Method for dyeing protein garment fabric by using acetylated blue derivative dye and application

Abstract

The invention belongs to the technical field of dyeing and finishing, and particularly relates to a method for dyeing a protein garment fabric by using an acetylated blue derivative dye and application. The method comprises the following steps: S1, soaking and wetting a protein garment fabric in a dyeing penetrant, taking out and draining, and keeping the interior of the fabric in a wet state; s2, dissolving the acetylated ornamental blue derivative dye in water, adding a reducing agent for reduction, and adjusting the pH value to 3.0-5.0 to obtain acetylated ornamental blue derivative dye mother liquor; s3, diluting the mother liquor in the step S2 to obtain a dyeing solution, soaking and dyeing the protein garment fabric treated in the step S1 in the dyeing solution, taking out, airing, oxidizing, washing with water, airing, soaping, and airing to obtain the dyed protein garment fabric. According to the dyeing process, protein garment fabric dyeing is successfully achieved under the weak acid and low-temperature conditions, damage to the protein garment fabric is reduced, energy consumption is reduced, and pollution is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of dyeing and finishing, and specifically relates to a method for dyeing protein clothing fabrics by using acetylated indigo derivative dyes and application thereof. Background Art

[0002] As a new type of biological natural pigment, indigo and acetylated indigo derivatives are natural pigments (natural degree reaches 97%) tested and certified by the US Department of Agriculture (USDA), and certified by the BioPreferred Program. They are natural, environmentally friendly, green and safe new biological dyes. According to the dye qualitative scheme mentioned in ISO 16373-1:2015 (General principles of testing coloured textiles for dyestuff identification), indigo and acetylated indigo derivatives are determined to be vat dyes. N-acetyl indigo and N,N'-diacetyl indigo are acetylated indigo derivatives prepared on the basis of indigo. N-acetyl indigo is a blue dye, and N,N'-diacetyl indigo is a red dye. Protein clothing fabrics, as typical protein fibers, are widely used in daily clothing and home textile industries. They often come into direct contact with human skin during use. It is most important to ensure their safety and non-toxicity. The commonly used red dye fuchsin was listed in the Class 2B carcinogen list by the World Health Organization on October 27, 2016, which will inevitably cause concerns among consumers when used.

[0003] Moreover, in the dyeing process of blue and N-acetyl blue in the past, the reducing agent used is insurance powder, and the common alkali solution includes caustic soda, ammonia water, etc., which not only has the danger of irritating smell and corrosiveness when used, but also produces wastewater with large pollution, increasing environmental pollution and processing costs. Although N-acetyl blue can be reduced under weak alkaline conditions and can be applied to textile dyeing, including plant fiber, regenerated fiber and chemical fiber, it has poor dyeing effect for protein fiber. Because protein clothing fabric is not alkali-resistant, protein fiber will be destroyed under alkaline conditions, hydrolyzed, and yellowing and fabric embrittlement will occur. Although weak alkaline dye liquor reduces the damage to silk fabric to a certain extent, it is not possible to increase the dyeing time, resulting in a lighter coloring of protein clothing fabric, and it is impossible to prepare dark protein clothing fabric products, and the color light and color depth are poor, which is difficult to meet the diversified color requirements of protein clothing fabric. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art and provide a method and application of dyeing protein clothing fabrics using acetylated indigo blue derivative dyes, so as to achieve the effects of easy coloring, bright colors, good level dyeing of protein clothing fabrics under weak acid and low temperature conditions, and to protect the protein clothing fabrics from being damaged to a large extent, while reducing environmental pollution and energy waste such as wastewater treatment.

[0005] To achieve the above objectives, the technical solutions adopted by the present invention include:

[0006] In a first aspect, the present invention provides a method for dyeing protein clothing fabrics using acetylated indigo blue derivative dyes, comprising the following steps:

[0007] S1. Soak the protein clothing fabric in the dye penetrant, take it out and drain it, keeping the inside of the fabric moist;

[0008] S2, dissolving the acetylated blue derivative dye in water, adding a reducing agent for reduction, and adjusting the pH to 3.0-5.0 to obtain an acetylated blue derivative dye mother solution;

[0009] S3, diluting the acetylated indigo blue derivative dye mother liquor of step S2 to obtain a dyeing solution, and then placing the protein clothing fabric of step S1 in the dyeing solution for immersion and dyeing, taking out and airing, oxidizing, then washing and drying, and then soaping and drying to obtain a dyed protein clothing fabric;

[0010] The acetylated indigo blue derivative dye includes N-acetyl indigo blue or N,N'-diacetyl indigo blue.

[0011] The method of the present invention aims at the problems of serious environmental pollution and difficulty in coloring protein clothing fabrics in the current fabric dyeing process, and invents a new process for dyeing protein clothing fabrics with acetylated indigo derivative dyes reduced under acidic conditions. The process has a high coloring rate and good color fastness for protein clothing fabrics, and the dyeing method does not use highly polluting insurance powder, thiourea dioxide, and caustic soda, thereby effectively reducing pollution and saving energy consumption.

