Structural color ink and its application

Abstract

The invention relates to the technical field of textile dyeing, in particular to a structural color ink and an application thereof. In order to improve the color development performance and water washability of a structural color textile, the invention uses soft monomers, hard monomers and other components as raw materials to synthesize a solvent-responsive nano-microsphere with a core-shell structure in which the Tg value of the shell layer is low and the Tg value of the core layer is high, and uses shell layers and core layers with different Tgs, thereby increasing the binding property and structural stability of the solvent-responsive nano-microsphere with the textile. On this basis, the invention also uses 5,5-dimethylhydantoin as a raw material, introduces an alkynyl group into the raw material, and reacts the alkynyl group with an azido group to prepare a diol with a hydantoin structure, and reacts the diol with substances such as isocyanate to prepare a polyurethane moisture absorption and perspiration antibacterial finishing agent. After the polyurethane is used in combination with the solvent-responsive nano-microsphere, the hydrophilicity of the structural color textile can be effectively improved, and the wearing comfort and antibacterial performance can be increased.

Description

Technical Field

[0001] The invention relates to the technical field of textile dyeing, in particular to a structural color ink and application thereof. Background Art

[0002] Structural color textiles are different from textiles dyed with traditional dyes. Traditional dyes usually absorb light of specific wavelengths to achieve different color expressions, while structural color dyes are a type of ink material that uses specific photonic crystal structures in the material to interfere with visible light to show color. Compared with conventional inks, structural color dyes are environmentally friendly and non-toxic, and have long-lasting colors that do not fade. They can be widely used in the dyeing of textile products, reducing the discomfort caused by conventional dyes. Summary of the invention

[0003] The object of the present invention is to provide a structural color ink and its application to solve the problems raised in the above background technology.

[0004] In order to solve the above technical problems, the present invention provides the following technical solution: a method for preparing a structural color ink, comprising the following steps:

[0005] S1. Mix the emulsifier with water, raise the temperature to 70-80°C, stir and mix for 5-15 minutes, slowly drop soft monomer, hard monomer, water-soluble monomer and functional monomer thereto in sequence, the dropping time is 0.5-1.5 hours, after the dropping is completed, continue to stir and mix for 5-15 minutes, add initiator thereto, keep warm, stir and polymerize for 0.5-1 hour to obtain monomer prepolymer emulsion;

[0006] S2. Slowly add soft monomer, hard monomer, water-soluble monomer and functional monomer to the monomer prepolymer emulsion for 0.5-1.5 hours. After the addition is completed, keep the temperature at 70-80°C, add initiator, continue to stir the polymerization reaction for 1.5-2.5 hours, and filter to obtain nanoparticles.

[0007] S3. The nanoparticles obtained in S2 are mixed with water to obtain a structural color ink with a concentration of 2-12wt%.

[0008] Further, the emulsifier is any one of the non-ionic emulsifiers;

[0009] The soft monomer is any one or more of ethyl acrylate, butyl acrylate, and isooctyl acrylate;

[0010] The hard monomer is any one or more of methyl methacrylate, styrene, and acrylonitrile;

[0011] The water-soluble monomer is any one or more of acrylic acid, methacrylic acid, and itaconic acid;

[0012] The functional monomer is any one or more of methacrylate and glycidyl methacrylate;

[0013] The initiator is one or more of ammonium persulfate, azobisisobutyramidine hydrochloride and azobisisobutyronitrile.

[0014] Further, in step S1, by weight, water accounts for 70-90 parts, emulsifier accounts for 0-0.05 parts, soft monomer accounts for 3-5 parts, hard monomer accounts for 5-15 parts, water-soluble monomer accounts for 1-2 parts, functional monomer accounts for 0-1 parts, and initiator accounts for 0.01-0.05 parts;

[0015] In step S2, the soft monomer accounts for 5-15 parts, the hard monomer accounts for 5-15 parts, the water-soluble monomer accounts for 1-2 parts, the functional monomer accounts for 0-1 parts, and the initiator accounts for 0.1-0.5 parts.

[0016] Furthermore, a structural color ink is prepared by the above method.

[0017] Furthermore, the structural color ink is used to prepare structural color textiles;

[0018] The preparation method of the structural color textile is as follows:

[0019] (1) Mix the polyurethane moisture wicking antibacterial finishing agent with deionized water to prepare a 10-20g / L polyurethane moisture wicking antibacterial finishing agent solution, dip the textile into the polyurethane moisture wicking antibacterial finishing agent solution, dip for 0.5-1h, then take out and dry at a drying temperature of 130-170℃ for 50-70s;

[0020] (2) Apply the structural color ink on the surface of the fabric obtained in step (1), and dry it to constant weight after coating at a temperature of 20-40°C;

[0021] (3) The polyurethane moisture wicking antibacterial finishing agent is mixed with deionized water again to prepare a 20-50 g / L polyurethane moisture wicking antibacterial finishing agent solution. The fabric obtained in step (2) is again dipped into the polyurethane moisture wicking antibacterial finishing agent solution for 0.5-1 h and then taken out and dried at a drying temperature of 130-170°C for 50-70 seconds to obtain a structural color textile.

