Preparation method of turquoise blue water-soluble dye

Abstract

The invention discloses a turquoise blue water-soluble dye preparation method, which comprises: (1) carrying out a sulfonation reaction on copper phthalocyanine and chlorosulfonic acid, carrying out a chlorination reaction on the copper phthalocyanine and thionyl chloride to obtain a chlorosulfonated material, and carrying out dilution and filter pressing to obtain a color base filter cake; (2) carrying out primary condensation reaction on cyanuric chloride and aniline-2. 5-disulfonic acid to obtain a primary condensation compound; (3) carrying out secondary condensation reaction on the primary condensation compound and a mixture of hydroxyethyl ethylenediamine and hydrochloric acid to obtain a secondary condensation compound; (4) carrying out third condensation reaction on the secondary condensation product, the color base filter cake and ammonium chloride to obtain primary pulp; and (5) sequentially carrying out resin adsorption, ultrafiltration membrane desalination, three-stage filtration and spray drying on the primary pulp to obtain turquoise blue water-soluble dye powder. The prepared turquoise blue water-soluble dye is bright in color, high in saturation degree, good in solubility, excellent in filtering performance, stable in color yield on different fabrics and good in depth synchronism, and can be directly used for active ink preparation.

Description

Technical Field

[0001] The invention belongs to the technical field of water-soluble dyes, and particularly relates to a method for preparing a turquoise water-soluble dye. Background Art

[0002] At present, there are few varieties of reactive turquoise dyes that can be used for ink preparation on the market. The most well-known ones are CIReactive Blue 15 and CIReactive Blue 72. Most domestic ink manufacturers use CIReactive Blue 72 more. This product has the advantages of stable color development on fabrics, high cost performance, and fast filtration speed, but the quality is generally not blue enough. After color development on fabrics, the yellow light is heavier. After compounding with other red and yellow colors, it is not bright enough and has poor saturation. Foreign ink manufacturers and a few domestic ink manufacturers mainly use CIReactive Blue 15 varieties. After compounding with red and yellow, the color is bright and the color saturation is high, but the color yield on rayon and pure cotton is inconsistent, which is manifested by 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 solubility of the product is 130g / L at 50°C, which can meet the market demand as a traditional printing product. In the field of ink formulation, there are extremely high requirements for the solubility of products. Generally, the solubility at 25°C is not less than 200g / L. Studies have found that the UV curve of the product prepared by this process is high on the left and low on the right, and the solubility is far from meeting the ink requirements, and the filtration performance is poor.

[0004] The article "Process Improvement of Reactive Turquoise Blue K-GL for Ink" published in Dyes and Colorants Volume 51, Issue 2 pointed out that the filterability of using thionyl chloride during chlorosulfonation is better than not using thionyl chloride, the filterability of using organic base B is better than that of ammonia water, and the condensation effect of acylated ethylenediamine and chlorosulfonation product is better than directly using ethylenediamine. Finally, the membrane filtration performance was shortened from 60 minutes to less than 10 minutes, achieving a significant improvement.

[0005] CN109651844A is about an improved product related to CIReactive Blue 72. The specification states that the degree of sulfonation of the product is 3.5≤a+b+c≤4.0, wherein 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 will affect the solubility of the product. The larger the c / b ratio, the better the solubility and the better the filtration performance. However, the color yield on different fabrics is not described.

[0006] Therefore, how to develop a turquoise blue product with bright color and stable color is a technical problem that needs to be solved urgently in the current field. Summary of the invention

[0007] The object of the present invention is to provide a method for preparing a turquoise water-soluble dye. The prepared turquoise water-soluble dye has bright color, high saturation, good solubility, excellent filtration performance, stable color on different fabrics, good synchronization of light and dark, and can be directly used for the preparation of active ink.

