High-rubbing-fastness reactive dye and nylon fiber using same

Abstract

The invention discloses a high-rubbing-fastness reactive dye and a nylon fiber using the same, and relates to the technical field of novel printing ink. The invention relates to a high rubbing fastness reactive dye, which is characterized by comprising the following components by mass: 60-85 parts of a reactive dye monomer, 10-25 parts of a dispersant, 5-15 parts of a compound synergist, 3-8 parts of a buffer salt system, 1-4 parts of an anti-coagulant, and 100 parts of a 50% ethanol solution, and the compound synergist comprises the following components: 2-6 parts of a triazine amine compound, and 3-9 parts of a pyrazolone compound. The color brightness of the dye is remarkably improved. By optimizing the molecular structure of the reactive dye monomer, the effect of a chromophoric group is enhanced, and by means of the synergistic effect of the compound synergist, the dye shows brighter and more saturated colors on nylon fibers, and the problem that a traditional dye is dark in color is effectively solved.

Description

Technical Field

[0001] This invention relates to the field of novel ink technology, specifically to a reactive dye with high rubbing fastness and nylon fibers using it. Background Technology

[0002] In the current dyeing field, especially in the dyeing application of nylon fibers, traditional reactive dyes have many problems that urgently need to be solved.

[0003] First, insufficient color vibrancy is a significant drawback. The limited number of chromophores in the molecular structure of traditional reactive dyes results in poor color performance, making it difficult to meet market demands for highly saturated colors. Furthermore, once dye molecules are combined with nylon fibers, they are easily affected by the external environment, causing the colors to become even duller.

[0004] Secondly, the problem of dye aging is prominent. Under the influence of light, heat, and chemicals, the chemical bonds within traditional reactive dye molecules are easily broken, leading to light fading, heat fading, and chemical fading. For example, unstable chemical bonds in dye molecules undergo redox reactions under light, or in high-temperature environments, the vibration of dye molecules intensifies, energy increases, and bond energy weakens, thereby accelerating the decomposition and fading process of dye molecules.

[0005] Furthermore, traditional reactive dyes have low fixation rates on nylon fibers. Because nylon fibers carry a positive charge on their surface, while reactive dyes are typically anionic, their binding ability is limited. This results in insufficient dye adsorption on the fiber surface, leading to a large amount of dye being washed away during post-dyeing treatment. This not only wastes dye but also increases the difficulty and cost of wastewater treatment.

[0006] Furthermore, traditional reactive dyes have poor rubbing fastness. When dyed nylon fibers are subjected to friction, dye particles easily detach from the fiber surface, leading to color transfer or fading. This is mainly because the dye's adhesion to the fiber surface is not strong enough to effectively resist the damage caused by friction.

[0007] Finally, traditional reactive dyes face difficulties in improving colorfastness during the dyeing process of nylon fibers. Colorfastness is one of the important indicators for measuring the quality of dyed products; however, current technologies struggle to maintain the stable color of dyed nylon fibers under conditions such as washing, soaping, perspiration, and sun exposure. This significantly limits the widespread application of reactive dyes in the dyeing of nylon fibers and makes it difficult to meet the demand for high-quality, durable dyed products. Summary of the Invention

[0008] This invention aims to solve the problems of dull color, easy aging, and low rubbing fastness of traditional reactive dyes in nylon fiber dyeing. It provides a reactive dye with high rubbing fastness. By optimizing the dye composition and preparation process, the color brightness, stability, and binding fastness of the dye to nylon fibers are significantly improved, meeting the requirements of high-quality dyeing.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is: a high rubbing fastness reactive dye, comprising the following components in parts by weight: 60-85 parts reactive dye monomer, 10-25 parts dispersant, 5-15 parts compound synergist, 3-8 parts buffer salt system, 1-4 parts anti-agglomeration agent, and 100 parts 50% ethanol solution.

[0010] The compound synergist comprises the following components: triazine amine compounds: 2-6 parts, pyrazolone compounds: 3-9 parts;

[0011] The reactive dye monomer is a compound represented by Formula 1:

[0012]

[0013] In Formula 1, R1 is a substituent, specifically tert-butyl, nitro, halogen, or phenyl.

[0014] Furthermore, the reactive dye monomer is a novel functional dye.

[0015] Furthermore, the dispersant is sodium lignosulfonate.

[0016] Furthermore, the triazine amine compound is melamine cyanurate; and the pyrazolone compound is 1-phenyl-3-methyl-5-pyrazolone.

