Long-acting anti-yellowing anti-dusting finishing agent, preparation method and application thereof

Abstract

The application provides a long-acting anti-yellowing anti-dust finishing agent and a preparation method and application thereof, the finishing agent comprising a basic long-acting finishing liquid and a temperature and humidity sensitive microcapsule finishing liquid, the basic long-acting finishing liquid being composed of an aliphatic aqueous polyurethane dispersion, a quaternary ammonium salt containing active hydroxyl groups, a polycarbodiimide crosslinking agent, a hindered phenol antioxidant and polyethylene glycol, and the temperature and humidity sensitive microcapsule having a mixed crosslinked network of temperature sensitive polymers and humidity sensitive polymers as a wall material and containing an antistatic agent and amino silicon oil as a core material. The application further provides a preparation method of the finishing agent and application thereof in fabric finishing, through the double structure of the basic long-acting layer and the microcapsule, the long-lasting retention and on-demand replenishment of the antistatic function are realized, meanwhile, the finishing agent has soft hand feeling and anti-yellowing performance, and can effectively inhibit the adhesion of pollen and dust on the surface of the fabric.

Description

Technical Field

[0001] This invention relates to the field of functional finishing technology for textiles, specifically to a long-lasting protective anti-yellowing and anti-ash finishing agent, its preparation method, and its application. Background Technology

[0002] The adhesion of pollen, dust, and other particulate matter to the surface of fabrics directly affects the cleanliness of textiles and can trigger respiratory discomfort and skin allergies in allergy sufferers. With increasing public awareness of health, developing fabrics with the ability to inhibit pollen and dust adhesion has become a key research direction in the textile industry.

[0003] The adsorption mechanism of pollen and dust on fabrics includes electrostatic attraction, the influence of fiber surface morphology, and the mechanical trapping effect of fabric pore structure. Currently, common techniques for reducing dust adhesion to fabrics include antistatic finishing and surface smoothing finishing. Antistatic finishing reduces fiber surface resistance by coating the fabric surface with quaternary ammonium salt antistatic agents or surfactants, allowing static charges to dissipate quickly and thus reducing the electrostatic attraction for dust. Surface smoothing finishing fills the uneven structure of the fiber surface with resin films, reducing mechanical adhesion sites for dust and making it easier to shake off already adhered dust under external force. However, antistatic agents mostly adhere to the fiber surface through physical adsorption, lacking chemical bonding with the fiber. After several washes or mechanical frictions, the antistatic agent is easily lost, leading to a significant decrease in antistatic effect and making it difficult to meet the requirements for long-term use. The polymer resins used in surface smoothing finishing can easily cause the fabric to feel stiff and produce creases after film formation. Some resins may also yellow during high-temperature baking, affecting the wearing comfort and appearance quality of the fabric.

[0004] To address the aforementioned technical challenges, developing an anti-dust finishing agent that can be firmly covalently bonded to fibers, providing both basic long-lasting protection and intelligent responsiveness, while also inhibiting yellowing and maintaining a soft hand feel, is of great significance for promoting the performance upgrade of high-end protective textiles. Summary of the Invention

[0005] The technical problem to be solved: The purpose of this invention is to provide a long-lasting protective anti-yellowing and anti-dust finishing agent, its preparation method, and its application. The finishing agent includes a basic long-lasting finishing liquid and a temperature and humidity sensitive microcapsule finishing liquid. During finishing, a basic long-lasting layer is constructed on the surface of the fabric, allowing the antistatic agent to form a covalent bond network with polyurethane and fibers through a crosslinking agent, achieving durable antistatic properties and surface smoothness. The temperature and humidity sensitive microcapsules are anchored to the surface of the basic long-lasting layer, releasing supplementary antistatic agents and amino silicone oil under changing temperature and humidity conditions, achieving on-demand reinforcement. By introducing hindered phenolic antioxidants and optimizing the baking process, the problems of hand hardening and yellowing are solved.

[0006] Technical solution: A long-lasting anti-yellowing and anti-dust finishing agent includes a basic long-lasting finishing liquid and a temperature and humidity sensitive microcapsule finishing liquid. The basic long-lasting finishing liquid contains an aliphatic aqueous polyurethane dispersion, a quaternary ammonium salt containing active hydroxyl groups, a polycarbodiimide crosslinking agent, a hindered phenolic antioxidant, and polyethylene glycol. The temperature and humidity sensitive microcapsule finishing liquid contains temperature and humidity sensitive microcapsules, Tris buffer solution, and dopamine hydrochloride. The wall material of the temperature and humidity sensitive microcapsules is a mixed crosslinked network of temperature-sensitive polymer and humidity-sensitive polymer, and the core material contains an antistatic agent and amino silicone oil.

[0007] Preferably, the mass fractions of each component in the base long-lasting finishing liquid are: 200-300 parts of aliphatic waterborne polyurethane dispersion, 10-25 parts of quaternary ammonium salt containing active hydroxyl groups, 2-6 parts of polycarbodiimide crosslinking agent, 0.5-1.5 parts of hindered phenolic antioxidant, 5-15 parts of polyethylene glycol, and 600-800 parts of water.

