CN114891368B - Magnetic optically variable pigment - Google Patents
Magnetic optically variable pigment Download PDFInfo
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- CN114891368B CN114891368B CN202210489739.8A CN202210489739A CN114891368B CN 114891368 B CN114891368 B CN 114891368B CN 202210489739 A CN202210489739 A CN 202210489739A CN 114891368 B CN114891368 B CN 114891368B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
- C09C1/003—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer
- C09C1/0033—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index comprising at least one light-absorbing layer consisting of a metal or an alloy
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/20—Interference pigments comprising a layer with a concentration gradient or a gradient of the refractive index
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/301—Thickness of the core
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/302—Thickness of a layer with high refractive material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/303—Thickness of a layer with low refractive material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/306—Thickness of an absorbing layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2210/00—Special effects or uses of interference pigments
- C09C2210/50—Fluorescent, luminescent or photoluminescent properties
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Abstract
The application provides a magnetic optically variable pigment. The magnetic optically variable pigment comprises: the application utilizes the light scattering enhancement characteristic of the metal nano particles and the interference effect of the film stack filter layer to apply strong white light-induced plasmas to the field of light variation to obtain a novel magnetic optically variable pigment, the pigment has the effect of changing angle-dependent different colors and light-shade dynamic changes under the environment light, the hidden color appears in a dark area under the strong white light, and simultaneously, the bright area color and the hidden color change alternately along with the rotation of a visual angle, so that the pigment has multiple anti-counterfeiting effects and the anti-counterfeiting force is greatly improved.
Description
Technical Field
The application relates to the technical field of anti-counterfeiting, in particular to a magnetic optically variable pigment.
Background
The market is filled with fake and inferior commodities in the current society, so that normal market order is destroyed, and the rights and interests of consumers and the economic benefits of manufacturers are infringed. In order to prevent and fight the false-vending activities, various anti-counterfeiting technologies have been researched and developed. In recent years, optically variable pigments are being widely used in the field of high-end security.
The magnetic optically variable pigment combines two physical properties of magnetism and optically variable, and the pigment can control the pigment flake position in the ink layer through the action of a magnetic field. The pattern after fixed magnetism is changed along with the visual angle change of the naked eyes of an observer, and the image can show the characteristics of color change, flowing effect, brightness change and the like. The technology is applied to the anti-counterfeiting fields of bank notes, passports, bank checks and the like, and is an advanced first-line anti-counterfeiting technology before a project.
The structure and implementation principle of the existing magnetic optically variable pigment are reported in a large number, for example, the technical principle, structural design and preparation process of the magnetic optically variable film are studied in detail in the section of the Xiamen university's graduate paper ' study and application of the magnetic optically variable anti-counterfeiting film '. In addition, some counterfeit coins or goods are also occasionally packaged with interference type optically variable pigments, so that the traditional interference type optically variable pigments are used as a first-line anti-counterfeiting means for identifying authenticity of the masses, and gradually lose the public confidence. Therefore, there is an urgent need to explore and prepare new anti-counterfeiting magnetic pigments.
Disclosure of Invention
The application provides a magnetic optically variable pigment, which utilizes the light scattering enhancement characteristic of plasma metal nano particles and the interference effect of a film stack filter layer to enable a magnetic optically variable raw material to have multiple anti-counterfeiting effects.
In order to solve the technical problems, the application adopts a technical scheme that: provided is a magnetic optically variable pigment comprising: the film stack filter layer is provided with a magnetic material and a plurality of metal nano particles arranged on the surface of the film stack filter layer, and the structure of the film stack filter layer is (a) 1 H 1 a 2 L 1 a 3 H 2 ) n1 bN(a 4 H 3 a 5 L 2 a 6 H 4 ) n2 cM, where H 1 For the first high refractive index layer, L 1 For the first low refractive index layer, H 2 For the second high refractive index layer, H 3 Is the third high refractive index layer, L 2 Is the second low refractive index layer, H 4 A fourth high refractive index layer, N is an absorption layer, M is a magnetic core layer containing magnetic material, a 1 A is the film thickness coefficient of the first high refractive index layer 2 A, which is the film thickness coefficient of the first low refractive index layer 3 A is the film thickness coefficient of the second high refractive index layer 4 A is the film thickness coefficient of the third high refractive index layer 5 A is the film thickness coefficient of the second low refractive index layer 6 B is the film thickness coefficient of the absorption layer, c is the film thickness coefficient of the magnetic core layer, n1 and n2 are the corresponding medium film stack periods, and 0 < a 1 ≤5、0≤a 2 ≤5、0≤a 3 ≤5、0≤a 4 ≤5、0≤a 5 ≤5、0≤a 6 B is more than or equal to 5 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 3, and n1 and n2 are the corresponding medium film stack periods.
