CN114966924A - Structural color pigment - Google Patents

Structural color pigment Download PDF

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Publication number
CN114966924A
CN114966924A CN202210489726.0A CN202210489726A CN114966924A CN 114966924 A CN114966924 A CN 114966924A CN 202210489726 A CN202210489726 A CN 202210489726A CN 114966924 A CN114966924 A CN 114966924A
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oxide
color pigment
layer
fluoride
structural color
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蔡宏亮
陈章荣
李金城
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Huizhou Foryou Optical Technology Co ltd
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Huizhou Foryou Optical Technology Co ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/003—Light absorbing elements

Abstract

The present application provides a structured color pigment. Specifically, the structural color pigment comprises a first medium layer, an absorption layer, a second medium layer and a reflection layer which are sequentially stacked, the refractive index or equivalent refractive index of the first medium layer and the second medium layer in a visible light wave band is larger than 1.8, and the phase change of reflected light of the structural color pigment is smaller than 30nm in a range from a vertical visual angle to an included angle of 70 degrees with the vertical visual angle. The structural color pigment has the advantages of simple structure, low angle dependence, high color saturation, comprehensive color, capability of covering the full visible light color gamut and strong practicability.

Description

Structural color pigment
Technical Field
The application relates to the technical field of optical pigments, in particular to a structural color pigment.
Background
The structural color is the color generated by the phenomena of interference, diffraction, scattering or absorption of incident light caused by the fine microstructure of the material. Because the optical phenomenon is determined by the characteristics of the material, the material is not easily influenced by the external environment, and the structural color is more stable than that of the traditional pigment and has longer service life. In recent years, the method has been widely applied to industries such as automobile paint, decoration, printing, beauty and make-up, anti-counterfeiting and the like.
At present, most of the main structural color materials are photonic crystal materials, and the photonic crystal materials are mainly used for obtaining a multi-beam interference or diffraction effect by utilizing different refractive indexes, specific sizes and regular arrangement of the photonic crystals, so that the photonic crystal materials show specific colors. However, due to the change of the incident light angle, the specific size is unstable and the arrangement cannot be completely consistent, and most structural color materials have the phenomenon that the color drifts along with the incident angle, namely, the structural color materials have strong angle dependence.
Disclosure of Invention
The application provides a structural color pigment to solve prior art, most structural color materials have the technical problem of stronger angle dependence.
In order to solve the technical problems, the technical scheme adopted by the application is to provide the structural color pigment which comprises a first dielectric layer, an absorption layer, a second dielectric layer and a reflection layer which are sequentially stacked, wherein the refractive indexes or equivalent refractive indexes of the first dielectric layer and the second dielectric layer in a visible light wave band are larger than 1.8, and the phase change of reflected light of the structural color pigment is smaller than 30nm in a range from a vertical visual angle to an included angle of 70 degrees with the vertical visual angle.
Further, the real part of the refractive index of the absorption layer is larger than 1.6, and the imaginary part extinction coefficient is larger than 2.4.
Further, the refractive index of the reflecting layer has a real part refractive index smaller than 1 and an imaginary part extinction coefficient larger than 2.
Further, the first dielectric layer and the second dielectric layer are single-layer dielectrics or dielectric film stacks.
Further, the materials of the first dielectric layer and the second dielectric layer include: silicon dioxide, aluminum oxide, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, calcium fluoride, lithium fluoride polystyrene, polyethylene, polymethyl methacrylate, polyamideimide, polyperfluoroethylene propylene, tetrafluoroethylene, chlorotrifluoroethylene, cellulose propionate, cellulose acetate butyrate, methylpentene polymer, homo-formaldehyde, acrylic resin, cellulose nitrate, ethyl cellulose, polypropylene, polysulfone, polyethersulfone, mica, hetero-homopolymer polymer, polybutene, ionomer, acrylic copolymer, thermoplastic, styrene butadiene, polyvinylchloride, urea-formaldehyde, styrene acrylonitrile, polycarbonate, lanthanum titanate, trititanium pentoxide, niobium pentoxide, zinc sulfide, zinc oxide, zirconium oxide, titanium dioxide, carbon, indium oxide, indium tin oxide, tantalum pentoxide, titanium oxide, At least one of cerium oxide, yttrium oxide, europium oxide, iron oxide, triiron tetroxide, hafnium nitride, hafnium carbide, hafnium oxide, lanthanum oxide, magnesium oxide, neodymium oxide, praseodymium oxide, samarium oxide, antimony trioxide, silicon carbide, silicon nitride, silicon monoxide, selenium trioxide, tin oxide, and tungsten trioxide.