[0012] Through the dyeing method of the present invention, N-acetyl indigo derivatives are used to dye protein clothing fabrics (such as leather and silk fabrics), and the color depth (K / S) and color fastness of the fabric are measured to explore its dyeing effect. Since protein clothing fabrics are not alkali-resistant, protein fibers will be destroyed under alkaline conditions, and the silk fibroin and sericin of the protein fibers will be eroded to hydrolyze them. The traditional dye indigo is reduced in an alkaline environment, and the dye solution environment is alkaline, so it is difficult to use it to dye protein clothing fabrics. In the previous dyeing process of N-acetyl indigo, the dye solution environment is weakly alkaline, and the dyeing time of protein clothing fabrics cannot be extended. The color depth is poor, the color is less, and the overall color is lighter. The method for dyeing protein fiber with an N-acetyl indigo derivative dye provided by the present invention can improve the K / S value by nearly 2-3 times at most, and the color fastness to dry rubbing is improved by one level compared with traditional dyeing, the color fastness to wet rubbing is improved by one level, and the color fastness to soaping is improved by one level, so as to effectively solve the problems that workers in the indigo dyeing and finishing industry cannot dye protein clothing fabrics and the N-acetyl indigo derivatives dye protein clothing fabrics lightly.

[0013] Through the dyeing method of the present invention, N,N'-diacetyl indigo blue derivatives are used to dye silk fabrics, and the color depth (K / S) and color fastness of the fabric are measured to be significantly improved compared with commercial vat red. Through experimental exploration, it is found that the dyeing method of silk fabrics with N,N'-diacetyl indigo blue dye provided by the present invention can increase the K / S value by nearly 1 times at most, and the color fastness to dry friction is also improved by 1 level compared with traditional dyeing, the color fastness to wet friction is improved by 1 level, and the color fastness to soaping is improved by 1 level, which effectively solves the problems of complex process, difficult coloring, poor color fastness, difficult degradation and difficult treatment of wastewater in the vat red dyeing and finishing industry.

[0014] Preferably, the reducing agent comprises sodium sulfite.

[0015] Preferably, in step S2, the mass ratio of the acetylated indigo blue derivative dye to the reducing agent is 1:(0.5-20).

[0016] In the traditional dyeing process, the use of sodium sulfite or thiourea dioxide as a reducing agent will lead to excessive reduction and affect the subsequent dyeing effect, and will cause pollution of the dye liquor wastewater, increasing the process and cost of wastewater treatment. The present invention uses sodium sulfite as a weak reducing agent to reduce the acetylated indigo derivative dye, and its effect is better than strong reducing agents such as sodium sulfite and thiourea dioxide, and will not produce more harmful gases such as hydrogen sulfide, sulfur dioxide, sulfuric acid and urea. In addition, experimental research has found that when the two are reduced using the above-mentioned preferred dosage ratio, the dye can be reduced to a water-soluble sodium salt, which is beneficial to subsequent coloring and reduces the pollution of dye wastewater.

[0017] Preferably, in step S2, a weak acid is used to adjust the pH to 3.0-5.0, and the weak acid includes at least one of citric acid, acetic acid and phosphoric acid.

[0018] In the preparation method of the acetylated indigo blue derivative dyeing solution of the present invention, by using the weak acid to adjust the pH to within the range of 3.0-5.0, the problem of protein clothing fabrics being not alkali-resistant can be effectively overcome, and the protein clothing fabrics have a better coloring effect in the acidic environment. In addition, the weak acid is different from strong acids such as hydrochloric acid and sulfuric acid, and can be used as a buffer to maintain the stability of the pH of the dye solution, thereby preventing the strong acid from causing the local pH of the dye solution to be too low, precipitating the leuco acid in the dye solution, causing the dye solution concentration to be reduced and the overall dye solution to be uneven.

[0019] Preferably, the protein clothing fabric includes silk fabric and leather.

[0020] When pre-treating protein clothing fabrics with dye penetrants, for silk fabrics, take them out after soaking, gently dry the surface moisture without dripping, and avoid over-drying the silk fabrics, which will affect the dyeing of the dye solution; for leather, it needs to be squeezed out with a little force after soaking, and the leather needs to be slightly pressed in the middle to squeeze out excess penetrants and bubbles. In addition, when using acetylated indigo derivative dyes to dye protein clothing fabrics, N-acetyl indigo can dye leather and silk fabrics, while N,N'-diacetyl indigo can only dye silk fabrics, and the effect of dyeing leather is poor.

[0021] Preferably, in step S3, the weight of the acetylated indigo blue derivative dye is 1-3% of the weight of the protein clothing fabric, and the mass volume ratio of the protein clothing fabric to the diluted dyeing solution is 1 g: (20-100) mL.

[0022] Through experimental research, it was found that when protein clothing fabrics and acetylated indigo blue derivative dyes are dyed using the above-mentioned preferred dosage ratio, good dyeing effects can be achieved, while relatively low or high dye dosages will lead to uneven dyeing of the fabrics, poor color fastness or waste.

[0023] Preferably, in step S2, the reduction condition is: reacting at 15-30° C. for 15-60 min to reduce the dye to a potential of -50 to -100 mv.

[0024] More preferably, in step S2, the reduction condition is: reacting at 25° C. for 20-30 min.

[0025] Experimental research has found that when the acetylated indigo blue derivative dye is reduced, the reduction conditions will have a certain impact on the dyeing effect. If the reduction time is too long, the acetylated indigo blue derivative dyeing solution will be over-reduced, thereby making the color depth lighter. If the reduction time is too short, the dye molecules will not be completely reduced, resulting in uneven dyeing, poor color fastness and other problems.

