A washing and fixing resistant emulsion, its preparation method and application

Abstract

This invention discloses a wash-resistant color-fixing emulsion, its preparation method, and its application. By mass, the raw materials for preparing this wash-resistant color-fixing emulsion include 3-8 parts of a vinyl-containing polyurethane prepolymer, 1-4 parts of carboxyl-modified silicone oil, 0.5-2 parts of a crosslinking agent, 0.8-2.5 parts of an emulsifier, 0.1-0.5 parts of a neutralizing agent, 0.004-0.024 parts of an initiator, and 80-95 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with a diisocyanate compound, and then reacted with hydroxyethyl acrylate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. Because the raw materials for preparing the wash-resistant color-fixing emulsion of this invention contain both the vinyl-containing polyurethane prepolymer and the carboxyl-modified silicone oil, they can form an interpenetrating network-ion trap structure through simultaneous crosslinking and molecular entanglement, imparting excellent hand feel, wash fastness, and rubbing fastness to fabrics.

Description

Technical Field

[0001] This invention relates to the field of color-fixing agents for textiles, and more particularly to a wash-resistant color-fixing emulsion, its preparation method, and its application. Background Technology

[0002] In the textile industry, nylon fabrics are widely used due to their excellent mechanical properties and wearing comfort. However, after repeated washing, the dyes in nylon fabrics dyed with cationic dyes are prone to detachment and migration from the fiber surface, resulting in fading and staining of the fabric, which seriously affects the appearance and service life of the product.

[0003] Most mainstream nylon color-fixing agents currently rely on a single electrostatic interaction to bind with the dye, that is, color fixation is achieved through the attraction between the cationic groups in the color-fixing agent and the anionic groups of the dye molecules. However, these color-fixing agents have obvious drawbacks: First, the color-fixing effect is singular, relying solely on chemical bonding force. Under the mechanical friction and water flow impact of repeated washing, the electrostatic bonding is easily lost, leading to a decrease in color-fixing effect; second, some color-fixing agents affect the fabric's hand feel, making the fabric surface stiff and reducing elasticity; third, their wash resistance stability is insufficient, and they are easily decomposed or desorbed in complex washing environments such as acids, alkalis, and salts, making it difficult to meet the requirements for long-term use.

[0004] In existing technologies, silicone-based finishing agents can improve the hand feel of fabrics but lack color-fixing functions; polyurethane-based finishing agents have good film-forming properties, but it is difficult to balance wash resistance and softness; while interpenetrating polymer network (IPN) structures are used to improve material stability, no related technologies have been reported to combine them with "ion trap" functions to construct a dual color-fixing system. In addition, authoritative standards such as the EU REACH regulation and OEKO-TEX® Standard 100 have increasingly stringent requirements for the environmental protection and safety of textile auxiliaries, and the sensitization and residual solvent problems of traditional color-fixing agents also limit their application.

[0005] Therefore, developing a novel finishing agent that combines long-lasting color fixation, excellent hand feel, and environmental stability to solve the problem of cationic dye migration in nylon fabrics through the dual effects of physical network trapping and electrostatic adsorption has become an urgent need in the field of textile auxiliaries. Summary of the Invention

[0006] The purpose of this invention is to provide a wash-resistant color-fixing emulsion, its preparation method, and its application. The raw materials for preparing this wash-resistant color-fixing emulsion contain two components: a vinyl-containing polyurethane prepolymer and a carboxyl-modified silicone oil. Through the synergistic effect of synchronous crosslinking and molecular entanglement, an interpenetrating network-ion trap structure is formed, which imparts excellent hand feel, wash fastness, and rubbing fastness to the fabric.

[0007] To achieve the above objectives, the first aspect of the present invention provides a wash-resistant and color-fixing emulsion, wherein the raw materials for preparation, by mass parts, include 3-8 parts of a vinyl-containing polyurethane prepolymer, 1-4 parts of a carboxyl-modified silicone oil, 0.5-2 parts of a crosslinking agent, 0.8-2.5 parts of an emulsifier, 0.1-0.5 parts of a neutralizing agent, 0.004-0.024 parts of an initiator, and 80-95 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with a diisocyanate compound to obtain a polyurethane prepolymer, and then adding hydroxyethyl acrylate to react. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid.

[0008] Compared with existing technologies, the raw materials for preparing the wash-resistant color-fixing emulsion of the present invention contain a vinyl-containing polyurethane prepolymer and a carboxyl-modified silicone oil. These two components can form a dense interpenetrating network-ion trap structure through synchronous crosslinking and molecular entanglement, giving the fabric excellent hand feel, wash fastness, and rubbing fastness. Specifically, firstly, the vinyl-containing polyurethane prepolymer undergoes a free radical polymerization reaction under high-temperature baking conditions to form a three-dimensional crosslinked polyurethane network. Since the raw materials for preparing the vinyl-containing polyurethane prepolymer include hydroxyl-terminated polyether silicone oil, its polyether silicone oil segments can give the prepolymer a certain degree of elasticity, making the formed polyurethane network a rigid-elastic skeleton structure that can provide a structural basis for physically trapping dyes. The carboxyl-modified silicone oil can give the fabric a soft and smooth hand feel. At the same time, in the presence of a crosslinking agent, the urethane groups in the prepolymer and the carboxyl groups in the carboxyl-modified silicone oil undergo covalent bonding, thereby anchoring the silicone oil segments in the polyurethane network. The two molecules interpenetrate and entangle with each other due to the cross-linking motion of their molecular chains, forming an interpenetrating network structure. This effectively overcomes the poor compatibility problem caused by the large difference in solubility between polyurethane and silicone oil, thus giving the wash-resistant color-fixing emulsion of the present invention better stability. Furthermore, on the one hand, the interpenetrating network structure formed by the two molecules can achieve physical encapsulation and trapping of dye molecules; on the other hand, the residual carboxyl anions in the interpenetrating network structure can also fix the dye through electrostatic adsorption, achieving a dual color-fixing effect. This gives the wash-resistant color-fixing emulsion of the present invention excellent hand feel, wash fastness, and rubbing fastness.

