Navy blue dye compound, synthetic method thereof and application of navy blue dye compound in moist crosslinking process

Abstract

The invention relates to the field of textile printing and dyeing, in particular to a navy blue dye compound as well as a synthesis method and application thereof in a moist crosslinking process, and the structural formula of the navy blue dye compound is as follows: # imgabs0. The dye has excellent color stability, and effectively fills up the blank of black and blue series dyes in a moist crosslinking process and yarn-dyed pure cotton non-ironing woven fabric.

Description

Technical Field

[0001] The present application relates to the field of textile printing and dyeing, and more specifically, to a navy blue dye compound and a synthesis method thereof and an application thereof in a moisture cross-linking process. Background Art

[0002] The moisture-crosslinking and wrinkle-free finishing process is a textile post-finishing process. It achieves wrinkle-free, wrinkle-resistant and wear-resistant effects by fully mixing cotton yarn and resin and / or finishing agent under certain temperature / humidity conditions. However, during the current processing, dyes will change color, especially some black and blue varieties are very sensitive to moisture-crosslinking process conditions, which seriously limits its product application.

[0003] Especially in the dyeing application of color-woven pure cotton non-iron woven fabrics, color-woven pure cotton non-iron woven fabrics are natural fabric products, because of their high-end style, high count and high density, soft hand feeling, comfortable wearing, excellent air permeability, easy care and other characteristics, they are favored by consumers; However, color control in the production process of the above-mentioned fabrics is more difficult than other finishing processes. Combined with the two, many fabric manufacturers are deterred from this. Therefore, there are no black and / or blue varieties of color-dyed pure cotton non-iron woven fabrics treated with a moisture cross-linking process on the market. In summary, a navy blue dye compound with excellent color stability in a moisture cross-linking process and a color-dyed pure cotton non-iron woven fabric is provided. Summary of the invention

[0004] In order to fill the application gap of black and / or blue varieties in tide cross-linking process and color-woven pure cotton non-ironing woven fabrics, the present application specifically provides a navy blue dye compound and its synthesis method and application.

[0005] In the first aspect, the present application provides a navy blue dye compound, the structural formula of which is as follows:

[0006] In a second aspect, the present application provides a method for synthesizing a navy blue dye compound, comprising the following preparation steps: S1. Disperse cyanuric chloride into ice water, add H acid aqueous solution, mix and stir, and then adjust the pH to 4-5 to obtain dispersed solution A; S2, dropwise add the aqueous solution of the para-ester acid to the dispersed solution A, and maintain the pH of the solution at 5.5-6.5 during the dropwise addition process, and stir to obtain a reaction solution B, wherein the reaction solution B contains a compound of the structural formula X; S3, adding sodium nitrite and concentrated hydrochloric acid to the aqueous solution of compound y, where compound y is a coupling compound of sulfonated para-ester and clevulinic acid, and stirring at 45-55° C. for 3-4 hours to obtain reaction solution C; S4, adding the reaction solution C obtained in S3 to the reaction solution B obtained in S2, maintaining the pH at 5.5-6.5 during the addition, stirring for 2-3 hours, and then vacuum concentrating or spray drying the reaction solution to obtain the target reactant, i.e., a navy blue dye compound; The reaction scheme of the above-mentioned preparation steps is as follows:

[0007] Preferably, the molar ratio of cyanuric chloride to H acid in S1 is 1:(0.8-1.2).

[0008] Preferably, the specific steps of S1 are as follows: Cyanuric chloride was dispersed and added into ice water at a molar ratio of (0.01-0.02):1, and then an aqueous solution of H acid with a molar concentration of 0.2-0.3 mol / L was added. After mixing and stirring, the pH was adjusted to 4-5 with an aqueous solution of NaOH to obtain a dispersed solution A.

[0009] Preferably, the specific steps of S2 are as follows: Add a 0.1-0.3 mol / L aqueous solution of the para-ester acid to the dispersed solution A, and maintain the pH of the solution at 5.5-6.5 by adding a 2 mol / L aqueous solution of NaOH during the dropping process, and stir for 5-8 hours to obtain a reaction solution B, which contains a compound with the structural formula X.

[0010] Preferably, the molar ratio of compound y, sodium nitrite and concentrated hydrochloric acid in S3 is 1:(1.0-1.5):(8.0-8.5).

[0011] Preferably, the specific steps of S4 are as follows: The reaction solution C obtained in S3 is added dropwise to the reaction solution B obtained in S2. During the addition, the pH is maintained at 5.5-6.5 with NaOH solution. After stirring for 2-3 hours, the reaction solution is vacuum concentrated or spray-dried to obtain the target reactant, i.e., the navy blue dye compound.

