Heat-resistant bionic structural color printed fabric and preparation method thereof

Abstract

The invention discloses a heat-resistant bionic structural color printed fabric and a preparation method thereof.The preparation method of the fabric comprises the following steps that S1, sodium bicarbonate and polyethane pyrrolidone are dissolved in deionized water, and then glycidyl methacrylate, styrene, divinylbenzene, a composite surfactant and an initiator are sequentially added for a polymerization reaction; after the reaction, cooling and filtering are performed to prepare the P (St-DVB-GMA) nano microspheres; s2, dispersing the P (St-DVB-GMA) nano-microspheres prepared in the S1 into deionized water, then treating dispersion liquid onto a fabric with a mask on the surface by adopting an atomization deposition or spraying mode, and drying to obtain the heat-resistant bionic structural color printed fabric. Structural color microspheres with a heat-resistant effect are synthesized, and a bright printing effect can be formed at room temperature.

Description

Technical Field

[0001] This invention relates to the field of structural color technology, and in particular to heat-resistant biomimetic structural color printed fabrics and their preparation methods. Background Technology

[0002] The vibrant colors in nature are mainly divided into chemical colors and physical colors. Traditional textile coloring is primarily achieved through chemical colorants (dyes and pigments). However, some organisms in nature produce bright colors due to their unique structures, known as structural colors. Structural colors are formed without any chemical colorants; they are based on the interaction between the organism's unique physical structure and incident light, such as scattering, interference, and diffraction. They are characterized by their vividness, brightness, and colorfastness, thus attracting widespread attention in the textile industry. Current research largely focuses on preparing structural colors using the self-assembly of colloidal microspheres. Colloidal microspheres can be classified into organic and inorganic nanospheres based on their material composition. Among them, organic nanospheres have advantages such as simple preparation, easy assembly, and mass production, and are widely used in industrial research. However, organic nanospheres still suffer from weak bonding strength with the matrix, resulting in poor color fastness and thermal stability. Summary of the Invention

[0003] Based on the technical problems existing in the background technology, this invention proposes a heat-resistant biomimetic structural color printed fabric and its preparation method, and synthesizes structural color microspheres with heat resistance, which can form a bright printing effect at room temperature.

[0004] The method for preparing heat-resistant biomimetic structural color printed fabric proposed in this invention comprises the following steps: S1: Preparation of P(St-DVB-GMA) nanospheres Sodium bicarbonate and polyvinylpyrrolidone were dissolved in deionized water, and then glycidyl methacrylate, styrene, divinylbenzene, composite surfactant and initiator were added in sequence to carry out polymerization reaction. After the reaction, P(St-DVB-GMA) nanospheres were obtained by cooling and filtration. S2: Preparation of Heat-Resistant Biomimetic Structural Color Printed Fabrics P(St-DVB-GMA) nanospheres prepared by S1 were dispersed in deionized water, and then the dispersion was applied to a fabric with a masked surface by atomization deposition or spraying. After drying, a heat-resistant biomimetic structural color printed fabric was obtained.

[0005] Preferably, the mass ratio of glycidyl methacrylate, styrene, divinylbenzene, composite surfactant and initiator in S1 is 100:400-500:100-200:3-6:2-3.

[0006] Preferably, the composite surfactant sodium dodecylbenzenesulfonate and the nonionic surfactant CO897 in S1 are composed in a mass ratio of 1:3-5.

[0007] Preferably, the initiator in S1 is potassium persulfate or ammonium persulfate.

[0008] Preferably, the polymerization reaction in S1 takes 3-5 hours.

[0009] Preferably, the particle size of the P(St-DVB-GMA) nanospheres in S1 is 100~1000nm, and the solid content is 5%~20%.

[0010] Preferably, the mass fraction of P(St-DVB-GMA) nanospheres in the S2 dispersion is 5%~20%.

[0011] Preferably, the fabric in S2 is one of the following: natural cellulose fabrics such as cotton or linen, natural protein fabrics such as wool or silk, and synthetic fiber fabrics such as polyester, acrylic, nylon, or spandex.