[0026] Preferably, in step S3, the dyeing conditions are: dyeing at 15-30°C for 5-90 minutes; the drying time is 5-10 minutes; the oxidation is carried out using hydrogen peroxide, the oxidation concentration of hydrogen peroxide is 0.5-10g / L, and the oxidation time is 1-30 minutes.

[0027] When dyeing the pretreated protein clothing fabric, the silk fabric must be completely immersed below the dye liquid surface to ensure that the silk cloth is fully unfolded and there is no adsorption and adhesion to itself; during the dyeing process, the silk must be handled gently to avoid excessive stirring and friction to prevent damage to the silk; for leather, after it is completely immersed below the dye liquid surface, the dye liquid needs to be slightly stirred to prevent the leather from sinking to the bottom and affecting the dyeing effect; and the use of the above conditions for dyeing and other treatments can effectively improve the color uptake and color fastness of protein clothing fabrics.

[0028] Preferably, in step S3, the soaping bath ratio of the soaping treatment is 1:(20-100), the soaping temperature is 20-60° C., and the soaping time is 5-15 min.

[0029] Preferably, in step S1, the dye penetrant includes TYL-020 dye penetrant.

[0030] The dye penetrant of the present invention can be derived from commercially available raw materials, such as the TYL-020 dye penetrant of Dongguan Taiyang Textile Products Co., Ltd., which can open the hydrophobic scales on the surface of the protein clothing fabric and quickly wet the inside of the protein clothing fabric so that it can be evenly contacted with the dye solution during dyeing, avoiding uneven dyeing and dye solution migration.

[0031] In a second aspect, the present invention also provides application of the dyeing method in dyeing protein clothing fabrics.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention provides a dyeing method with high coloring rate and good color fastness in view of the problems of serious environmental pollution and difficulty in coloring protein clothing fabrics in the current fabric dyeing process. The present invention selects a new acetylated indigo derivative dye, which makes full use of the characteristics of the dye being reduced under acidic conditions; compared with the previous indigo, fuchsin, and vat red dyes, the acetylated indigo derivative dye can not only dye protein clothing fabrics, but also is safer, has a higher coloring rate and better color fastness; in the dyeing method, no highly polluting chemicals such as insurance powder, thiourea dioxide and alkali are used, which effectively reduces pollution and saves energy consumption. In addition, the dyeing method of the present invention has a simple process, does not need to be heated to a high temperature for dyeing, and has a short dyeing time, which is conducive to energy saving and improving dyeing efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The pictures of the embodiment and comparative example of dyeing silk fabric with N-acetyl cyanine dye and N,N'-diacetyl cyanine dye;

[0035] Figure 2 These are pictures of an example and a comparative example of dyeing vegetable tanned cowhide with N-acetyl indigo dye. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical scheme and effect of the present invention clearer and more specific, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0037] Unless otherwise specified, all raw materials involved in the following examples and comparative examples are commercially available general raw materials.

[0038] The acetylated indigo blue derivative dye used in this example was developed by our company (Nanjing Hegu Life Biotechnology Co., Ltd.) and can be purchased from the company's official website; the penetrant used in this example was purchased from Dongguan Taiyang Textile Products Co., Ltd. and is TYL-020 dyeing penetrant.

[0039] The K / S value is used to characterize the depth of the dyed protein clothing fabric. The color fastness to rubbing and washing of protein clothing fabrics are tested with reference to GB / T 3920-2008 "Textiles - Tests for Color Fastness - Color Fastness to Rubbing" and GB / T 3921-2008 "Textiles - Tests for Color Fastness - Color Fastness to Washing".

[0040] The owf (on weight of fabric) mentioned in the present invention, which is used to indicate the percentage content of dye when dyeing, refers to the ratio of the amount of dye used to the weight of fabric; the bath ratio is a term used in textile dyeing and finishing, which refers to the ratio of the fabric weight to the volume of dye liquor in the immersion dyeing method.

[0041] Example 1

[0042] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, comprising the following steps:

[0043] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0044] (2) Preparation of N-acetyl cyanine dye mother solution: The dye mother solution was prepared with distilled water to a concentration of 10 g / L, and then 5 g / L of sodium sulfite was added. After reduction at room temperature for 60 min, the supernatant was collected after centrifugation at 9000 rpm for 10 min, and the pH was adjusted to 3.0 with 200 g / L citric acid to obtain N-acetyl cyanine dye mother solution;

[0045] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain N-acetyl indigo dyeing solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:25, so that the silk is completely immersed below the dyeing solution surface, dye at room temperature for 25 minutes, take out and air-dry, oxidize with 3.5g / L hydrogen peroxide for 10 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0046] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0047] Example 2

[0048] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, comprising the following steps:

[0049] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0050] (2) Preparation of N-acetyl cyanine dye mother solution: dissolve N-acetyl cyanine dye in distilled water to prepare a dye mother solution concentration of 20 g / L, add 100 g / L sodium sulfite, reduce at room temperature for 40 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, and adjust the pH to 4.0 with 200 g / L citric acid to obtain N-acetyl cyanine dye mother solution;

