Double-nano synergistic environment-friendly acidic color fixing agent as well as preparation method and application thereof

Abstract

The invention discloses a double-nano synergistic environment-friendly acidic color fixing agent as well as a preparation method and application thereof, and belongs to the technical field of fabric color fixing agents. The color fixing agent disclosed by the invention comprises the following components in parts by mass: 35-50 parts of water; 15 to 25 parts of gallic acid; 5-15 parts of a naphthalene sulfonic acid formaldehyde condensate; 4 to 12 parts of a nonionic surfactant; 1 to 3 parts of resorcinol; 5-9 parts of an aldehyde compound; 2 to 5 parts of methylacrolein; 3 to 6 parts of nano inorganic powder; 4-10 parts of an acidity regulator; 3-7 parts of an alkaline regulator; and 0.5 to 1.5 parts of polyethylene glycol. The color fixing agent obviously solves the technical problem that an existing color fixing agent is difficult to achieve excellent performance of environmental protection and color fixing firmness.

Description

Technical Field

[0001] This invention belongs to the field of fabric color-fixing agent technology, specifically relating to a dual-nano synergistic environmentally friendly acidic color-fixing agent, its preparation method, and its application. Background Technology

[0002] Fabrics such as nylon, silk, and wool are widely used in the textile industry due to their soft feel, excellent breathability, and wearing comfort. These fabrics are usually dyed with acid dyes. However, the water-soluble sulfonic acid groups and carboxyl groups in acid dye molecules mean that the binding of the dye to the fiber mainly relies on van der Waals forces and hydrogen bonds, resulting in poor fastness. After dyeing, the fabric is prone to problems such as color fading after washing and color staining from sweat, which seriously affects the user experience.

[0003] To address the aforementioned issues, the industry commonly employs color-fixing agents for post-treatment of dyed fabrics. Currently, mainstream acidic color-fixing agents mainly include anionic polymeric sulfonates and formaldehyde-free polyamine condensates, but existing products still have many shortcomings: some color-fixing agents contain harmful substances such as phenol and bisphenol A, failing to meet environmental regulations; the improvement in color fastness is limited, making it difficult to simultaneously meet multiple fastness requirements such as washing, perspiration, and rubbing resistance; some products can cause fabric discoloration and stiffening after use, or pose a risk of anion-cation conflict, easily resulting in color-fixing spots; and a few environmentally friendly color-fixing agents suffer from complex preparation processes, high costs, and failure to fully utilize the synergistic reinforcing effect of nanomaterials.

[0004] In existing technologies, some environmentally friendly color-fixing agents, although using plant extracts or bio-based components, do not incorporate a nano-reinforcing system, resulting in insufficient density and abrasion resistance of the color-fixed film. Other color-fixing agents still rely on irritating cross-linking agents such as formaldehyde, leading to poor environmental performance. Therefore, developing an acidic color-fixing agent that combines high color fastness, environmental friendliness and non-toxicity, no significant color change, minimal impact on hand feel, and synergistic reinforcement through dual nano-nano technology has become an urgent need in the textile industry. Summary of the Invention

[0005] The purpose of this invention is to provide a dual-nano synergistic environmentally friendly acidic color-fixing agent, its preparation method, and its application, in order to solve the technical problem that existing color-fixing agents are difficult to achieve excellent performance in terms of environmental protection and color fastness.

[0006] To achieve the above objectives, the present invention employs the following technical solution: This invention discloses a dual-nano synergistic environmentally friendly acidic color-fixing agent. By mass, the color-fixing agent comprises: 35-50 parts water; 15-25 parts gallic acid; 5-15 parts naphthalenesulfonic acid formaldehyde condensate; 4-12 parts nonionic surfactant; 1-3 parts resorcinol; 5-9 parts aldehyde compounds; 2-5 parts methacrolein; 3-6 parts nano-inorganic powder; 4-10 parts acidity regulator; 3-7 parts alkalinity regulator; and 0.5-1.5 parts polyethylene glycol.

[0007] Furthermore, the nonionic surfactant is at least one of nonylphenol, octylphenol, fatty alcohol polyoxyethylene ether, and isomeric tridecyl alcohol polyoxyethylene ether.

[0008] Further, the aldehyde compound is at least one of glutaraldehyde aqueous solution and furfural, wherein the mass fraction of glutaraldehyde aqueous solution is 25% to 35%.

[0009] Furthermore, the nano-inorganic powder is at least one of nano-silica and nano-montmorillonite, and the particle size of the nano-inorganic powder is less than 100 nm.