Further, the magnetic optically variable pigment comprises: the film stack filter layer is provided with a magnetic material, and a plurality of metal nano particles are arranged on the surface of the film stack filter layer; the structure of the film stack filter layer is (a) 1 H 1 a 2 L 1 a 3 H 2 ) n1 bN(a 4 H 3 a 5 L 2 a 6 H 4 ) n2 cM(a 6 H 4 a 5 L 2 a 4 H 3 ) n2 bN(a 3 H 2 a 2 L 1 a 1 H 1 ) n1 Wherein H is 1 For the first high refractive index layer, L 1 For the first low refractive index layer, H 2 For the second high refractive index layer, H 3 Is the third high refractive index layer, L 2 Is the second low refractive index layer, H 4 A fourth high refractive index layer, N is an absorption layer, M is a magnetic core layer containing magnetic material, a 1 A is the film thickness coefficient of the first high refractive index layer 2 A is the film thickness coefficient of the first low refractive index layer 3 A is the film thickness coefficient of the second high refractive index layer 4 A is the film thickness coefficient of the third high refractive index layer 5 A is the film thickness coefficient of the second low refractive index layer 6 B is the film thickness coefficient of the absorption layer, c is the film thickness coefficient of the magnetic core layer, wherein 0 < a 1 ≤5、0≤a 2 ≤5、0≤a 3 ≤5、0≤a 4 ≤5、0≤a 5 ≤5、0≤a 6 B is more than or equal to 5 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 3, and n1 and n2 are the corresponding medium film stack periods.
Further, the film stack filter layer is provided with a first main surface and a second main surface which are opposite, and a plurality of metal nano particles are arranged on the first main surface and the second main surface, so that the magnetic optically variable pigment is in a symmetrical structure taking the film stack filter layer as a center, or a plurality of metal nano particles are arranged on the first main surface or the second main surface.
Further, the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer and the fourth high refractive index layer are all materials with refractive indexes larger than 1.65; the first low refractive index layer and the second low refractive index layer are made of materials with refractive indexes smaller than or equal to 1.65.
Further, the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer and the fourth high refractive index layer are the same, or at least two of the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer and the fourth high refractive index layer are different.
Further, the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer, and the fourth high refractive index layer include: at least one of lanthanum titanate, titanium pentoxide, niobium pentoxide, zinc sulfide, zinc oxide, zirconium oxide, titanium dioxide, carbon, indium oxide, indium tin oxide, tantalum pentoxide, cerium oxide, yttrium oxide, europium oxide, iron oxide, ferric oxide, hafnium nitride, hafnium carbide, hafnium oxide, lanthanum oxide, magnesium oxide, neodymium oxide, praseodymium oxide, samarium oxide, antimony trioxide, silicon carbide, silicon nitride, silicon monoxide, selenium trioxide, tin oxide, and tungsten trioxide.
Further, the materials of the first low refractive index layer and the second low refractive index layer are the same, or the materials of the first low refractive index layer and the second low refractive index layer are different.
Further, the materials of the first low refractive index layer and the second low refractive index layer include: silica, alumina, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, calcium fluoride, lithium fluoride polystyrene, polyethylene, polymethyl methacrylate, polyamideimide, polyperfluoroethylene propylene, tetrafluoroethylene, chlorotrifluoroethylene, cellulose propionate, cellulose acetate butyrate, methylpentene polymer, homo-formaldehyde, acrylic resin, nitrocellulose, ethylcellulose, polypropylene, polysulfone, polyethersulfone, mica, heterogeneous isomorphous polymer, polybutene, ionomer, acrylic copolymer, styrene butadiene, polyvinyl chloride, urea formaldehyde, styrene acrylonitrile and polycarbonate.
