Process for the preparation of a turquoise blue water-soluble dye

Abstract

The application discloses a preparation method of a turquoise blue water-soluble dye, which comprises the following steps: (1) copper phthalocyanine is subjected to sulfonation reaction with chlorosulfonic acid, and then subjected to chlorination reaction with chlorosulfoxide to obtain a chlorosulfonated material, and then the chlorosulfonated material is subjected to dilution and pressure filtration to obtain a color base filter cake; (2) a primary condensation reaction of cyanuric chloride and aniline-2.5-bisulfonic acid is carried out to obtain a primary condensate; (3) a secondary condensation reaction of the primary condensate and a mixture of hydroxyethyl ethylenediamine and hydrochloric acid is carried out to obtain a secondary condensate; (4) a tertiary condensation reaction of the secondary condensate, the color base filter cake and ammonium chloride is carried out to obtain a raw slurry; and (5) the raw slurry is subjected to resin adsorption, desalination through an ultrafiltration membrane, three-stage filtration and spray drying in sequence to obtain a turquoise blue water-soluble dye powder. The turquoise blue water-soluble dye prepared by the method has bright color, high saturation, good solubility and excellent filtration performance, and the color obtained on different fabrics is stable, and the lightness and darkness are synchronous, so that the turquoise blue water-soluble dye can be directly used for preparation of reactive ink.

Description

Technical Field

[0001] This invention belongs to the field of water-soluble dye technology, and specifically relates to a method for preparing a turquoise blue water-soluble dye. Background Technology

[0002] Currently, there are few varieties of reactive turquoise blue dyes available for ink formulation on the market. The most well-known are CIReactive Blue 15 and CIReactive Blue 72. Most domestic ink manufacturers use CIReactive Blue 72 extensively. This product has advantages such as stable color development on fabrics, high cost-effectiveness, and fast filtration speed, but its quality is generally not high enough in blue, and it appears more yellowish on fabrics. When mixed with other reds and yellows, it is not vibrant enough and has poor saturation. Foreign ink manufacturers and a few domestic ink manufacturers mainly use CIReactive Blue 15. When mixed with reds and yellows, it produces vibrant colors with high saturation, but the color yield is inconsistent on rayon and cotton, manifested as different Integ ratios at different depths.

[0003] Page 287 of the Shanghai Dye Production Process Compilation discloses the synthesis process of Reactive Turquoise Blue K-GL. The resulting product has a solubility of 130 g / L at 50°C, which can meet market demand for traditional printing products. However, ink formulation requires extremely high solubility, generally not less than 200 g / L at 25°C. Research has found that the UV curve of the product prepared by this process is higher on the left and lower on the right, indicating that the solubility falls far short of ink requirements and results in poor filtration performance.

[0004] The article "Process Improvement of Reactive Turquoise Blue K-GL for Inks" published in Volume 51, Issue 2 of Dyes and Coloring points out that the filtration performance of thionyl chloride is better than that of thionyl chloride during chlorosulfonation, the filtration performance of organic base B is better than that of ammonia, and the condensation effect of acylated ethylenediamine with chlorosulfonation products is better than that of ethylenediamine directly. Finally, the membrane filtration performance is shortened from 60 minutes to less than 10 minutes, achieving a significant improvement.

[0005] CN109651844A concerns improved products related to CIReactive Blue 72. The instruction manual states that the product's degree of sulfonation is 3.5≤a+b+c≤4.0, where the number of active groups is a, the number of sulfonamide groups is b, and the number of sodium sulfonate groups is c. The ratio between a, b, and c affects the product's solubility; a higher c / b ratio results in better solubility and filtration performance. However, the manual does not address the color yield on different fabrics.

[0006] Therefore, how to develop a vibrant and stable turquoise blue product is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing a turquoise blue water-soluble dye. The prepared turquoise blue water-soluble dye has a bright color, high saturation, good solubility, excellent filtration performance, stable color on different fabrics, good synchronization of light and dark shades, and can be directly used in the formulation of reactive inks.

[0008] A method for preparing a turquoise blue water-soluble dye includes the following steps:

[0009] (1) Copper phthalocyanine first undergoes a sulfonation reaction with chlorosulfonic acid to obtain a sulfonated intermediate, and then thionyl chloride is added dropwise to undergo a chlorination reaction to obtain a chlorosulfonated material. Then, after bubbling, dilution and pressure filtration, a color base filter cake is obtained.

