CN110780371B - All-dielectric small-angle dependent pigment flakes - Google Patents
All-dielectric small-angle dependent pigment flakes Download PDFInfo
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- CN110780371B CN110780371B CN201910936661.8A CN201910936661A CN110780371B CN 110780371 B CN110780371 B CN 110780371B CN 201910936661 A CN201910936661 A CN 201910936661A CN 110780371 B CN110780371 B CN 110780371B
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- 239000000049 pigment Substances 0.000 claims abstract description 150
- 230000003287 optical effect Effects 0.000 claims abstract description 128
- 230000001419 dependent effect Effects 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003989 dielectric material Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- 229910001610 cryolite Inorganic materials 0.000 claims description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 4
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- 238000003475 lamination Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000002310 reflectometry Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000001055 blue pigment Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004038 photonic crystal Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
- G02B5/285—Interference filters comprising deposited thin solid films
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The application provides an all-dielectric small-angle dependent pigment flake. The all-dielectric small-angle dependent pigment flake comprises a dielectric base layer and at least one dielectric lamination period, wherein the dielectric base layer comprises a first sub-dielectric base layer, the at least one dielectric lamination period is arranged on at least one side of a main surface of the first sub-dielectric base layer in an overlapped mode, each dielectric lamination period comprises a first sub-dielectric lamination and a second sub-dielectric lamination, the refractive index of the first sub-dielectric lamination is smaller than that of the second sub-dielectric lamination and the first sub-dielectric base layer, the first sub-dielectric lamination is arranged closer to the first sub-dielectric base layer than that of the second sub-dielectric lamination in the same dielectric lamination period, and the optical thicknesses of the dielectric base layer and the dielectric lamination period are set to enable the color shift of the pigment flake in the range of 0-60 degrees relative to the normal direction of the main surface where the dielectric base layer is located to be smaller than 80 nm. The all-dielectric small-angle dependent pigment flake can be in a certain angle range, and the color of the pigment flake changes less along with the angle.
Description
Technical Field
The application relates to the technical field of pigment flakes, in particular to an all-dielectric small-angle dependent pigment flake.
Background
Structural colors have long been used. The materials with high refractive index and low refractive index are alternately arranged to form a periodic photonic crystal structure, so that light with specific wavelength cannot pass through the photonic band gap of the photonic crystal, and structural color is generated.
The pigment flakes with the optically variable characteristic can be prepared by utilizing the principle of multi-beam interference and the selective absorption characteristic of metal to light waves. Pigment flakes made of metal-dielectric material overlap have high brightness and distinct metallic luster, and are widely used. The all-dielectric pigment flakes with high and low refractive index stacked with each other also have wide application, and can realize angle-dependent color change by controlling the optical thickness of the dielectric layer.
At present, the research on the all-dielectric pigment flakes mainly focuses on the field of optically variable pigments, and the optically variable pigment flakes can be applied to the fields of anti-counterfeiting, decoration and cosmetics. However, as flakes have evolved, the market has a certain demand for small angle dependent flakes.
Disclosure of Invention
The application provides an all-dielectric small-angle dependence pigment piece to solve the big problem of colour shift when all-dielectric pigment piece is observed from different angles.
In order to solve the technical problem, the application adopts a technical scheme that: providing an all-dielectric small-angle dependent pigment flake, the pigment flake comprising a dielectric base layer and at least one dielectric stack period, the dielectric base layer comprising a first sub-dielectric base layer; at least one dielectric stack period is arranged on at least one side of the main surface of the first sub-dielectric base layer in a stacking mode, each dielectric stack period comprises a first sub-dielectric stack and a second sub-dielectric stack, the refractive index of the first sub-dielectric stack is smaller than that of the second sub-dielectric stack and the first sub-dielectric base layer, the first sub-dielectric stack is arranged closer to the first sub-dielectric base layer than the second sub-dielectric stack in the same dielectric stack period, and the optical thicknesses of the dielectric base layer and the dielectric stack period are set to enable the color shift of the pigment sheet in the range of 0-60 degrees deviated from the normal direction of the main surface where the dielectric base layer is located to be smaller than 80 nm.
The beneficial effect of this application is: in contrast to the related art, the all-dielectric small-angle dependent pigment flake provided by the present application includes a dielectric base layer and at least one dielectric stack period stacked on at least one major surface of the first sub-dielectric base layer, the dielectric base layer includes a first sub-dielectric base layer, each dielectric stack period includes a first sub-dielectric stack and a second sub-dielectric stack, the refractive index of the first sub-dielectric stack is smaller than that of the second sub-dielectric stack and the first sub-dielectric base layer, and the first sub-dielectric stack is disposed closer to the first sub-dielectric base layer than the second sub-dielectric stack in the same dielectric stack period, that is, the pigment flake is formed by stacking high and low refractive index dielectric materials, and since the position of the reflection peak of the reflected light of a specific wavelength by the dielectric depends on the size of the optical path difference, and the optical path difference depends on the refractive index, the thickness of the dielectric layer and the incident angle, therefore, the thickness coefficient of each dielectric layer and the total number of layers of the pigment flakes are set to determine the optical thickness of the pigment flakes so as to change the optical path difference, and the optical thicknesses of the dielectric base layer and the dielectric lamination period are set to enable the color shift of the pigment flakes within a range of 0-60 degrees of deviation relative to the normal direction of the main surface where the dielectric base layer is located to be less than 80nm, namely, the effect of enabling the color of the pigment flakes to change less with the angle within a certain angle range can be achieved.