[0009] Specifically, the mass fractions of the vinyl-containing polyurethane prepolymer may be, but are not limited to, 3, 4, 5, 6, 7, or 8 parts; the mass fractions of the carboxyl-modified silicone oil may be, but are not limited to, 1, 2, 3, or 4 parts; the mass fractions of the crosslinking agent may be, but are not limited to, 0.5, 1, 1.5, or 2 parts; the mass fractions of the emulsifier may be, but are not limited to, 0.8, 1, 1.5, 2, or 2.5 parts; and the mass fractions of the neutralizing agent may be, but are not limited to, 0.1 parts. The mass fractions of the initiator can be, but are not limited to, 0.004, 0.005, 0.008, 0.010, 0.012, 0.015, 0.018, 0.02, 0.022, or 0.024 parts; the weight fractions of the deionized water can be, but are not limited to, 80, 82, 84, 85, 88, 90, 92, 94, or 95 parts.

[0010] As a preferred technical solution, the molar ratio of isocyanate groups in the diisocyanate compound of the present invention to hydroxyl groups in the hydroxyl-terminated polyether silicone oil is 1.2~1.5:1. Specifically, the molar ratio of isocyanate to hydroxyl groups can be, but is not limited to, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1, or 1.5:1.

[0011] As a preferred technical solution, the molar ratio of hydroxyethyl acrylate to isocyanate groups in the polyurethane prepolymer of the present invention is 1.0~1.1:1. Specifically, the molar ratio of hydroxyethyl acrylate to isocyanate groups is 1.0:1, 1.02:1, 1.04:1, 1.05:1:1, 1.06:1, 1.08:1, and 1.1:1.

[0012] As a preferred technical solution, the molar ratio of mercaptoacetic acid to vinyl groups in the vinyl-terminated silicone oil of the present invention is 1.1 to 1.3:1. Specifically, the molar ratio of mercaptoacetic acid to vinyl groups is 1.1:1, 1.15:1, 1.2:1, 1.25:1, or 1.3:1.

[0013] As a preferred technical solution, the carboxyl content in the carboxyl-modified silicone oil of the present invention is 0.5 mmol / g to 1.5 mmol / g. Specifically, the carboxyl content in the carboxyl-modified silicone oil of the present invention can be, but is not limited to, 0.5 mmol / g, 0.6 mmol / g, 0.7 mmol / g, 0.8 mmol / g, 0.9 mmol / g, 1.0 mmol / g, 1.1 mmol / g, 1.2 mmol / g, 1.3 mmol / g, 1.4 mmol / g, or 1.5 mmol / g. By controlling the carboxyl content in the carboxyl-modified silicone oil within this range, the present invention allows the carboxyl groups to participate in cross-linking reactions and form an interpenetrating network structure with the vinyl-containing polyurethane prepolymer. Furthermore, the remaining carboxyl groups can ionize to form carboxyl anions during fabric finishing, thereby fixing the dye through electrostatic adsorption.

[0014] As a preferred technical solution, the hydroxyl-terminated polyether silicone oil of the present invention is prepared by hydrosilylation reaction of a vinyl-terminated functionalized polyether with a hydrogen-containing silicone oil. Specifically, the number-average molecular weight of the hydrogen-containing silicone oil can be 5000 g / mol to 8000 g / mol, and the active hydrogen content can be 0.1% to 0.3%; the vinyl-terminated functionalized polyether is prepared by reflux reaction of the hydroxyl-terminated polyether and acrylic acid under the conditions of a catalyst, a polymerization inhibitor, and a dehydrating agent. More specifically, the hydroxyl-terminated polyether can be PTMG2000, the catalyst can be p-toluenesulfonic acid, the polymerization inhibitor can be hydroquinone, and the dehydrating agent can be toluene; wherein, the mass ratio between PTMG2000, acrylic acid, p-toluenesulfonic acid, and hydroquinone is 100:8~10:0.5~0.8:0.1~0.2, and the amount of toluene used can be 50 mL to 80 mL.

[0015] As a preferred technical solution, the diisocyanate compound of the present invention is selected from at least one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

[0016] As a preferred technical solution, the number-average molecular weight of the terminal vinyl silicone oil of the present invention is 5000 g / mol to 8000 g / mol. Specifically, the molecular weight of the terminal vinyl silicone oil can be, but is not limited to, 5000 g / mol, 5500 g / mol, 6000 g / mol, 6500 g / mol, 7000 g / mol, 7500 g / mol, or 8000 g / mol.

[0017] As a preferred technical solution, the crosslinking agent of the present invention is selected from aziridine crosslinking agents. Specifically, the aziridine crosslinking agent can be trimethylolpropane-tris[3-(2-methylaziridine)]propionate. The trimethylolpropane-tris[3-(2-methylaziridine)]propionate used, as a multifunctional aziridine crosslinking agent, has high ring strain and high reactivity, and can rapidly open the ring at a relatively low baking temperature. Simultaneously, it can covalently bond at multiple points with the vinyl-containing polyurethane prepolymer, carboxyl-modified silicone oil, and amino and hydroxyl groups on nylon fibers of the present invention, forming a dense and stable interpenetrating network structure, significantly improving wash resistance and abrasion resistance.

[0018] As a preferred technical solution, the neutralizing agent of the present invention is selected from acetic acid. The addition of acetic acid can improve the compatibility of the wash-resistant color-fixing emulsion of the present invention, thereby enhancing the stability of the emulsion.

[0019] As a preferred technical solution, the emulsifier of the present invention is a composite emulsifier composed of a nonionic emulsifier and anionic emulsifier. Specifically, the nonionic emulsifier may be at least one of emulsifiers XP70, AEO-9, isomeric tridecyl alcohol polyoxyethylene ether 1307, and F68; the anionic emulsifier may be at least one of emulsifiers SDS, LAS, SAS-60, and AES. More specifically, the emulsifier of the present invention is a composite emulsifier composed of emulsifier XP70 and emulsifier SDS, wherein the mass ratio of emulsifier XP70 to emulsifier SDS is 1.2 to 1.7:1. As an example, the mass ratio of emulsifier XP70 to emulsifier SDS may be, but is not limited to, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, or 1.7:1. The combination of emulsifier XP70 and emulsifier SDS can effectively improve the mechanical stability and acid, alkali and salt resistance of the wash-resistant color-fixing emulsion of the present invention.