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

[0009] (1) copper phthalocyanine is first subjected to a sulfonation reaction with chlorosulfonic acid to obtain a sulfonated intermediate, and then thionyl chloride is added dropwise to cause a chlorination reaction to obtain a chlorosulfonated material, which is then subjected to bubbling, dilution, and filter pressing to obtain a color base filter cake;

[0010] (2) adding aniline-2,5-disulfonic acid solution to the cyanuric chloride pulp to carry out a primary condensation reaction, and filtering to obtain a primary condensation product after the reaction is complete;

[0011] (3) subjecting the primary condensation product obtained in step (2) to a secondary condensation reaction with a mixture of hydroxyethylethylenediamine and hydrochloric acid to obtain a secondary condensation product after the reaction is complete;

[0012] (4) adding the color base filter cake obtained in step (1) and ammonium chloride to the secondary condensate obtained in step (3) to carry out a third condensation reaction, and then adjusting the pH value to obtain an active turquoise blue slurry;

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

[0014] In the preparation method, firstly, copper phthalocyanine substituted with chlorosulfonyl is obtained through sulfonation reaction and chlorination reaction of copper phthalocyanine, wherein the chlorosulfonyl is generally substituted at the β position of copper phthalocyanine, and the number of substitutions can be controlled by the dosage ratio of copper phthalocyanine to chlorosulfonic acid and the sulfonation reaction temperature. When the copper phthalocyanine is fully substituted with chlorosulfonyl, the structures of two main components contained in the obtained chlorosulfonated material are shown in formula (B); at the same time, cyanuric chloride is reacted with aniline-2.5-disulfonic acid and hydroxyethylethylenediamine in sequence to obtain a substituted secondary condensate shown in formula (C); finally, under the condition of controlling the pH value, the copper phthalocyanine substituted with chlorosulfonyl reacts with the secondary condensate and ammonium chloride to obtain an active turquoise raw pulp.

[0015]

[0016] The structural formula of the active turquoise blue raw dye is as follows:

[0017]

[0018] In formula (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, and the obtained turquoise water-soluble dye is a mixture. The mixture jointly affects the application performance of the dye, especially the UV curve, solubility, color stability on different fabrics, color, hue and other aspects of the product, which is a unique mixing effect in the dye industry.

[0021] In the preparation method, in the secondary condensation: compared with the use of ethylenediamine, the amino groups on both sides of ethylenediamine are equally active, which easily causes a symmetrical reaction on both sides and produces by-products; the two amino groups in the hydroxyethylethylenediamine used in the present invention have different reactivities, 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 the preparation method, if hydroxyethylethylenediamine hydrochloride is used to carry out a condensation with the sulfonated filter cake first, because the condensation pH is 8.5-9.5, the primary amine and the secondary amine will be exposed and have the opportunity to react with the sulfonyl chloride group, so that the structure of formula (1) cannot be obtained. Therefore, the order of the primary condensation and the secondary condensation in the present invention is conducive 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. At this time, chlorosulfonic acid is both a solvent and a reactant, so that copper phthalocyanine can be fully replaced.

[0024] Preferably, in step (1), the temperature of the sulfonation reaction is 138-148° C.; the temperature of the chlorination reaction is 80-90° C. The temperature of 138-148° C. enables copper phthalocyanine to be fully sulfonated. When chlorination is performed using thionyl chloride, 80-90° C. 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 addition process to allow dispersion and dissolution, 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 dropwise for 2 hours, and the reaction time is 2 hours.

[0027] In step (1), after the chlorination reaction is completed, the reaction system is heated to 105° C. with steam, and kept at 100-110° C. for 2-4 hours, and compressed air is blown and bubbled into the reaction system for 4-6 hours. After the blowing and bubbling are completed, the reaction system is cooled to 50° C. with cooling water. Heating to 105° C. with steam can make the chlorination reaction more complete. The role of bubbling after the reaction is complete is to carry excess thionyl chloride out of the reactor with the air flow, and then to the tail gas absorption tower for treatment.

[0028] In step (2), the molar ratio of aniline-2,5-disulfonic acid to cyanuric chloride is 1-1.15:1, preferably, the molar ratio is 1.03:1, and all the cyanuric chloride is reacted. The more residual cyanuric chloride, the greater the impact on product quality, especially the storage stability. The role of adding a filtration 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, the reaction temperature is 0-5°C, 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 filtering, the pore size of the filter bag is 2-5 microns, and the material is PP non-woven fabric.