[0010] Furthermore, the acidity regulator is at least one of concentrated sulfuric acid and acetic acid; The polyethylene glycol is PEG-400.

[0011] Furthermore, the alkalinity regulator is selected from at least one of sodium hydroxide aqueous solution and ammonia water.

[0012] This invention also discloses a method for preparing the above-mentioned dual-nano synergistic environmentally friendly acidic color-fixing agent, comprising the following steps: S1: Weigh out no less than 5 parts by weight of water and polyethylene glycol and mix them together. Then, add the nano-inorganic powder under stirring and mix to obtain a nano-dispersion. S2: According to the mass fractions, mix the remaining parts of water, nano-dispersion, gallic acid, and naphthalenesulfonic acid formaldehyde condensate, heat and stir, then add nonionic surfactant and resorcinol, and continue stirring to obtain a mixed solution; S3: After cooling the mixed solution, aldehyde compounds and methacrolein are added dropwise to it under stirring. Then, stirring is continued and the reaction temperature is controlled to carry out the reaction, resulting in reaction solution A. S4: Cool reaction solution A, add acidic regulator dropwise while stirring continuously, adjust the pH of the system to 3.0~4.5, control the reaction temperature, raise the temperature and keep it warm after the addition is complete to obtain reaction solution B; S5: Cool the reaction solution B, add an alkaline regulator dropwise, continue stirring, adjust the pH of the system to 4.0-5.5, and then perform post-treatment to obtain a dual-nano synergistic environmentally friendly acidic color-fixing agent.

[0013] Further, in S2, the heating is raised to 40-50℃; the total stirring time is 25-45 min; the stirring time during heating and stirring is 10-15 min; and the stirring time during continued stirring is 10-30 min. In S3, the mixed solution is cooled to 20-40℃; the reaction temperature is controlled at 50-70℃; stirring is continued for 5-10 minutes; the total stirring time in S3 is 10-15 minutes.

[0014] Further, in S4, the reaction solution A is cooled to 40-60℃; the control of the reaction temperature is to control the reaction temperature to 50-70℃; the holding temperature after heating is specifically to heat to 60-80℃ and then hold for 0.5-2 hours.

[0015] Furthermore, in S5, the reaction solution B is cooled to 25-35°C; stirring is continued for 20-40 minutes. The post-processing consists of sequential cooling and filtration. The filtration process is carried out using a 1000-1200 mesh filter cloth.

[0016] This invention also discloses the application of the above-mentioned dual-nano synergistic environmentally friendly acidic color-fixing agent in the dyeing of knitted / woven nylon, silk, wool fabrics and white-based printed nylon fabrics.

[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a dual-nano synergistic environmentally friendly acidic color-fixing agent. The components utilize natural or environmentally friendly ingredients such as gallic acid and furfural, and replace traditional formaldehyde with an environmentally friendly cross-linking system of glutaraldehyde and furfural. It leaves no irritating residue and contains no harmful substances such as phenol, bisphenol A, B, S, F, or AF, complying with current environmental regulations and posing no potential threat to the health of production personnel and users. Furthermore, the components utilize the synergistic effect of the porous adsorption structure of nano-silica and the layered barrier structure of nano-montmorillonite, combined with the dispersion assistance of polyethylene glycol, to form a dense physical coating layer. This, combined with the adsorption properties of gallic acid and the anionic repulsive effect of naphthalenesulfonic acid formaldehyde condensate, integrates adsorption locking, repulsive blocking, and synergistic coating, significantly improving the wash fastness, perspiration fastness, and rubbing fastness of fabrics to levels 3.5-4 or higher. This significantly solves the technical problem of existing color-fixing agents failing to achieve both environmental friendliness and excellent color-fixing performance.

[0018] Furthermore, the dual-nano synergistic environmentally friendly acidic color-fixing agent of the present invention has strong formulation stability. Its dispersibility is optimized by polyethylene glycol. After mixing with common textile auxiliaries such as cationic leveling agents, there is no precipitation or turbidity, and it is not easy to produce color-fixing spots. It avoids the problem of fabric stiffness caused by excessive crosslinking agents. At the same time, polyethylene glycol can help improve the fabric hand feel. After color fixing, the fabric still maintains its soft original hand feel.

[0019] Furthermore, the present invention also discloses a method for preparing the above-mentioned dual-nano synergistic environmentally friendly acidic color-fixing agent. This method does not require special equipment. By adding nano-dispersion pretreatment and end-filtering steps, the product uniformity is ensured. The operating conditions are mild, the parameters of each step are easy to control, it is suitable for industrial mass production, and the cost is controllable.