[0017] Furthermore, the buffer salt system is a sodium dihydrogen phosphate-disodium hydrogen phosphate system.

[0018] Furthermore, the anti-coagulation agent is octylphenol polyoxyethylene ether OP-10.

[0019] Furthermore, the reactive dye monomer is any one of the compounds shown in the following structures:

[0020]

[0021] A method for preparing a reactive dye with high rubbing fastness includes the following steps:

[0022] (1) Add the dispersant to the 50% ethanol solution and stir at 40-60°C until completely dissolved to obtain a dispersion solution;

[0023] (2) Add the reactive dye monomer to the dispersion solution under stirring, keep the temperature at 50-65℃, and grind and disperse thoroughly for 2-4 hours to obtain a uniform slurry;

[0024] (3) Add compound synergist, buffer salt system and anti-coagulant to the homogeneous slurry, and continue stirring for 0.5-1.5 hours to obtain a mixture;

[0025] (4) The mixture is subjected to sand milling or homogenization treatment to control the dye particle size D90 to be less than 2μm, and then filtered to obtain the high rubbing fastness type reactive dye.

[0026] Furthermore, the grinding media used in step (4) is zirconia beads with a particle size of 0.3-1.0 mm.

[0027] Furthermore, step (3) is performed at 50-65°C.

[0028] Application of a high rubbing fastness reactive dye in nylon fiber dyeing.

[0029] The high rubbing fastness reactive dye described in this invention is blue and fluorescent under ultraviolet light.

[0030] A dyeing method for nylon fibers, characterized by using a high rubbing fastness reactive dye as described above, specifically comprising the following steps: adding the reactive dye composition to water at a bath ratio of 1:10-1:40, so that its concentration in the dye bath is 1%-8% owf (based on the weight of nylon fibers); adding a pH adjuster (such as sodium acetate / acetic acid or phosphate) to adjust the initial pH of the dye bath to 7.0-8.0; starting dyeing at 40-50℃, increasing the temperature to 90-105℃ at a rate of 1-2℃ / min; maintaining the dyeing temperature for 30-60 minutes; after maintaining the temperature, slowly cooling to 70-80℃; adding an alkaline fixing agent (such as sodium carbonate, sodium bicarbonate, trisodium phosphate) to adjust the pH of the dye bath to 8.5-10.0, and fixing the color at 70-80℃ for 20-40 minutes; washing with water, soaping (if necessary), washing with water again, and drying.

[0031] Furthermore, the alkaline fixing agent is added in two parts. The first part, 50-70% of the total amount, is added at 65-70°C and the color is fixed for 10 minutes. The second part, the remaining 30-50% of the amount, is added at 75-80°C and the color is fixed for another 15-30 minutes.

[0032] The reactive dye monomer described in this invention is anthraquinone-type reactive dye monomer, which has a large π-conjugated system in its structure, resulting in low electronic transition energy levels. This allows it to absorb longer wavelengths of visible light, exhibiting a bright blue color. The conjugated system of the structure is stable, the quinone group is not easily oxidized or reduced, and the intramolecular hydrogen bonds inhibit photodegradation reactions, significantly improving the dye's resistance to sunlight and heat aging. The synergistic effect of the substituent (R1) is also significant. When R1 is tert-butyl or phenyl, its large-volume structure inhibits dye molecule aggregation, improving solubility and dispersion uniformity; when R1 is nitro / halogen, it enhances the chromatic intensity of anthraquinone and promotes nucleophilic reactions.

[0033] This dye composition addresses the issues of dull color, low fixation, and aging in nylon dyeing through the synergistic effect of specific components: the reactive dye monomer serves as the main component, and its large π-conjugated system achieves low electronic transition energy levels, absorbing long-wavelength light to exhibit a bright blue color (fluorescence under ultraviolet light). Intramolecular hydrogen bonds inhibit photodegradation, and the quinone group significantly enhances resistance to sunlight and heat aging due to its antioxidant properties. The dispersant, as an anionic surfactant, forms a dispersion system in a 50% ethanol solution, adsorbing onto the surface of dye particles to generate electrostatic repulsion and prevent aggregation. It works synergistically with the anti-aggregator to construct a dual stabilization mechanism: OP-10 forms a steric hindrance layer, complementing the dispersant at the hydrophilic / hydrophobic ends, ensuring that the particle size D90 after sand milling is <2μm, improving fiber coverage and reducing the risk of shedding. In the compound synergist, triazine amines act as crosslinking agents, their polyamine structures forming hydrogen / covalent bonds with nylon amide groups to improve color fixation. Pyrazolone compounds act as dyeing auxiliaries, promoting monomer electron transfer to optimize color development while inhibiting oxidative aging. Both react with monomer substituents R1 in a neutral pH environment maintained by a buffer salt system to form stable complexes, preventing quinone hydrolysis and improving bonding efficiency. A 50% ethanol solution serves as a polar medium to ensure initial dispersion of the components. Its moderate volatility maintains a reaction temperature of 40-65℃ to avoid thermal degradation, and its low viscosity supports grinding and filtration processes. Through precise formulation and step-by-step processing, the core technical goals of improved color vibrancy, enhanced rubbing fastness, optimized anti-aging properties, and increased color fixation are ultimately achieved.