[0010] (2) After cyanuric chloride pulping, aniline-2,5-disulfonic acid solution was added to carry out a condensation reaction. After the reaction was complete, the mixture was filtered to obtain the primary condensate.

[0011] (3) The primary condensate obtained in step (2) is subjected to a secondary condensation reaction with a mixture of hydroxyethyl ethylenediamine and hydrochloric acid. After the reaction is complete, a secondary condensate is obtained.

[0012] (4) Add the color base filter cake and ammonium chloride obtained in step (1) to the secondary condensate obtained in step (3) to carry out a three-stage condensation reaction, and then adjust the pH value to obtain the active turquoise blue raw slurry.

[0013] (5) The active turquoise blue raw slurry is successively subjected to resin adsorption, ultrafiltration membrane desalination, three-stage filtration and spray drying to obtain turquoise blue water-soluble dye powder.

[0014] In this preparation method, chlorosulfonated copper phthalocyanine is first obtained through sulfonation and chlorination of copper phthalocyanine. The chlorosulfonyl group is generally substituted at the β-position of the copper phthalocyanine. The number of substitutions can be controlled by the ratio of copper phthalocyanine to chlorosulfonic acid and the sulfonation reaction temperature. When the copper phthalocyanine is fully substituted by chlorosulfonyl, the structure of the two main components in the obtained chlorosulfonated material is shown in formula (B). At the same time, cyanuric chloride reacts sequentially with aniline-2,5-disulfonic acid and hydroxyethyl ethylenediamine to obtain the substituted secondary condensate shown in formula (C). Finally, under controlled pH conditions, the chlorosulfonated copper phthalocyanine reacts with the secondary condensate and ammonium chloride to obtain an active turquoise blue raw material.

[0015]

[0016] The structural formula of the reactive turquoise blue dopant dye is as follows:

[0017]

[0018] In equation (1), 3.8 ≤ a + b + c ≤ 4, and a ≥ 1.5, b ≥ 1.0, c ≥ 1.0;

[0019]

[0020] The ratio of a, b and c in the structural formula (1) of the turquoise water-soluble dye is controlled by the material ratio. The resulting turquoise water-soluble dye is a mixture. This mixture affects the application performance of the dye, especially the UV curve, solubility, color stability on different fabrics, and color and hue of the product. It is a unique blending effect in the dye industry.

[0021] In this preparation method, during the secondary condensation: compared to using ethylenediamine, the amino groups on both sides of ethylenediamine have similar reactivity, which easily leads to a symmetrical reaction on both sides and the production of by-products; the hydroxyethyl ethylenediamine used in this invention has different reactivity of the two amino groups, and combined with steric hindrance, the primary amine is more active than the secondary amine, and the hydroxyethyl group is beneficial to improving the solubility of the dye.

[0022] In this preparation method, if hydroxyethyl ethylenediamine hydrochloride is used to first condense with sulfonated filter cake, the primary and secondary amines will be exposed due to the condensation pH of 8.5-9.5, and both will have the opportunity to react with sulfonyl chloride groups. Thus, the structure of formula (1) cannot be obtained. Therefore, the sequential arrangement of primary and secondary condensation in this invention is beneficial to improving the purity of the product.

[0023] Preferably, in step (1), the molar ratio of chlorosulfonic acid to copper phthalocyanine is 30-40:1. In this case, chlorosulfonic acid is both a solvent and a reactant, which can fully replace copper phthalocyanine.

[0024] Preferably, in step (1), the sulfonation reaction temperature is 138-148℃; the chlorination reaction temperature is 80-90℃. The temperature of 138-148℃ allows copper phthalocyanine to be fully sulfonated. When using thionyl chloride for chlorination, 80-90℃ allows the reaction to occur better. Too high a temperature will accelerate the decomposition rate of thionyl chloride.

[0025] In the sulfonation reaction of step (1), the temperature is controlled below 90°C during the feeding process to disperse and dissolve the material; otherwise, the local temperature will rise and the side reactions will increase. The sulfonation reaction time is 4-6 hours.

[0026] In the chlorination reaction of step (1), the molar ratio of thionyl chloride to copper phthalocyanine is 1-3:1, the thionyl chloride is added over a period of 2 hours, and the reaction time is 2 hours.

