CN114958182A - Photonic crystal structure color coating with high-intensity and continuously controllable color and preparation and application thereof - Google Patents
Photonic crystal structure color coating with high-intensity and continuously controllable color and preparation and application thereof Download PDFInfo
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- CN114958182A CN114958182A CN202210423851.1A CN202210423851A CN114958182A CN 114958182 A CN114958182 A CN 114958182A CN 202210423851 A CN202210423851 A CN 202210423851A CN 114958182 A CN114958182 A CN 114958182A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/30—Camouflage paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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Abstract
The invention discloses a photonic crystal structure color coating with high intensity and continuously controllable color, and preparation and application thereof, and belongs to the field of material preparation. The invention discloses a method for preparing a photonic crystal structure color coating solution with high-intensity color, which comprises the following steps: monodisperse SiO 2 Uniformly mixing the microsphere solution and the aqueous polyurethane emulsion diluent to obtain a photonic crystal structure color coating solution; wherein the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 4-36 wt% of microsphere solution and SiO 2 The average particle diameter of the microspheres is 190-200nm, the solid content of the aqueous polyurethane emulsion diluent is 3-4%, the viscosity is 20-40mPa.S, and the aqueous polyurethane emulsion diluent is light blue semitransparentIn the form of 10-15 wt%. The invention adjusts SiO 2 The amount of the aqueous polyurethane emulsion diluent in the microsphere solution is used for obtaining various continuous structural colors, so that SiO with single grain diameter is realized 2 The microspheres correspond to various structural colors, so that the requirement of accurately controlling SiO is avoided 2 The particle size of the microsphere obtains various structural colors.
Description
Technical Field
The invention relates to a photonic crystal structure color coating with high intensity and continuously controllable color, and preparation and application thereof, belonging to the field of material preparation.
Background
Color plays a crucial role in the evolution and survival of animals and plants, and can generally play roles in camouflage, hiding and information transfer. Colors can be classified into two broad categories, namely, a pigment color and a structural color, according to the color generation mechanism. Pigment color has a very significant disadvantage in that pigment molecules react with chemical components in the air over time to produce a fading phenomenon. Structural colors, also referred to as physical colors, are generated by physical actions such as reflection, scattering, interference, or diffraction of light with structures when light is incident on an object with a spatial period close to a wavelength. The color generation mechanism of the structural color is completely based on physical principles and does not substantially involve energy loss of light. Therefore, compared with the conventional pigment color, as long as the structure of the substance remains unchanged, the color thereof does not fade with the passage of time, and a vivid color can be permanently maintained.
The discovery of structural colors greatly broadens the research ideas of researchers on pigments applied to the coating and printing industries. The conventional industrial pigments are easy to decolorize, and are extremely easy to pollute the environment, and some pigments even contain toxicity. The structural color does not have the defects, so long as the physical microstructure is not damaged, the color of the material can not fade permanently regardless of time lapse and environmental change, and the material is green, environment-friendly and environment-friendly. Therefore, the replacement of the conventional pigments currently used with structural colors is an unavoidable development.
The existing method for preparing the structural color is mainly to prepare the photonic crystal by the technologies of ion beam etching, colloid self-assembly and the like so as to generate the structural color, but the ion beam etching is expensive and the operation is complex, so that the method cannot be applied to the practice in a large scale; the photonic crystal structure produced by colloid self-assembly has single color, and multiple structural colors can be obtained only by accurately adjusting the particle size of the microspheres, but the adjustment of the particle size of the microspheres needs to be very accurate, so that the application of the photonic crystal structure color coating is limited; in addition, the prepared photonic crystal structure color coating is poor in mechanical property because the connection between the microspheres in the photonic crystal is only point connection, and cannot be applied to practice.
Disclosure of Invention
[ problem ] to
The existing method for preparing the structural color is complex to operate and high in cost; and the prepared structural color coating has poor mechanical property.
[ solution ]
In order to solve the above problems, the present invention is to precisely control monodisperse SiO 2 The preparation of the photon structure color coating solution is realized by the use amount of the microsphere solution and the aqueous polyurethane emulsion, and the photon crystal structure color coating with high intensity and continuously controllable color is prepared by spraying. The preparation method of the photonic crystal structure color coating is simple, environment-friendly and wide in application range.
