Acid black dye with green light and preparation method thereof
By mixing dye compounds in specific proportions and optimizing the preparation process, the problem of acid black dyes failing to exhibit green light has been solved, resulting in the preparation of acid black dyes with ideal color fastness and unique color that exhibit green light, thus meeting market demand.
Patent Information
- Application Number
- CN202511391059.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-26
- Publication Date
- 2026-01-16
AI Technical Summary
Existing acid black dyes are unable to produce the desired green effect, resulting in products with colors that are not unique or vibrant enough to meet market demand for products with special color effects.
A green-tinted acid black dye was prepared by mixing dye compounds A, B, C, and D in a specific ratio, adjusting the black tone of dye compounds A and B, and adding the green light components of dye compounds C and D. The dye preparation process was optimized by uniformly mixing and reacting the dye with dispersant MF and emulsifier L-3.
The preparation of an acid black dye with a greenish tint was achieved, possessing ideal color fastness and unique color effects, meeting market demands.
Smart Images
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Abstract
Description
Technical Field
[0001] This application relates to the field of dye technology, and in particular to an acid black dye with a greenish sheen and a method for preparing the same. Background Technology
[0002] In the dye industry, with the continuous development of textiles, leather, and other related industries, the demand for various functional dyes is increasing. Acid black dye, as a commonly used type of dye, is widely used in the dyeing process of various fiber materials. It can impart a black hue to fabrics and other materials, meeting market demands for products in different colors and playing a vital role in enhancing product aesthetics and added value. Its application has resulted in a rich variety of colors for various textiles and leather products, driving the continuous development of related industries.
[0003] To obtain suitable acid black dyes, existing technologies typically employ dye compounds with a single structure for dyeing. One common approach is to use specific nitrogen-containing heterocyclic dye compounds, which are then directly applied to the dyeing process through simple mixing and formulation. Another method involves using aromatic dye compounds with specific substituents, synthesizing dyes through a series of chemical reactions, and then using these dyes to dye the target materials. In addition, some traditional acid dye formulations are also used; these formulations, through long-term practice and improvement, have developed relatively fixed compositions and preparation processes.
[0004] However, existing acid black dyes often fail to produce the desired greenish effect. Due to the limitations of their chemical structure and optical properties, single-structure dye compounds cannot be precisely formulated to produce a black color with a greenish tint during the dyeing process. This results in products with colors that are not unique or vibrant enough, failing to meet market demand for products with special color effects. Summary of the Invention
[0005] In order to obtain an acid black dye with a greenish luster, this application provides an acid black dye with a greenish luster and a method for preparing the same.
[0006] Firstly, this application provides an acid black dye with a greenish sheen, employing the following technical solution: A greenish-black acid dye comprises dye compound A with the structure shown in structural formula I, dye compound B with the structure shown in structural formula II, dye compound C with the structure shown in structural formula III, and dye compound D with the structure shown in structural formula IV. The molar ratio of dye compound A and dye compound B to dye compound C and dye compound D is (75-85):(25-15).
[0007] By adopting the above technical solution, by adjusting the mixing weight ratio between dye compound A and dye compound B and dye compound C and dye compound D, dye compound A and dye compound B lay the foundation for the black tone, and the addition of dye compound C and dye compound D introduces the green light component, reducing the problem of reddish color deviation of single dyes, thus obtaining an acid black dye with green light, and the obtained acid black dye with green light has ideal color fastness.
[0008] Secondly, this application provides a method for preparing a greenish acid black dye, which adopts the following technical solution: A method for preparing a greenish acid black dye includes the following steps: S1: Mix 2-naphthol, 30% liquid alkali and nonionic surfactant, heat to 60-65℃ and stir until the solution is clear, then add the resulting solution to a 6-nitrosol solution with pH 2-4, maintain the reaction temperature at 40-45℃ and the pH between 9-10.5 for 2 hours to obtain pre-chromosome I; S2: Mix anthranilic acid with hydrochloric acid, then add 30% sodium nitrite until sodium nitrite is slightly in excess, react at 5-8℃ for 1h, and remove excess sodium nitrite with aminosulfonic acid to obtain a diazonium solution; add 30% liquid alkali to a 1-(4-sulfonylphenyl)-3-methyl-5-pyrazolone solution, adjust the pH to 8-9, and maintain the temperature at 20-25℃ until the solution is clear, then lower the temperature to 3℃ and add it to the diazonium solution. React at pH 7-8 and temperature 5-8℃ for 3-4h to obtain pre-chromosome II; S3: After heating the pre-chromosome I to 60℃, add salicylic acid and chromium trioxide, and heat to 100-105℃. React at pH 4-6 for 3-4 hours to obtain reaction solution I. S4: Add the pre-chromophore II to reaction solution I, maintain the temperature at 100-105℃ and pH 5-6.5 to obtain a greenish acid black dye.
