CN110703377A - Red optical color-changing sheet and preparation method thereof - Google Patents
Red optical color-changing sheet and preparation method thereof Download PDFInfo
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Images
Classifications
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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
Abstract
The invention discloses a red optical color-changing sheet which is provided with a central reflecting layer, wherein a basic structure of a first medium layer, a first metal light splitting layer and a second medium layer is symmetrically or asymmetrically arranged from the central reflecting layer to the outside in sequence, a symmetrical structure or an asymmetrical structure is prepared by selecting proper materials and film layer thicknesses, a film system structure with a long red wave band is constructed, supersaturated red close to a CIE1931 system is constructed, the condition that the red interval is long is realized, the main peak of the red wave band is moved forward to a high-efficiency region of visual efficiency, the half-wave width of the red interval is reduced, the color purity and the color-changing performance are ensured, the red chromaticity region in the CIE1931 system is displayed by front-looking colors, the visual effect is optimized, and the purposes of reducing the film thickness, improving the material utilization rate and reducing the energy consumption are achieved.
Description
The technical field is as follows:
the invention relates to the technical field of optical anti-counterfeiting and the technical field of high-grade color printing and coating, in particular to a red optical color-changing sheet and a preparation method thereof.
Background art:
the optical color-changing pigment (OVP) prepared based on the principle of film multi-beam interference is a high-end anti-counterfeiting material in the anti-counterfeiting field, the displayed color of the optical color-changing pigment has the characteristic of changing along with the change of an observation visual angle, the color-changing characteristic can not be reproduced by common color copying and electronic scanning, the anti-counterfeiting performance is extremely strong, and the optical color-changing pigment can be identified by human eyes, so the optical color-changing pigment is widely applied to currency, valuable securities and the like, tobacco and wine and high-end coating markets, particularly the application in daily commodities, and the optical color-changing pigment has a good color display effect besides the optical color-changing anti-counterfeiting function. In particular, red or wine-red is particularly preferred by women.
In the prior art, the related patents US4779898, US5059245, ZL02816899.2 use symmetrical reflection type light-changing structures: the semi-absorption layer/dielectric layer/reflection layer/dielectric layer/semi-absorption layer, wherein the semi-absorption layer is usually made of metal chromium, nickel or nichrome material, the dielectric film layer is usually made of transparent dielectric material with a refractive index lower than 1.65, such as magnesium fluoride, silicon dioxide, aluminum oxide and other materials, and the reflection film layer is usually made of metal aluminum, iron, chromium or nichrome zinc, silver and other pure metal materials according to different preparation processes. For example, U.S. Pat. Nos. 5059245 and ZL02816899.2 propose optically variable thin film structures which are usually Cr/MgF2/Al/MgF2The sandwich symmetrical structure adopts different designed main wavelengths to construct different optical thicknesses, particularly the optical thickness of a dielectric film layer, so that the interference constructive condition of reflected light waves in a certain main wavelength region can be met, a reflection peak value in the wavelength region is formed, destructive interference is formed in adjacent wavelength regions, the reflection peak disappears, the region with the strongest reflection peak corresponds to a certain color waveband of a visible spectrum, and the observed color is finally determined.
However, when a red color display effect located in a long-wave band is constructed, a severe color cast phenomenon occurs, and it can be seen that, by adopting the five-layer symmetric structure of the optically variable film, a secondary reflection peak with enhanced interference is usually formed in a blue band, and a half-wave width ratio is wide, yellow and green bands retain a certain reflectivity, and the reflected lights are overlapped to cause that a usually displayed color region is Pink or Pink (Pink or Pink), which shows that the color depth is insufficient, the chromaticity coordinate is x ═ 0.407, and y ═ 0.262. According to the description of the color characteristics by the CIE-1931 standard colorimetry system, the chromaticity coordinates x and y represent the chromaticity values of the corresponding colors, and under the conditions of a white light illumination light source and a CIE-1931 standard observer, for a RED color domain (RED), the chromaticity coordinates of the RED color domain should be located in a color patch area constructed by x being 0.513 to 0.73 and y being 0.228 to 0.345, obviously, the purple color is displayed. It can be seen that the optically variable anti-counterfeiting film constructed by the semi-absorption layer/the dielectric layer/the reflection layer/the dielectric layer/the semi-absorption layer cannot realize a single main reflection peak in a red region, and cannot display red spectral color.
When this occurs, the design requirement is usually achieved by adding a film layer, for example, the patent CN105137519B proposes that: by adopting a new symmetrical structure of 7 layers, 9 layers, 11 layers or 13 layers … 7+ (2n), wherein n is an integer (0, 12 …), the reflection spectrum meets interference phase components at a red waveband by introducing a new film layer structure, interference cancellation is met at blue, green and yellow wavebands, secondary reflection peaks are eliminated, the phenomenon that a short-wave reflection sub-peak usually appears when a red reflection peak is constructed in a traditional 5-layer symmetrical light variation structure is overcome, and the effect that the integral display is vertically observed and the color is pure red is achieved.