[0012] In a third aspect, the present application provides a navy blue dye compound and / or the use of a navy blue dye compound obtained by any of the above-mentioned synthesis methods in a moisture cross-linking process.

[0013] In a fourth aspect, the present application provides a dyeing process, comprising the following steps: 1) providing a dye bath comprising the above-mentioned navy blue dye compound and / or a navy blue dye compound obtained by any of the above-mentioned synthesis methods; 2) Immerse the fabric to be dyed in the dye bath in 1) at a constant temperature of 60±2°C at a bath ratio of 1:10-15; 3) After dyeing for 30±1min, add 15-20g / L of sodium carbonate and continue the reaction for 60±2min, then wash with water, soap wash at 98℃ for 10-20min, wash with water, and dry to complete the dyeing.

[0014] In a fifth aspect, the present application provides a navy blue dye bath composition, comprising the above-mentioned navy blue dye compound and / or a navy blue dye compound obtained by any of the synthesis methods and a dyeing auxiliary, wherein the dyeing auxiliary is anhydrous sodium sulfate and / or sodium bicarbonate.

[0015] In summary, the present application has the following beneficial effects: 1) The dye compound, through its symmetry The group has obtained excellent color stability, making it effectively applicable to moisture cross-linking process and color-dyed pure cotton non-iron woven fabrics; In addition, due to its navy blue color, it fills the gap in the dyeing of black and blue series in the field of tide cross-linking process and / or yarn-dyed pure cotton non-iron woven fabrics, significantly broadening its application and market value; 2) The present application optimizes the conditions and steps of the synthesis to a great extent, and the purity and yield of the obtained product are high, and there are basically no by-products, which is conducive to large-scale production and has high industrial value. The synthesis process also has the advantages of high efficiency, low pollution and low emissions; 3) The dyeing process in the present application simplifies the implementation steps and conditions, and also reduces the color sensitivity of black and / or blue series by constant temperature dyeing based on auxiliaries. The combination of the two reduces the difficulty of producing special color fabrics, and after dyeing, it is suitable for most moisture cross-linking processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a dyeing process flow chart in this application; Figure 2 This is a comparison diagram after Example 1 (1.0% owf / moisture crosslinking) in this application; Figure 3 This is a comparison diagram after Example 1 (4.0% owf / moisture crosslinking) in this application; Figure 4 This is a comparison chart after Example 1 (0.5% / 2.0owf / liquid ammonia mercerization) in this application. DETAILED DESCRIPTION

[0017] The following is combined with the embodiment and Figure 1-4 This application is described in further detail.

[0018] Example 1 A navy blue dye compound, the specific structural formula of which is:

[0019] S1, first disperse 19g of cyanuric chloride into ice water consisting of 75g of water and 75g of ice, then add 30g of H acid dissolved in 350g of water H acid solution, mix and stir for 2 hours, and adjust the pH to 4 with NaOH aqueous solution to obtain dispersed solution A; S2, taking 29 grams of the para-ester acid, dissolving it in 500 grams of water, and then dropping the resulting solution into the dispersed solution A within 50 minutes, maintaining the solution pH at 6 with a 2N NaOH aqueous solution during the dropping process, and then stirring for 6 hours to obtain a reaction solution B, which contains a compound of structural formula X; S3, taking 56 g of the acid form of the compound of structural formula Y (a coupling compound of sulfonated para-ester and clevulinic acid), dissolving it in 500 g of water to obtain an aqueous solution of compound Y; Then, 9.6 g of sodium nitrite, 50 g of water and 30 g of hydrochloric acid were added to the aqueous solution of compound y, and the mixture was stirred at 50° C. for 3 hours, and the excess sodium nitrite was eliminated with aminosulfonic acid to obtain reaction solution C; S4. Add the reaction solution C obtained in S3 dropwise to the reaction solution B obtained in S2. During the dropping process, the pH is maintained at 6.0 by using NaOH solution. After stirring for 3 hours, when the reaction is complete, the reaction solution is vacuum concentrated or spray-dried to obtain a navy blue dye compound. The purity of the compound is 89.7% after analysis.

