CN1734009A - The colouring method of silk broadcloth - Google Patents

Abstract

The invention discloses a dyeing method of real silk, which mainly grafts cationic monomers or oligomers thereof with cationic monomers or oligomers thereof through ultraviolet irradiation grafting reaction with cationic monomers or oligomers thereof solution, Remove unreacted grafted monomers or their oligomers, and then carry out conventional dyeing treatment on the grafted silk with acid dyes at a temperature above 15°C. The method can improve the combination of real silk and acid dye anions, increase the dyeing rate and dyeing depth of acid dyes on real silk, and reduce the dyeing temperature; and it does not need to use photoinitiators and photosensitizers, which reduces the cost and has the advantages of dyeing High efficiency, continuous processing effect, and more in line with environmental protection and energy saving requirements.

Description

Silk dyeing method

technical field

The invention relates to the field of dyeing, in particular to a method for dyeing real silk.

Background technique

The raw material of real silk is silk, and its main component is silk fibroin. Silk fibroin is a protein formed by condensation of about 18 kinds of amino acids with certain rules, among which glycine and alanine with simple structure have the highest content (about 60%); therefore, the steric hindrance of silk protein peptide chain is small, which is conducive to the formation of Compact β-fold structure, high fiber crystallinity (the crystalline part accounts for about 40% to 60% of the total silk fibroin) (Zhou Hongxiang. New Silk Dyeing and Finishing Technology. Beijing: China Textile Press, 1997, 1-7 , 99-101). Like other proteins, silk fibroin is amphoteric in water, its isoelectric point pH is 3.5-5.2, and it is not resistant to alkali and strong acid.

At present, acid dyes are widely used in silk dyeing, among which weak acid dyes are commonly used, such as azo dyes, triphenylmethane dyes, anthraquinone dyes, etc., because weak acid dyes have moderate solubility and dyeability , The pH value of the dye bath is suitable. However, since the dye molecules cannot enter the fiber crystalline region with a tight structure, and there are fewer active groups (dyeing sites) that can combine with the dye molecules in the non-crystalline region of the silk fiber, the dyeing performance of real silk is poor. The main manifestations are: low dyeing rate, forming a large amount of dye waste water, increasing environmental pressure; high dyeing temperature, must be dyed in a dye solution close to the boiling point, high energy consumption, easy to damage silk; low color yield, difficult to dye dark colors The color fastness is low, and it is not resistant to washing, which affects the use of silk (Zhou Hongxiang. The way to improve the added value of real silk, Silk, 1995, 6: 28-30).

The focus of silk printing and dyeing finishing is to solve the problems of dyeing rate, chroma and color fastness. The prior art mainly improves the dyeing performance of real silk from the perspective of dyestuffs and auxiliary agents. However, because silk is not resistant to alkali, strong acid and high temperature, the use of many types of dyes and auxiliaries is limited. Some dyes with better color fastness, such as: reactive dyes, vat dyes, insoluble azo dyes, sulfur (condensation) dyes, disperse dyes, etc., are difficult to use due to the need for alkaline treatment or affinity. For example, if reactive dyes are used to dye silk, the dyes will be hydrolyzed during the dyeing process, the dye uptake rate is low, and the waste of dyes is large, and the dyeing must be carried out in alkaline dyeing solutions, and silk fibers are easily damaged by dyeing solutions (Chen, GQ; Xing, TL; Huang, CR; Zhou, X. Grafting of ethylene glycol dimethacrylate (EGDMA) onto silkin aqueous alcoholic solution, Chinese Journal of Polymer Science, 2003, 21(1):51-56.).

At present, silk is modified by grafting copolymerization reaction initiated by oxidation-reduction system or peroxide initiator, in order to improve its dyeing performance, but the reaction rate is uneven and difficult to control, and the reaction temperature still needs to be about 90-95°C. Higher temperature, and long reaction time, low efficiency, it is difficult to achieve continuous processing. On the other hand, in the field of grafting by ultraviolet light irradiation, due to its low energy, photoinitiators and photosensitizers are often needed to initiate graft copolymerization. The method of copolymer, this method can avoid using photoinitiator and photosensitizer (referring to application number is 03151467.7, and the title of invention is called the Chinese patent application of " the method for the formation of graft copolymer of direct irradiating silk with ultraviolet light "), but not yet Study the application of the above method in silk dyeing.