Further, the material of the absorbent layer includes: titanium, aluminum, chromium, nickel, palladium, titanium, silicon, vanadium, cobalt, iron, carbon, tin, tungsten, molybdenum, rhodium, niobium, and an alloy of at least two of these.
Further, the physical thickness of the absorption layer is 5nm to 100nm.
Further, the magnetic core layer has a single-layer structure; the material of the magnetic core layer includes: an oxide of at least one of iron, cobalt, nickel, gadolinium, terbium, dysprosium, and erbium, or an alloy of at least two; alternatively, the material of the magnetic core layer includes: at least one of ferrosilicon, ferroaluminum, ferrosilicon aluminum, ferrosilicon chromium, and ferronickel molybdenum.
Further, the magnetic core layer is a multilayer structure, and the structure of the magnetic core layer: m is M 1 M 0 M 2 、M 0 M 1 M 0 、M 0 M 1 、M 1 D 1 M 0 D 2 M 2 、M 0 D 1 M 1 D 2 M 0 Or M 1 D 1 M 0 Wherein M is 0 Is a magnetic film layer, M 1 And M 2 Is a metal film layer D 1 And D 2 Is a dielectric film layer.
Further, the materials of the magnetic film layer include: the material of the magnetic film layer comprises at least one of iron, cobalt, nickel, gadolinium, terbium, dysprosium, erbium or an oxide of at least one of the oxides or an alloy of at least two of the oxides, or at least one of ferrosilicon alloy, ferroaluminum alloy, ferrosilicon aluminum alloy, ferrosilicon chromium alloy and ferronickel molybdenum alloy; the materials of the metal film layer comprise: at least one of aluminum, silver, gold, copper, platinum, tin, titanium, palladium, rhodium, niobium, and chromium, or an alloy of at least two thereof; the dielectric film layer comprises the following materials: at least one of silica, alumina, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, and calcium fluoride.
Further, the metal nano particles are distributed at intervals, and the gaps among the metal nano particles are 2nm-1mm.
Further, the material of the metal nanoparticles includes: at least one of aluminum, silver, gold, copper, platinum, ruthenium, palladium, rhodium, cobalt, iron, nickel, lead, osmium, and iridium, or an alloy of at least two thereof.
The embodiment of the application has the beneficial effects that: unlike the prior art, the magnetic optically variable pigment of the present application comprises: the application utilizes the light scattering enhancement characteristic of metal nano particles and the interference effect of the film stack filter layer to apply strong white light-induced plasmas to the field of light variation to obtain a novel magnetic light-variable pigment, the pigment has the effect of changing angle-dependent different colors and light-shade dynamic changes under the environment light, the hidden color appears in a dark area under the strong white light, and meanwhile, the bright area color and the hidden color change alternately along with the rotation of a visual angle, so that the pigment has multiple anti-counterfeiting effects, the anti-counterfeiting force is greatly improved, and the pigment has higher color saturation and richer color gamut space.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a magnetic optically variable pigment according to one embodiment of the present application;
FIG. 2 is a schematic diagram of an embodiment of a film stack filter in the magnetic optically variable pigment of FIG. 1.
Detailed Description
The present application will be described in detail below with reference to specific embodiments shown in the drawings. These embodiments are not intended to limit the application and structural, methodological, or functional modifications of these embodiments that may be made by one of ordinary skill in the art are included within the scope of the application.
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 a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present application.
The application provides a magnetic optically variable pigment, which adopts a special arrangement structure, utilizes the scattered light enhancement characteristic of metal nano particles under local plasmon resonance, improves the F-P (Fabry-Perot) interference cavity structure, ensures that the magnetic optically variable pigment has multiple optical color changing effects, greatly increases the anti-counterfeiting force and further improves the color saturation of the pigment.
As shown in fig. 1, fig. 1 is a schematic structural diagram of an embodiment of a magnetic optically variable pigment provided in the present application, and the magnetic optically variable pigment 10 includes: the film stack filter layer 11 is provided with a magnetic material and a plurality of metal nano particles 12 arranged on the surface of the film stack filter layer 11.