[0020] As a preferred technical solution, the initiator of the present invention is a combination of di-tert-butyl peroxide (DTBP) and azobisisobutyronitrile (ABVN) in a mass ratio of 1:1.

[0021] A second aspect of this invention provides a method for preparing a wash-resistant color-fixing emulsion, comprising the steps of: (1) Mix the prescribed amount of emulsifier and deionized water in a reaction vessel to form an emulsion system; (2) Slowly add vinyl-containing polyurethane prepolymer and carboxyl-modified silicone oil to the emulsion system, then add a neutralizer to adjust the pH of the system, and perform high-speed stirring pre-emulsion under heating conditions to form a pre-emulsion; (3) After the pre-emulsion is cooled to a certain temperature, a crosslinking agent and an initiator are added and stirred at low speed to obtain a wash-resistant color-fixing emulsion.

[0022] As a preferred technical solution, the preparation method of the wash-resistant color-fixing emulsion of the present invention specifically includes the following steps: (1) The emulsifier and deionized water of the formula amount are stirred evenly in a reaction vessel at room temperature and a stirring speed of 300 rpm to 500 rpm to form an emulsion system; (2) Simultaneously and slowly add vinyl-containing polyurethane prepolymer and carboxyl-modified silicone oil to the emulsion system, then add acetic acid to adjust the pH of the system to 6.0~6.5, raise the temperature to 40℃~50℃ and stir for 20min~40min at a stirring speed of 1200rpm~1500rpm to form a pre-emulsion. (3) Cool the pre-emulsion to 30℃~35℃, add crosslinking agent and initiator, stir at 550rpm~650rpm for 5~15min to disperse it evenly, and then stir at 300rpm~500rpm for 10min~30min to obtain a wash-resistant color-fixing emulsion crude product. Filter the wash-resistant color-fixing emulsion crude product to remove impurities and obtain a wash-resistant color-fixing emulsion.

[0023] As a preferred technical solution, the preparation of the vinyl-containing polyurethane prepolymer of the present invention includes first reacting terminal hydroxyl polyether silicone oil and diisocyanate compound under the condition of organotin catalyst to obtain polyurethane prepolymer, and then adding hydroxyethyl acrylate to polyurethane prepolymer and heating reaction to obtain the prepolymer.

[0024] Specifically, the preparation of the vinyl-containing polyurethane prepolymer includes mixing a diisocyanate compound with a hydroxyl-terminated polyether silicone oil at a -NCO / -OH molar ratio of 1.2 to 1.5, adding 0.05 to 0.1 parts by mass of catalyst DBTDL, and reacting at 75°C to 85°C for 2 to 3 hours to obtain a polyurethane prepolymer; adding hydroxyethyl acrylate (HEA) to the polyurethane prepolymer, wherein the molar ratio of HEA to the remaining -NCO in the polyurethane prepolymer is 1.0 to 1.1, reacting at 60 to 70°C for 1 to 2 hours, and cooling to room temperature to obtain the vinyl-containing polyurethane prepolymer. More specifically, the -NCO / -OH molar ratio can be, but is not limited to, 1.2, 1.3, 1.4, or 1.5; the mass fraction of the catalyst DBTDL can be, but is not limited to, 0.05, 0.06, 0.07, 0.08, 0.09, or 1.0 parts; the reaction temperature can be, but is not limited to, 75℃, 76℃, 77℃, 78℃, 79℃, 80℃, 81℃, 82℃, 83℃, 84℃, or 85℃; and the reaction time can be, but is not limited to, 1.0 parts. The reaction time is limited to 2h, 2.5h, and 3h; the molar ratio of HEA to the remaining -NCO can be, but is not limited to, 1.0:1, 1.02:1, 1.04:1, 1.05:1:1, 1.06:1, 1.08:1, and 1.1:1; the reaction temperature can be, but is not limited to, 60℃, 61℃, 62℃, 63℃, 64℃, 65℃, 66℃, 67℃, 68℃, 69℃, and 70℃; and the reaction time can be, but is not limited to, 1h, 1.5h, and 2h.

[0025] As a preferred technical solution, the preparation of the carboxyl-modified silicone oil of the present invention includes reacting terminal vinyl silicone oil with mercaptoacetic acid under ultraviolet light irradiation at room temperature. Specifically, the molar ratio of mercaptoacetic acid to vinyl groups in the terminal vinyl silicone oil is 1.1~1.3:1. As an example, the molar ratio of mercaptoacetic acid to vinyl groups in the terminal vinyl silicone oil can be, but is not limited to, 1.1:1, 1.2:1, or 1.3:1; the ultraviolet light irradiation wavelength can be, but is not limited to, 365 nm; and the room temperature reaction time is 4h~6h. As an example, the room temperature reaction time can be, but is not limited to, 4h, 5h, or 6h.

[0026] The third aspect of this invention provides the application of the aforementioned wash-resistant color-fixing emulsion or the wash-resistant color-fixing emulsion prepared according to the aforementioned method for preparing the wash-resistant color-fixing emulsion in the color-fixing finishing of nylon fabrics. Specifically, the application of this invention includes: (1) preparing the aforementioned wash-resistant color-fixing emulsion into a finishing solution with a solid content of 5% to 10%; (2) using a padding process, fully immersing the nylon fabric dyed with cationic dyes in the finishing solution for 5 to 10 minutes, and then controlling the pick-up rate at 70% to 85% by a padding machine; (3) pre-drying the padded fabric at 80 to 100°C for 3 to 5 minutes, and then baking it at 140 to 160°C for 2 to 5 minutes, so that the finishing solution of this invention cross-links on the surface of the nylon fibers to form an interpenetrating network (IPN); (4) equilibrating the finished nylon fabric at standard temperature and humidity (20±2°C, 65±5% RH) for 24 hours.