There are several problems associated with analyzing the structure of the membrane system: 1. the film thickness is too thick, and the total film thickness in each period is about 1 mu m; 2. the position of the main peak is 700nm or even beyond, the half-wave width is very wide, from the visual color perspective, the wave band color after 680nm is black, and non-expert people can not see the wave band color and are in the human eye visual efficiency low-efficiency area, so that the lightness is insufficient; the secondary peak or blue-violet band is depressed or eliminated so that the only color region appearing is the Red region. Accordingly, some adverse effects are caused: 1. the stress in the film is large, the film layer is unstable in the production process, and the film is easy to explode; 2. the diameter-thickness ratio is small under the condition of the same particle size, the tiling property of the film layer is not good during printing, and the color display effect is greatly reduced; 3. more pigment is needed for printing the same area, which causes material waste; 4. the wave crest is positioned in a low efficiency area of human eye visual efficiency, the color is dark, the effect is poor 5, the range of the color display area is Red pure Red, and the wine Red (purple Red or Red purple) cannot be displayed.
In the process of film growth, along with the growth of a film layer, the stress is accumulated continuously, the thick film thickness causes the overlarge stress of the whole film system, and because a release layer exists in the film system, the release layer is used as a vulnerable layer to separate, is weaker, and easily causes film cracking due to the stress in the production process, thereby influencing the cycle number of each furnace and further influencing the productivity. Meanwhile, the coating time consumption of each period is relatively long, waste of raw materials, energy consumption and the like is caused, and the unit construction cost is increased in printing.
Because the common method in the field is to use the mode of combining resistance evaporation and electron gun evaporation in a box type film coating machine in the manufacturing process, the intermittent production is realized, and the productivity is relatively low. With the progress of laser technology, laser can be used as an evaporation source to perform continuous evaporation, so that the productivity is improved. Laser is led into a vacuum furnace through a plurality of strands of optical fibers, the angles and the arrangement of the optical fibers are adjusted, the optical fibers are focused into a linear evaporation source with controllable energy distribution, the uniformity of coating is ensured, the laser is from the outside of the vacuum chamber and cannot be polluted by materials, the vacuum is not broken when a fault occurs, the uniformity change caused by material pollution and discharge ignition is easy to happen unlike the evaporation of an electron gun, and only interruption can be realized when the fault occurs in the coating process.
The invention content is as follows:
the invention aims to provide a red optical color-changing sheet and a preparation method thereof, which select proper materials and film thickness, adjust the proportion of interference light and the interference level number, form a new light interference curve, wherein the curve is close to a supersaturated red spectrum curve in a CIE1931 system: the condition of interference phase length is met in a red interval, the main peak of a red waveband is moved forward to a high-efficiency visual efficiency area, and a narrow half-wave width design is adopted, so that the half-wave width of the red interval is reduced, the color purity and the color change performance are ensured, the reflectivity of a purple waveband is properly kept, and the color saturation is increased; the front view color display is realized in a Red or wine Red chromaticity area (Red, purple Red or Red purple) in a CIE1931 system, the optimization view effect is achieved, the color display effect of the Red chromaticity area is expanded, the film thickness is reduced, the thickness of each period is greatly reduced to about 0.6 mu m, the reduction amplitude is about 40%, the material utilization rate is improved, the energy consumption is reduced, and the problem that the waste of raw materials and energy consumption is caused by the fact that the film thickness is greatly increased and the layer number is weakened to weaken the display effect is avoided.
CIE XYZ is the CIE color System (CIEColor System) developed by the international commission on illumination in 1931 and revised in 1964, which is the basis for other color systems. The three colors corresponding to red, green and blue are used as three primary colors, and according to the principle of the three primary colors, the colors are actually physical quantities, and people can calculate and measure the physical quantities. Based on mathematical models of vision and the results of color matching experiments, the international commission on lighting has specified a specification called "1931 CIE standard observer", which is actually a set of color matching functions represented by three curves, and is therefore also referred to as "CIE 1931 standard matching functions" in many documents. In the color matching experiment, the observer's viewing angle was specified to be 2 degrees, and therefore, it is also referred to as a tribasic color stimulus value (tristimulus values) curve of a standard observer. The red color of fig. 2 is defined as oversaturated red, and thus it is advantageous to design to allow some reflectivity in the violet band to increase the saturation of the red color. But if the reflection of this band is too strong, it becomes purplish red, and becomes another color. Thus, in the present invention, a supersaturated red spectral curve is defined as one that is highly reflective in the red band, has a certain reflectance in violet, and is low reflective in other bands, the visible color being red or wine-red.