[0009] Preferably, S1 includes the following steps: mixing 6-nitro, oxygen, and water and stirring for 30 minutes, then adding a dispersant and soda ash, and adjusting the pH to 2-4 with sodium bicarbonate to obtain a 6-nitro solution; heating 2-naphthol, water, nonionic surfactant, and 30% liquid alkali to 60-65°C and stirring until dissolved and clear to obtain mixed solution I; adding mixed solution I to the 6-nitro solution for coupling, reacting at a temperature of 40-45°C and maintaining the pH in the range of 9-10.5 for 2 hours, and determining the endpoint by detecting the absence of color at the permeation zone of the coupling solution with m-phenylenediamine solution to obtain pre-chromosome I.
[0010] Preferably, the dispersant is dispersant MF.
[0011] By adopting the above technical solution, the use of dispersant MF as a dispersant in the preparation process of green-light acid black dye can make the mixing of 6-nitro, oxygen and water more uniform, which is conducive to the smooth progress of subsequent coupling reaction, and thus helps to prepare green-light acid black dye.
[0012] Preferably, the nonionic surfactant is emulsifier L-3.
[0013] By adopting the above technical solution, in the preparation process of green-light acid black dye, the use of emulsifier L-3 as a nonionic surfactant helps to make the solution easier to stir until clear when 2-naphthol and 30% liquid alkali are mixed and heated to 60-65℃ in step S1. This facilitates the subsequent reaction with 6-nitro solution, thereby better participating in the preparation of green-light acid black dye and helping to obtain green-light acid black dye that meets the requirements.
[0014] Preferably, S2 includes the following steps: adding o-aminobenzoic acid to water, then adding 30% hydrochloric acid and stirring for 30 minutes, then adding ice to cool to 0°C, adding 30% sodium nitrite solution and completing the addition within 40 minutes, the solution turns blue when tested with Congo red test paper and potassium iodide starch test paper, reacting at 5-8°C for 1 hour, then using aminosulfonic acid to eliminate excess sodium nitrite, obtaining a diazonium solution; mixing 1-(4-sulfonylphenyl)-3-methyl-5-pyrazolone with water, adjusting the pH to 8-9 with 30% liquid alkali, and dissolving until clear at 20-25°C, obtaining mixed solution II; cooling mixed solution II to 3°C with ice, adding the diazonium solution to it with stirring over 40 minutes, adjusting the pH to 7-8 with 30% liquid alkali, reacting at 5-8°C for 3-4 hours, with the endpoint being the absence of a color reaction when tested with m-phenylenediamine solution.
[0015] Preferably, S3 includes the following steps: heating the pre-chromosome I to 60°C, adding salicylic acid and chromium trioxide, heating to 100-105°C, adjusting the pH to 4-6 with 30% liquid alkali, and reacting for 3-4 hours. The reaction is considered complete when no red substance is detected by TLC, thus obtaining reaction solution I.
[0016] Preferably, S4 includes the following steps: adding the pre-chromophore II to the reaction solution I, maintaining the temperature at 100-105°C, adjusting the pH to 5-6.5 with 30% liquid alkali, and determining the endpoint by TLC detection of no yellow substance, thus obtaining an acid black dye with green light.