Specifically, the structure of the film stack filter layer 11 is (a 1 H 1 a 2 L 1 a 3 H 2 ) n1 bN(a 4 H 3 a 5 L 2 a 6 H 4 ) n2 cM, where H 1 For the first high refractive index layer, L 1 For the first low refractive index layer, H 2 For the second high refractive index layer, H 3 Is the third high refractive index layer, L 2 Is the second low refractive index layer, H 4 A fourth high refractive index layer, N is an absorption layer, M is a magnetic core layer containing magnetic material, a 1 A is the film thickness coefficient of the first high refractive index layer 2 Film thickness coefficient for the first low refractive index layer、a 3 A is the film thickness coefficient of the second high refractive index layer 4 A is the film thickness coefficient of the third high refractive index layer 5 A is the film thickness coefficient of the second low refractive index layer 6 B is the film thickness coefficient of the absorption layer, c is the film thickness coefficient of the magnetic core layer, n1 and n2 are the corresponding medium film stack periods, wherein 0 < a 1 ≤5、0≤a 2 ≤5、0≤a 3 ≤5、0≤a 4 ≤5、0≤a 5 ≤5、0≤a 6 B is more than or equal to 5 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 3, and n1 and n2 are the corresponding medium film stack periods.
For example, a 1 ＝1，a 2 ＝1，a 3 ＝1，a 4 ＝1，a 5 ＝1，a 6 =1, b=1, c=1, n1=1, n2=1, and the corresponding structure of the stack filter 11 is H 1 L 1 H 2 NH 3 L 2 H 4 M, that is, the film thickness coefficient of the first high refractive index layer is 1, the film thickness coefficient of the first low refractive index layer is 1, the film thickness coefficient of the second high refractive index layer is 1, the film thickness coefficient of the third high refractive index layer is 1, the film thickness coefficient of the second low refractive index layer is 1, the film thickness coefficient of the fourth high refractive index layer is 1, the film thickness coefficient of the absorption layer is 1, and the film thickness coefficient of the magnetic core layer containing the magnetic material is 1. As shown in fig. 2, the stack filter layer 11 has a structure in which a first high refractive index layer 111, a first low refractive index layer 112, a second high refractive index layer 113, an absorption layer 114, a third high refractive index layer 115, a second low refractive index layer 116, a fourth high refractive index layer 117, and a magnetic core layer 118 containing a magnetic material are stacked in this order.
In another embodiment, the magnetic optically variable pigment 10 includes a film stack filter layer 11 with a magnetic material and a plurality of metal nanoparticles 12 disposed on the surface of the film stack filter layer 11.
Wherein the structure of the film stack filter layer 11 is (a) 1 H 1 a 2 L 1 a 3 H 2 ) n1 bN(a 4 H 3 a 5 L 2 a 6 H 4 ) n2 cM(a 6 H 4 a 5 L 2 a 4 H 3 ) n2 bN(a 3 H 2 a 2 L 1 a 1 H 1 ) n1 . Wherein H is 1 For the first high refractive index layer, L 1 For the first low refractive index layer, H 2 For the second high refractive index layer, H 3 Is the third high refractive index layer, L 2 Is the second low refractive index layer, H 4 A fourth high refractive index layer, N is an absorption layer, M is a magnetic core layer containing magnetic material, a 1 A is the film thickness coefficient of the first high refractive index layer 2 A is the film thickness coefficient of the first low refractive index layer 3 A is the film thickness coefficient of the second high refractive index layer 4 A is the film thickness coefficient of the third high refractive index layer 5 A is the film thickness coefficient of the second low refractive index layer 6 B is the film thickness coefficient of the absorption layer, c is the film thickness coefficient of the magnetic core layer, wherein 0 < a 1 ≤5、0≤a 2 ≤5、0≤a 3 ≤5、0≤a 4 ≤5、0≤a 5 ≤5、0≤a 6 B is more than or equal to 5 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 3, and n1 and n2 are the corresponding medium film stack periods.