The invention is realized by the following technical scheme:
the red optical color-changing sheet is provided with a central reflecting layer, and a basic structure of a first dielectric layer, a first metal light splitting layer and a second dielectric layer is symmetrically or asymmetrically arranged from the central reflecting layer to the outside in sequence, wherein the central reflecting layer is made of more than one of Al, Cr, Ti, Ni, Fe, Cu, Ag, Au, Sn, Mn, Co, Zr, Mo, W and Sm, particularly, the central reflecting layer is a composite central reflecting layer and a magnetic core central reflecting layer which are of a multilayer structure or an alloy structure and are composed of the materials, such as an Al/Ni-Fe/Al magnetic core reflecting layer, and the first dielectric layer is made of MgF2、AlF3、Na3AlF6、BaF2、NdF3、CaF3、LiF、SiO2、SiO、Al2O3、TiOX、LiTiOx、Ta2O5、ZrO2、Nb2O5、HfO2、Sb2O3、Fe2O3、CuO、NiO、Sm2O3、Nd2O3Wherein, X is in the range of 1-2, the preferable refractive index is less than 1.6, the material of the first metal light splitting layer is more than one of Al, Cr, Ti, Ni, Fe, Cu, Ag, Au, Sn, Mn, Co, Zr, Mo, W, Sm, etc., and the material of the second dielectric layer is more than one of SiO, Cr, Ti, Ni, Fe, Cu, Ag, Au, Sn, Mn, Co, Zr, Mo, W, Sm, etc2、SiO、Al2O3、TiOX、LiTiOx、Ta2O5、ZrO2、Nb2O5、HfO2、Sb2O3、Fe2O3、CuO、NiO、Sm2O3、Nd2O3Wherein, X is in the range of 1-2, the thickness of the central reflecting layer is between 30-150nm, the thickness of the first dielectric layer is 100-240nm, and the thickness of the first metal light splitting layer is as follows: 1-38nm, and the thickness of the second dielectric layer is 10-150nm, preferably 15-90 nm.
In particular, a second metal light splitting layer is arranged outside the second dielectric layer, and the thickness of the second metal light splitting layer is as follows: 0-7nm, and the second metal light splitting layer is made of one of Al, Cr, Ti, Ni, Fe, Au, Sn, Mn, Co, Zr, Mo, W, Sm and the like.
Particularly, a third dielectric layer is arranged outside the second metal light splitting layer, the thickness of the third dielectric layer is 0-250nm, and the material of the third dielectric layer is SiO2、SiO、Al2O3、TiOX、LiTiOx、Ta2O5、ZrO2、Nb2O5、HfO2、Sb2O3、Fe2O3、CuO、NiO、Sm2O3、Nd2O3Wherein X is in the range of 1-2.
The invention also provides a preparation method of the red photochromic flake, which comprises the following steps:
1) sequentially plating/coating an isolation film layer on a glass or stainless steel or flexible plastic substrate;
2) sequentially plating a second metal light splitting layer, a second medium layer, a first metal light splitting layer, a first medium layer, a central reflecting layer, a first medium layer, a first metal light splitting layer, a second medium layer and a second metal light splitting layer; the materials of the first half period and the second half period of the film layer can be the same or different;
3) circulating the step 1) and the step 2) for a plurality of times;
4) demoulding, cleaning, crushing, surface modifying and other post-treatments to obtain the required red light variable slice.
Or, directly and sequentially plating a central reflecting layer, a first dielectric layer, a first metal light splitting layer, a second dielectric layer and a second metal light splitting layer on the substrate.
The coating method comprises Physical Vapor Deposition (PVD)/Chemical Vapor Deposition (CVD), such as laser evaporation, resistance evaporation, electron beam evaporation, sputtering deposition, etc.
According to the description of the color characteristics by the CIE-1931 standard colorimetry system, chromaticity coordinates x and y are used for representing chromaticity values of corresponding colors, and under the condition of a white light source, the chromaticity coordinates of a Red color domain are located in an irregular color block (Red, Purplish Red) area constructed by x being 0.4-0.73 and y being 0.135-0.345.
The invention has the following beneficial effects:
1) the invention firstly proposes to prepare supersaturated red photochromic flakes, the structure of which is close to that of supersaturated red in a CIE1931 system: the reflectivity of the purple waveband is properly kept, and the color saturation is increased; the peak re-peaking in 0-3 quarter wave thickness (QWOT) was found to be a more optimal choice at about 2 QWOT main peaks, although a five layer design is now used (first metal splitting layer M1: Ti-19nm first dielectric layer D1: MgF)2170nm central reflecting layer MR Cu 100nm first dielectric layer D1 MgF2170nm first metal splitting layer M1: Ti-19nm) is unimodal but half-waveThe width is very wide, see fig. 4, showing yellow, and therefore the design needs to be optimized by increasing the number of layers. This makes it possible to obtain: 1. the thickness is thin; 2. certain reflectivity is reserved in the blue-violet wave band; 3. the red wave band is a single reflection peak, the half wave width is narrow, and the color change performance is equivalent.
