate of reactive dyes to improve the levelness of soybean protein composite fibers.
It can be seen from Table 2 that the S and R values ​​of the Remazol RR series reactive dye yellow Y-RR on the soy protein composite fiber are not much different from the S and R values ​​of the cotton fiber, but since the series is a reactive dye for cotton, it is suitable. Dyeing cotton, so they have higher dyeing rate and leveling factor for cotton fiber than for soy protein composite fiber.
In the processing of practical problems, the reactive dyes should be selected according to the actual situation and the dyeing characteristic values ​​as the reference basis to meet the actual production requirements.
3. Conclusions 3.1 DyStar's Remazol RR series reactive dye-dyed soy protein composite fiber has high dye uptake and fixation rate, and has good reproducibility.
3.2 Soy protein composite fiber showed different dyeing behavior with cotton fiber before adding alkali, that is, adsorption and fixation were carried out simultaneously; after adding alkali, whether it is cotton fiber or soy protein composite fiber, fixing color of reactive dye The rate is accelerated and eventually reaches the dyeing balance. However, the fixing mechanism of the reactive dyes on soybean protein composite fibers and cotton fibers is different.
3.3 When dyeing soy protein composite fiber with reactive dyes in production, the SERF characteristic value of cotton fiber reactive dyeing can not be used to characterize the dyeing characteristics of soy protein composite fiber reactive dyes. The dye should be selected according to the actual situation. Adapt to the needs of actual production.
References [1] Tang Rencheng. Study on the structural properties and dyeing and finishing of soybean fiber [D]. Shanghai: Donghua University, 2006.
[2] DyStar Company. New reactive dye Remazol (Rimasol) RR three primary color system [J]. Textile Guide, 1998 (2): 44-45.
[3] Feng Kailu, Xue Jiadong. Pre-printing treatment [M]. Beijing: China Textile Press, 2006.
[4] Libo. Discussion on the dyeing properties of soy fiber by acid and reactive dyes [D]. Suzhou: Suzhou University, 2005.
[5] Zhao Tao. Dyeing and Finishing Technology Course: Volume 2 [M]. Beijing: China Textile Press, 2005.
[6] He Yuxin. Dye Chemistry [M]. Beijing: China Textile Press, 2004.
[7] Yin Yu, Wang Chunmei, Han Haijun, et al. Reactive dye SERF value test and compatibility performance [J]. Dyes and Dyeing, 2003, 40(1): 26-29.
[8] Chen Rongzhen. Dyeing characteristic value of reactive dyes for exhaustion and its application (2) [J]. Printing and dyeing, 1994, 20 (4): 36-40.
[9] Tang Rencheng, Mei Shiying, Wang Huajie, et al. Reactive dye dyeing of soybean fiber and its fixing mechanism [J]. Printing and dyeing, 2003, 29 (9): 5-9.
[10] Fang Xuejuan. Relationship between soybean fiber structure and dyeing performance [J]. Woolen Technology, 2002 (6): 21-23.
Note: This article is an excellent paper on the 24th (2011) National Knitting Dyeing and Finishing Symposium.
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