[0027] In step (1), after the chlorination reaction is completed, the mixture is heated to 105°C with steam and kept at 100-110°C for 2-4 hours. Compressed air is then used to purge and bubble the reaction system for 4-6 hours. After purging and bubbling, the mixture is cooled to 50°C with cooling water. Heating to 105°C with steam ensures a more complete chlorination reaction. The bubbling after the reaction is complete allows excess thionyl chloride to be carried out of the reactor by the gas flow and then treated in the tail gas absorption tower.

[0028] In step (2), the molar ratio of aniline-2,5-disulfonic acid to cyanuric chloride is 1-1.15:1, preferably 1.03:1, to completely react with the cyanuric chloride. The more residual cyanuric chloride, the greater the impact on product quality, especially on storage stability. The purpose of adding a filter in this step is to remove the residual cyanuric chloride.

[0029] In step (2), sodium bicarbonate is used to maintain the pH value at 2-3 for the reaction, the reaction temperature is 0-5℃, the reaction pH value is 2-3, and the reaction time is 2-3 hours.

[0030] Preferably, in step (2), a filter bag is used for filtration. The filter bag has a pore size of 2-5 micrometers and is made of PP non-woven fabric.

[0031] Preferably, in step (3), the mixture of hydroxyethyl ethylenediamine and hydrochloric acid is prepared by adding an aqueous solution of hydrochloric acid (such as a 30% aqueous solution of hydrochloric acid) dropwise to the hydroxyethyl ethylenediamine until the pH = 6.5-7, and controlling the temperature below 18°C ​​during the dropwise addition.

[0032] Preferably, in step (3), the primary condensate and the mixture of hydroxyethyl ethylenediamine and hydrochloric acid are simultaneously added to another reactor in an equimolar ratio, with the pH value controlled at 5-7 (e.g., using a 10% NaOH aqueous solution), and the addition is completed in 4-5 hours. This is beneficial for the primary condensate to selectively undergo a substitution reaction with the primary amine of hydroxyethyl ethylenediamine to generate a secondary condensate.

[0033] In step (3), the reaction temperature is 20-25℃ and the reaction time is 2-3 hours.

[0034] In step (4), the reaction time is 6 hours. For the first 3 hours, the temperature is 0-15℃ and the pH value is maintained between 8 and 10 (the pH value is adjusted by using a 30% NaOH aqueous solution). For the next 3 hours, the temperature is 45-55℃ and the pH value is maintained between 10 and 11 (the pH value is adjusted by using a 30% NaOH aqueous solution). Then, the pH value is adjusted back to 7.0-7.5 (10% HCl aqueous solution).

[0035] As a preferred option, in step (4), the temperature is 5-10℃ and the pH value is 8.5-9.5 for the first 3 hours. High temperature and high pH value will cause the sulfonyl chloride group in the system to hydrolyze into sodium sulfonate group, resulting in a larger proportion of a in structural formula (1); low pH value is not conducive to the release of secondary amine hydrochloride in the secondary condensation product, affecting the smaller proportion of b in structural formula (1); therefore, the reaction in the first 3 hours is the core technology of the product.

[0036] Preferably, in step (4), the molar ratio of the secondary condensate, color base filter cake and ammonium chloride is 1-1.2:1:1.0-1.5. The ratio of the three raw materials can affect the ratio of a, b and c in the product structure formula (1), thereby further affecting the UV curve, solubility, color stability on different fabrics and the performance of color and luster of the product.

[0037] In step (5), after the resin adsorption column removes calcium and magnesium ions, the concentration of calcium and magnesium ions in the slurry is less than 1 mg / L.

[0038] In step (5), after ultrafiltration, the sodium chloride concentration is less than 50 mg / L, the sodium sulfate concentration is less than 25 mg / L, and the solid content is greater than 20%.

[0039] The present invention also provides a turquoise blue water-soluble dye prepared by the above method.

[0040] The present invention also provides the application of the above-mentioned turquoise blue water-soluble dye in reactive inks.

[0041] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0042] This invention combines the relationship between the performance of Reactive Blue K-GL (CIReactive Blue 14), CIReactive Blue 15 and CIReactive Blue 72 products, and obtains a water-soluble turquoise blue dye with structural formula (1) by selecting raw materials and controlling process steps. It has the advantages of bright color, high color saturation, good filtration performance and stable color on different fabrics.