2) The invention uses the principle of light interference, prepares a symmetrical structure or an asymmetrical structure by selecting proper materials and film layer thickness, adjusts the proportion and the interference level of interference light, re-seeks peaks to form a new light interference curve, constructs a film system structure with long red wavelength band, and constructs supersaturated red which is close to that in a CIE1931 system: the reflectivity of a purple waveband is properly kept, the Red waveband of a high-efficiency area with the maximum visual efficiency is increased, the color saturation is increased, the condition of phase lengthening in a Red area is realized, the main peak of the Red waveband is moved forward to the high-efficiency area with the visual efficiency, the half-wave width of the Red area is reduced, the color purity and the color change performance are guaranteed, the aim of displaying a Red (Red, purple Red) chromaticity area in a CIE1931 system by the orthographic color is realized, the visual effect is optimized, the thickness of each period is greatly reduced to about 0.6 mu m, the amplitude is reduced by 40%, the purposes of reducing the film thickness, improving the material utilization rate and reducing the energy consumption are achieved, the phenomenon that a short-wave reflection secondary peak usually occurs when a Red reflection peak is constructed by a traditional 5-layer symmetrical optical variable structure is overcome, and the problem that the waste of raw materials and the energy consumption is caused by the fact that the display effect is. Also solves the problems that the prior optical color changing pigment produced by vacuum coating has low efficiency and high production cost, and restricts the application field of the pigment.
In conclusion, the invention selects proper materials and film thickness, adjusts the proportion of interference light and the interference level number, forms a new light interference curve which is close to the supersaturated red spectrum curve in the CIE1931 system: the condition of interference phase length is met in a red interval, the main peak of a red waveband is moved forward to a high-efficiency visual efficiency area, and a narrow half-wave width design is adopted, so that the half-wave width of the red interval is reduced, the color purity and the color change performance are ensured, the reflectivity of a purple waveband is properly kept, and the color saturation is increased; the front view color display is realized in a Red or wine Red chromaticity region (Red, purple Red or Reddish pure) in a CIE1931 system, the optimization view effect is achieved, the color display effect of the Red chromaticity region is expanded, the film thickness is reduced, the thickness of each period is greatly reduced to about 0.6 mu m, the reduction amplitude is about 40%, the material utilization rate is improved, the energy consumption is reduced, and the problem that the waste of raw materials and energy consumption is caused by the fact that the film thickness is greatly increased and the layer number is weakened to the display effect is avoided.
Description of the drawings:
figure 1 is a graph of the visual efficiency,
FIG. 2 is a supersaturated red in the CIE system;
figure 3 is a schematic diagram of the structure of a red photochromic flake of the present invention,
the MR, the central reflecting layer, the D1, the first dielectric layer, the M1, the first metal light splitting layer, the D2, the second dielectric layer, the M2 and the second metal light splitting layer.
Fig. 4 is a light variation curve of the five-layer structure of the present design 5;
wherein the first metal light splitting layer M1 is Ti-19nm
First dielectric layer D1 MgF2-170nm
The central reflecting layer MR is Cu-100nm
First dielectric layer D1 MgF2-170nm
The first metal splitting layer M1: Ti-19 nm.
FIG. 5 is a vertically observed reflectance spectrum of the 7-layer structure of example 1;
FIG. 6 is a 0-60 degree chromaticity variation trace for the 7-layer structure of example 1;
FIG. 7 is a vertically observed reflectance spectrum of the 7-layer structure of comparative example 1;
FIG. 8 is a 0-60 degree chromaticity variation trace for the 7-layer structure of comparative example 1;
FIG. 9 is a vertically observed reflectance spectrum of the 7-layer structure of example 2;
fig. 10 is a 0-60 degree chromaticity variation trace for the 7-layer structure of example 2.
FIG. 11 is the vertical observation reflectance spectrum of the 9-layer structure of example 3;
FIG. 12 is a 0-60 degree chromaticity variation trace for the 9-layer structure of example 3;
FIG. 13 is a vertically observed reflectance spectrum of the 7-layer structure of example 5;
fig. 14 is a 0-60 degree chromaticity variation trace for the 7-layer structure of example 5.
FIG. 15 is a vertically observed reflectance spectrum of the 7-layer structure of comparative example 2;
fig. 16 is a 0-60 degree chromaticity variation trace of the 7-layer structure of comparative example 2.
FIG. 17 is a vertically observed reflectance spectrum of the 11-layer structure of example 6;
fig. 18 is a 0-60 degree chromaticity variation trace for the 11-layer structure of example 6.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
the red optical color-changing sheet is provided with a central reflecting layer, and a first dielectric layer, a first metal light splitting layer and a second dielectric layer are symmetrically arranged from the central reflecting layer to the outside in sequence, wherein the specific film system structure is as follows:
second dielectric layer D2: Fe2O3-50nm
The first metal light splitting layer M1 is Ti-19nm
First dielectric layer D1 MgF2-170nm
The central reflecting layer MR is Cu-100nm
First dielectric layer D1 MgF2-170nm
The first metal light splitting layer M1 is Ti-19nm
Second dielectric layer D2: Fe2O3-50nm。
The central reflecting layer provides reflecting action, the dielectric layer determines the position of the main peak, and the first metal light splitting layer, the second dielectric layer and the subsequent layers play the roles of reducing half wave width, improving color purity and ensuring color changing performance. The color-changing performance of the film is determined by the thickness of the dielectric layer, the thicker the film layer is, the stronger the color-changing performance is, but in the film system structure, the narrow half-wave width design is adopted, and the equivalent color-changing performance can be obtained by the smaller thickness.
