Dye capable of dyeing spandex as well as preparation method and application of dye

Abstract

The invention discloses a dye capable of dyeing spandex as well as a preparation method and application thereof, and belongs to the field of dye chemical industry, the dye capable of dyeing spandex at least comprises a compound shown as a formula (I), in the formula, R1 is independently selected from C1-4 alkyl; r2 is independently selected from H, methyl and acetamido; n = 1 or n = 2; d is independently selected from H, Cl, Br and CN, and R3 and R4 are respectively and independently selected from H, Cl, Br and CN. After the dye prepared by the invention is used for coloring spandex and carrying out reduction cleaning, the spandex has bright light color and is not easy to fade, and various fastness requirements can be met.

Description

Technical Field

[0001] This invention relates to the field of dye chemical technology, and more specifically, to a dye that can dye spandex, its preparation method, and its application. Background Technology

[0002] Spandex (polyurethane elastic fiber) has become a key material for improving fabric comfort due to its excellent elasticity and resilience, and its application in the clothing industry is becoming increasingly widespread. However, the dyeing problem of spandex has always been a major technical bottleneck restricting its high-end applications. Traditional spandex dyeing faces three major industry challenges: low dye uptake after fabric treatment, poor color fastness (especially heat migration fastness), and insufficient color vibrancy. These problems are particularly prominent in dark-colored fabrics.

[0003] Currently, spandex dyeing mainly employs two systems: disperse dyes and acid dyes, but each has significant drawbacks. Disperse dyes, due to their non-polar characteristics, have some compatibility with the hydrophobic components of spandex and can be dyed via van der Waals forces, but they suffer from poor color fastness and severe thermal migration. Acid dyes (especially metal complex dyes) can bind to a small number of urethane matrix cationic sites in spandex under weakly acidic conditions, but the number of dye sites on ordinary spandex is limited, resulting in a low dyeing rate, and they also face the challenge of insufficient fastness. Reactive dyes and cationic dyes are essentially unable to dye conventional spandex due to the charge repulsion between them and the spandex molecular structure.

[0004] Furthermore, in practical applications, spandex-containing elastic fabrics often exhibit a "white exposure" phenomenon during stretching or molding, where undyed spandex core fibers are exposed, severely affecting the product's appearance quality, especially noticeable in dark-colored fabrics such as black and dark red. During the high-temperature setting process after spandex dyeing, the dye migrates from the fiber's interior to the outer surface, easily causing color changes and staining.

[0005] Therefore, it is necessary to provide a dye with high thermal migration fastness that can dye spandex. Summary of the Invention

[0006] To address the problems existing in the prior art, the present invention aims to provide a dye for dyeing spandex. After dyeing spandex and performing reduction cleaning, the spandex has a bright color and is not easy to fade, and can meet various fastness requirements.

[0007] To solve the above problems, the present invention adopts the following technical solution.

[0008] A dye for dyeing spandex, comprising at least one compound as shown in formula (I):

[0009]

[0010] Among them, R1 is independently selected from C 1-4 Alkyl groups;

[0011] R2 is independently selected from H, methyl, and acetamino; n = 1 or n = 2;

[0012] D is selected independently.

[0013] Among them, R3 and R4 are independently selected from H, Cl, Br and CN, respectively.

[0014] Furthermore, R1 stands for Me or Et.

[0015] Furthermore, the dyes for dyeable spandex prepared in this application include at least one compound with the structure shown in (Formula I-1)-(Formula I-12):

[0016]

[0017]

[0018]

[0019] This application also provides a method for preparing one of the dyes for dyeing spandex, the chemical equation of which is shown below:

[0020]

[0021] Where R1 represents C 1-4 Alkyl; R2 is independently selected from H, methyl and acetamido; n = 1 or n = 2;

[0022] The preparation steps are as follows:

[0023] S1: After adding the compound shown in formula (II), the compound shown in formula (III) and soda ash to the flask, the mixture is heated under reflux to obtain the coupled component;

[0024] S2: The diazonium component reacts with nitrosylsulfuric acid in sulfuric acid to yield the diazonium salt;

[0025] S3: The coupling component obtained in step S1 and the diazonium salt obtained in step S2 are coupled under acidic conditions to obtain the target dye.