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, it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
fig. 1 is a schematic structural diagram of an embodiment of an all-dielectric small-angle dependent pigment flake according to the present application;
FIG. 2 is a spectral plot of reflectance versus wavelength for an embodiment of an all-dielectric small angle dependent pigment flake according to the present application;
fig. 3 is a schematic structural diagram of another embodiment of an all-dielectric small-angle dependent pigment flake according to the present application;
fig. 4 is a spectral plot of reflectance versus wavelength for another embodiment of an all-dielectric, small angle dependent pigment flake according to the present application;
fig. 5 is a schematic diagram of a further embodiment of an all-dielectric small angle dependent pigment flake according to the present application.
Fig. 6 is a spectral plot of reflectance versus wavelength for yet another embodiment of an all-dielectric, small angle dependent pigment flake according to the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that if directional indications (such as up, down, left, right, front, and back … …) are referred to in the embodiments of the present application, the directional indications are only used to explain the relative positional relationship between the components, the movement situation, and the like in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indications are changed accordingly.
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 reflection of light by the medium follows the principle of multi-beam reflection, so the position of the reflection peak of the medium for the reflected light with a specific wavelength greatly depends on the size of the optical path difference, and the size of the optical path difference (Δ ═ 2ndcos θ, Δ is the optical path difference, n is the refractive index, d is the thickness of the medium layer, and θ is the incident angle) depends on the refractive index, the thickness of the medium layer, and the incident angle. Therefore, when the material and the thickness are constant, the reflection peak of the medium has angle dependence when the material and the thickness are constant.
In the related art, in order to make the pigment flakes have good monochromaticity, the QWOT system often requires a thickness of tens or even tens of layers stacked, which increases the production cost in terms of process and material.
The inventors of the present application have found in long-term studies that, in order to achieve small angle dependence, that is, in order to make the range of variation of the optical path difference Δ smaller when the incident angle (i.e., the observation angle) θ is varied, the reflection peak is suppressed from occurring a color shift phenomenon when the incident angle is varied, thereby achieving small angle dependence characteristics.
Based on this, the present application provides an all-dielectric small angle dependent pigment flake. Referring to fig. 1, fig. 1 is a schematic structural diagram of an embodiment of an all-dielectric small-angle dependent pigment flake according to the present application. It should be noted that fig. 1 only schematically includes one dielectric stack period 120, but the pigment flake 100 of the embodiment of the application may include a plurality of dielectric stack periods 120, i.e., two or more than two.
This embodiment provides an all-dielectric small angle dependent pigment flake 100. the all-dielectric small angle dependent pigment flake 100 includes a dielectric base layer 110 and at least one dielectric stack period 120.
The media base layer 110 includes a first sub-media base layer.
The dielectric base layer 110 includes at least one dielectric layer, i.e., a first sub-dielectric base layer.
At least one dielectric stack period 120 is stacked on at least one major surface of the first sub-dielectric substrate, each dielectric stack period 120 includes a first sub-dielectric stack 121 and a second sub-dielectric stack 122, wherein the refractive index of the first sub-dielectric stack 121 is smaller than that of the second sub-dielectric stack 122 and the first sub-dielectric substrate, and the first sub-dielectric stack 121 is disposed closer to the first sub-dielectric substrate than the second sub-dielectric stack 122 in the same dielectric stack period 120.
The number of the dielectric stack periods 120 is at least one, and each dielectric stack period 120 includes a first sub-dielectric stack 121 and a second sub-dielectric stack 122, where the refractive index of the first sub-dielectric stack 121 is smaller than that of the second sub-dielectric stack 122 and the first sub-dielectric base layer, and the first sub-dielectric stack 121 is disposed closer to the first sub-dielectric base layer than the second sub-dielectric stack 122 in the same dielectric stack period 120, so that the all-dielectric small-angle dependent pigment sheet 100 provided in the present application is stacked by high-refractive-index dielectric materials and low-refractive-index dielectric layers on the upper and lower main surfaces of the pigment sheet 100 are higher than those of the dielectric layers adjacent to the first sub-dielectric stack.
Wherein the dielectric base layer 110 and the dielectric stack periods 120 have optical thicknesses such that the color shift of the pigment flake 100 is less than 80nm in a range of 0 degrees to 60 degrees from normal to the major surface of the dielectric base layer 110.