Fig. 5 is a reflectance spectrum of the 7-layer red optical color-changing flake structure of the embodiment, and it can be seen that, in the visible spectrum range of 380nm-780nm, a certain reflectance is retained for bluish violet, the reflectance for green spectrum band is lower, the reflectance for red band is higher, and the peak is located at 640 nm. The color and the variation curve are shown in fig. 6, according to the description of the color characteristics by the CIE-1931 standard chromaticity system, under the conditions of a white light source and a CIE-1931 standard observer, for the above 7-layer symmetric Red light variation structure, the chromaticity coordinate is 0.588, 0.306, and the irregular color block (Red) area is constructed by 0.513-0.73, 0.228-0.345, the chromaticity coordinate is 0.4, 0.451, and the corresponding color is yellow green when observed at an angle of 60 degrees.
The preparation method comprises the following steps: firstly, providing a substrate for bearing a light-variable film, wherein the substrate can be a flat stainless steel substrate/glass/PET/PPT and other plastic substrates; the preparation method of the film is realized by Physical Vapor Deposition (PVD)/Chemical Vapor Deposition (CVD), such as resistance evaporation, electron beam evaporation, sputtering deposition and the like. An isolation film layer is prepared on the substrate by PVD or coating, and then a second dielectric layer D2/a first metal light splitting layer M1/a first dielectric layer D1/a central reflecting layer MR/a first dielectric layer D1/a first metal light splitting layer M1/a second dielectric layer D2 are sequentially formed. The material of the first half period and the second half period of the film layer can be the same or different, namely symmetrical or asymmetrical structures, the film layer is repeated for N times by taking the structure as a period, after the repeated growth is completed, the substrate bearing the periodic film layer structure is taken out from a vacuum chamber and placed in a specific solvent for a film removing procedure, the isolation film layer is melted in the film removing solvent, the periodic light variable structure is peeled off from the rigid substrate, a plurality of repeated light variable structures are separated, then the separated light variable material is collected for rinsing, filtering and particle crushing according to the printing process requirement, and finally the crushed powder is subjected to surface modification treatment, so that the final light variable red sheet product can be obtained.
Wherein, the central reflective layer MR of this embodiment can also adopt a magnetic core such as Cu/Fe/Cu or Cr/Cu/Au/Cr with enhanced bonding force in a layered or alloy structure, Cr plays a role of a bonding layer, anda dielectric layer material MgF with refractive index close to that of the dielectric layer material2、AlF3、Na3AlF6、BaF2、NdF3、CaF3、LiF、SiO2、Al2O3One or more selected from the group consisting of Al and the second dielectric layer2O3、TiOX、LiTiOx、Ta2O5、ZrO2、Nb2O5、HfO2、Sb2O3、Fe2O3、CuO、NiO、Sm2O3、Nd2O3One or more than one of them is selected. The material of the first half period and the material of the second half period of the film layer can be the same or different, namely, the film layer has a symmetrical or asymmetrical structure, the light-variable film layer structure combination according to the embodiment can vertically display red, display another color at a second observation angle, and the color of the second viewing angle is yellow, yellow green and green generally according to the design structure.
Comparative example 1:
reference example 1: the difference lies in the thickness of the first dielectric layer, the first metal light splitting layer and the second dielectric layer.
The red optical color-changing sheet is provided with a central reflecting layer, and a first dielectric layer, a first metal light splitting layer and a second dielectric layer are symmetrically arranged from the central reflecting layer to the outside in sequence, wherein the specific film system structure is as follows:
second dielectric layer D2: Fe2O3-90nm
The first metal light splitting layer M1 is Ti-15nm
First dielectric layer D1 MgF2-190nm
The central reflecting layer MR is Cu-100nm
First dielectric layer D1 MgF2-190nm
The first metal light splitting layer M1 is Ti-15nm
Second dielectric layer D2: Fe2O3-90nm。
Fig. 7 is a reflectance spectrum of the 7-layer red optical color-changing flake structure of the present comparative example, and it can be seen that in the visible spectrum range of 380nm to 780nm, a certain reflectance is retained for bluish violet, the reflectance for green spectral band is lower, the reflectance for red spectral band is higher, and the peak is at 700 nm. The color and the variation curve are shown in fig. 8, according to the description of the color characteristics by the CIE-1931 standard chromaticity system, under the conditions of a white light source and a CIE-1931 standard observer, for the above 7-layer symmetric Red light variation structure, the chromaticity coordinate is 0.459, y is 0.22, and is located in an irregular color block (purple Red) region constructed by 0.4-0.73, x is 0.135-0.345, the chromaticity coordinate of the structure is 0.451, y is 0.447, and the corresponding color is yellow when observed at an angle of 60 degrees.