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

[0032] Preferably, in step (3), the primary condensate and the mixture of hydroxyethylethylenediamine and hydrochloric acid are added to another reaction kettle at the same time in an equimolar ratio, the pH value is controlled at 5-7 (such as using a 10% NaOH aqueous solution), and the addition is controlled to be completed within 4-5 hours, which is conducive to the primary condensate being able to selectively undergo a substitution reaction with the primary amine of hydroxyethylethylenediamine to generate a secondary condensate.

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

[0034] In step (4), the reaction time is 6 hours, the temperature is 0-15° C. for the first 3 hours, and the pH value is maintained between 8 and 10 (adjusting the pH value with a 30% NaOH aqueous solution); the temperature is 45-55° C. for the next 3 hours, and the pH value is maintained between 10 and 11 (adjusting the pH value with a 30% NaOH aqueous solution), and then the pH value is adjusted to 7.0-7.5 (10% HCl aqueous solution).

[0035] Preferably, in step (4), the temperature is 5 to 10° C. and the pH is 8.5 to 9.5 for the first 3 hours. High temperature and high pH will hydrolyze the sulfonyl chloride groups in the system into sodium sulfonate groups, resulting in a larger proportion of a in the structural formula (1). Low pH is not conducive to the release of secondary amine hydrochloride in the secondary condensation product, which affects the smaller proportion of b in the 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, the color base filter cake and the 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 structural formula (1), thereby further affecting the UV curve, solubility, color stability on different fabrics, color, color and other performances of the product.

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

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

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

[0040] The invention also provides application of the turquoise water-soluble dye in active ink.

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

[0042] The present invention combines the relationship between the product properties of reactive turquoise blue K-GL (CIReactive Blue 14), CIReactive Blue 15 and CIReactive Blue 72, and obtains a turquoise blue water-soluble dye of structural formula (1) by selecting raw material types and controlling process steps. The dye has the advantages of bright color, high color saturation, good filtering performance, stable color on different fabrics, etc.

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

[0044] The preparation method provided by the present invention can effectively reduce by-products by adding a filtering step in the primary condensation and using hydroxyethylethylenediamine for secondary condensation. After being used in the preparation of active ink, the influence of by-products on the storage stability of ink can be reduced. Furthermore, through the post-treatment of step (5), the limit requirements for inorganic salts and calcium and magnesium ions in the active ink are met, and the problem of difficulty in filtering the active ink after preparation is solved after the three-stage filtration. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 UV curves of samples prepared in Examples 1-2 and Comparative Examples 1-3. DETAILED DESCRIPTION

[0046] Example 1

[0047] (a) Sulfonation reaction: 2500 kg of chlorosulfonic acid were added to the dry No. 1 reactor, and stirring was started. 350 kg of copper phthalocyanine were slowly added. The temperature was controlled at below 90 ° C during the feeding process. Stirring was performed for 60 minutes. After the materials were all dissolved, the materials were all transferred to the No. 2 reactor. The No. 2 reactor was started and stirred, and slowly heated with steam. The temperature was raised to 142 ° C in 2 hours, and was kept at 140-142 ° C for 6 hours. After the insulation reaction finished, cooling water was used to cool to 85 ° C. In 2 hours, 175 kg of thionyl chloride was dripped, and the temperature was controlled at 86-87 ° C when the thionyl chloride was dripped. After the thionyl chloride was dripped, stirring was performed for 2 hours. The thionyl chloride was heated to 105 ° C with steam, and was kept at 104-106 ° C for 3 hours. Compressed air was used to blow and bubble from the bottom valve of the No. 2 reactor for 6 hours. After blowing and bubbling, cooling water was used to cool to 50 ° C. to obtain the chlorosulfonated material.

[0048] (b) Dilution and filter pressing: Add sufficient ice and 3000L of water into the dilution pot, slowly add the chlorosulfonated material that has reacted well into the dilution pot, control the temperature of the dilution process at 0-10°C, and add ice appropriately. Stir for 1 hour after the dilution is completed, filter press, wash the filter cake with an appropriate amount of washing water below 5°C, and squeeze it with compressed air for 4 hours after the washing is completed to obtain the color base filter cake.