[0022] Furthermore, the preparation method of the polyurethane moisture absorption and perspiration antibacterial finishing agent is:

[0023] a. Disperse 5,5-dimethylhydantoin in a methanol aqueous solution, stir and mix for 5-15 minutes, add sodium hydroxide thereto, continue stirring and mixing for 5-10 minutes, heat to 60-65°C, add iodopropyne, stir and reflux for 4-8 hours, remove excess solvent by rotary evaporation, wash the product with ethanol 2-3 times, and evaporate in vacuo to constant weight to obtain an alkynylhydantoin intermediate;

[0024] b. Disperse dibromoneopentyl glycol in dimethyl sulfoxide, protect under nitrogen atmosphere, stir and disperse for 15-30 minutes, add potassium azide, heat to 105-115°C, reflux and stir to react for 4-24 hours, stop heating, remove excess solvent by rotary evaporation, disperse the resulting product in deionized water, extract the organic phase with ethyl acetate, wash the organic phase with saturated potassium chloride solution, and vacuum dry the remaining organic phase to constant weight to obtain an azidodiol intermediate;

[0025] c. The azidodiol intermediate was dispersed in DMF, and under nitrogen atmosphere, cuprous bromide was added thereto. Mixing was continued for 5-15 minutes, and then the alkynyl hydantoin intermediate was added. The temperature was raised to 35-40°C, and the reaction was continued for 1-4 hours. The mixture was evaporated in vacuo to a constant weight to obtain the hydantoindiol intermediate.

[0026] d. Mix polyether polyol, hydantoin intermediate, side chain modified silicone and anionic hydrophilic chain extender, stir and heat to 110-120°C, dehydrate under negative pressure for 1-1.5h, heat to 135-140°C at normal pressure and keep for 10min, add isocyanate, adjust the reaction R value to 1.15-1.3, heat to 90-95°C, stir and react for 4-5h to obtain polyurethane prepolymer;

[0027] e. Add solvent to the polyurethane prepolymer, stir evenly, cool to 30-40°C, add triethylamine, the neutralization degree is 90-110%, the neutralization time is 20-40min, after neutralization, add deionized water, stir and mix at a rate of 2000-3000rpm for 1-3h, and obtain a polyurethane moisture absorption and perspiration antibacterial finishing agent with a solid content of 30-40%.

[0028] Furthermore, in step a, the mass ratio of 5,5-dimethylhydantoin, sodium hydroxide and iodopropynyl is 1:(0.2-0.3):(1-1.3).

[0029] Furthermore, in step b, the mass ratio of dibromoneopentyl glycol to potassium azide is 10:(5-6.3).

[0030] Furthermore, in step c, the mass ratio of the azidodiol intermediate, cuprous bromide, and alkynylhydantoin intermediate is 10:(0.08-0.12):(11.5-14).

[0031] Further, in step d, the mass ratio of the polyether polyol, the hydantoin intermediate, the side chain modified silicone and the anionic hydrophilic chain extender is 10: (1-3): (0.2-0.5): (0.2-0.3);

[0032] Wherein, the polyether polyol is any one of polytetrahydrofuran diol and polyethylene glycol monomethyl ether, wherein the polytetrahydrofuran diol Mn=1000-2000, and the polyethylene glycol monomethyl ether Mn=500-2000; the anionic hydrophilic chain extender is any one of dimethylol propionic acid and dimethylol butyric acid;

[0033] The side chain modified silicone is a self-made single-terminated dihydroxyl polydimethylsiloxane, Mn=1000-2000, and the structure is as follows:

[0034] ;

[0035] In step e, the solvent is any one of acetone, butanone, and N-methylpyrrolidone;

[0036] The added amount of the solvent is 5% of the mass of the prepolymer.

[0037] Furthermore, the fabric is commercially available black cotton-polyester plain weave fabric or black polyester plain weave fabric.

[0038] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0039] 1. In order to improve the color rendering performance and water washing resistance of structural color textiles, the present invention uses soft monomers, hard monomers and other components as raw materials, and changes the component raw materials and reaction conditions in different synthesis steps to finally synthesize a solvent-responsive nano-microsphere with a core-shell structure having a low Tg value (-22~-70℃) of the shell layer and a high Tg value (80~105℃) of the core layer. During the dyeing process, the shell layer with a low Tg value is closely combined with the polyurethane moisture absorption and perspiration antibacterial finishing agent during the drying process, which can improve the water washing fastness of the structural color textiles, while the high Tg core layer can improve the stability of the structural color structure and maintain the color reality effect for a long time;