For example, a 1 ＝1，a 2 ＝1，a 3 ＝1，a 4 ＝1，a 5 ＝1，a 6 =1, b=1, c=1, n1=1, n2=1, and the corresponding structure of the stack filter 11 is H 1 L 1 H 2 NH 3 L 2 H 4 MH 4 L 2 H 3 NH 2 L 1 H 1 . That is, the film stack filter layer 11 has a structure in which a first high refractive index layer/a first low refractive index layer/a second high refractive index layer/an absorption layer/a third high refractive index layer/a second low refractive index layer/a fourth high refractive index layer/a magnetic core layer/a fourth high refractive index layer/a second low refractive index layer/a third high refractive index layer/an absorption layer/a second high refractive index layer/a first low refractive index layer/a first high refractive index layer are laminated in this order. That is, the magnetic optically variable pigment 10 of the present embodiment is symmetrically disposed along the center of the magnetic core layer 118.
The film stack filter layer 11 in the magnetic optically variable pigment 10 in the above embodiment contains magnetic materials, and the pigment can be aligned in the printing process by utilizing the interaction of the magnetic materials and the magnetic field, so that the pigment has the effect of changing the color with angle and the brightness dynamically under the ambient light, and the hidden color (third color) appears in the dark area color under the strong white light, and meanwhile, the novel optical color changing effect of alternately changing the bright area color and the hidden color along with the rotation of the visual angle can greatly increase the anti-counterfeiting force. For example, the authenticity identification can be completed by visually observing the color change by using a flashlight or a mobile phone flashlight for home use, and the novel first-line anti-counterfeiting technology is simple and efficient.
Further, as shown in fig. 1, the film stack filter layer 11 has a first main surface 101 and a second main surface 102 opposite to each other, and a plurality of metal nanoparticles 12 are disposed on each of the first main surface 101 and the second main surface 102, so that the magnetic optically variable pigment 10 has a symmetrical structure centered on the film stack filter layer 11.
Alternatively, in another embodiment, the magnetic optically variable pigment 10 may have an asymmetric structure, for example, the metal nanoparticles 12 are disposed only on the first main surface 101 of the stack filter layer 11, or the metal nanoparticles 12 are disposed only on the second main surface 102 of the stack filter layer 11.
Further, the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer and the fourth high refractive index layer are all materials with refractive indexes greater than 1.65, for example, the refractive indexes of the materials are 1.7, 1.75, 1.8 or 1.9; the materials of the first low refractive index layer and the second low refractive index layer are materials with refractive indexes less than or equal to 1.65, for example, the refractive indexes of the materials are 1.1, 1.3, 1.6, 1.65 and the like.
Specifically, the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer, and the fourth high refractive index layer include: at least one of lanthanum titanate, titanium pentoxide, niobium pentoxide, zinc sulfide, zinc oxide, zirconium oxide, titanium dioxide, carbon, indium oxide, indium tin oxide, tantalum pentoxide, cerium oxide, yttrium oxide, europium oxide, iron oxide, ferric oxide, hafnium nitride, hafnium carbide, hafnium oxide, lanthanum oxide, magnesium oxide, neodymium oxide, praseodymium oxide, samarium oxide, antimony trioxide, silicon carbide, silicon nitride, silicon monoxide, selenium trioxide, tin oxide, and tungsten trioxide.
In particular embodiments of the present application, the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer, and the fourth high refractive index layer may be identical or not identical, that is, at least two of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer, and the fourth high refractive index layer are different, which is not limited herein.
Specifically, the materials of the first low refractive index layer and the second low refractive index layer include: silica, alumina, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, calcium fluoride, lithium fluoride polystyrene, polyethylene, polymethyl methacrylate, polyamideimide, polyperfluoroethylene propylene, tetrafluoroethylene, chlorotrifluoroethylene, cellulose propionate, cellulose acetate butyrate, methylpentene polymer, homo-formaldehyde, acrylic resin, nitrocellulose, ethylcellulose, polypropylene, polysulfone, polyethersulfone, mica, heterogeneous isomorphous polymer, polybutene, ionomer, acrylic copolymer, styrene butadiene, polyvinyl chloride, urea formaldehyde, styrene acrylonitrile and polycarbonate.
In particular embodiments of the present application, the materials of the first low refractive index layer and the second low refractive index layer may be the same, or the materials of the first low refractive index layer and the second low refractive index layer may be different, which is not limited herein.