[0049] (c) Primary condensation: water and ice were added to reaction pot #3, stirring was started, 116 kg of cyanuric chloride was added, and after stirring for 1 hour, aniline-2.5-disulfonic acid solution (175 kg of aniline-2.5-disulfonic acid, 1500 kg of water, pH adjusted to 6-7 with a 30% aqueous solution of NaOH) was added, the reaction temperature was controlled at 0-5°C, and sodium bicarbonate was used to maintain pH at 2-3. The reaction was allowed to proceed for 2-3 hours. The reaction was terminated when no cyanuric chloride remained, and then filtered with a 2-micron filter bag to obtain a primary condensate.

[0050] (d) Secondary condensation: Add appropriate amount of water and ice into the 4# reaction pot, add the primary condensate obtained in step c and the pre-prepared mixture of hydroxyethylethylenediamine and hydrochloric acid (48 kg of hydroxyethylethylenediamine, 500 kg of water, add 30% aqueous hydrochloric acid solution dropwise at a temperature below 18°C ​​until the pH is 6.5-7) into the 4# reaction pot in an equimolar ratio, control the pH value at 5-7 with a 10% aqueous solution of NaOH, and the reaction temperature is 20-25°C. The addition is controlled to be completed within 4-5 hours, and then the reaction is continued at a temperature of 2-3 hours to obtain a secondary condensate.

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

[0052]

[0053] f) The original pulp is passed through a resin adsorption column to remove calcium and magnesium ions; then passed through an ultrafiltration membrane to remove inorganic salts such as sodium chloride and sodium sulfate, and the solid content is concentrated to 20%; then passed through a 2 micron-0.45 micron-0.2 micron filter element for three-stage filtration to remove dust, microorganisms, colloids and other impurities; finally, spray-dried to obtain active dye powder. Recorded as implementation sample 1.

[0054] like Figure 1 As shown in Table 1, the UV curve of the sample 1 prepared into a 20 mg / L dye solution has a ratio of ABS value of the high point on the right to the ABS value of the low point on the left of 2.0.

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

[0056] As shown in Table 3, sample 1 was prepared into an ink with a concentration of 12%. After printing on rayon and pure cotton, the Integ value had 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 1# dry reactor, open and stir, slowly add 350 kg of copper phthalocyanine, temperature is controlled below 90 ℃ in the feeding process, stir for 60 minutes, after the material is all dissolved, the material is all transferred to the 2# reactor, the 2# reactor is opened and stirred, slowly heated with steam, warmed to 140 ℃ in 2 hours, and kept warm at 138-140 ℃ for 6 hours, after the insulation reaction finishes, cool to 85 ℃ with cooling water, drip 210 kg of thionyl chloride in 2 hours, and temperature control 86-87 ℃ when dripping thionyl chloride, stir 2 hours after thionyl chloride is added dropwise, heat to 105 ℃ with steam, and keep warm at 104-106 ℃ for 3 hours, blow and bubble for 6 hours from the bottom valve of the 2# reactor with compressed air, blow and bubble and finish and cool to 50 ℃ with cooling water, obtain the chlorosulfonated material.

[0059] (b) Dilution and filter pressing: Add sufficient ice and 3000L of water into the dilution pot, slowly add the chlorosulfonated material that has reacted well into the dilution pot, control the temperature of the dilution process at 0-10°C, and add ice appropriately. Stir for 1 hour after the dilution is completed, filter press, wash the filter cake with an appropriate amount of washing water below 5°C, and squeeze it with compressed air for 4 hours after the washing is completed to obtain the color base filter cake.

[0060] (c) Primary condensation: water and ice were added to reaction pot #3, stirring was started, 150 kg of cyanuric chloride was added, and after stirring for 1 hour, 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) was added, the reaction temperature was controlled at 0-5°C, and sodium bicarbonate was used to maintain pH at 2-3. The reaction was allowed to proceed for 2-3 hours, and the reaction was terminated when no cyanuric chloride remained.

