Preparation and application of structural color polymer dispersion liquid
By mixing colloidal emulsion with sodium alginate to prepare structural color fibers, the problem of seaweed fibers being difficult to dye is solved, and an environmentally friendly and stable coloring method is achieved, which is applied in fields such as coatings and 3D printing.
Patent Information
- Application Number
- CN202510991203.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-18
- Publication Date
- 2025-09-26
AI Technical Summary
Existing seaweed fibers are difficult to dye, which limits their application in the textile and environmental protection fields.
The colloidal emulsion was mixed with sodium alginate and the structural color fibers were prepared by wet spinning. Black cuttlefish juice was used as dye and combined with calcium chloride coagulation bath to prepare the structural color sodium alginate fibers.
An environmentally friendly and pollution-free stable coloring method has been achieved. The fiber is humidity responsive and can be used in coatings, 3D printing and other fields with simple operation.
Smart Images
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Abstract
Description
1. Technical Field
[0001] The present invention relates to a method for preparing a structural color polymer dispersion. This dispersion can be used to prepare structural color fibers, 3D print structural color models, and cast into 3D structural color hydrogels and structural color hydrogel coatings. More specifically, using sodium alginate as an example, the present invention relates to a method for preparing a structural color dispersion by mixing a colloidal emulsion with a sodium alginate solution, and then wet-spinning the resulting structural color sodium alginate fibers. 2. Technical Background
[0002] Structural color is a physical color created by the periodic arrangement of colloidal particles, creating a photonic band gap. This prevents waves within a certain frequency range from propagating through this periodic structure, and they are therefore reflected. When the reflected wavelength is within the visible light range, structural color is observed. Photonic crystals can be categorized as one-dimensional, two-dimensional, and three-dimensional, depending on their spatial arrangement. They all conform to the Bragg diffraction equation, and structural color changes with changes in the lattice spacing, the refractive index of the medium, and the angle of the incident light.
[0003] Sodium alginate is a natural polysaccharide extracted from seaweed. It has the advantages of being non-toxic, biocompatible, widely available, and biodegradable. Its molecular chain contains a large number of hydrophilic groups, which give the fiber a higher moisture regain and improve the comfort of the fabric. These properties make it an ideal choice for environmentally friendly textile materials.
[0004] Currently, researchers have conducted extensive research on seaweed fibers, but they are difficult to dye. Therefore, the preparation of fibers with structural colors has important application value in the fields of textiles, environmental protection, etc. 3. Summary of the Invention
[0005] This invention proposes a method for producing structural color fibers by mixing a colloidal emulsion with sodium alginate and then wet-spinning them. Compared to traditional dyes, the structural color is more stable, the method is simpler, and it reduces the environmental pollution caused by chemical pigments. The specific invention content is as follows:
[0006] The technical solution of the present invention provides a method for preparing structural color sodium alginate fiber, which comprises the following steps:
[0007] (1) Prepare a colloidal emulsion with monodisperse properties, and fully mix the emulsion and sodium alginate solution to obtain a pre-dispersed solution.
[0008] (2) Add black cuttlefish ink to the pre-dispersion prepared in (1), and stir thoroughly to obtain a structural color sodium alginate dispersion.
[0009] (3) A calcium chloride aqueous solution is prepared as a coagulation bath, and the dispersion prepared in (2) is squeezed out from a nozzle into the calcium chloride coagulation bath by pressure, and immersed and solidified to obtain structural color fibers with uniform thickness, and the fibers are collected and dried at room temperature.
[0010] In some embodiments, the present invention further includes the following methods:
[0011] (4) The colloidal emulsion, sodium alginate solution, and cuttlefish juice are mixed evenly to obtain a structural color dispersion, and a calcium chloride aqueous solution is prepared. Two syringe pumps and a coaxial needle are used to inject the calcium chloride solution into the outer tube and the structural color dispersion into the inner tube. The flow rate ratio is adjusted to achieve 3D printing.