Example 2:
the red optical color-changing sheet is provided with a central reflecting layer, and a first dielectric layer, a first metal light splitting layer and a second dielectric layer are symmetrically arranged from the central reflecting layer to the outside in sequence, wherein the specific film system structure is as follows:
second dielectric layer D2: Fe2O3-52nm
The metal light splitting layer M1 is Ti-25nm
First dielectric layer D1 TiO2-100nm
The central reflecting layer MR is Ni-100nm
First dielectric layer D1 TiO2-100nm
The metal light splitting layer M1 is Ti-25nm
Second dielectric layer D2: Fe2O3-52nm。
In this embodiment, the central reflective layer MR may also adopt a layered or alloy structure of Cr, Ti, Ni, Fe, Mn, Co, Zr, Mo, W, Sm, and the first dielectric layer may also be SiO, SiO2、Al2O3、TiOX、LiTiOx、Ta2O5、ZrO2、Nb2O5、HfO2、Sb2O3、Fe2O3、CuO、NiO、Sm2O3、Nd2O3One or more of them. According to the structure combination of the light-variable film layer of the embodiment, the effect of displaying red at a first observation angle and displaying red at a second observation angle in a certain direction can be realizedThe second color of the first color, depending on the design, is typically a yellow pink color.
Fig. 9 is a reflectance spectrum of the structure of the 7-layer Red photochromic sheet of the present embodiment, it can be seen that, in the visible spectrum range of 380nm-780nm, a certain reflectance is retained in bluish-purple color, the average reflectance in green color is very low, the average reflectance in Red color band is high, the main peak wavelength is located after 700nm, the color and the variation curve are shown in fig. 10, according to the description of the color characteristics by the CIE-1931 standard chromaticity system, under the conditions of a white light source and a CIE-1931 standard observer, for the above 7-layer symmetric Red photochromic structure, the chromaticity coordinate is 0.557 and y is 0.3 when observed vertically, the irregular color block region is constructed by the Red chromaticity coordinate (Red) x being 0.513-0.73 and y being 0.228-0.345, the structure has the chromaticity coordinate being 0.467 when observed at an angle of 60 degrees, y is 0.364, and the corresponding color is shown as yellow pink.
The preparation method comprises the following steps: the method is realized by adopting laser evaporation winding type continuous plating on plastic substrates such as PET/PPT and the like: firstly, an isolation film layer is prepared on the substrate by PVD or coating, and then a second dielectric layer D2/a first metal light splitting layer M1/a first dielectric layer D1/a central reflecting layer MR/a first dielectric layer D1/a first metal light splitting layer M1/a second dielectric layer D2 are sequentially formed. The material of the first half period and the second half period of the film layer can be the same or different, namely a symmetrical or asymmetrical structure, the film layer is taken as the period and repeated for N times, after the repeated growth is completed, the substrate bearing the film layer structure of the period is taken out from the vacuum chamber and placed in a specific solvent for a film removing procedure, the isolation film layer is melted in the film removing solvent, then the separated optically variable material is collected for rinsing, filtering and particle crushing according to the printing process requirement, and finally the crushed powder is subjected to surface modification treatment, so that the final red optically variable thin sheet product can be obtained.
Example 3:
a red optical color-changing slice is provided with a central reflecting layer, and a first dielectric layer, a first metal light splitting layer, a second dielectric layer and a second metal light splitting layer are symmetrically arranged from the central reflecting layer to the outside in sequence, and the specific film system structure is as follows:
second metal-splitting layer M2: cr-4nm
Second dielectric layer D2: Fe2O3-60nm
First metal light splitting layer M1 Cu-38nm
First dielectric layer D1 MgF2-195nm
The central reflecting layer MR is Cu-150nm
First dielectric layer D1 MgF2-195nm
First metal light splitting layer M1 Cu-38nm
Second dielectric layer D2: Fe2O3-60nm
Second metal-splitting layer M2: cr-4 nm.
Fig. 11 is a reflectance spectrum of the 9-layer Red photochromic sheet structure of this embodiment, it can be seen that, in the visible spectrum range of 380nm-780nm, a certain reflectance is retained in blue-violet, the average reflectance of green is very low, the average reflectance of Red wavelength band is high, the main peak wavelength is at 660nm, the color and the variation curve are shown in fig. 12, according to the description of the color characteristics by the international commission on illumination CIE-1931 standard chromaticity system, under the conditions of a white light source and a CIE-1931 standard observer, for the 9-layer symmetric Red photochromic structure, the chromaticity coordinate is x-0.581, y-0.311, and the irregular color block region is constructed by the Red chromaticity coordinate (Red) x-0.513-0.73, y-0.228-0.345, the chromaticity coordinate is x-0.336, y-0.434 when observed at an angle of 60 degrees, the corresponding color is displayed as yellow-green.
The preparation method is similar to example 1.
According to the structure combination of the optically variable film layer of the embodiment, the vertically displayed image can be red, and a second color of another color can be displayed at a second viewing angle, and the colors at the second viewing angle are usually yellow, yellow-green and green according to the design structure.
Example 4:
red 8 layer metal medium asymmetric light becomes anti-fake membranous layer structure, for the combination of embodiment 1 with implement 3, central reflection stratum adopts multilayer composite construction, outwards is equipped with first dielectric layer, first metal beam splitting layer, second dielectric layer, second metal beam splitting layer by central reflection stratum in proper order asymmetry, and its asymmetric membrane system structure is:
second dielectric layer D2: Fe2O3-50nm
The first metal light splitting layer M1 is Ti-26nm
First dielectric layer D1 MgF2-170nm
The central reflecting layer MR is Cu-100nm
First dielectric layer D1 MgF2-195nm
First metal light splitting layer M1 Cu-38nm
Second dielectric layer D2: Fe2O3-60nm
Second metal-splitting layer M2: cr-4 nm.