Further, the material of the absorption layer includes at least one of titanium, chromium, silicon, germanium, iron, and vanadium.
Further, the material of the reflective layer includes one or an alloy of at least two of aluminum, silver, platinum, and gold.
Further, the structural color pigment is a symmetric or asymmetric flaky thin film material, a photonic crystal, a super-surface structure or a pearlescent pigment.
Further, the materials of the first dielectric layer and the second dielectric layer are the same, or the materials of the first dielectric layer and the second dielectric layer are different.
Further, the structural color pigment is prepared by a chemical vapor deposition method, a sputtering method, a solution coating method, an electron beam evaporation method, an ion plating method, a dipping method, a chemical synthesis method, a sintering method or a spraying method.
The beneficial effects of the embodiment of the application are that: different from the prior art, the structural color pigment provided by the application comprises a first medium layer, an absorption layer, a second medium layer and a reflection layer which are sequentially stacked, the refractive indexes or equivalent refractive indexes of the first medium layer and the second medium layer in a visible light wave band are larger than 1.8, and the phase change of reflected light of the structural color pigment is smaller than 30nm in the range from a vertical visual angle to an included angle of 70 degrees with the vertical visual angle. The application provides a structural color pigment's simple structure, the cost is lower, easily preparation, and this structural color pigment has low angle dependence, and the color saturation is higher, and the colour is comprehensive, covers full visible light colour gamut.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic structural view of one embodiment of a structured color pigment provided herein;
FIG. 2 is a schematic diagram of the phase change of the reflected light phase of an embodiment of the structured color pigment provided herein.
Detailed Description
The present application will now be described in detail with reference to specific embodiments thereof as illustrated in the accompanying drawings. These embodiments are not intended to limit the present disclosure, and structural, methodological, or functional changes made by those skilled in the art in light of these embodiments are intended to be within the scope of the present disclosure.
In addition, if there is a description of "first", "second", etc. in the embodiments of the present application, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present application.
The existing structural color material is obtained by chemical synthesis, photoetching treatment or deposition technology, the production process is complicated, and the preparation process is long. In addition, a large amount of precious metals and expensive chemical reagents are used, which results in high costs. In addition, the thin film type structural color material obtained by deposition is affected by its absorption characteristics by using a metal material, and thus a color with high reflectance and high saturation cannot be obtained.
The application provides a structural color pigment, this structural color pigment's simple structure, easily preparation, the cost is lower, has lower angle dependence, and this structural color pigment's color saturation is high, and the colour is comprehensive, can cover full visible light colour gamut, can realize the high saturated structural color of the low angle dependence of panchromatic gamut.
As shown in fig. 1, fig. 1 is a schematic structural diagram of an embodiment of a structural color pigment provided herein, and the structural color pigment 10 includes a first medium layer 11 with specific optical characteristics, a specific absorption layer 12, a specific second medium layer 13, and a reflection layer 14, which are sequentially stacked. In the range from the vertical viewing angle to the angle of 70 degrees with the vertical viewing angle, the phase change of the reflected light of the structural color pigment 10 is less than 30nm, the hue of the structural color pigment is almost unchanged when observed by naked eyes, and the structural color pigment 10 has smaller angle dependence. The vertical viewing angle herein means that the viewing angle of the user is perpendicular to the surface of the structural color pigment 10.
The structural color pigment 10 may be prepared by a chemical vapor deposition method, a sputtering method, a solution coating method, an electron beam evaporation method, an ion plating method, a dipping method, a chemical synthesis, a sintering or a spraying method, or the like. The above preparation method is within the scope understood by those skilled in the art, and will not be described in detail herein.