[0020] Furthermore, during the preparation process, the parameters of each step form a synergistic effect: In S1, the nano-dispersion pretreatment uses polyethylene glycol-assisted high-speed shear dispersion to ensure that the nanoparticle size is less than 100 nm and that no agglomeration occurs after 24 hours of standing, laying the foundation for the uniformity of the subsequent color-fixing film; in S3, the crosslinking agent is added dropwise in the order of furfural, then glutaraldehyde, and finally methacrolein, designed according to the reactivity gradient of the crosslinking agent to avoid premature crosslinking leading to system viscosity, while controlling the dropping rate to less than 0.3 parts / min and the reaction temperature to 50-70℃ to ensure a gentle and sufficient crosslinking reaction; in S4, the heat preservation time is adjusted according to the fabric type (1-2 hours for nylon, 0.5-1 hour for silk or wool) to ensure the pre-binding effect of the color-fixing agent and the fiber while avoiding damage to the protein fibers; in S5, the pH is roughly adjusted with sodium hydroxide aqueous solution and then finely adjusted with ammonia. The adjustment method ensures that the pH of the system remains stable between 4.0 and 5.5, avoiding overshoot that could cause fluctuations in product performance. The refined control of each step further improves the stability and industrial applicability of the product. Detailed Implementation

[0021] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0022] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0023] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0024] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0025] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0026] This invention provides a dual-nano synergistic environmentally friendly acidic color-fixing agent, comprising the following components by weight: 1) Water 35-50 parts; 2) Gallic acid 15-25 parts; 3) Naphthalenesulfonic acid formaldehyde condensate 5-15 parts; 4) Nonionic surfactant 4-12 parts; 5) Resorcinol 1-3 parts; 6) Aldehyde compounds 5-9 parts; 7) Methacrolein 2-5 parts; 8) Nano-inorganic powder 3-6 parts; 9) Acidity regulator 4-10 parts; 10) Alkalinity regulator 3-7 parts; 11) Polyethylene glycol 0.5-1.5 parts.

[0027] This invention also discloses a method for preparing the above-mentioned dual-nano synergistic environmentally friendly acidic color-fixing agent, comprising the following steps: S1: First, take at least 5 parts of deionized water, add polyethylene glycol (PEG-400), and stir at 500 rpm for 5 minutes until completely dissolved to ensure uniform distribution of the dispersant; then slowly add nano-silica and nano-montmorillonite (feeding rate ≤ 0.5 parts / min) to avoid local agglomeration caused by one-time addition; turn on high-speed shearing and stir at 3000-5000 rpm for 15 minutes. During this period, use a laser particle size analyzer to check the particle size every 5 minutes. If the particle size exceeds the standard, extend the shearing time by 5-10 minutes; the key control point in this step is the stability of the nano-dispersion (no stratification or precipitation after standing for 24 hours), which is a prerequisite for the uniformity of the subsequent color-fixing film; S2: Use the same reactor and adjust the stirring speed to 500-800 rpm (gentle stirring to avoid damaging the nano-dispersion); first add the remaining water, nano-dispersion, gallic acid, and naphthalenesulfonic acid formaldehyde condensate, and stir at 500 rpm for 10 minutes to allow the solid components to initially dissolve and the nano-dispersion to fully integrate with the solvent; then raise the temperature to 40-50℃ at a rate of 5℃ / min. This temperature range can accelerate the dissolution of gallic acid and avoid the sulfonation hydrolysis of the naphthalenesulfonic acid formaldehyde condensate; finally add the phenolic compounds and resorcinol, adjust the stirring speed to 800 rpm, and continue stirring for 10-30 minutes (stop when the phenols are completely dissolved). The logic of segmented stirring is to first integrate at a low speed, then accelerate the temperature increase, and finally achieve high speed for uniformity, avoiding incomplete local dissolution caused by a single stirring speed.

[0028] S3: The reactor must be equipped with a temperature control device (temperature control accuracy ±1℃) to avoid temperature fluctuations affecting the crosslinking effect. First, cool the mixed solution to 20-40℃ at a rate of 3℃ / min to reduce the reactivity of the crosslinking agent and avoid premature crosslinking that would cause the system to become viscous. Then, add furfural, glutaraldehyde, and methacrolein in the following order (dropping rate ≤0.3 parts / min). This order is designed based on the reactivity of the crosslinking agents: furfural has the lowest activity and is added first to form basic crosslinking; glutaraldehyde has medium activity and is added in the middle to strengthen crosslinking; methacrolein has the highest activity and is added last to improve wear resistance.

