A mixed dyeing solution of biological blue dye and biological black dye and a dyeing method thereof

Abstract

This invention relates to a blended dyeing solution of biological blue dye and biological black dye and its dyeing method, belonging to the field of dyeing and finishing technology. This invention utilizes a blend of biological blue dye and biological black dye, including a co-bath dyeing solution and an over-dyeing solution. Dyeing textiles using the co-bath dyeing solution, or using the black dye solution in the over-dyeing solution for initial base dyeing followed by over-dyeing with the blue dyeing solution, can significantly enhance the depth of the blue color, resulting in a navy blue textile with a reddish correction effect. Dyeing textiles using the co-bath dyeing solution and the over-dyeing solution of this invention can achieve a color depth and luster that are different from the insufficient depth achieved by dyeing the two dyes individually. Furthermore, it can synergistically improve the color fastness to dry and wet rubbing by 0.5-1 grade, and achieve a light fastness of 6-7 grade.

Description

Technical Field

[0001] This invention relates to the field of dyeing and finishing technology, and in particular to a mixed dyeing solution of biological blue dye and biological black dye and its dyeing method. Background Technology

[0002] Indigo is a novel blue bio-dyed, belonging to the vat dye category. Under the action of a reducing agent, it transforms into a soluble leuco form. This leuco form binds to the fiber, achieving dyeing. Further oxidation in air restores the leuco form to its original blue color. The main advantage of indigo as a bio-dyed is its bright hue. Furthermore, the bio-fermentation process produces various complex intermediates, some of which cannot be completely purified and separated, resulting in a natural, vibrant, and fluid blue hue. Currently, indigo has a certain production capacity and a complete and standardized production and dyeing process, demonstrating significant development potential. However, its unique and vibrant blue can have a reddish tint. Additionally, the rapid binding rate between the leuco form and the fiber, along with its own rapid oxidation, can hinder further dyeing, leading to insufficient dyeing depth and weak dye enhancement performance. These factors still present some obstacles to its application in high-end textiles.

[0003] Melanin, a novel black dye disclosed in patent number 2024109786742, is prepared by microbial fermentation and does not contain heavy metals or other toxic and harmful substances, unlike traditional black dyes. Its key feature is that it possesses both acid dye and direct dye properties. It can dye fibers suitable for acid dyeing, such as wool and nylon, as well as cellulosic fibers such as cotton, linen, and viscose. After dyeing, textiles of varying shades can exhibit colors such as khaki, dark brown, tan, and black, showcasing a variety of visual effects and styles.

[0004] In order to expand the application styles and color advantages of blue pigment and melanin, two high-performance biological dyes, this invention mixes the two dyes to obtain a richer color range and color effects. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a mixed dyeing solution of biological blue dye and biological black dye and a dyeing method thereof.

[0006] The melanin of this invention is a novel black dye disclosed in patent number 2024109786742. Because melanin maintains good dispersion and dyeing stability even in alkaline and strong reducing agent environments, it can be used for both co-bath dyeing with indigo dye and step-by-step over-dyeing. Furthermore, the numerous amino groups in the indigo dye structure and the numerous carbonyl and hydroxyl groups in the melanin molecule structure have good affinity, allowing the two dyes to synergistically improve various color fastness properties after dyeing through weak interactions on textile fibers. This invention utilizes a blend of biological blue and biological black dyes, including two dyeing schemes: ① Mixing melanin dye with indigo dye for co-bath dyeing. ② First, dyeing the textile fibers with melanin dye as a base color, then performing reduction dyeing with indigo dye. Both methods can achieve color depth and hue different from dyeing with either dye alone, and can synergistically improve dry and wet rubbing color fastness by 0.5-1 grade, and achieve a light fastness grade of 7.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a mixed dyeing solution of a biological blue dye and a biological black dye, wherein the mass concentration of blue dye is 2-30 g / L, the mass concentration of melanin is 0.02-15 g / L, the mass concentration of sodium hydrosulfite is 1-2 times the mass concentration of blue dye, and the mass concentration of alkali is 0.1-2 times the total mass concentration of blue dye and melanin.

[0008] This invention dyes textiles using a blended dyeing solution (including co-bath dyeing solution and over-dyeing solution) containing melanin and blue pigment at a specific concentration. This results in a significant increase in the depth of the blue pigment, producing a navy blue textile with a reddish correction effect. The solvent in the blended dyeing solution is water.

[0009] As a preferred embodiment of the mixed dyeing solution of the present invention, the mixed dyeing solution includes a co-bath dyeing solution or a combined dyeing solution containing indigo and melanin. The same bath dyeing solution is a mixed dyeing solution containing indigo, melanin, sodium hydrosulfite and alkali agent; The combined dyeing solution is a combination of indigo dyeing solution and melanin dyeing solution. The melanin dyeing solution contains melanin and a portion of the alkali agent, while the indigo dyeing solution contains indigo, sodium hydrosulfite, and the remaining alkali agent; the sum of the portion of the alkali agent and the remaining alkali agent is the total amount of alkali agent. Both the co-bath dyeing solution and the combined dyeing solution are solvents for water.

[0010] As a preferred embodiment of the mixed dyeing solution of the present invention, the total mass concentration of indigo and melanin in the same bath dyeing solution is 5~30 g / L, wherein the mass concentration of melanin is 0.5%~50% of the mass concentration of indigo, the mass concentration of sodium hydrosulfite in the same bath dyeing solution is 1~2 times the mass concentration of indigo, and the mass concentration of alkali agent in the same bath dyeing solution is 0.1~2 times the total mass concentration of indigo and melanin.

[0011] This invention utilizes a co-bath dyeing solution obtained from a specific concentration of melanin, indigo, sodium hydrosulfite, and alkali to dye textiles. This solution significantly enhances the depth of the indigo blue, resulting in navy blue textiles with a reddish-brown correction effect. The color depth of the co-bath dyed textiles is 9-38. The value ranges from 9.4 to 30.1. The value ranges from -0.78 to 1.14. The values ​​are -22 to -17, the color fastness to dry rubbing is 4 to 5, the color fastness to wet rubbing is 3 to 5, and the color fastness to light is 6 to 7. By using the same bath dyeing solution of the present invention to dye textiles, a color depth and hue that are different from those of dyeing with two dyes alone is insufficient can be obtained, and the color fastness to dry rubbing and wet rubbing can also be synergistically improved by 0.5 to 1 grade.

[0012] When the melanin concentration in the same dye bath is less than 0.5% of the blue concentration, the color and color depth change little, and there is almost no melanin blending effect; when the melanin concentration is greater than 50% of the blue concentration, the fabric of the dyed textile is darker and appears blackish-brown, the blue light is more obviously blocked, and the blue blending effect is weak.

[0013] The mass concentration of sodium hydrosulfite in the same bath dye solution is 1 to 2 times that of indigo. As a reducing agent, sodium hydrosulfite is only used for the reduction of indigo. At this addition amount, it can ensure that indigo is fully reduced.

[0014] The mass concentration of the alkali agent in the same bath dyeing solution is 0.1 to 0.5 times the mass concentration of the pigment. The alkali agent adjusts the pH and provides an alkaline dyeing environment. At this alkali agent mass concentration, a pH 9.0 to 10.0 dyeing environment can be provided for melanin, while ensuring the dispersion stability and blue structure stability of melanin.