[0027] Compared with existing technologies, the wash-resistant color-fixing emulsion of this invention, when used to finish nylon fabrics, utilizes the highly reactive amino groups in nylon. These amino groups can undergo ring-opening reactions with the three-membered ring structure of aziridine crosslinking agents, forming a covalently bridging structure of fiber-N-CH2-CH2-N-color-fixing emulsion. This structure firmly anchors the IPN network to the fiber surface, preventing the color-fixing agent film from detaching during washing and fundamentally improving wash resistance. Furthermore, the amide bonds in the nylon molecular chain form multiple hydrogen bonds with the urethane groups and carboxyl groups in the IPN network, and the hydrophobic segments of the nylon fiber generate van der Waals forces with the silicone oil segments in the IPN network. This further enhances the interfacial bonding between the color-fixing agent film and the nylon fiber, reducing mechanical peeling during washing. Simultaneously, in the baking and washing environment, the terminal amino groups of the nylon protonate to form cations, which can react with the anions (-COO-) generated in the IPN network. - ) and cationic dye molecules (D + ) Forms fibers -NH3 + -- - OOC-IPN--D + The ion bridge structure not only strengthens the bond between the IPN network and the fiber, but also further fixes the dye molecules, achieving synergistic locking of the fiber, fixing agent, and dye, thereby endowing the nylon fabric with excellent wash fastness and rubbing fastness after finishing.

[0028] The preparation process of this invention leaves no toxic solvent residues, and the crosslinking agents and auxiliaries used all meet the environmental requirements of OEKO-TEX® Standard 100. The emulsion is non-allergenic and suitable for high-end fields such as infant and toddler textile products. The finishing process uses an aqueous system, resulting in low emissions of volatile organic compounds (VOCs), which is in line with the concept of green production. Detailed Implementation

[0029] To better illustrate the purpose, technical solution, and beneficial effects of this invention, the invention will be further described below with reference to specific embodiments. It should be noted that the methods described below are further explanations of this invention and should not be construed as limiting it.

[0030] In the embodiments and comparative examples of the present invention, the hydroxyl-terminated polyether silicone oil was prepared by the following method: 100g PTMG2000, 9g acrylic acid, 0.6g p-toluenesulfonic acid, 0.2g hydroquinone, and 80mL toluene were added to a four-necked flask equipped with a water separator and a reflux condenser. The mixture was heated to 118°C and refluxed for 5 hours under nitrogen protection, during which water was separated by the water separator. After the reaction was completed, the temperature was lowered to 60°C, and the pH was neutralized to 7 with a 5% sodium carbonate solution. The mixture was then washed three times with water to remove salt and unreacted acrylic acid. Then, vacuum distillation (100℃, -0.095MPa) was performed to remove toluene and water, yielding vinyl-terminated functionalized polyether (number average molecular weight ≈2100, vinyl content 0.48mmol / g). 300g of hydrogen-containing silicone oil (number average molecular weight 6000g / mol, hydrogen content 0.2%) and 24.2g of chloroplatinic acid solution (platinum concentration 1000ppm) were added to the vinyl-terminated functionalized polyether and reacted at 85℃ for 5h. Low-boiling substances were removed by vacuum distillation to obtain hydroxyl-terminated polyether silicone oil.

[0031] Example 1 This embodiment provides a wash-resistant color-fixing emulsion, which, by mass, comprises 3 parts of vinyl-containing polyurethane prepolymer, 1 part of carboxyl-modified silicone oil, 0.5 parts of trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 0.5 parts of emulsifier XP70, 0.3 parts of emulsifier SDS, 0.1 parts of acetic acid, 0.02 parts of initiator (DTBP:ABVN=1:1), and 94.55 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with hexamethylene diisocyanate, and then reacted with hydroxyethyl acrylate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. The molar ratio of isocyanate groups in hexamethylene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.2:1; the molar ratio of isocyanate groups in hydroxyethyl acrylate to polyurethane prepolymer is 1.0:1; the molar ratio of mercaptoacetic acid to vinyl groups in vinyl-terminated silicone oil is 1.1:1; the molecular weight of vinyl-terminated silicone oil is 5000; and the carboxyl content in carboxyl-modified silicone oil is 1.0 mmol / g.

[0032] The preparation method of this wash-resistant color-fixing emulsion includes the following steps: (1) The emulsifier XP70, emulsifier SDS and deionized water in the formula amount are stirred evenly in a reaction vessel at room temperature and a stirring speed of 400 rpm to form an emulsion system; (2) Simultaneously and slowly add vinyl-containing polyurethane prepolymer and carboxyl-modified silicone oil to the emulsion system, then add acetic acid to adjust the pH of the system to 6.5, heat to 45°C and pre-emulsify for 20 min at a stirring speed of 1500 rpm to form a pre-emulsion. (3) Cool the pre-emulsion to 32°C, add trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate and initiator, stir at 600 rpm for 10 min to make it evenly dispersed, and then stir at 400 rpm for 20 min to obtain a wash-resistant color-fixing emulsion crude product. Filter the wash-resistant color-fixing emulsion crude product through a 200-mesh filter to remove impurities and obtain a wash-resistant color-fixing emulsion.

[0033] The preparation of the vinyl-containing polyurethane prepolymer includes mixing hexamethylene diisocyanate and hydroxyl-terminated polyether silicone oil at a -NCO / -OH molar ratio of 1.2, adding 0.05 parts by mass of catalyst DBTDL, and reacting at 80°C for 2 hours to obtain a polyurethane prepolymer; adding hydroxyethyl acrylate (HEA) to the polyurethane prepolymer, with a HEA to the remaining -NCO molar ratio in the polyurethane prepolymer of 1.0:1, reacting at 65°C for 1 hour, introducing crosslinkable vinyl double bonds through end-capping with hydroxyethyl acrylate, and cooling to room temperature to obtain a vinyl-containing polyurethane prepolymer.

[0034] The preparation of carboxyl-modified silicone oil involves reacting terminal vinyl silicone oil with mercaptoacetic acid (the molar ratio of mercaptoacetic acid to vinyl is 1.1:1) under ultraviolet light (wavelength 365nm) at room temperature for 5 hours.