[0051] (3) Dyeing process: dilute the N-acetyl indigo dye mother solution obtained in step (2) to a dye concentration of 1.0% owf to obtain a dyeing solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:30, immerse the silk completely below the dyeing solution surface, dye at room temperature for 30 minutes, take out and air-dry, oxidize with 4.5g / L hydrogen peroxide for 8 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0052] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0053] Example 3

[0054] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, comprising the following steps:

[0055] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0056] (2) Preparation of N-acetyl cyanine dye mother solution: dissolve N-acetyl cyanine dye in distilled water to prepare a dye mother solution concentration of 20 g / L, add 200 g / L sodium sulfite, reduce at room temperature for 25 min, collect the supernatant after suction filtration, and adjust the pH to 5.0 with 200 g / L citric acid to obtain N-acetyl cyanine dye mother solution;

[0057] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 2% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:100, and immerse the silk completely below the dye solution surface, dye at room temperature for 35 minutes, take out and air-dry, oxidize with 2.5g / L hydrogen peroxide for 15 minutes, wash with water for 1 minute, and dry to obtain a dyed silk fabric;

[0058] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0059] Example 4

[0060] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, comprising the following steps:

[0061] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0062] (2) Preparation of N-acetyl indigo blue dye mother solution: dissolve N-acetyl indigo blue dye in distilled water to prepare a dye mother solution concentration of 10 g / L, add 200 g / L sodium sulfite, reduce at room temperature for 8 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, adjust the pH to 4.0 with acetic acid, and obtain an N-acetyl indigo blue derivative dye mother solution;

[0063] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:45, so that the silk is completely immersed below the liquid surface of the dye solution, dye at room temperature for 45 minutes, take out and air-dry, oxidize with 10g / L hydrogen peroxide for 3 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0064] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0065] Example 5

[0066] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, comprising the following steps:

[0067] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0068] (2) Preparation of N,N'-diacetyl cyanine dye mother solution: distilled water was used to prepare the dye mother solution to a concentration of 20 g / L, and then 10 g / L of sodium sulfite was added. After reduction at room temperature for 60 min, the supernatant was collected after centrifugation at 9000 rpm for 10 min, and the pH was adjusted to 3.5 with 200 g / L citric acid to obtain N,N'-diacetyl cyanine dye mother solution;

[0069] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1% owf to obtain N,N'-diacetyl indigo dyeing solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:20, immerse the silk completely below the dyeing solution surface, dye at room temperature for 20 minutes, take out and air-dry, oxidize with 3.5g / L hydrogen peroxide for 10 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0070] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0071] Example 6

[0072] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, comprising the following steps:

[0073] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0074] (2) Preparation of N,N'-diacetyl cyanine dye mother solution: distilled water was used to prepare the dye mother solution with a concentration of 15 g / L, 75 g / L of sodium sulfate was added, and the mixture was reduced at room temperature for 40 min, centrifuged at 9000 rpm for 10 min, and the supernatant was collected. The pH was adjusted to 4.5 with 200 g / L citric acid to obtain N,N'-diacetyl cyanine dye mother solution;

[0075] (3) Dyeing process: dilute the N,N'-diacetyl indigo dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dyeing solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:30, immerse the silk completely below the dyeing solution surface, dye at room temperature for 15 minutes, take out and air-dry, oxidize with 4.5g / L hydrogen peroxide for 10 minutes, wash with water for 1 minute, and dry to obtain a dyed silk fabric;

[0076] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0077] Example 7

[0078] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, comprising the following steps:

[0079] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0080] (2) Preparation of N,N'-diacetyl cyanine dye mother solution: distilled water was used to prepare the dye mother solution with a concentration of 20 g / L, 200 g / L of sodium sulfite was added, and the mixture was reduced at room temperature for 30 min, centrifuged at 9000 rpm for 10 min, and the supernatant was collected. The pH was adjusted to 5.0 with 200 g / L citric acid to obtain N,N'-diacetyl cyanine dye mother solution;

[0081] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 2% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:25, so that the silk is completely immersed below the liquid surface of the dye solution, dye at room temperature for 10 minutes, take out and air-dry, oxidize with 7.5g / L hydrogen peroxide for 5 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0082] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0083] Example 8

[0084] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, comprising the following steps:

[0085] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0086] (2) Preparation of N,N'-diacetyl cyanine dye mother solution: prepare the dye mother solution with distilled water to a concentration of 10 g / L, add 200 g / L sodium sulfite, reduce at room temperature for 10 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, adjust the pH to 4.0 with acetic acid, and obtain N,N'-diacetyl cyanine dye mother solution;

[0087] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:20, and immerse the silk completely below the dye solution surface, dye at room temperature for 15 minutes, take out and air-dry, oxidize with 10g / L hydrogen peroxide for 15 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0088] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0089] Example 9

[0090] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is vegetable tanned cowhide, comprising the following steps:

[0091] (1) Pretreatment of vegetable tanned cowhide: Cut vegetable tanned cowhide with a thickness of 1.8-2.0 mm into 2.5 cm*5 cm specifications, soak it in 10 g / L TYL-020 penetrant, roll it to expel bubbles, take it out after it is completely wetted, and absorb the excess penetrant with filter paper to obtain pretreated vegetable tanned cowhide;