[0040] 2. In order to further improve the water-washing resistance and color development effect of the solvent-responsive nano-microspheres, the present invention further prepares a polyurethane moisture absorption and perspiration antibacterial finishing agent. In the process of dyeing textiles, the present invention uses the polyurethane moisture absorption and perspiration antibacterial finishing agent twice, and the solvent-responsive microsphere solution is mixed in the two polyurethane moisture absorption and perspiration antibacterial finishing agent to dye the textiles. The solvent-responsive microspheres are initially coated between the film-like protective layers formed by the polyurethane moisture absorption and perspiration antibacterial finishing agent, thereby protecting the anti-shedding performance of the solvent-responsive microspheres during washing and maintaining the color development performance of the textiles for a long time; and the polyurethane moisture absorption and perspiration antibacterial finishing agent prepared by the present invention also has sufficient hydrophilicity, which can accelerate the release of water vapor such as sweat when worn, avoiding wearing discomfort caused by factors such as sweat, and the hydrophilicity of the polyurethane moisture absorption and perspiration antibacterial finishing agent can also assist the solvent-responsive microspheres to contact with water vapor such as sweat, avoiding the conventional film-forming material coating the solvent-responsive microspheres, causing the microspheres to be unable to contact with water vapor and other solvents, thereby affecting the color change performance of the microspheres.

[0041] 3. At the same time, the present invention also introduces a hydantoin diol intermediate with antibacterial function in the process of preparing the polyurethane moisture absorbing and perspiration antibacterial finishing agent. The present invention first uses 5,5-dimethylhydantoin as a raw material, mixes it with iodopropyne for reaction, thereby introducing an alkynyl group into the hydantoin, and then uses dibromoneopentyl glycol to react with potassium azide to prepare an azidodiol intermediate with two azido groups and two alcoholic hydroxyl groups. After mixing it with the alkynyl hydantoin intermediate, the azide group reacts with the alkynyl group, thereby introducing an alcoholic hydroxyl group into the hydantoin group, and further mixes it with components such as isocyanate for reaction, and finally prepares the polyurethane moisture absorbing and perspiration antibacterial finishing agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

[0043] Figure 1 is a color change comparison diagram of the structural color textile prepared in Example 1 of the present invention;

[0044] In the figure: 1-the area that turns green when exposed to water; 2-the area that does not change color when dry. DETAILED DESCRIPTION

[0045] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] The side chain modified silicone used in this application has Mn=1000-2000 and the structure is as follows: ;

[0047] The textile used was a commercially available black cotton-polyester plain weave fabric;

[0048] Example 1. A method for preparing a structural color textile, comprising the following steps:

[0049] (1) Mix the polyurethane moisture wicking antibacterial finishing agent with deionized water to prepare a 10 g / L polyurethane moisture wicking antibacterial finishing agent solution, dip the textile into the polyurethane moisture wicking antibacterial finishing agent solution, dip for 0.5 h, then take out and dry at a temperature of 160 ° C for 60 s;

[0050] Wherein, the preparation method of the polyurethane moisture absorption and perspiration antibacterial finishing agent is:

[0051] a. Disperse 10 parts of 5,5-dimethylhydantoin in a methanol aqueous solution by weight, stir and mix for 10 minutes, add 2 parts of sodium hydroxide thereto, continue to stir and mix for 5 minutes, heat to 65°C, add 10 parts of iodopropyne, stir and reflux for 4 hours, remove excess solvent by rotary evaporation, wash the product twice with ethanol, and evaporate in vacuo to constant weight to obtain an alkynylhydantoin intermediate;

[0052] b. Disperse 10 parts of dibromoneopentyl glycol in dimethyl sulfoxide by weight, protect under nitrogen atmosphere, stir and disperse for 15 minutes, add 5 parts of potassium azide, heat to 115°C, reflux and react for 12 hours, stop heating, remove excess solvent by rotary evaporation, disperse the resulting product in deionized water, extract the organic phase with ethyl acetate, wash the organic phase with saturated potassium chloride solution, and vacuum dry the remaining organic phase to constant weight to obtain an azidodiol intermediate;

[0053] c. Disperse 10 parts of the azidodiol intermediate in DMF under nitrogen atmosphere, add 0.8 parts of cuprous bromide, continue mixing for 5 minutes, add 11.5 parts of the alkynyl hydantoin intermediate, heat to 38 ° C, react for 2.5 hours, and evaporate in vacuo to constant weight to obtain a hydantoin intermediate;

[0054] d. By weight, 10 parts of polyether polyol, 1 part of hydantoin intermediate, 0.3 parts of side chain modified silicone and 0.2 parts of anionic hydrophilic chain extender were mixed, stirred and heated to 120°C, the pressure was adjusted to -0.1MPa, dehydrated under negative pressure for 1h, heated to 140°C at normal pressure and kept for 10min, isocyanate was added thereto, the reaction R value was adjusted to 1.2, the temperature was raised to 90-95°C, stirred and reacted for 4h to obtain a polyurethane prepolymer;

[0055] e. Add 5% of the weight of acetone solvent to the polyurethane prepolymer, stir evenly, cool to 30°C, add triethylamine, adjust the neutralization degree to 100%, and neutralize for 40 minutes. After neutralization, add deionized water, stir and mix at a rate of 3000 rpm for 3 hours to obtain a polyurethane moisture wicking antibacterial finishing agent with a solid content of 30%;

[0056] (2) Spray the structural color ink onto the fabric obtained in (1) using a spraying device, with the solution concentration being 7 wt % and the drying temperature being 30° C.

