Disclosure of Invention
In order to solve the problems of the prior art, the invention provides an iron-based optically variable pigment and a manufacturing method and application thereof.
In one aspect, there is provided an iron-based optically variable pigment comprising: an iron oxide center layer, a plurality of high refractive index layers, and a plurality of low refractive index layers; the high-refractive-index layers and the low-refractive-index layers are alternately stacked and symmetrically arranged on the upper main surface and the lower main surface of the iron oxide central layer; and a plurality of cavity structures are arranged inside the iron oxide central layer.
Further, the material of the high refractive index layer is a transparent medium material with a refractive index higher than 2.0, and the material of the low refractive index layer is a transparent medium material with a refractive index lower than 1.65.
Further, the material of the high refractive index layer is at least one of titanium dioxide, hafnium dioxide, tantalum pentoxide, zirconium dioxide and zinc sulfide.
Further, the material of the low refractive index layer is one of silicon dioxide, aluminum oxide and magnesium fluoride or a mixture of the silicon dioxide, the aluminum oxide and the magnesium fluoride.
Further, the material of the iron oxide central layer is one of ferrous oxide, ferric oxide and ferroferric oxide.
Further, the thickness of the iron oxide central layer is 20 nm-100 nm.
Further, the core structure of the iron-based optically variable pigment is as follows: (aLbH)SF(bHaL)SOr (aLbHcL)SF(cLbHaL)SOr (bHaL)SF(aLbH)SOr (dHaLbH)SF(bHaLdH)S;
Wherein, F represents the iron oxide central layer, H represents the central quarter optical thickness of the high refractive index layer, L represents the central quarter optical thickness of the low refractive index layer, a, b, c, d represent the thickness coefficient factor taking the quarter optical thickness as the unit, a, b, c, d are equal or unequal, are real numbers larger than zero, are distributed around F as central symmetry, and S represents the repeated periodicity, is a positive integer larger than zero.
In another aspect, there is provided a method of manufacturing an iron-based optically variable pigment, the method including:
providing two iron oxide material film layers and a plurality of iron oxide material film layer strips,
binding two iron oxide material film layers to form a cavity structure through iron oxide material film layers to obtain an iron oxide center layer;
symmetrically vacuum evaporating and plating a plurality of high-refractive-index layers and a plurality of low-refractive-index layers which are alternately stacked on the main surfaces of the upper side and the lower side of the iron oxide central layer to obtain an optically variable pigment layer;
crushing the optically variable pigment layer;
and screening the iron-based optically variable pigment from the crushed optically variable pigment layer.
Further, the iron oxide material film layer strip comprises: the cavity structure comprises warp-wise iron oxide material film layers and weft-wise iron oxide material film layers, wherein the warp-wise iron oxide material film layers are used for binding the two iron oxide material film layers along the warp direction, and the weft-wise iron oxide material film layers are used for binding the two iron oxide material film layers along the weft direction to form the cavity structure.
The invention also provides an application, which comprises the iron-based optically variable pigment, and the iron-based optically variable pigment is used for preparing cosmetics.
The technical scheme provided by the embodiment of the invention has the following beneficial effects: the invention provides the full-medium optically variable pigment which is composed of the iron oxide material as the symmetrical center layer and the transparent medium material with high and low refractive indexes, and the iron oxide is utilized to increase the freedom degree of color regulation and control, so that better secondary peak absorption can be realized, and a better reflection spectrum is formed to show more saturated colors. Secondly, a cavity structure is arranged in the iron oxide center layer, so that the surface of the iron oxide center layer is provided with a convex structure, and the color modulation of the convex structure formed by the cavity structure depends on incident light and an observation angle, therefore, when the observation angle changes, the color of the optically variable pigment can obviously change along with the change of the observation angle, bright color information can be provided, the defect that the color information of the traditional optically variable pigment is reduced under a large angle is overcome, the problem that the optically variable pigment of the all-dielectric material can realize higher saturation degree only by the deposition of multiple layers of films is solved, and the manufacturing cost is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example one
An iron-based optically variable pigment comprising: an iron oxide center layer, a plurality of high refractive index layers, and a plurality of low refractive index layers; the plurality of high-refractive-index layers and the plurality of low-refractive-index layers are alternately stacked and symmetrically arranged on the upper main surface and the lower main surface of the iron oxide central layer; a plurality of cavity structures are arranged inside the iron oxide central layer.