A first object of the present invention is to provide a method for preparing a photonic crystal structure color coating solution having a high intensity color, comprising the steps of:
monodisperse SiO 2 Uniformly mixing the microsphere solution and the aqueous polyurethane emulsion diluent to obtain a photonic crystal structure color coating solution; wherein the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 4 wt% -36 wt% of microsphere solution.
In one embodiment of the present invention, the mixing is performed by ultrasonic oscillation at 100-300W power for 20-40min at 25-45 ℃.
In one embodiment of the present invention, the monodisperse SiO 2 SiO in microsphere solution 2 The actual average particle diameter of the microspheres is 190-200nm, more preferably 193 nm.
In one embodiment of the present invention, the monodisperse SiO 2 The microsphere solution is SiO 2 The mass concentration of the microsphere aqueous solution is 5-7%, and more preferably 6%.
In one embodiment of the present invention, the monodisperse SiO 2 The preparation method of the microsphere solution comprises the following steps:
mixing anhydrous ethanol and ammonia water, and stirring at 20-30 deg.C for 20-40min to obtain mixed solution of anhydrous ethanol and ammonia water; slowly adding tetraethyl orthosilicate into a mixed solution of absolute ethyl alcohol and ammonia water, stirring and reacting for 8-9h at 25-55 ℃, centrifuging and washing after the reaction is finished to obtain SiO 2 Microspheres; finally, SiO is mixed 2 Dispersing the microspheres in water to obtain monodisperse SiO 2 A microsphere solution;
wherein the volume ratio of the absolute ethyl alcohol to the ammonia water to the tetraethyl orthosilicate is 110: 6-10: 5-7; the dropping speed of the tetraethyl orthosilicate is 2-4 mL/min.
In one embodiment of the invention, the aqueous polyurethane emulsion diluent has a solid content of 3-4%, a viscosity of 20-40mPa.S, a light blue semitransparent state and a concentration of 10-15 wt%.
In one embodiment of the invention, the aqueous polyurethane emulsion diluent is obtained by diluting an aqueous polyurethane emulsion with water.
In one embodiment of the present invention, the aqueous polyurethane emulsion may be commercially available or may be prepared by itself, and the specific preparation method includes:
uniformly mixing polypropylene glycol 2000 and 2, 2-dimethylolpropionic acid, and stirring and reacting at 40-50 ℃ for 20-40 min; continuously heating to 95-105 ℃, adding isophorone diisocyanate, and stirring to react for 3-5h at 95-105 ℃; cooling to room temperature, adding acetone to reduce viscosity, then adding mixed solution of triethylamine and ethylenediamine, and obtaining aqueous polyurethane emulsion after reaction;
wherein the mass ratio of the polypropylene glycol 2000 to the 2, 2-dimethylolpropionic acid to the isophorone diisocyanate to the acetone to the triethylamine to the diethylamine is 60: 4-6: 12-16: 30-35: 1-3: 2-6.
In one embodiment of the invention, the solid content of the aqueous polyurethane emulsion is 25-35%, the viscosity is 190-210mPa.S, and the aqueous polyurethane emulsion is light blue and semitransparent.
The second purpose of the invention is to prepare the photonic crystal structure color coating solution by the method.
The third purpose of the invention is to provide a method for preparing a substrate containing the photonic crystal structure color coating, wherein the method is to apply the photonic crystal structure color coating solution on the surface of the substrate by spraying.
In one embodiment of the invention, the spraying is carried out with a spray gun at a pressure of 1.5-3.5 MPa.
In one embodiment of the invention, the thickness of the spray coating is 80 μm to 100 μm.
In one embodiment of the present invention, the substrate comprises one of glass, an iron plate, an aluminum plate, and a wood plate.
The fourth object of the invention is a substrate containing a photonic crystal structure color coating prepared by the method of the invention.
The fifth purpose of the invention is the application of the photonic crystal structure color coating solution and the substrate containing the photonic crystal structure color coating in the preparation of anti-counterfeiting materials.