[0008] Preferably, the concentration of Tris buffer in the temperature and humidity sensitive microcapsule finishing solution is 10~50 mmol / L, the pH is 8.0~8.5, the concentration of temperature and humidity sensitive microcapsules in the microcapsule finishing solution is 10~30 g / L, and the concentration of dopamine hydrochloride is 0.5~2 g / L.

[0009] The preparation method of any of the above finishing agents includes the following steps: S1. Mix aliphatic waterborne polyurethane dispersion, quaternary ammonium salt containing active hydroxyl groups, polycarbodiimide crosslinking agent, hindered phenolic antioxidant, polyethylene glycol and water evenly to obtain basic long-lasting finishing liquid; S2. Prepare temperature and humidity sensitive microcapsules. Disperse the temperature and humidity sensitive microcapsules in Tris buffer, add dopamine hydrochloride, mix well, and obtain temperature and humidity sensitive microcapsule finishing solution.

[0010] Preferably, the preparation method of the temperature and humidity sensitive microcapsules includes the following steps: S11. Mix the temperature-sensitive polymer and the humidity-sensitive polymer in a certain proportion, add water, stir to dissolve, and obtain the wall material prepolymer solution; S12. Mix the antistatic agent and amino silicone oil, heat and stir until uniformly dissolved to obtain a core material mixture; S13. Add the core material mixture to the wall material prepolymer liquid, emulsify at high speed to form an oil-in-water emulsion, add a depositing agent to the emulsion, and slowly cool it while stirring to allow the wall material to be deposited and coated on the surface of the core material. Then add a crosslinking agent to cure and crosslink the wall material into shape. S14. Centrifuge to separate, collect the precipitate, wash, and vacuum dry to obtain temperature and humidity sensitive microcapsules.

[0011] Preferably, in step S11, the mass ratio of the temperature-sensitive polymer to the humidity-sensitive polymer is 1:(0.5~2), the temperature-sensitive polymer is poly(N-isopropylacrylamide) or a copolymer thereof, and the humidity-sensitive polymer is selected from either hydroxypropyl methylcellulose or polyvinyl alcohol.

[0012] Preferably, in step S12, the mass ratio of antistatic agent to amino silicone oil is (1~3):1, and the ammonia value of amino silicone oil is 0.3~0.6 mmol / g.

[0013] Preferably, the high-speed emulsification temperature in step S13 is 40~60℃, the rotation speed is 1000~2000r / min, the deposition agent is any one of sodium chloride, sodium sulfate or borax, the amount added is 0.5~15% of the total mass of the wall material prepolymer liquid, the cooling rate is 0.5~2℃ / min, the crosslinking agent is genipin, the amount added is 0.1~1% of the total mass of the wall material prepolymer liquid, and the curing temperature is 15~30℃.

[0014] The application of any of the above finishing agents is characterized by comprising the following steps: S21. Immerse the cotton or polyester-cotton blended fabric in the base long-lasting finishing solution, and use a padding machine to control the fabric liquid carrying rate to 70-80%; S22. The impregnated fabric is pre-dried at 80~100℃ for 1~5min, and then baked at 140~160℃ for 1~5min to obtain the basic long-lasting layer fabric. S23. Immerse the basic long-lasting layer fabric in the microcapsule finishing solution, remove it and air dry at room temperature to obtain a long-lasting protective anti-yellowing fabric.

[0015] Beneficial effects: The long-lasting protective and anti-yellowing anti-dust finishing agent of the present invention has the following advantages: The finishing agent of this invention contains a temperature and humidity sensitive microcapsule finishing solution. The wall material of the microcapsules is a composite cross-linked network of poly(N-isopropylacrylamide) and hydroxypropyl methylcellulose or polyvinyl alcohol. Under normal temperature and humidity conditions, the wall material remains in a swollen state, and the core material is completely sealed. When the ambient temperature rises above the lower critical dissolution temperature or the humidity changes significantly, the wall material undergoes a volume phase change, transforming from a swollen state to a collapsed state, allowing the antistatic agent and amino silicone oil in the core material to be released in a controllable manner, realizing the on-demand supply of functional components. The dopamine in the finishing solution undergoes in-situ self-polymerization on the surface of the microcapsules and the long-lasting layer of the fabric base to form a polydopamine layer. Combined with the chemical bonds formed by the cross-linking agent and the carboxyl groups in the wall material and the long-lasting layer of the base, the microcapsules are firmly anchored to the fabric surface, ensuring the long-term effectiveness of the finished fabric.

[0016] The finishing agent of this invention achieves long-lasting antistatic function and on-demand replenishment through the dual action of a basic long-lasting finishing liquid and a microcapsule finishing liquid. In the basic long-lasting finishing liquid, the quaternary ammonium salt containing active hydroxyl groups forms a covalent bond network with the aliphatic waterborne polyurethane and active groups on the fiber surface under the action of a polycarbodiimide crosslinking agent. This firmly anchors the antistatic agent to the fiber surface, continuously reducing fiber surface resistance and accelerating the dissipation of static charge. The temperature and humidity sensitive microcapsules responsively release the antistatic agent and amino silicone oil from the core material under dry and high-temperature conditions, further reducing the fiber surface friction coefficient and making the fiber surface smoother. Through the dual action of weakened electrostatic attraction and enhanced physical desorption, pollen, dust, and other particulate matter are less likely to adhere to the fabric surface, giving the fabric excellent dust resistance.

