Finishing agent, its preparation method and application

Abstract

The application discloses a finishing agent and a preparation method and application thereof, and preparation raw materials include modified anti-ultraviolet absorbent and silicone modified water-based polyurethane; preparation raw materials of the silicone modified water-based polyurethane include polyglycol, diisocyanate and silicone; the silicone includes at least one of aminoalkyl silicone, silanol hydroxyl silicone, hydrocarbon-based polyether silicone, single-end double-hydrocarbon-based silicone and double-end double-hydrocarbon-based silicone; preparation raw materials of the modified anti-ultraviolet absorbent include ultraviolet absorbent and emulsifying dispersant; the ultraviolet absorbent includes at least one of benzotriazole ultraviolet absorbent and benzophenone ultraviolet absorbent.

Description

Technical Field

[0001] This invention belongs to the technical field of anti-ultraviolet radiation and waterproof materials, specifically relating to a finishing agent, its preparation method, and its application. Background Technology

[0002] Fluorocarbon-based waterproofing agents are widely used in the field of waterproofing finishing agents. However, during their production and use, they generate perfluorooctane sulfonyl compounds (PFOS) and perfluorooctanoic acid (PFOA), which have bioaccumulation and toxicity to the ecological environment and human health. Currently, there is no effective method to completely solve the problem of PFOS and PFOA pollution. Compared with fluorocarbon-based waterproofing agents, fluorine-free waterproofing agents are characterized by their resistance to deposition in organisms, easy degradation, and harmlessness to humans, making them safer and more environmentally friendly products. Organosilicon-modified waterborne polyurethane waterproofing agents are a type of fluorine-free waterproofing agent. When applied to fabrics, organosilicon-modified waterborne polyurethane waterproofing agents can form a hydrophobic film with low surface energy, high abrasion resistance, and high adhesion on the fabric surface. However, although fabrics treated with silicone-modified waterborne polyurethane waterproofing agents have a certain waterproofing effect, in areas with long-term sun exposure or heavy rain, after prolonged exposure to sunlight, the photosensitive substances in the waterproof fabric undergo photochemical reactions, which damage the polymer macromolecular chains. This not only severely reduces the waterproofing performance of the treated fabric, but also damages the original physical and mechanical properties of the fabric fibers. As a result, the fabric suffers irreversible physical damage such as fading, loss of luster, chalking, cracking, splitting, blurring, embrittlement, reduced strength, and oxidation, thus reducing the service life of the waterproof fabric.

[0003] Therefore, developing a finishing agent and its preparation method that can solve the shortcomings of existing finishing agents in terms of poor durability of waterproof and UV radiation resistance is an urgent task. Summary of the Invention

[0004] This invention aims to at least solve one of the technical problems existing in the prior art. To this end, this invention proposes a finishing agent, its preparation method, and its application. This invention combines an ultraviolet absorber with an organosilicon-modified waterborne polyurethane waterproof finishing agent, so that the ultraviolet protectant and the hydrophobic organosilicon material in the finishing agent exert a synergistic effect, thereby improving the ultraviolet radiation resistance and waterproof performance of the finished fabric.

[0005] According to a first aspect of the present invention, a finishing agent is prepared from raw materials including: a modified UV absorber and an organosilicon-modified waterborne polyurethane;

[0006] The raw materials for preparing the organosilicon-modified waterborne polyurethane include polydiol, diisocyanate and organosilicon.

[0007] The organosilicon includes at least one of aminoalkyl organosilicon, silanol hydroxyl organosilicon, hydroxyalkyl polyether organosilicon, single-terminated dihydroxyalkyl organosilicon, and double-terminated dihydroxyalkyl organosilicon.

[0008] The raw materials for preparing the modified UV absorber include UV absorbers and emulsifying dispersants;

[0009] The ultraviolet absorber includes at least one of benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers.

[0010] A method for recovering phosphorus and iron according to an embodiment of the present invention has at least the following beneficial effects:

[0011] The ultraviolet absorber in this invention is an organic compound. Unlike ultraviolet shielding agents that physically shield or reflect ultraviolet rays, this anti-ultraviolet absorber can efficiently absorb ultraviolet rays and convert the absorbed energy into less destructive heat energy or other harmless and low-energy radiation chemical energy, long-wave light energy, etc. It can then quickly quench the high-energy excited states in the polymer excited by ultraviolet rays and return them to the ground state. At the same time, it can effectively capture the free radicals generated by ultraviolet irradiation in the polymer, thereby reducing the probability of irreversible physical damage to textile fabrics.