[0035] Example 2 This embodiment provides a wash-resistant color-fixing emulsion, which, by mass, is prepared from 5 parts of vinyl-containing polyurethane prepolymer, 2 parts of carboxyl-modified silicone oil, 1 part of trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 0.8 parts of emulsifier XP70, 0.5 parts of emulsifier SDS, 0.2 parts of acetic acid, 0.02 parts of initiator (DTBP:ABVN=1:1), and 90.4 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with hexamethylene diisocyanate, and then reacted with hydroxyethyl acrylate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. The molar ratio of isocyanate groups in hexamethylene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.2:1; the molar ratio of isocyanate groups in hydroxyethyl acrylate to polyurethane prepolymer is 1.0:1; the molar ratio of mercaptoacetic acid to vinyl groups in vinyl-terminated silicone oil is 1.1:1; the molecular weight of vinyl-terminated silicone oil is 5000; and the carboxyl content in carboxyl-modified silicone oil is 1.0 mmol / g.

[0036] The wash-resistant color-fixing emulsion was prepared according to the preparation method of Example 1.

[0037] Example 3 This embodiment provides a wash-resistant color-fixing emulsion, which, by mass, is prepared from 6 parts of vinyl-containing polyurethane prepolymer, 3 parts of carboxyl-modified silicone oil, 1.5 parts of trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 1 part of emulsifier XP70, 0.7 parts of emulsifier SDS, 0.3 parts of acetic acid, 0.02 parts of initiator (DTBP:ABVN=1:1), and 87.35 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with hexamethylene diisocyanate, and then reacted with hydroxyethyl acrylate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. The molar ratio of isocyanate groups in hexamethylene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.2:1; the molar ratio of isocyanate groups in hydroxyethyl acrylate to polyurethane prepolymer is 1.0:1; the molar ratio of mercaptoacetic acid to vinyl groups in vinyl-terminated silicone oil is 1.1:1; the molecular weight of vinyl-terminated silicone oil is 5000; and the carboxyl content in carboxyl-modified silicone oil is 1.0 mmol / g.

[0038] The wash-resistant color-fixing emulsion was prepared according to the preparation method of Example 1.

[0039] Example 4 This embodiment provides a wash-resistant color-fixing emulsion. By mass, the raw materials include 7 parts of vinyl-containing polyurethane prepolymer, 3.5 parts of carboxyl-modified silicone oil, 1.8 parts of trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 1.2 parts of emulsifier XP70, 0.9 parts of emulsifier SDS, 0.4 parts of acetic acid, 0.02 parts of initiator (DTBP:ABVN=1:1), and 85.02 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with hexamethylene diisocyanate, and then reacted with hydroxyethyl acrylate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. The molar ratio of isocyanate groups in hexamethylene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.2:1; the molar ratio of isocyanate groups in hydroxyethyl acrylate to polyurethane prepolymer is 1.0:1; the molar ratio of mercaptoacetic acid to vinyl groups in vinyl-terminated silicone oil is 1.1:1; the molecular weight of vinyl-terminated silicone oil is 5000; and the carboxyl content in carboxyl-modified silicone oil is 1.0 mmol / g.

[0040] The wash-resistant color-fixing emulsion was prepared according to the preparation method of Example 1.

[0041] Example 5 This embodiment provides a wash-resistant and color-fixing emulsion. By mass, the raw materials include 8 parts of vinyl-containing polyurethane prepolymer, 4 parts of carboxyl-modified silicone oil, 2 parts of trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 1.5 parts of emulsifier XP70, 1 part of emulsifier SDS, 0.5 parts of acetic acid, 0.02 parts of initiator (DTBP:ABVN=1:1), and 82.8 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with hexamethylene diisocyanate, and then reacted with hydroxyethyl acrylate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. The molar ratio of isocyanate groups in hexamethylene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.2:1; the molar ratio of isocyanate groups in hydroxyethyl acrylate to polyurethane prepolymer is 1.0:1; the molar ratio of mercaptoacetic acid to vinyl groups in vinyl-terminated silicone oil is 1.1:1; the molecular weight of vinyl-terminated silicone oil is 5000; and the carboxyl content in carboxyl-modified silicone oil is 1.0 mmol / g.

[0042] The wash-resistant color-fixing emulsion was prepared according to the preparation method of Example 1.

[0043] Example 6 The difference between this embodiment and Example 3 is that 1.5 parts of toluene diisocyanate trimer are used instead of 1.5 parts of trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate. Example 7 This embodiment provides a wash-resistant color-fixing emulsion, which, by mass, is prepared from 6 parts of vinyl-containing polyurethane prepolymer, 3 parts of carboxyl-modified silicone oil, 1.5 parts of trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 1 part of emulsifier XP70, 0.7 parts of emulsifier SDS, 0.3 parts of acetic acid, 0.02 parts of initiator (DTBP:ABVN=1:1), and 87.35 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with toluene diisocyanate, and then reacted with hydroxyethyl acrylate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. The molar ratio of isocyanate groups in toluene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.4:1; the molar ratio of isocyanate groups in hydroxyethyl acrylate to polyurethane prepolymer is 1.1:1; the molar ratio of mercaptoacetic acid to vinyl groups in vinyl-terminated silicone oil is 1.2:1; the molecular weight of vinyl-terminated silicone oil is 6000; and the carboxyl content in carboxyl-modified silicone oil is 1.2 mmol / g.

[0044] The wash-resistant color-fixing emulsion was prepared according to the preparation method of Example 1.

[0045] Comparative Example 1 This comparative example provides a wash-resistant color-fixing emulsion, which, by mass, comprises 3 parts carboxyl-modified silicone oil, 1.5 parts trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 1 part emulsifier XP70, 0.7 parts emulsifier SDS, 0.3 parts acetic acid, and 87.35 parts deionized water. The carboxyl-modified silicone oil is prepared by reacting terminal vinyl silicone oil and mercaptoacetic acid. The molar ratio of mercaptoacetic acid to vinyl groups in the terminal vinyl silicone oil is 1.1:1, the molecular weight of the terminal vinyl silicone oil is 5000, and the carboxyl content in the carboxyl-modified silicone oil is 1.0 mmol / g.