[0029] During the dropwise addition process, the reaction temperature is controlled at 50-70℃, and the temperature is controlled by the reactor jacket to ensure a gentle crosslinking reaction. After the dropwise addition is completed, continue stirring for 5-10 minutes (total stirring time including the dropwise addition process is 10-15 minutes) until the viscosity of the reaction solution reaches 80-90 mPa. s (25℃) to ensure that the crosslinking agent reacts fully with the system.

[0030] S4. Cool the cross-linked solution to 40-60℃ at a rate of 4℃ / min. At this temperature, the acid reactivity is moderate, avoiding high-temperature corrosion of the fiber. Add diluted concentrated sulfuric acid and acetic acid dropwise (dropping rate ≤ 0.5 parts / min), stirring for 2 minutes after each drop of acid to ensure a uniform pH decrease. Control the reaction temperature at 50-70℃. After the addition is complete, raise the temperature to 60-80℃ and keep it at that temperature for 0.5-2 hours. The purpose of keeping it at that temperature is to activate the positively charged adsorption sites on the fiber and promote the pre-combination of the fixing agent molecules with the fiber. For nylon, keep it at that temperature for 1-2 hours, and for silk or wool, keep it at that temperature for 0.5-1 hour.

[0031] In step S4, the cooling specifically refers to cooling to 40-60℃, and the reaction temperature control specifically refers to controlling the reaction temperature at 50-70℃; the heating and heat preservation specifically refers to heating to 60-80℃ and then heat preservation for 0.5-2 hours (the heat preservation time is adjusted according to the fabric type: nylon fabrics are heat preservation for 1-2 hours, and protein fabrics such as silk / wool are heat preservation for 0.5-1 hour. The heat preservation endpoint is based on the fiber surface zeta potential reaching +5~+10mV).

[0032] S5. Cool the reaction solution to 25-35℃; add 10-50% sodium hydroxide aqueous solution and ammonia water dropwise, using the order of sodium hydroxide aqueous solution first and then ammonia water: the sodium hydroxide aqueous solution quickly pulls the pH close to the target value, and the ammonia water finely adjusts it to 4.0-5.5 to avoid pH over-adjustment; continue stirring for 20-40 minutes to allow the pH to stabilize and the color-fixing agent molecules to fully mature, improving the stability for subsequent use.

[0033] S6. After cooling to room temperature (25±5℃), filter using a 1000-mesh filter cloth. This type of filter cloth has a pore size of approximately 13μm, which can effectively remove trace amounts of nano-agglomerated particles and undissolved impurities, ensuring a uniform appearance of the color-fixing agent. After filtration, pour into a capped corrosion-resistant plastic bottle and store at 15-30℃ in a dark and sealed environment. The shelf life is 1 month. Shake well for 30 seconds before use to ensure that the nanoparticles are redispersed evenly.

[0034] This invention uses an environmentally friendly cross-linking network as the basic framework for color fixing, achieving stable bonding through multi-element chemical cross-linking without harmful substances. Naturally derived gallic acid (containing three phenolic hydroxyl groups) undergoes a phenolic condensation reaction with the aldehyde groups of glutaraldehyde and furfural to form COC covalent bonds. Simultaneously, it cross-links with the active groups of fabric fibers (such as nylon amino groups and wool hydroxyl groups). The chemical bonds between the color fixing agent and the fiber replace traditional formaldehyde and bisphenol cross-linking agents, and the aldehyde groups fully participate in the bonding during the reaction, leaving no free residue, thus ensuring environmental friendliness at the molecular level.

[0035] The dual-nano synergistic structure and triple fixation mechanism jointly enhance the fixation effect: With the assistance of PEG-400 dispersion, the porous nano-silica adsorbs free dyes and cross-linking groups, while the layered nano-montmorillonite blocks water and sweat penetration, both of which play the roles of adsorption and barrier; at the same time, the ionic bond adsorption of gallic acid and dye, the anionic repulsion blocking of naphthalenesulfonic acid formaldehyde condensate, and the physical coating of cross-linking network and nano-layer constitute a triple mechanism to prevent dye dissolution or migration, and significantly improve the fastness to washing and perspiration.

[0036] The interface design balances color change and hand feel: the fixing agent molecular chain matches the fiber surface groups to avoid interface gaps; the mild cross-linking reaction (≤70℃) does not damage the dye color development system, and the total color difference ΔE is less than 0.7; and the small particle size of the nanoparticles does not affect the touch, while PEG-400 lubrication reduces friction, ensuring that the fabric remains soft after fixing, and has high fastness and environmental protection properties.