[0012] Preferably, the drying temperature in S2 is 40~100℃ and the time is 30-300s.

[0013] The heat-resistant biomimetic structural color printed fabric prepared by the above method proposed in this invention.

[0014] Beneficial technical effects of the present invention: The structural color nanospheres prepared by the emulsion polymerization method of this invention can produce blue, purple and green colors on the surface of fabrics. The structural color nanospheres still have obvious structural color at 200℃, showing excellent heat resistance and stability. After washing with water for 1 hour, the reflection peak decreased by only 0.27%, and the color did not change significantly after 50 rubs. This indicates that the fabrics prepared by the structural color nanospheres have good wash fastness and rubbing fastness.

[0015] The structural color microspheres prepared by this invention have a solid content of 5%~20%, and not only possess the same efficiency as high solid content (≥55%) in rapid self-assembly and color development of structural colors, but also achieve rapid assembly of structural colors under natural environmental conditions (1m). 2 The structural color sample can be completely dried and developed under sunlight irradiation for 4 minutes. Attached Figure Description

[0016] Figure 1 The infrared spectra proposed in this invention are: (a) St, (b) GMA, (c) DVB, and (d) P(St-DVB-GMA). Figure 2 This is a particle size distribution diagram of the P(St-DVB-GMA) nanospheres proposed in this invention; Figure 3 SEM image of the P(St-DVB-GMA) nanosphere structured color-printed fabric proposed in this invention; Figure 4 The images show the colored printed fabrics with different particle sizes of P(St-DVB-GMA) nanospheres proposed in this invention. Figure 5 The reflectance curves of P(St-DVB-GMA) nanosphere structured colored printed fabrics of different colors proposed in this invention; Figure 6 This invention presents P(St-DVB-GMA) nanosphere structured color printed fabrics under different viewing angles.

[0017] Figure 7 A comparison diagram of the heat resistance of (a) P(St-co-GMA) nanospheres and (b) P(St-DVB-GMA) nanospheres proposed in this invention; Figure 8 The glass transition temperatures of the P(St-co-GMA) nanospheres and P(St-DVB-GMA) nanospheres proposed in this invention are given. Figure 9 The graphs show the heat resistance test results of P(St-DVB-GMA) nanospheres at different temperatures proposed in this invention. Figure 10 The reflectance curves of P(St-DVB-GMA) nanosphere structured color printed fabrics at different temperatures proposed in this invention are shown. Figure 11 This is a comparison image of the effects of washing on the P(St-DVB-GMA) nanosphere structured color printed fabric proposed in this invention; Figure 12 The reflectance curves of the P(St-DVB-GMA) nanosphere structured color printed fabric before and after washing are shown in the present invention. Figure 13 The image shows the test results of the friction properties of the P(St-DVB-GMA) nanosphere structured color printed fabric proposed in this invention. Figure 14 This image shows the actual effect of rapid color development of the P(St-DVB-GMA) nanosphere structured colored fabric proposed in this invention under natural light conditions. Detailed Implementation

[0018] The present invention will be further explained below with reference to specific embodiments.

[0019] Example 1 The preparation method of the heat-resistant biomimetic structural color printed fabric proposed in this invention has the following steps: Weigh out 0.015 g PVP and 0.25 g NaHCO3 and dissolve them completely in 250 g deionized water as the reaction base solution. Under constant stirring, transfer the solution to a 500 mL four-necked flask under nitrogen protection and heat to 75 °C. Then, add a pre-emulsion containing 45 g St, 15 g DVB, 10 g GMA, 100 g deionized water, 0.1 g sodium dodecyl sulfate (SDS), and 0.35 g nonionic surfactant CO897 dropwise to the four-necked flask. Then, slowly add an initiator (containing 0.25 g KPS and 15 g deionized water) to initiate the polymerization reaction. Continue the reaction for 5 h, cool to room temperature, filter out impurities, and set aside for later use.