[0015] In a preferred embodiment of the mixed dyeing solution of the present invention, the melanin concentration in the melanin dyeing solution of the mixed dyeing solution is 0.05~15 g / L, and the mass concentration of the alkali agent is 0.2~0.5 times the melanin mass concentration; the indigo dyeing solution of the mixed dyeing solution has a mass concentration of 2~30 g / L, the sodium hydrosulfite mass concentration is 1~2 times the indigo mass concentration, and the remaining alkali agent mass concentration is 0.1~0.5 times the indigo mass concentration.

[0016] This invention utilizes a dyeing solution prepared with a specific concentration of melanin, indigo, sodium hydrosulfite, and alkali to dye textiles. This results in a significantly enhanced blue depth after dyeing, producing a navy blue textile with a reddish-brown correction effect. The color depth of the dyed textiles obtained from this solution ranges from 11 to 40. The value ranges from 8.9 to 30.5. The value ranges from -1.1 to 1.8. The values ​​are -21.2 to -18.3, the color fastness to dry rubbing is 4 to 5, the color fastness to wet rubbing is 3 to 5, and the color fastness to light is 7. Using the over-dyeing solution of the present invention to dye textiles can achieve a color depth and luster that is different from the insufficient dyeing depth of two dyes alone, and can also synergistically improve the color fastness to dry and wet rubbing by 0.5 to 1 grade.

[0017] When the concentration of melanin in the dyeing solution is less than 0.05 g / L, the color depth is not significantly improved and there is no red light elimination effect. When the concentration of melanin in the dyeing solution exceeds 15 g / L, the brightness of the dyed textile is too low, the blue light is significantly blocked, the blue blending effect is weakened, and it appears as a dark brown.

[0018] The mass concentration of the alkali agent in the melanin dyeing solution is 0.2 to 0.5 times the mass concentration of melanin. With this amount of alkali agent, a pH 10.0 to 12.0 dyeing solution environment can be provided for melanin, ensuring the stable dispersion of melanin in the dyeing solution.

[0019] In overdyeing, the concentration of indigo in the dye bath is 2-30 g / L, which can achieve a covering effect on the base color, resulting in a deeper blue color after overdyeing, resembling navy blue with a red correction effect. When the concentration of indigo is less than 2 g / L, the covering effect on the base color is poor, the hue of the textile changes, and the dyeing is uneven; when the concentration of indigo is greater than 30 g / L, the covering power of indigo on the base color is too strong, making it impossible to achieve the purpose of overdyeing and color matching.

[0020] The mass concentration of sodium hydrosulfite in the indigo dyeing solution is 1 to 2 times that of indigo. As a reducing agent, sodium hydrosulfite is only used for the reduction of indigo. At this addition amount, it can ensure that indigo is fully reduced.

[0021] The mass concentration of the remaining alkali in the indigo dyeing solution is 0.1 to 0.5 times the mass concentration of indigo. This amount of alkali can ensure the structural stability of indigo.

[0022] In a preferred embodiment of the mixed dyeing solution described in this invention, the alkaline agent in the same bath includes sodium hydroxide (caustic soda), potassium hydroxide, sodium carbonate, sodium bicarbonate, etc. Sodium hydroxide is preferred.

[0023] In a preferred embodiment of the mixed dyeing solution described in this invention, the alkaline agents in the melanin dyeing solution and the indigo dyeing solution include sodium hydroxide (caustic soda), potassium hydroxide, sodium carbonate, sodium bicarbonate, etc. Sodium hydroxide is preferred.

[0024] Secondly, the present invention provides a dyeing method for the above-mentioned mixed dyeing solution, including a co-bath dyeing method using a co-bath dyeing solution, or an over-dyeing method using an over-dyeing solution.

[0025] As a preferred embodiment of the staining method of the present invention, the same-bath staining method includes the following steps: S1. Mix and dissolve the blue pigment and melanin in water, then add sodium hydrosulfite and alkali, mix well, reduce the material, and obtain the same bath dye solution; S2. The textile is immersed in the dye bath obtained in step S1 for dyeing, and then oxidized in air to obtain pre-dyed textile. S3. Wash the pre-dyed textile obtained in step S2 with soap for 5-30 minutes, and air dry to obtain the same-bath dyed textile. The soap washing solution used is a soap flake solution with a mass concentration of 1-10 g / L.

[0026] In a preferred embodiment of the same-bath dyeing method described in this invention, in step S1, the temperature of the reducing agent is 25~90℃, and the time is 10~90 min. Preferably, the temperature of the reducing agent is 25~60℃, and the time is 30~60 min; these conditions ensure that the indigo dye is completely reduced and the melaninized material is uniform and free of suspended particles.

[0027] As a preferred embodiment of the same-bath staining method in the staining method of the present invention, in step S2, the immersion staining temperature is 25~90℃ and the time is 0.1~10 min.

[0028] As a preferred embodiment of the same-bath staining method in the staining method of the present invention, in step S2, the immersion staining temperature is 40~50℃ and the time is 0.5~2 min.

[0029] In a preferred embodiment of the same-bath staining method in the staining method of the present invention, the air oxidation time in step S2 is 1~10 min. Preferably, the air oxidation time is 1~5 min.

[0030] In a preferred embodiment of the same-bath dyeing method described in this invention, in step S2, the number of dyeing passes in the immersion dyeing is 1 to 10. Different numbers of dyeing passes result in different color depths. As the number of passes increases, the dyeing depth gradually increases, and the color light gradually shifts towards shorter wavelengths. Different color light styles are developed depending on the number of passes.

[0031] As a preferred embodiment of the same-bath staining method in the staining method of the present invention, in step S3, the bath ratio of the soaping is 50:1 to 200:1.

[0032] In a preferred embodiment of the same-bath dyeing method in the dyeing method of the present invention, the temperature of the soaping in step S3 is 25~60℃.

[0033] As a preferred embodiment of the dyeing method of the present invention, the over-dyeing method includes the following steps: s1. Dissolve melanin in water, then add some alkali, stir the mixture to obtain melanin dye solution; s2. Dissolve indigo in water, then add sodium hydrosulfite and the remaining alkali, mix well, reduce the material, and obtain indigo dye solution; s3. The textile is immersed in the black dye solution obtained in step s1 for dyeing, and then washed with water to obtain a black dye base textile; the obtained black dye base textile is immersed in the blue dye solution obtained in step s2 for over-dyeing, and then oxidized in air to obtain an over-dyed pre-dyed textile. s4. Wash the pre-dyed textile obtained in step s3 with soap and dry it to obtain the dyed textile.

[0034] In a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, in step s1, the temperature of the stirring mixture is 40~95℃ and the time is 60~150 min. Preferably, the temperature of the stirring mixture is 80~95℃ and the time is 60~120 min, which ensures that the melanin is uniform and free of suspended particles.

[0035] In a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, in step s2, the temperature of the reducing agent is 25~60℃ and the time is 10~90 min. Preferably, the temperature of the reducing agent is 30~60℃ and the time is 10~30 min, which ensures that the indigo dye is completely reduced.

[0036] In a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, in step s3, the immersion dyeing temperature is 60~95℃ and the time is 0.5~10 min. Preferably, the immersion dyeing temperature is 80~90℃ and the time is 0.5~2 min.

[0037] In a preferred embodiment of the over-dyeing method in the dyeing method described in this invention, the number of immersion dyeing passes in step s3 is 1 to 5. Depending on the number of under-dyeing passes, the lightness value will exhibit different shades of light and dark.