[0057] Wherein, the preparation method of the structural color ink is:

[0058] S1. By weight, 0.05 parts of emulsifier were mixed with 75 parts of water, the temperature was raised to 75°C, and after stirring and mixing for 10 minutes, 4 parts of ethyl acrylate, 4 parts of methyl methacrylate, 1.5 parts of methacrylic acid and 1 part of methacrylate were slowly added dropwise thereto in sequence, and the addition time was 1 hour. After the addition was completed, stirring and mixing was continued for 10 minutes, and 0.01 parts of azobisisobutyronitrile initiator were added dropwise thereto, and the temperature was kept and stirred for polymerization reaction for 1 hour to obtain a monomer prepolymer emulsion;

[0059] S2. Continue to slowly drop 10 parts of ethyl acrylate, 10 parts of methyl methacrylate, 1.5 parts of methacrylic acid and 0.5 parts of methacrylate into the monomer prepolymer emulsion for a total of 1.5 hours. After the dropwise addition is completed, keep the temperature at 75°C, drop 0.3 parts of azobisisobutyronitrile initiator therein, continue stirring the polymerization reaction for 2 hours, and filter. The D90 of the nanoparticles is 250 nm.

[0060] S3. The nanoparticles obtained in S2 were mixed with water to obtain a structural color ink having a solid content of 8wt%;

[0061] (3) Mix the polyurethane moisture wicking antibacterial finishing agent with deionized water to prepare a 30 g / L polyurethane moisture wicking antibacterial finishing agent solution. Dip the fabric obtained in (2) into the polyurethane moisture wicking antibacterial finishing agent solution again. After dipping for 0.5 h, take out and dry at a temperature of 170°C for 60 seconds to obtain a structural color textile that turns green when exposed to water.

[0062] Example 2. A method for preparing a structural color textile, comprising the following steps:

[0063] Compared with Example 1, this example increases the amount of hydantoin intermediate added in step d;

[0064] Wherein, the preparation method of the polyurethane moisture absorption and perspiration antibacterial finishing agent is:

[0065] a. Disperse 10 parts of 5,5-dimethylhydantoin in a methanol aqueous solution by weight, stir and mix for 10 minutes, add 2 parts of sodium hydroxide thereto, continue to stir and mix for 5 minutes, heat to 65°C, add 10 parts of iodopropyne, stir and reflux for 4 hours, remove excess solvent by rotary evaporation, wash the product twice with ethanol, and evaporate in vacuo to constant weight to obtain an alkynylhydantoin intermediate;

[0066] b. Disperse 10 parts of dibromoneopentyl glycol in dimethyl sulfoxide by weight, protect under nitrogen atmosphere, stir and disperse for 15 minutes, add 5 parts of potassium azide, heat to 115°C, reflux and react for 12 hours, stop heating, remove excess solvent by rotary evaporation, disperse the resulting product in deionized water, extract the organic phase with ethyl acetate, wash the organic phase with saturated potassium chloride solution, and vacuum dry the remaining organic phase to constant weight to obtain an azidodiol intermediate;

[0067] c. Disperse 10 parts of the azidodiol intermediate in DMF under nitrogen atmosphere, add 0.8 parts of cuprous bromide, continue mixing for 5 minutes, add 11.5 parts of the alkynyl hydantoin intermediate, heat to 38 ° C, react for 2.5 hours, and evaporate in vacuo to constant weight to obtain a hydantoin intermediate;

[0068] d. By weight, 10 parts of polyether polyol, 3 parts of hydantoin intermediate, 0.3 parts of side chain modified silicone and 0.2 parts of anionic hydrophilic chain extender were mixed, stirred and heated to 120°C, the pressure was adjusted to -0.1MPa, dehydrated under negative pressure for 1h, heated to 140°C at normal pressure and kept warm for 10min, isocyanate was added thereto, the reaction R value was adjusted to 1.2, the temperature was raised to 90-95°C, stirred and reacted for 4h to obtain a polyurethane prepolymer;

[0069] e. Add 5% by weight of acetone solvent to the polyurethane prepolymer, stir evenly, cool to 30°C, add triethylamine, adjust the neutralization degree to 100%, and neutralize for 40 minutes. After neutralization, add deionized water, stir and mix at a rate of 3000 rpm for 3 hours to obtain a polyurethane moisture absorption and perspiration antibacterial finishing agent with a solid content of 30%.