[0020] The patterned fabric surface is constructed by mask atomization. The specific steps are as follows: dilute the emulsion with water at a ratio of 1:3, take 20mL of solution each time and atomize for 15min, atomize continuously for 4 times. After each atomization, take it out and dry it completely in a forced-air drying oven at 60℃ to obtain a blue structural color patterned fabric.

[0021] Example 2 The preparation method of the heat-resistant biomimetic structural color printed fabric proposed in this invention has the following steps: Weigh out 0.015 g PVP and 0.25 g NaHCO3 and dissolve them completely in 250 g deionized water as the reaction base solution. Under constant stirring, transfer the solution to a 500 mL four-necked flask under nitrogen protection and heat to 75 °C. Then, add a pre-emulsion containing 45 g St, 15 g DVB, 10 g GMA, 100 g deionized water, 0.092 g sodium dodecyl sulfate (SDS), and 0.366 g nonionic surfactant CO897 dropwise to the four-necked flask. Then, slowly add an initiator (containing 0.25 g KPS and 15 g deionized water) to initiate the polymerization reaction. Continue the reaction for 5 h, cool to room temperature, filter out impurities, and set aside for later use.

[0022] Patterning was created on the fabric surface using mask atomization. The specific steps are as follows: the emulsion was diluted with water at a ratio of 1:3. 20 mL of solution was atomized for 15 min each time, and the atomization was repeated 4 times. After each atomization, the fabric was taken out and dried completely in a forced-air drying oven at 60°C to obtain a purple structural color patterned fabric.

[0023] Example 3 The preparation method of the heat-resistant biomimetic structural color printed fabric proposed in this invention has the following steps: Weigh out 0.015 g PVP and 0.25 g NaHCO3 and dissolve them completely in 250 g deionized water as the reaction base solution. Under constant stirring, transfer the solution to a 500 mL four-necked flask under nitrogen protection and heat to 75 °C. Then, add a pre-emulsion containing 45 g St, 15 g DVB, 10 g GMA, 100 g deionized water, 0.088 g sodium dodecyl sulfate (SDS), and 0.38 g nonionic surfactant CO897 dropwise to the four-necked flask. Then, slowly add an initiator (containing 0.25 g KPS and 15 g deionized water) to initiate the polymerization reaction. Continue the reaction for 5 h, cool to room temperature, filter out impurities, and set aside for later use.

[0024] The patterned fabric surface is constructed by mask atomization. The specific steps are as follows: dilute the emulsion with water at a ratio of 1:3, take 20mL of solution each time and atomize for 15min, atomize continuously for 4 times. After each atomization, take it out and dry it completely in a forced-air drying oven at 60℃ to obtain a green structural color patterned fabric.

[0025] Comparative Example A soap-free emulsion polymerization method was used. Glycidyl methacrylate and styrene were mixed at a mass ratio of 1:2 and then added to a round-bottom flask containing 90 mL of deionized water along with 0.05 g of NaHCO3. Nitrogen gas was then continuously purged into the four-necked flask and maintained for 15 min. The flask was then placed in a water bath at 80 °C and stirred continuously for 30 min. 0.036 g of potassium persulfate (KPS) was dissolved in 10 mL of deionized water as an initiator solution. This initiator solution was added to the reaction round-bottom flask and the reaction was maintained at 80 °C for 4 h. After cooling to room temperature, impurities were filtered off to obtain P(St-co-GMA) nanospheres. P(St-co-GMA) nanosphere-structured colored fabrics were then prepared using the method described in Example 1.