It is a sixth object of the present invention to provide a method for preparing a continuously controllable photonic crystal structure color coating by controlling SiO 2 The particle size of the microspheres is not changed, and the aqueous polyurethane emulsion diluent is adjusted to be in monodisperse SiO 2 The regulation and control of the structural color are realized by the proportion of the microsphere solution; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 4 wt% of the microsphere solution, the coating appeared blue; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 12 wt% of the microsphere solution, the coating showed a blue-green color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 20 wt% of the microsphere solution, the coating showed green color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 28 wt% of the microsphere solution, the coating showed a yellow-green color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 36 wt% of the microsphere solution, the coating showed a yellow color.
In one embodiment of the present invention, the SiO 2 The actual average particle size of the microspheres is 190-200 nm; the solid content of the aqueous polyurethane emulsion diluent is 3-4%, the viscosity is 20-40mPa.S, the aqueous polyurethane emulsion diluent is light blue and semitransparent, and the concentration is 10-15 wt%.
[ advantageous effects ]
(1) The invention adjusts the monodisperse SiO 2 The amount of the aqueous polyurethane emulsion diluent in the microsphere solution is used for obtaining various continuous structural colors, so that SiO with single grain diameter is realized 2 The microspheres correspond to various structural colors, so that the requirement of accurately controlling SiO is avoided 2 The particle size of the microspheres obtains various structural colors.
(2) The photonic crystal structure color coating has high strength and small angle dependence.
(3) The spraying method is simple, easy to operate, low in requirement on the base material, suitable for surfaces of various materials and wide in application range.
Drawings
FIG. 1 is an SEM image of a glass sheet containing a photonic crystal structure color coating prepared in examples 1-5 and comparative example 1; wherein (a) comparative example 1, (b) example 1, (c) example 2, (d) example 3, (e) example 4, and (f) example 5.
Fig. 2 is a uv reflection chart and an optical photograph of the photonic crystal structure color coating layers prepared in examples 1 to 5 and comparative example 1.
FIG. 3 is a different perspective view of the glass sheets containing the photonic crystal structure color coating obtained in examples 2, 3 and 5.
FIG. 4 is a graph of the intensity of glass sheets containing photonic crystal structured color coatings prepared in examples 1-5, comparative example 1.
Fig. 5 is a uv reflection diagram of the coating prepared in comparative example 2.
Fig. 6 is a uv reflection diagram of the coating prepared in comparative example 3.
Fig. 7 is a graph of the uv reflection of the coating prepared in comparative example 4.
Fig. 8 is a uv reflection diagram of the coating prepared in comparative example 5.
Fig. 9 is a uv reflectance graph of a photonic crystal structure color coating prepared in example 6.
Fig. 10 is an optical photograph of the clear coat prepared in comparative example 6.
Fig. 11 is an optical photograph of the white coating prepared in comparative example 7.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The test method comprises the following steps:
testing the particle size distribution: the hydrated particle size was measured by a Zeta potential nanometer particle sizer. Before the test, the test solution was diluted to be transparent with deionized water, and the measurement was performed at 25 ℃ with 5-time measurement of each sample as an average. The actual average particle size was measured by SEM pictures of the samples using ImageJ software, and 100 measurements were averaged for each sample.
And (3) ultraviolet reflection test: the ultraviolet reflection test of the photonic crystal structure color coating is carried out by an ultraviolet-visible spectrophotometer, the scanning wavelength range is 400-800nm, and the scanning speed is 1 nm/s.
And (3) testing the strength: the strength test of the photonic crystal structure color coating is carried out by a universal tensile testing machine, a 3M adhesive tape with the width of 19mm is attached to the coating, the adhesive tape is turned for 180 degrees and clamped at an upper clamp of the testing machine, the photonic crystal structure color coating is clamped at a lower clamp of the testing machine, the universal tensile testing machine is started, the speed is 2mm/s, and the coating is completely stripped from the adhesive tape, so that the stripping force of the coating is obtained.
Zeta potential test: the Zeta potential is tested by a Zeta potential nanometer particle analyzer, the tested liquid is diluted to be transparent by deionized water before testing, the testing is carried out at 25 ℃, and each sample is tested for 3 times to obtain an average value.