[0012] The modified UV absorber of this invention combines with organosilicon-modified polyurethane polymers through chemical bonding and supramolecular effects of hydroxyl functional groups, resulting in synergistic effects and giving the finishing agent superior overall performance. This not only improves the UV resistance and waterproof performance of the finished fabric, but also extends the fabric's service life.

[0013] Compared with products obtained by simply physically blending nanoparticle UV shielding agents and organosilicon-modified waterborne polyurethane waterproofing finishing agents, the resulting UV-resistant waterproofing finishing agent has the characteristics of UV-absorbing functional groups not easily migrating and long-lasting stable performance.

[0014] In this invention, an ultraviolet absorber is combined with an organosilicon-modified waterborne polyurethane waterproof finishing agent, so that the ultraviolet protectant in the finishing agent and the hydrophobic organosilicon material can play a synergistic effect, thereby improving the ultraviolet radiation resistance and waterproof performance of the finished fabric.

[0015] According to some embodiments of the present invention, the raw materials for preparing the finishing agent further include emulsifying dispersants, solvents, small molecule chain extenders, hydrophilic chain extenders, salt-forming agents, and pure water.

[0016] According to some embodiments of the present invention, the raw materials for preparing the finishing agent, by weight, include 0.25-1.25 parts of UV absorber, 0.9-2.3 parts of emulsifying dispersant, 8.3-9.2 parts of solvent, 19.2-20.5 parts of organosilicon, 26.2-28.3 parts of diisocyanate, 4.7-6.1 parts of polydiol, 0.9-1.7 parts of small molecule chain extender, 3.5-5.6 parts of hydrophilic chain extender, 0.9-1.7 parts of salt-forming agent, and 27.4-31.2 parts of pure water.

[0017] According to some embodiments of the present invention, the emulsifying dispersant includes at least one of styrene-phenol polyoxyethylene ether (16EO), styrene-phenol polyoxyethylene ether (20EO), isotridecyl alcohol polyoxyethylene ether (5EO), isotridecyl alcohol polyoxyethylene ether (9EO), fatty alcohol polyoxyethylene ether AEO9, and cashew phenol polyoxyethylene ether.

[0018] According to some embodiments of the present invention, the diisocyanate includes at least one selected from isophorone diisocyanate, 1,6-hexane diisocyanate, toluene diisocyanate, trimethylhexane diisocyanate, and diphenylmethane diisocyanate.

[0019] According to some embodiments of the present invention, the polydiol includes at least one of polyethers such as polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol, and polycarbonate glycol.

[0020] According to some embodiments of the present invention, the hydrophilic chain extender includes at least one of N-methyldiethanolamine, diethylenetriamine, diethanolamine, and triethanolamine.

[0021] According to some embodiments of the present invention, the hydrophilic chain extender includes at least one of N-methyldiethanolamine, diethylenetriamine, diethanolamine, and triethanolamine.

[0022] According to some preferred embodiments of the present invention, the hydrophilic chain extender includes at least one of N-methyldiethanolamine and diethylenetriamine.

[0023] According to some embodiments of the present invention, the solvent includes at least one selected from propylene glycol, diethylene glycol, isobutyl acetate, diethylene glycol butyl ether, acetone, and butanone.

[0024] According to some embodiments of the present invention, the UV absorber includes at least one of benzotriazole UV-1130, benzophenone UV-2, and BP-1.

[0025] According to some preferred embodiments of the present invention, the anti-ultraviolet absorber includes at least one of benzophenone-based ultraviolet absorbers BP-2 and BP-1.

[0026] According to some more preferred embodiments of the present invention, the UV absorber is BP-2.

[0027] According to an embodiment of a second aspect of the present invention, a method for preparing a finishing agent is provided, the method comprising mixing the modified UV absorber and the organosilicon-modified waterborne polyurethane.

[0028] According to some embodiments of the present invention, the preparation method of the modified UV absorber includes: mixing the emulsifying dispersant and the UV absorber and then crushing them.

[0029] According to some preferred embodiments of the present invention, the preparation method of the modified UV absorber includes: stirring and dissolving the emulsifying dispersant and solvent, then slowly adding the UV absorber at a low stirring speed, then increasing the stirring speed and stirring for 0.5 h to perform pre-dispersion treatment to obtain a pre-dispersion liquid, then adding the obtained pre-dispersion liquid to a sand mill, adding zirconium beads to grind the pre-dispersion liquid, taking an appropriate amount of the ground dispersion every 30 min to test the particle size in a laser particle size analyzer, grinding until the particle size is between 0.25 μm and 4.85 μm; ending the grinding, filtering the zirconium beads, and the resulting filtrate is the modified UV absorber.