[0070] Example 3. A method for preparing a structural color textile, comprising the following steps:

[0071] Compared with Example 1, this example increases the amount of iodopropynyl added in step a;

[0072] Wherein, the preparation method of the polyurethane moisture absorption and perspiration antibacterial finishing agent is:

[0073] a. Disperse 10 parts of 5,5-dimethylhydantoin in a methanol aqueous solution by weight, stir and mix for 10 minutes, add 2 parts of sodium hydroxide thereto, continue to stir and mix for 5 minutes, heat to 65°C, add 13 parts of iodopropyne, stir and reflux for 4 hours, remove excess solvent by rotary evaporation, wash the product twice with ethanol, and evaporate in vacuo to constant weight to obtain an alkynylhydantoin intermediate;

[0074] b. Disperse 10 parts of dibromoneopentyl glycol in dimethyl sulfoxide by weight, protect under nitrogen atmosphere, stir and disperse for 15 minutes, add 5 parts of potassium azide, heat to 115°C, reflux and react for 12 hours, stop heating, remove excess solvent by rotary evaporation, disperse the resulting product in deionized water, extract the organic phase with ethyl acetate, wash the organic phase with saturated potassium chloride solution, and vacuum dry the remaining organic phase to constant weight to obtain an azidodiol intermediate;

[0075] c. Disperse 10 parts of the azidodiol intermediate in DMF under nitrogen atmosphere, add 0.8 parts of cuprous bromide, continue mixing for 5 minutes, add 11.5 parts of the alkynyl hydantoin intermediate, heat to 38 ° C, react for 2.5 hours, and evaporate in vacuo to constant weight to obtain a hydantoin intermediate;

[0076] d. By weight, 10 parts of polyether polyol, 1 part of hydantoin intermediate, 0.3 parts of side chain modified silicone and 0.2 parts of anionic hydrophilic chain extender were mixed, stirred and heated to 120°C, the pressure was adjusted to -0.1MPa, dehydrated under negative pressure for 1h, heated to 140°C at normal pressure and kept for 10min, isocyanate was added thereto, the reaction R value was adjusted to 1.2, the temperature was raised to 90-95°C, stirred and reacted for 4h to obtain a polyurethane prepolymer;

[0077] e. Add 5% by weight of acetone solvent to the polyurethane prepolymer, stir evenly, cool to 30°C, add triethylamine, adjust the neutralization degree to 100%, and neutralize for 40 minutes. After neutralization, add deionized water, stir and mix at a rate of 3000 rpm for 3 hours to obtain a polyurethane moisture absorption and perspiration antibacterial finishing agent with a solid content of 30%.

[0078] Example 4. A method for preparing a structural color textile, comprising the following steps:

[0079] Compared with Example 1, this example increases the amount of potassium azide added in step b;

[0080] Wherein, the preparation method of the polyurethane moisture absorption and perspiration antibacterial finishing agent is:

[0081] a. Disperse 10 parts of 5,5-dimethylhydantoin in a methanol aqueous solution by weight, stir and mix for 10 minutes, add 2 parts of sodium hydroxide thereto, continue to stir and mix for 5 minutes, heat to 65°C, add 10 parts of iodopropyne, stir and reflux for 4 hours, remove excess solvent by rotary evaporation, wash the product twice with ethanol, and evaporate in vacuo to constant weight to obtain an alkynylhydantoin intermediate;

[0082] b. Disperse 10 parts of dibromoneopentyl glycol in dimethyl sulfoxide by weight, protect under nitrogen atmosphere, stir and disperse for 15 minutes, add 6.3 parts of potassium azide, heat to 115°C, reflux and react for 12 hours, stop heating, remove excess solvent by rotary evaporation, disperse the resulting product in deionized water, extract the organic phase with ethyl acetate, wash the organic phase with saturated potassium chloride solution, and vacuum dry the remaining organic phase to constant weight to obtain an azidodiol intermediate;

[0083] c. Disperse 10 parts of the azidodiol intermediate in DMF under nitrogen atmosphere, add 0.8 parts of cuprous bromide, continue mixing for 5 minutes, add 11.5 parts of the alkynyl hydantoin intermediate, heat to 38 ° C, react for 2.5 hours, and evaporate in vacuo to constant weight to obtain a hydantoin intermediate;

[0084] d. By weight, 10 parts of polyether polyol, 1 part of hydantoin intermediate, 0.3 parts of side chain modified silicone and 0.2 parts of anionic hydrophilic chain extender were mixed, stirred and heated to 120°C, the pressure was adjusted to -0.1MPa, dehydrated under negative pressure for 1h, heated to 140°C at normal pressure and kept for 10min, isocyanate was added thereto, the reaction R value was adjusted to 1.2, the temperature was raised to 90-95°C, stirred and reacted for 4h to obtain a polyurethane prepolymer;

[0085] e. Add 5% by weight of acetone solvent to the polyurethane prepolymer, stir evenly, cool to 30°C, add triethylamine, adjust the neutralization degree to 100%, and neutralize for 40 minutes. After neutralization, add deionized water, stir and mix at a rate of 3000 rpm for 3 hours to obtain a polyurethane moisture absorption and perspiration antibacterial finishing agent with a solid content of 30%.

