A dark green reactive dye and its preparation method and application

Abstract

The present application relates to the field of textile printing and dyeing, and specifically, to a dark green reactive dye and its preparation method and application. The dark green reactive dye has the following structural formula:. The dark green reactive dye provided in the present application exhibits excellent color stability by virtue of its unique structure, so it can be used as a non-photosensitive dye, and is ideally applied to outdoor or sun-resistant fabrics. It also has excellent color fastness to sunlight, perspiration and chlorine; in addition, the dye can be used as a preferred substitute for blue in the three primary color matching scheme where black is biased towards cyan because of its unique dark green tone, which can not only improve the light fastness of the dyed fabric, but also make the fabric as a whole present a more obvious cyan effect, so that it is more convenient for market customers to adjust the desired target color.

Description

Technical Field

[0001] The present application relates to the field of textile printing and dyeing, and in particular to a dark green reactive dye and a preparation method and application thereof. Background Art

[0002] Vinyl sulfone type reactive dyes, as the second largest category in the reactive dye field, especially the domestic KN series, have shown strong competitiveness in the market with their excellent reactivity, excellent acid resistance and comprehensive chromatographic range.

[0003] However, the common vinyl sulfone reactive dyes on the market, such as reactive turquoise KN-G and reactive brilliant blue KN-R, often face the problems of insufficient dyeing stability, easy photosensitivity discoloration and lack of light fastness in actual dyeing applications, which to a certain extent limits their application scope.

[0004] In view of the above problems, it is urgent to develop a dye that can maintain highly stable hue under different lighting conditions. Summary of the invention

[0005] In order to solve the problem that traditional dyes are prone to photosensitivity discoloration and lack light fastness, the present application hereby provides a dark green reactive dye and its preparation method and application, aiming to optimize and upgrade the photosensitivity of the dye.

[0006] In the first aspect, the present application provides a dark green reactive dye, the structural formula of which is as follows: .

[0007] In a second aspect, the present application provides a method for synthesizing a dark green reactive dye, comprising the following steps: S1. First, disperse PBE into ice water, then add concentrated hydrochloric acid, keep the temperature at 3-5°C and stir evenly, then add an aqueous solution of sodium nitrite and stir to react. After the reaction is completed, add aminosulfonic acid to obtain a reaction solution A1 containing compound X; S2, add H acid to the reaction solution A1, maintain the temperature at 15-18°C, stir for 1.0h, and after the reaction is complete, obtain the reaction solution A2 containing compound Y; S3, dispersing the raw material M into ice water, controlling the pH value to 6.0-6.5, maintaining the temperature at 3-5°C and stirring evenly, then adding an aqueous solution of sodium nitrite and stirring to react, after the reaction is completed, adding aminosulfonic acid to obtain a reaction solution B containing compound Z; S4, adding the above reaction solution A2 to the reaction solution B, controlling the temperature to 15-18°C, and keeping the solution pH at 5.5-6.0, and stirring the reaction. After the reaction is completed, the dark green dye compound can be obtained by salting out and drying through a membrane; The reaction scheme of the above-mentioned preparation steps is as follows:

[0008]

[0009]

[0010] .

[0011] Preferably, the feed ratio of PBE, concentrated hydrochloric acid and sodium nitrite aqueous solution in step S1 is 1:(0.25-0.30):(0.95-1.05) in molar ratio.

[0012] Preferably, the specific steps of step S1 are as follows: PBE was dispersed in ice water at a molar ratio of (0.003-0.005):1, and then 30% concentrated hydrochloric acid was added. After stirring evenly while maintaining the temperature at 3-5°C, a 10% aqueous sodium nitrite solution was added and stirred for 1 hour. After the reaction was completed, aminosulfonic acid was added to eliminate unreacted sodium nitrite to obtain a reaction solution A1 containing compound X.

[0013] Preferably, the amount of H acid added in step S2 is calculated as PBE:H acid=1:(0.98-1.05) in molar ratio.