In the all-dielectric small-angle dependent pigment flake 100, the optical thickness of each dielectric layer (including the first sub-dielectric base layer, the first sub-dielectric stack 121 and the second sub-dielectric stack 122 of each dielectric stack period 120) is: the QWOT/4 multiple, i.e., the optical thickness of each layer of the medium is QWOT/4 multiplied by the thickness factor. Wherein QWOT is defined as the wavelength when the optical thickness of the layer is equal to a quarter-wavelength, and is generally defined by the equation QWOT-4 nd.
Different from the situation of the related art, the all-dielectric small-angle dependent pigment sheet 100 provided by the application is formed by stacking dielectric materials with high refractive index and low refractive index, and the position of the reflection peak of the medium for reflected light with specific wavelength greatly depends on the size of the optical path difference, and the optical path difference depends on the refractive index, the thickness of the dielectric layer and the incident angle, so that the optical thickness of the pigment sheet 100 can be determined by setting the thickness coefficient of each dielectric layer and the total number of layers of the pigment sheet 100, the change of the optical path difference caused by the change of the incident angle is further reduced, the blue shift phenomenon of the reflection peak when the incident angle is changed can be inhibited, and the small-angle dependent characteristic is realized. The optical thicknesses of the dielectric base layer 110 and the dielectric stack period 120 can be set such that the color shift of the pigment flakes 100 in the range of 0 degrees to 60 degrees from normal to the major surface of the dielectric base layer 110 is less than 80nm, i.e., an effect of less angular color shift of the pigment flakes 100 over a range of angles.
In addition, the pigment flake 100 provided by the embodiment has a structure of an all-dielectric film layer, and thus has the characteristics of transparency and controllable transparency.
Optionally, the main peak of the reflection peak of the pigment flake 100 has a central wavelength between 400-500nm, and has one and only one main peak within 380-780 nm.
Since the main peak of the reflection peak has a central wavelength between 400-500nm, the color of the pigment flake 100 is blue, and the blue pigment flake 100 can be obtained.
When the color of the pigment flake 100 is blue, the optical thickness of the pigment flake 100 is lower, the color shift (i.e., blue shift) is smaller, the influence of the color shift on the visual effect is smaller, and only one main peak exists within 380-780nm, which means that the blue pigment flake 100 can effectively inhibit the generation of secondary peaks and improve the color purity of the pigment flake 100.
Of course, the main peak of the reflection peak of the pigment flake 100 may have a central wavelength in other wavelength bands, so that the pigment flake 100 may have other colors, i.e., blue pigment flakes 100 of different colors.
For example, the main peak of the reflection peak of the pigment flake 100 has a central wavelength between 640-780nm, so that the pigment flake 100 is red in color, and the red pigment flake 100 can be obtained.
For example, the main peak of the reflection peak of the pigment flake 100 has a central wavelength between 530 nm and 610nm, so that the pigment flake 100 is yellow in color, and the yellow pigment flake 100 can be obtained.
The specific structure and color characteristics of the pigment flake 100 will be described in detail below using the blue pigment flake 100 as an example.
Optionally, the number of dielectric stack periods 120 located on the same side of the dielectric base layer 110 is no greater than 2.
By reducing the number of dielectric stack periods 120 on the same side of the dielectric base layer 110, the total number of layers of the pigment flake 100 can be reduced, thereby reducing the overall thickness of the pigment flake 100, resulting in a smaller range of optical path difference variations as the angle of incidence is varied, thereby reducing the color-to-angle dependence. And because the number of layers is small, the optical thickness is small, the manufacturing process is relatively simple, and the material consumption is reduced, so that the cost is lower.
Optionally, the total number of dielectric layers of the pigment flake 100 is 7 or less.
Alternatively, the pigment flake 100 can have a physical thickness of 170nm to 400 nm. For example, the pigment flake 100 can have a physical thickness of 170nm, 190nm, 200nm, 220nm, 240nm, 280nm, 320nm, 340nm, 380nm, or 400 nm.
Preferably, the pigment flakes 100 have a physical thickness of 250nm to 300 nm. For example, the pigment flake 100 can have a physical thickness of 250nm, 260nm, 270nm, 280nm, 290nm, or 300 nm.
By reducing the total number of dielectric layers and the total optical thickness of the pigment flakes 100, the influence of the incident angle on the change of the optical path difference can be further reduced, thereby reducing the sensitivity of the color of the pigment flakes 100 to the incident angle and realizing the all-dielectric pigment flakes 100 with good monochromaticity and small angle dependence.
Optionally, the optical thickness of the second sub-dielectric stack 122 within the same dielectric stack period 120 is smaller than the optical thickness of the first sub-dielectric stack 121.
Alternatively, the optical thickness of the second sub-dielectric stack 122 may be 0.1-1 QWOT, such as 0.1 QWOT, 0.5 QWOT, 0.8 QWOT, 1 QWOT.
The optical thickness of the first sub-dielectric stack 122 may be 0.5-2 QWOT, such as 0.5 QWOT, 1 QWOT, 1.6 QWOT, or 2 QWOT.