[0061] (d) Secondary condensation: Add appropriate amount of water, ice and the primary condensate obtained in step c and a prepared mixture of hydroxyethylethylenediamine and hydrochloric acid (wherein, 62 kg of hydroxyethylethylenediamine, 700 kg of water, 30% aqueous hydrochloric acid solution is added dropwise until pH = 6.5-7, temperature below 18°C) into reaction pot #4 in an equimolar ratio, and control the pH value at 5-7 with 10% aqueous NaOH solution. The addition is completed within 4-5 hours; the reaction temperature is 20-25°C, and the reaction time is 2-3 hours to obtain a secondary condensate.

[0062] (e) Tertiary condensation: Add an appropriate amount of ice to the secondary condensate in the 4# reaction pot, control the temperature below 10°C, add the color base filter cake obtained in step b, add 45 kg of ammonium chloride, keep the temperature at 5-10°C for the first 3 hours, and use a 30% NaOH aqueous solution to maintain pH=8.5-9.5; then control the temperature at 45-55°C, and react for 3 hours at a pH value between 10 and 11 as the end point, and adjust the pH value to 7.0-7.5 with a 10% HCl aqueous solution to obtain the active turquoise blue original paste. The dye of formula (3) is obtained:

[0063]

[0064] (f) The original pulp is passed through a resin adsorption column to remove calcium and magnesium ions; then passed through an ultrafiltration membrane to remove inorganic salts such as sodium chloride and sodium sulfate, and the solid content is concentrated to 20%; then passed through a 2 micron-0.45 micron-0.2 micron filter element for three-stage filtration to remove dust, microorganisms, colloids and other impurities; finally, spray-dried to obtain active dye powder. This is recorded as implementation sample 2.

[0065] like Figure 1 As shown in Table 1, the UV curve of the implementation sample 2 prepared into a 20 mg / L dye solution has a ratio of the ABS value of the high point on the right to the ABS value of the low point on the left of 1.3.

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

[0067] As shown in Table 3, sample 2 was formulated into an ink with a concentration of 12%. After printing on rayon and pure cotton, the Integ ratios of pure cotton and rayon were different at different depths. The shallower the depth, the larger the ratio. As the depth increases, the ratio gradually decreases from 2.7 to 2.1, and the synchronization is poor. Therefore, the proportion relationship of a, b, and c in the structure cannot be adjusted casually.

[0068] Comparative Example 1

[0069] According to the synthesis process of Reactive Turquoise Blue K-GL disclosed on page 287 of the Shanghai Dye Production Process Compilation, a batch of raw pulp was prepared, and the raw pulp was then treated through step (f) to obtain comparative sample 1.

[0070] Comparative Example 2

[0071] According to the synthesis process of Example 1 of CN109651844A, a batch of raw pulp was prepared, and the raw pulp was further 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 further processed through step (f) to obtain comparative sample 3.

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

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

[0076]

[0077] From the ABS ratio in Table 1, we can see that the different ratios of the number of a, b, and c groups in the structural formula can be reflected in the UV curve. The larger the ratio is, the larger the number of sulfonic acid groups a is, and the smaller the ratio is. From the ratio, we can infer the approximate proportion of the active group c in the turquoise structure. The different active groups in the structures of samples 1-3 do not affect the test ratio.

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

[0079]

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

[0081] It can be seen from Table 2 that the ratio of the number of a, b, and c groups in the structural formula directly affects the filtration performance. If the proportion of the active group c is large, the solubility of the dye will deteriorate. For example, the c value of the dye synthesized in Comparative Example 1 is about 2.1. The problem of slow filtration speed of the dye can be effectively solved by treating the dyes with different structures in step (f), except for the low solubility of the dye itself due to its structure.