[0017] The basic long-lasting finishing liquid of this invention uses aliphatic waterborne polyurethane as the film-forming resin, whose molecular chain does not contain benzene ring structures that are easily oxidized and yellowed. Hindered phenolic antioxidants are embedded in the polyurethane crosslinking network through a polycarbodiimide crosslinking agent, which can capture free radicals generated during high-temperature baking and long-term use, interrupting the thermal oxidation chain reaction. Furthermore, due to chemical bonding, they are not easily migrated or lost, achieving a long-lasting anti-yellowing effect. In addition, the aliphatic waterborne polyurethane molecular chain itself has good flexibility, and the combination with polyethylene glycol as a plasticizer further increases the chain segment mobility, allowing the finished fabric to maintain a soft hand feel. Detailed Implementation

[0018] The present invention will be further described below with reference to embodiments. These embodiments are illustrative of the present invention, but the present invention is not limited to these embodiments: Aliphatic waterborne polyurethane was purchased from Shanghai Bolino New Material Technology Co., Ltd., model PU-710; the quaternary ammonium salt containing active hydroxyl groups was dodecyl dihydroxyethyl methyl ammonium chloride, purchased from Shanghai Boyun New Material Co., Ltd., CAS No. 22340-01-8; the polycarbodiimide crosslinking agent was purchased from Shanghai Deyude Trading Co., Ltd., model E-330-01; the hindered phenolic antioxidant was purchased from Shanghai Tebo Chemical Technology Co., Ltd., CAS No. 27676-62-6; the polyethylene glycol was purchased from Shandong Qianfanshun Chemical Co., Ltd., molecular weight 600, CAS No. 25322-68-3; and the antistatic agent was Atmer 190.

[0019] Example 1

[0020] A method for preparing a long-lasting protective and anti-yellowing anti-ash finishing agent includes the following steps: S1. Take 200g of aliphatic waterborne polyurethane dispersion, 10g of quaternary ammonium salt containing active hydroxyl groups, 2g of polycarbodiimide crosslinking agent, 0.5g of hindered phenolic antioxidant, 5g of polyethylene glycol, and 800g of water. Stir at 300r / min for 15min and mix evenly to obtain the basic long-lasting finishing liquid. S2. Add 10g of poly(N-isopropylacrylamide) and 5g of hydroxypropyl methylcellulose to 200mL of water, stir to dissolve, and obtain the wall material prepolymer solution; S3. Mix 10g Atmer 190 and 10g amino silicone oil, and stir at 60℃ until uniformly dissolved to obtain a core material mixture; S4. Add 20g of core material mixture to the wall material prepolymer liquid, emulsify at 40℃ and 1000r / min for 30min to form an oil-in-water emulsion, add 1.2g of sodium chloride to the emulsion, and slowly cool down at a rate of 0.5℃ / min while stirring, so that the wall material is deposited and coated on the surface of the core material. Then add 0.3g of genipin and cure at 15℃ to cross-link and form the wall material. S5. Centrifuge, collect the precipitate, wash, and vacuum dry to obtain temperature and humidity sensitive microcapsules; S6. Disperse 10g of temperature and humidity sensitive microcapsules in 1000mL of Tris buffer with a concentration of 10mmol / L and a pH of 8.0, and add 0.5g of dopamine hydrochloride to obtain the temperature and humidity sensitive microcapsule finishing solution.

[0021] The above finishing solution is used for fabric finishing, including the following steps: S21. The desized cotton fabric is immersed in a base long-lasting finishing solution at a liquor ratio of 1:20, and then pressed using a padding machine to control the fabric's liquid carrying rate to 70%. S22. The impregnated fabric is pre-dried at 80°C for 5 minutes, and then baked at 140°C for 5 minutes to obtain a fabric with a basic long-lasting layer. S23. Immerse the basic long-lasting layer fabric in the microcapsule finishing solution, remove it and air dry at room temperature to obtain a long-lasting protective anti-yellowing fabric.