[0026] Preferably, n=1.

[0027] Furthermore, in step S1, the molar ratio of the compound shown in formula (II), the compound shown in formula (III), and soda ash is 1:1-1.5:0.5-1; in step S2, the molar ratio of the diazo component and nitrosyl sulfuric acid is 1:1-1.05.

[0028] Furthermore, the reaction temperature of step S1 is 90-110℃ and the reaction time is 12-24 hours; the reaction temperature of step S2 is 0-30℃ and the reaction time is 1-5 hours; the reaction temperature of step S3 is -5-25℃ and the reaction time is 1-5 hours.

[0029] Furthermore, in step S2, the diazo component is p-nitroaniline, 2-chloro-p-nitroaniline, 2-amino-5-nitrothiazole, 2-cyano-p-nitroaniline, 2,6-dichloro-p-nitroaniline, 2,6-dibromo-p-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2-cyano-4-nitro-6-bromoaniline, or 3-amino-5-nitrobenzisisothiazole.

[0030] Furthermore, step S3 also includes the addition of excipients, namely, sulfamethoxazole and aminosulfonic acid.

[0031] This application also provides the application of the aforementioned dyeable spandex dye in dyeing.

[0032] This application also provides the application of the aforementioned dyeable spandex in spandex dyeing.

[0033] This application also provides a disperse black dye, including the aforementioned dyeable spandex dye.

[0034] Compared with the prior art, the advantages of this invention are:

[0035] The dyes provided in this solution, after being applied to spandex and then reduced and cleaned, result in virtually no color fading of the spandex. Furthermore, the dyed spandex exhibits a brighter and more vibrant color, meeting various fastness requirements, particularly heat migration fastness. Detailed Implementation

[0036] Example 1:

[0037] Preparation:

[0038] Add 450g water, 225g N-methylaniline, 133.6g soda ash, and 451g 2,4-dichlorobenzyl chloride to a flask, heat to 100-105℃, reflux for 16 hours, adjust the pH to neutral with hydrochloric acid, cool to crystallize, and filter to obtain 550g of the coupling component, with a yield of 98.3%.

[0039] 160g of sulfuric acid and 132g of 40% nitrosyl sulfuric acid were added to a flask. 83g of 2,6-dichloro-p-nitroaniline was slowly added while maintaining the temperature at 25-30℃. After the addition was complete, the temperature was maintained for 3 hours to obtain the diazonium salt.

[0040] Add 400g of water and 110g of coupling component to a beaker, beat at high speed for 1 hour, add 1g of Pingpingjia O and 2g of aminosulfonic acid, add ice to cool to 0℃, add diazonium salt dropwise to start coupling, react for 3 hours after addition, then crystallize, filter, and wash with water to obtain 185g of orange dye.

[0041] Example 2:

[0042] Preparation:

[0043] Add 450g water, 225g N-methylaniline, 133.6g soda ash, and 451g 2,4-dichlorobenzyl chloride to a flask, heat to 100-105℃, reflux for 16 hours, adjust the pH to neutral with hydrochloric acid, cool to crystallize, and filter to obtain 550g of the coupling component, with a yield of 98.3%.

[0044] 160g of sulfuric acid and 132g of 40% nitrosyl sulfuric acid were added to a flask. 119g of 2,6-dibromo-p-nitroaniline was slowly added while maintaining the temperature at 25-30℃. After the addition was complete, the temperature was maintained for 3 hours to obtain the diazonium salt.

[0045] Add 400g of water and 110g of coupling component to a beaker, beat at high speed for 1 hour, add 1g of Pingpingjia O and 2g of aminosulfonic acid, add ice to cool to 0℃, add diazonium salt dropwise to start coupling, react for 3 hours after addition, crystallize and filter, wash with water to obtain 220g of orange dye.