According to the structure combination of the light-variable film layer of the embodiment, the effect of displaying red at a first observation angle and displaying a second color different from the first color at a second observation angle can be achieved in a certain direction, and the second color is usually yellow-green according to the design structure.
Red when viewed vertically, yellow-green when viewed at an angle of 60 degrees,
the preparation method is similar to example 1.
Example 5:
the red optical color-changing sheet is provided with a central reflecting layer, and a first dielectric layer, a first metal light splitting layer and a second dielectric layer are symmetrically arranged from the central reflecting layer to the outside in sequence. The specific film system structure is as follows:
second dielectric layer D2 TiO2-135nm
The first metal light splitting layer M1 is Ti-17nm
First dielectric layer D1 SiO2-200nm
The central reflecting layer R is Al-100nm
First dielectric layer D1 SiO2-200nm
The first metal light splitting layer M1 is Ti-17nm
Second dielectric layer D2 TiO2-135nm。
The central reflecting layer can be replaced by a layered or alloy structure of Ag, Sn, and Al, and the structure combination of the light-variable film layer according to this embodiment can display red at a vertical angle and another color at a second viewing angle, and the color at the second viewing angle is usually yellow, yellow-green, and green according to the design structure.
FIG. 13 is the normal observed reflectance spectrum (left) for the 7-layer structure of example 5; 0 degree-60 degree chromaticity variation track (right)
Referring to fig. 13, it can be seen that, in the visible spectrum range of 380nm-780nm, the average reflectances of the blue, green and yellow spectral bands are low, the average reflectivity of the red band is high, and the main peak is 670nm for the reflectance spectrum of the 7-layer red optical color-changing flake structure of this embodiment. The color and the variation curve are shown in fig. 14, according to the description of the color characteristics by the CIE-1931 standard colorimetry system, under the conditions of a white light source and a CIE-1931 standard observer, for the above 7-layer symmetric Red light variation structure, the chromaticity coordinate is 0.573 and y is 0.309 when viewed perpendicularly, the irregular color block area is constructed by the Red chromaticity coordinate (Red) of 0.513-0.73 and y of 0.228-0.345, the structure has the chromaticity coordinate of 0.381 and y of 0.485 when viewed at an angle of 60 degrees, and the corresponding color is displayed as yellow green.
Comparative example 2:
reference example 5: the difference lies in the thickness of the first dielectric layer and the first metal light splitting layer.
The red optical color-changing sheet is provided with a central reflecting layer, and a first dielectric layer, a first metal light splitting layer and a second dielectric layer are symmetrically arranged from the central reflecting layer to the outside in sequence, wherein the specific film system structure is as follows:
second dielectric layer D2 TiO2-135nm
The first metal light splitting layer M1 is Ti-16nm
First dielectric layer D1 SiO2-224nm
The central reflecting layer R is Al-100nm
First dielectric layer D1 SiO2-224nm
The metal light splitting layer M1 is Ti-17nm
Second dielectric layer D2 TiO2-135nm。
Referring to fig. 15, it can be seen that, in the visible spectrum range of 380nm-780nm, the average reflectivity of blue, green and yellow spectrum bands is low, the average reflectivity of red band is high, and the main peak is at 730nm, for the reflectivity spectrum of the 7-layer red optical color-changing flake structure of this comparative example. The color and the variation curve are shown in fig. 16, according to the description of the color characteristics by the CIE-1931 standard colorimetry system, under the conditions of a white light source and a CIE-1931 standard observer, for the above 7-layer symmetric Red light variation structure, the chromaticity coordinate is 0.573 and y is 0.309 when viewed perpendicularly, the color block irregular area is constructed by the purple Red chromaticity coordinate (purple Red) of the invention, x is 0.513-0.73 and y is 0.228-0.345, the structure has the chromaticity coordinate of 0.381 and y is 0.485 when viewed at an angle of 60 degrees, and the corresponding color shows yellow green.
The preparation method and the steps are similar to those of the example 1.