[0022] Example 2

[0023] A method for preparing a long-lasting protective and anti-yellowing anti-ash finishing agent includes the following steps: S1. Take 300g of aliphatic waterborne polyurethane dispersion, 25g of quaternary ammonium salt containing active hydroxyl groups, 6g of polycarbodiimide crosslinking agent, 1.5g of hindered phenolic antioxidant, 15g of polyethylene glycol, and 600g of water. Stir at 500r / min for 30min and mix evenly to obtain the basic long-lasting finishing liquid. S2. Mix 10g of poly(N-isopropylacrylamide) and 20g of polyvinyl alcohol, add 200mL of water, stir to dissolve, and obtain the wall material prepolymer solution; S3. Mix 10g Atmer 190 and 10g amino silicone oil, and stir at 60℃ until uniformly dissolved to obtain a core material mixture; S4. Add 20g of core material mixture to the wall material prepolymer liquid, emulsify at 40℃ and 1000r / min for 30min to form an oil-in-water emulsion, add 4.6g of borax to the emulsion, and slowly cool down at a rate of 0.5℃ / min while stirring, so that the wall material is deposited and coated on the surface of the core material. Then add 0.3g of genipin and cure at 15℃ to cross-link and form the wall material. S5 centrifugation, collection of precipitate, washing, vacuum drying, to obtain temperature and humidity sensitive microcapsules; S6. Disperse 30g of temperature and humidity sensitive microcapsules in 1000mL of Tris buffer with a concentration of 50mmol / L and a pH of 8.5, and add 2g of dopamine hydrochloride to obtain the temperature and humidity sensitive microcapsule finishing solution.

[0024] The above finishing solution is used for fabric finishing, including the following steps: S21. The desized cotton fabric is immersed in a base long-lasting finishing solution at a liquor ratio of 1:20, and then pressed using a padding machine to control the fabric's liquid carrying rate to 80%. S22. The impregnated fabric is pre-dried at 100°C for 1 min and then baked at 160°C for 1 min to obtain a fabric with a basic long-lasting layer. S23. Immerse the basic long-lasting layer fabric in the microcapsule finishing solution, remove it and air dry at room temperature to obtain a long-lasting protective anti-yellowing fabric.

[0025] Example 3

[0026] A method for preparing a long-lasting protective and anti-yellowing anti-ash finishing agent includes the following steps: S1. Take 250g of aliphatic waterborne polyurethane dispersion, 18g of quaternary ammonium salt containing active hydroxyl groups, 4g of polycarbodiimide crosslinking agent, 1g of hindered phenolic antioxidant, 10g of polyethylene glycol, and 700g of water. Stir at 400r / min for 20min and mix evenly to obtain the basic long-lasting finishing liquid. S2. Mix 10g of poly(N-isopropylacrylamide) and 10g of polyvinyl alcohol, add 200mL of water, stir to dissolve, and obtain the wall material prepolymer solution; S3. Mix 20g Atmer 190 and 10g amino silicone oil, and stir at 70℃ until uniformly dissolved to obtain a core material mixture; S4. Add 30g of core material mixture to the wall material prepolymer liquid, emulsify at 50℃ and 1500r / min for 20min to form an oil-in-water emulsion, add 6g of borax to the emulsion, and slowly cool down while stirring at a rate of 1℃ / min to allow the wall material to be deposited and coated on the surface of the core material. Then add 1g of genipin and cure at 20℃ to allow the wall material to cross-link and form. S5. Centrifuge, collect the precipitate, wash, and vacuum dry to obtain temperature and humidity sensitive microcapsules; S6. Disperse 20g of temperature and humidity sensitive microcapsules in 1000mL of Tris buffer with a concentration of 30mmol / L and a pH of 8.2, and add 1.2g of dopamine hydrochloride to obtain the temperature and humidity sensitive microcapsule finishing solution.

[0027] The above finishing solution is used for fabric finishing, including the following steps: S21. The desized cotton fabric is immersed in a base long-lasting finishing solution at a liquor ratio of 1:20, and then pressed using a padding machine to control the fabric's liquid carrying rate to 75%. S22. The impregnated fabric is pre-dried at 90°C for 2 minutes, and then baked at 150°C for 2 minutes to obtain a fabric with a basic long-lasting layer. S23. Immerse the basic long-lasting layer fabric in the microcapsule finishing solution, remove it and air dry at room temperature to obtain a long-lasting protective anti-yellowing fabric.

[0028] Example 4

[0029] A method for preparing a long-lasting protective and anti-yellowing anti-ash finishing agent includes the following steps: S1. Take 220g of aliphatic waterborne polyurethane dispersion, 15g of quaternary ammonium salt containing active hydroxyl groups, 3g of polycarbodiimide crosslinking agent, 0.8g of hindered phenolic antioxidant, 8g of polyethylene glycol, and 650g of water. Stir at 350r / min for 25min and mix evenly to obtain the basic long-lasting finishing liquid. S2. Mix 10g of poly(N-isopropylacrylamide) and 15g of hydroxypropyl methylcellulose, add 200mL of water, stir to dissolve, and obtain a wall material prepolymer solution; S3. Mix 15g Atmer 190 and 10g amino silicone oil, and stir at 68℃ until uniformly dissolved to obtain a core material mixture; S4. Add 25g of core material mixture to the wall material prepolymer liquid, emulsify at 45℃ and 1200r / min for 25min to form an oil-in-water emulsion, add 16g of sodium chloride to the emulsion, and slowly cool down while stirring at a rate of 1.5℃ / min to allow the wall material to be deposited and coated on the surface of the core material. Then add 0.6g of genipin and cure at 20℃ to allow the wall material to cross-link and form. S5. Centrifuge, collect the precipitate, wash, and vacuum dry to obtain temperature and humidity sensitive microcapsules; S6. Disperse 15g of temperature and humidity sensitive microcapsules in 1000mL of Tris buffer with a concentration of 20mmol / L and a pH of 8.1, and add 0.8g of dopamine hydrochloride to obtain the temperature and humidity sensitive microcapsule finishing solution.