[0046] Example 3:

[0047] Preparation:

[0048] Add 450g water, 225g N-methylaniline, 133.6g soda ash, and 451g 2,6-dichlorobenzyl chloride to a flask, heat to 100-105℃, reflux for 16 hours, adjust the pH to neutral with hydrochloric acid, cool to crystallize, and filter to obtain 532g of the coupling component, with a yield of 95.1%.

[0049] Add 160g of sulfuric acid and 132g of 40% nitrosyl sulfuric acid to a flask, control the temperature at 25-30℃, and slowly add 101g of 2-chloro-6-bromo-4-nitroaniline. After the addition is complete, keep the temperature for 3 hours to obtain the diazonium salt.

[0050] Add 400g of water and 110g of coupling component to a beaker, beat at high speed for 1 hour, add 1g of Pingpingjia O and 2g of aminosulfonic acid, add ice to cool to 0℃, add diazonium salt dropwise to start coupling, react for 3 hours after addition, after coupling is completed, convert crystal to filter, wash with water to obtain 191g of orange dye.

[0051] Example 4:

[0052] Preparation:

[0053] Add 450g water, 284g N-ethyl-m-toluidine, 133.6g soda ash, and 451g 2,4-dichlorobenzyl chloride to a flask, heat to 100-105℃, reflux for 16 hours, adjust the pH to neutral with hydrochloric acid, cool to crystallize, and filter to obtain 605g of coupling component 3, with a yield of 97.9%.

[0054] 433g of sulfuric acid and 130g of 40% nitrosyl sulfuric acid were added to a flask. 96.8g of 2-cyano-4-nitro-6-bromo-aniline was slowly added while maintaining the temperature at 5-10℃. After the addition was complete, the temperature was kept at that temperature for 3 hours to obtain the diazonium salt.

[0055] Add 400g of water and 120g of coupling component 3 to a beaker, beat at high speed for 1 hour, add 1g of Pingpingjia O and 2g of aminosulfonic acid, add ice to cool to 0℃, add diazonium salt dropwise to start coupling, after the reaction is complete, react for 3 hours, crystallize and filter, wash with water to obtain 204g of purple dye.

[0056] Example 5:

[0057] Preparation:

[0058] Add 450g water, 225g N-ethyl-m-toluidine, 133.6g soda ash, and 451g 2,6-dichlorobenzyl chloride to a flask, heat to 100-105℃, reflux for 16 hours, adjust the pH to neutral with hydrochloric acid, cool to crystallize, and filter to obtain 532g of the coupled component, with a yield of 95.1%.

[0059] 184g of sulfuric acid and 132g of 40% nitrosyl sulfuric acid were added to a flask. 80g of 3-amino-5-nitro-benzisothiazole was slowly added while maintaining the temperature at 0-5℃. After the addition was complete, the temperature was kept at 3 hours to obtain the diazonium salt.

[0060] Add 400g of water and 120g of coupling component to a beaker, beat at high speed for 1 hour, add 1g of Pingpingjia O and 2g of aminosulfonic acid, add ice to cool to 0℃, add diazonium salt dropwise to start coupling, react for 3 hours after addition, crystallize and filter, wash with water to obtain 173g of blue dye.

[0061] Application Example 1:

[0062] High-temperature and high-pressure dyeing of polyester-spandex fabrics was carried out: 2.5g of dye from Example 1 was dispersed in 97.5mL of water, and 12mL of the dye was mixed with 88mL of water. The pH of the dye bath was adjusted to 4.0±0.2 with acetic acid. At the same time, 10g of polyester-spandex fabric was added for dyeing. The temperature was raised to 130℃ in 40min and kept at that temperature for 50min. After cooling, the dyed fabric was removed, and the fabric was subjected to reduction washing, water washing, and setting to obtain an orange dye sample.

[0063] Application Example 2:

[0064] The difference between this application example and application example 1 is that the dye in example 1 of application example 1 is replaced with the dye involved in example 2.

[0065] Application Example 3:

[0066] The difference between this application example and application example 1 is that the dye in example 1 of application example 1 is replaced with the dye involved in example 3.

[0067] Application Example 4:

[0068] The difference between this application example and application example 1 is that the dye in example 1 of application example 1 is replaced with the dye involved in example 4.