[0092] (2) Preparation of N-acetyl cyanine dye mother solution: The dye mother solution was prepared with distilled water to a concentration of 20 g / L, and then 10 g / L of sodium sulfite was added. After reduction at room temperature for 60 min, the supernatant was collected after centrifugation at 9000 rpm for 10 min, and the pH was adjusted to 3.0 with 200 g / L citric acid to obtain N-acetyl cyanine dye mother solution;

[0093] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain N-acetyl blue dyeing solution, add the vegetable tanned cowhide pretreated in step (1) at a bath ratio of 1:25, immerse the vegetable tanned cowhide completely below the dyeing solution surface, dye at room temperature for 15 minutes, take out and air-dry, oxidize with 3.5g / L hydrogen peroxide for 10 minutes, wash with water for 1 minute, and dry to obtain dyed vegetable tanned cowhide;

[0094] (4) Soaping process: The dyed vegetable tanned cowhide obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the leather is taken out and air-dried.

[0095] Example 10

[0096] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is vegetable tanned cowhide, comprising the following steps:

[0097] (1) Pretreatment of vegetable tanned cowhide: Cut vegetable tanned cowhide with a thickness of 1.8-2.0 mm into 2.5 cm*5 cm specifications, soak it in 10 g / L TYL-020 penetrant, roll it to expel bubbles, take it out after it is completely wetted, and absorb the excess penetrant with filter paper to obtain pretreated vegetable tanned cowhide;

[0098] (2) Preparation of N-acetyl cyanine dye mother solution: dissolve N-acetyl cyanine dye in distilled water to a concentration of 10 g / L, then add 50 g / L of sodium sulfate, reduce at room temperature for 40 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, and adjust the pH to 5.0 with 200 g / L citric acid to obtain N-acetyl cyanine dye mother solution;

[0099] (3) Dyeing process: dilute the N-acetyl indigo dye mother solution obtained in step (2) to a dye concentration of 1.0% owf to obtain a dyeing solution, add the vegetable tanned cowhide pretreated in step (1) at a bath ratio of 1:30, immerse the vegetable tanned cowhide completely below the liquid surface of the dyeing solution, dye at room temperature for 30 minutes, take out and air-dry, oxidize with 4.5g / L hydrogen peroxide for 8 minutes, wash with water for 1 minute, and dry to obtain the dyed vegetable tanned cowhide;

[0100] (4) Soaping process: The dyed vegetable tanned cowhide obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the leather is taken out and air-dried.

[0101] Embodiment 11

[0102] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is vegetable tanned cowhide, comprising the following steps:

[0103] (1) Pretreatment of vegetable tanned cowhide: Cut vegetable tanned cowhide with a thickness of 1.8-2.0 mm into 2.5 cm*5 cm specifications, soak it in 10 g / L TYL-020 penetrant, roll it to expel bubbles, take it out after it is completely wetted, and absorb the excess penetrant with filter paper to obtain pretreated vegetable tanned cowhide;

[0104] (2) Preparation of N-acetyl cyanine dye mother solution: dissolve N-acetyl cyanine dye in distilled water to a concentration of 10 g / L, then add 100 g / L of sodium sulfite, reduce at room temperature for 30 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, and adjust the pH to 4.0 with 200 g / L citric acid to obtain N-acetyl cyanine dye mother solution;

[0105] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 2% owf to obtain a dyeing solution, add the vegetable tanned cowhide pretreated in step (1) at a bath ratio of 1:100, immerse the vegetable tanned cowhide completely below the liquid surface of the dyeing solution, dye at room temperature for 20 minutes, take out and air-dry, oxidize with 2.5g / L hydrogen peroxide for 15 minutes, wash with water for 1 minute, and dry to obtain dyed vegetable tanned cowhide;

[0106] (4) Soaping process: The dyed vegetable tanned cowhide obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the leather is taken out and air-dried.

[0107] Example 12

[0108] This embodiment provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is vegetable tanned cowhide, comprising the following steps:

[0109] (1) Pretreatment of vegetable tanned cowhide: Cut vegetable tanned cowhide with a thickness of 1.8-2.0 mm into 2.5 cm*5 cm specifications, soak it in 10 g / L TYL-020 penetrant, roll it to expel bubbles, take it out after it is completely wetted, and absorb the excess penetrant with filter paper to obtain pretreated vegetable tanned cowhide;

[0110] (2) Preparation of N-acetyl cyanine dye mother solution: dissolve N-acetyl cyanine dye in distilled water to a concentration of 10 g / L, then add 200 g / L of sodium sulfite, reduce at room temperature for 10 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, and adjust the pH to 4.5 with acetic acid to obtain N-acetyl cyanine dye mother solution;

[0111] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dyeing solution, add the vegetable tanned cowhide pretreated in step (1) at a bath ratio of 1:45, immerse the vegetable tanned cowhide completely below the liquid surface of the dyeing solution, dye at room temperature for 45 minutes, take out and air-dry, oxidize with 10g / L hydrogen peroxide for 3 minutes, wash with water for 1 minute, and dry to obtain the dyed vegetable tanned cowhide;

[0112] (4) Soaping process: The dyed vegetable tanned cowhide obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the leather is taken out and air-dried.