[0037] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0038] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0039] Example 1 A method for preparing a dual-nano synergistic environmentally friendly acidic color-fixing agent includes the following steps: 42 parts water, 20 parts gallic acid, 10 parts naphthalenesulfonic acid formaldehyde condensate, 6 parts nonylphenol, 2 parts resorcinol, 2.5 parts 5% glutaraldehyde aqueous solution, 4.5 parts furfural, 3.5 parts methacrolein, 3 parts nano silica, 1.5 parts nano montmorillonite, 4 parts concentrated sulfuric acid, 3 parts acetic acid, 2 parts sodium hydroxide aqueous solution, 2 parts ammonia, and 1 part polyethylene glycol (PEG-400); The specific preparation method is as follows: S1. Take 5 parts water, add 1 part polyethylene glycol (PEG-400) and stir to dissolve. Under stirring conditions, add 3 parts nano silica and 1.5 parts nano montmorillonite, stir for 15 minutes to make the nano silica and nano montmorillonite dispersed evenly and without agglomeration, and obtain a nano dispersion. S2. Mix the remaining 37 parts of water, the nano-dispersion obtained in step S1, 20 parts of gallic acid, and 10 parts of naphthalenesulfonic acid formaldehyde condensate, heat to 45°C and stir for 10 min, then add 6 parts of nonylphenol and 2 parts of resorcinol, and continue stirring for 20 min. The total stirring time is 35 min, and a mixed solution is obtained. S3. Cool the mixed solution obtained in step S2 to 30°C, and add 4.5 parts furfural, 2.5 parts 25% glutaraldehyde aqueous solution and 3.5 parts methacrolein dropwise to it in sequence, stirring continuously and controlling the reaction temperature at 60°C. After the addition is completed, continue stirring for 8 minutes. The total stirring time, including the dropwise addition process, is 12 minutes. S4. Cool the above solution to 50°C, then add 4 parts of diluted concentrated sulfuric acid and 3 parts of acetic acid dropwise while stirring continuously, controlling the reaction temperature at 60°C; after the addition is complete, raise the temperature to 70°C and keep it at that temperature for 1 hour. S5. Cool the reaction solution obtained in step S4 to 30°C, add dropwise a 30% sodium hydroxide aqueous solution and 3 parts ammonia water, and continue stirring for 30 minutes. S6. Cool to room temperature and filter with a 1000-mesh filter cloth to remove any possible trace agglomerates, obtaining a dual-nano synergistic environmentally friendly acidic color-fixing agent.

[0040] Example 2 A method for preparing a dual-nano synergistic environmentally friendly acidic color-fixing agent includes the following steps: 35 parts water, 15 parts gallic acid, 5 parts naphthalenesulfonic acid formaldehyde condensate, 5 parts fatty alcohol polyoxyethylene ether (AEO-9), 1 part resorcinol, 2 parts 25% glutaraldehyde aqueous solution, 3 parts furfural, 2 parts methacrolein, 2 parts nano silica, 1 part nano montmorillonite, 2 parts concentrated sulfuric acid, 2 parts acetic acid, 1 part sodium hydroxide aqueous solution, 2 parts ammonia, and 0.5 parts polyethylene glycol (PEG-400); The specific preparation method is as follows: S1. Take 4.5 parts of water, add 0.5 parts of polyethylene glycol (PEG-400) and stir to dissolve. Under stirring conditions, add 2 parts of nano silica and 1 part of nano montmorillonite, stir for 15 minutes to make the nano silica and nano montmorillonite dispersed evenly and without agglomeration, and obtain a nano dispersion. S2. Mix the remaining 30.5 parts of water, the nano-dispersion obtained in step S1, 15 parts of gallic acid, and 5 parts of naphthalenesulfonic acid formaldehyde condensate, heat to 40°C and stir for 10 min, then add 5 parts of fatty alcohol polyoxyethylene ether (AEO-9) and 1 part of resorcinol, and continue stirring for 10 min. The total stirring time is 25 min to obtain a mixed solution. S3. Cool the mixed solution obtained in step S2 to 20°C, and add 3 parts furfural, 2 parts 25% glutaraldehyde aqueous solution and 2 parts methacrolein dropwise to it in sequence. Stir continuously and control the reaction temperature at 50°C. After the addition is completed, continue stirring for 5 minutes. The total stirring time, including the dropwise addition process, is 10 minutes. S4. Cool the above solution to 40°C, then add 2 parts diluted concentrated sulfuric acid and 2 parts acetic acid dropwise while stirring continuously, controlling the reaction temperature at 50°C. After the addition is complete, raise the temperature to 60°C and keep it at that temperature for 0.5 hours. S5. Cool the reaction solution obtained in step S4 to 25°C, add dropwise a 10% sodium hydroxide aqueous solution and 2 parts ammonia water, and continue stirring for 20 minutes. S6. Cool to room temperature and filter with a 1000-mesh filter cloth to obtain a dual-nano synergistic environmentally friendly acidic color-fixing agent.