[0069] Application Example 5:

[0070] The difference between this application example and application example 1 is that the dye in example 1 of application example 1 is replaced with the dye involved in example 5.

[0071] Comparative Example 1:

[0072] The difference between this comparative example and Application Example 1 is that the dye in Example 1 of Application Example 1 is replaced with an existing disperse orange dye.

[0073] Comparative Example 2:

[0074] The difference between this comparative example and Application Example 1 is that the dye in Example 1 of Application Example 1 is replaced with an existing disperse violet dye.

[0075] Comparative Example 3:

[0076] The difference between this comparative example and Application Example 1 is that the dye in Example 1 of Application Example 1 is replaced with an existing disperse blue dye.

[0077] Experimental Example 1:

[0078] Fastness tests were conducted on the polyester-spandex fabric samples obtained from Examples 1-5 and Comparative Examples 1-3, respectively. The specific tests were as follows: color fastness to sublimation (ISO105-P01 180℃ x30S); color fastness to rubbing (ISO105-X12); color fastness to washing (AATCC-61-2A); and color fastness to acid perspiration (AATCC15). The test results are shown in Table 1.

[0079] Table 1 shows the fastness test results of the dyed samples obtained from Application Examples 1-5 and Comparative Examples 1-3.

[0080]

[0081]

[0082] Test Example 2:

[0083] The thermal migration fastness of polyester-spandex fabric samples obtained from Application Examples 1-5 and Comparative Examples 1-3 was determined. The testing method referred to GB / T 44161-2024 "Determination of Thermal Migration of Disperse Dyes". The evaluation method was based on the provisions of GB / T 251-2008 "Textiles - Tests for Color Fastness - Assessment of Staining - Gray Scale". The evaluated level was used as the result of the thermal migration fastness test. The test results are shown in Table 2.

[0084] Table 2 shows the results of the thermal migration fastness determination of the dyed samples obtained from Application Examples 1-5 and Comparative Examples 1-3.

[0085] Thermal migration fastness Application Example 1 4-5 Application Example 2 4-5 Application Example 3 4-5 Comparative Example 1 4 Application Example 4 4-5 Comparative Example 2 4 Application Example 5 4-5 Comparative Example 3 3-4

[0086] Data from Test Examples 1 and 2 show that the dyeable spandex dye prepared in this application exhibits key color fastness indicators such as sublimation fastness, rubbing fastness, washing fastness, and acid perspiration fastness after dyeing that are no lower than those of existing dyes; in some test methods, it even surpasses existing dyes in a few aspects. For example, when testing sublimation fastness according to ISO 105-P01 180℃ x 30S standard, the cotton staining rating and polyester staining rating of the dyed samples in Comparative Examples 1-3 are 4 and 2-3, respectively; while the cotton staining rating of the dyed samples in Application Examples 1-5 is 4-5; the polyester staining rating of Application Examples 1, 3, and 5 is 3-4, and the polyester staining rating of Application Examples 2 and 4 is 4; significantly higher than Comparative Examples 1-3. This indicates that the sublimation fastness (ISO 105-P01 180℃) of the dyeable spandex dye prepared in this application is superior. x30S) is superior; in addition, the color fastness rating of the dyed samples obtained in Application Examples 1-5 after the test (AATCC-61-2A) was 4-5, while the color fastness rating of the dyed samples in Comparative Examples 1-3 was 4, which was significantly lower than that in Application Examples 1-5. This shows that the color fastness of the dyed spandex involved in this application is not obvious after the test, and the color fastness (AATCC-61-2A) is superior.

[0087] Furthermore, the heat migration fastness ratings of the dyed samples involved in Application Examples 1-5 are all higher than those of the dyed samples involved in Comparative Examples 1-3, and some properties are even significantly higher than those of the comparative examples. For example, the heat migration fastness rating of the dyed sample in Application Example 5 is 4-5, while the heat migration fastness rating of the dyed sample in Comparative Example 3 is 3-4, which is significantly lower than that of Application Example 5. This shows that the heat migration fastness of the dyes for dyeable spandex involved in this application is superior to that of existing dyes for dyeable spandex.