The material of the high refractive index layer may be at least one of titanium dioxide, hafnium dioxide, tantalum pentoxide, zirconium dioxide, and zinc sulfide, or another transparent dielectric material with a refractive index higher than 2.0; the material of the low refractive index layer can be one of silicon dioxide, aluminum oxide, magnesium fluoride or a mixture of the silicon dioxide, the aluminum oxide and the magnesium fluoride, or other low refractive index materials with a refractive index smaller than 1.65. The iron oxide central layer can be ferrous oxide, ferric oxide and ferroferric oxide. Iron oxide is a ubiquitous compound in nature, and the shadow of iron oxide can be found in various parts of ecosystems such as atmosphere, soil, biosphere, water circle, rock circle and the like. For a multilayer structure consisting of such centers of symmetry, the maximum achievable reflectivity depends not only on the number of layers and the refractive indices of the layers, but also on the thickness of the central iron oxide, preferably 20nm to 100 nm.
In addition, the core structure of the iron-based optically variable pigment is as follows: (aLbH)SF(bHaL)SOr (aLbHcL)SF(cLbHaL)SOr (bHaL)SF(aLbH)SOr (dHaLbH)SF(bHaLdH)S(ii) a Wherein, F represents the iron oxide central layer, H represents the central quarter optical thickness of the high refractive index layer, L represents the central quarter optical thickness of the low refractive index layer, a, b, c, d represent the thickness coefficient factor with the quarter optical thickness as the unit, a, b, c, d are equal or unequal and are real numbers larger than zero and are distributed symmetrically around the F as the center, and S represents the repeated periodicity and is a positive integer larger than zero. The interference color gamut and the effect of the interference colors on flop depend on the thickness of the layers of the multilayer system and on the number of layers. The thickness of the corresponding film layer is adjusted according to the refractive indexes of all the materials and the central ferrite material and the cavity structure arranged in the iron oxide central layer, and the pigments can be selectively reflected within the range of 400 nanometers (ultraviolet light) to 750 nanometers (red light) in wavelength. In precision optics, such as the production of mirror layers, beam splitters or filters, all-dielectric materials use up to 100 or more layers to meet transmission and reflectivity requirements, which are not necessary for the preparation of pigments, the number of layers of iron-based optically variable pigments being typically less than 30.
The invention also provides an all-dielectric optical change pigment which is composed of an iron oxide material as a symmetrical central layer and a high-low refractive index transparent dielectric material, and the layered structure has the characteristics of bright color and obvious color variation with angle. Based on the all-dielectric structure, the freedom degree of color regulation is increased by utilizing the iron oxide, and better secondary peak absorption can be realized, so that a better reflection spectrum is formed to show more saturated colors, the limitation of chromium and nickel heavy metal materials is solved, and the environmental protection of the materials is realized.
Secondly, a cavity structure is arranged inside the iron oxide center layer, so that the surface of the iron oxide center layer is provided with a convex structure, the color modulation of the convex structure formed by the cavity structure depends on incident light and an observation angle, when the observation angle changes, the color of the optically variable pigment can obviously change along with the change of the observation angle, for the traditional optically variable pigment structure, the chroma and the brightness of the color of the traditional optically variable pigment structure are greatly reduced, the color is dark, the convex structure formed by the cavity structure arranged inside the iron oxide center layer has large-angle diffraction, bright color information can be provided, and the defect that the color information of the traditional optically variable pigment is reduced under large angles is overcome.