[0041] Example 3 A method for preparing a dual-nano synergistic environmentally friendly acidic color-fixing agent includes the following steps: 50 parts water, 25 parts gallic acid, 15 parts naphthalenesulfonic acid formaldehyde condensate, 9 parts isomeric tridecyl alcohol polyoxyethylene ether (1307), 3 parts resorcinol, 3 parts 25% glutaraldehyde aqueous solution, 6 parts furfural, 5 parts methacrolein, 4 parts nano silica, 2 parts nano montmorillonite, 6 parts concentrated sulfuric acid, 4 parts acetic acid, 3 parts sodium hydroxide aqueous solution, 4 parts ammonia, and 1.5 parts polyethylene glycol (PEG-400); The specific preparation method is as follows: S1. Take 7 parts of water, add 1.5 parts of polyethylene glycol (PEG-400) and stir to dissolve. Under stirring conditions, add 4 parts of nano silica and 2 parts of nano montmorillonite, stir for 15 minutes to make the nano silica and nano montmorillonite dispersed evenly and without agglomeration, and obtain a nano dispersion. S2. Mix the remaining 43 parts of water, the nano-dispersion obtained in step S1, 25 parts of gallic acid, and 15 parts of naphthalenesulfonic acid formaldehyde condensate, heat to 50°C and stir for 10 min, then add 9 parts of isomeric tridecyl alcohol polyoxyethylene ether (1307) and 3 parts of resorcinol, and continue stirring for 30 min. The total stirring time is 45 min, and a mixed solution is obtained. S3. Cool the mixed solution obtained in step S2 to 40°C, and add 6 parts furfural, 3 parts 25% glutaraldehyde aqueous solution and 5 parts methacrolein dropwise to it in sequence. Stir continuously and control the reaction temperature at 70°C. After the addition is completed, continue stirring for 10 minutes. The total stirring time, including the dropwise addition process, is 15 minutes. S4. Cool the above solution to 60°C, then add 6 parts of diluted concentrated sulfuric acid and 4 parts of acetic acid dropwise while stirring continuously, controlling the reaction temperature at 70°C. After the addition is complete, raise the temperature to 80°C and keep it at that temperature for 2 hours. S5. Cool the reaction solution obtained in step S4 to 35°C, add dropwise a 50% sodium hydroxide aqueous solution and 4 parts ammonia water, and continue stirring for 40 minutes. S6. Cool to room temperature and filter with a 1000-mesh filter cloth to obtain a dual-nano synergistic environmentally friendly acidic color-fixing agent.

[0042] Example 4 A method for preparing a dual-nano synergistic environmentally friendly acidic color-fixing agent includes the following steps: 43 parts water, 20 parts gallic acid, 10 parts naphthalenesulfonic acid formaldehyde condensate, 7.5 parts fatty alcohol polyoxyethylene ether (AEO-9), 2 parts resorcinol, 2.5 parts 25% glutaraldehyde aqueous solution, 4.5 parts furfural, 3.5 parts methacrolein, 3 parts nano silica, 1.5 parts nano montmorillonite, 4 parts concentrated sulfuric acid, 3 parts acetic acid, 2 parts sodium hydroxide aqueous solution, 3 parts ammonia, 1 part polyethylene glycol (PEG-400); The specific preparation method is as follows: S1. Take 5.5 parts of water, add 1 part of PEG-400 and stir to dissolve, add 3 parts of nano silica and 1.5 parts of nano montmorillonite, stir at 3500 rpm for 15 min to obtain a nano dispersion; S2. The remaining 37.5 parts of water, nano-dispersion, gallic acid, and naphthalenesulfonic acid formaldehyde condensate were mixed and stirred at 500 rpm for 10 min. The mixture was then heated to 45°C, and AEO-9 and resorcinol were added. The mixture was stirred at 800 rpm for 20 min (total stirring time 35 min). S3. Cool to 30℃, then add furfural, glutaraldehyde, and methacrolein dropwise (dropping rate 0.2 parts / min), controlling the temperature at 60℃, and stirring for a total of 12 minutes (including the dropwise addition). S4. Cool to 50℃, add diluted concentrated sulfuric acid and acetic acid dropwise, control the temperature at 60℃, raise the temperature to 70℃ and keep it at that temperature for 1 hour. S5. Cool to 30°C, add 30% sodium hydroxide aqueous solution and ammonia water dropwise, and stir for 30 minutes; S6. After cooling to room temperature, filter through a 1000-mesh filter cloth to obtain a dual-nano synergistic environmentally friendly acidic color-fixing agent.