[0030] The above finishing solution is used for fabric finishing, including the following steps: S21. The desized cotton fabric is immersed in a base long-lasting finishing solution at a liquor ratio of 1:20, and then pressed using a padding machine to control the fabric's liquid carrying rate to 76%. S22. The impregnated fabric is pre-dried at 85°C for 3 minutes, and then baked at 145°C for 3 minutes to obtain a fabric with a basic long-lasting layer. S23. Immerse the basic long-lasting layer fabric in the microcapsule finishing solution, remove it and air dry at room temperature to obtain a long-lasting protective anti-yellowing fabric.

[0031] Example 5

[0032] A method for preparing a long-lasting protective and anti-yellowing anti-ash finishing agent includes the following steps: S1. Take 280g of aliphatic waterborne polyurethane dispersion, 22g of quaternary ammonium salt containing active hydroxyl groups, 5g of polycarbodiimide crosslinking agent, 1.2g of hindered phenolic antioxidant, 12g of polyethylene glycol, and 750g of water. Stir at 450r / min for 18min and mix evenly to obtain the basic long-lasting finishing liquid. S2. Mix 10g of poly(N-isopropylacrylamide) and 8g of hydroxypropyl methylcellulose, add 200mL of water, stir to dissolve, and obtain the wall material prepolymer solution; S3. Mix 25g Atmer 190 and 10g amino silicone oil, and stir at 75℃ until uniformly dissolved to obtain a core material mixture; S4. Add 35g of core material mixture to the wall material prepolymer liquid, emulsify at 55℃ and 1800r / min for 15min to form an oil-in-water emulsion, add 20g of sodium sulfate to the emulsion, and slowly cool down while stirring at a rate of 1.5℃ / min to allow the wall material to be deposited and coated on the surface of the core material. Then add 1.6g of genipin and cure at 20℃ to allow the wall material to cross-link and form. S5. Centrifuge, collect the precipitate, wash, and vacuum dry to obtain temperature and humidity sensitive microcapsules; S6. Disperse 25g of temperature and humidity sensitive microcapsules in 1000mL of Tris buffer with a concentration of 40mmol / L and a pH of 8.3, and add 1.6g of dopamine hydrochloride to obtain the temperature and humidity sensitive microcapsule finishing solution.

[0033] The above finishing solution is used for fabric finishing, including the following steps: S21. The desized cotton fabric is immersed in a base long-lasting finishing solution at a liquor ratio of 1:20, and then pressed using a padding machine to control the fabric's liquid carrying rate to 78%. S22. The impregnated fabric is pre-dried at 95°C for 2 min, and then baked at 155°C for 2 min to obtain a fabric with a basic long-lasting layer. S23. Immerse the basic long-lasting layer fabric in the microcapsule finishing solution, remove it and air dry at room temperature to obtain a long-lasting protective anti-yellowing fabric.

[0034] Comparative Example 1 The difference between Comparative Example 1 and Example 3 is that Comparative Example 1 does not prepare a basic long-lasting finishing solution, but only prepares a temperature and humidity sensitive microcapsule finishing solution. The desized cotton fabric is immersed in the microcapsule finishing solution, taken out and dried at room temperature to obtain the finished fabric.

[0035] Comparative Example 2 The difference between Comparative Example 2 and Example 3 is that Comparative Example 2 does not prepare a temperature and humidity sensitive microcapsule finishing solution, but only prepares a basic long-acting finishing solution, and uses the basic long-acting finishing solution to finish the desized cotton fabric according to the steps of Example 3.

[0036] Comparative Example 3 The difference between Comparative Example 3 and Example 3 is that the microcapsule wall material of Comparative Example 3 is a single temperature-sensitive polymer, while the remaining steps are the same as those of Example 3.

[0037] The preparation method of the finishing agent includes the following steps: S1. Take 250g of aliphatic waterborne polyurethane dispersion, 18g of quaternary ammonium salt containing active hydroxyl groups, 4g of polycarbodiimide crosslinking agent, 1g of hindered phenolic antioxidant, 10g of polyethylene glycol, and 700g of water. Stir at 400r / min for 20min and mix evenly to obtain the basic long-lasting finishing liquid. S2. Dissolve 10g of poly(N-isopropylacrylamide) in 200mL of water by stirring to obtain a prepolymer solution for wall materials; S3. Mix 20g Atmer 190 and 10g amino silicone oil, and stir at 70℃ until uniformly dissolved to obtain a core material mixture; S4. Add 30g of core material mixture to the wall material prepolymer liquid, emulsify at 50℃ and 1500r / min for 20min to form an oil-in-water emulsion, slowly cool while stirring at a rate of 1℃ / min to allow the wall material to be deposited and coated on the surface of the core material, then add 1g of genipin and cure at 20℃ to allow the wall material to cross-link and form. S5. Centrifuge, collect the precipitate, wash, and vacuum dry to obtain temperature-sensitive microcapsules; S6. Disperse 20g of temperature-sensitive microcapsules in 1000mL of Tris buffer with a concentration of 30mmol / L and a pH of 8.2, and add 1.2g of dopamine hydrochloride to obtain the temperature-sensitive microcapsule finishing solution.