[0014] Preferably, the feed ratio of the raw material M and the aqueous solution of sodium nitrite in step S3 is 1:(1-1.05) by molar ratio.

[0015] Preferably, the specific steps of the S3 step are as follows: The raw material M is dispersed into ice water in a molar ratio of (0.003-0.005):1, and then sodium bicarbonate is added to adjust the solution pH to 6.0-6.5. At this time, the temperature is maintained at 3-5°C and stirred evenly, and then a 10% sodium nitrite aqueous solution is added, and the reaction is stirred for 1 hour. After the reaction is completed, aminosulfonic acid is added to eliminate unreacted sodium nitrite to obtain a reaction solution B containing compound Z.

[0016] In the third aspect, the present application provides a dark green reactive dye and / or a dark green reactive dye prepared by the synthesis method described in any one of claims 2-4 for use in the preparation of black with a cyan color, as a color matching product of black with a cyan color: a substitute for blue, one of the three primary colors.

[0017] In a fourth aspect, the present application provides a dyeing process comprising the following steps: 1) providing a dye bath comprising the dark green reactive dye described in claim 1 and / or a dark green reactive dye prepared by any of the above-mentioned synthesis methods, for standby use; 2) Immersing the fabric to be dyed in the dye bath prepared in 1) at a constant temperature of 55-65° C. at a bath ratio of 1:15-20, wherein 50 g / L of anhydrous sodium sulfate is also added to the dye bath; 3) After dyeing for 30±5 minutes, add 20-25g / L of sodium carbonate and continue to react for 60 minutes. Then wash with water, soap wash at 98℃ for 20 minutes, wash with water, and dry to complete the dyeing.

[0018] In a fifth aspect, the present application provides a dark green reactive dye composition, comprising the above-mentioned dark green reactive dye and / or a dark green reactive dye obtained by any of the above-mentioned synthesis methods and a dyeing auxiliary, wherein the dyeing auxiliary is anhydrous sodium sulfate and / or sodium carbonate.

[0019] In summary, this application has the following beneficial effects: 1. The above-mentioned dark green reactive dye has excellent color stability through its amide group, so that it can be effectively used as a non-photosensitive dye for outdoor or sun-resistant fabrics, and has good color fastness to sunlight, sweat and chlorine; In addition, due to its dark green color, it can be used as a superior replacement for blue in the three primary colors of black and cyan. It can improve the light fastness of dyed fabrics and make the overall cyan of dyed fabrics more obvious, making it easier for market customers to adjust the target color. 2. The dark green reactive dye is a medium-temperature reactive dye with good dyeing performance and excellent compatibility with other medium-temperature reactive dyes. It is not easy to produce color spots or uneven colors. It can be used for medium-temperature (40-60°C) immersion dyeing, pad dyeing, cold-batch dyeing and other dyeing processes for cotton, linen, viscose, wool, silk and other fabrics; 3. The present application optimizes the synthesis process route of dark green reactive dyes to obtain dark green reactive dyes with higher purity, thereby reducing the generation of impurities and by-products. At the same time, the synthesis process route is stable and reliable, and is easy to realize industrial production and automated control. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the process flow chart of 60℃ constant temperature water bath dyeing for this application; Figure 2 This is a one-dip-one-pad dyeing process flow chart for this application. DETAILED DESCRIPTION

[0021] The following is combined with the embodiments and the attached Figure 1-2 This application is described in further detail. Example