[0012] (5) The colloidal emulsion, sodium alginate solution and cuttlefish ink are mixed evenly to prepare a structural color dispersion, calcium carbonate and gluconolactone are added for post-crosslinking, and the dispersion is used as a printing ink, coating or filler.
[0013] In some embodiments, the colloid is any one of inorganic colloidal nanoparticles and organic colloidal nanoparticles; the inorganic nanoparticles are silica; the organic nanoparticles are any one of polystyrene, polymethyl methacrylate, poly(styrene-acrylic acid-methyl methacrylate) or colloidal particles with them as the main components, the particle size dispersion of the nanoparticles is less than 0.1, and the particle size range is 100-500nm.
[0014] In some embodiments, sodium alginate can be replaced by polysaccharides and organic polymers, wherein the polysaccharide is any one of starch and its modifications, dextran and its modifications, sodium carboxymethyl cellulose and its modifications, and agarose, and the organic polymer is any one of polyacrylic acid, polyacrylamide and related polymers.
[0015] In some embodiments, for the above-mentioned polysaccharides and organic polymers, the coagulation bath can be replaced accordingly as follows: starch can be replaced with any one of sodium dihydrogen phosphate, phosphorus oxychloride, epichlorohydrin and peroxide; dextran can be replaced with any one of dextran and epichlorohydrin; sodium carboxymethyl cellulose, polyacrylic acid and polyacrylamide can be replaced with metal ions.
[0016] In some embodiments, the cuttlefish ink can be replaced with other black nano additives, such as carbon black, carbon nanotubes, graphene, polydopamine and other black light-absorbing nano substances.
[0017] The amount of the emulsion added to the mixed dispersion in step (1) is 0.1%-10.0% w / v.
[0018] The amount of sodium alginate added to the mixed dispersion in step (1) is 0.1%-10% w / v.
[0019] The amount of cuttlefish ink added to the mixed dispersion in step (2) is 0.01%-3% w / v.
[0020] The concentration of the calcium chloride solution in step (3) is 0.5%-20% w / v.
[0021] The present invention provides a sodium alginate fiber with structural color prepared according to the above method. Compared with the previous technology, the advantages and positive effects of the present invention are:
[0022] 1. The present invention directly compounds structural color with sodium alginate fibers, achieving an environmentally friendly, pollution-free, and color-stable coloring method. Furthermore, the structural color fibers are humidity-responsive; the structural color dispersion has scalable applications such as coatings and 3D printing.
[0023] 2. The present invention does not require subsequent spraying of fibers or textiles, and the preparation conditions are mild and the operation is simple. IV. Description of the Figures
[0024] Figure 1 These are optical photographs of the colloidal emulsion smears with particle sizes of 186 nm, 204 nm and 240 nm prepared in the present invention after drying, as well as optical photographs of the structural color dispersion obtained by mixing with sodium alginate and cuttlefish ink.
[0025] Figure 2 These are the reflection spectra of photonic crystal films with different particle sizes and structural color dispersions prepared in the present invention.
[0026] Figure 3 These are optical photographs of the color change of the dispersion when the colloidal emulsion with a particle size of 204 nm is added in an amount ranging from 0.6% to 3% w / v, and optical photographs of the color change of the dispersion when the sodium alginate addition amount is from 0.06% to 1.2% w / v.
[0027] Figure 4 This is an optical photograph showing the color change of the dispersion when the amount of cuttlefish ink prepared by the present invention is added is 0.025%-0.3% w / v.
[0028] Figure 5 The optical photograph of the fiber color when the emulsion prepared by the present invention is added at a calcium chloride concentration of 0.5%-5% w / v.
[0029] Figure 6 This is a stress-strain diagram of the mechanical strength of the fiber prepared in the present invention when the calcium chloride concentration is 0.5%-5% w / v.