[0030] This invention grinds a crystalline powdered UV absorber to the desired particle size range in the presence of an emulsifying dispersant and a solvent. This improves the dispersion stability of the UV absorber in the dispersed phase, avoids its tendency to agglomerate and its difficulty in dispersion, enhances the compatibility of the UV absorber dispersion system with the silicone-modified waterborne polyurethane dispersion system, reduces the formation of interfacial defects, and strengthens the storage stability of the product. Compared with products obtained by simply physically blending nanoparticle UV shielding agents and silicone-modified waterborne polyurethane, the UV-resistant waterproofing agent obtained in this invention has the characteristics of UV-absorbing functional groups not easily migrating and long-lasting stable performance.

[0031] According to some preferred embodiments of the present invention, the method for preparing the organosilicon-modified polyurethane includes:

[0032] A1. The polydiol is dehydrated to obtain anhydrous polydiol;

[0033] A2. In the presence of a catalyst, diisocyanate is added to the anhydrous polydiol, and after mixing, a prepolymer with isocyanate groups at both ends is obtained;

[0034] A3. Add organosilicon to the prepolymer with isocyanate groups at both ends, and mix to obtain a dispersion of organosilicon-modified polyurethane.

[0035] According to some preferred embodiments of the present invention, in step A1, the dehydration temperature is 115-125°C.

[0036] According to some preferred embodiments of the present invention, in step A1, the vacuum degree of the dehydration is -0.08 to -0.1 MPa.

[0037] According to some embodiments of the present invention, the preparation method of the finishing agent includes: mixing the modified UV absorber, the organosilicon modified polyurethane, the small molecule chain extender, the hydrophilic chain extender, the salt forming agent and the pure water.

[0038] According to some embodiments of the present invention, the preparation method of the finishing agent includes: mixing the modified UV absorber and the organosilicon modified polyurethane, then adding the small molecule chain extender and the hydrophilic chain extender, and then adding the salting agent and the pure water.

[0039] A third aspect of the invention proposes the application of the finishing agent described herein in waterproof materials. Detailed Implementation

[0040] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0041] Example 1

[0042] This embodiment provides a finishing agent and its preparation method, the specific steps of which include:

[0043] A1: Benzophenone-based UV absorber BP-2 (CAS No. 156327-07-0) 0.5 parts, emulsifier and dispersant isotridecyl alcohol polyoxyethylene ether (5EO) 1.5 parts, methyl ethyl ketone 4 parts, isobutyl acetate 5.1 parts, hydroxyalkyl polyether silicone (CAS No. 156327-07-0) 19.4 parts, isophorone diisocyanate 26.7 parts, polypropylene glycol 5.4 parts, 1,4-butanediol 1.4 parts, hydrophilic chain extender MDEA 4.8 parts, acetic acid 1.3 parts, pure water 29.9 parts, the total mass of the above components is 100;

[0044] A2: Place the isomeric tridecyl alcohol polyoxyethylene ether (5EO) and butanone weighed in step A1 into a shear emulsifying mixer and stir until uniformly dissolved (3000 r / min). Then, slowly add BP-2 at 1500 r / min, and then increase the stirring speed to 3000 r / min and stir for 0.5 h for pre-dispersion treatment. Then, add the obtained pre-dispersion liquid into a sand mill and add 70 parts by mass of zirconium beads for grinding. Take an appropriate amount of grinding liquid every 30 min and test the particle size in a laser particle size analyzer until the particle size is less than 3.17 μm. After grinding, filter the zirconium beads. The obtained filtrate is the modified anti-ultraviolet absorber that can exist stably in the dispersion system in the preliminary preparation.

[0045] A3: Preparation of Organosilicon Modified Polyurethane

[0046] A3.1: The polyoxypropylene glycol is added to a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is then subjected to vacuum distillation at 120°C and a vacuum of -0.08 MPa to obtain anhydrous polyoxypropylene glycol.

[0047] A3.2: Isophorone diisocyanate is added to the anhydrous polyoxypropylene glycol in the presence of a catalyst, and the mixture is stirred evenly in a water bath to carry out a prepolymerization reaction to obtain a prepolymer with isocyanate groups at both ends.

[0048] A3.3: Add hydroxyl-based polyether organosilicon that has been completely dissolved in isobutyl acetate to the prepolymer with isocyanate groups at both ends, stir evenly in a water bath at 65-70°C and modify it to obtain a preliminary pre-dispersion of organosilicon-modified polyurethane waterproofing agent.

[0049] A3.4: The modified UV absorber prepared in step A2 is slowly added to the silicone-modified polyurethane in step A3. The mixture is stirred at 60°C for 3 hours. Then, 1,4-butanediol and MDEA are added sequentially at 60°C to carry out chain extension reaction. The mixture is then cooled to 35°C, and acetic acid is slowly added dropwise for neutralization. Finally, pure water is added for emulsification to obtain the desired UV-resistant waterproof finishing agent.