[0022] A dark green reactive dye, the specific structural formula is: ; and prepared by the following method: S1. Take 28 g of PBE and add it to ice water consisting of 250 g of water and 250 g of ice, then add 25 mL of a solution having a mass ratio of hydrochloric acid to water of 3:7, keep the temperature at 3-5°C and stir evenly, then add 70 mL of a solution having a mass ratio of sodium nitrite to water of 1:9 and stir to react for 1.0 h. After the reaction is complete, add 10 g of aminosulfonic acid to eliminate unreacted sodium nitrite, thereby obtaining a reaction solution A1 containing compound X; S2, add 33g of H acid to the above reaction solution A1, keep the temperature at 15-18°C, stir for 1.0h, and after the reaction is complete, obtain reaction solution A2 containing compound Y; S3, add 44g of raw material M to ice water composed of 250g of water and 250g of ice, add 5.8g of sodium bicarbonate to keep the pH of the solution at 6.0-6.5, keep the temperature at 3-5°C and stir evenly, add 70mL of a solution with a mass ratio of sodium nitrite to water of 1:9 and stir to react for 1.0h, after the reaction is complete, add 10g of aminosulfonic acid to eliminate unreacted sodium nitrite, and obtain a reaction solution B containing compound Z; S4. Add the above reaction solution A2 to the reaction solution B, maintain the temperature at 15-18°C, gradually add appropriate amount of sodium bicarbonate to keep the solution pH at 5.5-6.0, and stir for 1.0h. After the reaction is complete, pass through a membrane for salting out and drying to obtain a dark green dye compound.

[0023] The reaction scheme of the above-mentioned preparation steps is as follows:

[0024]

[0025]

[0026] .

[0027] Comparative Example 1 A dark green reactive dye, the specific structural formula is: .

[0028] Comparative Example 2 A dark green reactive dye, the specific structural formula is: .

[0029] Performance testing First, the dark green dye compound prepared in each embodiment and comparative example is selected as the test object for standby use, and after dyeing according to the following specific dyeing method, its rating and color difference (D65 10-DL* / Da* / Db* / DE*) are tested respectively to evaluate its color fastness to sunlight and color fastness to chlorine. The specific dyeing method and test steps and conditions are as follows: Fabric to be dyed, specifically cotton unmercerized double-sided knitted fabric (4g) The dyeing method adopts immersion dyeing, refer to Figure 1 , the specific steps are as follows: 1) providing a dye bath containing the dark green dye compound prepared in the example or comparative example for standby use, wherein the amount of the dark green dye compound used is 1.0% and 3.0% owf (dye relative to fabric weight), respectively; 2) Immerse the fabric to be dyed in the dye bath prepared in 1) at a constant temperature of 60°C according to a bath ratio of 1:15, wherein 50 g / L of anhydrous sodium sulfate is also added to the dye bath; 3) After dyeing for 30 minutes, add 20g / L sodium carbonate and continue to react for 60 minutes. Then wash with water, place it in a soap solution of ARGACELSW CONC 2g / l and ARGAQUEST ARSK 4g / l and soap it at 98℃ for 20 minutes, wash it with water, and dry it at 70℃ to complete the dyeing.

[0030] Fabric to be dyed, specifically pure cotton 3 / 1 twill khaki (15×20cm) The dyeing method adopts pad dyeing, refer to Figure 2 , the specific steps are as follows: 1) providing a pad dyeing solution containing a dark green dye compound prepared in an example or a comparative example (the pad dyeing solution contains 8 g / L sodium alginate and 10 g / L sodium sulfate) for standby use, wherein the amount of the dark green dye compound used is 10 g / L and 30 g / L respectively; 2) Pour the pad dyeing liquid in 1) into the pad dyeing tank, and wait until the pad dyeing liquid is evenly applied on the roller, vertically place the cut fabric sample into the pad dyeing tank, dip and roll it, and then place the fabric sample in a 70℃ oven to dry; 3) Pour the fixing solution (containing 250g / L sodium chloride and 30g / L anhydrous sodium carbonate) into the roller dyeing tank, and evenly spread the fixing solution on the roller. Put the dried fabric sample vertically into the roller dyeing tank for dipping and rolling, and then put the fabric sample containing the fixing solution into the steamer for steaming (102℃*90s, air inlet pressure of 0.4MPa, steam flow rate of 150kg / h); 4) Wash the steamed fabric sample with room temperature water for 10 minutes, 60℃ water for 10 minutes, 98℃ soap for 15 minutes (the soap solution contains ARGACEL SW CONC 3g / l), 60℃ water for 10 minutes, room temperature water for 10 minutes, and dry at 70℃ to complete the dyeing.