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

[0083]

[0084] The samples were formulated into active inks, and different depths of ink were printed on rayon and pure cotton, and then the Integ values ​​were measured with a colorimeter after drying, steaming, washing, ironing and other processes. From the data analysis in Table 3, it can be seen that the Integ value ratio of pure cotton and rayon in implementation sample 1 is about 2.1, and the ratios at different depths are basically 2.1; but the ratios of implementation sample 2 and comparison sample 3 from low printing depth to high printing depth show a downward trend, from 2.7 to 2.1, and from 3.1 to 2.1, respectively, which shows that the synchronization of depth is poor.

[0085] The above embodiments are only used to explain the inventive concept of the present invention, rather than to limit the protection of the rights of the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiments based on the essence of the technology and method of the present invention are still within the scope of the technology and method solutions of the present invention.

Claims

1. A method for preparing a turquoise water-soluble dye, characterized in that: The preparation method comprises the following steps: (1) copper phthalocyanine is first subjected to a sulfonation reaction with chlorosulfonic acid to obtain a sulfonated intermediate, and then thionyl chloride is added dropwise to cause a chlorination reaction to obtain a chlorosulfonated material, which is then subjected to bubbling, dilution, and filter pressing to obtain a color base filter cake; (2) adding aniline-2,5-disulfonic acid solution to the cyanuric chloride pulp to carry out a primary condensation reaction, and filtering to obtain a primary condensation product after the reaction is complete; (3) subjecting the primary condensation product obtained in step (2) to a secondary condensation reaction with a mixture of hydroxyethylethylenediamine and hydrochloric acid to obtain a secondary condensation product after the reaction is complete; (4) adding the color base filter cake obtained in step (1) and ammonium chloride to the secondary condensate obtained in step (3) to carry out a third condensation reaction, and then adjusting the pH value to obtain an active turquoise blue slurry; (5) The active turquoise blue stock is sequentially subjected to resin adsorption, ultrafiltration membrane desalination, three-stage filtration and spray drying to obtain turquoise blue water-soluble dye powder.

2. The method for preparing the turquoise 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 temperature of the sulfonation reaction is 138-148°C, and the reaction time is 4-6 hours; the temperature of the chlorination reaction is 80-90°C, and the reaction time is 2 hours.

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

4. The method for preparing the turquoise 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°C, and the reaction time is 2-3 hours.

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

6. The method for preparing the turquoise water-soluble dye according to claim 1, characterized in that: In step (3), the molar ratio of the primary condensate to hydroxyethylethylenediamine is 1-1.05:1, and the mixture of hydroxyethylethylenediamine and hydrochloric acid is prepared by the following method: adding aqueous hydrochloric acid solution to hydroxyethylethylenediamine until the pH value is 6.5-7, and controlling the temperature below 18°C ​​during the dropping process; the primary condensate and the mixture of hydroxyethylethylenediamine and hydrochloric acid are added to another reaction container at the same time in an equimolar ratio, during which the pH value is controlled at 5-7, the reaction temperature is 20-25°C, the addition is controlled to be completed within 4-5 hours, and then the reaction is continued at the temperature for 2-3 hours.

7. The method for preparing the turquoise water-soluble dye according to claim 1, characterized in that: In step (4), the three condensation reactions are carried out for 6 hours, with the temperature at 0-15°C for the first 3 hours and the pH value maintained between 8 and 10; the temperature at 45-55°C for the second 3 hours and the pH value maintained between 10 and 11, and then the pH value is adjusted back to 7.0-7.

5.

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

5.

9. The method for preparing the turquoise water-soluble dye according to any one of claims 1 to 8, characterized in that: The structural formula of the turquoise water-soluble dye is as follows: In formula (1), 3.8≤a+b+c≤4, and a≥1.5, b≥1.0, c≥1.0; 10. The method for preparing the turquoise water-soluble dye according to any one of claims 1 to 8, characterized in that: In step (5), the calcium and magnesium ion concentrations of the active turquoise blue pulp are less than 1 mg / L after resin adsorption; after desalination by ultrafiltration membrane, the sodium chloride is less than 50 mg / L, the sodium sulfate is less than 25 mg / L, and the solid content is greater than 20%; the three-stage filtration is a 2 micron-0.45 micron-0.2 micron filter element.

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