The examples used the starting materials:
monodisperse SiO used in the examples 2 The preparation method of the microsphere solution comprises the following steps:
uniformly mixing 110mL of absolute ethyl alcohol and 8mL of ammonia water, and stirring and reacting for 30min at normal temperature; then adding 6mL tetraethyl orthosilicate into the mixed solution of absolute ethyl alcohol and ammonia water at the speed of 3mL/min, and adding the tetraethyl orthosilicate into the mixed solutionStirring and reacting for 8h at 40 ℃, after the reaction is finished, centrifugally washing for 4 times by using deionized water at 6000rpm, and finally obtaining the SiO 2 Dispersing the microspheres in deionized water to obtain monodisperse SiO with the average particle size of 193nm and the mass concentration of 6% 2 A microsphere solution.
The preparation method of the self-prepared aqueous polyurethane emulsion diluent adopted in the embodiment comprises the following steps:
60g of polypropylene glycol 2000 and 4g of 2, 2-dimethylolpropionic acid are uniformly mixed and stirred at a low speed (100rpm) at the temperature of 45 ℃ for reaction for 30 min; continuously heating to 100 ℃, adding 14g of isophorone diisocyanate, and stirring and reacting for 4 hours at 100 ℃ in a violent (1000rpm) manner; after cooling to room temperature, adding dropwise 35g of acetone at a speed of 2g/min until the viscosity of the system is reduced to below 300mPa.S, then adding a mixed solution of 2g of triethylamine and 4g of ethylenediamine, and obtaining an aqueous polyurethane emulsion after the reaction is finished; wherein the solid content of the aqueous polyurethane emulsion is 30%, the viscosity is 200mPa.S, and the aqueous polyurethane emulsion is light blue and semitransparent; then diluting the obtained waterborne polyurethane emulsion by using deionized water to obtain a waterborne polyurethane emulsion diluent; wherein the concentration of the aqueous polyurethane emulsion diluent is 12.5 wt%, the solid content is 3.75%, the viscosity is 25mPas, and the aqueous polyurethane emulsion diluent is light blue and semitransparent.
Example 1
A method of making a glass sheet having a photonic crystal structured color coating comprising the steps of:
(1) preparing a photonic crystal structure color coating solution:
monodisperse SiO 2 Mixing the microsphere solution with a self-prepared waterborne polyurethane emulsion diluent, and ultrasonically oscillating for 30min at the power of 100W at the temperature of 30 ℃ to obtain a photonic crystal structure color coating solution; wherein the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 4 wt% of microsphere solution;
(2) pretreatment of the glass sheet:
soaking the glass sheet in acetone, ultrasonically washing for 6h, and wiping the glass sheet to dry after the ultrasonic washing is finished to obtain a pretreated glass sheet;
(3) preparing a glass sheet containing the photonic crystal structure color coating:
and (3) spraying the photonic crystal structure color coating solution obtained in the step (1) on the pretreated glass sheet by using a spray gun under the pressure of 3MPa, wherein the spraying thickness is 85 microns, and thus obtaining the glass sheet containing the photonic crystal structure color coating.
Example 2
Adjustment example 1 step (1) aqueous polyurethane emulsion Diluent in monodisperse SiO 2 12 wt% of microsphere solution; the rest of the procedure was identical to that of example 1, and a glass sheet having a color coating of photonic crystal structure was obtained.
Example 3
Adjustment example 1 step (1) aqueous polyurethane emulsion Diluent in monodisperse SiO 2 20 wt% of the microsphere solution; the rest of the procedure was identical to that of example 1, and a glass sheet having a color coating of photonic crystal structure was obtained.
Example 4
Adjustment example 1 step (1) aqueous polyurethane emulsion Diluent in monodisperse SiO 2 28 wt% of microsphere solution; the rest was kept the same as in example 1, and a glass sheet having a color coating of photonic crystal structure was obtained.
Example 5
Adjustment example 1 in step (1), the aqueous polyurethane emulsion diluent in the step (1) is in the form of monodisperse SiO 2 36 wt% of microsphere solution; the rest of the procedure was identical to that of example 1, and a glass sheet having a color coating of photonic crystal structure was obtained.
Comparative example 1
The addition of the aqueous polyurethane emulsion diluent in example 1 was omitted, and the procedure was otherwise the same as in example 1, to obtain a glass sheet having a photonic crystal structure color coating.