Further, when the dielectric stack period 120 is stacked on only one major surface of the first sub-dielectric base layer, the optical thicknesses of the first sub-dielectric base layer and the second sub-dielectric stack 122 may be equal. In the pigment flake 100, all the dielectric layers with relatively low refractive indexes have the same optical thickness, and all the dielectric layers with relatively high refractive indexes have the same optical thickness, so that the difficulty of the manufacturing process is reduced, and a more stable and reliable interference effect can be obtained.
Optionally, the first sub-dielectric base layer and the second sub-dielectric stack 122 are made of dielectric materials with refractive indexes larger than 2, and the first sub-dielectric stack 121 is made of dielectric materials with refractive indexes smaller than 2.
Wherein, the material of the first sub-dielectric base layer and the second sub-dielectric stack layer 122 may be selected from at least one of lanthanum titanate, titanium dioxide, hafnium dioxide, and zinc sulfide. That is, the first sub-dielectric base layer and the second sub-dielectric stack 122 may each be composed of one material or a mixture of at least two of the above materials.
The material of the first sub-dielectric stack 121 may be selected from at least one of silicon dioxide, magnesium fluoride, and cryolite. That is, the first sub-dielectric stack 121 may be composed of one material or a mixture of at least two of the above materials.
In one embodiment, the pigment flake 100 can be comprised of a first sub-dielectric base layer and a dielectric stack period 120. That is, one dielectric stack period 120 is disposed in layers on one major surface of the first sub-dielectric base layer, and the number of dielectric layers of the pigment flake 100 is three.
Wherein the optical thicknesses of the first sub-dielectric base layer and the second sub-dielectric stack 122 are equal, and the optical thickness of the second sub-dielectric stack 122 is smaller than the optical thickness of the first sub-dielectric stack 121.
Specifically, the optical thickness of the first sub-dielectric stack 121 may be 1 QWOT, and the optical thickness of the second sub-dielectric stack 122 may be 0.5 QWOT. The physical thickness of the first sub-dielectric stack 121 may be 420nm and the optical thickness of the second sub-dielectric stack 122 may be 122 nm.
When the dielectric layers of the pigment flake 100 are three layers, the pigment flake 100 exhibits minimal color shift due to the low number of layers, and the pigment flake 100 exhibits a color shift of less than 30nm in the range of 0 degrees to 60 degrees from normal to the major surface of the dielectric base layer 110.
However, the number of layers is low, so that the reflectivity of the pigment flake 100 is relatively low, the half-peak width is wide, and the pigment flake is suitable for being applied to fields with low requirements on color vividness and monochromaticity, such as external packaging.
Referring to fig. 2, fig. 2 is a graph showing reflectance versus wavelength spectra for an embodiment of an all-dielectric small angle dependent pigment flake 100 according to the present application.
The pigment flake 100 has a three-layer structure, the material of the first sub-dielectric base layer and the second sub-dielectric stack 122 is selected from lanthanum titanate, and the material of the first sub-dielectric stack 121 is selected from silicon dioxide.
The optical thickness of the first sub-dielectric stack 121 may be 1 QWOT, the optical thickness of the second sub-dielectric stack 122 may be 0.5 QWOT, and the optical thickness of the first sub-dielectric stack 121 may be equal to the optical thickness of the first sub-dielectric base layer. Central wavelength lambda of reflection peak0450nm and the total physical thickness of the pigment flake 100 is 163 nm.
Referring to fig. 2, wherein the ordinate is reflectance and the abscissa is wavelength, the solid line represents the spectrum curve of the color sheet 100 at the viewing angle of 0 degree, and the dotted line represents the spectrum curve of the color sheet 100 at the viewing angle of 60 degrees.
As can be seen from the figure, the color shift of the pigment flake 100 observed at angles of 0 degree and 60 degrees in the example of the application is 20nm, which fully illustrates the effect of reducing the angle dependence of the color of the pigment flake 100, effectively suppresses the generation of secondary peaks, and improves the purity of the color of the pigment flake 100.
Referring to fig. 3, fig. 3 is a schematic structural diagram of another embodiment of an all-dielectric small angle dependent pigment flake according to the present application. It should be noted that fig. 3 only schematically includes two dielectric stack periods 120, but in the pigment flake 100 of the embodiment of the present application, the number of the dielectric stack periods 120 may be an even number greater than two, and the dielectric stack periods 120 are symmetrically disposed on two opposite sides of the first sub-dielectric substrate layer, and the number of the dielectric stack periods 120 is, for example, four or six dielectric stack periods.
In this embodiment, the two opposite sides of the first sub-dielectric base layer are symmetrically provided with the dielectric stack period 120.
Optionally, the optical thickness of the second sub-dielectric stack 122 within the same dielectric stack period 120 is smaller than the optical thickness of the first sub-dielectric stack 121, the optical thickness of the first sub-dielectric stack 121 is smaller than or equal to the optical thickness of the first sub-dielectric base layer, and the optical thickness of the first sub-dielectric base layer is smaller than or equal to twice the optical thickness of the second sub-dielectric stack 122.