Contents of the invention

The technical problem to be solved by the present invention is the above-mentioned subject, that is, to provide a method for dyeing real silk.

The above-mentioned technical problems are solved by the following technical scheme: a dyeing method of real silk, which mainly grafts cationic monomers and cationic monomers or oligomer solutions of cationic monomers or their oligomer solutions by ultraviolet irradiation grafting reaction. Monomer or its oligomer, remove the unreacted grafted monomer or its oligomer, and then carry out conventional dyeing treatment on the grafted silk with acid dye at a temperature above 15°C.

When the grafting rate of cationic monomers or oligomers grafted by ultraviolet light irradiation on real silk is 4-25%, the dyeing effect of the method of the invention is the best.

Among them, the cationic monomer or its oligomer is preferably selected from amino group-containing acrylic acid, acrylate, vinyl acetate, vinyl, acrylonitrile, acrylamide monomers and other unsaturated double bond-containing monomers. Cationic monomers, their corresponding derivatives, substituents, and their oligomers. According to conventional methods: for water-soluble grafting monomers or their oligomers, they can be directly formulated into aqueous solutions; for water-insoluble grafting monomers or their oligomers, they can be formulated into mixed solutions of water and organic solvents or water and The emulsion that surfactant is formed, the selection of organic solvent or surfactant is as the criterion that can disperse monomer evenly; This cationic monomer or its oligomer aqueous solution, mixed solution or emulsion are collectively referred to as cationic monomer in the present invention or its oligomer solution.

Among them, the preferred ones are: ethyl methacrylate-2-(dimethylamine) ester [2-(Dimethylamino)ethyl methacrylate, abbreviated as DMAEMAA] or propyl methacrylate-2-(dimethylamine) ester Or derivatives, substitutes, or oligomers thereof.

The ethyl methacrylate-2-(dimethylamine) ester concentration is 0.12～1.66M, the bath ratio of padding (or impregnation) is: silk: solution=1:20～1:40, padding (or impregnation) ) rate: 100±2%.

The pH value of the cationic monomer or its oligomer solution is preferably 2-7. More preferably, it is 4-7.

The light source of the ultraviolet light irradiation in the inventive method can adopt low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, metal halide mercury lamp, xenon lamp, xenon lamp or iodine gallium lamp etc., wherein low pressure mercury lamp is because of its cheap, Long life, high UV luminous efficiency and extremely low calorific value are the best; and the irradiation time is generally 3 to 40 minutes.

When ultraviolet light is irradiated, in addition to reacting in the air, it can also be filled with an inert protective gas, such as nitrogen, carbon dioxide or the same monomer atmosphere, in order to remove oxygen, as in other photografting reactions.

The acid dyes are generally azo dyes, triphenylmethane dyes or anthraquinone dyes, and the dyeing temperature is generally 50-90°C.

The positive and progressive effect of the present invention is: the cationic organic monomer or oligomer is grafted on real silk to form a graft copolymer, and the cationic group on the graft is combined with the anion of the acid dye to improve the acid dye in the The dyeing performance on silk, that is, the dyeing rate and dyeing depth, reduces the lower limit of the dyeing processing temperature to 15°C; and does not require the use of photoinitiators and photosensitizers, which reduces costs, has high dyeing efficiency, and can be continuously processed. , and more in line with environmental protection, energy saving requirements.

Description of drawings

Fig. 1 is a graph showing the relationship between the grafting rate of real silk of the present invention and the dyeing uptake rate E of weak acid brilliant red B dyeing at 90°C.

Fig. 2 is a graph showing the relationship between the grafting rate of silk of the present invention and the color difference value DE* of weak acid Brilliant Red B dyeing at 90°C.

Figure 3 is a graph showing the relationship between the grafting rate of silk and the dyeing uptake rate E of weak acid brilliant red B dyeing at 75°C.