[0043] The preparation method provided by the present invention can control the ratio of a, b and c in structural formula (1) to adjust the dye performance, which can be directly reflected in the UV curve. The UV curve reproducibility between different batches is good. When the ratio of the ABS value at the high point on the right to the ABS value at the low point on the left in the UV curve is controlled between 1.9 and 2.1, the high solubility is greater than 250g / L. The color is stable on different fabrics and the color and hue meet the requirements of active ink formulation.

[0044] The preparation method provided by the present invention can effectively reduce byproducts by adding a filtration step in the first condensation and using hydroxyethyl ethylenediamine for the second condensation. After being used in the formulation of active ink, the byproducts can reduce the impact of the byproducts on the storage stability of the ink. Furthermore, the post-processing in step (5) meets the limit requirements for inorganic salts and calcium and magnesium ions in active ink, and the three-stage filtration solves the problem of difficult filtration after the formulation of active ink. Attached Figure Description

[0045] Figure 1 The UV curves are for the samples prepared in Examples 1-2 and Comparative Examples 1-3. Detailed Implementation

[0046] Example 1

[0047] (a) Sulfonation reaction: Add 2500 kg of chlorosulfonic acid to the dry No. 1 reaction vessel, start stirring, and slowly add 350 kg of copper phthalocyanine. During the addition process, the temperature is controlled below 90°C. Stir for 60 minutes. After the material is completely dissolved, transfer the material to No. 2 reaction vessel. Start stirring in No. 2 reaction vessel and slowly heat with steam. Raise the temperature to 142°C within 2 hours and keep it at 140-142°C for 6 hours. After the heat preservation reaction is completed, cool the temperature to 85°C with cooling water. Add 175 kg of thionyl chloride dropwise within 2 hours, and control the temperature at 86-87°C during the dropwise addition of thionyl chloride. After the dropwise addition of thionyl chloride is completed, stir for 2 hours, heat with steam to 105°C, and keep it at 104-106°C for 3 hours. Blow air and bubble with compressed air from the bottom valve of No. 2 reaction vessel for 6 hours. After blowing air and bubbling, cool the temperature to 50°C with cooling water to obtain the chlorosulfonated material.

[0048] (b) Dilution and filtration: Add sufficient ice and 3000L of water to the dilution pot, and slowly add the above-reacted chlorosulfonated material to the dilution pot. Control the temperature during the dilution process at 0-10℃. Add ice as needed. After dilution, stir for 1 hour, filter, and wash the filter cake with an appropriate amount of washing water below 5℃. After washing, squeeze with compressed air for 4 hours to obtain the color base filter cake.

[0049] (c) Primary condensation: Add water and ice to reaction vessel #3, start stirring, add 116 kg of cyanuric chloride, stir for 1 hour, then add aniline-2,5-disulfonic acid solution (175 kg of aniline-2,5-disulfonic acid, 1500 kg of water, pH adjusted to 6-7 with 30% NaOH aqueous solution), control the reaction temperature at 0-5℃, and maintain pH at 2-3 with sodium bicarbonate. React for 2-3 hours, with the reaction endpoint being the absence of cyanuric chloride residue. Then filter through a 2-micron filter bag to obtain the primary condensate.

[0050] (d) Secondary condensation: Add appropriate amounts of water and ice to reaction vessel #4. Add the primary condensate obtained in step c, along with the pre-prepared mixture of hydroxyethyl ethylenediamine and hydrochloric acid (48 kg of hydroxyethyl ethylenediamine, 500 kg of water, and 30% hydrochloric acid solution added dropwise at a temperature below 18°C ​​until pH = 6.5-7) to reaction vessel #4 in an equimolar ratio. During this process, use 10% NaOH solution to control the pH value at 5-7 and the reaction temperature at 20-25°C. The addition should be completed within 4-5 hours, and then continue the reaction at the controlled temperature for 2-3 hours to obtain the secondary condensate.

[0051] (e) Triple condensation: Add an appropriate amount of ice to the secondary condensate in reaction vessel #4, control the temperature below 10°C, add the chromophore filter cake obtained in step b, add 45 kg of ammonium chloride, maintain the temperature at 5-10°C for the first 3 hours, and use a 30% NaOH aqueous solution to maintain the pH at 8.5-9.5; then control the temperature at 45-55°C, and the pH value between 10 and 11 for 3 hours as the endpoint, and use a 10% HCl aqueous solution to adjust the pH value to 7.0-7.5 to obtain the active turquoise blue raw material. The dye as shown in formula (2) is obtained:

[0052]

[0053] f) The raw pulp is passed through a resin adsorption column to remove calcium and magnesium ions; then through an ultrafiltration membrane to remove inorganic salts such as sodium chloride and sodium sulfate, and the solid content is concentrated to 20%; then through a three-stage filtration process using 2-micron-0.45-micron-0.2-micron filter cartridges to remove impurities such as dust, microorganisms, and colloids; finally, it is spray-dried to obtain reactive dye powder. This is designated as Sample 1.