[0038] In a preferred embodiment of the over-dyeing method described in this invention, step s3 involves 1 to 3 washes. Washing removes excess melanin, preventing it from affecting the over-dyeing of indigo. Without washing after the base dyeing, excess melanin will affect the color uniformity of the over-dyeed indigo; more than 3 washes remove excess melanin.

[0039] In a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, in step s3, the immersion and over-dyeing temperature is 25~60℃ and the time is 0.1~10 min. Preferably, the immersion and over-dyeing temperature is 25~40℃ and the time is 0.5~2 min.

[0040] In a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, in step s3, the number of over-dyeing passes is 1 to 7. Depending on the number of over-dyeing passes, the over-dyeing depth varies, and as the number of base passes increases, the color will shift towards shorter wavelengths.

[0041] In a preferred embodiment of the over-staining method in the staining method of the present invention, the air oxidation time in step s3 is 1~10 min. Preferably, the air oxidation time is 1~5 min.

[0042] As a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, in step s4, the bath ratio of the soaping is 50:1 to 200:1 to ensure that the dyed textiles are thoroughly washed and surface impurities and floating dye are removed.

[0043] In a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, the temperature of the soaping in step s4 is 25~60℃; preferably, the temperature of the soaping is 40~60℃. The washing effect of the soaping solution increases with increasing temperature; however, if the temperature exceeds 60℃, the washing effect no longer improves.

[0044] In a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, the soaping time in step s4 is 5-30 minutes. If it is less than 5 minutes, the removal of impurities and floating dye on the fabric surface is insufficient; if it is more than 30 minutes, the washing effect of the soap solution no longer changes.

[0045] In a preferred embodiment of the over-dyeing method in the dyeing method of the present invention, in step s4, the soaping solution used for soaping is a soap flake solution with a mass concentration of 1~10 g / L. If the concentration is lower than 1 g / L, the removal of impurities and floating dye on the fabric surface is insufficient; if the concentration is higher than 10 g / L, the washing effect of the soap solution no longer changes, resulting in waste of soap flakes.

[0046] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention utilizes a blend of biological blue and biological black dyes, comprising both co-dyeing and over-dyeing solutions. By using the co-dyeing solution to dye textiles, or by first applying a base dye using the black dye in the over-dyeing solution followed by over-dyeing with the blue dye, a significant increase in the depth of the blue color can be achieved, resulting in navy blue textiles with a reddish correction effect. Dyeing textiles using the co-dyeing and over-dyeing solutions of this invention yields a color depth and luster that differs from the insufficient depth achieved by either dye alone. Furthermore, it synergistically improves dry and wet rubbing colorfastness by 0.5-1 grade and lightfastness by 6-7 grade. Attached Figure Description

[0047] Figure 1 This is an appearance diagram of the same-bath dyed textile obtained in Example 4 of the present invention; Figure 2 This is an appearance diagram of the same-bath dyed textile obtained in Example 8 of the present invention; Figure 3 This is an appearance diagram of the over-dyed textile obtained in Embodiment 19 of the present invention; Figure 4 This is an appearance diagram of the over-dyed textile obtained in Embodiment 21 of the present invention; Figure 5 This is an appearance diagram of the over-dyed textile obtained in Embodiment 27 of the present invention; Figure 6 This is an appearance diagram of the over-dyed textile obtained in Embodiment 28 of the present invention; Figure 7 This is an appearance diagram of the over-dyed textile obtained in Embodiment 29 of the present invention; Figure 8 This is an appearance diagram of the same-bath dyed textile obtained in Comparative Example 1 of the present invention; Figure 9 This is an appearance diagram of the over-dyed textile obtained in Comparative Example 10 of the present invention; Figure 10 This is an appearance diagram of the over-dyed textile obtained in Comparative Example 14 of the present invention. Detailed Implementation

[0048] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0049] Unless otherwise specified, all other materials and reagents used in the examples are commercially available.

[0050] The blue pigment and melanin were provided by Nanjing Hegu Life Biotechnology Co., Ltd.

[0051] Example 1 A mixed dyeing solution of a biological blue dye and a biological black dye and a dyeing method thereof, wherein the mixed dyeing solution is a co-bath dyeing solution containing indigo, melanin, sodium hydrosulfite, alkali, and water, wherein the total mass concentration of indigo and melanin in the co-bath dyeing solution is 5 g / L, wherein the mass concentration of melanin is 0.5% of the mass concentration of indigo, the mass concentration of sodium hydrosulfite in the co-bath dyeing solution is 1 times the mass concentration of indigo, and the mass concentration of alkali in the co-bath dyeing solution is 0.1 times the total mass concentration of indigo and melanin; wherein the alkali is caustic soda.

[0052] The staining method using the same bath dye solution includes the following steps: S1. Mix and dissolve the blue pigment and melanin in water, then add sodium hydrosulfite and alkali, stir evenly, and reduce the dye at 25°C for 90 min to obtain the same bath dye solution; S2. The textile is immersed and dyed in the same bath dye solution obtained in step S1 at 25°C for 10 min at a bath ratio of 20:1, then oxidized in air for 1 min, and dyed once to obtain the pre-dyed textile. S3. The pre-dyed textile obtained in step S2 is immersed in a soap flake solution at a bath ratio of 50:1 at 25°C for 30 minutes and then dried to obtain a dyed textile in the same bath; the mass concentration of the soap flake solution is 1 g / L.

[0053] Example 2 A mixed dyeing solution of a biological blue dye and a biological black dye and a dyeing method thereof, wherein the mixed dyeing solution is a co-bath dyeing solution containing indigo, melanin, sodium hydrosulfite, alkali, and water, wherein the total mass concentration of indigo and melanin in the co-bath dyeing solution is 10 g / L, wherein the mass concentration of melanin is 20% of the mass concentration of indigo, the mass concentration of sodium hydrosulfite in the co-bath dyeing solution is 1.5 times the mass concentration of indigo, and the mass concentration of alkali in the co-bath dyeing solution is 0.4 times the total mass concentration of indigo and melanin; wherein the alkali is caustic soda.

[0054] The staining method using the same bath dye solution includes the following steps: S1. Mix and dissolve the blue pigment and melanin in water, then add sodium hydrosulfite and alkali, stir evenly, and reduce the dye at 60°C for 30 minutes to obtain the same bath dye solution; S2. The textile is immersed and dyed in the same bath dyeing solution obtained in step S1 at 45°C at a bath ratio of 20:1 for 0.5 min, then oxidized in air for 2 min, and dyed once to obtain the pre-dyed textile. S3. The pre-dyed textile obtained in step S2 is immersed in a soap flake solution at 50°C with a bath ratio of 100:1 and rinsed for 10 min. After drying, the textile is dyed in the same bath. The mass concentration of the soap flake solution is 5 g / L.

[0055] Example 3 A mixed dyeing solution of a biological blue dye and a biological black dye and a dyeing method thereof, wherein the mixed dyeing solution is a co-bath dyeing solution containing indigo, melanin, sodium hydrosulfite, alkali, and water, wherein the total mass concentration of indigo and melanin in the co-bath dyeing solution is 30 g / L, wherein the mass concentration of melanin is 50% of the mass concentration of indigo, the mass concentration of sodium hydrosulfite in the co-bath dyeing solution is twice the mass concentration of indigo, and the mass concentration of alkali in the co-bath dyeing solution is 0.5 times the total mass concentration of indigo and melanin; wherein the alkali is caustic soda.