Experimental studies have found that the pigment flakes 100 have the best overall effect under the conditions that the optical thickness of the second sub-dielectric stack 122 is less than the optical thickness of the first sub-dielectric stack 121 and less than or equal to twice the optical thickness of the first sub-dielectric stack 122. The higher reflectivity and narrower half-peak width, i.e., purer color and higher brightness, can be obtained on the basis of ensuring the small angle dependence of the pigment flake 100.
The optical thickness of the first sub-medium base layer should be adjusted in combination with the optical thickness of the first sub-medium stack 121 and the optical thickness of the second sub-medium stack 122, for example, if the optical thickness of the first sub-medium base layer is increased, the optical thickness of the second sub-medium stack 122 and the optical thickness of the first sub-medium stack 121 are correspondingly decreased, so as to achieve a better light filtering effect.
Alternatively, the optical thickness of the first sub-medium base layer may be 1-2 QWOT, e.g. 1 QWOT, 1.5 QWOT, 2 QWOT. The physical thickness of the first sub-dielectric base layer 122 may be 10-105nm, such as 10nm, 30nm, 50nm, 80nm, 105nm.
Optionally, the optical thicknesses of the first sub-dielectric stacks 121 in each dielectric stack period 120 are all equal, and the optical thicknesses of the second sub-dielectric stacks 122 in each dielectric stack period 120 are all equal. Therefore, all the dielectric stacking periods 120 in the pigment flake 100 have the same optical thickness, so as to reduce the difficulty of the manufacturing process, and the light rays incident from both sides of the pigment flake 100 have equivalent optical path difference, thereby obtaining more stable and reliable interference effect.
In addition, the optical thickness of the first sub-medium base layer can also regulate and control the transparency and the reflectivity of the film so as to meet different color and brightness requirements.
Optionally, the first sub-dielectric base layer and the second sub-dielectric stack 122 are made of dielectric materials with refractive indexes larger than 2, and the first sub-dielectric stack 121 is made of dielectric materials with refractive indexes smaller than 2. That is, the first sub-dielectric base layer and the second sub-dielectric stack 122 may each be composed of one material or a mixture of at least two of the above materials.
Wherein, the material of the first sub-dielectric base layer and the second sub-dielectric stack layer 122 may be selected from at least one of lanthanum titanate, titanium dioxide, hafnium dioxide, and zinc sulfide. That is, the first sub-dielectric base layer and the second sub-dielectric stack 122 may be composed of one material or a mixture of at least two materials.
The material of the first sub-dielectric stack 121 may be selected from at least one of silicon dioxide, magnesium fluoride, and cryolite. That is, the first sub-dielectric stack 121 may be composed of one material or a mixture of at least two of the above materials.
In one embodiment, the pigment flake 100 is comprised of a first sub-dielectric base layer and a dielectric stack period 120 disposed on each side of the first sub-dielectric base layer. I.e., five dielectric layers of the pigment flake 100.
The dielectric stack periods 120 on either side of the first sub-dielectric base layer are symmetrically arranged and the pigment flake 100 has a symmetrical structure centered on the first sub-dielectric base layer.
The optical thickness of the second sub-dielectric stack 122 is smaller than the optical thickness of the first sub-dielectric stack 121 and smaller than the optical thickness of the first sub-dielectric base layer, and the optical thickness of the first sub-dielectric base layer is smaller than or equal to twice the optical thickness of the second sub-dielectric stack 122.
In particular, the optical thickness of the first sub-dielectric stack 121 may be 0.8-1.5 QWOT, e.g. 0.8 QWOT, 0.9 QWOT, 1.1 QWOT, 1.2 QWOT or 1.5 QWOT. The optical thickness of the second sub-dielectric stack 122 may be 0.3-0.7 QWOT, e.g., 0.3 QWOT, 0.4 QWOT, 0.5 QWOT, 0.6 QWOT, or 0.7 QWOT. The optical thickness of the first sub-medium base layer may be 1-3 QWOTs, e.g. 1 QWOT, 2 QWOT or 3 QWOT.
When the dielectric layers of the pigment flake 100 are five layers, the pigment flake 100 exhibits a small color shift due to the low number of layers, and the pigment flake 100 exhibits a color shift of less than 50nm in the range of 0 degrees to 60 degrees from normal to the major surface of the dielectric base layer 110.
Due to the moderate number of layers, on the basis of ensuring low color shift, the reflectivity of the main peak of the reflection peak of the pigment sheet 100 is more than 50%, the half-peak width is wide, and the color-shifting pigment is suitable for being applied to the fields with low requirements on color vividness and monochromaticity, such as outer packaging.
Referring to fig. 4, fig. 4 is a spectral plot of reflectance versus wavelength for another embodiment of the all-dielectric small angle dependent pigment flake 100 of the present application.