[0038] Comparative Example 4 The difference between Comparative Example 4 and Example 3 is that the microcapsule wall material of Comparative Example 4 is a single moisture-sensitive polymer, while the remaining steps are the same as those of Example 3.

[0039] The preparation method of the finishing agent includes the following steps: S1. Take 250g of aliphatic waterborne polyurethane dispersion, 18g of quaternary ammonium salt containing active hydroxyl groups, 4g of polycarbodiimide crosslinking agent, 1g of hindered phenolic antioxidant, 10g of polyethylene glycol, and 700g of water. Stir at 400r / min for 20min and mix evenly to obtain the basic long-lasting finishing liquid. S2. Dissolve 10g of polyvinyl alcohol in 200mL of water by stirring to obtain a prepolymer solution for wall materials; S3. Mix 20g Atmer 190 and 10g amino silicone oil, and stir at 70℃ until uniformly dissolved to obtain a core material mixture; S4. Add 30g of core material mixture to the wall material prepolymer liquid, emulsify at 50℃ and 1500r / min for 20min to form an oil-in-water emulsion, add 6g of borax to the emulsion, and slowly cool down while stirring at a rate of 1℃ / min to allow the wall material to be deposited and coated on the surface of the core material. Then add 1g of genipin and cure at 20℃ to allow the wall material to cross-link and form. S5. Centrifuge to separate, collect the precipitate, wash, and vacuum dry to obtain moisture-sensitive microcapsules.

[0040] S6. Disperse 20g of moisture-sensitive microcapsules in 1000mL of Tris buffer with a concentration of 30mmol / L and a pH of 8.2, and add 1.2g of dopamine hydrochloride to obtain the moisture-sensitive microcapsule finishing solution.

[0041] Comparative Example 5 The difference between Comparative Example 5 and Example 3 is that: in step S6 of Comparative Example 5, dopamine hydrochloride is not added, and the microcapsules are only attached to the surface of the basic long-lasting layer by physical adsorption. The rest is the same as in Example 3.

[0042] Comparative Example 6 The difference between Comparative Example 6 and Example 3 is that no polycarbodiimide crosslinking agent is added to the base long-lasting finishing solution of Comparative Example 6, and the quaternary ammonium salt containing active hydroxyl groups is only physically dispersed in polyurethane without a covalent bond network. The rest is the same as Example 3.

[0043] Comparative Example 7 The difference between Comparative Example 7 and Example 3 is that the base long-lasting finishing solution of Comparative Example 7 does not contain hindered phenolic antioxidants, while the rest is the same as Example 3.

[0044] Testing: Antistatic performance was tested according to GB / T 12703.1-2021. The electrostatic voltage half-life of the fabric was determined under the conditions of 20±2℃ and 40±2% relative humidity. Dust adhesion testing used chalk dust as the test material. A 6cm×6cm fabric sample and 0.1g of chalk dust were placed in a sealed plastic bag and shaken vigorously for 15 minutes. The dust resistance level was assessed using a staining gray card (grades 1-5). Samples were tested before washing and after 50 washes to evaluate the fabric's ability to inhibit dust adhesion. After heat treatment in a 150℃ oven for 2 hours, the ΔE value and whiteness change before and after treatment were measured using a colorimeter to evaluate the fabric. Anti-yellowing ability during high-temperature baking and long-term use; the fabrics of Example 4, Comparative Example 3 and Comparative Example 4 were placed in constant temperature and humidity chambers under four different temperature and humidity conditions for 24 hours: Condition A (25℃ / 65%RH, simulating daily wearing environment), Condition B (40℃ / 30%RH, simulating dry high temperature environment), Condition C (40℃ / 65%RH, simulating high temperature environment), and Condition D (25℃ / 30%RH, simulating dry environment). The change in surface resistance before and after treatment was measured, the resistance reduction rate was calculated, and the temperature and humidity dual-sensitivity release performance was evaluated.