The glass sheets containing the photonic crystal structure color coating obtained in examples 1 to 5 and comparative example 1 were subjected to a performance test, and the test results were as follows:
FIG. 1 is an SEM image of a glass sheet coated with a color coating having a photonic crystal structure. As can be seen from fig. 1: synthesized SiO 2 The microsphere is regular spherical, has smooth surface, uniform particle size and good monodispersity. And SiO is not changed by adding the aqueous polyurethane emulsion diluent 2 The microspheres are arranged among the microspheres and the microspheres are stillThe state of short-range order and long-range disorder is maintained.
FIG. 2 is a reflectance spectrum and photomicrograph of a glass sheet containing a photonic crystal structured color coating. As can be seen from fig. 2: along with the increase of the addition amount of the aqueous polyurethane emulsion diluent, the photonic crystal structure color coating is gradually changed into blue-green, yellow-green and yellow from the original blue, the structure color is continuously changed, the maximum reflection wavelength is gradually increased from 437nm to 510nm, and the obvious red shift of the photonic crystal structure color coating can also be known. The red shift phenomenon can be explained by a Bragg diffraction formula, and because the aqueous polyurethane emulsion diluent and the monodisperse SiO 2 Difference in refractive index of microsphere solution and SiO 2 The microspheres and the waterborne polyurethane emulsion are in short-range order, and the photonic crystal structure color coating is in continuous color change due to the long-range disordered arrangement. This indicates that the photonic crystal structure color coating with continuously variable color corresponding to single particle size is successfully prepared.
FIG. 3 is a view of the photonic crystal structure color coating obtained in examples 2, 3 and 5 from different viewing angles. As can be seen from fig. 3: due to SiO 2 The arrangement of the microspheres and the waterborne polyurethane emulsion shows short-range order and long-range disorder, so that the photonic crystal structure color coating is hardly changed along with the change of the angle of an observer, and the angle dependence is small.
FIG. 4 is a graph of the intensity of a glass sheet containing a photonic crystal structure color coating. As can be seen in fig. 4: the adhesion of the photonic crystal structure color coating without the aqueous polyurethane emulsion diluent is extremely poor, and the average adhesion is less than 50N/m. When the aqueous polyurethane emulsion diluent is added, the using amount of the aqueous polyurethane emulsion diluent only accounts for the monodisperse SiO 2 At 4 wt% of the microsphere solution, the average adhesion of the photonic crystal structure color coating reaches 195N/m. The reason is that SiO in the photonic crystal structure color coating of the polyurethane emulsion diluent is not added 2 The microspheres are only connected with points, the mechanical property is weak, and after the aqueous polyurethane emulsion diluent is added, the aqueous polyurethane emulsion diluent permeates into SiO 2 In the microsphere, SiO is added 2 The microspheres provide certain mechanical properties, and the waterborne polyurethane emulsion is basicThe coating has certain viscosity, so that the mechanical property of the photonic crystal structure color coating is improved. And the strength of the photonic crystal structure color coating is increased along with the increase of the using amount of the aqueous polyurethane emulsion diluent. The adhesion force of the photonic crystal structure color coating without the aqueous polyurethane emulsion diluent is poor, the photonic crystal structure color coating cannot be applied to practice, the strength and the adhesion force of the photonic crystal structure color coating with the aqueous polyurethane emulsion diluent are increased, the standard of practical application is reached, and the generated structure color of the photonic crystal is not influenced by the aqueous polyurethane emulsion diluent.
Comparative example 2
The aqueous polyurethane emulsion of example 1 was prepared by diluting an aqueous solution of polyvinyl alcohol (concentration: 2 wt%) in monodisperse SiO 2 0 wt%, 4 wt%, 12 wt%, 20 wt%, 28 wt% and 36 wt% of the microsphere solution; otherwise, in accordance with example 1, a coated glass sheet was obtained.
The coating uv reflection curve is shown in fig. 5, from which fig. 5 it can be seen that: aqueous solutions of polyvinyl alcohol have no way of achieving a continuous change in the color of the coating.
Comparative example 3
The aqueous polyurethane emulsion in example 1 was a commercially available fluorocarbon emulsion (solid content 45%, viscosity 15mpa.s) comprising monodisperse SiO 2 0 wt%, 4 wt%, 12 wt%, 20 wt%, 28 wt% and 36 wt% of the microsphere solution; otherwise, in accordance with example 1, a coated glass sheet was obtained.
The ultraviolet reflection curve of the coating is shown in fig. 6, and can be seen from fig. 6: fluorocarbon emulsions have no way to achieve a continuous change in coating color.