The pigment flake 100 is a five-layer structure symmetrical in the middle of a first sub-dielectric base layer, the materials of the first sub-dielectric base layer and a second sub-dielectric stack 122 are selected from lanthanum titanate, the material of the first sub-dielectric stack 121 is selected from silicon dioxide, the optical thickness of the second sub-dielectric stack 122 is 0.5 QWOT, the optical thickness of the first sub-dielectric stack 121 is 1 QWOT, the optical thickness of the first sub-dielectric base layer is 1 QWOT, and the central wavelength lambda of a reflection peak is0450nm and the total physical thickness of the pigment flake 100 is 243 nm.
Referring to fig. 4, wherein the ordinate is reflectance and the abscissa is wavelength, the solid line represents the spectrum curve of the color sheet 100 at the viewing angle of 0 degree, and the dotted line represents the spectrum curve of the color sheet 100 at the viewing angle of 60 degrees.
As can be seen from the figure, the color shift of the pigment flake 100 observed at angles of 0 degree and 60 degrees in the example of the application is 47nm, which fully illustrates the effect of reducing the angle dependence of the color of the pigment flake 100, effectively suppresses the generation of secondary peaks, and improves the purity of the color of the pigment flake 100.
Referring to fig. 5, fig. 5 is a schematic diagram of another embodiment of an all-dielectric small angle dependent pigment flake according to the present application. It should be noted that fig. 5 only schematically includes two dielectric stack periods 120, but in the pigment flake 100 of the embodiment of the present application, the number of the dielectric stack periods 120 may be an even number greater than two, and the dielectric stack periods 120 are symmetrically disposed on two opposite sides of the dielectric base layer 110, and the number of the dielectric stack periods 120 is, for example, four or six dielectric stack periods.
In this embodiment, on the basis of any of the above embodiments, the dielectric substrate 110 further includes a second sub-dielectric substrate 112, the refractive index of the second sub-dielectric substrate 112 is smaller than that of the first sub-dielectric substrate 111 and the second sub-dielectric stack 122, and the first sub-dielectric substrate 111 and the dielectric stack period 120 are symmetrically disposed on two sides of the second sub-dielectric substrate 112 opposite to each other.
The symmetrical arrangement of the first sub-medium base layer 111 and the medium stack period 120 on two opposite sides of the second sub-medium base layer 112 means that: the pigment flake 100 includes a second sub-dielectric base layer 112, two first sub-dielectric base layers 111, and at least two dielectric stack periods 120, wherein the two first sub-dielectric base layers 111 are symmetrically disposed on two opposite sides of the second sub-dielectric base layer 112 to form a dielectric base layer 110, and the two opposite sides of the dielectric base layer 110 are symmetrically disposed with the dielectric stack periods 120.
Optionally, the optical thickness of the second sub-dielectric stack 122 within the same dielectric stack period 120 is smaller than the optical thickness of the first sub-dielectric stack 121, the optical thickness of the first sub-dielectric stack 121 is smaller than or equal to the optical thickness of the first sub-dielectric base layer 111, and the optical thickness of the first sub-dielectric base layer 111 is smaller than or equal to twice the optical thickness of the second sub-dielectric stack 122.
Experimental studies have found that the pigment flakes 100 have the best overall effect under the conditions that the optical thickness of the second sub-dielectric stack 122 is less than the optical thickness of the first sub-dielectric stack 121 and less than the optical thickness of the first sub-dielectric base layer 111, and the optical thickness of the first sub-dielectric base layer 111 is less than or equal to twice the optical thickness of the second sub-dielectric stack 122. The higher reflectivity and narrower half-peak width, i.e., purer color and higher brightness, can be obtained on the basis of ensuring the small angle dependence of the pigment flake 100.
The optical thickness of the first sub-medium base layer 111 should be adjusted in combination with the optical thickness of the second sub-medium stack 122 and the optical thickness of the first sub-medium stack 121, for example, if the optical thickness of the first sub-medium base layer 111 is increased, the optical thickness of the second sub-medium stack 122 and the optical thickness of the first sub-medium stack 121 are correspondingly decreased, so as to achieve a better light filtering effect.
Optionally, the optical thicknesses of the first sub-dielectric stacks 121 in each dielectric stack period 120 are all equal, and the optical thicknesses of the second sub-dielectric stacks 122 in each dielectric stack period 120 are all equal. So that all the dielectric stack periods 120 in the pigment flake 100 have the same optical thickness, the difficulty of the fabrication process is reduced, and the interference effect is more stable and reliable.
Further, the optical thicknesses of the two first sub-dielectric base layers 111 are equal, so that the pigment flakes 100 form a symmetrical structure centered on the second sub-dielectric base layer 112. The difficulty of the manufacturing process is reduced, and the light rays incident from the two sides of the pigment flake 100 have equivalent optical path difference, so that the interference effect is more stable and reliable.
Optionally, the first sub-medium base layer 111 and the second sub-medium stack layer 122 are made of a medium material with a refractive index greater than 2, and the first sub-medium stack layer 121 and the second sub-medium base layer 112 are made of a medium material with a refractive index less than 2.