Further, the material of the absorbent layer includes: titanium, aluminum, chromium, nickel, palladium, titanium, silicon, vanadium, cobalt, iron, carbon, tin, tungsten, molybdenum, rhodium, niobium, and an alloy of at least two of these.
The physical thickness of the absorption layer is 5nm-100nm. For example, the physical thickness of the absorber layer may be 5nm, 7nm, 20nm, 50nm, 70nm, 90nm, 100nm, or the like.
Alternatively, the magnetic core layer may be a single-layer structure. The material of the magnetic core layer includes: at least one of iron, cobalt, nickel, gadolinium, terbium, dysprosium, and erbium, or an oxide of at least one of the same, or an alloy of at least two of the same. Or the magnetic material in the magnetic core layer comprises: at least one of ferrosilicon, ferroaluminum, ferrosilicon aluminum, ferrosilicon chromium, and ferronickel molybdenum.
Alternatively, the magnetic core layer may be a multilayer structure, for example, a structure of the magnetic core layer: m is M 1 M 0 M 2 、M 0 M 1 M 0 、M 0 M 1 、M 1 D 1 M 0 D 2 M 2 、M 0 D 1 M 1 D 2 M 0 Or M 1 D 1 M 0 Wherein M is 0 Is a magnetic film layer, M 1 And M 2 Is a metal film layer D 1 And D 2 Is a dielectric film layer.
Specifically, the materials of the magnetic film layer include: the material of the magnetic film layer comprises at least one of iron, cobalt, nickel, gadolinium, terbium, dysprosium, erbium, or an oxide of at least one of the oxides or an alloy of at least two, or at least one of iron-silicon alloy, iron-aluminum alloy, iron-silicon-chromium alloy and iron-nickel-molybdenum alloy.
The materials of the metal film layer comprise: at least one of aluminum, silver, gold, copper, platinum, tin, titanium, palladium, rhodium, niobium, and chromium, or an alloy of at least two thereof.
The dielectric film layer comprises the following materials: at least one of silica, alumina, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, and calcium fluoride.
In this embodiment, the metal nanoparticles 12 are distributed at intervals, and the gaps between the metal nanoparticles 12 are 2nm-1mm. For example, the gap between the metal nanoparticles 12 may be 2nm, 200nm, 1000nm, 20000nm, 100000nm, or 1mm, etc.
Specifically, the materials of the metal nanoparticles 12 include: at least one of aluminum, silver, gold, copper, platinum, ruthenium, palladium, rhodium, cobalt, iron, nickel, lead, osmium, and iridium, or an alloy of at least two thereof.
Specifically, the shape of the metal nanoparticle 12 may be any shape, such as a sphere, a hemisphere, an ellipsoid, a cube, a cuboid, an octahedron, a dodecahedron, a hexadecimal body, a rod shape, a star shape, a cone shape, a triangle, a cylinder shape, or the like. The metal nanoparticles 12 may have the same shape or may have a mixture of shapes.
Unlike absorption color development by localized plasmon metal nanoparticle resonance (Local plasmon resonance, LSPR), the color development of the metal nanoparticles 12 in the present application under high intensity white light is that of scattered light enhanced by LSPR, and the high intensity white light color-changing effect is only achieved when the film layer in direct contact with the metal particles (the outermost film layer of the interference film stack) is a high refractive index film layer (n > 1.75).
For example, an Ag NPs layer is arranged on the SiO2 film layer or an Ag NPs layer is arranged on the surface of the MgF2/AL2O3/MgF2 film stack, and the structure can generate color due to LSPR wavelength selective light absorption of the Ag NPs, but can not generate color change due to illumination under strong white light. And the Ag NPs arranged on the surface of the ZrO2 film layer of the single layer can not generate high-light color change. In the prior art, most of the plasma color developing devices utilize LSPR light absorption, and LSPR light scattering enhancement features are rarely used.