[0020] The reaction scheme of the above-mentioned preparation steps is as follows:

[0021] Comparative Example 1 A navy blue dye compound, which is different from Example 1 in that the structural formula is as follows:

[0022] Comparative Example 2 A navy blue dye compound, which is different from Example 1 in that the structural formula is as follows:

[0023] Performance testing First, the navy blue dye compound prepared in each embodiment and comparative example is selected as the test object for standby use, and then its rating and color difference (D65 10-DL* / Da* / Db* / DE*) are tested respectively after dyeing according to the following specific dyeing method to evaluate its moisture cross-linking fastness and liquid ammonia mercerization fastness. The specific dyeing method and corresponding test steps and conditions are as follows: Fabric to be dyed, specifically poplin 40X40 110X90X; Staining method, see Figure 1 , the specific steps are as follows: 1) providing a dye bath containing the navy blue dye compound prepared in the embodiment or comparative example for standby use, wherein the amount of the navy blue dye compound used is 0.5%, 1.0%, 2.0%, and 4.0% owf (dye relative to fabric weight), respectively; 2) Immersing the fabric to be dyed in the dye bath prepared in 1) at a constant temperature of 60° C. at 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 in a soap solution of ARGACELSW CONC 2g / l and ARGAQUEST ARSK 4g / l and soap wash at 98°C for 20 minutes, wash with water, and dry at 70°C to complete dyeing.

[0024] When the finishing process of the fabric to be dyed is a moisture cross-linking process, the specific steps are as follows: 1) First, the dyed fabric is dipped into a resin finishing agent at room temperature and pH 2 by a two-dipping and two-padding method, wherein the resin finishing agent comprises the following components: 200g / L low formaldehyde resin finishing agent NDL, 100g / L catalyst MCI LIQ; 2) Dry the impregnated fabric at 80°C x 33s to a moisture content of 8%, then wrap it with plastic film and stack it (30°C x 24h); 3) Wash with water, neutralize with soap (10 g / L soda ash, 3 g / L detergent SW, 60°C), wash with water, pickle with acid (1 g / L HAc), wash with water and dry.

[0025] When the finishing process of the fabric to be dyed is liquid ammonia mercerizing process, the specific steps are as follows: 1) soaking the dyed fabric in liquid ammonia to remove dirt and impurities on the surface of the fabric, and then drying the fabric at 80°C x 33s to a moisture regain of 2%; 2) The dried fabric is mercerized by the Italian LAfer PermaFix liquid ammonia finishing machine: it is dipped in liquid ammonia for 30±2s at -3℃ and negative pressure, then enters the recovery tank, washed with water at 50℃ and dried at 80℃ to complete the liquid ammonia mercerization process.

[0026] Then, the rating and color difference (D65 10-DL* / Da* / Db* / DE*) were tested using the gray scale for evaluating color change in GB 250-1995, the gray scale in ISO 105 / A02-1993, and the Datacolor 800 colorimeter, and then their moisture cross-linking fastness and liquid ammonia mercerization fastness were evaluated.

[0027] The navy blue dye compounds in the above-mentioned Example 1 and Comparative Examples 1-2 were extracted and treated according to the above-mentioned moisture cross-linking or liquid ammonia mercerizing finishing method. The rating and color difference (D65 10-DL* / Da* / Db* / DE*) of the fabric to be dyed at different concentrations were tested respectively, and the average value of the test results was recorded in the following table.

[0028] Table 1: Test results of moisture crosslinking fastness properties of Example 1 and Comparative Examples 1-2 Table 2: Test results of liquid ammonia mercerization fastness properties of Example 1 and Comparative Examples 1-2 From the above table and Figure 2-4 It can be seen that the dye compound prepared in Example 1 has excellent moisture crosslinking fastness after dyeing. When the dye dosage is 1.0% owf, the rating is 4, DL* is 0.88, Da* is 0.16, Db* is 0.74, and DE* is 0.68; when the dye dosage is 4.0% owf, the rating is 4, DL* is -1.24, Da* is -0.52, Db* is 0.22, and DE* is 0.95; It also has excellent liquid ammonia mercerization fastness. When the dye dosage is 0.5% owf, the rating is 4, DL* is -0.6, Da* is 0.54, Db* is 1.9, and DE* is 1.22; when the dye dosage is 2.0% owf, the rating is 4, DL* is -2.13, Da* is 0.21, Db* is 1.81, and DE* is 1.67; In summary, the various properties of Example 1, namely, color stability and fastness, are improved to varying degrees compared to Comparative Examples 1-2. Combining the above data, the following conclusions and analyses can be drawn: Only the symmetric The base navy blue dye compound has excellent color stability, so it is suitable for tide cross-linking process and color-woven pure cotton non-iron woven fabrics; In contrast, Comparative Examples 1 and 2, which have very similar main structures, still do not have the corresponding color stability. As can be seen from the examples, the conditions and steps for their synthesis are relatively simple, and the purity and yield of the obtained products are high, and there are basically no by-products, which is conducive to large-scale production.