[0113] Comparative Example 1

[0114] This comparative example provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, and caustic soda is used to adjust the pH to 7.5 when preparing the dye mother solution. The specific method comprises the following steps:

[0115] (1) Silk pretreatment: 12 momme silk fabric was cut into pieces of 5 cm*5 cm in size, and soaked in 10 g / L TYL-020 dye penetrant, and bubbles were discharged. After the silk fabric was completely wetted, it was taken out, and the surface liquid of the silk fabric was slightly dried to keep the inside of the silk fabric moist, thereby obtaining a pretreated silk fabric;

[0116] (2) The method used in the past, the preparation of N-acetyl indigo dye mother solution: dissolve N-acetyl indigo dye derivative in distilled water to a concentration of 10 g / L, add 10 g / L of hydrosulfite, reduce at room temperature for 20 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, adjust the pH to 7.5 with 200 g / L caustic soda, and obtain N-acetyl indigo dye mother solution;

[0117] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:40, and immerse the silk completely below the dye solution surface. Dye at room temperature for 45 minutes, take out and air-dry, oxidize with 12g / L hydrogen peroxide for 3 minutes, wash with water for 1 minute, and dry to obtain a dyed silk fabric;

[0118] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0119] Comparative Example 2

[0120] This comparative example provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, the fabric is silk fabric, and commercial vat red dye (purchased from Hebei Dihongsheng Chemical Industry and Trade Co., Ltd., powdered, used after being dissolved in distilled water) is selected as a comparison. The specific method includes the following steps:

[0121] (1) Silk pretreatment: 12 momme silk fabric was cut into pieces of 5 cm*5 cm in size, and soaked in 10 g / L TYL-020 dye penetrant, and bubbles were discharged. After the silk fabric was completely wetted, it was taken out, and the surface liquid of the silk fabric was slightly dried to keep the inside of the silk fabric moist, thereby obtaining a pretreated silk fabric;

[0122] (2) Preparation of vat red dye mother solution: dissolve vat red dye in distilled water to a concentration of 15 g / L, then add 30 g / L of hydrosulfite, reduce at 65°C for 20 min, adjust pH to 11.5 with NaOH, centrifuge at 9000 rpm for 10 min, collect supernatant, and obtain vat red dye mother solution;

[0123] (3) Dyeing process: dilute the vat red dye mother solution obtained in step (2) to a vat red dye concentration of 1% owf to obtain a vat red dyeing solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:20, immerse the silk completely below the dyeing solution surface, perform reduction dyeing at 60° C. for 30 min, take out and air-dry, oxidize with 5.0 g / L hydrogen peroxide for 25 min, wash with water for 1 min, and dry to obtain a dyed silk fabric;

[0124] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0125] Comparative Example 3

[0126] This comparative example provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric, and a reducing agent, insurance powder (purchased from Nanjing Unojia Experimental Equipment Technology Co., Ltd., in powder form) is selected as a comparison. The specific method comprises the following steps:

[0127] (1) Silk pretreatment: 12 momme silk fabric was cut into pieces of 5 cm*5 cm in size, and soaked in 10 g / L TYL-020 dye penetrant, and bubbles were discharged. After the silk fabric was completely wetted, it was taken out, and the surface liquid of the silk fabric was slightly dried to keep the inside of the silk fabric moist, thereby obtaining a pretreated silk fabric;

[0128] (2) Preparation of N,N'-diacetyl cyanine dye mother solution: dissolve N,N'-diacetyl cyanine dye in distilled water to a concentration of 20 g / L, then add 30 g / L of hydrosulfite, reduce at 25°C for 30 min, adjust the pH to 10.5 with NaOH, centrifuge at 9000 rpm for 10 min, and collect the supernatant to obtain N,N'-diacetyl cyanine dye mother solution;

[0129] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:20, immerse the silk completely below the dye solution surface, perform reduction dyeing for 30 minutes, take out and air-dry, oxidize with 5.0 g / L hydrogen peroxide for 25 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0130] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0131] Comparative Example 4

[0132] This comparative example provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is vegetable tanned cowhide, and caustic soda is used to adjust the pH to 7.0 when preparing the dye mother solution. The specific method comprises the following steps:

[0133] (1) Pretreatment of vegetable tanned cowhide: Cut vegetable tanned cowhide with a thickness of 1.8-2.0 mm into 2.5 cm*5 cm specifications, soak it in 10 g / L TYL-020 penetrant, roll it to expel bubbles, take it out after it is completely wetted, and absorb the excess penetrant with filter paper to obtain pretreated vegetable tanned cowhide;

[0134] (2) The method used in the past, the preparation of N-acetyl indigo dye mother solution: dissolve N-acetyl indigo dye derivative in distilled water to a concentration of 10 g / L, then add 10 g / L of hydrosulfite, reduce at room temperature for 20 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, and adjust the pH to 7.0 with 200 g / L caustic soda to obtain N-acetyl indigo dye mother solution;

[0135] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dyeing solution, add the vegetable tanned cowhide pretreated in step (1) at a bath ratio of 1:40, immerse the vegetable tanned cowhide completely below the liquid surface of the dyeing solution, dye at room temperature for 45 minutes, take out and air-dry, oxidize with 12g / L hydrogen peroxide for 3 minutes, wash with water for 1 minute, and dry to obtain the dyed vegetable tanned cowhide;

[0136] (4) Soaping process: The dyed vegetable tanned cowhide obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the leather is taken out and air-dried.