Example two
The iron-based optically variable pigment is in a structure of changing red into golden optically variable pigment, a film layer in the structure is only a layer number schematic diagram, an iron oxide central layer prepared from ferrous oxide materials is adopted in the middle of the iron oxide central layer, a silicon dioxide material low-refractive-index layer is arranged on the upper side of the iron oxide central layer, a titanium dioxide material high-refractive-index layer is arranged on the silicon dioxide material low-refractive-index layer, the high-refractive-index layer and the low-refractive-index layer are alternately arranged, six layers are arranged on the upper side, the lower side is symmetrical and identical in six layers, and the distances between the materials and the thicknesses on two sides are symmetrically distributed. The specific film arrangement is as follows in table 1:
table 1: example two iron-based optically variable pigment layer Structure and thickness parameters
FIG. 2 is a graph of reflectance versus wavelength of an iron-based optically variable pigment according to a second embodiment of the present invention; the absorption of the all-dielectric material in a visible light wave band is not obvious enough, the absorption effect of the middle iron oxide material as an interlayer can be seen to be obvious, the weakening effect of a secondary peak is always obvious along with the increase of the angle of an incident light source through the cavity structure, and the absorption at a long wave position is increased along with the increase of the angle. The 0-45 degree reflectivity spectrum is shown in fig. 2, and it can be seen that the first-order interference peak bandwidth of the material spectral reflectivity curve in the long wave band is narrowed, the identification capability of human eyes for color drift is increased, the color saturation of the material is increased, the central wavelength is 650nm when the structure is vertically observed, the central wavelength is 590nm when the structure is observed with an inclination angle of 45 degrees, the structure is orange, and the central wavelength is 560nm when the structure is observed with an inclination angle of 60 degrees, and the structure is golden.
Fig. 3 is a coordinate variation graph of 0-60 degree chromaticity of an iron-based optically variable pigment provided by a second embodiment of the present invention; the structural chromaticity shift trajectory is shown in fig. 3 and table 2:
table 2: example two iron-based optically variable pigment chromaticity coordinate change tables
| Type (B)
|
x
|
y
|
z
|
C*
|
| Incident angle of 0 °
|
0.48405
|
0.42380
|
0.09215
|
116.86
|
| Incident angle of 45 °
|
0.42511
|
0.44853
|
0.12635
|
97.976
|
| Incident angle of 60 °
|
0.39826
|
0.44500
|
0.15674
|
88.018 |
Therefore, the invention utilizes the interference absorption mode to increase the obvious absorption effect of short wave, thereby increasing the saturation of color. Meanwhile, by utilizing the iron-based optically variable pigment and the iron oxide central layer cavity structure, the absorption response to short waves and long waves at different angles is different, the bandwidth of a first-order interference peak is reduced, the maximum reflectivity is not reduced, and the color saturation is increased at a large angle. The problem that the all-dielectric optically variable pigment can realize higher saturation only by depositing a plurality of films is solved.
EXAMPLE III
The iron-based optically variable pigment is in a structure that green becomes blue, the film layers in the figure are only schematic in number of layers, an iron oxide center layer prepared from a ferric oxide material is adopted in the middle of the iron oxide center layer, a silica material low-refractive-index layer is arranged on the upper side of the iron-based optically variable pigment, a high-refractive-index material titanium dioxide layer is arranged on the low-refractive-index material silicon dioxide layer, the high-refractive-index material film layers and the low-refractive-index material film layers are alternately arranged, the upper side of the iron-based optically variable pigment is provided with 3 layers, the lower side of the iron-based optically variable pigment is symmetrical to the same 3 layers, and the materials with the same distance on the two sides and the thickness of the iron-based optically variable pigment are symmetrically distributed. The specific film arrangement is shown in table 3 below:
table 3: example Structure and thickness parameter of optically variable three-iron-based pigment layer
FIG. 5 is a graph of reflectance versus wavelength of an iron-based optically variable pigment provided in example III of the present invention; the absorption of the all-dielectric material in a visible light wave band is not obvious enough, the absorption effect of the middle iron oxide material as an interlayer can be seen to be obvious, the weakening effect of a secondary peak is always obvious along with the increase of the angle of an incident light source through the cavity structure, and the absorption at a long wave position is increased along with the increase of the angle. The 0-45-degree reflectivity spectrum is shown in fig. 5, and the first-order interference peak bandwidth of the reflectivity curve of the discharge spectrum in a long wave band is narrowed, the identification capability of human eyes on color drift is improved, the color saturation of the material is improved, the central wavelength is 530nm when the structure is vertically observed, the spectral line width is only 100nm, the central wavelength is 500nm when emerald green is observed in an inclined 45-degree angle, the spectral line width is reduced to 80nm, the color saturation is further improved, cyan is shown, the central wavelength is 470nm when the structure is observed in an inclined 60-degree angle, and sky blue is shown.