[0029] Embodiment 2-5 A navy blue dye compound, which differs from Example 1 in that the material feed ratio in S1 and the purity of the final product are different, as shown in the following table.

[0030] Table: Material feed ratio and final product purity in S1 in Example 2-5 Embodiment 6-10 A navy blue dye compound, which differs from Example 1 in that the molar ratio of the reaction raw materials in S3 and the purity of the final product are different, as shown in the following table.

[0031] Table: Molar ratio of reaction raw materials in S3 and purity of final product in Examples 6-10.

[0032] It can be seen from the above table that the navy blue dye compounds prepared in Examples 2-10 all have a relatively high purity, with a purity of ≧80.0%, which means that the conditions and steps of the synthesis are optimized to a great extent while ensuring the purity of the obtained product, and there are basically no by-products, which is conducive to large-scale production.

[0033] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A navy blue dye compound, characterized in that The structural formula is as follows: 。 2. The method for synthesizing the navy blue dye compound according to claim 1, characterized in that: The method comprises the following preparation steps: S1. Disperse cyanuric chloride into ice water, add H acid aqueous solution, mix and stir, and then adjust the pH to 4-5 to obtain dispersed solution A; S2, dropwise add the aqueous solution of the para-ester acid to the dispersed solution A, and maintain the pH of the solution at 5.5-6.5 during the dropwise addition process, and stir to obtain a reaction solution B, wherein the reaction solution B contains a compound of the structural formula X; S3, adding sodium nitrite and concentrated hydrochloric acid to the aqueous solution of compound y, where compound y is a coupling compound of sulfonated para-ester and clevulinic acid, and stirring at 45-55° C. for 3-4 hours to obtain reaction solution C; S4, adding the reaction solution C obtained in S3 to the reaction solution B obtained in S2, maintaining the pH at 5.5-6.5 during the addition, stirring for 2-3 hours, and then vacuum concentrating or spray drying the reaction solution to obtain the target reactant, i.e., a navy blue dye compound; The reaction scheme of the above-mentioned preparation steps is as follows: 。 3. The method for synthesizing a navy blue dye compound according to claim 2, characterized in that: The molar ratio of cyanuric chloride to H acid in S1 is 1:(0.8-1.2).

4. The method for synthesizing a navy blue dye compound according to claim 3, characterized in that: The specific steps of S1 are as follows: Disperse cyanuric chloride into ice water at a molar ratio of (0.01-0.02):1, then add H acid aqueous solution with a molar concentration of 0.2-0.3 mol / L, mix and stir, and adjust the pH to 4-5 with NaOH aqueous solution to obtain dispersed solution A.

5. The method for synthesizing a navy blue dye compound according to claim 2, characterized in that: The specific steps of S2 are as follows: Add a 0.1-0.3 mol / L aqueous solution of the para-ester acid to the dispersed solution A, and maintain the pH of the solution at 5.5-6.5 by adding a 2 mol / L aqueous solution of NaOH during the dropping process, and stir for 5-8 hours to obtain a reaction solution B, which contains a compound with the structural formula X.

6. The method for synthesizing a navy blue dye compound according to claim 2, characterized in that: The molar ratio of compound y, sodium nitrite and concentrated hydrochloric acid in S3 is 1:(1.0-1.5):(8.0-8.5).

7. The method for synthesizing a navy blue dye compound according to claim 2, characterized in that: The specific steps of S4 are as follows: The reaction solution C obtained in S3 is added dropwise to the reaction solution B obtained in S2. During the addition, the pH is maintained at 5.5-6.5 with NaOH solution. After stirring for 2-3 hours, the reaction solution is vacuum concentrated or spray-dried to obtain the target reactant, i.e., the navy blue dye compound.

8. Use of the navy blue dye compound described in claim 1 and / or the navy blue dye compound prepared by the synthesis method described in any one of claims 2 to 4 in a moisture cross-linking process.

9. A dyeing process, characterized in that: The following steps are involved: 1) Providing a dye bath comprising the navy blue dye compound described in claim 1 and / or the navy blue dye compound prepared by the synthesis method described in any one of claims 2 to 4; 2) Immerse the fabric to be dyed into the dye bath in 1) at a constant temperature of 60±2℃ with a bath ratio of 1:10-15; 3) After dyeing for 30±1min, add 15-20g / L of sodium carbonate and continue the reaction for 60±2min. Then wash with water, soap wash at 98℃ for 10-20min, wash with water, and dry to complete the dyeing.

10. A navy blue dye bath composition, characterized in that The invention comprises the navy blue dye compound described in claim 1 and / or the navy blue dye compound 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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