[0045] Table 1 Antistatic Performance Test

[0046] Referring to Table 1, the embodiments of the present invention exhibit excellent antistatic properties when not washed. This is due to the fact that the quaternary ammonium salt containing active hydroxyl groups in the basic long-lasting layer forms a covalent bond network with the aliphatic waterborne polyurethane and fiber surface active groups through the polycarbodiimide crosslinking agent, which chemically anchors the antistatic agent to the fiber surface and constructs a stable and efficient charge dissipation pathway. Comparative Example 1 lacked a basic long-lasting layer, and its initial antistatic performance was weaker than that of the Example. After washing, the microcapsules detached, resulting in a significantly prolonged half-life. Without the support of a covalent bond network, relying solely on microcapsules could not achieve long-lasting antistatic effects. Comparative Example 2 had no microcapsule replenishment, and its initial performance was comparable to that of the Example. After washing, the antistatic agent was gradually consumed and could not be regenerated, resulting in a half-life inferior to that of the Example. Having only a basic layer without an intelligent replenishment mechanism made it difficult to maintain long-term performance. Comparative Example 5 lacked dopamine chemical anchoring, and the microcapsules relied solely on physical adsorption. A large number of them detached during the washing process, resulting in a half-life significantly inferior to that of the Example. This highlighted the crucial role of the chemical bond anchoring formed by the polydopamine layer and genipin crosslinking in ensuring the firm adhesion of the microcapsules. Comparative Example 6, due to the absence of a crosslinking agent in the basic layer, had quaternary ammonium salts containing active hydroxyl groups physically dispersed in the polyurethane film without forming a covalent bond network. The large-scale migration and loss of antistatic agent after washing confirmed the role of the covalent bond network in the long-term fixation of the antistatic agent.

[0047] Table 2 Dustproof Performance Test

[0048] Referring to Table 2, the embodiments of the present invention all exhibited excellent dustproof ratings before washing, and the dustproof ratings remained at a high level after 50 standard washes. In the basic long-lasting layer of the present invention, the quaternary ammonium salt containing active hydroxyl groups forms a covalent bond network with aliphatic waterborne polyurethane and fiber surface active groups under the action of polycarbodiimide crosslinking agent. This network continuously reduces the fiber surface resistance, accelerates the dissipation of static charge, and reduces the adsorption of dust by electrostatic attraction. Comparative Example 1 lacked a basic long-lasting layer, and its initial dustproof level was lower than that of the Example. After washing, the microcapsules detached, resulting in a decrease in static dissipation ability and a significant increase in dust adsorption. Comparative Example 2 had a complete basic layer but no microcapsules to replenish it. Its initial dustproof level was close to that of the Example. However, after washing, the antistatic agent was gradually consumed and the amino silicone oil could not be regenerated, causing the coefficient of friction on the fiber surface to rise and the smoothness to decrease. Comparative Example 5 lacked dopamine chemical anchoring, and the microcapsules relied solely on physical adsorption. A large number of microcapsules detached during the washing process, resulting in a significant decrease in the dustproof level. Comparative Example 6 lacked a crosslinking agent in its basic layer, and the quaternary ammonium salt containing active hydroxyl groups was only physically dispersed. After washing, a large amount of antistatic agent migrated and was lost, and static adsorption was enhanced, resulting in a decrease in the dustproof level.

[0049] Table 3 Yellowing Resistance Test

[0050] Referring to Table 3, the examples exhibited excellent anti-yellowing properties and high whiteness retention after heat treatment at 150℃. The basic long-lasting layer of this invention uses aliphatic waterborne polyurethane as the film-forming resin, whose molecular chain does not contain benzene ring structures that are easily oxidized and yellowed, thus reducing the tendency to yellow from the material's inherent nature. The hindered phenolic antioxidant is embedded in the polyurethane crosslinking network through a polycarbodiimide crosslinking agent, which contains sterically hindered phenolic hydroxyl structures. It can efficiently capture peroxide free radicals and alkoxy free radicals generated during high-temperature baking and long-term use, converting the free radicals into stable quinones or coupling products, interrupting the thermal oxidation chain reaction, and still maintaining excellent antioxidant capacity after high-temperature heat treatment. Comparative Example 1 fabric, lacking hindered phenolic antioxidants, exhibited significant thermal oxidative yellowing after heat treatment at 150°C, with a marked increase in color difference and a substantial decrease in whiteness retention. The inherent anti-yellowing ability of cotton fibers alone was far from sufficient to resist high-temperature thermal oxidative damage. Comparative Example 2, possessing an intact base layer and containing antioxidants, showed anti-yellowing performance similar to the examples, indicating that the absence of microcapsules does not affect yellowing performance. Comparative Example 7, lacking hindered phenolic antioxidants, showed a significant increase in color difference and a substantial decrease in whiteness retention.

[0051] Table 4 Temperature and Humidity Dual-Sensitive Release Performance

[0052] Referring to Table 4, the embodiments of the present invention show a significant decrease in resistance under high temperature and low humidity conditions, while the resistance changes are small under normal temperature and humidity, low humidity, and high temperature conditions. This is because the microcapsule wall material is a composite cross-linked network of poly(N-isopropylacrylamide) and hydroxypropyl methylcellulose or polyvinyl alcohol. Under normal temperature and humidity conditions, the wall material remains in a swollen state, and the core material is completely sealed. When the ambient temperature rises above the lower critical dissolution temperature and the humidity decreases, the hydrogen bonds between the temperature-sensitive polymer chains and water molecules break and collapse. At the same time, the humidity-sensitive polymer shrinks due to water loss. The synergistic effect of these two factors leads to a significant increase in the permeability of the wall material, allowing the antistatic agent in the core material to be released rapidly. Comparative Example 3 uses a single temperature-sensitive wall material, which, under condition D, lacks a humidity-sensitive component and cannot respond to humidity changes, thus having almost no release effect. Comparative Example 4 uses a single humidity-sensitive wall material, which does not possess temperature-sensitive collapse characteristics under high temperature conditions, therefore the antistatic core material release is minimal.