[0043] Example 5 A method for preparing a dual-nano synergistic environmentally friendly acidic color-fixing agent includes the following steps: 44 parts water, 21 parts gallic acid, 11 parts naphthalenesulfonic acid formaldehyde condensate, 6.5 parts isomeric tridecyl alcohol polyoxyethylene ether (1307), 2.2 parts resorcinol, 2.6 parts 25% glutaraldehyde aqueous solution, 4.8 parts furfural, 3.8 parts methacrolein, 3.2 parts nano silica, 1.6 parts nano montmorillonite, 4.5 parts concentrated sulfuric acid, 3.2 parts acetic acid, 2.2 parts sodium hydroxide aqueous solution, 3.2 parts ammonia, 1.1 parts polyethylene glycol (PEG-400); The specific preparation method is as follows: S1. Take 6 parts of water, add 1.1 parts of PEG-400 and stir to dissolve, add 3.2 parts of nano silica and 1.6 parts of nano montmorillonite, stir at 4000 rpm for 15 min to obtain a nano dispersion; S2. The remaining 38 parts of water, nano-dispersion, gallic acid, and naphthalenesulfonic acid formaldehyde condensate were mixed and stirred at 500 rpm for 10 min. The mixture was then heated to 46°C, and 1307 and resorcinol were added. The mixture was stirred at 800 rpm for 22 min (total stirring time 32 min). S3. Cool to 32℃, then add furfural, glutaraldehyde, and methacrolein dropwise (dropping rate 0.25 parts / min), while maintaining the temperature at 62℃ and stirring for a total of 13 minutes (including the dropwise addition). S4. Cool to 55℃, add diluted concentrated sulfuric acid and acetic acid dropwise, control the temperature at 65℃, raise the temperature to 75℃ and keep it at that temperature for 1.2 hours. S5. Cool to 32°C, add 40% sodium hydroxide aqueous solution and ammonia water dropwise, and stir for 35 minutes; S6. After cooling to room temperature, filter through a 1000-mesh filter cloth to obtain a dual-nano synergistic environmentally friendly acidic color-fixing agent.

[0044] Comparative Example 1 An acidic color-fixing agent, compared with Example 1, differs only in that it does not contain nano-silica, nano-montmorillonite and polyethylene glycol (PEG-400), while the remaining components, weight parts and preparation methods are the same as in Example 1.

[0045] Comparative Example 2 Commercially available conventional acidic color-fixing agents (containing bisphenol S and formaldehyde).

[0046] Effect test Color fixing application process: color fixing agent dosage 3% owf, color fixing temperature 70℃, color fixing time 30min, liquor ratio 1:25, subsequent water washing temperature 40℃.

[0047] The standard tests are shown in Table 1.

[0048] Table 1 Standard Tests

[0049] The performance of the fixing agents in Examples 1-5 and Comparative Examples 1-2 was tested using the same methods as before, and the test results are shown in Table 2 below.

[0050] Table 2. Performance test data of the fixing agent in different embodiments and comparative examples.

[0051] The test results show that the dual-nano synergistic environmentally friendly acidic color-fixing agents in Examples 1-5 were free of formaldehyde, phenol, and bisphenol-related harmful substances. In contrast, the commercially available Comparative Example 2 contained 3.2 ppm of formaldehyde and bisphenol S, demonstrating a significant advantage in environmental friendliness. Regarding color fastness, the unfixed fabrics exhibited only a grade 2 fastness in washing, perspiration, and dry rubbing (1.5 grade in wet rubbing). Comparative Example 1, which did not contain dual nanoparticles, achieved a grade 3 fastness, while Examples 1-5 reached grades 3.5-4. Even Example 2 achieved a grade 3.5 fastness, superior to Comparative Example 1 and better than or comparable to Comparative Example 2. In summary, the color-fixing agent of this invention, with its environmentally friendly and residue-free characteristics, far surpasses commercially available products. The synergistic effect of dual nanoparticles further enhances its color fastness significantly compared to products without nanoparticle components, truly achieving a balance between environmental friendliness and high color fastness, effectively meeting the color-fixing needs of nylon, silk, and other fabrics.