[0031] Then carry out the corresponding color fastness test on the dyed fabric, the specific method is as follows: (I) Color fastness to sunlight: Artificial light source method (xenon arc lamp), refer to GB 8427-2019 The textile sample and the reference standard sample (blue standard wool) are exposed to artificial light (xenon arc lamp) under specified conditions at the same time, and then the degree of color change of the two is compared. The light fastness grade of the sample is determined by the blue wool light fastness standard sample exposed at the same time.

[0032] Note: The exposure condition is exposure cycle A1, simulating temperate climate conditions. The air temperature in the experimental chamber is 43±2℃, the black standard temperature is 47±3℃, the black board temperature is 45±3℃, the effective humidity is maintained at about 40%, and the wavelength is 300nm-400nm.

[0033] (ii) Composite color fastness to light and artificial sweat: Artificial light source method (xenon arc lamp), refer to ISO 105-B07:2009 (E) 1. Soak in sweat Place the sample in a sweat box, add 50 mL of freshly prepared sweat, and completely immerse the sample in the sweat. Soak for about 30 minutes at room temperature. During this period, the sample should be slightly pressed and stirred to ensure that the sample is completely wet. Take the sample out of the sweat, remove the excess sweat on the sample, and weigh the mass of the sample so that its liquid carrying rate is (100 ± 5)%; The sweat formula is as follows: 1) Acid Sweat Solution I, use Grade III water (4.8), prepare immediately before use (see AATCC TM 15), each liter of solution contains: 0.25g L-histidine hydrochloride monohydrate (C6H9N3O2·HCl·H20) 10g sodium chloride (NaCl) 1g anhydrous disodium hydrogen phosphate (Na2HPO4) 1g lactic acid (85%) (CH3CHOHCOOH) The pH value of the solution should be 4.3 (± 0.2); 2) Acid sweat solution II, use third-grade water (4.8), prepare it immediately before use (according to ISO 105-E04), each liter of solution contains: 0.5g L-histidine hydrochloride monohydrate (C6H9N3O2·HCl·H20) 5g sodium chloride (NaCl) 2.2 g sodium dihydrogen phosphate dihydrate (NaH2PO4·2H20) The pH value of the solution should be 5.5 (±0.2), adjusted with 0.1 mol / L sodium hydroxide; 3) Alkaline sweat solution, prepared with grade 3 water (4.8), ready for use (according to ISO 105-E04), each liter of solution contains: 0.5g L-histidine hydrochloride monohydrate (C6H9N3O2·HCl·H20) 5g sodium chloride (NaCl) 5g disodium hydrogen phosphate dodecahydrate (Na2HPO4·12H20) or 2.5g disodium hydrogen phosphate dihydrate (Na2HPO4·H20) The pH was adjusted to 8.0 (±0.2) with 0.1 mol / L sodium hydroxide.

[0034] 2. Exposure Fix the sweat-soaked sample on a waterproof white board without covering it. Fix the level 4 blue wool standard sample on another white board, be careful not to get it soaked by sweat, and cover it with a half baffle. Place the sample rack with the fixed sample and blue wool standard sample in the exposure chamber of the light-attached test machine, and expose it according to the European temperate exposure conditions specified in GB / T8427-2008 (medium effective humidity, humidity control standard sample level 5, maximum black standard temperature 50°C). Expose continuously until the color change of the level 4 blue wool standard sample reaches gray card level 4 to 5, and then the exposure can be terminated.