The material of the first sub-dielectric base layer 111 and the second sub-dielectric stack layer 122 may be selected from at least one of lanthanum titanate, titanium dioxide, hafnium dioxide, and zinc sulfide. The first sub-dielectric base layer 111 and the second sub-dielectric stack 122 may be composed of one material or a mixture of at least two materials.
The material of the first sub-dielectric stack 121 and the second sub-dielectric base layer 112 may be selected from at least one of silicon dioxide, magnesium fluoride and cryolite. The first sub-dielectric stack 121 and the second sub-dielectric base layer 112 may be composed of one material or a mixture of at least two materials.
In one embodiment, the dielectric base layer 110 includes one second sub-dielectric base layer 112, two first sub-dielectric base layers 111, and two dielectric stack periods 120.
The pigment flake 100 is composed of a second sub-dielectric base layer 112 and a first sub-dielectric base layer 111 and a dielectric stack period 120 on either side of the second sub-dielectric base layer 112. I.e., seven dielectric layers of the pigment flake 100, the pigment flake 100 has a symmetrical structure centered on the second sub-dielectric base layer 112.
The optical thickness of the second sub-dielectric stack 122 is smaller than the optical thickness of the first sub-dielectric stack 121 and smaller than the optical thickness of the first sub-dielectric base layer 111, the optical thickness of the first sub-dielectric base layer 111 is smaller than or equal to twice the optical thickness of the second sub-dielectric stack 122, and the optical thickness of the second sub-dielectric base layer 112 is equal to the optical thickness of the first sub-dielectric base layer 111.
In particular, the optical thickness of the first sub-dielectric stack 121 may be 0.8-1.5 QWOT, e.g. 0.8 QWOT, 0.9 QWOT, 1.1 QWOT, 1.2 QWOT or 1.5 QWOT. The optical thickness of the second sub-dielectric stack 122 may be 0.3-0.7 QWOT, e.g., 0.3 QWOT, 0.4 QWOT, 0.5 QWOT, 0.6 QWOT, or 0.7 QWOT. The optical thickness of the first sub-medium base layer 111 may be 1-3 QWOTs, e.g., 1 QWOT, 2 QWOT or 3 QWOT.
The optical thickness of the second sub medium base layer 112 may be equal to the optical thickness of the first sub medium base layer 111.
When the number of dielectric layers of the pigment flake 100 is seven, the half-peak width is further narrowed and the reflectivity is improved to 80% due to the increase of the number of dielectric layers. At the same time, the color shift of the pigment flake 100 will increase as the number of layers increases, but the color shift of the pigment flake 100 will be less than 80nm in the range of 0 degrees to 60 degrees from normal to the major surface of the dielectric base layer 110.
Due to the fact that the number of layers is high, the pigment flake 100 is good in monochromaticity, namely pure in color, high in color brightness and suitable for being applied to the fields of paint and the like with high requirements on color vividness and monochromaticity.
Referring to fig. 6, fig. 6 is a graph showing reflectance versus wavelength spectra for an embodiment of an all-dielectric small angle dependent pigment flake 100 according to the present application.
The pigment flake 100 has a seven-layer structure, the material of the first sub-dielectric base layer 111 and the second sub-dielectric stack layer 122 is selected from lanthanum titanate, and the material of the first sub-dielectric stack layer 121 and the second sub-dielectric base layer 11 is selected from silicon dioxide.
The optical thickness of the first sub-dielectric stack 121 may be 1 QWOT, the optical thickness of the second sub-dielectric stack 122 may be 0.5 QWOT, the optical thickness of the first sub-dielectric base layer 111 may be 1 QWOT, and the optical thickness of the second sub-dielectric base layer 112 may be equal to the optical thickness of the first sub-dielectric base layer 111. Central wavelength lambda of reflection peak0450nm and the total physical thickness of the pigment flake 100 is 365 nm.
Referring to fig. 6, wherein the ordinate is reflectance and the abscissa is wavelength, the solid line represents the spectrum curve of the color sheet 100 at the viewing angle of 0 degree, and the dotted line represents the spectrum curve of the color sheet 100 at the viewing angle of 60 degrees.
As can be seen, the color shift of the pigment flakes 100 of the examples of the present application is 87nm at 0 and 60 degrees with an 80% improvement in reflectivity. It is fully demonstrated that the effect of reducing the angle dependence of the color of the pigment flake 100 is achieved, and that the generation of secondary peaks is effectively suppressed, the purity of the color of the pigment flake 100 is improved, and the pigment flake 100 has better monochromaticity and higher color brightness.