[0017] In summary, this application includes at least one of the following beneficial technical effects: 1. This application describes a greenish-black acid dye composed of dye compound A, dye compound B, dye compound C, and dye compound D. In dye compounds A and B, the central chromium ion forms a planar macrocyclic structure with symmetrical ligands; these complexes typically exhibit a reddish-black hue. In dye compounds C and D, the central chromium ion connects to ligands with greater steric hindrance, readily producing a greenish-black complex. By adjusting the ratio of dye compounds A and B to dye compounds C and D, the effect of a "greenish-black acid dye" is achieved. 2. In this application, the molar ratio of dye compound A and dye compound B to dye compound C and dye compound D is (75-85):(25-15). When the proportion of dye compound A and dye compound B is too high, the black depth provided by dye compound A and dye compound B is too high, which causes the green light to be blocked and cannot effectively improve the reddish light problem of original acid black 172#. Detailed Implementation
[0018] The raw materials used in this application include the following: 6-Nitro: a commercially available product with CAS number 5366-84-7; Oxygen gas: Commercially available products with CAS number 20680-48-2; 2-Naphthol: A commercially available product with CAS number 135-19-3; anthranilic acid: a commercially available product with CAS number 118-92-3; 1-(4-sulfonylphenyl)-3-methyl-5-pyrazolone: a commercially available product with CAS number 89-36-1; Dispersant MF: A commercially available product with CAS number 9084-06-4; Emulsifier L-3: The active ingredient used is fatty alcohol polyoxyethylene ether L-3 with 99% active ingredient from Jingzhou Yinjie Chemical Co., Ltd.
[0019] The present application will be further described in detail below with reference to embodiments and comparative examples.
[0020] Example 1 A greenish-black acid dye comprises dye compound A with the structure shown in structural formula I, dye compound B with the structure shown in structural formula II, dye compound C with the structure shown in structural formula III, and dye compound D with the structure shown in structural formula IV. The molar ratio of dye compound A and dye compound B to dye compound C and dye compound D is 85:15.
[0021] A method for preparing a greenish acid black dye includes the following steps: Synthesis of S1 and pre-chromophore I: S1.1. Add 800 kg of water, 340 kg of 6-nitrate, and 51 kg of oxygen to a 5000 L reactor and stir and disperse for 30 min. Then add dispersant MF at a weight ratio of 0.025 to 6-nitrate, soda ash at a weight ratio of 0.075 to 6-nitrate, and sodium bicarbonate at a weight ratio of 0.08 to 6-nitrate. Adjust the pH to 2-4 to obtain a 6-nitrate solution. S1.2. Add 600 kg of water, 2-naphthol at a 6-nitro weight ratio of 0.6, emulsifier L-3 at a 6-nitro weight ratio of 0.005, and 30% liquid alkali at a 6-nitro weight ratio of 0.49 to a 2000 L reactor. Raise the solution temperature to 60-65 °C and stir until the solution is dissolved and clear to obtain mixed solution I. S1.3. Add mixed solution I to 6-nitro solution for coupling reaction, maintain the reaction temperature at 40-45℃ and the pH between 9-10.5 for 2 hours. The endpoint is determined by the absence of color development at the percolation zone of the coupling solution using resorcinol solution, yielding pre-chromophore I; S2. Synthesis of pre-chromophore II: S2.1 Add 500 kg of water to a 2000 L reactor, add o-aminobenzoic acid at a weight ratio of 0.096 to 6-nitro and 30% hydrochloric acid at a weight ratio of 0.192 to 6-nitro. Stir for 30 min, then add an appropriate amount of ice to lower the solution temperature to 0 °C. Add 30% sodium nitrite within 40 min. The solution turns blue when tested with Congo red test paper. After reacting for 1 h, the solution turns blue when tested with potassium iodide starch test paper. Then, use aminosulfonic acid to eliminate excess sodium nitrite to obtain diazonium solution. S2.2. Add 800 kg of water, 1-(4-sulfonylphenyl)-3-methyl-5-pyrazolone (6-nitrate weight ratio 0.181), and 30% liquid alkali (6-nitrate weight ratio 0.12) to a 2000 L reactor to adjust the pH to 8-9. Dissolve the solution at 20-25 °C until clear to obtain mixed solution II. S2.3 Add ice to the diazo solution to lower the solution temperature to 3℃. Add mixed solution II to the cooled diazo solution within 40 min while stirring. Add 340 kg of 30% liquid alkali to adjust the pH of the solution to 7-8. React at 5-8℃ for 3-4 h. The endpoint is when no color development is detected by m-phenylenediamine solution to obtain prechromogen II. S3. Complexation reaction of pre-chromium base I with chromium ions: After heating pre-chromium base I to 60℃, add salicylic acid at a weight ratio of 0.3 times that of 6-nitro and chromium trioxide at a weight ratio of 0.706 times that of 6-nitro. Then raise the solution temperature to 100-105℃ and adjust the pH to 4-6 with 30% liquid alkali. React for 3-4 hours. The endpoint is determined by the absence of red substances detected by TLC, yielding reaction solution I. S4. Complexation reaction between pre-chromium base I, pre-chromium base II and chromium ions: Add pre-chromium base II to reaction solution I, maintain the temperature in the range of 100-105℃, and adjust the pH to 5-6.5 with 30% liquid alkali. The endpoint is determined by the absence of yellow substances detected by TLC, yielding a greenish acidic black dye.