[0054] like Figure 1 As shown in Table 1, the UV curves of the sample 1 prepared with a 20 mg / L dye solution are shown. The ratio of the ABS value at the high point on the right to the ABS value at the low point on the left is 2.0.

[0055] As shown in Table 2, the sample 1 was prepared into 1000 ml of 15% dye solution and filtered using a 0.22 μm φ47 mm polyvinylidene fluoride membrane. The filtration time could be controlled within 600 s.

[0056] As shown in Table 3, the ink of sample 1 was prepared with a concentration of 12%. After printing on rayon and cotton, the Integ value showed good synchronization, as shown in the data of sample 1 in Table 3.

[0057] Example 2

[0058] (a) Sulfonation reaction: Add 2800 kg of chlorosulfonic acid to the dry No. 1 reaction vessel, start stirring, and slowly add 350 kg of copper phthalocyanine. During the addition process, the temperature is controlled below 90°C. Stir for 60 minutes. After the material is completely dissolved, transfer the material to No. 2 reaction vessel. Start stirring in No. 2 reaction vessel and slowly heat with steam. Raise the temperature to 140°C within 2 hours and keep it at 138-140°C for 6 hours. After the heat preservation reaction is completed, cool the temperature to 85°C with cooling water. Add 210 kg of thionyl chloride dropwise within 2 hours, and control the temperature at 86-87°C during the dropwise addition of thionyl chloride. After the dropwise addition of thionyl chloride is completed, stir for 2 hours, heat with steam to 105°C, and keep it at 104-106°C for 3 hours. Blow air and bubble with compressed air from the bottom valve of No. 2 reaction vessel for 6 hours. After blowing air and bubbling, cool the temperature to 50°C with cooling water to obtain the chlorosulfonated material.

[0059] (b) Dilution and filtration: Add sufficient ice and 3000L of water to the dilution pot, and slowly add the above-reacted chlorosulfonated material to the dilution pot. Control the temperature during the dilution process at 0-10℃. Add ice as needed. After dilution, stir for 1 hour, filter, and wash the filter cake with an appropriate amount of washing water below 5℃. After washing, squeeze with compressed air for 4 hours to obtain the color base filter cake.

[0060] (c) Primary condensation: Add water and ice to reaction vessel #3, start stirring, add 150 kg of cyanuric chloride, stir for 1 hour, then add aniline-2,5-disulfonic acid solution (226 kg of aniline-2,5-disulfonic acid, 2000 kg of water, pH adjusted to 6-7 with 30% NaOH aqueous solution), control the reaction temperature at 0-5℃, and maintain pH at 2-3 with sodium bicarbonate, react for 2-3 hours, and take the reaction endpoint as no cyanuric chloride residue is left.

[0061] (d) Secondary condensation: Add appropriate amounts of water, ice, and the primary condensate obtained in step c to reaction vessel #4, along with a prepared mixture of hydroxyethyl ethylenediamine and hydrochloric acid (62 kg of hydroxyethyl ethylenediamine, 700 kg of water, and 30% hydrochloric acid aqueous solution added dropwise until pH = 6.5-7, temperature below 18℃). Add the mixture simultaneously in an equimolar ratio, using 10% NaOH aqueous solution to control the pH value at 5-7, and complete the addition over 4-5 hours. The reaction temperature is 20-25℃, and the reaction time is 2-3 hours to obtain the secondary condensate.

[0062] (e) Triple condensation: Add an appropriate amount of ice to the secondary condensate in reactor #4, control the temperature below 10°C, add the chromophore filter cake obtained in step b, add 45 kg of ammonium chloride, maintain the temperature at 5-10°C for the first 3 hours, and use a 30% NaOH aqueous solution to maintain the pH at 8.5-9.5; then control the temperature at 45-55°C, and the pH value between 10 and 11 for 3 hours as the endpoint, and use a 10% HCl aqueous solution to adjust the pH value to 7.0-7.5 to obtain the active turquoise blue raw material. The dye as shown in formula (3) is obtained:

[0063]

[0064] (f) The raw pulp was subjected to a resin adsorption column to remove calcium and magnesium ions; then, it was subjected to an ultrafiltration membrane to remove inorganic salts such as sodium chloride and sodium sulfate, and the solid content was concentrated to 20%; then, it was subjected to a three-stage filtration process using 2-micron-0.45-micron-0.2-micron filter cartridges to remove impurities such as dust, microorganisms, and colloids; finally, it was spray-dried to obtain reactive dye powder. This is designated as Sample 2.