[0034] Compared with the prior art, the beneficial effects of the present invention are:

[0035] First, this invention significantly improves the color vibrancy of dyes. By optimizing the molecular structure of reactive dye monomers, the effect of chromophores is enhanced, and with the synergistic effect of compound synergists, the dyes exhibit brighter and more saturated colors on nylon fibers, effectively solving the problem of dull colors in traditional dyes.

[0036] Secondly, this invention significantly improves the rubbing fastness of dyes. By introducing specific dispersants and anti-agglomerates into the formulation, a dual stabilization mechanism is constructed, ensuring the tight bonding of dye particles to the fiber surface, thereby enhancing the dye's resistance to friction and reducing the phenomenon of dye particles falling off due to friction.

[0037] Finally, this invention enhances the stability and anti-aging properties of dyes. The stable structure of the reactive dye monomer, intramolecular hydrogen bonds, and the synergistic effect of the compounding synergists jointly improve the dye's resistance to sunlight, heat, and chemical aging, enabling it to maintain good color stability under various environmental conditions. Attached Figure Description

[0038] Figure 1 This is the NMR spectrum of the reactive dye monomer 1 described in this invention. Detailed Implementation

[0039] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] Preparation Example 1

[0041] Synthesis of reactive dye monomer 1:

[0042]

[0043] Under a nitrogen atmosphere, 15.00 g of starting material 1, 11.22 g of starting material 2, 0.48 g of triphenylphosphine, 0.13 g of palladium on carbon, 7.47 g of triethylamine, and 250 mL of toluene were added to the reaction system. The mixture was heated to 120 °C and refluxed for 12 hours. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered using diatomaceous earth. The filtrate was cooled to room temperature, washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and evaporated to dryness. Silica gel column chromatography was performed using a mixture of petroleum ether and ethyl acetate as eluent. The solution was evaporated to dryness to give 10.01 g of intermediate 1. MS[M+H] + =579.

[0044]

[0045] Under a nitrogen atmosphere, 17.01 g of intermediate 1, 7.00 g of starting material 3, 3.50 g of triethylamine, and 200 mL of DMSO were added to the reaction system. The mixture was heated to 85 °C and reacted for 16 h. After cooling, the pH of the system was adjusted to neutral with 0.1 mol / L HCl. The organic phase was washed five times with water and then twice with saturated NaCl solution. Finally, the combined organic phases were dried over anhydrous Na₂SO₄, evaporated to dryness, and purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent. The solution was evaporated to dryness to obtain 11.65 g of reactive dye monomer 1. MS[M+H] + =835. See MRI. Figure 1 .

[0046] Preparation Example 2

[0047] In Preparation Example 2, reactive dye monomer 2 was prepared by referring to the preparation method in Preparation Example 1, except that raw material 2 was replaced with: The rest is the same as in Preparation Example 1. MS[M+H] + =824.

[0048] Preparation Example 3

[0049] In Preparation Example 2, reactive dye monomer 3 was prepared by referring to the preparation method in Preparation Example 1, except that raw material 2 was replaced with: The rest is the same as in Preparation Example 1. MS[M+H] + =855.

[0050] Example 1

[0051] Preparation of a reactive dye with high rubbing fastness:

[0052] 1. Raw materials:

[0053] 70 parts of reactive dye monomer, selected from: reactive dye monomer 1 prepared in Preparation Example 1;

[0054] 15 parts of dispersant, selected from sodium lignosulfonate;

[0055] The compound synergist, consisting of 10 parts of melamine cyanurate and 6 parts of 1-phenyl-3-methyl-5-pyrazolone;

[0056] Five portions of a buffer salt system were selected from sodium dihydrogen phosphate and disodium hydrogen phosphate, with a pH buffer range of 7.0-7.5.