[0022] Example 2 In Example 2, the molar ratio of dye compound A, dye compound B, dye compound C, and dye compound D is 80:20.
[0023] A method for preparing a greenish acid black dye includes the following steps: Synthesis of S1 and pre-chromophore I: S1.1. Add 800 kg of water, 340 kg of 6-nitrate, and 51 kg of oxygen to a 5000 L reactor and stir and disperse for 30 min. Then add dispersant MF at a weight ratio of 0.025 to 6-nitrate, soda ash at a weight ratio of 0.075 to 6-nitrate, and sodium bicarbonate at a weight ratio of 0.08 to 6-nitrate. Adjust the pH to 2-4 to obtain a 6-nitrate solution. S1.2. Add 600 kg of water, 2-naphthol at a 6-nitro weight ratio of 0.6, emulsifier L-3 at a 6-nitro weight ratio of 0.005, and 30% liquid alkali at a 6-nitro weight ratio of 0.49 to a 2000 L reactor. Raise the solution temperature to 60-65 °C and stir until the solution is dissolved and clear to obtain mixed solution I. S1.3. Add mixed solution I to 6-nitro solution for coupling reaction, maintain the reaction temperature at 40-45℃ and the pH between 9-10.5 for 2 hours. The endpoint is determined by the absence of color development at the percolation zone of the coupling solution using resorcinol solution, yielding pre-chromophore I; S2. Synthesis of pre-chromophore II: S2.1 Add 500 kg of water to a 2000 L reactor, add o-aminobenzoic acid at a weight ratio of 0.137 to 6-nitro and 30% hydrochloric acid at a weight ratio of 0.271 to 6-nitro. Stir for 30 min, then add an appropriate amount of ice to lower the solution temperature to 0 °C. Add 30% sodium nitrite within 40 min. The solution turns blue when tested with Congo red test paper. After reacting for 1 h, the solution turns blue when tested with potassium iodide starch test paper. Then, use aminosulfonic acid to eliminate excess sodium nitrite to obtain a diazonium solution. S2.2. Add 600 kg of water, 1-(4-sulfonylphenyl)-3-methyl-5-pyrazolone (6-nitrate weight ratio 0.256), and 30% liquid alkali (6-nitrate weight ratio 0.17) to a 2000 L reactor to adjust the pH to 8-9. Dissolve the solution at 20-25 °C until clear to obtain mixed solution II. S2.3 Add ice to the diazo solution to lower the solution temperature to 3℃. Add mixed solution II to the cooled diazo solution within 40 min while stirring. Add 63 kg of 30% liquid alkali to adjust the pH of the solution to 7-8. React at 5-8℃ for 3-4 h. The endpoint is when no color development is detected by m-phenylenediamine solution to obtain prechromogen II. S3. Complexation reaction of pre-chromium group I with chromium ions: After heating pre-chromium group I to 60℃, add salicylic acid at a weight ratio of 0.3 times that of 6-nitrate and chromium trioxide at a weight ratio of 0.75 times that of 6-nitrate. Then raise the solution temperature to 100-105℃ and adjust the pH to 4-6 with 30% liquid alkali for 3-4 hours. The reaction is considered complete when no red substance is detected by TLC. The reaction solution I is then obtained. S4. Complexation reaction between pre-chromium ion I, pre-chromium ion II and chromium ion: Pre-chromium ion II is added to reaction solution I, the temperature is maintained in the range of 100-105℃, and the pH is adjusted to between 5-6.5 with 30% liquid alkali. The reaction endpoint is when no yellow substance is detected by TLC, and green acidic black stain is obtained.
[0024] Example 3 In Example 3, the molar ratio of dye compound A, dye compound B, dye compound C, and dye compound D is 75:25.