[0088] In summary, the fastness ratings of the dyes for dyeable spandex prepared in this application are no lower than those of existing dyes.

[0089] Test Example 3:

[0090] The dyes involved in Examples 1-5 and Comparative Examples 1-3 were used to dye polyester-spandex fabrics, and the color intensity of the fabric samples before and after reduction cleaning was compared. The results are shown in Table 3.

[0091] Table 3. Results of color intensity measurements of polyester / spandex fabrics before and after dyeing, reduction, and washing using the dyes involved in Examples 1-5 and Comparative Examples 1-3.

[0092]

[0093]

[0094] As shown in the table above, the dyeing intensity of the dyes in Examples 1-5 on the polyester-spandex fabrics was significantly higher than that of the dyes involved in Comparative Examples 1-3. This indicates that the dyes prepared in this application for dyeing spandex have a superior dyeing effect. Furthermore, the dyes in Examples 1-5, after dyeing and reducing the polyester-spandex fabrics, exhibited higher intensity and more stable color properties. Therefore, the dyes prepared in these examples are superior to the comparative examples in both dyeing effect and color stability.

Claims

1. A dye for dyeing spandex, characterized in that: It includes at least one compound as shown in formula (I): Among them, R1 is independently selected from C 1-4 Alkyl groups; R2 is independently selected from H, methyl, and acetamido; n = 1 or n = 2; D is selected independently. Among them, R4 and R5 are independently selected from H, Cl, Br and CN, respectively.

2. The dye for dyeing spandex according to claim 1, characterized in that: R1 represents Me or Et.

3. The dye for dyeing spandex according to claim 1, characterized in that: It includes at least one compound with the structure shown in (Formula I-1)-(Formula I-12): (Formula I-1) (Formula I-2) (Formula I-3) (Formula I-4) (Formula I-5) (Formula I-6) (Formula I-7) (Formula I-8) (Formula I-9) (Formula I-10) (Formula I-11) (Formula I-12) 4. A method for preparing a dye for dyeing spandex according to any one of claims 1-3, characterized in that: The chemical equation is shown below: Where R1 represents C 1-4 Alkyl; R2 is independently selected from H, methyl and acetamido; n = 1 or n = 2; The preparation steps are as follows: S1: After adding the compound shown in formula (II), the compound shown in formula (III) and soda ash to the flask, the mixture is heated under reflux to obtain the coupled component; S2: The diazonium component reacts with nitrosylsulfuric acid in sulfuric acid to yield the diazonium salt; S3: The coupling component obtained in step S1 and the diazonium salt obtained in step S2 are coupled under acidic conditions to obtain the target dye.

5. A method for preparing a dye for dyeing spandex according to claim 4, characterized in that: In step S1, the molar ratio of the compound shown in formula (II), the compound shown in formula (III), and soda ash is 1:1-1.5:0.5-1. In step S2, the molar ratio of the diazo component to nitrosylsulfuric acid is 1:1-1.

05.

6. A method for preparing a dye for dyeing spandex according to claim 4, characterized in that: The reaction temperature of step S1 is 90-110℃ and the reaction time is 12-24 hours; the reaction temperature of step S2 is 0-30℃ and the reaction time is 1-5 hours; the reaction temperature of step S3 is -5-25℃ and the reaction time is 1-5 hours.

7. A method for preparing a dye for dyeing spandex according to claim 4: In step S2, the diazo component is p-nitroaniline, 2-chloro-p-nitroaniline, 2-amino-5-nitrothiazole, 2-cyano-p-nitroaniline, 2,6-dichloro-p-nitroaniline, 2,6-dibromo-p-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2-cyano-4-nitro-6-bromoaniline, or 3-amino-5-nitrobenzisisothiazole.

8. The application of a dye for dyeing spandex according to any one of claims 1-3 in dyeing.

9. The application of a dye for spandex as described in any one of claims 1-3 in spandex dyeing.

10. A disperse black dye, characterized in that: The dye includes the dyeable spandex as described in any one of claims 1-3.

Images