[0056] The staining method using the same bath dye solution includes the following steps: S1. Mix and dissolve the blue pigment and melanin in water, then add sodium hydrosulfite and alkali, stir evenly, and reduce the dye at 90℃ for 10 min to obtain the same bath dye solution; S2. The textile is immersed and dyed in the same bath dyeing solution obtained in step S1 at 60°C at a bath ratio of 20:1 for 0.1 min, then oxidized in air for 10 min, and dyed once to obtain the pre-dyed textile. S3. The pre-dyed textile obtained in step S2 is immersed in a soap flake solution at 60°C with a bath ratio of 200:1 for 5 minutes and then dried to obtain a dyed textile in the same bath; the mass concentration of the soap flake solution is 10 g / L.

[0057] Examples 4-8 Five examples of dyeing solutions and dyeing methods for mixed biological blue and biological black dyes are provided. The difference between the dyeing solutions in Examples 4-8 and Example 2 is only the mass concentration of melanin in the pigments. Specifically, Example 4: Compared with Example 2, the mass concentration of melanin in the same bath dye solution of Example 2 was adjusted from 20% of the mass concentration of blue to 0.5% of the mass concentration of blue, and the same bath dye solution was obtained; Example 5: Compared with Example 2, the mass concentration of melanin in the same bath dye solution of Example 2 was adjusted from 20% of the mass concentration of blue to 5% of the mass concentration of blue, thus obtaining the same bath dye solution; Example 6: Compared with Example 2, the mass concentration of melanin in the same bath dye solution of Example 2 was adjusted from 20% of the mass concentration of blue to 10% of the mass concentration of blue, thus obtaining the same bath dye solution; Example 7: Compared with Example 2, the mass concentration of melanin in the same bath dye solution of Example 2 was adjusted from 20% of the mass concentration of blue to 30% of the mass concentration of blue, thus obtaining the same bath dye solution; Example 8: Compared with Example 2, the mass concentration of melanin in the same bath dye solution of Example 2 was adjusted from 20% of the mass concentration of blue to 50% of the mass concentration of blue, thus obtaining the same bath dye solution.

[0058] The dyeing methods in Examples 4-8 are the same as in Example 2, and textiles dyed in the same bath are obtained respectively.

[0059] The appearance of the same-bath dyed textiles obtained in Example 4 is shown in the figure below. Figure 1 As shown.

[0060] The appearance of the same-bath dyed textiles obtained in Example 8 is shown in the figure below. Figure 2 As shown.

[0061] Examples 9-11 Three examples of dyeing solutions and dyeing methods for mixed biological blue and biological black dyes are provided. The difference between the dyeing solutions in Examples 9-11 and Example 2 lies only in the content of the alkali and / or its concentration. Specifically, Example 9: Compared with Example 2, the alkali agent caustic soda in the same bath dyeing solution of Example 2 was adjusted to sodium carbonate, and the mass concentration of the alkali agent was adjusted from 0.4 times the total mass concentration of blue and melanin to 2 times the total mass concentration of blue and melanin to obtain the same bath dyeing solution; Example 10: Compared with Example 2, the alkali agent caustic soda in the same bath dyeing solution of Example 2 was adjusted to potassium hydroxide to obtain the same bath dyeing solution; Example 11: Compared with Example 2, the alkali agent caustic soda in the same bath dyeing solution of Example 2 was adjusted to sodium bicarbonate, and the mass concentration of the alkali agent was adjusted from 0.4 times the total mass concentration of blue and melanin to 2 times the total mass concentration of blue and melanin to obtain the same bath dyeing solution.

[0062] The dyeing methods in Examples 9-11 are the same as in Example 2, and textiles dyed in the same bath are obtained respectively.

[0063] Examples 12-15 Four examples of a mixed dyeing solution of biological blue dye and biological black dye and its dyeing method are provided. The dyeing solution used in Examples 12-15 is the same as that in Example 2; the only difference between the dyeing methods in Examples 12-15 and Example 2 is the number of dyeing passes in step S2. Specifically, Example 12: Compared with Example 2, the number of dyeing passes in step S2 of the dyeing method in Example 2 was adjusted from 1 to 2, resulting in textiles dyed in the same bath; Example 13: Compared with Example 2, the number of dyeing passes in step S2 of the dyeing method in Example 2 was adjusted from 1 to 4, resulting in textiles dyed in the same bath; Example 14: Compared with Example 2, the number of dyeing passes in step S2 of the dyeing method in Example 2 was adjusted from 1 to 7, resulting in textiles dyed in the same bath; Example 15: Compared with Example 2, the number of dyeing passes in step S2 of the dyeing method in Example 2 was adjusted from 1 to 10, resulting in textiles dyed in the same bath.

[0064] Example 16 A mixed dyeing solution of a biological blue dye and a biological black dye and its dyeing method are disclosed. The mixed dyeing solution is a combined dyeing solution, which consists of a melanin dyeing solution and an indigo dyeing solution. The melanin dyeing solution includes water, melanin, and an alkali agent. The mass concentration of melanin in the melanin dyeing solution is 0.05 g / L, and the mass concentration of the alkali agent is 0.2 times the mass concentration of melanin. The indigo dyeing solution includes water, indigo, sodium hydrosulfite, and an alkali agent. The mass concentration of indigo in the indigo dyeing solution is 2 g / L, the mass concentration of sodium hydrosulfite is 1 times the mass concentration of indigo, and the mass concentration of the alkali agent is 0.1 times the mass concentration of indigo. All alkali agents are caustic soda.

[0065] The dyeing method using the aforementioned dyeing solution includes the following steps: s1. Dissolve melanin in water, then add caustic soda, and stir at 40°C for 150 min to obtain melanin dye solution; s2. Dissolve indigo in water, then add sodium hydrosulfite and caustic soda, stir evenly, and reduce the solution at 25°C for 90 minutes to obtain indigo dye solution; s3. The textile is immersed and dyed in the melanin dye solution obtained in step s1 at 60℃ with a liquor ratio of 20:1 for 10 minutes, washed with water, dyed and washed once to obtain a melanin-based textile; the obtained melanin-based textile is immersed and dyed in the indigo dye solution obtained in step s2 at 25℃ with a liquor ratio of 20:1 for 10 minutes, then oxidized in air for 10 minutes, and dyed once to obtain a pre-dyed textile. s4. The pre-dyed textile obtained in step s3 is immersed in a soap flake solution at 50°C with a bath ratio of 100:1 and rinsed for 10 min. After drying, the pre-dyed textile is obtained. The mass concentration of the soap flake solution is 5 g / L.

[0066] Example 17 A mixed dyeing solution of a biological blue dye and a biological black dye and its dyeing method are disclosed. The mixed dyeing solution is an over-dyeing solution, which is composed of a melanin dyeing solution and an indigo dyeing solution. The melanin dyeing solution includes water, melanin, and an alkali agent. The mass concentration of melanin in the melanin dyeing solution is 5 g / L, and the mass concentration of the alkali agent is 0.4 times the mass concentration of melanin. The indigo dyeing solution includes water, indigo, sodium hydrosulfite, and an alkali agent. The mass concentration of indigo in the indigo dyeing solution is 10 g / L, the mass concentration of sodium hydrosulfite is 1.5 times the mass concentration of indigo, and the mass concentration of the alkali agent is 0.4 times the mass concentration of indigo. All alkali agents are caustic soda.