[0046] The preparation method of this wash-resistant color-fixing emulsion includes the following steps: (1) The emulsifier XP70, emulsifier SDS and deionized water in the formula amount are stirred evenly in a reaction vessel at room temperature and a stirring speed of 400 rpm to form an emulsion system; (2) Carboxyl-modified silicone oil was slowly added dropwise to the emulsion system, and then acetic acid was added to adjust the pH of the system to 6.5. The system was heated to 45°C and pre-emulsified for 20 minutes under the condition of stirring at 1500 rpm to form a pre-emulsion. (3) Cool the pre-emulsion to 32°C, add trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, stir at 600 rpm for 10 min to disperse it evenly, and then continue to mature and stir at 400 rpm for 20 min to obtain a wash-resistant color-fixing emulsion crude product. Filter the wash-resistant color-fixing emulsion crude product through a 200-mesh filter to remove impurities and obtain a wash-resistant color-fixing emulsion.

[0047] The carboxyl-modified silicone oil was prepared according to the preparation method in Example 1.

[0048] Comparative Example 2 This comparative example provides a wash-resistant color-fixing emulsion. The raw materials, by mass, include 6 parts of a vinyl-containing polyurethane prepolymer, 1.5 parts of trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 1 part of emulsifier XP70, 0.7 parts of emulsifier SDS, 0.3 parts of acetic acid, 0.02 parts of initiator (DTBP:ABVN=1:1), and 87.35 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with hexamethylene diisocyanate, and then reacted with hydroxyethyl acrylate. The molar ratio of isocyanate groups in hexamethylene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.2:1, and the molar ratio of hydroxyethyl acrylate to isocyanate groups in the polyurethane prepolymer is 1.0:1.

[0049] The preparation method of this wash-resistant color-fixing emulsion includes the following steps: (1) The emulsifier XP70, emulsifier SDS and deionized water in the formula amount are stirred evenly in a reaction vessel at room temperature and a stirring speed of 400 rpm to form an emulsion system; (2) Simultaneously and slowly add vinyl-containing polyurethane prepolymer to the emulsion system, then add acetic acid to adjust the pH of the system to 6.5, heat to 45°C and pre-emulsify for 20 min at a stirring speed of 1500 rpm to form a pre-emulsion; (3) Cool the pre-emulsion to 32°C, add trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate and initiator, stir at 600 rpm for 10 min to make it evenly dispersed, and then stir at 400 rpm for 20 min to obtain a wash-resistant color-fixing emulsion crude product. Filter the wash-resistant color-fixing emulsion crude product through a 200-mesh filter to remove impurities and obtain a wash-resistant color-fixing emulsion.

[0050] The vinyl-containing polyurethane prepolymer was prepared using the method described in Example 1.

[0051] Comparative Example 3 This comparative example provides a wash-resistant and color-fixing emulsion. By mass, the raw materials include 6 parts polyurethane prepolymer, 3 parts carboxyl-modified silicone oil, 1.5 parts trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, 1 part emulsifier XP70, 0.7 parts emulsifier SDS, 0.3 parts acetic acid, and 87.35 parts deionized water. The polyurethane prepolymer is prepared by reacting hydroxyl-terminated polyether silicone oil with hexamethylene diisocyanate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. The molar ratio of isocyanate groups in hexamethylene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.2:1, the molar ratio of mercaptoacetic acid to vinyl groups in vinyl-terminated silicone oil is 1.1:1, the molecular weight of vinyl-terminated silicone oil is 5000, and the carboxyl content in the carboxyl-modified silicone oil is 1.0 mmol / g.

[0052] The preparation method of this wash-resistant color-fixing emulsion includes the following steps: (1) The emulsifier XP70, emulsifier SDS and deionized water in the formula amount are stirred evenly in a reaction vessel at room temperature and a stirring speed of 400 rpm to form an emulsion system; (2) Polyurethane prepolymer and carboxyl modified silicone oil are slowly added dropwise to the emulsion system at the same time, and then acetic acid is added to adjust the pH of the system to 6.5. The temperature is raised to 45°C and pre-emulsified for 20 minutes under the condition of stirring speed of 1500 rpm to form a pre-emulsion. (3) Cool the pre-emulsion to 32°C, add trimethylolpropane-tris[3-(2-methylaziridinyl)]propionate, stir at 600 rpm for 10 min to disperse it evenly, and then stir at 400 rpm for 20 min to obtain a wash-resistant color-fixing emulsion crude product. Filter the wash-resistant color-fixing emulsion crude product through a 200-mesh filter to remove impurities and obtain a wash-resistant color-fixing emulsion.

[0053] The polyurethane prepolymer and carboxyl-modified silicone oil were prepared according to the method in Example 1.

[0054] Comparative Example 4 This comparative example provides a wash-resistant color-fixing emulsion. By mass, the raw materials include 6 parts of vinyl-containing polyurethane prepolymer, 3 parts of carboxyl-modified silicone oil, 1 part of emulsifier XP70, 0.7 parts of emulsifier SDS, 0.3 parts of acetic acid, 0.02 parts of initiator (DTBP:ABVN=1:1), and 87.35 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with hexamethylene diisocyanate, and then reacted with hydroxyethyl acrylate. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid. The molar ratio of isocyanate groups in hexamethylene diisocyanate to hydroxyl groups in hydroxyl-terminated polyether silicone oil is 1.2:1; the molar ratio of isocyanate groups in hydroxyethyl acrylate to polyurethane prepolymer is 1.0:1; the molar ratio of mercaptoacetic acid to vinyl groups in vinyl-terminated silicone oil is 1.1:1; the molecular weight of vinyl-terminated silicone oil is 5000; and the carboxyl content in carboxyl-modified silicone oil is 1.0 mmol / g.