Further, the first dielectric layer 11 and the second dielectric layer 13 are single-layer dielectrics or dielectric film stacks. That is, the first dielectric layer 11 may be a single-layer dielectric structure or a dielectric film stack formed by a multi-layer dielectric stack; the second dielectric layer 13 may be a single layer dielectric structure or a stack of dielectric films formed from a multi-layer dielectric stack.
When the first medium layer 11 and the second medium layer 13 are single-layer media, the refractive indexes of the first medium layer 11 and the second medium layer 13 in the visible light band are greater than 1.8, for example, the refractive indexes of the first medium layer 11 and the second medium layer 13 are 1.9, 2.0, 2.1, or the like. When the first medium layer 11 and the second medium layer 13 are dielectric film stacks, the equivalent refractive indexes of the first medium layer 11 and the second medium layer 13 in the visible light band are greater than 1.8, for example, the equivalent refractive indexes of the first medium layer 11 and the second medium layer 13 are 1.85, 1.92, 2.2, or the like.
Further, the material of the first dielectric layer 11 and the second dielectric layer 13 may include silicon dioxide, aluminum oxide, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, calcium fluoride, lithium fluoride polystyrene, polyethylene, polymethyl methacrylate, polyamideimide, polyperfluoroethylene propylene, tetrafluoroethylene, chlorotrifluoroethylene, cellulose propionate, cellulose acetate butyrate, methylpentene polymer, homo-formaldehyde, acrylic resin, cellulose nitrate, ethyl cellulose, polypropylene, polysulfone, polyethersulfone, mica, hetero-isomorphous polymer, polybutene, ionomer, acrylic copolymer, thermoplastic, styrene butadiene, polyvinyl chloride, urea formaldehyde, styrene acrylonitrile, polycarbonate, lanthanum titanate, trititanium pentoxide, niobium pentoxide, zinc sulfide, zinc oxide, magnesium fluoride, cerium fluoride, lanthanum fluoride, barium fluoride, calcium fluoride, lithium fluoride polystyrene, polyethylene, polymethyl methacrylate, polyamide imide, polyether sulfone, mica, allophanate, polyethylene terephthalate, polypropylene, At least one of zirconium oxide, titanium dioxide, carbon, indium oxide, indium tin oxide, tantalum pentoxide, cerium oxide, yttrium oxide, europium oxide, iron oxide, triiron tetroxide, hafnium nitride, hafnium carbide, hafnium oxide, lanthanum oxide, magnesium oxide, neodymium oxide, praseodymium oxide, samarium oxide, antimony trioxide, silicon carbide, silicon nitride, silicon monoxide, selenium trioxide, tin oxide, and tungsten trioxide.
The material of the first dielectric layer 11 and the second dielectric layer 13 may be the same to reduce the material type of the structural color pigment 10. In other embodiments, the materials of the first dielectric layer 11 and the second dielectric layer 13 may also be different, and may be specifically selected and set according to requirements.
Further, the real part of the refractive index of the absorption layer 12 is larger than 1.6, and the imaginary part extinction coefficient is larger than 2.4. For example, the real part of the refractive index of the absorption layer 12 is 1.7 or 1.8, and the imaginary part extinction coefficient is 2.5 or 2.6.
The material of the absorption layer 12 includes at least one of titanium, chromium, silicon, germanium, iron, and vanadium.
The refractive index of the reflective layer 14 has a real part of the refractive index less than 1 and an imaginary part of the extinction coefficient greater than 2. For example, the refractive index of the reflective layer 14 has a real part of 0.9, and an imaginary part of 2.1. The material of the reflective layer 14 includes one or an alloy of at least two of aluminum, silver, platinum, and gold.
Further, the structured color pigment 10 may be a symmetric or asymmetric platelet-shaped film material. In other embodiments, the structured color pigment 10 may also be a photonic crystal, a super-surface structure, or a pearlescent pigment, among others.
The technical principle of the design of the structural color pigment 10 is described below:
the optical characteristics of the structural color pigment 10 of the above embodiment are according to the planar electromagnetic wave theory:
Figure BDA0003630721790000051
wherein E is an electric field intensity vector, H is an magnetic field intensity vector, D is an electric displacement vector, B is a magnetic induction intensity vector, j is a conduction current density vector,
Figure BDA0003630721790000061
is the displacement current density vector, ρ is the charge bulk density, ε is the dielectric constant, μ is the permeability, σ is the conductivity, and t is the time. The solution to the wave equation is: e ═ E 0 exp[iω(t-x/v)]，E 0 Let us denote the initial electric field amplitude, ω the angular frequency of the plane wave, t the time, x the propagation direction and v the propagation velocity in the medium. It indicates an amplitude of E 0 A plane wave with an angular frequency ω, propagating positively in x with a velocity v.
In the structured color pigment 10 described herein, the transmission characteristic matrix for each film is:
Figure BDA0003630721790000062