Figure 4 is a graph showing the relationship between the grafting rate of silk and the dyeing uptake rate E of weak acid brilliant red B dyeing at 50°C.

Figure 5 is a graph showing the relationship between the grafting rate of silk and the dyeing uptake rate E of acid red G dyeing at 90°C.

Figure 6 is a graph showing the relationship between the grafting rate of silk and the color difference value DE* of acid red G dyeing at 90°C.

Figure 7 is a graph showing the relationship between the grafting rate of silk and the dyeing uptake rate E of acid red G dyeing at 80°C.

Figure 8 is a graph showing the relationship between the grafting rate of silk and the dyeing uptake rate E of acid red G dyeing at 50°C.

Figure 9 is a graph showing the relationship between the grafting rate of silk and the dyeing uptake rate E of acid red G dyeing at 15°C.

Figure 10 is a graph showing the relationship between the grafting rate of silk and the dyeing rate E of acid lake blue A dyeing at 90°C.

Figure 11 is a graph showing the relationship between the grafting rate of silk and the color difference value DE* of acid lake blue A dyeing at 90°C.

Figure 12 is a graph showing the relationship between the grafting rate of silk and the dyeing rate E of acid lake blue A dyeing at 75°C.

Figure 13 is a graph showing the relationship between the grafting rate of silk and the dyeing rate E of weakly acidic brilliant green GS dyeing at 90°C.

Figure 14 is a graph showing the relationship between the grafting rate of silk and the dyeing rate E of weakly acidic brilliant green GS dyeing at 75°C.

Detailed ways

In order to better illustrate the method and effect of the present invention, the following examples and effect examples are used to further illustrate it. The specific process is as follows: ①After the cationic monomer or oligomer is grafted on the silk by ultraviolet light irradiation, the unreacted monomer or oligomer is washed and removed. ② Drying, use the weighing method (Ha Hongfei, Wu Jilan. Polymer Radiation Chemistry—Principles and Applications. Beijing: Peking University Press, 2002, 55-56) to calculate the grafting rate according to the following formula:

Yg＝(WW ₀ )/W ₀ ×100％

Among them, W ₀ and W are the mass of the fabric before and after grafting, respectively. ③ Then, at different temperatures, dye with acid dyes according to the conventional method. ④ After dyeing, use a UV spectrophotometer to measure the absorbance of the dye solution at the maximum absorption wavelength, and calculate the dye uptake rate according to the following formula:

Dyeing rate $\mathrm{E.}(\%)=\frac{A_0-A_u}{{\mathrm{<figure-callout\; id="0"\; label="A"\; filenames="A20041009324500111.png,A20041009324500121.png"\; state="\{\{state\}\}">A</figure-callout>}}_0}\&times;100$

Among them, A ₀ is the absorbance of the original dye solution in the dye bath, and Au is the absorbance of the undyed residual dye solution in the dye bath; and after the silk is dried, the color difference between the dyed sample and the standard white plate is measured with a spectrophotometer DE ^* value to characterize the depth of staining.

Because the present invention focuses on the application and efficacy of the method of grafting cationic monomers or oligomers by UV irradiation on real silk in dyeing. Therefore the present invention is not limited by the following examples, particularly wherein the specific silk ultraviolet light irradiation grafting cationic monomer aspect, more embodiments about this aspect can be found in detail in the above-mentioned inventor's application number is 03151467.7 Prior patent application.

The ultraviolet light source used in the following examples is a low-pressure mercury lamp with a power density of 0.075 W/cm ² and an irradiation distance of 8 cm.

Example 1

The grafting monomer is selected from ethyl methacrylate-2-(dimethylamine) ester (DMAEMAA), its concentration is 0.32mol/L, and the solvent is a mixed solution of ethanol and water (volume ratio is 4: 1). Dilute hydrochloric acid adjusts the pH value to 2, the padding (or dipping) bath ratio is: silk: solution=1: 40, the padding (or dipping) rate: 100 ± 2%; the ultraviolet light irradiation time is 20 minutes, obtains The grafting rate of real silk is about 6.5%.