[0086] Example 5. A method for preparing a structural color textile, comprising the following steps:

[0087] Compared with Example 1, this example increases the amount of the alkynyl hydantoin intermediate added in step c;

[0088] Wherein, the preparation method of the polyurethane moisture absorption and perspiration antibacterial finishing agent is:

[0089] a. Disperse 10 parts of 5,5-dimethylhydantoin in a methanol aqueous solution by weight, stir and mix for 10 minutes, add 2 parts of sodium hydroxide thereto, continue to stir and mix for 5 minutes, heat to 65°C, add 10 parts of iodopropyne, stir and reflux for 4 hours, remove excess solvent by rotary evaporation, wash the product twice with ethanol, and evaporate in vacuo to constant weight to obtain an alkynylhydantoin intermediate;

[0090] b. Disperse 10 parts of dibromoneopentyl glycol in dimethyl sulfoxide by weight, protect under nitrogen atmosphere, stir and disperse for 15 minutes, add 5 parts of potassium azide, heat to 115°C, reflux and react for 12 hours, stop heating, remove excess solvent by rotary evaporation, disperse the resulting product in deionized water, extract the organic phase with ethyl acetate, wash the organic phase with saturated potassium chloride solution, and vacuum dry the remaining organic phase to constant weight to obtain an azidodiol intermediate;

[0091] c. Disperse 10 parts of the azidodiol intermediate in DMF under nitrogen atmosphere, add 0.8 parts of cuprous bromide, continue mixing for 5 minutes, add 14 parts of the alkynyl hydantoin intermediate, heat to 38 ° C, react for 2.5 hours, and evaporate in vacuo to constant weight to obtain a hydantoin diol intermediate;

[0092] d. By weight, 10 parts of polyether polyol, 1 part of hydantoin intermediate, 0.3 parts of side chain modified silicone and 0.2 parts of anionic hydrophilic chain extender were mixed, stirred and heated to 120°C, the pressure was adjusted to -0.1MPa, dehydrated under negative pressure for 1h, heated to 140°C at normal pressure and kept for 10min, isocyanate was added thereto, the reaction R value was adjusted to 1.2, the temperature was raised to 90-95°C, stirred and reacted for 4h to obtain a polyurethane prepolymer;

[0093] e. Add 5% by weight of acetone solvent to the polyurethane prepolymer, stir evenly, cool to 30°C, add triethylamine, adjust the neutralization degree to 100%, and neutralize for 40 minutes. After neutralization, add deionized water, stir and mix at a rate of 3000 rpm for 3 hours to obtain a polyurethane moisture absorption and perspiration antibacterial finishing agent with a solid content of 30%.

[0094] Comparative Example 1. A method for preparing a structural color textile, comprising the following steps:

[0095] Compared with Example 1, this comparative example did not prepare the addition of hydantoin diol intermediate;

[0096] (1) Mix the polyurethane moisture wicking antibacterial finishing agent with deionized water to prepare a 10 g / L polyurethane moisture wicking antibacterial finishing agent solution, dip the textile into the polyurethane moisture wicking antibacterial finishing agent solution, dip for 0.5 h, then take out and dry at a temperature of 160 ° C for 60 s;

[0097] Wherein, the preparation method of the polyurethane moisture absorption and perspiration antibacterial finishing agent is:

[0098] a. By weight, 10 parts of polyether polyol, 0.3 parts of side chain modified silicone and 0.2 parts of anionic hydrophilic chain extender were mixed, stirred and heated to 120°C, the pressure was adjusted to -0.1MPa, and dehydrated under negative pressure for 1h, and heated to 140°C at normal pressure for 10min, and isocyanate was added thereto, and the reaction R value was adjusted to 1.2, and the temperature was raised to 90-95°C, and the reaction was stirred for 4h to obtain a polyurethane prepolymer;

[0099] b. Add 5% of the mass of acetone solvent to the polyurethane prepolymer, stir evenly, cool to 30°C, add triethylamine, adjust the neutralization degree to 100%, and neutralize for 40 min. After neutralization, add deionized water, stir and mix at a rate of 3000 rpm for 3 h to obtain a polyurethane moisture wicking and antibacterial finishing agent with a solid content of 30%;

[0100] (2) Spray the structural color ink onto the fabric obtained in (1) using a spraying device, with the solution concentration being 7 wt % and the drying temperature being 30° C.