[0035] (III) Color fastness to chlorinated water: swimming pool water, refer to ISO 105-E03:2010 1. Prepare the test solution: According to the requirements of standard GB / T 8433-2013, prepare a sodium hypochlorite (NaClO) aqueous solution. For swimwear fabrics, it is necessary to prepare a sodium hypochlorite aqueous solution with 100 mg or 50 mg of available chlorine per liter and a pH value of 7.50±0.05; for bathrobes or towels, it is necessary to prepare a sodium hypochlorite aqueous solution with 20 mg of available chlorine per liter and a pH value of 7.50±0.05. Prepare and use immediately; 2. Sample preparation: Prepare samples of the required size and specifications according to the type of sample to be tested. For fabric samples, cut a sample of (40±2) mm×(100±2) mm from the fabric to be tested; 3. Weigh the sample and add liquid: After weighing the prepared sample, add the prepared sodium hypochlorite aqueous solution to ensure that the sample is completely soaked; 4. Machine test: put the sample after adding liquid into the test equipment for testing, and operate according to the conditions specified in the standard; 5. Drying out of the machine: After the test, take out the sample and dry it; 6. Rating report: Finally, the rating and color difference (D65 10-DL* / Da* / Db* / DE*) are tested by the "Gray Sample Scale for Color Change Evaluation in GB 250-1995", the gray sample scale in ISO 105 / A02-1993 and the Datacolor 800 colorimeter, and then used to evaluate the fastness to chlorinated water.

[0036] The dark green dye compound in the above embodiment was extracted and treated according to the above dyeing process. The rating and color difference (D65 10-DL* / Da* / Db* / DE*) of the fabric to be dyed were tested at different concentrations. The average value of the test results was recorded in the following table.

[0037] Table 1: Example light fastness performance test results (dyeing)

[0038] Table 2: Example light fastness, artificial sweat composite color fastness performance test results (dyeing)

[0039] Table 3: Example chlorinated water resistance color fastness performance test results (immersion dyeing)

[0040] It can be seen from Tables 1-3 above that the dark green reactive dye prepared in Example 1 has good light fastness after dyeing. When the dye dosage is 1.0% owf, the rating is 3-4, DL* is 0.88, Da* is -0.16, Db* is 0.74, and DE* is 0.68; when the dye dosage is 3.0% owf, the rating is 3, DL* is 0.41, Da* is -0.74, Db* is -0.65, and DE* is 1.07; It also performs well in terms of composite color fastness to light and artificial sweat, with minimal color change and good color stability. This shows that even at higher dye concentrations, the active dye can effectively resist the dual effects of light and artificial sweat and maintain good color fastness performance.

[0041] In terms of color fastness to chlorinated water, both the dye dosage of 1.0% owf and 3.0% owf showed excellent performance, and the dye samples were rated no less than level 2, which means that they can well resist the influence of swimming pool water or other chlorinated water environments on the color of fabrics, maintaining the brightness and durability of the colors.

[0042] Table 4: Test results of color fastness to sunlight of the embodiment (padding dyeing)

[0043] Table 5: Example light fastness, artificial sweat composite color fastness performance test results (padding dyeing)

[0044] Table 6: Example chlorinated water resistance color fastness performance test results (padding dyeing)

[0045] It can be seen from Tables 4-6 above that the dark green reactive dye prepared in Example 1 has good light fastness after pad dyeing. When the dye dosage is 10 g / L, the rating is 4, DL* is 0.37, Da* is 0.10, Db* is 0.76, and DE* is 0.85; when the dye dosage is 30 g / L, the rating is >4, DL* is 0.36, Da* is -0.05, Db* is 0.16, and DE* is 0.40; At the same time, it has excellent performance in light resistance and artificial sweat composite color fastness. It has strong adaptability in both acidic and alkaline environments, and can maintain stable dyeing performance at different concentrations without being affected by concentration. Regarding color fastness to chlorinated water, the dark green reactive dye prepared in Example 1 showed outstanding performance at different dye dosages, whether 10 g / L or 30 g / L. Specifically, the ratings of the dye samples were all maintained at level 2 or above, which strongly proved that they can effectively resist the erosion of the color of the fabric by swimming pool water or other chlorinated water environments, ensuring the brightness of the color and long-term stability.