[0026] The chemical structure of P(St-DVB-GMA) prepared in Example 3 was characterized by FT-IR, such as... Figure 1 As shown. Curve a is the infrared spectrum of monomer St, at 3076 cm⁻¹. -1 The characteristic peak at 1641 cm⁻¹ is caused by the =CH stretching vibration on the benzene ring. -1 The characteristic peak at 908 cm⁻¹ is due to the tensile vibration of the C=C bond. -1 The characteristic peak at 2978 cm⁻¹ is caused by -CH=CH₂. Curve b is the infrared spectrum of monomeric GMA, at 2978 cm⁻¹. -1 and 2947cm -1 These are the peak values ​​of saturated and unsaturated CH tensile vibrations, respectively, at 1720 cm⁻¹. -1 and 1637cm -1Characteristic peaks for ester C=O and C=C bonds are present at 1442 cm⁻¹, respectively. -1 and 1303cm -1 A CH deformation vibration peak exists at 1163 cm⁻¹. -1 The peak at 906 cm⁻¹ is considered to be the stretching vibration peak of the COC bond. Curve c is the infrared spectrum of monomeric DVB, at 906 cm⁻¹. -1 The characteristic peaks are caused by the two -CH=CH2 groups on the benzene ring. Curve d is the infrared spectrum of copolymer P(St-DVB-GMA), at 2924 cm⁻¹. -1 The peak value at 1950 cm⁻¹ corresponds to the stretching vibration of the CH bond on the benzene ring. -1 and 1122cm -1 These are the absorption peaks of the ester C=O and CC(=O)-O, respectively, while 908 cm⁻¹ is the absorption peak of the ester. -1 The decrease in the peak value is due to the breaking of the -CH=CH2 group on the benzene ring during the polymerization reaction. The results indicate that St, GMA, and DVB were successfully polymerized into P(St-DVB-GMA) nanospheres.

[0027] The particle size of the P(St-DVB-GMA) nanospheres prepared in Examples 1-3 was determined using a Zetasizer NanoS Malvern particle size analyzer. Figure 2 As shown, the narrow particle size distribution of P(St-DVB-GMA) nanospheres indicates their excellent monodispersity. By changing the mass ratio of CO897 to SDS, P(St-DVB-GMA) nanospheres with particle sizes of 245 nm, 332 nm, and 398 nm can be synthesized. In classic emulsion polymerization, anionic surfactants impart electrostatic charges to the outer layer of particles, preventing ion aggregation and ensuring the mechanical stability of the emulsion; nonionic surfactants are chemically stable. When these two emulsifiers are used in combination, they adsorb onto the surface of the emulsion particles. The emulsion colloids exhibit both electrostatic repulsion and the formation of a hydration layer on the latex particle surface, resulting in a synergistic effect. Therefore, changing the mass ratio of anionic and nonionic surfactants not only affects the dispersion of the monomer and the stability of the emulsion but also influences the particle size of the emulsion microspheres.

[0028] The surface morphology of the P(St-DVB-GMA) nanospheres prepared in Example 3 was observed using an S-4800 field emission scanning electron microscope (SEM). Figure 3As shown, the P(St-DVB-GMA) nanospheres exhibit relatively uniform and regular dimensions, approximating a spherical shape. These nanospheres can self-assemble on the surface of polyester fabrics, forming a random close-packed amorphous colloidal array structure with short-range order and long-range disorder. Simultaneously, due to the random close-packed amorphous colloidal array structure and the rough surface of the P(St-DVB-GMA) nanospheres, photons undergo multiple scattering processes in the medium, forming an isotropic bandgap under interference, resulting in non-iridescent structural colors.

[0029] The formation effect of P(St-DVB-GMA) nanospheres of different particle sizes on polyester fabrics is as follows: Figure 4 As shown, changing the ratio of the two surfactants alters the particle size of the microspheres, leading to changes in the lattice spacing and the wavelength that satisfies Bragg's law, thus resulting in a change in the structural color. When the particle size of P(St-DVB-GMA) nanospheres is 245 nm, they can self-assemble to form blue on polyester fabrics; when the particle size is 332 nm, they can form purple on polyester fabrics; and when the particle size is 398 nm, they can form green on polyester fabrics.