[0053] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A long-lasting protective and anti-yellowing anti-dust finishing agent, characterized in that, The finishing agent includes a basic long-lasting finishing solution and a temperature and humidity sensitive microcapsule finishing solution. The basic long-lasting finishing solution contains an aliphatic aqueous polyurethane dispersion, a quaternary ammonium salt containing active hydroxyl groups, a polycarbodiimide crosslinking agent, a hindered phenolic antioxidant, and polyethylene glycol. The temperature and humidity sensitive microcapsule finishing solution contains temperature and humidity sensitive microcapsules, Tris buffer, and dopamine hydrochloride. The wall material of the temperature and humidity sensitive microcapsules is a mixed crosslinked network of temperature-sensitive polymer and humidity-sensitive polymer, and the core material contains an antistatic agent and amino silicone oil.

2. The finishing agent according to claim 1, characterized in that: The mass fractions of each component in the basic long-lasting finishing liquid are as follows: 200-300 parts of aliphatic waterborne polyurethane dispersion, 10-25 parts of quaternary ammonium salt containing active hydroxyl groups, 2-6 parts of polycarbodiimide crosslinking agent, 0.5-1.5 parts of hindered phenolic antioxidant, 5-15 parts of polyethylene glycol, and 600-800 parts of water.

3. The finishing agent according to claim 1, characterized in that: The concentration of Tris buffer in the temperature and humidity sensitive microcapsule finishing solution is 10~50 mmol / L, the pH is 8.0~8.5, the concentration of temperature and humidity sensitive microcapsules in the microcapsule finishing solution is 10~30 g / L, and the concentration of dopamine hydrochloride is 0.5~2 g / L.

4. The method for preparing the finishing agent according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Mix aliphatic waterborne polyurethane dispersion, quaternary ammonium salt containing active hydroxyl groups, polycarbodiimide crosslinking agent, hindered phenolic antioxidant, polyethylene glycol and water evenly to obtain basic long-lasting finishing liquid; S2. Prepare temperature and humidity sensitive microcapsules. Disperse the temperature and humidity sensitive microcapsules in Tris buffer, add dopamine hydrochloride, mix well, and obtain temperature and humidity sensitive microcapsule finishing solution.

5. The preparation method according to claim 4, characterized in that: The preparation method of the temperature and humidity sensitive microcapsules includes the following steps: S11. Mix the temperature-sensitive polymer and the humidity-sensitive polymer in a certain proportion, add water, stir to dissolve, and obtain the wall material prepolymer solution; S12. Mix the antistatic agent and amino silicone oil, heat and stir until uniformly dissolved to obtain a core material mixture; S13. Add the core material mixture to the wall material prepolymer liquid, emulsify at high speed to form an oil-in-water emulsion, add a depositing agent to the emulsion, and slowly cool it while stirring to allow the wall material to be deposited and coated on the surface of the core material. Then add a crosslinking agent to cure and crosslink the wall material into shape. S14. Centrifuge to separate, collect the precipitate, wash, and vacuum dry to obtain temperature and humidity sensitive microcapsules.

6. The preparation method according to claim 5, characterized in that: In step S11, the mass ratio of the temperature-sensitive polymer to the humidity-sensitive polymer is 1:(0.5~2). The temperature-sensitive polymer is poly(N-isopropylacrylamide) or a copolymer thereof, and the humidity-sensitive polymer is selected from either hydroxypropyl methylcellulose or polyvinyl alcohol.

7. The preparation method according to claim 5, characterized in that: In step S12, the mass ratio of antistatic agent to amino silicone oil is (1~3):1, and the ammonia value of amino silicone oil is 0.3~0.6 mmol / g.

8. The preparation method according to claim 5, characterized in that: In step S13, the high-speed emulsification temperature is 40~60℃, the rotation speed is 1000~2000r / min, the deposition agent is any one of sodium chloride, sodium sulfate or borax, the amount added is 0.5~15% of the total mass of the wall material prepolymer liquid, the cooling rate is 0.5~2℃ / min, the crosslinking agent is genipin, the amount added is 0.1~1% of the total mass of the wall material prepolymer liquid, and the curing temperature is 15~30℃.

9. The application of the finishing agent according to any one of claims 1 to 3, characterized in that, Includes the following steps: S21. Immerse the cotton or polyester-cotton blended fabric in the base long-lasting finishing solution, and use a padding machine to control the fabric liquid carrying rate to 70-80%; S22. The impregnated fabric is pre-dried at 80~100℃ for 1~5min, and then baked at 140~160℃ for 1~5min to obtain the basic long-lasting layer fabric. S23. Immerse the basic long-lasting layer fabric in the microcapsule finishing solution, remove it and air dry at room temperature to obtain a long-lasting protective anti-yellowing fabric.

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