[0067] The dyeing method using the aforementioned dyeing solution includes the following steps: s1. Dissolve melanin in water, then add caustic soda, and stir at 80°C for 120 min to obtain melanin dye solution; s2. Dissolve indigo in water, then add sodium hydrosulfite and caustic soda, stir evenly, and reduce the solution at 30°C for 30 minutes to obtain indigo dye solution; s3. The textile is immersed and dyed in the melanin dye solution obtained in step s1 at 80℃ with a liquor ratio of 20:1 for 0.5 min, washed with water, dyed once, washed twice with water to obtain the melanin-based textile; the obtained melanin-based textile is immersed and dyed in the indigo dye solution obtained in step s2 at 30℃ with a liquor ratio of 20:1 for 0.5 min, then oxidized in air for 2 min, dyed once to obtain the pre-dyed textile; s4. The pre-dyed textile obtained in step s3 is immersed in a soap flake solution at 50°C with a bath ratio of 100:1 and rinsed for 10 min. After drying, the pre-dyed textile is obtained. The mass concentration of the soap flake solution is 5 g / L.

[0068] Example 18 A mixed dyeing solution of biological blue dye and biological black dye and its dyeing method are disclosed. The mixed dyeing solution is a combined dyeing solution, which consists of a melanin dyeing solution and an indigo dyeing solution. The melanin dyeing solution includes water, melanin, and an alkali agent. The mass concentration of melanin in the melanin dyeing solution is 15 g / L, and the mass concentration of the alkali agent is 0.5 times the mass concentration of melanin. The indigo dyeing solution includes water, indigo, sodium hydrosulfite, and an alkali agent. The mass concentration of indigo in the indigo dyeing solution is 30 g / L, the mass concentration of sodium hydrosulfite is twice the mass concentration of indigo, and the mass concentration of the alkali agent is 0.5 times the mass concentration of indigo. All alkali agents are caustic soda.

[0069] The dyeing method using the aforementioned dyeing solution includes the following steps: s1. Dissolve melanin in water, then add caustic soda, and stir at 95°C for 60 min to obtain melanin dye solution; s2. Dissolve indigo in water, then add sodium hydrosulfite and caustic soda, stir evenly, and reduce the solution at 60℃ for 10 minutes to obtain indigo dye solution; s3. The textile is immersed and dyed at 95°C in the melanin dye solution obtained in step s1 at a liquor ratio of 20:1 for 2 minutes, washed with water, dyed once, washed three times, to obtain a melanin-based textile; the obtained melanin-based textile is immersed and dyed at 60°C in the indigo dye solution obtained in step s2 at a liquor ratio of 20:1 for 0.1 minutes, then oxidized in air for 1 minute, dyed once, to obtain a pre-dyed textile; s4. The pre-dyed textile obtained in step s3 is immersed in a soap flake solution at 50°C with a bath ratio of 100:1 and rinsed for 10 min. After drying, the pre-dyed textile is obtained. The mass concentration of the soap flake solution is 5 g / L.

[0070] Examples 19-22 Four examples of mixed dyeing solutions and dyeing methods for biological blue and biological black dyes are provided. The difference between the dyeing solutions in Examples 19-22 and those in Example 17 lies only in the mass concentration of melanin in the melanin dyeing solution. Specifically, Example 19: Compared with Example 17, the melanin mass concentration of the melanin dyeing solution in the dyeing solution of Example 17 was adjusted from 5 g / L to 0.05 g / L to obtain the melanin dyeing solution; Example 20: Compared with Example 17, the melanin mass concentration of the melanin dyeing solution in the dyeing solution of Example 17 was adjusted from 5 g / L to 1 g / L to obtain the melanin dyeing solution; Example 21: Compared with Example 17, the melanin mass concentration of the melanin dyeing solution in the dyeing solution of Example 17 was adjusted from 5 g / L to 10 g / L to obtain the melanin dyeing solution; Example 22: Compared with Example 17, the melanin mass concentration of the melanin dyeing solution in the dyeing solution of Example 17 was adjusted from 5 g / L to 15 g / L to obtain the melanin dyeing solution; The dyeing methods in Examples 19-22 are the same as those in Example 17, and the resulting textiles are obtained by over-dyeing.

[0071] The appearance of the over-dyed textile obtained in Example 19 is shown in the figure below. Figure 3 As shown.

[0072] The appearance of the over-dyed textile obtained in Example 21 is shown in the figure below. Figure 4 As shown.

[0073] Examples 23-26 Four examples of mixed dyeing solutions of biological blue dye and biological black dye and their dyeing methods are provided. The dyeing solutions in Examples 23-26 are the same as those in Example 17; the only difference between the dyeing methods of the mixed dyeing solutions in Examples 23-26 and Example 17 is the number of dyeing passes in step S3. Specifically, Example 23: Compared with Example 17, the number of dyeing passes in step S3 of the dyeing method in Example 17, which was 1 pass, was adjusted to 2 passes to obtain over-dyed textiles. Example 24: Compared with Example 17, the number of dyeing passes in step S3 of the dyeing method in Example 17, which was 1 pass, was adjusted to 3 passes to obtain over-dyed textiles. Example 25: Compared with Example 17, the number of dyeing passes in step S3 of the dyeing method in Example 17, which was 1 pass, was adjusted to 4 passes to obtain over-dyed textiles. Example 26: Compared with Example 17, the number of dyeing passes in step S3 of the dyeing method in Example 17, which was 1 pass, was adjusted to 5 passes to obtain over-dyed textiles.

[0074] Examples 27-29 Three examples of mixed dyeing solutions of biological blue dye and biological black dye and their dyeing methods are provided. The dyeing solutions in Examples 27-29 are the same as those in Example 17; the only difference between the dyeing methods of the mixed dyeing solutions in Examples 27-29 and those in Example 17 is the number of dyeing passes in step S3. Specifically, Example 27: Compared with Example 17, the number of dyeing passes in step S3 of the dyeing method in Example 17, which was 1 pass, was adjusted to 2 passes to obtain over-dyed textiles. Example 28: Compared with Example 17, the number of dyeing passes in step S3 of the dyeing method in Example 17, which was 1 pass, was adjusted to 4 passes to obtain over-dyed textiles. Example 29: Compared with Example 17, the number of dyeing passes in step S3 of the dyeing method in Example 17, which was 1 pass, was adjusted to 7 passes to obtain over-dyed textiles.

[0075] The appearance of the over-dyed textile obtained in Example 27 is shown in the figure below. Figure 5 As shown.

[0076] The appearance of the over-dyed textile obtained in Example 28 is shown in the figure below. Figure 6 As shown.

[0077] The appearance of the over-dyed textile obtained in Example 29 is shown in the figure below. Figure 7 As shown.

[0078] Comparative Example 1 A comparative example of a mixed dyeing solution of biological blue dye and biological black dye and its dyeing method. The only difference between the dyeing solution of this comparative example and Example 2 is that the pigment does not contain melanin. The mass concentration of blue dye in the dyeing solution of this comparative example is 10 g / L, the mass concentration of sodium hydrosulfite in the dyeing solution is 1.5 times the mass concentration of blue dye, and the mass concentration of alkali in the dyeing solution is 0.4 times the mass concentration of blue dye; the alkali is caustic soda.