[0052] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A dual-nano synergistic environmentally friendly acidic color-fixing agent, characterized in that, The color-fixing agent comprises, by weight, 35-50 parts water; 15-25 parts gallic acid; 5-15 parts naphthalenesulfonic acid formaldehyde condensate; 4-12 parts nonionic surfactant; 1-3 parts resorcinol; 5-9 parts aldehyde compounds; 2-5 parts methacrolein; 3-6 parts nano-inorganic powder; 4-10 parts acidity regulator; 3-7 parts alkalinity regulator; and 0.5-1.5 parts polyethylene glycol.

2. The dual-nano synergistic environmentally friendly acidic color-fixing agent according to claim 1, characterized in that, The nonionic surfactant is at least one of nonylphenol, octylphenol, fatty alcohol polyoxyethylene ether, and isomeric tridecyl alcohol polyoxyethylene ether.

3. The dual-nano synergistic environmentally friendly acidic color-fixing agent according to claim 1, characterized in that, The aldehyde compound is at least one of glutaraldehyde aqueous solution and furfural, wherein the mass fraction of glutaraldehyde aqueous solution is 25% to 35%.

4. The dual-nano synergistic environmentally friendly acidic color-fixing agent according to claim 1, characterized in that, The nano-inorganic powder is at least one of nano-silica and nano-montmorillonite, and the particle size of the nano-inorganic powder is less than 100 nm.

5. The dual-nano synergistic environmentally friendly acidic color-fixing agent according to claim 1, characterized in that, The acid regulator is at least one of concentrated sulfuric acid and acetic acid; The polyethylene glycol is PEG-400.

6. The dual-nano synergistic environmentally friendly acidic color-fixing agent according to claim 1, characterized in that, The alkalinity regulator is selected from at least one of sodium hydroxide aqueous solution and ammonia water.

7. A method for preparing a dual-nano synergistic environmentally friendly acidic color-fixing agent according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1: Weigh out no less than 5 parts by weight of water and polyethylene glycol and mix them together. Then, add the nano-inorganic powder under stirring and mix to obtain a nano-dispersion. S2: According to the mass fractions, mix the remaining parts of water, nano-dispersion, gallic acid, and naphthalenesulfonic acid formaldehyde condensate, heat and stir, then add nonionic surfactant and resorcinol, and continue stirring to obtain a mixed solution; S3: After cooling the mixed solution, aldehyde compounds and methacrolein are added dropwise to it under stirring. Then, stirring is continued and the reaction temperature is controlled to carry out the reaction, resulting in reaction solution A. S4: Cool reaction solution A, add acidic regulator dropwise while stirring continuously, adjust the pH of the system to 3.0~4.5, control the reaction temperature, raise the temperature and keep it warm after the addition is complete to obtain reaction solution B; S5: Cool the reaction solution B, add an alkaline regulator dropwise, continue stirring, adjust the pH of the system to 4.0-5.5, and then perform post-treatment to obtain a dual-nano synergistic environmentally friendly acidic color-fixing agent.

8. The preparation method of a dual-nano synergistic environmentally friendly acidic color-fixing agent according to claim 7, characterized in that, In S2, the heating is raised to 40-50℃; the total stirring time is 25-45 min; the stirring time during heating and stirring is 10-15 min; and the stirring time during continued stirring is 10-30 min. In S3, the mixed solution is cooled to 20-40℃; the reaction temperature is controlled at 50-70℃; stirring is continued for 5-10 minutes; the total stirring time in S3 is 10-15 minutes.

9. The preparation method of a dual-nano synergistic environmentally friendly acidic color-fixing agent according to claim 7, characterized in that, In S4, reaction solution A is cooled to 40-60℃; the reaction temperature is controlled to 50-70℃; the holding temperature after heating is specifically heated to 60-80℃ and then held for 0.5-2 hours.

10. The preparation method of a dual-nano synergistic environmentally friendly acidic color-fixing agent according to claim 7, characterized in that, In step S5, the reaction solution B is cooled to 25-35℃; stirring is continued for 20-40 minutes. The post-processing consists of sequential cooling and filtration. The filtration process is carried out using a 1000-1200 mesh filter cloth.

11. The application of a dual-nano synergistic environmentally friendly acidic color-fixing agent according to any one of claims 1 to 6 in the dyeing of knitted / woven nylon, silk, wool fabrics and white-based printed nylon fabrics.

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