[0025] A method for preparing a greenish acid black dye includes the following steps: Synthesis of S1 and pre-chromophore I: S1.1. Add 800 kg of water, 340 kg of 6-nitrate, and 51 kg of oxygen to a 5000 L reactor and stir and disperse for 30 min. Then add dispersant MF at a weight ratio of 0.025 to 6-nitrate, soda ash at a weight ratio of 0.075 to 6-nitrate, and sodium bicarbonate at a weight ratio of 0.08 to 6-nitrate. Adjust the pH to 2-4 to obtain a 6-nitrate solution. S1.2. Add 600 kg of water, 2-naphthol at a 6-nitro weight ratio of 0.6, emulsifier L-3 at a 6-nitro weight ratio of 0.005, and 30% liquid alkali at a 6-nitro weight ratio of 0.49 to a 2000 L reactor. Raise the solution temperature to 60-65 °C and stir until the solution is dissolved and clear to obtain mixed solution I. S1.3. Add mixed solution I to 6-nitro solution for coupling reaction, maintain the reaction temperature at 40-45℃ and the pH between 9-10.5 for 2 hours. The endpoint is determined by the absence of color development at the percolation zone of the coupling solution using resorcinol solution, yielding pre-chromophore I; S2. Synthesis of pre-chromophore II: S2.1 Add 500 kg of water to a 2000 L reactor, add o-aminobenzoic acid at a weight ratio of 0.182 times that of 6-nitro and 30% hydrochloric acid at a weight ratio of 0.364 times that of 6-nitro. Stir for 30 min, then add an appropriate amount of ice to lower the solution temperature to 0 °C. Add 30% sodium nitrite within 40 min. The solution turns blue when tested with Congo red test paper. After reacting for 1 h, the solution turns blue when tested with potassium iodide starch test paper. Then, use aminosulfonic acid to eliminate excess sodium nitrite to obtain diazonium solution. S2.2. Add 600 kg of water, 1-(4-sulfonylphenyl)-3-methyl-5-pyrazolone (6-nitrate weight ratio 0.341), and 30% liquid alkali (6-nitrate weight ratio 0.23) to a 2000 L reactor to adjust the pH to 8-9. Dissolve the solution at 20-25 °C until clear to obtain mixed solution II. S2.3 Add ice to the diazo solution to lower the solution temperature to 3℃. Add mixed solution II to the cooled diazo solution within 40 min while stirring. Add 72 kg of 30% liquid alkali to adjust the pH of the solution to 7-8. React at 5-8℃ for 3-4 h. The endpoint is when no color development is detected by m-phenylenediamine solution to obtain prechromogen II. S3. Complexation reaction of pre-chromium group I with chromium ions: After heating pre-chromium group I to 60℃, add salicylic acid at a weight ratio of 0.3 times that of 6-nitrate and chromium trioxide at a weight ratio of 0.80 times that of 6-nitrate. Then raise the solution temperature to 100-105℃ and adjust the pH to 4-6 with 30% liquid alkali. React for 3-4 hours. The reaction is considered complete when no red substance is detected by TLC. The reaction solution I is then obtained. S4. Complexation reaction between pre-chromium ion I, pre-chromium ion II and chromium ion: Pre-chromium ion II is added to reaction solution I, the temperature is maintained in the range of 100-105℃, and the pH is adjusted to between 5-6.5 with 30% liquid alkali. The reaction endpoint is when no yellow substance is detected by TLC, and green acidic black stain is obtained.
[0026] Comparative Example 1 In Comparative Example 1, the molar ratio of dye compound A, dye compound B, dye compound C, and dye compound D is 100:0.
[0027] A method for preparing an acid black dye includes the following steps: Synthesis of S1 and pre-chromophore I: S1.1. Add 800 kg of water, 340 kg of 6-nitrate, and 51 kg of oxygen to a 5000 L reactor and stir and disperse for 30 min. Then add dispersant MF at a weight ratio of 0.025 to 6-nitrate, soda ash at a weight ratio of 0.075 to 6-nitrate, and sodium bicarbonate at a weight ratio of 0.08 to 6-nitrate. Adjust the pH to 2-4 to obtain a 6-nitrate solution. S1.2. Add 600 kg of water, 2-naphthol at a 6-nitro weight ratio of 0.6, emulsifier L-3 at a 6-nitro weight ratio of 0.005, and 30% liquid alkali at a 6-nitro weight ratio of 0.49 to a 2000 L reactor. Raise the solution temperature to 60-65 °C and stir until the solution is dissolved and clear to obtain mixed solution I. S1.3 Add mixed solution I to 6-nitro solution for coupling reaction, maintain reaction temperature at 40-45℃ and pH between 9-10.5 for 2h. The endpoint is determined by the absence of color at the penetration zone of the coupling solution using resorcinol solution, yielding pre-chromosome I; S2. Complexation reaction of pre-chromosome I with chromium ions: Heat pre-chromosome I to 60℃ and add salicylic acid at a weight ratio of 0.3 times that of 6-nitro and chromium trioxide at a weight ratio of 0.61 times that of 6-nitro. Then raise the solution temperature to 100-105℃ and adjust the pH to 4-6 using 30% liquid alkali, reacting for 3-4h. The endpoint is determined by the absence of red substance detected by TLC, yielding acid black dye.