[0079] The dyeing method using the same dye bath as in Example 2 yields textiles dyed in the same bath. The appearance of the textiles dyed in the same bath as in Comparative Example 1 is shown in the image below. Figure 8 As shown.

[0080] Comparative Examples 2-3 Two comparative examples of dyeing solutions and dyeing methods for mixed biological blue and biological black dyes were presented. The only difference between the dyeing solutions of Comparative Examples 2 and 3 and Example 2 was the mass concentration of melanin in the pigments. Specifically, Comparative Example 2: Compared with Example 2, the mass concentration of melanin in the same bath dye solution of Example 2 was adjusted from 20% of the mass concentration of blue to 0.1% of the mass concentration of blue, and the same bath dye solution was obtained. Comparative Example 3: Compared with Example 2, the mass concentration of melanin in the same bath dye solution of Example 2 was adjusted from 20% of the mass concentration of blue to 70% of the mass concentration of blue, thus obtaining the same bath dye solution.

[0081] The dyeing methods of Comparative Examples 2 and 3 are the same as those of Example 2, and textiles dyed in the same bath are obtained respectively.

[0082] Comparative Example 4-5 Two comparative examples of dyeing solutions and dyeing methods for mixed biological blue and biological black dyes are presented. The only difference between the dyeing solutions of Comparative Examples 4-5 and Example 2 is the mass concentration of sodium hydrosulfite. Specifically, Comparative Example 4: Compared with Example 2, the mass concentration of sodium hydrosulfite in the same bath dyeing solution of Example 2 was adjusted from 1.5 times the mass concentration of indigo to 0.5 times the mass concentration of indigo, thus obtaining the same bath dyeing solution; Comparative Example 5: Compared with Example 2, the mass concentration of sodium hydrosulfite in the same bath dyeing solution of Example 2 was adjusted from 1.5 times the mass concentration of indigo to 3 times the mass concentration of indigo, thus obtaining the same bath dyeing solution.

[0083] The dyeing methods of Comparative Examples 4-5 were the same as those in Example 2, and textiles dyed in the same bath were obtained respectively.

[0084] Comparative Examples 6-7 Two comparative examples of dyeing solutions and dyeing methods for mixed biological blue and biological black dyes are presented. The only difference between the dyeing solutions of Comparative Examples 6-7 and Example 2 is the mass concentration of the alkali agent; specifically, Comparative Example 6: Compared with Example 2, the mass concentration of the alkali agent in the same bath dyeing solution of Example 2 was adjusted from 0.4 times the mass concentration of the pigment to 0.05 times the mass concentration of the pigment, thus obtaining the same bath dyeing solution; Comparative Example 7: Compared with Example 2, the mass concentration of alkali in the same bath dyeing solution of Example 2 was adjusted from 0.4 times the mass concentration of pigment to 0.8 times the mass concentration of pigment to obtain the same bath dyeing solution.

[0085] The dyeing methods of Comparative Examples 6-7 were the same as those in Example 2, and textiles dyed in the same bath were obtained respectively.

[0086] Comparative Example 8 A comparative example of a mixed dyeing solution of biological blue dye and biological black dye and its dyeing method. The dyeing solution in this comparative example is the same as that in Example 2. The only difference between the dyeing method in this comparative example and that in Example 2 is the mass concentration of the soap flake solution in step S3. In this comparative example, the mass concentration of the soap flake solution in step S3 of the dyeing method in Example 2 is adjusted from 5 g / L to 0.5 g / L to obtain textiles dyed in the same bath.

[0087] Comparative Example 9 A comparative example of a mixed dyeing solution of biological blue dye and biological black dye and its dyeing method. The dyeing solution in this comparative example is the same as that in Example 2. The only difference between the dyeing method in this comparative example and that in Example 2 is the rinsing time of soap flake solution in step S3. In this comparative example, the rinsing time of soap flake solution in step S3 of the dyeing method in Example 2 is adjusted from 10 min to 2 min to obtain textiles dyed in the same bath.

[0088] Comparative Example 10 A comparative example of a mixed dyeing solution of biological blue dye and biological black dye and its dyeing method. The dyeing solution used in this comparative example is the same as that in Example 17. The only difference between the dyeing method of this comparative example and that of Example 17 is the order in which the melanin dye solution and the blue dye solution are applied in step S3. The specific steps of the dyeing method of the mixed dyeing solution in this comparative example are as follows: s1, Same as step s1 in Example 17; s2, same as step s2 in Example 17; s3. The textile is immersed and dyed in the indigo dyeing solution obtained in step s2 at 30℃ with a liquor ratio of 20:1 for 0.5 min, then oxidized in air for 2 min, and dyed once to obtain the indigo base textile; the obtained indigo base textile is immersed and dyed in the melanin dyeing solution obtained in step s1 at 80℃ with a liquor ratio of 20:1 for 0.5 min, washed with water, dyed once, and washed twice to obtain the pre-dyed textile. s4. Same as step s4 in Example 17, to obtain the over-dyed textile.

[0089] The appearance of the over-dyed textile obtained in Comparative Example 10 is shown in the figure below. Figure 9 As shown.

[0090] Comparative Examples 11-12 Two comparative examples of mixed dyeing solutions and dyeing methods for biological blue and biological black dyes are presented. The difference between the dyeing solutions of Comparative Examples 11-12 and Example 17 lies only in the mass concentration of melanin in the melanin dyeing solution. Specifically, Comparative Example 11: Compared with Example 17, the melanin mass concentration of the melanin dyeing solution in the dyeing solution of Example 17 was adjusted from 5 g / L to 0.01 g / L to obtain the melanin dyeing solution; Comparative Example 12: Compared with Example 17, the melanin mass concentration of the melanin dyeing solution in the dyeing solution of Example 17 was adjusted from 5 g / L to 20 g / L to obtain the melanin dyeing solution. The dyeing methods of Comparative Examples 11-12 are the same as those of Example 17, and the resulting textiles are obtained by over-dyeing.

[0091] Comparative Examples 13-14 Two comparative examples of mixed dyeing solutions and dyeing methods for biological blue and biological black dyes are presented. The difference between the dyeing solutions of Comparative Examples 13-14 and Example 17 lies only in the mass concentration of blue dye in the blue dyeing solution. Specifically, Comparative Example 13: Compared with Example 17, the concentration of blue dye in the blue dye solution in the dyeing solution of Example 17 was adjusted from 10 g / L to 1 g / L to obtain the blue dye solution; Comparative Example 14: Compared with Example 17, the concentration of blue dye in the blue dye solution in the dyeing solution of Example 17 was adjusted from 10 g / L to 40 g / L to obtain the blue dye solution; The dyeing methods of Comparative Examples 13-14 are the same as those of Example 17, and the resulting textiles are obtained by over-dyeing.

[0092] The appearance of the over-dyed textile obtained in Comparative Example 14 is shown in the figure below. Figure 10 As shown.

[0093] Comparative Examples 15-16 Two comparative examples of mixed dyeing solutions and dyeing methods for biological blue and biological black dyes are presented. The difference between the dyeing solutions of Comparative Examples 15-16 and Example 17 lies only in the mass concentration of the alkali agent in the melanin dyeing solution. Specifically, Comparative Example 15: Compared with Example 17, the mass concentration of alkali in the melanin dyeing solution of Example 17 was adjusted from 0.4 times the mass concentration of melanin to 0.1 times the mass concentration of melanin to obtain the melanin dyeing solution. Comparative Example 16: Compared with Example 17, the mass concentration of alkali in the melanin dyeing solution of Example 17 was adjusted from 0.4 times the mass concentration of melanin to 0.8 times the mass concentration of melanin to obtain the melanin dyeing solution. The dyeing methods of Comparative Examples 15-16 are the same as those of Example 17, and the resulting textiles are obtained by over-dyeing.