[0057] Two parts of anti-coagulation agent, selected from: octylphenol polyoxyethylene ether OP-10;

[0058] 100 portions of 50% ethanol solution.

[0059] 2. Preparation method:

[0060] (1) Add 15 parts of sodium lignosulfonate to 100 parts of 50% ethanol solution and stir at 50°C (500 rpm) until completely dissolved to obtain a dispersion solution;

[0061] (2) Under stirring (speed 600 rpm), slowly add 70 parts of reactive dye monomer 1 to the dispersion solution, keep the temperature at 60℃, and use a ball mill (medium is zirconium oxide beads, particle size 0.5 mm) to fully grind and disperse for 3 hours to obtain a uniform slurry;

[0062] (3) Add 2 parts of melamine cyanurate, 5 parts of 1-phenyl-3-methyl-5-pyrazolone, 5 parts of sodium dihydrogen phosphate-disodium hydrogen phosphate buffer system and 2 parts of octylphenol polyoxyethylene ether OP-10 to the uniform slurry, and continue stirring at 60°C for 1 hour (400 rpm) to obtain the mixture.

[0063] (4) Transfer the mixture to a sand mill (using zirconium oxide beads as the medium, with a particle size of 0.5 mm) and sand mill for 2 hours. Control the dye particle size D90 to be less than 2 μm. Filter with a 50-mesh filter to obtain a high rubbing fastness reactive dye.

[0064] 3. A dyeing method for nylon fibers:

[0065] Weigh 100g of nylon fiber sample and pre-wash with deionized water to remove impurities. Add 2L of water to the dye bath at a liquor ratio of 1:20 (fiber weight: dye bath volume), and add the finished dye (4% owf, i.e., 4g of dye). Add a pH adjuster (sodium acetate / acetic acid mixture) to adjust the initial pH of the dye bath to 7.5. Start dyeing at 45℃, increasing the temperature to 95℃ at a rate of 1.5℃ / min. Maintain the dyeing temperature for 45 minutes to ensure the dye is fully adsorbed onto the fiber surface. After maintaining the temperature, slowly lower the temperature to 75℃ (cooling rate 2℃ / min). Add an alkaline fixing agent (sodium carbonate solution, total amount 2g), in two steps: first, add 70% of the fixing agent (1.4g) at 65℃ and fix for 10 minutes; second, add the remaining 30% of the fixing agent (0.6g) at 75℃ and fix for 20 minutes. This step-by-step fixing method improves bonding efficiency. Adjust the pH of the dye bath to 9.0 to enhance the covalent bonding between the dye and the nylon amide groups during the fixation process. Perform the following steps in sequence: water wash (room temperature, 10 minutes), soap wash (neutral soap solution, 50°C, 15 minutes), water wash, and drying (80°C, 30 minutes).

[0066] Example 2

[0067] The preparation of a high rubbing fastness reactive dye and a dyeing method for nylon fibers are described. The preparation method is the same as in Example 1, except that the reactive dye monomer is replaced with reactive dye monomer 2, and the rest is the same as in Example 1.

[0068] Example 3

[0069] The preparation of a high rubbing fastness reactive dye and a dyeing method for nylon fibers are described. The preparation method is the same as in Example 1, except that the reactive dye monomer is replaced with reactive dye monomer 3, and the rest is the same as in Example 1.

[0070] Comparative Example 1

[0071] The preparation of a high rubbing fastness reactive dye and a dyeing method for nylon fibers are described. The preparation method is the same as in Example 1, except that the reactive dye monomer is replaced with comparative compound 1, and the rest is the same as in Example 1.

[0072] Comparative Example 2

[0073] The preparation of a high rubbing fastness reactive dye and a dyeing method for nylon fibers are described. The preparation method is the same as in Example 1, except that the reactive dye monomer is replaced with comparative compound 2, and the rest is the same as in Example 1.

[0074] Comparative Example 3

[0075] The preparation of a high rubbing fastness reactive dye and a dyeing method for nylon fibers are described. The preparation method is the same as in Example 1, except that the reactive dye monomer is replaced with comparative compound 3, and the rest is the same as in Example 1.

[0076] Comparative Example 4

[0077] The preparation of a high rubbing fastness reactive dye and a dyeing method for nylon fibers are described. The preparation method is the same as in Example 1, except that the reactive dye monomer is replaced with comparative compound 4, and the rest is the same as in Example 1.