Fig. 6 is a coordinate variation graph of 0-60 degree chromaticity of an iron-based optically variable pigment provided by a third embodiment of the present invention; the structural chromaticity shift trajectory is shown in fig. 6 and table 4:
table 4: example two iron-based optically variable pigment chromaticity coordinate change tables
| Type (B)
|
x
|
y
|
z
|
C*
|
| Incident angle of 0 °
|
0.31533
|
0.49780
|
0.18688
|
92.16
|
| Incident angle of 45 °
|
0.18558
|
0.39054
|
0.42388
|
80.646
|
| Incident angle of 60 °
|
0.19526
|
0.24312
|
0.56162
|
57.913 |
Therefore, the iron-based optically variable pigment and the iron oxide central layer cavity structure are utilized, the absorption response to short waves and long waves at different angles is different, the bandwidth of a first-order interference peak is reduced, the maximum reflectivity is not reduced, and the color saturation is increased at a large angle. The problem that the all-dielectric optically variable pigment can realize higher saturation only by depositing a plurality of films is solved.
Example four
An iron-based optically variable pigment is shown in figure 7 and is in a structure that gold becomes green, the film layers in the figure are only schematic in number of layers, an iron oxide central layer prepared from a ferric oxide material is adopted in the middle, a silica material low-refractive-index layer is arranged on the upper side of the iron-based optically variable pigment, a titanium dioxide material high-refractive-index layer is arranged on the silica material low-refractive-index layer, the high-refractive-index layer and the low-refractive-index layer are alternately arranged, six layers are arranged on the upper side, six layers are symmetrically arranged on the lower side of the iron-based optically variable pigment, and the materials with the same distance on the two sides and the thickness are symmetrically distributed. The specific film arrangement is shown in table 5 below:
table 5: example four iron-based optically variable pigment layer Structure and thickness parameters
Fig. 8 is a graph of reflectivity-wavelength of an iron-based optically variable pigment according to the fourth embodiment of the present invention, where the absorption of all dielectric materials in the visible light band is not significant enough, and it can be seen that the absorption of the intermediate iron oxide material as an interlayer is significant, the attenuation of the secondary peak is always significant along with the increase of the angle of the incident light source through the cavity structure, and the absorption at the long wavelength is increased along with the increase of the angle. The 0-45-degree reflectivity spectrum is shown in fig. 8, and the first-order interference peak bandwidth of the reflectivity curve of the discharge spectrum in a long wave band is narrowed, the identification capability of human eyes on color drift is improved, the color saturation of a material is increased, the central wavelength is located at 575nm when the structure is vertically observed, the spectral line width is only 100nm, the central wavelength is located at 525nm when golden yellow is observed at an inclined 45-degree angle, the spectral line width is reduced to 80nm, the color saturation is further improved, the grass green is presented, the central wavelength is located at 510nm when the structure is observed at an inclined 60-degree angle, and the emerald green is presented.
Fig. 9 is a 0-60 degree chromaticity coordinate diagram of an iron-based optically variable pigment provided in the fourth embodiment of the present invention; the structural chromaticity shift trajectory is shown in fig. 9 and table 6:
table 6: example four iron-based optical variable pigment chromaticity coordinate change table
| Type (B)
|
x
|
y
|
z
|
C*
|
| Incident angle of 0 °
|
0.39185
|
0.43042
|
0.17773
|
60.049
|
| Incident angle of 45 °
|
0.27481
|
0.47049
|
0.25471
|
76.389
|
| Incident angle of 60 °
|
0.22177
|
0.40925
|
0.36898
|
66.573 |
Therefore, the iron-based optically variable pigment and the iron oxide central layer cavity structure are utilized, the absorption response to short waves and long waves at different angles is different, the bandwidth of a first-order interference peak is reduced, the maximum reflectivity is not reduced, and the color saturation is increased at a large angle. The problem that the all-dielectric optically variable pigment can realize higher saturation only by depositing a plurality of films is solved.