[0030] Figure 7 These are optical photos of bracelets and Chinese knots made of sodium alginate fibers with different structural colors according to the present invention.
[0031] Figure 8 The present invention shows patterns sewn on fabrics of different colors using structural color sodium alginate fibers, including the effects on black and white fabrics, and optical photographs showing the color contrast between dry and wet states.
[0032] Figure 9 The present invention utilizes a coaxial printing method to achieve printing of 3D patterns.
[0033] Figure 10 These are optical photos of planar patterns and three-dimensional castings drawn using the structural color dispersion as a coating in a post-crosslinking manner according to the present invention.
[0034] Figure 11 Optical photographs of the dry and wet states of the fabric coated with the structural color dispersion as a coating using post-crosslinking.
[0035] Figure 12 These are optical photographs of structural color dispersions prepared using different polymers according to the present invention. V. Specific Implementation Methods
[0036] The technical solution of the present invention is further explained and illustrated in the following by way of specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative work fall within the scope of protection of the present invention.
[0037] Example 1
[0038] This embodiment discloses a method for preparing sodium alginate fiber, comprising the following steps:
[0039] (1) Prepare a series of structural color dispersions with different ratios of colloidal emulsion, sodium alginate, and cuttlefish ink.
[0040] (2) The flow rate is controlled by a syringe pump, and the dispersion is evenly squeezed into a calcium chloride coagulation bath of different concentrations.
[0041] (3) The fibers are collected and dried at room temperature for specific applications such as weaving and sewing.
[0042] The structural color dispersion prepared in step (1) is as follows Figure 3 As shown in the figure, as the concentration of the colloidal emulsion decreases, the saturation and brightness of the structural color decreases accordingly. When the concentration range is 1.8%-3.0% w / v, the color of the dispersion is better. As the concentration of sodium alginate decreases, the color of the dispersion gradually shifts from red to colorless. When the concentration range is 0.3%-1.2% w / v, the color of the dispersion is better. Figure 4 As shown in the figure, when the concentration of cuttlefish ink reaches 0.175% w / v, the color of the dispersion becomes obviously darker, while the color is better when the concentration is 0.125% w / v.
[0043] The structural color fiber prepared in step (2) is as follows Figure 5 As shown in the figure, the appearance of the prepared fibers is uniform in thickness, and the calcium chloride concentration of 0.5%-5% w / v has no obvious effect on the structural color of the fibers. The mechanical function tests of the fibers prepared at four calcium chloride concentrations were carried out using a mechanical tensile machine, as shown in the figure. Figure 6 As shown in the figure, with the increase of calcium chloride concentration, the stress that the fiber can withstand gradually increases, while the ability to withstand tensile strain gradually decreases. The appropriate calcium chloride concentration can be selected according to different application scenarios.
[0044] The weaving application of the fiber in step (3) is as follows Figure 7 As shown in the optical photos of hand-woven bracelets and Chinese knots, the colors are bright and the fiber strength is good, which can adapt to a variety of weaving and knotting methods; the structural color fiber is used for sewing clothes after drying. Figure 8 As shown, the fiber has good strength and can be used for textile sewing. The color is more obvious on black cloth than on white cloth. The color is darker in dry state and brighter in wet state, and it has humidity responsiveness.
[0045] Example 2
[0046] This embodiment discloses a 3D printing method for structural color sodium alginate fibers, comprising the following steps:
[0047] (1) Prepare a structural color dispersion with a colloidal emulsion concentration of 1.8% w / v, a sodium alginate concentration of 0.6% w / v, and a cuttlefish ink concentration of 0.125% w / v, and place the mixture into syringe 1.
[0048] (2) Prepare a 5% w / v calcium chloride solution as a coagulation bath and load it into syringe 2.
[0049] (3) Using two syringe pumps and a coaxial needle (14G / 19G), the outer tube injects calcium chloride solution and the inner tube injects structural color dispersion. The flow rate ratio is adjusted to 1.2:1, and 3D printing can be achieved.