[0078]

[0079] Performance testing:

[0080] 1. Color Vividness Assessment: The color difference (ΔE) of the dyed fibers was measured using a spectrophotometer (model: X-Rite Color i7). * (Referencing the CIE Labs color space standard.) ΔE * The smaller the value, the closer the color is to standard blue (L). * =30,a * =5,b * =-50), the higher the vividness. The data is shown in Table 2.

[0081] 2. Friction fastness test: According to GB / T 3920-2008, a friction fastness tester (pressure 9N, reciprocating cycles 100 times) was used to conduct wet friction tests. The fastness grade was evaluated from 1 to 5 (grade 5 being the best). The data are shown in Table 2.

[0082] 3. Aging resistance test: A xenon lamp aging tester (irradiance 1.1W / m²) was used. 2 Expose the material to sunlight at 50℃ for 250 hours and assess the color change (ΔE). * The data is shown in Table 2.

[0083] Table 2.

[0084]

[0085] The dyes in the examples exhibit excellent color vibrancy, ΔE * The value is significantly lower, and the color is closer to the ideal standard blue; at the same time, the rubbing fastness grade is high, indicating that the dye has strong adhesion to the nylon fiber and is not easily rubbed off. In addition, the color change after aging is small, ΔE * The limited improvement in color vibrancy highlights the dye's excellent anti-aging stability. In contrast, the comparative example showed a poor trend in all indicators, with significant deviations in color brightness, low rubbing fastness, and severe color degradation after aging. Overall, the dye examples of this invention exhibit more stable and durable performance compared to the comparative examples, particularly demonstrating significant optimization in improving color performance, enhancing rubbing fastness, and inhibiting aging degradation, thus verifying the effective synergistic effect of the inventive components and process.

[0086] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A reactive dye with high rubbing fastness, characterized in that, The product contains the following components in parts by weight: 60-85 parts reactive dye monomer, 10-25 parts dispersant, 5-15 parts compound synergist, 3-8 parts buffer salt system, 1-4 parts anti-agglomerate, and 100 parts 50% ethanol solution. The compound synergist comprises the following components: triazine amine compounds: 2-6 parts, pyrazolone compounds: 3-9 parts; The reactive dye monomer is a compound represented by Formula 1: In Formula 1, R1 is a substituent, specifically tert-butyl, nitro, halogen, or phenyl.

2. The high rubbing fastness reactive dye according to claim 1, characterized in that, The dispersant is sodium lignosulfonate.

3. The high rubbing fastness reactive dye according to claim 1, characterized in that, The triazine amine compound is melamine cyanurate; the pyrazolone compound is 1-phenyl-3-methyl-5-pyrazolone.

4. A high rubbing fastness reactive dye according to claim 1, characterized in that, The buffer salt system is a sodium dihydrogen phosphate-disodium hydrogen phosphate system.

5. A high rubbing fastness reactive dye according to claim 1, characterized in that, The anticoagulant is octylphenol polyoxyethylene ether OP-10.

6. A high rubbing fastness reactive dye according to claim 1, characterized in that, The reactive dye monomer is any one of the compounds shown in the following structures:

7. A method for preparing a high rubbing fastness reactive dye according to any one of claims 1-6, characterized in that, Includes the following steps: (1) Add the dispersant to the 50% ethanol solution and stir at 40-60°C until completely dissolved to obtain a dispersion solution; (2) Add the reactive dye monomer to the dispersion solution under stirring, keep the temperature at 50-65℃, and grind and disperse thoroughly for 2-4 hours to obtain a uniform slurry; (3) Add compound synergist, buffer salt system and anti-coagulant to the homogeneous slurry, and continue stirring for 0.5-1.5 hours to obtain a mixture; (4) The mixture is subjected to sand milling or homogenization treatment to control the dye particle size D90 to be less than 2μm, and then filtered to obtain the high rubbing fastness type reactive dye.

8. The method for preparing a high rubbing fastness reactive dye according to claim 7, characterized in that, The grinding media used in step (4) are zirconia beads with a particle size of 0.3-1.0 mm.

9. The method for preparing a high rubbing fastness reactive dye according to claim 7, characterized in that, Step (3) is performed at 50-65°C.

10. The application of a high rubbing fastness reactive dye as described in any one of claims 1-6 in the dyeing of nylon fibers.

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