Example 6:
the utility model provides a red optics thin slice that discolours, the thin slice has central reflection stratum, outwards is equipped with first dielectric layer, first metal beam splitting layer, second dielectric layer, second metal beam splitting layer, third dielectric layer symmetrically in proper order by central reflection stratum, and specific film system structure is as follows:
third dielectric layer D3 TiO2-60nm。
The second metal light splitting layer M2 is Ti-5nm
Second dielectric layer D2 TiO2-35nm
The first metal light splitting layer M1 is Ti-11nm
First dielectric layer D1 SiO2-190nm
The central reflecting layer R is Ti-100nm
First dielectric layer D1 SiO2-190nm
The first metal light splitting layer M1 is Ti-11nm
Second dielectric layer D2 TiO2-35nm。
The second metal light splitting layer M2 is Ti-5nm
Third dielectric layer D3 TiO2-60nm。
The structure combination of the optically variable film according to this embodiment can display red at a vertical angle and another color at a second viewing angle, and the colors at the second viewing angle are usually orange, yellow, or black,
Referring to fig. 17, it can be seen that, in the visible spectrum range of 380nm-780nm, the average reflectances of the blue, green and yellow spectral bands are low, the average reflectivity of the red band is high, and the main peak is located at 720nm for the reflectivity spectrum of the 7-layer red optical color-changing flake structure of this embodiment. The color and the variation curve are shown in fig. 18, according to the description of the color characteristics by the CIE-1931 standard colorimetry system, under the conditions of a white light source and a CIE-1931 standard observer, for the above 11-layer symmetric Red light variation structure, the chromaticity coordinate is 0.552, the chromaticity coordinate is 0.319, the color block structure is located in an irregular area constructed by 0.513-0.73 of the Red chromaticity coordinate (Red) x, and 0.228-0.345, the chromaticity coordinate is 0.4, and the y is 0.43, when observed at an angle of 60 degrees, the corresponding color block structure shows yellow.
The preparation method and the steps are similar to those of the example 1.
Claims (7)
1. The red optical color-changing sheet is characterized by comprising a central reflecting layer, wherein a basic structure of a first dielectric layer, a first metal light-splitting layer and a second dielectric layer is symmetrically or asymmetrically arranged from the central reflecting layer to the outside in sequence, and the central reflecting layer is made of more than one of Al, Cr, Ti, Ni, Fe, Cu, Ag, Au, Sn, Mn, Co, Zr, Mo, W and Sm; the first dielectric layer is made of MgF2、AlF3、Na3AlF6、BaF2、NdF3、CaF3、LiF、SiO2、SiO、Al2O3、TiOX、LiTiOx、Ta2O5、ZrO2、Nb2O5、HfO2、Sb2O3、Fe2O3、CuO、NiO、Sm2O3、Nd2O3Wherein X is in the range of 1-2; the first metal light splitting layer is made of Al, Cr, Ti, Ni,Fe. More than one of Cu, Ag, Au, Sn, Mn, Co, Zr, Mo, W, Sm and the like, and the material of the second dielectric layer is SiO2、SiO、Al2O3、TiOX、LiTiOx、Ta2O5、ZrO2、Nb2O5、HfO2、Sb2O3、Fe2O3、CuO、NiO、Sm2O3、Nd2O3Wherein, the value range of X is 1-2, the thickness of the central reflecting layer is 30-150nm, the thickness of the first dielectric layer is 100-250nm, the thickness of the first metal light splitting layer is 1-38nm, and the thickness of the second dielectric layer is 10-150 nm.
2. The red photochromic flake of claim 1, wherein the second dielectric layer has a thickness of from 15 to 90 nm.
3. The red optically variable sheet according to claim 1 or 2, wherein the central reflective layer is a composite central reflective layer or a magnetic core central reflective layer having a multilayer structure or an alloy structure of Al, Cr, Ti, Ni, Fe, Cu, Ag, Au, Sn, Mn, Co, Zr, Mo, W, Sm.
4. The red optically variable sheet according to claim 1 or 2, wherein a second metal-light-splitting layer is provided on the outside of the second dielectric layer, the second metal-light-splitting layer has a thickness of 0 to 7nm, and the material of the second metal-light-splitting layer is one of Al, Cr, Ti, Ni, Fe, Au, Sn, Mn, Co, Zr, Mo, W, Sm.
5. The red photochromic flake according to claim 1 or 2, wherein a third dielectric layer is arranged outside the second metal light-splitting layer, the thickness of the third dielectric layer is 0-250nm, and the material of the third dielectric layer is SiO2、SiO、Al2O3、TiOX、LiTiOx、Ta2O5、ZrO2、Nb2O5、HfO2、Sb2O3、Fe2O3、CuO、NiO、Sm2O3、Nd2O3Wherein X is in the range of 1-2.
6. A method of making a red photochromic flake according to claim 4 comprising the steps of:
1) sequentially plating/coating an isolation film layer on a glass or stainless steel or flexible plastic substrate;
2) sequentially plating a second metal light splitting layer, a second medium layer, a first metal light splitting layer, a first medium layer, a central reflecting layer, a first medium layer, a first metal light splitting layer, a second medium layer and a second metal light splitting layer; the materials of the first half period and the second half period of the film layer can be the same or different;
3) circulating the step 1) and the step 2) for a plurality of times;
4) demoulding, cleaning, crushing, surface modifying and other post-treatments to obtain the required red light variable slice;
or, directly and sequentially plating a central reflecting layer, a first dielectric layer, a first metal light splitting layer, a second dielectric layer and a second metal light splitting layer on the substrate.
7. The method of claim 6, wherein the coating is performed by physical vapor deposition/chemical vapor deposition.
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| CN111665577A (en) * | 2020-04-20 | 2020-09-15 | 湖北卫东化工股份有限公司 | Inspection mirror capable of visually identifying snowfield camouflage and preparation method |
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