[0050] Example 2

[0051] This embodiment provides a finishing agent and its preparation method, the specific steps of which include:

[0052] A1: Weigh the following raw materials according to the following mass percentages: 0.45 parts of benzophenone-based UV absorber BP-2 (CAS No. 156327-07-0), 1.35 parts of emulsifying dispersant styrene-phenol polyoxyethylene ether (20EO), 3.6 parts of methyl ethyl ketone (MEK), 5.4 parts of isobutyl acetate, 19.7 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 27.2 parts of isophorone diisocyanate, 5.7 parts of polyoxypropylene glycol, 1.2 parts of 1,4-butanediol, 4.3 parts of hydrophilic chain extender MDEA, 1.1 parts of acetic acid, and 30 parts of pure water. The total mass percentage of all the above components is 100.

[0053] A2: Place the styrene-phenol polyoxyethylene ether (20EO) and butanone weighed in step A1 into a shear emulsifying mixer and stir until uniformly dissolved (2500 r / min). Then, slowly add BP-2 at 1500 r / min, and then increase the stirring speed to 3000 r / min and stir for 0.5 h for pre-dispersion treatment. Then, add the obtained pre-dispersion liquid into a sand mill and add 75 parts by mass of zirconium beads for grinding. Take an appropriate amount of grinding liquid every 30 min and test the particle size in a laser particle size analyzer until the particle size is less than 3.17 μm. After grinding, filter the zirconium beads. The obtained filtrate is the modified anti-ultraviolet absorber that can exist stably in the dispersion system in the preliminary preparation.

[0054] A3: Preparation of Organosilicon Modified Polyurethane

[0055] A3.1: The polypropylene glycol weighed in step A1 is added to a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is then subjected to vacuum distillation at 120±5℃ and a vacuum degree of -0.08 to -0.1MPa to obtain anhydrous polypropylene glycol.

[0056] A3.2: Isophorone diisocyanate is added to the anhydrous polyoxypropylene glycol in the presence of a catalyst, and the mixture is stirred evenly in a water bath to carry out a prepolymerization reaction to obtain a prepolymer with isocyanate groups at both ends.

[0057] A3.3: Add the hydroxyl-based polyether organosilicon weighed in step A1 and completely dissolved in isobutyl acetate to the prepolymer with isocyanate groups at both ends. Stir evenly in a water bath at 65°C and modify it to obtain a preliminary organosilicon-modified polyurethane waterproofing agent predispersant.

[0058] A3.4: Slowly add the modified UV absorber initially prepared in step A2 to the organosilicon-modified polyurethane waterproofing pre-dispersion prepared in step A3, stir at 55°C for 3.5 hours, then add 1,4-butanediol and MDEA at 55°C to carry out chain extension reaction, then cool to 35°C, slowly add acetic acid to neutralize, and then add pure water to emulsify, thus obtaining the desired UV-resistant waterproofing pre-dispersion.

[0059] Example 3

[0060] This embodiment provides a finishing agent and its preparation method, the specific steps of which include:

[0061] A1: Weigh the following raw materials according to the following mass percentages: 0.5 parts of benzophenone-based UV absorber BP-1 (CAS No. 131-56-6), 1.2 parts of emulsifying and dispersing agents isotridecyl alcohol polyoxyethylene ether (5EO) and 0.3 parts of tristyrene phenol polyoxyethylene ether (16EO), 3.2 parts of methyl ethyl ketone (MEK), 5.7 parts of isobutyl acetate, 20.4 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 28.1 parts of isophorone diisocyanate, 5.1 parts of polytetrahydrofuran glycol, 1.1 parts of 1,4-butanediol, 3.9 parts of hydrophilic chain extender MDEA, 1 part of acetic acid, and 29.5 parts of pure water. The total mass percentage of all the above components is 100.

[0062] A2: The isomeric tridecyl alcohol polyoxyethylene ether (5EO), tristyrene phenol polyoxyethylene ether (16EO), and methyl ethyl ketone weighed in step A1 are placed in a shear emulsifying mixer and stirred until uniformly dissolved (2800 r / min). Then, BP-1 is slowly added at 1500 r / min, and the stirring speed is increased to 3200 r / min and stirred for 0.5 h for pre-dispersion treatment. The resulting pre-dispersion liquid is then added to a sand mill, and 80 parts by mass of zirconium beads are added for grinding. Every 30 min, an appropriate amount of grinding liquid is taken and the particle size is tested in a laser particle size analyzer until the particle size is less than 3.17 μm. The grinding is then stopped, and the zirconium beads are filtered. The resulting filtrate is the modified UV absorber that can exist stably in the dispersion system in the preliminary preparation.