[0094] Comparative Examples 17-18 Two comparative examples of mixed dyeing solutions and dyeing methods for biological blue and biological black dyes are presented. The difference between the dyeing solutions of Comparative Examples 17-18 and Example 17 lies only in the mass concentration of sodium hydrosulfite in the blue dyeing solution. Specifically, Comparative Example 17: Compared with Example 17, the mass concentration of sodium hydrosulfite in the indigo dye solution of Example 17 was adjusted from 1.5 times the mass concentration of indigo to 0.5 times the mass concentration of indigo, thus obtaining the indigo dye solution; Comparative Example 18: Compared with Example 17, the mass concentration of sodium hydrosulfite in the indigo dye solution of Example 17 was adjusted from 1.5 times the mass concentration of indigo to 3 times the mass concentration of indigo, thus obtaining the indigo dye solution. The dyeing methods of Comparative Examples 17-18 are the same as those of Example 17, and the resulting textiles are obtained by over-dyeing.

[0095] Comparative Examples 19-20 Two comparative examples of mixed dyeing solutions and dyeing methods for biological blue and biological black dyes are presented. The difference between the dyeing solutions of Comparative Examples 19-20 and Example 17 lies only in the mass concentration of the alkali agent in the blue dyeing solution. Specifically, Comparative Example 19: Compared with Example 17, the mass concentration of alkali in the indigo dyeing solution of Example 17 was adjusted from 0.4 times the mass concentration of indigo to 0.05 times the mass concentration of indigo, thus obtaining the indigo dyeing solution; Comparative Example 20: Compared with Example 17, the mass concentration of alkali in the indigo dyeing solution of Example 17 was adjusted from 0.4 times the mass concentration of indigo to 0.8 times the mass concentration of indigo, thus obtaining the indigo dyeing solution; The dyeing methods of Comparative Examples 19-20 are the same as those of Example 17, and the resulting textiles are obtained by over-dyeing.

[0096] Comparative Example 21 A comparative example of a mixed dyeing solution of biological blue dye and biological black dye and its dyeing method. The dyeing solution of this comparative example is the same as that of Example 17. The only difference between the dyeing method of this comparative example and that of Example 17 is the number of water washing passes after dyeing with the black dye solution in step s3. In this comparative example, the number of water washing passes after dyeing with the black dye solution in step s3 of Example 17 is adjusted from 2 passes to 0 passes (i.e. no water washing), and the mixed dyed textile is obtained.

[0097] Test case The color depth (K / S), hue, and color fastness of the dyed textiles prepared in Examples 1-29 and Comparative Examples 1-21 were measured.

[0098] Color depth (K / S): Measured using a colorimeter. The colorimeter measures the reflectance R of the dyed textile, and then R is used according to the Kubelka-Munk formula: K / S = (1-R). 2 / 2R is used to calculate color depth (K / S), where R is reflectance. Average color depth (K / S) is calculated from average reflectance.

[0099] Color: The lightness value of dyed textiles is measured using a colorimeter. ), red-green value ( ) and yellow-blue value ( ). The higher the number, the brighter it is; The value indicates positive red light bias, and the value indicates negative green light bias; The value indicates positive yellow light, and the value indicates negative blue light. , , Used to describe the color and light changes on the surface of dyed textiles.

[0100] Color fastness to dry and wet rubbing: Tested in accordance with GB / T 3920-2008 "Textiles - Tests for color fastness to rubbing".

[0101] Color fastness to light: Tested in accordance with GB / T 8427-2019 "Textiles - Tests for color fastness to artificial light: Xenon arc".

[0102] At least three textile fabric samples should be taken from each group for testing, and the average results should be statistically analyzed.

[0103] The test results of color depth, hue, and color fastness of the same-bath dyed textiles of Examples 1-15 and Comparative Examples 1-9 are shown in Table 1. Table 1 According to the results in Table 1, Examples 1-3 and Comparative Example 1 show that after dyeing with a mixture of melanin and blue pigment, the a value significantly decreased, the red light intensity weakened, and all color fastness grades significantly improved. The weak interaction between blue pigment and melanin synergistically enhanced the binding between the pigment and the fiber.

[0104] Examples 4-8 show that as the proportion of melanin blending increases, the red light in the melanin gradually appears, the a value gradually increases, while the blue light gradually weakens, so that the textiles exhibit gradient color depth and color light changes, thus broadening the color range and application space of blue pigment.

[0105] Examples 2, 9-11 show that the use of different alkalis has different effects on the color of pigments. In terms of color depth, potassium hydroxide and caustic soda (sodium hydroxide) have better effects and similar effects. Considering all factors, sodium hydroxide is more recommended as an alkali for chemical dyeing.

[0106] Examples 12-15 show that as the number of dyeing channels increases, the color superposition effect is obvious. While the color depth increases, red light and blue light are superimposed to a certain extent, presenting different color styles.

[0107] Examples 2 and Comparative Examples 2 and 3 show that when the blending ratio of melanin is less than 0.5% of the blue light concentration, the effect of melanin is no longer significant. The color difference from the comparative examples is not substantial, and the improvement in colorfastness is no longer apparent. When the blending amount of melanin exceeds 50% of the blue light concentration, the covering power of the melanin is too strong, resulting in insignificant blue light and excessively dark color, with the L value significantly decreasing to below 9, presenting a darker color.

[0108] Examples 2 and Comparative Examples 4 and 5 show that when the concentration of sodium hydrosulfite exceeds the optimal range, the reduction effect of blue is poor, resulting in a decrease in color depth. Both excessively low (low reduction) and excessively high (over-reduction) sodium hydrosulfite concentrations will affect the presentation of blue.

[0109] Examples 2 and Comparative Examples 6 and 7 show that when the concentration of the alkali exceeds the optimal range, the color depth decreases and the color is significantly affected. Too low an alkali concentration (too weak) results in insufficient blue reduction and poor melanin dispersion and dissolution, while too high an alkali concentration (too strong) affects blue appearance and easily leads to over-reduction, resulting in significant color changes.

[0110] Examples 2 and Comparative Examples 8 and 9 show that insufficient soaping leads to more loose dye and a significant decrease in the fastness of textiles.

[0111] The test results of color depth, hue, and color fastness of the over-dyed textiles of Examples 16-29 and Comparative Examples 10-21 are shown in Table 2. Table 2 According to the results in Table 2, Examples 16-18 show that the color range of blue can be broadened by using a melanin dye solution as a base dye and then over-dyeing with indigo dye solution. In Example 17, compared to Comparative Example 10, the red light was significantly reduced, and the color fastness was improved. This indicates that over-dyeing with indigo dye solution after using a melanin dye solution as a base dye not only broadens the color range of blue but also improves its fastness. After the melanin base dye, the weak interaction between the indigo dye and the melanin during over-dyeing allows the indigo dye to adhere more firmly to the fiber surface, improving the various color fastness properties of the textile.