[0028] Performance testing The green-tinted acid black samples from Examples 1-3 and Comparative Example 1 were analyzed using the following specific detection methods: 1. Testing of color tones in dyed fabrics According to GB / T2379-2020, the determination of color and intensity of acidic complex dyes was performed. A plain woven fabric of 18% spandex and 82% nylon was used as the dyed fabric. The dye-to-fabric weight ratios were 0.5%, 2%, and 4% respectively. After dyeing and drying, the hue and chroma of the dyed fabric were tested using a Datacolor 850 colorimeter. Da represents the degree of red and green in the dyed color. When the dyed color is more greenish than the reference dye, the Da value is negative; the greener the color, the larger the negative value.
[0029] Based on the above detection method, the test results of Examples 1-3 and Comparative Example 1 were obtained, as shown in Table 1 below.
[0030] Table 1. Mixing ratios and performance tests of dye compounds A and B with dye compounds C and D in Examples 1-3 and Comparative Example 1. Referring to Table 1, comparing Examples 1-3 and Comparative Example 1, it can be seen that the higher the proportion of dye compound C and dye compound D, the greener the resulting acid black dye with green light. This may be because dye compound C and dye compound D contain azo groups, which are strong chromophores and are the basis for color production. Furthermore, the azo groups are connected to a larger, interconnected carbon ring structure, forming a longer "conjugated system" that allows electrons to move freely. At the same time, dye compound D contains nitro groups, which further reduces the energy required to absorb light, making the wavelength of light absorbed by the molecule longer. It mainly absorbs the orange-red to red part of the visible light, thus presenting a green color.
[0031] Performance testing The fabric was immersed in the greenish acid black dye of Examples 1-3 and Comparative Example 1, and a leveling agent was added for dyeing under acidic conditions at a dyeing concentration of 2%. The dyed fabric was then analyzed using the following specific testing methods: 1. Test the color fastness to washing of the fabric according to the method specified in ISO 105C02; 2. Test the color fastness to water immersion of the fabric according to the method specified in ISO 105E01; 3. Test the color fastness of the fabric to perspiration (alkali) according to the method specified in ISO 105E04.
[0032] Based on the above detection method, the test results of Examples 1-3 and Comparative Example 1 were obtained, as shown in Tables 2-4 below.
[0033] Table 2. Results of water wash fastness tests for the acid black dyes with green luster in Examples 1-3 and Comparative Example 1. Table 3. Results of water fastness tests for the green-tinted acid black dyes of Examples 1-3 and Comparative Example 1. Table 4. Test results of color fastness to perspiration (alkali) for Examples 1-3 and Comparative Example 1. Referring to Tables 2-4, a comparison of Examples 1-3 and Comparative Example 1 shows that the green-light acid black dye of Example 2 has better performance. This may be because dye compounds A and B are rigid macromolecules that can be firmly fixed to the fabric through ionic bonds, coordination bonds, and π-π stacking. In contrast, dye compounds C and D contain multiple sulfonic acid groups, which are hydrophilic groups. This makes the dye molecules on the fabric easily dissolved and removed by water molecules after dyeing. When the proportion of dye compounds A and B is too low, dye compounds A and B cannot fix dye compounds C and D through spatial network encapsulation and charge complementarity adsorption, resulting in a decrease in the color fastness of the green-light acid black dye.
[0034] In summary, the green-tinted acid black dye obtained in Example 2 not only possesses ideal color fastness under ideal tint conditions, but also exhibits ideal color fastness.
[0035] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.