[0046] In summary, the dark green reactive dye prepared in Example 1 of the present application has significant performance under different dyeing processes (dip dyeing and pad dyeing) compared with Comparative Examples 1-2, and has excellent color fastness to sunlight, which means that under long-term sunlight exposure, its color can still remain stable and not easy to fade. At the same time, the dye also shows excellent light resistance and artificial sweat composite color fastness, which means that under the joint action of light and human sweat, its color can still remain bright and not easy to change. In addition, the color fastness to chlorinated water of the dye is also very outstanding, even if it is soaked in water containing chloride ions for a long time, its color can still remain unchanged; This may be due to the unique amide group, which enables it to obtain excellent color stability. In contrast, comparative examples 1 and 2, which have a strong similarity to the main structure of Example 1, are inferior to Example 1 in terms of color stability. In addition, its synthesis route is relatively easy, the yield is high, and it is suitable for large-scale production.

[0047] These remarkable performances make this dark green reactive dye have a wide range of application prospects in the textile printing and dyeing industry. Whether in the field of outdoor products, sportswear, etc. that need to withstand long-term sunlight and human sweat erosion, or in the field that needs to withstand chlorinated water treatment (such as textiles near swimming pools), this dye can provide a long-lasting and stable color effect.

[0048] Embodiment 2-5 A dark green reactive dye, which is different from Example 1 in that the feed ratios of the materials in step S1 are different, as shown in the following table: Table 7: Material feed ratio and yield in S1 in Example 2-5 Group Material feed ratio in S1 Yield Example 2 The molar ratio of PBE, concentrated hydrochloric acid, and sodium nitrite aqueous solution is 1:0.25:0.95 89.2% Example 3 The molar ratio of PBE, concentrated hydrochloric acid, and sodium nitrite aqueous solution is 1:0.25:1.05 88.6% Example 4 The molar ratio of PBE, concentrated hydrochloric acid, and sodium nitrite aqueous solution is 1:0.30:1.05 91.1% Example 5 The molar ratio of PBE, concentrated hydrochloric acid, and sodium nitrite aqueous solution is 1:0.30:0.95 90.7% Embodiment 6-7 A dark green reactive dye, which is different from Example 1 in that the feed ratios of the materials in step S2 are different, as shown in the following table: Table 8: Material feed ratio and yield in S2 in Example 6-7 Group Material feed ratio in S2 Yield Example 6 The molar ratio of PBE to H acid is 1:0.98 94.3% Example 7 The molar ratio of PBE to H acid is 1:1.05 92.5% Embodiment 8-9 A dark green reactive dye, which is different from Example 1 in that the feed ratios of the materials in step S3 are different, as shown in the following table: Table 9: Material feed ratio and yield in S3 in Example 8-9 Group Material feed ratio in S3 Yield Example 6 The molar ratio of raw material M and aqueous solution of sodium nitrite is 1:1.02 91.9% Example 7 The molar ratio of raw material M and aqueous solution of sodium nitrite is 1:1.0 93.8% It can be seen from the above table that the dark green reactive dyes prepared in Examples 2-9 all have relatively high yields, which are maintained at 88.6%-94.3%, and the synthetic process routes are stable and reliable, and are easy to realize industrial production and automated control.

[0049] The above are all modifications without creative contribution or solutions that obviously constitute technical inspiration that can be made to the present embodiment as needed by technical personnel in this field after reading this specification, but they should be protected by patent law as long as they are within the scope of the claims of this application.