[0063] A3: Preparation of Organosilicon Modified Polyurethane

[0064] A3.1: The polytetrahydrofuran diol weighed in step A1 is added to a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is then subjected to vacuum distillation at 120±5℃ and a vacuum degree of -0.08 to -0.1MPa to obtain anhydrous polytetrahydrofuran diol.

[0065] A3.2: Isophorone diisocyanate is added to the anhydrous polytetrahydrofuran diol in the presence of a catalyst, and the mixture is stirred evenly in a water bath to carry out a prepolymerization reaction to obtain a prepolymer with isocyanate groups at both ends.

[0066] A3.3: Add the hydroxyl-based polyether organosilicon weighed in step A1 and completely dissolved in isobutyl acetate to the prepolymer with isocyanate groups at both ends. Stir evenly in a water bath at 65-70°C and modify it to obtain a preliminary organosilicon-modified polyurethane waterproofing agent predispersant.

[0067] A3.4: Slowly add the modified UV absorber initially prepared in step A2 to the organosilicon-modified polyurethane waterproofing pre-dispersion initially prepared in step A3, stir at 55-60℃ for 4.5h, then add 1,4-butanediol and MDEA at 55-60℃ to carry out chain extension reaction, then cool to 35℃, slowly add acetic acid to neutralize, and then add pure water to emulsify, thus obtaining the desired UV-resistant waterproofing pre-dispersion.

[0068] Example 4

[0069] This embodiment provides a finishing agent and its preparation method, the specific steps of which include:

[0070] A1: Weigh the following raw materials according to the following mass percentages: 0.25 parts of benzophenone-based UV absorber BP-1 (CAS No. 131-56-6), 0.8 parts of benzotriazole-based UV absorber UV-1130 (CAS No. 104810-48-2), 1.7 parts of emulsifying dispersant isotridecyl alcohol polyoxyethylene ether (9EO), 3.4 parts of methyl ethyl ketone (MEK), 5.4 parts of isobutyl acetate, 19.8 parts of hydroxyalkyl polyether silicone (CAS No. 156327-07-0), 27.1 parts of isophorone diisocyanate, 4.2 parts of polytetrahydrofuran glycol, 1.15 parts of 1,4-butanediol, 4.8 parts of hydrophilic chain extender MDEA, 1.3 parts of acetic acid, and 30.1 parts of pure water. The total mass percentage of all the above components is 100.

[0071] A2: Place the weighed isomeric tridecyl alcohol polyoxyethylene ether (9EO) and butanone in a shear emulsifying mixer and stir until uniformly dissolved (2500 r / min). Then, slowly add BP-2 and UV-1130 at 1500 r / min, and then increase the stirring speed to 3500 r / min and stir for 0.5 h for pre-dispersion treatment. Add the obtained pre-dispersion liquid to a sand mill and add 85 parts by mass of zirconium beads for grinding. Take an appropriate amount of grinding liquid every 30 min and test the particle size in a laser particle size analyzer until the particle size is less than 3.17 μm. End the grinding. Filter the zirconium beads. The obtained filtrate is the modified UV absorber that can exist stably in the dispersion system in the preliminary preparation.

[0072] A3: Preparation of Organosilicon Modified Polyurethane

[0073] A3.1: The polytetrahydrofuran diol weighed in step A1 is added to a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is then subjected to vacuum distillation at 120±5℃ and a vacuum degree of -0.08 to -0.1MPa to obtain anhydrous polytetrahydrofuran diol.

[0074] A3.2: Isophorone diisocyanate is added to the anhydrous polytetrahydrofuran diol in the presence of a catalyst, and the mixture is stirred evenly in a water bath to carry out a prepolymerization reaction to obtain a prepolymer with isocyanate groups at both ends.

[0075] A3.3: Add the hydroxyl-based polyether organosilicon weighed in step A1 and completely dissolved in isobutyl acetate to the prepolymer with isocyanate groups at both ends. Stir evenly in a water bath at 65-70°C and modify it to obtain a preliminary organosilicon-modified polyurethane waterproofing agent predispersant.

[0076] A3.4: Slowly add the UV absorber initially prepared in step A2 to the silicone-modified polyurethane waterproofing agent pre-dispersion initially prepared in step A3, stir at 55-60℃ for 5 hours, then add 1,4-butanediol and MDEA at 55-60℃ to carry out chain extension reaction, then cool down to 35℃, slowly add acetic acid to neutralize, and then add pure water to emulsify, thus obtaining the desired UV-resistant waterproofing agent.