Claims
1. A green light acid black dye, characterized by, The dye compound A, the dye compound B, the dye compound C and the dye compound D are respectively shown as the structural formula I, the structural formula II, the structural formula III and the structural formula IV. The molar ratio of the dye compound A and the dye compound B to the dye compound C and the dye compound D is (75-85):(25-15).
2. The method for preparing a greenish-green acid black dye according to claim 1, characterized in that, The method comprises the following steps: S1: mixing 2-naphthol, 30% liquid alkali and non-ionic surfactant, stirring to dissolve until the solution is clear at 60-65°C, then adding the obtained solution into 6-nitro solution with pH 2-4, maintaining the reaction temperature at 40-45°C, and reacting for 2h at pH 9-10.5 to obtain the precursor base I; S2: mixing o-aminobenzoic acid with hydrochloric acid, then adding 30% sodium nitrite to a slight excess of sodium nitrite, reacting for 1h at 5-8°C, and eliminating the excess sodium nitrite with sulfamic acid to obtain a diazonium solution; adding 30% liquid alkali to 1-(4-sulfonic acid phenyl)-3-methyl-5-pyrazolone solution and adjusting the pH to 8-9, dissolving until clear at 20-25°C, then lowering the temperature to 3°C, and adding into the diazonium solution to react for 3-4h at pH 7-8 and temperature 5-8°C to obtain the precursor base II; S3: adding salicylic acid and chromium trioxide to the precursor base I after heating to 60°C, and heating to 100-105°C, and reacting for 3-4h at pH 4-6 to obtain reaction solution I; S4: adding the precursor base II into the reaction solution I, maintaining the temperature at 100-105°C and pH 5-6.5 to obtain the green light acid black dye.
3. The method for preparing a greenish-green acid black dye according to claim 2, characterized in that, S1 comprises the following steps: Mixing 6-nitro, oxygen and water and stirring for 30min, then adding dispersant, soda ash, and adjusting the pH to 2-4 with sodium bicarbonate to obtain 6-nitro solution; heating 2-naphthol, water, non-ionic surfactant and 30% liquid alkali to 60-65°C to dissolve until clear to obtain mixed solution I; adding the mixed solution I into the 6-nitro solution for coupling, the reaction temperature is 40-45°C and the pH is maintained in the range of 9-10.5, and the reaction time is 2h, and the end point is detected by the non-coloring of the coupling solution at the bleeding circle with m-phenylenediamine solution to obtain the precursor base I.
4. The method for preparing a greenish-green acid black dye according to claim 3, characterized in that, The dispersant is dispersant MF.
5. The method for preparing a greenish-green acid black dye according to claim 3, characterized in that, The non-ionic surfactant is emulsifier L-3.
6. The method for preparing a greenish-green acid black dye according to claim 2, characterized in that, S2 includes the following steps: adding o-aminobenzoic acid in water, then adding 30% hydrochloric acid and stirring for 30 min, then adding ice to cool to 0°C, then adding 30% sodium nitrite solution and adding it completely within 40 min, then using Congo red test paper to detect blue color, using potassium iodide starch test paper to detect blue color, then reacting for 1 h at 5-8°C, then eliminating excess sodium nitrite using sulfamic acid, to obtain a diazonium liquid; mixing 1-(4-sulfonic acid phenyl)-3-methyl-5-pyrazolone with water, adjusting the pH to 8-9 using 30% liquid alkali, and dissolving it to be clear at 20-25°C, to obtain a mixed solution II; cooling the mixed solution II to 3°C using ice, then adding the diazonium liquid thereto under stirring within 40 min, and adjusting the pH to 7-8 using 30% liquid alkali, and reacting for 3-4 h at 5-8°C, to obtain an end point using m-phenylenediamine solution to detect no color reaction.
7. The method for preparing a greenish-green acid black dye according to claim 2, characterized in that, S3 includes the following steps: adding salicylic acid and chromium trioxide to the previous color base I after warming it to 60°C, then warming to 100-105°C, adjusting the pH to 4-6 using 30% liquid alkali, and reacting for 3-4 h, to obtain a reaction solution I, using TLC to detect no red material as an end point.
8. The method for preparing a greenish-green acid black dye according to claim 2, characterized in that, S4 includes the following steps: adding the previous color base II to the reaction solution I, maintaining the temperature at 100-105°C, adjusting the pH to 5-6.5 using 30% liquid alkali, and using TLC to detect no yellow material as an end point, to obtain the green light acid black dye.