[0030] Figure 5 The reflectance curves of structurally colored printed fabrics made from P(St-DVB-GMA) nanospheres of different colors are shown. It can be seen that the reflectance peak positions of the structurally colored fabrics with P(St-DVB-GMA) microspheres of different particle sizes are different. When the particle size of the P(St-DVB-GMA) microspheres is 245 nm, the maximum reflectance wavelength of the structurally colored fabric is 400 nm, and the peak reflectance is 12.65%; when the particle size of the P(St-DVB-GMA) microspheres is 325 nm, the maximum reflectance wavelength of the structurally colored fabric is 390 nm, and the peak reflectance is 19.46%; when the particle size of the P(St-DVB-GMA) nanospheres is 398 nm, the maximum reflectance wavelength of the structurally colored fabric is 530 nm, and the peak reflectance is 13.58%. Therefore, P(St-DVB-GMA) nanospheres of different particle sizes can be assembled on polyester fabrics to form structural colors of different colors.

[0031] Figure 6 The structural color printed fabrics of P(St-DVB-GMA) nanospheres prepared in Example 3 are shown under different observation angles. It can be seen that as the observation angle changes from 30° to 90°, the structural color on the fabric does not change with the angle; the color rendering of the structural color is independent of the angle, exhibiting a non-iridescent effect. This further verifies that P(St-DVB-GMA) nanospheres can self-assemble on the surface of polyester fabrics to form a random close-packed amorphous colloidal array structure with short-range order and long-range disorder.

[0032] Color comparison of the structural colors of P(St-DVB-GMA) nanospheres and P(St-co-GMA) nanospheres prepared in Example 3 at different temperatures, as shown in the figure. Figure 7 As shown. By Figure 7 (a) It can be seen that when P(St-co-GMA) nanosphere structured colored fabric is placed at 60℃, 80℃, 100℃ and 110℃ for 10 min respectively, the color of the structured colored fabric gradually dims as the temperature increases, and the color disappears completely at 110℃. Figure 7 (b) It can be seen that when the P(St-DVB-GMA) nanosphere structured fabric is placed at 60℃, 80℃, 100℃ and 110℃ for 10 min, the color brightness of the structured color on the fabric surface decreases slightly with the increase of temperature. After treatment at 110℃ for 10 min, the color of the structured fabric is still relatively obvious.

[0033] The glass transition temperatures of P(St-co-GMA) nanospheres and P(St-DVB-GMA) nanospheres prepared in Example 3 are as follows: Figure 8 As shown, the glass transition temperature (Tg) of P(St-co-GMA) nanospheres is 96℃, while that of P(St-DVB-GMA) nanospheres is increased to 150℃. Clearly, the higher glass transition temperature of P(St-DVB-GMA) nanospheres imparts greater thermal stability to the structural color. Therefore, introducing the crosslinking agent DVB can improve the crosslinking between monomers, thereby effectively improving the thermal resistance of the microspheres, which is one of the reasons for the difference in thermal stability between the two types of microspheres.

[0034] The thermal stability of the P(St-DVB-GMA) nanospheres prepared in Example 3 at different temperatures is tested as follows: Figure 9 As shown, when P(St-DVB-GMA) nanosphere structured color fabrics were kept at different temperatures (60~200℃) for 10 minutes, the fabric color gradually lightened with increasing temperature, but the color did not completely disappear at 200℃, and the structural color was still quite obvious on the surface. This indicates that the P(St-DVB-GMA) nanosphere structured color still has good stability at 200℃.

[0035] The reflectance spectra of the P(St-DVB-GMA) nanosphere structured fabric prepared in Example 3 after treatment at different temperatures are shown below. Figure 10As shown, after treating P(St-DVB-GMA) nanosphere structured fabrics of the same color at different temperatures ranging from 60 to 200℃, the position of the reflectance peak of the structured fabric did not change, but the peak reflectance gradually decreased with increasing treatment temperature. Compared with the original structured fabric, the peak reflectance of the structured fabric treated at 60-70℃ decreased by an average of about 1%; the peak reflectance of the structured fabric treated at 80-120℃ decreased by an average of about 2%; the peak reflectance of the structured fabric treated at 140-180℃ decreased by an average of about 3%; and the peak reflectance of the structured fabric treated at 200℃ decreased significantly, by about 5%, indicating that P(St-DVB-GMA) nanosphere structured fabrics have good heat resistance stability.