[0050] The 3D printing model prepared in Example 2 is as follows Figure 9 As shown, the coaxially printed fibers will not collapse, the fiber thickness is uniform, the pattern can maintain a three-dimensional shape, and at the same time have structural color; by controlling the movement of the needle, different patterns can also be printed.
[0051] Example 3
[0052] This embodiment discloses a method for preparing a structural color sodium alginate coating, comprising the following steps:
[0053] (1) Prepare a structural color dispersion with a colloidal emulsion concentration of 1.8% w / v, a sodium alginate concentration of 0.6% w / v, and a cuttlefish ink concentration of 0.125% w / v.
[0054] (2) Calcium carbonate and gluconolactone were added in a ratio of 0.5 wt % to 1.8 wt % to post-crosslink the dispersion.
[0055] (3) When the dispersion becomes viscous during the crosslinking process, it can be drawn on paper, coated on cloth, or poured on the surface of an object like ink.
[0056] The application of the structural color sodium alginate prepared in Example 3 as a coating is as follows Figure 10 As shown, the colors used for drawing on paper with ink are bright, and the colors are even when poured on three-dimensional shapes. Figure 11 As shown, the coating on the cloth is humidity responsive, with a lighter color in the dry state and a bright color in the wet state.
[0057] Example 4
[0058] This embodiment discloses a method for preparing structural color dispersions using different polymers, comprising the following steps:
[0059] (1) Prepare a sodium carboxymethyl cellulose solution and prepare a structural color dispersion according to the following ratios: 1.5% w / v of colloidal emulsion, 0.6% w / v of sodium carboxymethyl cellulose, and 0.125% w / v of cuttlefish ink.
[0060] (2) Prepare a dextran solution and prepare a structural color dispersion according to the ratio of 1.5% w / v colloidal emulsion, 0.9% w / v dextran, and 0.125% w / v cuttlefish ink.
[0061] (3) Prepare a starch solution and prepare a structural color dispersion according to the ratio of 1.5% w / v of colloidal emulsion, 3% w / v of starch, and 0.175% w / v of cuttlefish ink.
[0062] (4) Prepare a polyacrylic acid solution and prepare a structural color dispersion according to the ratio of 1.5% w / v colloidal emulsion, 7.5% polyacrylic acid, and 0.175% w / v cuttlefish ink.
[0063] (5) Prepare anionic polyacrylamide solution, and prepare structural color dispersion according to the ratio of colloidal emulsion 1.5% w / v, anionic polyacrylamide 3%, and cuttlefish ink 0.175% w / v.
[0064] The results of the different polymer structure color dispersions prepared in Example 4 above are as follows Figure 12As shown, both exhibit distinct structural color. The colloidal emulsion can be any of silica, polymethyl methacrylate, poly(styrene-acrylic acid-methyl methacrylate), or polystyrene; and the cuttlefish ink can be replaced with any of carbon black, carbon nanotubes, graphene, or polydopamine. The material selection process avoids mixing anions and cations, as this can cause agglomeration, resulting in uneven particle arrangement and a failure to exhibit structural color.
Claims
1. A method for preparing a structural color polymer dispersion. The ink can be used to prepare structural color fibers, 3D printing, and casting into 3D structural color hydrogels. Taking sodium alginate as an example, it is characterized by: The following steps are involved: (1) preparing colloidal emulsions of different particle sizes, and fully mixing the emulsions and sodium alginate solution to obtain a pre-dispersion solution; (2) adding cuttlefish ink to the pre-dispersion liquid and mixing thoroughly to obtain a structural color sodium alginate dispersion liquid; (3) preparing a calcium chloride aqueous solution as a coagulation bath, extruding the structural color sodium alginate dispersion from a nozzle into the calcium chloride coagulation bath by pressure, immersing and curing the dispersion to obtain structural color fibers with uniform thickness, collecting the fibers and drying them at room temperature; (4) Using a coaxial needle and syringe pump, calcium chloride and sodium alginate dispersions are extruded simultaneously to achieve 2D and 3D pattern printing; (5) The structural color dispersion is post-crosslinked with calcium carbonate and gluconolactone, and can be used as a coating for drawing and pouring on flat and three-dimensional shapes.