Comparative example 4
The aqueous polyurethane emulsion in preparation example 1 was a commercially available polyethylene wax emulsion (solid content 30%, viscosity 25mPa. S), which was a monodisperse SiO 2 0 wt%, 4 wt%, 12 wt%, 20 wt%, 28 wt% and 36 wt% of the microsphere solution; otherwise, in accordance with example 1, a coated glass sheet was obtained.
The coating uv reflection curve is shown in fig. 7, from which it can be seen in fig. 7: as a result, it was found that: the polyethylene wax emulsion has no way of achieving a continuous change in the color of the coating.
Comparative example 5
The aqueous polyurethane emulsion in example 1 was prepared as an aqueous solution of polyvinylpyrrolidone (5 wt% concentration) in monodisperse SiO 2 0 wt%, 4 wt%, 12 wt%, 20 wt%, 28 wt% and 36 wt% of the microsphere solution; otherwise, in accordance with example 1, a coated glass sheet was obtained.
The coating uv reflection curve is shown in fig. 8, from which fig. 8 it can be seen that: there is no way for an aqueous solution of polyvinylpyrrolidone to achieve a continuous change in the color of the coating.
Example 6
Adjusting monodisperse SiO 2 The dosage of ammonia water in the preparation method of the microsphere solution is 10mL, and the method comprises the following specific steps:
uniformly mixing 110mL of absolute ethyl alcohol and 10mL of ammonia water, and stirring at normal temperature for reaction for 30 min; then adding 6mL tetraethyl orthosilicate into the mixed solution of absolute ethyl alcohol and ammonia water at the speed of 3mL/min, stirring and reacting for 8h at the temperature of 40 ℃, after the reaction is finished, centrifugally washing for 4 times by using deionized water at the speed of 6000rpm, and finally obtaining the SiO 2 Dispersing the microspheres in deionized water to obtain monodisperse SiO with the average particle size of 200nm and the mass concentration of 6% 2 A microsphere solution;
the obtained monodisperse SiO 2 Mixing the microsphere solution with a self-prepared waterborne polyurethane emulsion diluent, and ultrasonically oscillating for 30min at the power of 100W at the temperature of 30 ℃ to obtain a photonic crystal structure color coating solution; wherein the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 0 wt%, 4 wt%, 12 wt%, 20 wt%, 28 wt% and 36 wt% of the microsphere solution; the rest of the procedure was identical to that of example 1, and a glass sheet having a color coating of photonic crystal structure was obtained.
As a result, it was found that: SiO 2 2 The change of the particle size of the solution does not affect the continuous change of the color of the photonic crystal structure color coating, FIG. 9 is the ultraviolet reflection curve of the photonic crystal structure color coating, and it can be known from FIG. 9 that the color of the coating gradually changes from yellow to red with the increase of the amount of the aqueous polyurethane emulsion diluent, wherein when the aqueous polyurethane emulsion is diluted, the color of the coating gradually changes from yellow to redLiquid-in-monodisperse SiO 2 At 4 wt% of the microsphere solution, the coating showed yellow color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 12 wt% of the microsphere solution, the coating showed orange color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 20 wt% of the microsphere solution, the coating showed orange color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 28 wt% of the microsphere solution, the coating showed red color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 36 wt% of the microsphere solution, the coating showed a high red color.
Comparative example 6
The self-prepared aqueous polyurethane emulsion in example 1 was adjusted to be a commercially available aqueous polyurethane emulsion (with a solid content of 27% to 37%, a viscosity of less than 3000mpa.s, and a bluish translucent emulsion), and after being diluted with deionized water, the concentration of the polyurethane emulsion diluent was 12.5 wt%, the solid content was 3.375% to 4.625%, and the viscosity was 37.5 mpa.s; aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 12 wt% of the microsphere solution; otherwise, in accordance with example 1, a coated glass sheet was obtained.
Comparative example 7
The self-prepared aqueous polyurethane emulsion in example 1 is adjusted to be a commercially available aqueous polyurethane emulsion (solid content is 50-55%, viscosity is 4000CPS, and the emulsion is a milky liquid), and after the emulsion is diluted by deionized water, the concentration of a polyurethane emulsion diluent is 12.5 wt%, the solid content is 6.25-6.875%, and the viscosity is 500 CPS; the aqueous polyurethane emulsion accounts for monodisperse SiO 2 12 wt% of microsphere solution; otherwise, in accordance with example 1, a coated glass sheet was obtained.