[0036] The wash fastness of the P(St-DVB-GMA) nanosphere structured dyed fabric prepared in Example 3 was tested. Figure 11 It can be seen that washing the P(St-DVB-GMA) nanosphere structured fabric with deionized water did not result in a significant change in the structural color before and after washing. Figure 12 It can be seen that the reflectance curves of the structured dyed fabrics after 1 hour of washing are basically the same, and the peak reflectance decreases by 0.27% compared with that before washing. The results indicate that the P(St-DVB-GMA) nanosphere structured dyed fabrics have good color fastness to washing.

[0037] The surface of the P(St-DVB-GMA) nanosphere structured fabric prepared in Example 3 was subjected to rubbing fastness tests. The surface of the structured fabric was subjected to 1, 10, 30, and 50 rubbing tests, respectively. Figure 13 As shown, the staining phenomenon becomes more pronounced with increasing number of rubbing cycles; Figure 13 (c) After 50 cycles of rubbing, the structured colored fabric and... Figure 13 (a) No significant color change was observed compared to before rubbing. Therefore, the P(St-DVB-GMA) nanosphere structured fabric exhibits good rubbing fastness.

[0038] Figure 14 This image shows the rapid color development effect of the P(St-DVB-GMA) nanosphere structured fabric prepared in Example 3 under natural light conditions. It can be seen that the microspheres can achieve rapid structural color assembly even under natural environmental conditions. (1m) 2 The structural color sample can be completely dried and developed in 4 minutes under sunlight.

Claims

1. A method for preparing heat-resistant bionic structural color printed fabric, characterized in that: The steps are as follows: S1: Preparation of P(St-DVB-GMA) nanospheres Sodium bicarbonate and poly(ethylene pyrrolidone) are dissolved in deionized water, and then glycidyl methacrylate, styrene, divinylbenzene, a composite surfactant and an initiator are sequentially added to carry out polymerization reaction, and after the reaction, the reaction is cooled and filtered to obtain P(St-DVB-GMA) nanoparticles; S2: Preparation of heat-resistant bionic structural color printed fabrics The P(St-DVB-GMA) nanospheres prepared in S1 are dispersed in deionized water, and then the dispersion is treated onto a fabric with a mask on the surface by atomization deposition or spraying. After drying, a heat-resistant bionic structural color printed fabric is obtained.

2. The method for preparing heat-resistant bionic structural color printed fabric according to claim 1, characterized in that: The mass ratio of glycidyl methacrylate, styrene, divinylbenzene, composite surfactant and initiator in S1 is 100:400-500:100-200:3-6:2-3.

3. The method for preparing heat-resistant bionic structural color printed fabric according to claim 1, characterized in that: The composite surfactant sodium dodecylbenzene sulfonate and the nonionic surfactant CO897 in S1 are composed in a mass ratio of 1:3-5.

4. The method for preparing heat-resistant bionic structural color printed fabric according to claim 1, characterized in that: The initiator in S1 is potassium persulfate or ammonium persulfate.

5. The method for preparing heat-resistant bionic structural color printed fabric according to claim 1, characterized in that: The polymerization time in S1 is 3-5 h.

6. The method for preparing heat-resistant bionic structural color printed fabric according to claim 1, characterized in that: The particle size of P(St-DVB-GMA) nanospheres in S1 is 100~1000nm, and the solid content is 5%~20%.

7. The method for preparing heat-resistant bionic structural color printed fabric according to claim 1, characterized in that: The mass fraction of P(St-DVB-GMA) nanoparticles in the S2 dispersion is 5%-20%.

8. The method for preparing heat-resistant bionic structural color printed fabric according to claim 1, characterized in that: The fabric in S2 is one of natural cellulose fabrics such as cotton or linen, natural protein fabrics such as wool or silk, and synthetic fiber fabrics such as polyester, acrylic, nylon or spandex.

9. The method for preparing heat-resistant bionic structural color printed fabric according to claim 1, characterized in that: The drying temperature in S2 is 40-100°C and the drying time is 30-300s.

10. The heat-resistant bionic structural color printed fabric prepared by the method according to any one of claims 1 to 9.

Images