[0065] like Figure 1 As shown in Table 1, the UV curves of the sample 2 prepared with a 20 mg / L dye solution are shown. The ratio of the ABS value at the high point on the right to the ABS value at the low point on the left is 1.3.

[0066] As shown in Table 2, the sample 2 was prepared into 1000 ml of 15% dye solution and filtered using a 0.22 μm φ47 mm polyvinylidene fluoride membrane. The filtration time could be controlled within 600 s.

[0067] As shown in Table 3, the ink of sample 2 was prepared into a 12% concentration. After printing on rayon and cotton, the Integ ratio of cotton to rayon was different at different depths. The ratio was larger at shallower depths. As the depth increased, the ratio gradually decreased from 2.7 to 2.1, indicating poor synchronicity. Therefore, the ratio of a, b, and c in the structure cannot be adjusted arbitrarily.

[0068] Comparative Example 1

[0069] The synthesis process of Reactive Turquoise Blue K-GL is disclosed on page 287 of the Shanghai Dye Production Process Compilation. One batch of raw slurry was prepared, and the raw slurry was then processed through step (f) to obtain control sample 1.

[0070] Comparative Example 2

[0071] According to the synthesis process of Example 1 in CN109651844A, one batch of raw pulp was prepared, and the raw pulp was then processed through step (f) to obtain comparative sample 2.

[0072] Comparative Example 3

[0073] According to the synthesis process of Example 1 of CN103333517B, a batch of raw pulp was prepared, and the raw pulp was then processed through step (f) to obtain comparative sample 3.

[0074] The UV curves, filtration performance, and color development of the fabrics were compared between samples 1-2 prepared in the examples and comparative samples 1-3.

[0075] Table 1 UV ratio of 20 mg / L dye aqueous solution

[0076]

[0077] As can be seen from the ABS ratios in Table 1, the different proportions of groups a, b, and c in the structural formula are reflected in the UV curves. A higher proportion of sulfonic acid groups (a) results in a larger ratio, while a higher proportion of active groups (c) results in a smaller ratio. From the ratios, the approximate proportion of active groups (c) in the turquoise structure can be inferred. The different active groups in samples 1-3 do not affect the test ratios.

[0078] Table 2. Filtration performance of 15% aqueous solution with chemical concentration.

[0079]

[0080] Note: When the control sample 1 was processed in step (f), the solid content could not be concentrated to 20%, but only 12.3%, and the speed was extremely slow during the three-stage filtration.

[0081] As can be seen from Table 2, the ratio of a, b, and c groups in the structural formula directly affects the filtration performance. A higher proportion of the active c group results in poorer dye solubility; for example, the c value of the dye synthesized in Comparative Example 1 is approximately 2.1. Treatment of dyes with different structures through step (f) can effectively solve the problem of slow dye filtration speed, except for cases where the dye's inherent solubility is low due to its structure.

[0082] Table 3. Color measurement data after color development of rayon and cotton.

[0083]

[0084] The samples were formulated with reactive ink and printed on rayon and cotton at different ink depths. After drying, steaming, washing, and ironing, the Integ values ​​were measured using a colorimeter. Analysis of the data in Table 3 shows that the Integ value ratio between rayon and cotton in Sample 1 was approximately 2.1, and this ratio remained relatively consistent across different ink depths. However, the ratios for Sample 2 and Comparative Sample 3 decreased from low to high ink depth, specifically from 2.7 to 2.1 and from 3.1 to 2.1, respectively. This indicates poor synchronicity between ink depths.

[0085] The above embodiments are only used to explain the inventive concept of the present invention, and are not intended to limit the protection of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical and methodological essence of the present invention shall still fall within the scope of the technical and methodological solutions of the present invention.