EXAMPLE five
An iron-based optically variable pigment is shown in figure 10, and is of an emerald green, deep blue optically variable pigment structure, an iron oxide center layer made of a ferroferric oxide material is adopted in the middle of the optically variable pigment, a silica material low-refractive-index layer is arranged on the upper side of the optically variable pigment, a titanium dioxide material high-refractive-index layer is arranged on the silica material low-refractive-index layer, the high-refractive-index layer and the low-refractive-index layer are alternately arranged, 5 layers are arranged on the upper side of the optically variable pigment, the lower side of the optically variable pigment is symmetrical and identical in 5 layers, and materials with the same distance on two sides and the same thickness are symmetrically distributed. The specific film arrangement is shown in table 7 below:
table 7: example two iron-based optically variable pigment layer Structure and thickness parameters
Fig. 11 is a graph of reflectivity-wavelength curve of an iron-based optically variable pigment provided in example five of the present invention; the absorption of the all-dielectric material in a visible light wave band is not obvious enough, the absorption effect of the middle iron oxide material as an interlayer can be seen to be obvious, the weakening effect of a secondary peak is always obvious along with the increase of the angle of an incident light source through the cavity structure, and the absorption at a long wave position is increased along with the increase of the angle. The 0-45 degree reflectivity spectrum is shown in fig. 11, and it can be seen that the first-order interference peak bandwidth of the material spectrum reflectivity curve in the long wave band is narrowed, the identification capability of human eyes for color drift is increased, the color saturation of the material is increased, the central wavelength is 510nm when the structure is vertically observed, the spectral line width is only 70nm, the central wavelength is 470nm when emerald green is observed in an inclined 45 degree angle, the spectral line width is reduced to 60nm, the color saturation is further improved, sky blue is presented, the central wavelength is 460nm when the structure is observed in an inclined 60 degree angle, and deep blue is presented.
Fig. 12 is a 0-60 degree chromaticity coordinate diagram of an iron-based optically variable pigment provided in the fifth embodiment of the present invention; the structural chromaticity shift trajectory is shown in fig. 12 and table 8:
table 8: example wu-fe-based optically variable pigment chromaticity coordinate transformation table
| Type (B)
|
x
|
y
|
z
|
C*
|
| Incident angle of 0 °
|
0.19742
|
0.49258
|
0.31001
|
107.986
|
| Incident angle of 45 °
|
0.15198
|
0.21881
|
0.62921
|
76.471
|
| Incident angle of 60 °
|
0.19104
|
0.13740
|
0.67157
|
90.369 |
Therefore, the full-medium optically variable pigment based on the iron oxide as the central layer utilizes the interference absorption mode to increase the color regulation and control effect of the optically variable pigment, so that the structure has obvious absorption effect on short waves to weaken secondary peaks, thereby increasing the saturation of colors. Meanwhile, the structure is utilized to have different absorption responses to short waves and long waves at different angles, so that the bandwidth of a first-order interference peak is reduced, the maximum reflectivity is not reduced, and the color saturation is increased at a large angle. The problem that the full-medium material optically variable pigment can realize higher saturation only by the deposition of multiple layers of films is solved. The raw material adopts the compound iron oxide which is commonly existing in nature and is easy to synthesize in a laboratory. The iron and oxygen are chemically combined to form the iron oxide, so that the material has the characteristic of environmental friendliness and is beneficial to large-scale preparation of the material.
EXAMPLE six
A method for manufacturing an iron-based optically variable pigment, the method comprising the steps of:
step (1): providing two iron oxide material film layers and a plurality of iron oxide material film layer strips.
Step (2): and (3) binding the two iron oxide material film layers through the iron oxide material film layer strips to form a cavity structure, so as to obtain the iron oxide center layer.
Referring to fig. 13, the iron oxide material film strip includes: the iron oxide material film layer 501 is connected with the two iron oxide material film layers along the warp direction, and the iron oxide material film layer 502 is connected with the two iron oxide material film layers along the weft direction, so that the hollow cavity structure is formed.
And (3): and symmetrically vacuum evaporating and plating a plurality of high-refractive-index layers and a plurality of low-refractive-index layers which are alternately stacked on the main surfaces of the upper side and the lower side of the iron oxide central layer to obtain the optically variable pigment layer.
And (4): and crushing the optically variable pigment layer.
And (5): and screening the iron-based optically variable pigment from the crushed optically variable pigment layer.
The invention also provides an application, which comprises the iron-based optically variable pigment, and the iron-based optically variable pigment is used for preparing cosmetics. Is particularly applied to the preparation of color cosmetics, eye shadows, lip gloss, lipstick, eye liner liquid, eye liner paste, eyebrow pencils, nail beautifiers, nail glue, nail polish, nail sheets and the like.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.