Example 2

The pH value of the grafting monomer solution was adjusted to 4, and the rest was the same as in Example 1, and the grafting rate of silk was about 8.6%.

Example 3

The pH value of the grafting monomer solution was adjusted to 7, and the remainder was the same as that in Example 1, and the grafting rate of real silk was about 9.1%.

Example 4

The concentration of the grafting monomer was 0.12 mol/L, the pH value of the solution was 4.5, and other conditions were the same as in Example 1, and the grafting rate of real silk was about 4.2%.

Example 5

The concentration of the grafting monomer was 0.71 mol/L, the pH value of the solution was 4.5, and other conditions were the same as in Example 1, and the grafting rate of real silk was about 17.6%.

Example 6

The concentration of the grafting monomer was 1.66 mol/L, the pH value of the solution was 4.5, and other conditions were the same as in Example 1, and the grafting rate of real silk was about 26.1%.

Example 7

The concentration of the grafting monomer was 0.24 mol/L, the pH value of the solution was 4.5, the ultraviolet light irradiation time was 3 minutes, and other conditions were the same as in Example 1, and the grafting rate of real silk was about 4.3%.

Example 8

The concentration of the grafting monomer was 0.24 mol/L, the pH value of the solution was 4.5, the ultraviolet light irradiation time was 20 minutes, and other conditions were the same as in Example 1, and the grafting rate of real silk was about 6.8%.

Example 9

The concentration of the grafting monomer was 0.24 mol/L, the pH value of the solution was 4.5, the ultraviolet light irradiation time was 40 minutes, and other conditions were the same as in Example 1, and the grafting rate of real silk was about 7.8%.

Example 10

The grafting monomer concentration is 0.71mol/L, and the solution pH value is 4.5, and the bath ratio of padding (or dipping) is: silk: solution=1: 20;, the ultraviolet light irradiation time is 10 minutes, and other conditions are with embodiment 1. The grafting rate of real silk is about 8.3%.

Carry out grafting treatment to real silk according to the above-mentioned embodiment method, then dye real silk, the dyestuffs are weak acid brilliant red B, acid red G, acid lake blue A, weak acid brilliant green GS respectively, and the dye concentration is: 0.02% , the bath ratio is 50:1, the pH value of the dye solution is 4～6, and the dyeing performance is compared with the ungrafted real silk dyed under the same conditions, please refer to the accompanying drawings for details (grafting rate Yg= The data of 0, representing the real silk without grafting treatment) is specified by the following effect examples.

Effect Example 1 The present invention affects the dyeing performance of azo acid dyes—weak acid brilliant red B

1) The dyeing temperature is 90°C, and the dyeing time is 30 minutes. The dye uptake E and the color difference DE ^* are shown in Figures 1 and 2, which illustrate that the present invention is grafted with ungrafted silk after ultraviolet irradiation. Compared with branches, the dyeing rate and dyeing depth were significantly improved.

2) The dyeing temperature is 75°C, and the dyeing time is 30 minutes. The dye uptake rate E is shown in Figure 3, which shows that the dye uptake rate is still significantly improved after the dyeing temperature is lowered to 75°C in the present invention.

3) The dyeing temperature is 50°C, and the dyeing time is 30 minutes. The dye uptake E is shown in Figure 4, which shows that the dye uptake rate is still significantly improved after the dyeing temperature is lowered to 50°C in the present invention.

Effect example 2 The present invention is to the influence of azo acid dyes---acid red G dyeing performance

1) The dyeing temperature is 90°C, and the dyeing time is 30 minutes. The dye uptake E and the color difference DE ^* are shown in Figures 5 and 6, which illustrate that the present invention grafts silk with ungrafted silk after ultraviolet irradiation. Compared with branches, the dyeing rate and dyeing depth were significantly improved.

2) The dyeing temperature is 80°C, and the dyeing time is 30 minutes. The dye uptake rate E is shown in Figure 7, which shows that the dye uptake rate is still significantly improved after the dyeing temperature is lowered to 80°C in the present invention.