[0077] Example 5

[0078] This embodiment provides a finishing agent and its preparation method, the specific steps of which include:

[0079] A1: Benzophenone-based UV absorber BP-2 (CAS No. 156327-07-0) is 0.45 parts, emulsifiers and dispersants fatty alcohol polyoxyethylene ether AEO9 and tristyrene phenol polyoxyethylene ether (20EO) are 1.35 and 0.25 parts respectively, methyl ethyl ketone (MEK) is 3.6 parts, isobutyl acetate is 4.9 parts, hydroxyalkyl polyether silicone (CAS No. 156327-07-0) is 20.1 parts, isophorone diisocyanate is 26.4 parts, polypropylene glycol is 5.55 parts, 1,4-butanediol is 1.5 parts, hydrophilic chain extender MDEA is 5.4 parts, acetic acid is 1.4 parts, and pure water is 29.1 parts. The total mass of all the above components is 100.

[0080] A2: Place the fatty alcohol polyoxyethylene ether AEO9, tristyrene-phenol polyoxyethylene ether (20EO), and methyl ethyl ketone weighed in step A1 into a shear emulsifying mixer and stir until uniformly dissolved (3000 r / min). Then, slowly add BP-2 at 1500 r / min, and then increase the stirring speed to 3000 r / min and stir for 0.5 h for pre-dispersion treatment. Add the obtained pre-dispersion liquid into a sand mill and add 95 parts by mass of zirconium beads for grinding. Take an appropriate amount of grinding liquid every 30 min and test the particle size in a laser particle size analyzer until the particle size is less than 3.17 μm. After grinding, filter the zirconium beads. The resulting filtrate is the modified UV absorber that can exist stably in the dispersion system in the preliminary preparation.

[0081] A3: Preparation of Organosilicon Modified Polyurethane

[0082] A3.1: The polypropylene glycol weighed in step A1 is added to a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is then subjected to vacuum distillation at 120±5℃ and a vacuum degree of -0.08 to -0.1MPa to obtain anhydrous polypropylene glycol.

[0083] A3.2: Isophorone diisocyanate is added to the anhydrous polyoxypropylene glycol in the presence of a catalyst, and the mixture is stirred evenly in a water bath to carry out a prepolymerization reaction to obtain a prepolymer with isocyanate groups at both ends.

[0084] A3.3: Add the hydroxyl-based polyether organosilicon weighed in step A1 and completely dissolved in isobutyl acetate to the prepolymer with isocyanate groups at both ends. Stir evenly in a water bath at 65-70°C and carry out the modification reaction to obtain the organosilicon-modified polyurethane waterproofing agent predispersant.

[0085] A3.4: Slowly add the UV absorber initially prepared in step A2 to the silicone-modified polyurethane waterproofing pre-dispersion initially prepared in step A3, stir at 55-60℃ for 4.5h, then add 1,4-butanediol and MDEA at 55-60℃ to carry out chain extension reaction, then cool to 35℃, slowly add acetic acid to neutralize, and then add pure water to emulsify, thus obtaining the desired UV-resistant waterproofing pre-dispersion.

[0086] Example 6

[0087] This embodiment provides a finishing agent and its preparation method, the specific steps of which include:

[0088] A1: Benzophenone-based UV absorber BP-2 (CAS No. 156327-07-0) is 0.5 parts, emulsifying dispersant styrene-phenol polyoxyethylene ether (16EO) is 1.5 parts, methyl ethyl ketone (MEK) is 4 parts, isobutyl acetate is 5.8 parts, hydroxyalkyl polyether silicone (CAS No. 156327-07-0) is 19.9 parts, isophorone diisocyanate is 27.1 parts, polypropylene glycol is 5.1 parts, 1,4-butanediol is 1.5 parts, hydrophilic chain extender MDEA is 5.4 parts, acetic acid is 1.4 parts, and pure water is 27.8 parts. The total mass of all the above components is 100.

[0089] A2: Place the styrene-phenol polyoxyethylene ether (16EO) and butanone weighed in step A1 into a shear emulsifying mixer and stir until they are uniformly dissolved (3500 r / min). Then, slowly add BP-2 at 1500 r / min, and then increase the stirring speed to 3500 r / min and stir for 0.5 h for pre-dispersion treatment. Then, add the obtained pre-dispersion liquid into a sand mill and add 85 parts by mass of zirconium beads for grinding. Take an appropriate amount of grinding liquid every 30 min and test the particle size in a laser particle size analyzer until the particle size is less than 3.17 μm. After grinding, filter the zirconium beads. The obtained filtrate is the initially prepared UV absorber that can exist stably in the dispersion system.