[0137] Comparative Example 5

[0138] This comparative example provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, the fabric is silk fabric, and the only difference between it and Example 4 is that caustic soda is used to adjust the pH of the dyeing solution to 8.0, and the rest of the dyeing process is the same.

[0139] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0140] (2) Preparation of N-acetyl indigo blue dye mother solution: dissolve N-acetyl indigo blue dye in distilled water to prepare a dye mother solution concentration of 10 g / L, add 200 g / L sodium sulfite, reduce at room temperature for 8 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, and adjust the pH to 8.0 with caustic soda to obtain an N-acetyl indigo blue derivative dye mother solution;

[0141] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:45, so that the silk is completely immersed below the liquid surface of the dye solution, dye at room temperature for 45 minutes, take out and air-dry, oxidize with 10g / L hydrogen peroxide for 3 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0142] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0143] Comparative Example 6

[0144] This comparative example provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, the fabric is silk fabric, and the only difference between it and Example 4 is that hydrosulfite is used instead of sodium sulfite, and the rest of the dyeing process is the same.

[0145] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0146] (2) Preparation of N-acetyl indigo blue dye mother solution: dissolve N-acetyl indigo blue dye in distilled water to prepare a dye mother solution concentration of 10 g / L, add 200 g / L of hydrosulfite, reduce at room temperature for 8 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, adjust the pH to 4.0 with acetic acid, and obtain an N-acetyl indigo blue derivative dye mother solution;

[0147] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:45, so that the silk is completely immersed below the liquid surface of the dye solution, dye at room temperature for 45 minutes, take out and air-dry, oxidize with 10g / L hydrogen peroxide for 3 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0148] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0149] Comparative Example 7

[0150] This comparative example provides a method for dyeing protein clothing fabric using acetylated indigo blue derivative dye, wherein the fabric is silk fabric. The difference between this method and Example 4 is that in step (2), the dye mother liquor concentration is 10 g / L, 300 g / L of sodium sulfite is added, and the rest of the dyeing process is the same.

[0151] (1) Pretreatment of silk fabric: Cut 12 momme silk fabric into pieces of 5 cm*5 cm in size, soak them in 10 g / L TYL-020 dye penetrant, expel bubbles, take them out after they are completely wetted, slightly absorb the surface liquid of the silk fabric, keep the inside of the silk fabric moist, and obtain pretreated silk fabric;

[0152] (2) Preparation of N-acetyl indigo blue dye mother solution: dissolve N-acetyl indigo blue dye in distilled water to prepare a dye mother solution concentration of 10 g / L, add 300 g / L sodium sulfite, reduce at room temperature for 8 min, centrifuge at 9000 rpm for 10 min, collect the supernatant, adjust the pH to 4.0 with acetic acid, and obtain an N-acetyl indigo blue derivative dye mother solution;

[0153] (3) Dyeing process: dilute the dye mother solution obtained in step (2) to a dye concentration of 1.5% owf to obtain a dye solution, add the silk fabric pretreated in step (1) at a bath ratio of 1:45, so that the silk is completely immersed below the liquid surface of the dye solution, dye at room temperature for 45 minutes, take out and air-dry, oxidize with 10g / L hydrogen peroxide for 3 minutes, wash with water for 1 minute, and dry to obtain the dyed silk fabric;

[0154] (4) Soaping process: The dyed silk fabric obtained in step (3) is subjected to soaping treatment by mixing 2 g / L neutral soap and 2 g / L sodium carbonate to prepare a soap solution with a soaping bath ratio of 1:20. The soaping is carried out at room temperature for 5 minutes, and the fabric is taken out and air-dried.

[0155] Effect Example 1

[0156] The above-mentioned Examples 1-8, Comparative Examples 1-3 and Comparative Examples 5-7 were dyed multiple times, and the color depth (K / S) and color fastness of the fabrics were measured, wherein the color fastness test was carried out with reference to GB / T 3920-2008 "Textiles - Tests for Color Fastness - Color Fastness to Rubbing" and GB / T 3921-2008 "Textiles - Tests for Color Fastness - Color Fastness to Soaping". At least 3 pieces of cloth were taken from each group for testing, and the average result was calculated. The specific results are shown in Table 1 below.

[0157] Table 1 Silk fabric dyeing parameters (three repeated experimental data per group)

[0158]

[0159]

[0160]

[0161] Due to the characteristics of silk fabrics, they are neither resistant to high temperatures nor to strong alkalis. The highest temperature that silk fabrics can withstand is generally around 60°C, otherwise protein denaturation will occur. Therefore, dyeing is best when the pH is 3-5, otherwise it will cause protein fiber hydrolysis. Generally, vat red is not suitable for dyeing silk fabrics. Vat red is a vat dye that is difficult to dissolve in water. It needs to be reduced to a soluble leuco sodium salt under alkaline conditions before it can dye the fiber; and vat red requires at least 65°C high temperature dyeing. In order to protect the principle of silk fabrics, adjusting the dyeing temperature to 60°C will affect the dyeing effect of the dye solution on silk, and then affect the average color depth (K / S) and color fastness of the fabric. Compared with traditional commodity vat red, the dyeing method of N,N'-diacetyl blue dye for protein clothing fabrics can increase the K / S value by nearly 1 times, and the color fastness to dry friction is also improved by 1 level compared with traditional dyeing, and the color fastness to wet friction is improved by 1 level.