[0055] The preparation method of this wash-resistant color-fixing emulsion includes the following steps: (1) The emulsifier XP70, emulsifier SDS and deionized water in the formula amount are stirred evenly in a reaction vessel at room temperature and a stirring speed of 400 rpm to form an emulsion system; (2) Simultaneously and slowly add vinyl-containing polyurethane prepolymer and carboxyl-modified silicone oil to the emulsion system, then add acetic acid to adjust the pH of the system to 6.5, heat to 45°C and pre-emulsify for 20 min at a stirring speed of 1500 rpm to form a pre-emulsion. (3) Cool the pre-emulsion to 32°C, add the initiator, stir at 600 rpm for 10 min to make it evenly dispersed, and then stir at 400 rpm for 20 min to obtain a wash-resistant color-fixing emulsion crude product. Filter the wash-resistant color-fixing emulsion crude product through a 200-mesh filter to remove impurities and obtain a wash-resistant color-fixing emulsion.

[0056] The vinyl-containing polyurethane prepolymer and the carboxyl-modified silicone oil were prepared according to the method of Example 1.

[0057] Comparative Example 5 This comparative example provides a commercially available color-fixing agent (Acidic Color-Fixing Agent SP660 from Guangdong Honghao Chemical Co., Ltd.) The wash-resistant color-fixing emulsions of Examples 1-7 and Comparative Examples 1-5 were subjected to stability tests. Nylon fabrics dyed with cationic dyes were treated with the wash-resistant color-fixing emulsions of Examples 1-7 and Comparative Examples 1-5, and the performance of the treated nylon fabrics was tested. The specific finishing process and performance testing methods are as follows, and the test results are shown in Table 1.

[0058] 1. Emulsion stability (1) Emulsion centrifugation stability: Take 5 mL of emulsion (choose one of the wash-resistant color-fixing emulsions of Examples 1-7 and Comparative Examples 1-5) into a centrifuge tube, centrifuge at 3000 r / min for 30 min, and observe whether there is precipitation, layering or demulsification. If there is no abnormal phenomenon, it is considered to pass.

[0059] (2) Alkali resistance stability of emulsion: The emulsion (choose one of the wash-resistant color-fixing emulsions of Examples 1-7 and Comparative Examples 1-5) is diluted with deionized water to a solid content of 3%, and soda ash is added to adjust the pH to 10. After standing for 30 minutes, observe whether there is any floating oil or flocculent matter. If there is no abnormal phenomenon, it is considered to pass.

[0060] (3) Acid resistance stability of emulsion: The emulsion (choose one of the wash-resistant color-fixing emulsions of Examples 1-7 and Comparative Examples 1-5) is diluted with deionized water to a solid content of 3%, hydrochloric acid is added to adjust the pH to 4, and the emulsion is allowed to stand for 30 minutes. Observe whether there is any floating oil or flocculent matter. If there is no abnormal phenomenon, it is considered to pass.

[0061] (4) Salt resistance stability: The emulsion (choose one of the wash-resistant color-fixing emulsions of Examples 1-7 and Comparative Examples 1-5) is diluted with deionized water to a solid content of 3%, and sodium sulfate is added to make the concentration of sodium sulfate in the emulsion 5g / L. After standing for 30min, the state of the emulsion is observed. If there are no abnormal phenomena, it is considered to pass.

[0062] 2. Fabric finishing process (1) Fabric to be treated: Nylon 6 fabric dyed with cationic dye; (2) Preparation of finishing solution: The emulsions of Examples 1-7 and Comparative Examples 1-5 were diluted with deionized water to prepare finishing solutions with a solid content of 10% and stirred evenly; (3) Finishing process: The “two-dip two-nip” process is adopted. The nylon 6 fabric is immersed in the finishing solution and fully immersed for 5-10 minutes. The nip rate is controlled at 80% by the nip machine. (4) Drying and baking: The impregnated fabric is pre-dried at 90°C for 5 min and then baked at 150°C for 5 min to allow the emulsion to cross-link on the fiber surface to form an IPN structure; (5) Conditioning: After the finished fabric is equilibrated at standard temperature and humidity (20±2℃, 65±5% RH) for 24 hours, the following performance tests are performed.

[0063] Hand feel evaluation: Five experienced testers were selected to give sensory scores on the softness and elasticity of the finished fabric using a 1-5 point scale (5 points being the best), and the average value was taken.

[0064] Color fastness to washing test: According to AATCC 61-2A standard, 50 cycles of washing were performed, and the color difference (ΔE) of the fabric after washing was tested. The smaller the value, the better the color fastness.

[0065] Color fastness to rubbing test: According to ISO 105-X12:2001 standard, the color fastness to dry rubbing and wet rubbing is tested, and the rating standard is 1 to 5 (5 is the best).

[0066] Table 1 Performance test results of the examples and comparative examples

[0067] Please refer to the test results in Table 1 for details. Compared with the commercially available color-fixing agent in Comparative Example 5, the wash-resistant color-fixing emulsions of Examples 1-7 of this invention have superior stability, hand feel, wash fastness, and rubbing fastness. Further, as shown in Examples 3 and 6, when using aziridine crosslinking agents, the system can be endowed with superior emulsion stability against media, wash fastness, and dry and wet rubbing fastness, while achieving a balance between high color-fixing effect and soft fabric hand feel. This may be because: Firstly, aziridine crosslinking agents are stable in the weakly acidic system (pH 6.0-6.5) controlled by this invention, and will not prematurely open the ring and cause crosslinking side reactions, completely avoiding the problems of emulsion viscosity spikes, demulsification, and oil separation caused by the pre-reaction of isocyanate crosslinking agents with water and hydroxyl groups in the system; simultaneously, their trifunctional structure can maintain a low degree of crosslinking before the emulsion forms a film, without affecting the uniform dispersion of emulsion particles, significantly improving the stability of the emulsion against acid, alkali, and salt media. Secondly, aziridine tricyclic rings exhibit high ring strain and reactivity, rapidly and completely opening under 150°C baking conditions. This allows for multi-point covalent crosslinking with vinyl-containing polyurethane prepolymers and carboxyl-modified silicone oils, quickly constructing a dense, continuous IPN interpenetrating network. This network provides strong physical confinement of cationic dye molecules, fundamentally preventing dye dissolution and detachment during washing. The active groups after ring opening can directly covalently bond with the amino and hydroxyl groups on the nylon fiber surface, firmly anchoring the entire color-fixing crosslinked film to the fiber surface. Furthermore, its trifunctional structure enables three-dimensional crosslinking with uniform crosslinking points, resulting in a network density far exceeding that of linearly crosslinked isocyanate systems. Therefore, by employing aziridine crosslinking agents, this invention maintains the integrity of the network structure even after 50 high-intensity washes, ensuring no significant attenuation of the color-fixing effect. Secondly, the interpenetrating network formed by aziridine crosslinking combines the strength of polyurethane with the softness of silicone, creating a continuous and flexible color-fixing film on the fiber surface. This film tightly encapsulates the loose dye, preventing it from detaching during dry rubbing. Simultaneously, because the film is firmly bonded to the fiber via covalent bonds, it is not prone to swelling or peeling even under wet rubbing conditions, thus significantly improving wet rubbing color fastness and meeting the requirements for use and testing of high-end nylon fabrics. Finally, the aziridine crosslinking agent has a mild and controllable reaction, avoiding the problems of fabric stiffness and hardening caused by excessive crosslinking of traditional isocyanate crosslinking agents. Its crosslinking process does not damage the supple structure of silicone, maintaining the soft and smooth properties of silicone while constructing a high-strength color-fixing network. This ensures that while achieving high wash fastness, the fabric remains soft to the touch, solving the traditional dilemma of "color fastness and hand feel being mutually exclusive."