[0101] (3) Mix the polyurethane moisture wicking antibacterial finishing agent with deionized water to prepare a 30 g / L polyurethane moisture wicking antibacterial finishing agent solution. Dip the fabric obtained in (2) into the polyurethane moisture wicking antibacterial finishing agent solution again. After dipping for 0.5 h, take out and dry at a temperature of 170°C for 60 seconds to obtain a structural color textile that turns green when exposed to water.

[0102] Comparative Example 2. A method for preparing a structural color textile, comprising the following steps:

[0103] Compared with Example 1, this comparative example did not prepare the addition of polyurethane moisture absorption and perspiration antibacterial finishing agent;

[0104] A method for preparing a structural color textile comprises the following steps:

[0105] (1) The structural color ink is sprayed on the fabric using a spraying device, with the solution concentration being 7wt% and the drying temperature being 30°C, to obtain a structural color textile that turns green when exposed to water;

[0106] Wherein, the preparation method of the structural color ink is:

[0107] S1. By weight, 0.05 parts of emulsifier were mixed with 75 parts of water, the temperature was raised to 75°C, and after stirring and mixing for 10 minutes, 4 parts of ethyl acrylate, 4 parts of methyl methacrylate, 1.5 parts of methacrylic acid and 1 part of methacrylate were slowly added dropwise thereto in sequence, and the addition time was 1 hour. After the addition was completed, stirring and mixing was continued for 10 minutes, and 0.01 parts of azobisisobutyronitrile initiator were added dropwise thereto, and the temperature was kept and stirred for polymerization reaction for 1 hour to obtain a monomer prepolymer emulsion;

[0108] S2. Continue to slowly drop 10 parts of ethyl acrylate, 10 parts of methyl methacrylate, 1.5 parts of methacrylic acid and 0.5 parts of methacrylate into the monomer prepolymer emulsion for a total of 1.5 hours. After the dropwise addition is completed, keep the temperature at 75°C, drop 0.3 parts of azobisisobutyronitrile initiator therein, continue stirring the polymerization reaction for 2 hours, and filter. The D90 of the nanoparticles is 250 nm.

[0109] S3. The nanoparticles obtained in S2 are mixed with water to obtain a structural color ink with a solid content of 8 wt %.

[0110] Testing: The samples prepared in Examples 1-5 and Comparative Examples 1-2 were tested for color fastness grade according to GB / T 250-2008;

[0111] The samples prepared in Examples 1-5 and Comparative Examples 1-2 were tested for moisture absorption and quick-drying performance according to GB / T 21655.1-2008;

[0112] According to WS / T 650-2019, the antibacterial properties of the samples prepared in Examples 1-5 and Comparative Examples 1-2 were tested. The test results are shown in the following table

[0113] ;

[0114] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0115] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An application of a structural color ink, characterized in that: The structural color ink is used to prepare structural color textiles; The preparation method of the structural color textile is as follows: (1) Mix the polyurethane moisture wicking antibacterial finishing agent with deionized water to prepare a 10-20g / L polyurethane moisture wicking antibacterial finishing agent solution, dip the textile into the polyurethane moisture wicking antibacterial finishing agent solution, dip for 0.5-1h, then take out and dry, the drying temperature is 130-170°C, and the drying time is 50-70s; (2) The structural color ink is coated on the surface of the fabric obtained in step (1), and dried to constant weight after coating at a drying temperature of 20-40°C; (3) The polyurethane moisture wicking antibacterial finishing agent is mixed with deionized water again to prepare a 20-50g / L polyurethane moisture wicking antibacterial finishing agent solution, and the fabric obtained in step (2) is again dipped in the polyurethane moisture wicking antibacterial finishing agent solution, and then taken out and dried after dipping for 0.5-1h, the drying temperature is 130-170°C, and the drying time is 50-70s to obtain a structural color textile; The preparation method of the polyurethane moisture absorption and perspiration antibacterial finishing agent is: a. Disperse 5,5-dimethylhydantoin in a methanol aqueous solution, stir and mix for 5-15 minutes, add sodium hydroxide thereto, continue stirring and mixing for 5-10 minutes, heat to 60-65°C, add iodopropyne, stir and reflux for 4-8 hours, remove excess solvent by rotary evaporation, wash the product with ethanol 2-3 times, and evaporate in vacuo to constant weight to obtain an alkynylhydantoin intermediate; b. Disperse dibromoneopentyl glycol in dimethyl sulfoxide, protect under nitrogen atmosphere, stir and disperse for 15-30 minutes, add potassium azide, heat to 105-115°C, reflux and stir to react for 4-24 hours, stop heating, remove excess solvent by rotary evaporation, disperse the resulting product in deionized water, extract the organic phase with ethyl acetate, wash the organic phase with saturated potassium chloride solution, and vacuum dry the remaining organic phase to constant weight to obtain an azidodiol intermediate; c. Disperse the azidodiol intermediate in DMF, protect with nitrogen atmosphere, add cuprous bromide, continue mixing for 5-15 minutes, add alkynyl hydantoin intermediate, raise the temperature to 35-40°C, react for 1-4 hours, and evaporate in vacuo to constant weight to obtain hydantoindiol intermediate; d. Mix the polyether polyol, hydantoin intermediate, side chain modified silicone and anionic hydrophilic chain extender, stir and heat to 110-120°C, dehydrate under negative pressure for 1-1.5h, heat to 135-140°C at normal pressure and keep warm for 10min, add isocyanate, adjust the reaction R value to 1.15-1.3, heat to 90-95°C, stir and react for 4-5h to obtain a polyurethane prepolymer; e. Add solvent to the polyurethane prepolymer, stir evenly, cool to 30-40°C, add triethylamine, the neutralization degree is 90-110%, the neutralization time is 20-40min, after neutralization, add deionized water, stir and mix at a rate of 2000-3000rpm for 1-3h to obtain a polyurethane moisture absorption and perspiration antibacterial finishing agent with a solid content of 30-40%.