In contrast to the related art, the all-dielectric small-angle dependent pigment flake provided by the present application includes a dielectric base layer and at least one dielectric stack period stacked on at least one major surface of the first sub-dielectric base layer, the dielectric base layer includes a first sub-dielectric base layer, each dielectric stack period includes a first sub-dielectric stack and a second sub-dielectric stack, the refractive index of the first sub-dielectric stack is smaller than that of the second sub-dielectric stack and the first sub-dielectric base layer, and the first sub-dielectric stack is disposed closer to the first sub-dielectric base layer than the second sub-dielectric stack in the same dielectric stack period, that is, the pigment flake is formed by stacking high and low refractive index dielectric materials, and since the position of the reflection peak of the reflected light of a specific wavelength by the dielectric depends on the size of the optical path difference, and the optical path difference depends on the refractive index, the thickness of the dielectric layer and the incident angle, therefore, the thickness coefficient of each dielectric layer and the total number of layers of the pigment flakes are set to determine the optical thickness of the pigment flakes so as to change the optical path difference, and the optical thicknesses of the dielectric base layer and the dielectric lamination period are set to enable the color shift of the pigment flakes within a range of 0-60 degrees of deviation relative to the normal direction of the main surface where the dielectric base layer is located to be less than 80nm, namely, the effect of enabling the color of the pigment flakes to change less with the angle within a certain angle range can be achieved.
The above description is only for the purpose of illustrating embodiments of the present invention and is not intended to limit the scope of the present invention, and all modifications, equivalents, and equivalent structures or equivalent processes that can be used directly or indirectly in other related fields of technology shall be encompassed by the present invention.
Claims (13)
1. An all-dielectric small angle dependent pigment flake, comprising:
a media base layer comprising a first sub-media base layer;
at least one dielectric stack period disposed in a stack on at least one major surface of the first sub-dielectric substrate, each of the dielectric stack periods comprising a first sub-dielectric stack and a second sub-dielectric stack, wherein the first sub-dielectric stack has a refractive index smaller than that of the second sub-dielectric stack and the first sub-dielectric substrate, and the first sub-dielectric stack is disposed closer to the first sub-dielectric substrate than the second sub-dielectric stack in the same dielectric stack period, wherein the optical thicknesses of the dielectric substrate and the dielectric stack period are set such that the color shift of the pigment flake in a range of 0-60 degrees from the normal direction of the major surface on which the dielectric substrate is disposed is less than 80 nm.
2. The pigment flake of claim 1, wherein the first sub-dielectric base layer is symmetrically disposed with the dielectric stack period on opposite sides of the first sub-dielectric base layer.
3. The pigment flake of claim 1, wherein the dielectric base layer further comprises a second sub-dielectric base layer having a refractive index smaller than that of the first sub-dielectric base layer and the second sub-dielectric stack, respectively, and the first sub-dielectric base layer and the dielectric stack are disposed symmetrically on opposite sides of the second sub-dielectric base layer.
4. The pigment flake of claim 1, wherein the number of dielectric stack periods on the same side of the dielectric base layer is not greater than 2.
5. The pigment flake of claim 1, wherein the second sub-stack of dielectric layers within a same period of the dielectric stack has an optical thickness less than an optical thickness of the first sub-stack of dielectric layers.
6. The pigment flake of claim 2 or 3, wherein an optical thickness of the second sub-dielectric stack within a same period of the dielectric stack is less than an optical thickness of the first sub-dielectric stack, wherein an optical thickness of the first sub-dielectric stack is less than or equal to an optical thickness of the first sub-dielectric base layer, and wherein an optical thickness of the first sub-dielectric base layer is less than or equal to twice an optical thickness of the second sub-dielectric stack.
7. The pigment flake of claim 1, wherein the pigment flake has a physical thickness of from 170nm to 400 nm.
8. The pigment flake of claim 2, wherein the pigment flake has a physical thickness of from about 250nm to about 300 nm.
9. The pigment flake of claim 1, wherein the first sub-dielectric base layer and the second sub-dielectric stack are comprised of dielectric materials having an index of refraction greater than 2, and wherein the first sub-dielectric stack is comprised of dielectric materials having an index of refraction less than 2.
10. The pigment flake of claim 9, wherein the first sub-dielectric base layer and the second sub-dielectric stack are made of at least one material selected from the group consisting of lanthanum titanate, titanium dioxide, hafnium dioxide, and zinc sulfide;
the material of the first sub-dielectric stack is selected from at least one of silicon dioxide, magnesium fluoride and cryolite.
11. The pigment flake of claim 1, wherein the pigment flake comprises a layer of the first sub-dielectric base layer and a period of the dielectric stack, or comprises a layer of the first sub-dielectric base layer and a period of the dielectric stack on each side of the first sub-dielectric base layer.
12. The pigment flake of claim 1, wherein the dielectric base layer further comprises a second sub-dielectric base layer, and wherein the pigment flake comprises a layer of the second sub-dielectric base layer and a layer of the first sub-dielectric base layer and a layer of the dielectric stack periods on opposite sides of the second sub-dielectric base layer.
13. The pigment flake of claim 1, wherein the main peak of the reflection peak of the pigment flake has a central wavelength between 400-780 nm and has only one main peak within 380-780 nm.
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