Claims

1. A dark green reactive dye, characterized in that: Its chemical structure is as follows:

2. A method for synthesizing the dark green reactive dye according to claim 1, characterized in that: The steps include: S1. First, disperse PBE into ice water, then add concentrated hydrochloric acid, keep the temperature at 3-5°C and stir evenly, then add an aqueous solution of sodium nitrite and stir to react. After the reaction is completed, add aminosulfonic acid to obtain a reaction solution A1 containing compound X; S2, add H acid to the reaction solution A1, maintain the temperature at 15-18°C, stir for 1.0h, and after the reaction is complete, obtain the reaction solution A2 containing compound Y; S3, dispersing the raw material M into ice water, controlling the pH value to 6.0-6.5, maintaining the temperature at 3-5°C and stirring evenly, then adding an aqueous solution of sodium nitrite and stirring to react, after the reaction is completed, adding aminosulfonic acid to obtain a reaction solution B containing compound Z; S4, adding the above reaction solution A2 to the reaction solution B, controlling the temperature to 15-18°C, and keeping the solution pH at 5.5-6.0, and stirring the reaction. After the reaction is completed, the dark green dye compound can be obtained by salting out and drying through a membrane; The reaction scheme of the above-mentioned preparation steps is as follows: 。 3. The synthetic method of dark green reactive dye according to claim 2, characterized in that, In the step S1, the feed ratio of PBE, concentrated hydrochloric acid and sodium nitrite aqueous solution is calculated as 1:(0.25-0.30):(0.95-1.05) in terms of molar ratio.

4. The synthetic method of dark green reactive dye according to claim 3, characterized in that, The specific steps of the S1 step are as follows: PBE was dispersed in ice water at a molar ratio of (0.003-0.005):1, and then 30% concentrated hydrochloric acid was added. After stirring evenly while maintaining the temperature at 3-5°C, a 10% aqueous sodium nitrite solution was added and stirred for 1 hour. After the reaction was completed, aminosulfonic acid was added to eliminate unreacted sodium nitrite to obtain a reaction solution A1 containing compound X.

5. The synthetic method of dark green reactive dye according to claim 2, characterized in that, The amount of H acid added in the step S2 is calculated as PBE:H acid=1:(0.98-1.05) in molar ratio.

6. The synthetic method of dark green reactive dye according to claim 2, characterized in that, The feed ratio of the raw material M and the aqueous solution of sodium nitrite in the step S3 is calculated as 1:(1-1.05) in terms of molar ratio.

7. The synthetic method of dark green reactive dye according to claim 2, characterized in that, The specific steps of the S3 step are as follows: The raw material M is dispersed into ice water in a molar ratio of (0.003-0.005):1, and then sodium bicarbonate is added to adjust the solution pH to 6.0-6.

5. At this time, the temperature is maintained at 3-5°C and stirred evenly, and then a 10% sodium nitrite aqueous solution is added, and the reaction is stirred for 1 hour. After the reaction is completed, aminosulfonic acid is added to eliminate unreacted sodium nitrite to obtain a reaction solution B containing compound Z.

8. Use of the dark green reactive dye according to claim 1 and / or the dark green reactive dye prepared by any one of the synthetic methods of claims 2 to 4 in the preparation of black with a cyan color, characterized in that: As a color combination of black and cyan: a substitute for blue, one of the three primary colors.

9. A dyeing process, characterized in that: The steps include: 1) providing a dye bath comprising the dark green reactive dye described in claim 1 and / or the dark green reactive dye prepared by any one of the synthesis methods described in claims 2 to 4, for standby use; 2) Immersing the fabric to be dyed in the dye bath prepared in 1) at a constant temperature of 55-65° C. at a bath ratio of 1:15-20, wherein 50 g / L of anhydrous sodium sulfate is also added to the dye bath; 3) After dyeing for 30±5 minutes, add 20-25g / L of sodium carbonate and continue to react for 60 minutes. Then wash with water, soap wash at 98℃ for 20 minutes, wash with water, and dry to complete the dyeing.

10. A dark green reactive dye composition, characterized in that: The invention comprises the dark green reactive dye described in claim 1 and / or the dark green reactive dye prepared by the synthesis method described in any one of claims 2 to 4 and a dyeing auxiliary, wherein the dyeing auxiliary is anhydrous sodium sulfate and / or sodium carbonate.

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