[0090] A3: Preparation of Organosilicon Modified Polyurethane

[0091] A3.1: The polypropylene glycol weighed in step A1 is added to a dry four-necked round-bottom flask equipped with a thermocouple, a mechanical stirrer, a nitrogen inlet, a condenser, and a gas outlet. The flask is then subjected to vacuum distillation at 120±5℃ and a vacuum degree of -0.08 to -0.1MPa to obtain anhydrous polypropylene glycol.

[0092] A3.2: Isophorone diisocyanate is added to the anhydrous polyoxypropylene glycol in the presence of a catalyst, and the mixture is stirred evenly in a water bath to carry out a prepolymerization reaction to obtain a prepolymer with isocyanate groups at both ends.

[0093] A3.3: Add the hydroxyl-based polyether organosilicon weighed in step A1 and completely dissolved in isobutyl acetate to the prepolymer with isocyanate groups at both ends. Stir evenly in a water bath at 65-70°C and modify it to obtain a preliminary organosilicon-modified polyurethane waterproofing agent predispersant.

[0094] A3.4: Slowly add the UV absorber initially prepared in step A2 to the silicone-modified polyurethane waterproofing pre-dispersion initially prepared in step A3, stir at 55-60℃ for 4 hours, then add 1,4-butanediol and MDEA at 55-60℃ to carry out chain extension reaction, then cool down to 35℃, slowly add acetic acid to neutralize, and then add pure water to emulsify, thus obtaining the desired UV-resistant waterproofing pre-dispersion.

[0095] Comparative Example 1

[0096] This comparative example provides a finishing agent and its preparation method. The difference between this comparative example and Example 1 is that a nanoparticle ultraviolet shielding agent is used instead of the modified anti-ultraviolet absorber in Example 1, while the other conditions are the same.

[0097] Comparative Example 2

[0098] This comparative example provides a finishing agent and its preparation method. The difference between this comparative example and Example 1 is that the UV absorber is directly and physically blended with organosilicon-modified polyurethane without modification, while the other conditions are the same.

[0099] Test Example 1

[0100] Regarding the product's UV absorption and water resistance tests:

[0101] The finishing agent prepared in this invention is suitable for various fabrics such as natural fibers, synthetic fibers, and man-made fibers. Finishing methods can include coating, impregnation, spraying, pad dyeing, or a combination of these methods.

[0102] Specific method: Immerse the fabric in the obtained finishing agent for 5 minutes, then dip and rub twice (residual rate 85%), then bake at 140℃ for 4 minutes, remove and let stand.

[0103] At room temperature, add water to a beaker, weigh out a piece of fabric with a mass of m0, immerse it in the water, remove it after 60 seconds, quickly wipe off the water on the surface of the fabric with filter paper, and weigh it as m1. Repeat the above steps 3 times, take the average value, and then calculate the water absorption rate of the fabric using formula (1).

[0104] Water absorption rate = (m1-m0) / m0 × 100% Equation (1)

[0105] The treated fabric was tested at room temperature using a water contact angle meter. Each sample was tested in triplicate, and the average value was taken.

[0106] The UV resistance of the treated fabric was tested according to AATCC TM 183-2014 "Test standard for UV protection factor (UPF) of fabrics". The testing instruments were a spectrophotometer or a spectroradiometer equipped with an integrating sphere, a filter (Schott Class UG11 model), AATCC absorbent paper, etc. The light fastness test was performed according to ISO 105B02 "Textiles - Tests for color fastness to light".

[0107] ISO 105B02 is applicable to the determination of the color fastness of textiles of various types and forms to artificial light (simulated natural daylight D65). The test sample is exposed to artificial light under the same set of standard blue wool under specified conditions. The color change of the sample is compared with the color change of the standard blue wool to determine the color fastness. The standard material is ISO:1-8 grade, where "Grade 1" indicates very low color fastness, "Grade 5" indicates medium color fastness, and "Grade 8" indicates very high color fastness.

[0108] Table 1 shows the water contact angle, UV protection factor (UPF), and light fastness rating of the fabrics treated with the finishing agents prepared in each example and comparative example.

[0109] Table 1: Performance Tests of Finishing Agents

[0110]

[0111] The correspondence between "UPF rating" and "protection category" is shown in Table 2:

[0112] Table 2: Performance Tests of Finishing Agents

[0113] UPF Rating Protection Category - It does not have UV protection properties. 15,20 Liangliang 25,30,35 Very good 40,45,50,50+ Excellent

[0114] As shown in Table 1, the fabrics treated with the finishing agents obtained in each embodiment of the present invention have lower water absorption rates than the untreated fabrics and the two comparative fabrics, and higher water contact angles than the untreated fabrics and the two comparative fabrics, indicating that the fabrics treated with the finishing agents obtained in the present invention have excellent water resistance.