3) The dyeing temperature is 50°C, and the dyeing time is 30 minutes. The dye uptake E is shown in Figure 8, which shows that the dye uptake rate is still significantly improved after the dyeing temperature is lowered to 50°C in the present invention.

4) The dyeing temperature is 15°C, and the dyeing time is 15 hours. The dye uptake E is shown in Figure 9, which shows that the dye uptake rate is still significantly improved after the dyeing temperature is lowered to 15°C in the present invention.

Effect example 3 The present invention is to the influence of triphenylmethane acid dyestuff---acid lake blue A dyeing performance

1) The dyeing temperature is 90°C, and the dyeing time is 30 minutes. The dye uptake E and the color difference DE ^* are shown in Figures 10 and 11, which illustrate that the present invention grafts silk with ungrafted silk after ultraviolet irradiation. Compared with branches, the dyeing rate and dyeing depth were significantly improved.

2) The dyeing temperature is 75°C, and the dyeing time is 30 minutes. The dye uptake rate E is shown in Figure 12, which shows that the dye uptake rate is still significantly improved after the dyeing temperature is lowered to 75°C in the present invention.

Effect Example 4 The Influence of the Present Invention on the Dyeing Properties of Anthraquinones Acid Dyes—Weakly Acid Brilliant Green GS

1) The dyeing temperature is 90°C, and the dyeing time is 30 minutes. The dye uptake E is shown in Figure 13, which shows that the present invention compares the real silk grafted with ultraviolet light irradiation with the ungrafted, and the dye uptake is the same as The depth of staining is noticeably improved.

2) The dyeing temperature is 75°C, and the dyeing time is 30 minutes. The dye uptake rate E is shown in Figure 14, which shows that the dye uptake rate is still significantly improved after the dyeing temperature is lowered to 75°C in the present invention.

It can be seen from the above effect examples and accompanying drawings that a better dyeing effect can be obtained with a grafting rate of 4-25%.

The reagents and dyes used in the above examples and effect examples are all conventional commercially available products.

Claims (10)

1, a kind of colouring method of silk broadcloth, it is characterized in that earlier with silk broadcloth by with cationic monomer or its oligomer solution through the ultraviolet light irradiation graft reaction and grafting cationic monomer or its oligomer, remove grafted monomers or its oligomer of unreacted, the silk broadcloth of under the temperature more than 15 ℃ grafting being handled carries out the normal dyeing processing with ACID DYES then.

2, method according to claim 1, the percent grafting that it is characterized in that this silk broadcloth grafting cationic monomer or its oligomer is 4～25%.

3, method according to claim 1 and 2 is characterized in that this cationic monomer or its oligomer are selected from: contain amino acrylic compounds, esters of acrylic acid, vinylacetate class, vinyl-based, vinyl cyanide, acrylamide monomers and its derivative, substituent and their oligomer.

4, method according to claim 3 is characterized in that this cationic monomer or its oligomer are methacrylic acid ethyl-2-(dimethyl amine) ester or methacrylic acid propyl group-2-(dimethyl amine) ester or derivatives thereof, substituent or its oligomer.

5, method according to claim 4 is characterized in that this methacrylic acid ethyl-2-(dimethyl amine) ester concentration is 0.12～1.66M, and the pad bath ratio is: silk: solution=1: 20～1: 40, the rate of padding is: 100 ± 2%.

6, method according to claim 1 and 2, the pH value that it is characterized in that this cationic monomer or its oligomer solution is 2～7.

7, method according to claim 6, the pH value that it is characterized in that this cationic monomer or its oligomer solution is 4～7.

8, method according to claim 1 and 2 is characterized in that the light source of this ultraviolet light irradiation adopts low pressure mercury lamp, and exposure time is 3～40 minutes.

9, method according to claim 1 and 2 is when is characterized in that this ultraviolet light irradiation, in air or fill to react in the inert protective gas.

10, method according to claim 1 and 2 is characterized in that this ACID DYES is azo dyes, triphenylmethane dye or anthraquinone dyes, and this dyeing temperature is 50～90 ℃.

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