Claims

1. A method for preparing a turquoise blue water-soluble dye, characterized in that, The preparation method includes the following steps: (1) Copper phthalocyanine first undergoes a sulfonation reaction with chlorosulfonic acid to obtain a sulfonated intermediate, and then thionyl chloride is added dropwise to undergo a chlorination reaction to obtain a chlorosulfonated material. Then, the material is bubbled, diluted, and filtered to obtain a color base filter cake. (2) After cyanuric chloride is pulped, aniline-2,5-disulfonic acid solution is added to carry out a condensation reaction. After the reaction is complete, the mixture is filtered to obtain the primary condensate. (3) The primary condensate obtained in step (2) is subjected to a secondary condensation reaction with a mixture of hydroxyethyl ethylenediamine and hydrochloric acid. After the reaction is complete, a secondary condensate is obtained. (4) Add the color base filter cake and ammonium chloride obtained in step (1) to the secondary condensate obtained in step (3) to carry out a three-stage condensation reaction, and then adjust the pH value to obtain the active turquoise blue original slurry. (5) The active turquoise blue raw slurry was successively subjected to resin adsorption, ultrafiltration membrane desalination, three-stage filtration and spray drying to obtain turquoise blue water-soluble dye powder; The structural formula of the turquoise blue water-soluble dye is as follows: Equation (1) In equation (1), 3.8 ≤ a + b + c ≤ 4, and a ≥ 1.5, b ≥ 1.0, c ≥ 1.0; 。 2. The method for preparing the turquoise blue water-soluble dye according to claim 1, characterized in that, In step (1), the molar ratio of chlorosulfonic acid, thionyl chloride and copper phthalocyanine is 30-40:1-3:1, the sulfonation reaction temperature is 138-148℃, and the reaction time is 4-6 hours; the chlorination reaction temperature is 80-90℃, and the reaction time is 2 hours.

3. The method for preparing the turquoise blue water-soluble dye according to claim 1, characterized in that, In step (1), after the chlorination reaction is completed, the mixture is kept at 100-110°C for 2-4 hours, and then bubbled at the same temperature for 4-6 hours.

4. The method for preparing the turquoise blue water-soluble dye according to claim 1, characterized in that, In step (2), the molar ratio of aniline-2,5-disulfonic acid to cyanuric chloride is 1-1.15:1, sodium bicarbonate is used to maintain the pH value at 2-3, the reaction temperature is 0-5℃, and the reaction time is 2-3 hours.

5. The method for preparing the turquoise blue water-soluble dye according to claim 1, characterized in that, In step (2), a filter bag is used for filtration. The filter bag has a pore size of 2-5 micrometers and is made of PP non-woven fabric.

6. The method for preparing the turquoise blue water-soluble dye according to claim 1, characterized in that, In step (3), the molar ratio of the primary condensate to hydroxyethyl ethylenediamine is 1-1.05:

1. The mixture of hydroxyethyl ethylenediamine and hydrochloric acid is prepared by the following method: adding hydrochloric acid aqueous solution dropwise to hydroxyethyl ethylenediamine until pH=6.5-7, and controlling the temperature below 18°C ​​during the dropwise addition; the primary condensate and the mixture of hydroxyethyl ethylenediamine and hydrochloric acid are simultaneously added to another reaction vessel in an equimolar ratio, controlling the pH value at 5-7, the reaction temperature at 20-25°C, and controlling the addition to be completed in 4-5 hours, and then continuing the reaction at the temperature for 2-3 hours.

7. The method for preparing the turquoise blue water-soluble dye according to claim 1, characterized in that, In step (4), the three condensation reactions take 6 hours. The temperature is 0~15℃ for the first 3 hours, and the pH value is maintained between 8 and 10. The temperature is 45~55℃ for the next 3 hours, and the pH value is maintained between 10 and 11. Then the pH value is adjusted back to 7.0-7.

5.

8. The method for preparing the turquoise blue water-soluble dye according to claim 1, characterized in that, In step (4), the molar ratio of the secondary condensate, the chromosome filter cake and the ammonium chloride is 1-1.2:1:1.0-1.

5.

9. The method for preparing the turquoise blue water-soluble dye according to any one of claims 1-8, characterized in that, In step (5), the concentration of calcium and magnesium ions in the active turquoise blue slurry after resin adsorption is less than 1 mg / L; after desalination by ultrafiltration membrane, the sodium chloride concentration is less than 50 mg / L, the sodium sulfate concentration is less than 25 mg / L, and the solid content is greater than 20%; the three-stage filtration consists of 2 micron-0.45 micron-0.2 micron filter elements.

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