2. The sodium alginate fiber with structural color prepared according to claim 1, characterized in that: The colloidal nanoparticles are any one of inorganic colloidal nanoparticles and organic colloidal nanoparticles; the inorganic nanoparticles are silica or other inorganic nanoparticles that can be assembled into photonic crystals; the organic nanoparticles are any one of polystyrene, polymethyl methacrylate, poly(styrene-acrylic acid-methyl methacrylate) or colloidal particles with them as the main components.
3. The structural color ink prepared according to claim 1, characterized in that: The sodium alginate can be replaced by any one of a polysaccharide polymer and an organic polymer; the polysaccharide polymer is any one of starch and its modified products, sodium carboxymethyl cellulose and its derivatives, dextran, and agarose; the organic polymer is any one of polyacrylic acid, polyacrylamide, and their hydrolyzates.
4. The structural color ink prepared according to claim 1, characterized in that: The cuttlefish ink can be replaced by other black nano additives, such as carbon black, carbon nanotubes, graphene, polydopamine and other black light-absorbing nano substances.
5. The polysaccharide and organic polymer according to claim 3, characterized in that: The coagulation bath can be replaced accordingly as follows: starch can be replaced with any one of sodium dihydrogen phosphate, phosphorus oxychloride, epichlorohydrin and peroxide; dextran can be replaced with any one of dextran and epichlorohydrin; sodium carboxymethyl cellulose, polyacrylic acid and polyacrylamide can be replaced with metal ion solution.
6. The structural color ink prepared according to claim 1, characterized in that: The structural color dispersion can be obtained by directly mixing the colloidal emulsion and the polymer solution. The preparation method is simple, wherein the addition amount of the colloidal emulsion is 0.1%-10.0% w / v, and the addition amount of sodium alginate is 0.1%-10% w / v.
7. The structural color ink prepared according to claim 1, characterized in that: Inks of different colors can be prepared by adjusting the size of the colloid particles. The particle size dispersion of the colloid particles is less than 0.1, and the particle size is 100-500nm.
8. The structural color ink prepared according to claim 1, characterized in that: The addition of black additives can reduce light scattering, making the sodium alginate dispersion present a brighter structural color. The addition amount is 0.01%-3% w / v.
9. The sodium alginate fiber with structural color prepared according to claim 1, characterized in that: The wet spinning method is used, calcium chloride is used as a coagulation bath, and uniform structural color fibers are produced through an injection pump. The concentration of the calcium chloride aqueous solution is 0.5%-20% w / v, and the curing time is 1-60 minutes.
10. The sodium alginate fiber with structural color prepared according to claim 1, characterized in that: The extrusion speed of the dispersion in wet spinning is 500-1200 μL / min, and the inner diameter of the syringe is 1.5-3 mm.
11. The sodium alginate dispersion with structural color prepared according to claim 1, characterized in that: Calcium carbonate and gluconolactone are added to the dispersion for post-crosslinking, allowing it to be applied as a coating on 2D and 3D shapes, or it can be directly poured into a mold and cured into a 3D structural color hydrogel.
12. The sodium alginate fiber with structural color prepared according to claim 1, characterized in that: The fiber is humidity responsive. Under dry conditions, the structural color of the fiber becomes dim, and under wet conditions, the structural color will recover. It can be used in textile, anti-counterfeiting and other fields. The coaxial needle can be used to print flat and three-dimensional patterns. Post-crosslinking of the dispersion can be used in color coatings.