wherein, δ 1 is the phase thickness of the film, η is the angle correction admittance, and θ is the light wave angle. When the electromagnetic wave is obliquely incident, the orientation of the incident plane of the electromagnetic wave can be generalized as a combination of two standard orientations, one is a transverse magnetic wave when a parallel polarized wave is obliquely incident on the surface of an ideal conductor. Transverse magnetic waves (TM waves, P-polarized waves) are electromagnetic waves in which there is no magnetic field component but an electric field component in the propagation direction of the electromagnetic waves. When the other vertically polarized wave is obliquely incident on the surface of an ideal conductor, the resultant wave becomes a transverse electric wave (TE wave, i.e., S-polarized wave), and there is no electric field component but a magnetic field component in the propagation direction of the electromagnetic wave.
Further, the air conditioner is characterized in that,
Figure BDA0003630721790000063
η s ＝Ncosθ，η p ＝N/cosθ
in the above formula, η S Effective admittance, eta, of the S-polarized wave p Represents the effective admittance of the p-polarized wave, N is the refractive index of the layer material, and d represents the geometric thickness of the layer film. The dielectric material has only a real part refractive index, the imaginary part extinction coefficient is approximately zero, and the refractive indexes of the materials of the absorbing layer 12 and the reflecting layer 14 comprise the real part refractive index and the imaginary part extinction coefficient.
As a multi-layer thin film material, the electromagnetic field relationship of the upper and lower surfaces of the J-th film is as follows:
Figure BDA0003630721790000064
wherein eta is j Represents the effective admittance of the j-th layer, delta j The film phase thickness of the j-th layer is shown.
Then the film system composed of k layers of film, the electromagnetic field in the incident medium and the electromagnetic field in the emergent medium can establish the relationship:
Figure BDA0003630721790000071
wherein E is 0 Electric field intensity vector, H, for the incident medium 0 As vector of magnetic field strength, E S Is the electric field intensity vector, H, of the emergent medium S Is a vector of magnetic field strength.
Order:
Figure BDA0003630721790000072
due to H 0 ＝Y·E 0 And H S ＝η S ·E S And Y is the multilayer film equivalent admittance (equivalent refractive index) which is as follows:
Figure BDA0003630721790000073
Y＝C/B
thus, the spectral characteristics of an arbitrary k-layer thin film system are the reflection coefficients of the thin films:
Figure BDA0003630721790000074
reflected light phase of pigment phi r The following formula is satisfied:
Figure BDA0003630721790000075
for the structured color pigment 10 provided by the present application, the reflection spectrum changes little during the observation angle change, and the reflection color of the material has no change basically. The conditions for achieving a low angle dependent structured color pigment 10 can be calculated from the light propagation process described above. According to the principle, the refractive index or equivalent refractive index of the first medium layer 11 and the second medium layer 13 of the structural color pigment 10 in the visible light band is greater than 1.8, the real part refractive index of the absorption layer 12 is greater than 1.6, the imaginary part extinction coefficient is greater than 2.4, and the real part refractive index of the reflection layer 14 is less than 1, and the imaginary part extinction coefficient is greater than 2. As shown in FIG. 2, the structural color pigment 10 provided by the present application has a phase change of the reflected light phase of less than 30nm at 0-70 degrees (i.e., the range from the vertical viewing angle of the structural color pigment 10 to the angle of 70 degrees with the vertical viewing angle), so as to obtain the structural color pigment 10 having a specific reflection peak in the visible light range of 380nm-780 nm. The hue of the product was observed with the naked eye to be almost unchanged. Furthermore, by changing the film layer material or the film layer thickness of the structural color pigment 10, a low angle-dependent structural color pigment of various colors can be obtained.
Therefore, the structured color pigment 10 provided by the application has the advantages of simple structure, low angle dependence, high color saturation and comprehensive color, can cover the full visible light color gamut, and can realize the high-saturation structured color with low angle dependence of the full color gamut.
It should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments may be appropriately combined to form other embodiments as will be appreciated by those skilled in the art. The above detailed description is given for the purpose of illustrating a practical embodiment of the present application and is not to be construed as limiting the scope of the present application, and any equivalent embodiments or modifications that do not depart from the technical spirit of the present application are intended to be included therein.