[0112] Examples 19-22 and 23-26 show that increasing the melanin concentration in the melanin dyeing solution for base dyeing, increasing the number of base dyeing passes, or increasing the proportion of melanin mixed in over-dyeing can make the fabric surface of the textile exhibit a gradient color range, and the color depth also shows a gradient increase.

[0113] Examples 27-29 show that increasing the number of dyeing passes in the preparation of the indigo dye solution for over-dyeing, and increasing the proportion of indigo in the over-dyeing process, can increase the color depth gradient of the textile fabric and gradually deepen the blue light, presenting a deeper blue color, thus giving the over-dyeing a layered blue effect.

[0114] Examples 17 and 10 show that if a blue dye solution is used as a base before applying a melanin dye solution, the color depth will decrease and the blue light will be significantly weakened. Because the oxidized state of blue dye is greatly affected by pH, and the melanin dyeing environment is in a high pH alkaline condition, the blue dye color is affected. Therefore, the method of using a melanin dye solution as a base before applying the blue dye solution is superior.

[0115] Examples 17 and Comparative Examples 11-14 show that when the concentration of melanin dye solution is too low in the base dyeing process or the concentration of blue dye solution is too high in the over-dyeing process, the effect of melanin is no longer significant, and the improvement in fastness is no longer apparent. When the concentration of melanin dye solution is too high in the base dyeing process or the concentration of blue dye solution is too low in the over-dyeing process, the covering power of melanin is too strong, resulting in insignificant blue light.

[0116] Examples 17 and Comparative Examples 15 and 16 show that insufficient alkali in the melanin dyeing solution or excessive alkali in the base dyeing process will result in poor melanin base dyeing effect. This is because insufficient alkali leads to poor dissolution and dispersion of melanin, which is not conducive to melanin dyeing of fibers. If the alkali is too strong, the washing after base dyeing cannot effectively remove the alkali from the fibers, resulting in pigment loss during indigo overdyeing and thus affecting the color.

[0117] Examples 17 and Comparative Examples 17 and 18 show that when the concentration of sodium hydrosulfite exceeds the optimal range, the reduction effect of blue is poor, resulting in a decrease in color depth. Both too low a concentration of sodium hydrosulfite (low reduction) and too high a concentration (over-reduction) will affect the presentation of blue.

[0118] Examples 17 and Comparative Examples 19 and 20 show that when the optimal concentration of alkali is exceeded, the color depth decreases and the color light is significantly affected. Too low an alkali concentration (too weak alkali) will result in insufficient blue reduction, while too high an alkali concentration (too strong alkali) will affect the blue color and easily lead to an over-reduction state, resulting in a large change in color.

[0119] Examples 17 and 21 show that not washing after priming with melanin dye leads to a decrease in color depth and a reduction in blue light. This is because melanin dye is highly alkaline, and blue pigment is sensitive to high pH environments, resulting in a lighter color and a significant decrease in the colorfastness of the textiles.

[0120] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A dyeing solution containing a mixture of biological blue dye and biological black dye, characterized in that, The mass concentration of indigo in the mixed dyeing solution is 2-30 g / L, the mass concentration of melanin is 0.02-15 g / L, the mass concentration of sodium hydrosulfite is 1-2 times the mass concentration of indigo, and the mass concentration of alkali is 0.1-2 times the total mass concentration of indigo and melanin.

2. The mixed dyeing solution as described in claim 1, characterized in that, The mixed dyeing solution includes a co-bath dyeing solution or a combined dyeing solution containing indigo and melanin. The same bath dyeing solution is a mixed dyeing solution containing indigo, melanin, sodium hydrosulfite and alkali agent; The set of dyeing solutions is a combination of indigo dyeing solution and melanin dyeing solution. The melanin dyeing solution contains melanin and a portion of alkali agent, and the indigo dyeing solution contains indigo, sodium hydrosulfite, and the remaining alkali agent. The sum of the portion of alkali agent and the remaining alkali agent is the total amount of alkali agent.

3. The mixed dyeing solution as described in claim 2, characterized in that, The total mass concentration of blue and melanin in the same bath dye solution is 5~30 g / L, of which the mass concentration of melanin is 0.5%~50% of the mass concentration of blue.

4. The mixed dyeing solution as described in claim 2, characterized in that, The melanin dyeing solution of the set-dyeing solution has a melanin concentration of 0.05~15 g / L, and the mass concentration of the alkali agent is 0.2~0.5 times the melanin concentration; the indigo dyeing solution of the set-dyeing solution has an indigo concentration of 2~30 g / L, and the mass concentration of the remaining alkali agent is 0.1~0.5 times the indigo concentration.

5. The mixed dyeing solution as described in claim 1 or 2, characterized in that, The alkaline agent includes sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium bicarbonate.

6. The dyeing method using the mixed dye solution according to any one of claims 1 to 5, characterized in that, This includes the same-bath staining method, which uses the same dye bath for staining, or the over-dyeing method, which uses an over-dyeing solution for staining.

7. The staining method as described in claim 6, characterized in that, The same-bath staining method includes the following steps: S1. Mix and dissolve the blue pigment and melanin in water, then add sodium hydrosulfite and alkali, mix well, reduce the material, and obtain the same bath dye solution; S2. The textile is immersed in the dye bath obtained in step S1 for dyeing, and then oxidized in air to obtain pre-dyed textile. S3. Wash the pre-dyed textile obtained in step S2 with soap for 5-30 minutes, and air dry to obtain the same-bath dyed textile. The soap washing solution used is a soap flake solution with a mass concentration of 1-10 g / L.

8. The staining method as described in claim 7, characterized in that, In step S1, the temperature of the reducing agent is 25~90℃ and the time is 10~90 min.

9. The staining method as described in claim 7, characterized in that, In step S2, the immersion dyeing temperature is 25~90℃ and the time is 0.1~10 min; the air oxidation time is 1~10 min; and the number of dyeing passes in the immersion dyeing is 1~10.

10. The staining method as described in claim 7, characterized in that, In step S3, the soaping ratio is 50:1 to 200:1; the soaping temperature is 25 to 60°C.

11. The staining method as described in claim 6, characterized in that, The over-dyeing method includes the following steps: s1. Dissolve melanin in water, then add some alkali, stir the mixture to obtain melanin dye solution; s2. Dissolve indigo in water, then add sodium hydrosulfite and the remaining alkali, mix well, reduce the material, and obtain indigo dye solution; s3. The textile is immersed in the black dye solution obtained in step s1 for dyeing, and then washed with water to obtain a black dye base textile; the obtained black dye base textile is immersed in the blue dye solution obtained in step s2 for over-dyeing, and then oxidized in air to obtain an over-dyed pre-dyed textile. s4. Wash the pre-dyed textile obtained in step s3 with soap and dry it to obtain the dyed textile.

12. The staining method as described in claim 11, characterized in that, In step s1, the temperature of the stirred material is 40~95℃ and the time is 60~150 min.

13. The staining method as described in claim 11, characterized in that, In step s2, the temperature of the reducing agent is 25~60℃ and the time is 10~90 min.

14. The staining method as described in claim 11, characterized in that, In step s3, the immersion dyeing temperature is 60~95℃ and the time is 0.5~10 min; the number of immersion dyeing passes is 1~5; the number of water washing passes is 1~3; the immersion over-dyeing temperature is 25~60℃ and the time is 0.1~10 min; the number of immersion over-dyeing passes is 1~7.

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