[0162] Since silk is a protein fiber with poor alkali resistance, when vat red is used to dye silk under alkaline conditions, it will cause the protein fiber to hydrolyze, which will have a certain destructive effect on the fiber interior of silk fabrics, and will also destroy the gloss of the silk fabric surface, reduce the silk strength, and thus cause the silk fabric to be not resistant to soap washing. Although vat red leuco body can be converted into leuco acid, thereby converting the alkaline environment dye solution into an acidic environment, vat red leuco acid has low solubility and does not color silk. In the method of dyeing protein clothing fabrics with N,N'-diacetyl indigo dye, the dye solution is in a weak acid condition, there is no damage to the protein fiber, and the color fastness to soap washing is improved by one level compared with traditional dyeing.

[0163] Effect Example 2

[0164] The above-mentioned Examples 9-12 and Comparative Example 4 were dyed multiple times, and the color depth (K / S) and color fastness of the fabrics were measured, wherein the color fastness was tested with reference to GB / T 3920-2008 "Textiles - Tests for Color Fastness - Color Fastness to Rubbing" and GB / T 3921-2008 "Textiles - Tests for Color Fastness - Color Fastness to Soaping". At least 3 pieces of cloth were taken from each group for testing, and the average result was calculated. The specific results are shown in Table 2 below.

[0165] Table 2 Leather dyeing parameters (three repeated experimental data per group)

[0166]

[0167]

[0168] Since leather is a protein fiber with poor alkali resistance, the previous dyeing conditions of N-acetyl indigo blue are weakly alkaline environments. The alkali solution will corrode the fibroin and sericin of the protein fiber, causing them to hydrolyze, which will have a certain destructive effect on the fiber interior of the leather fabric, and will also destroy the gloss of the leather fabric surface, reduce the leather toughness and strength, and thus cause the leather fabric to be not resistant to soap washing. In the dyeing method provided by the present invention, the dye solution is in a weakly acidic condition, there is no damage to the protein fiber, and the color fastness to soap washing can be improved by one level compared with traditional dyeing.

[0169] At the same time, in an acidic environment, the rate of sodium salt of leucoate is higher, and the dye can be more firmly adsorbed and fixed inside the fiber, thereby improving the color depth (K / S) and color fastness of the fabric. Compared with the previous dyeing method, the dyeing method provided by the present invention can increase the K / S value by nearly 2 to 3 times, and the color fastness to dry friction is also improved by 1 level compared with traditional dyeing, and the color fastness to wet friction is improved by 1 level.

[0170] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for dyeing protein clothing fabrics using acetylated indigo blue derivative dyes, characterized in that: The following steps are involved: S1. Soak the protein clothing fabric in the dye penetrant, take it out and drain it, keeping the inside of the fabric moist; S2, dissolving the acetylated blue derivative dye in water, adding a reducing agent for reduction, and adjusting the pH to 3.0-5.0 to obtain an acetylated blue derivative dye mother solution; S3, diluting the acetylated indigo blue derivative dye mother liquor of step S2 to obtain a dyeing solution, and then placing the protein clothing fabric obtained in step S1 in the dyeing solution for immersion and dyeing, taking out and airing, oxidizing, washing and drying, and then performing soap washing and drying to obtain a dyed protein clothing fabric; The acetylated indigo blue derivative dye includes N-acetyl indigo blue or N,N'-diacetyl indigo blue.

2. The dyeing method according to claim 1, characterized in that The reducing agent includes sodium sulfite.

3. The dyeing method according to claim 1, characterized in that In the step S2, the mass ratio of the acetylated indigo blue derivative dye to the reducing agent is 1:(0.5-20).

4. The dyeing method according to claim 1, characterized in that In the step S2, a weak acid is used to adjust the pH to 3.0-5.0, and the weak acid includes at least one of citric acid, acetic acid and phosphoric acid.

5. The dyeing method according to claim 1, characterized in that The protein clothing fabrics include silk fabrics and leather.

6. The dyeing method according to claim 1, characterized in that In the step S3, the weight of the acetylated indigo blue derivative dye is 1-3% of the weight of the protein clothing fabric, and the mass volume ratio of the protein clothing fabric to the diluted dyeing solution is 1 g: (20-100) mL.

7. The dyeing method according to claim 1, characterized in that In the step S2, the reduction condition is: reacting at 15-30° C. for 15-60 min.

8. The dyeing method according to claim 1, characterized in that In step S3, the dyeing conditions are: dyeing at 15-30°C for 5-90 minutes; the drying time is 5-10 minutes; the oxidation is carried out using hydrogen peroxide, the oxidation concentration of hydrogen peroxide is 0.5-10g / L, and the oxidation time is 1-30 minutes.

9. The dyeing method according to claim 1, characterized in that In the step S1, the dye penetrant includes TYL-020 dye penetrant.

10. Application of the dyeing method as claimed in claims 1 to 9 in dyeing protein clothing fabrics.

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