Claims (10)

1. The structural color pigment is characterized by comprising a first medium layer, an absorption layer, a second medium layer and a reflection layer which are sequentially stacked, wherein the refractive index or equivalent refractive index of the first medium layer and the second medium layer in a visible light wave band is larger than 1.8, and the phase change of reflected light of the structural color pigment is smaller than 30nm from a vertical visual angle to an included angle of 70 degrees with the vertical visual angle.
2. The structured color pigment of claim 1, wherein the refractive index of the absorbing layer has a real part of refractive index of greater than 1.6 and an imaginary part of extinction coefficient of greater than 2.4.
3. The structured color pigment of claim 1, wherein the refractive index of the reflective layer has a real part of the refractive index of less than 1 and an imaginary part of the extinction coefficient of greater than 2.
4. The structural color pigment of claim 1, wherein the first dielectric layer and the second dielectric layer are single layer dielectrics or stacks of dielectric films.
5. The structured color pigment of any one of claims 1 to 4, wherein the materials of said first dielectric layer and said second dielectric layer comprise: silicon dioxide, aluminum oxide, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, calcium fluoride, lithium fluoride polystyrene, polyethylene, polymethyl methacrylate, polyamideimide, polyperfluoroethylpropylene, tetrafluoroethylene, chlorotrifluoroethylene, cellulose propionate, cellulose acetate butyrate, methylpentene polymer, homopolyformaldehyde, acrylic resin, cellulose nitrate, ethyl cellulose, polypropylene, polysulfone, polyethersulfone, mica, heteroisomorphous polymer, polybutene, ionomer, acrylic copolymer, thermoplastic, styrene butadiene, polyvinyl chloride, urea formaldehyde, styrene acrylonitrile, polycarbonate, lanthanum titanate, trititanium pentoxide, niobium pentoxide, zinc sulfide, zinc oxide, zirconium oxide, titanium dioxide, carbon, indium oxide, indium tin oxide, tantalum pentoxide, titanium dioxide, carbon, indium oxide, indium tin oxide, tantalum pentoxide, titanium oxide, and mixtures thereof, At least one of cerium oxide, yttrium oxide, europium oxide, iron oxide, triiron tetroxide, hafnium nitride, hafnium carbide, hafnium oxide, lanthanum oxide, magnesium oxide, neodymium oxide, praseodymium oxide, samarium oxide, antimony trioxide, silicon carbide, silicon nitride, silicon monoxide, selenium trioxide, tin oxide, and tungsten trioxide.
6. The structural color pigment of any one of claims 1-4, wherein the material of the absorbing layer comprises at least one of titanium, chromium, silicon, germanium, iron, vanadium.
7. The structured color pigment of any one of claims 1 to 4, wherein the material of the reflective layer comprises one or an alloy of at least two of aluminum, silver, platinum and gold.
8. The structured color pigment of claim 1, wherein the structured color pigment is a symmetric or asymmetric platelet-shaped thin film material, a photonic crystal, a super-surface structure, or a pearlescent pigment.
9. The structured color pigment of claim 1, wherein the materials of the first dielectric layer and the second dielectric layer are the same or the materials of the first dielectric layer and the second dielectric layer are different.
10. The structural color pigment of claim 1, wherein the structural color pigment is prepared by a chemical vapor deposition method, a sputtering method, a solution coating method, an electron beam evaporation method, an ion plating method, a dipping method, a chemical synthesis, a sintering or a spraying method.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105824066A (en) * 2015-01-28 2016-08-03 丰田自动车工程及制造北美公司 Durable mixed omnidirectional structured color pigment for external applications
CN106461834A (en) * 2014-04-01 2017-02-22 丰田自动车工程及制造北美公司 Non-color shifting multilayer structures
CN109752782A (en) * 2019-03-12 2019-05-14 江南大学 The insensitive color filter of angle based on multiple layer metal dielectric film
CN110658581A (en) * 2019-08-20 2020-01-07 深圳市融光纳米科技有限公司 Color filter, nano color filter crystal and coating
CN110776758A (en) * 2019-09-29 2020-02-11 惠州市华阳光学技术有限公司 Pigment flake and coating
CN110780371A (en) * 2019-09-29 2020-02-11 惠州市华阳光学技术有限公司 All-dielectric small-angle dependent pigment flakes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106461834A (en) * 2014-04-01 2017-02-22 丰田自动车工程及制造北美公司 Non-color shifting multilayer structures
CN105824066A (en) * 2015-01-28 2016-08-03 丰田自动车工程及制造北美公司 Durable mixed omnidirectional structured color pigment for external applications
CN109752782A (en) * 2019-03-12 2019-05-14 江南大学 The insensitive color filter of angle based on multiple layer metal dielectric film
CN110658581A (en) * 2019-08-20 2020-01-07 深圳市融光纳米科技有限公司 Color filter, nano color filter crystal and coating
CN110776758A (en) * 2019-09-29 2020-02-11 惠州市华阳光学技术有限公司 Pigment flake and coating
CN110780371A (en) * 2019-09-29 2020-02-11 惠州市华阳光学技术有限公司 All-dielectric small-angle dependent pigment flakes

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