As a result, it was found that: the Zeta potential of the aqueous polyurethane emulsion in comparative examples 6 and 7 is about-10 mV, and the negative electricity is not strong enough to cause SiO 2 Agglomeration occurs when microspheres are blended with it. The particle size of the aqueous polyurethane emulsion of the comparative example 6 is 85.3nm, and the larger particle size enables the blended SiO 2 The microsphere arrangement changes, the ordered arrangement is no longer present and the structural color disappears, and the coating is translucent, as shown in fig. 10. The particle size of the aqueous polyurethane emulsion of comparative example 7 was 178.3nm, which is close to SiO 2 Microsphere size, aqueous polyComplete coating of SiO with urethane emulsion 2 The color of the microsphere and the aqueous polyurethane emulsion with the particle size of more than 100nm is white, so that the prepared coating is white, and the figure 11 shows.
The Zeta potential of the self-made waterborne polyurethane emulsion is-36.5, and the stronger negative electricity enables the waterborne polyurethane emulsion and SiO 2 The microspheres can stably coexist, the hydrated particle size is only 23.4nm, and SiO is not influenced by the small particle size 2 The surface shape and distribution of the microspheres, the microspheres still maintain short-range ordered and long-range disordered arrangement, so that the monodisperse SiO 2 The microsphere solution and the aqueous polyurethane emulsion can still show structural color after being blended.
TABLE 1
| Example (b) | Zeta potential (mV) | Hydrated particle size (nm) | PDI |
| Example 2 | -36.5 | 23.4 | 0.002 |
| Comparative example 6 | -10.4 | 85.3 | 0.054 |
| Comparative example 7 | -9.6 | 178.3 | 0.063 |
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method of preparing a photonic crystal structure color coating solution having a high intensity color, comprising the steps of:
monodisperse SiO 2 Uniformly mixing the microsphere solution and the aqueous polyurethane emulsion diluent to obtain a photonic crystal structure color coating solution; wherein the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 4 wt% -36 wt% of microsphere solution.
2. The method of claim 1, wherein the monodisperse SiO 2 SiO in microsphere solution 2 The actual average particle size of the microspheres is 190-200 nm.
3. The method as claimed in claim 1, wherein the aqueous polyurethane emulsion diluent has a solid content of 3 to 4%, a viscosity of 20 to 40mpa.s, a light blue translucent color, and a concentration of 10 to 15 wt%.
4. A photonic crystal structure color coating solution prepared by the method of any one of claims 1 to 3.
5. A method for preparing a substrate with a photonic crystal structure color coating, which is characterized in that the photonic crystal structure color coating solution of claim 4 is coated on the surface of the substrate by spraying.
6. The method of claim 5, wherein the thickness of the spray coating is 80 μm to 100 μm.
7. A substrate comprising a coating of a photonic crystal structure color produced by the method of claim 5 or 6.
8. Use of a photonic crystal structure color coating solution according to claim 4, a substrate comprising a photonic crystal structure color coating according to claim 7 for the preparation of a security material.
9. A method for preparing a continuously controllable photonic crystal structure color coating is characterized in that the method is realized by controlling SiO 2 The particle size of the microspheres is not changed, and monodisperse SiO is adjusted 2 The ratio of the microsphere solution to the aqueous polyurethane emulsion diluent is used for realizing the regulation and control of the structural color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 4 wt% of the microsphere solution, the coating appeared blue; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 12 wt% of the microsphere solution, the coating showed a blue-green color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 20 wt% of the microsphere solution, the coating showed green color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 28 wt% of the microsphere solution, the coating showed a yellow-green color; when the aqueous polyurethane emulsion diluent accounts for monodisperse SiO 2 At 36 wt% of the microsphere solution, the coating showed a yellow color.
10. The method of claim 9, wherein the SiO 2 The actual average particle size of the microspheres is 190-200 nm; the solid content of the aqueous polyurethane emulsion diluent is 3-4%, the viscosity is 20-40mPa.S, the aqueous polyurethane emulsion diluent is light blue and semitransparent, and the concentration is 10-15 wt%.
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