[0068] Comparing Example 3 with Comparative Examples 1-4, it can be seen that Comparative Example 1, lacking a vinyl-containing polyurethane prepolymer, exhibits significantly worse acid, alkali, and salt resistance, wash fastness, and rubbing fastness. Comparative Example 2, lacking carboxyl-modified silicone oil, also shows a significant decline in hand feel, wash fastness, and rubbing fastness. This indicates that only when vinyl-containing polyurethane prepolymer and carboxyl-modified silicone oil work synergistically can a balance of stability, hand feel, wash fastness, and rubbing fastness be achieved. In Comparative Example 3, the polyurethane prepolymer lacks vinyl groups and cannot participate in crosslinking to form a complete IPN network, resulting in decreased wash fastness and rubbing fastness. Although the wash-resistant color-fixing emulsion of Comparative Example 4 contains both vinyl-containing polyurethane prepolymer and carboxyl-modified silicone oil, the two components are only physically blended without the addition of a crosslinking agent, preventing the formation of an IPN network structure. Consequently, the emulsion exhibits poor stability and a significant decrease in wash fastness and rubbing fastness.

[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, it is not limited to those listed in the embodiments. Those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A wash-resistant color-fixing emulsion, characterized in that, The raw materials, by mass, include 3-8 parts of vinyl-containing polyurethane prepolymer, 1-4 parts of carboxyl-modified silicone oil, 0.5-2 parts of crosslinking agent, 0.8-2.5 parts of emulsifier, 0.1-0.5 parts of neutralizer, 0.004-0.024 parts of initiator, and 80-95 parts of deionized water. The vinyl-containing polyurethane prepolymer is first prepared by reacting hydroxyl-terminated polyether silicone oil with a diisocyanate compound to obtain a polyurethane prepolymer, and then adding hydroxyethyl acrylate to react. The carboxyl-modified silicone oil is prepared by reacting vinyl-terminated silicone oil with mercaptoacetic acid.

2. The wash-resistant and color-fixing emulsion according to claim 1, characterized in that, The molar ratio of isocyanate groups in the diisocyanate compound to hydroxyl groups in the hydroxyl-terminated polyether silicone oil is 1.2~1.5:1, and the molar ratio of hydroxyethyl acrylate to isocyanate groups in the polyurethane prepolymer is 1.0~1.1:

1.

3. The wash-resistant and color-fixing emulsion according to claim 1, characterized in that, The molar ratio of the mercaptoacetic acid to the vinyl group in the terminal vinyl silicone oil is 1.1 to 1.3:

1.

4. The wash-resistant and color-fixing emulsion according to claim 1, characterized in that, The carboxyl content in the carboxyl-modified silicone oil is 0.5 mmol / g to 1.5 mmol / g.

5. The wash-resistant and color-fixing emulsion according to claim 1, characterized in that, The diisocyanate compound is selected from at least one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, and the number average molecular weight of the terminal vinyl silicone oil is 5000 g / mol to 8000 g / mol.

6. The wash-resistant and color-fixing emulsion according to claim 1, characterized in that, The crosslinking agent is selected from aziridine crosslinking agents, and the neutralizing agent is selected from acetic acid.

7. The wash-resistant color-fixing emulsion according to claim 1, characterized in that, The emulsifier is a composite emulsifier composed of a nonionic emulsifier and anionic emulsifier.

8. A method for preparing a wash-resistant color-fixing emulsion according to any one of claims 1 to 7, characterized in that, Including the following steps: (1) The emulsifier and the deionized water in the formula amount are stirred evenly in a reaction vessel to form an emulsion system; (2) The vinyl-containing polyurethane prepolymer and the carboxyl-modified silicone oil are slowly added to the emulsion system, and the neutralizing agent is added to adjust the pH of the system. The system is then pre-emulsified by high-speed stirring under heating conditions to form a pre-emulsion. (3) After the pre-emulsion is cooled to a certain temperature, a crosslinking agent and an initiator are added and stirred at low speed to obtain a wash-resistant color-fixing emulsion.

9. The method for preparing the wash-resistant color-fixing emulsion according to claim 8, characterized in that, The preparation of the vinyl-containing polyurethane prepolymer includes reacting hydroxyl-terminated polyether silicone oil and diisocyanate compound under the condition of organotin catalyst to obtain polyurethane prepolymer, and then adding hydroxyethyl acrylate to the polyurethane prepolymer and heating to obtain the prepolymer; the preparation of the carboxyl-modified silicone oil includes reacting vinyl-terminated silicone oil with mercaptoacetic acid under ultraviolet light irradiation at room temperature.

10. The application of a wash-resistant color-fixing emulsion prepared by any one of claims 1 to 7 or by any one of claims 8 to 9 in the color-fixing finishing of nylon fabrics.

Images