2. The use of a structural color ink according to claim 1, characterized in that: The preparation method of the structural color ink is as follows: S1. Mix the emulsifier with water, raise the temperature to 70-80°C, stir and mix for 5-15 minutes, and then slowly drop the soft monomer, hard monomer, water-soluble monomer and functional monomer thereto in sequence, the dropping time is 0.5-1.5 hours, after the dropping is completed, continue to stir and mix for 5-15 minutes, add the initiator thereto, keep warm, stir and polymerize for 0.5-1 hour to obtain a monomer prepolymer emulsion; S2. To the monomer prepolymer emulsion, continue to slowly drop soft monomer, hard monomer, water-soluble monomer and functional monomer for a total of 0.5-1.5h. After the addition is completed, keep the temperature at 70-80°C, add the initiator dropwise, continue stirring the polymerization reaction for 1.5-2.5h, and filter; S3. The nanoparticles obtained in S2 are mixed with water to obtain a structural color ink having a concentration of 2-12wt%; In terms of weight, in step S1, water accounts for 70-90 parts, emulsifier accounts for 0-0.05 parts, soft monomer accounts for 3-5 parts, hard monomer accounts for 5-15 parts, water-soluble monomer accounts for 1-2 parts, functional monomer accounts for 0-1 parts, and initiator accounts for 0.01-0.05 parts; In step S2, the soft monomer accounts for 5-15 parts, the hard monomer accounts for 5-15 parts, the water-soluble monomer accounts for 1-2 parts, the functional monomer accounts for 0-1 parts, and the initiator accounts for 0.1-0.5 parts.

3. The use of a structural color ink according to claim 2, characterized in that: The emulsifier is any one of the non-ionic emulsifiers; The soft monomer is any one or more of ethyl acrylate, butyl acrylate, and isooctyl acrylate; The hard monomer is any one or more of methyl methacrylate, styrene, and acrylonitrile; The water-soluble monomer is any one or more of acrylic acid, methacrylic acid, and itaconic acid; The functional monomer is any one or more of hydroxyethyl methacrylate and glycidyl methacrylate; The initiator is one or more of ammonium persulfate, azobisisobutyramidine hydrochloride and azobisisobutyronitrile.

4. The use of a structural color ink according to claim 1, characterized in that: In step a, the mass ratio of 5,5-dimethylhydantoin, sodium hydroxide and iodopropynyl is 1:(0.2-0.3):(1-1.3).

5. The use of a structural color ink according to claim 1, characterized in that: In step b, the mass ratio of dibromoneopentyl glycol to potassium azide is 10:(5-6.3).

6. The use of a structural color ink according to claim 1, characterized in that: In step c, the mass ratio of the azidodiol intermediate, cuprous bromide, and alkynylhydantoin intermediate is 10:(0.08-0.12):(11.5-14).

7. The use of a structural color ink according to claim 1, characterized in that: In step d, the mass ratio of the polyether polyol, the hydantoin intermediate, the side chain modified silicone and the anionic hydrophilic chain extender is 10:(1-3): (0.2-0.5)：(0.2-0.3)； Wherein, the polyether polyol is any one of polytetrahydrofuran diol and polyethylene glycol monomethyl ether, wherein the polytetrahydrofuran diol Mn=1000-2000, and the polyethylene glycol monomethyl ether Mn=500-2000; the anionic hydrophilic chain extender is any one of dimethylol propionic acid and dimethylol butyric acid; The side chain modified silicone is a self-made single-terminated dihydroxyl polydimethylsiloxane, Mn=1000-2000, and the structure is as follows: In step e, the solvent is any one of acetone, butanone, and N-methylpyrrolidone; The added amount of the solvent is 5% of the mass of the prepolymer.

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