[0115] As shown in Table 1, the fabrics treated with the finishing agents obtained in each embodiment of the present invention have higher light fastness than the untreated fabrics and the two comparative fabrics.

[0116] As shown in Tables 1 and 2, the fabrics treated with the finishing agents prepared in the various embodiments of the present invention all have a UV protection factor (UPF) of 50 or higher, which is higher than that of the untreated fabric and the two comparative fabrics.

[0117] In summary, for both the untreated fabric and the two comparative fabrics, the ultraviolet absorber and the hydrophobic organosilicon-modified waterborne polyurethane material in the finishing agent obtained by each embodiment of the present invention have a synergistic effect, enabling the fabric to have both superior waterproof performance and ultraviolet protection and light fastness performance.

[0118] The foregoing description of specific exemplary embodiments of the present invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and those skilled in the art can make various corresponding changes and modifications based on the above technical solutions and concepts. The exemplary embodiments were chosen and described to reveal the specific principles and practical applications of the invention, thereby enabling those skilled in the art to implement and utilize various different exemplary experimental schemes and various choices and modifications of the invention. All such changes and modifications are defined by the claims and their equivalents.

Claims

1. A finishing agent, characterized by, The raw materials for preparation include: modified UV absorbers and silicone-modified polyurethane; The raw materials for preparing the organosilicon-modified polyurethane include polydiol, diisocyanate and organosilicon. The organosilicon includes at least one of aminoalkyl organosilicon, silanol hydroxyl organosilicon, hydroxyalkyl polyether organosilicon, single-terminated dihydroxyalkyl organosilicon, and double-terminated dihydroxyalkyl organosilicon. The raw materials for preparing the modified UV absorber include UV absorbers and emulsifying dispersants; The ultraviolet absorber includes at least one of benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers; The preparation method of the modified UV absorber includes: The emulsifying dispersant and solvent are stirred and dissolved. Then, a UV absorber is added while stirring. The stirring speed is then increased and the mixture is stirred for 0.5 hours to obtain a pre-dispersion liquid. The obtained pre-dispersion liquid is then added to a sand mill and zirconium beads are added to grind the pre-dispersion liquid. Every 30 minutes, an appropriate amount of the ground dispersion liquid is taken and the particle size is tested in a laser particle size analyzer until the particle size is between 0.25 μm and 4.85 μm. The preparation method of the organosilicon-modified polyurethane includes: A1. The polydiol is dehydrated to obtain anhydrous polydiol; A2. In the presence of a catalyst, diisocyanate is added to the anhydrous polydiol, and after mixing, a prepolymer with isocyanate groups at both ends is obtained; A3. Add organosilicon to the prepolymer with isocyanate groups at both ends, and mix to obtain a dispersion of organosilicon-modified polyurethane; The preparation method of the finishing agent includes: The modified UV absorber was added to the dispersion of organosilicon-modified polyurethane obtained in step A3, and stirred at 55-60°C for 4.5 h. Then, 1,4-butanediol and N-methyldiethanolamine were added at 55-60°C to carry out chain extension reaction. The temperature was then lowered to 35°C, and acetic acid was slowly added dropwise for neutralization before pure water was added for emulsification.

2. The finishing agent according to claim 1, characterized in that, The raw materials for preparing the finishing agent, by weight, include 0.25-1.25 parts of ultraviolet absorber, 0.9-2.3 parts of emulsifying dispersant, 8.3-9.2 parts of solvent, 19.2-20.5 parts of organosilicon, 26.2-28.3 parts of diisocyanate, 4.7-6.1 parts of polydiol, and 27.4-31.2 parts of pure water.

3. The finishing agent according to claim 1, characterized in that, The emulsifying dispersant includes at least one of 16EO of styrene-phenol polyoxyethylene ether, 20EO of styrene-phenol polyoxyethylene ether, 5EO of isotridecyl alcohol polyoxyethylene ether, 9EO of isotridecyl alcohol polyoxyethylene ether, AEO9 of fatty alcohol polyoxyethylene ether, and cashew nut phenol polyoxyethylene ether.

4. The finishing agent according to claim 1, characterized in that, The diisocyanate includes at least one of isophorone diisocyanate, 1,6-hexane diisocyanate, toluene diisocyanate, trimethylhexane diisocyanate, and diphenylmethane diisocyanate.

5. The finishing agent of claim 1, wherein The polydiol includes at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol, and polycarbonate glycol.

6. The application of a finishing agent as described in any one of claims 1 to 5 in a waterproof material.

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