Macroscopic scattering color realization has strict requirements on the F-P stack structure. Similarly, there is a certain requirement for ambient light, and different from the traditional interference type optically variable pigment, the optically variable pigment needs to observe the bright color in a bright environment, and the scattering type optically variable pigment in the application needs to be irradiated with white light (high-intensity white light) with preset intensity in a dark field environment to have a photochromic effect. Specifically, the magnetic optically variable pigment 10 has a good high photochromic effect with an ambient illuminance < 300lx, a light source illuminance > 3000lx, and preferably a light source illuminance > 5000 lx. And in the outdoor environment of sunny days, if the ambient illuminance is more than 3000lx, the sample does not have the high photochromic effect.
Thus, the magnetic optically variable pigment 10 provided by the present application is a strong white color-changing pigment in dark field environments, which is quite different from conventional pigments. The essence of its discoloration is the transition of the reflected color under ambient light to the scattered color under high-white intense light.
Moreover, the present application provides the magnetic optically variable pigment 10 with higher color saturation and richer color gamut space through adjustment of the interference stack in the pigment film system and specific selection of some materials.
It should be understood that although the present disclosure describes embodiments in terms of examples, not every embodiment is provided with a single embodiment, and that this description is for clarity only, and that the skilled artisan should recognize that the embodiments may be combined appropriately to form other embodiments that will be understood by those skilled in the art. The above list of detailed descriptions is only specific to practical embodiments of the present application, and is not intended to limit the scope of the present application, and all equivalent embodiments or modifications that do not depart from the spirit of the present application should be included in the scope of the present application.
Claims (15)
1. A magnetic optically variable pigment, characterized in that the magnetic optically variable pigment comprises: a film stack filter layer with magnetic material and a plurality of metal nano particles arranged on the surface of the film stack filter layer,
the structure of the film stack filter layer is (a) 1 H 1 a 2 L 1 a 3 H 2 ) n1 bN(a 4 H 3 a 5 L 2 a 6 H 4 ) n2 cM, where H 1 For the first high refractive index layer, L 1 For the first low refractive index layer, H 2 For the second high refractive index layer, H 3 Is the third high refractive index layer, L 2 Is the second low refractive index layer, H 4 A fourth high refractive index layer, N is an absorption layer, M is a magnetic core layer containing magnetic material, a 1 A, which is the film thickness coefficient of the first high refractive index layer 2 A, which is the film thickness coefficient of the first low refractive index layer 3 A is the film thickness coefficient of the second high refractive index layer 4 A is the film thickness coefficient of the third high refractive index layer 5 A is the film thickness coefficient of the second low refractive index layer 6 B is the film thickness coefficient of the absorption layer, c is the film thickness coefficient of the magnetic core layer, n1 and n2 are the corresponding dielectric film stack periods, and 0 < a 1 ≤5、0≤a 2 ≤5、0≤a 3 ≤5、0≤a 4 ≤5、0≤a 5 ≤5、0≤a 6 B is more than or equal to 5 and less than or equal to 0 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 3, and n1 and n2 are the corresponding medium film stack periods;
the magnetic optically variable pigment has a photochromic effect under the irradiation of white light with preset intensity, wherein the preset intensity comprises at least one of ambient light intensity less than 300lx and light source intensity greater than 3000 lx.
2. A magnetic optically variable pigment, characterized in that the magnetic optically variable pigment comprises: the film stack filter layer is provided with a magnetic material, and a plurality of metal nano particles are arranged on the surface of the film stack filter layer;
the structure of the film stack filter layer is (a) 1 H 1 a 2 L 1 a 3 H 2 ) n1 bN(a 4 H 3 a 5 L 2 a 6 H 4 ) n2 cM(a 6 H 4 a 5 L 2 a 4 H 3 ) n2 bN(a 3 H 2 a 2 L 1 a 1 H 1 ) n1 ，
Wherein H is 1 For the first high refractive index layer, L 1 For the first low refractive index layer, H 2 For the second high refractive index layer, H 3 Is the third high refractive index layer, L 2 Is the second low refractive index layer, H 4 A fourth high refractive index layer, N is an absorption layer, M is a magnetic core layer containing magnetic material, a 1 A is the film thickness coefficient of the first high refractive index layer 2 A is the film thickness coefficient of the first low refractive index layer 3 A is the film thickness coefficient of the second high refractive index layer 4 A is the film thickness coefficient of the third high refractive index layer 5 A is the film thickness coefficient of the second low refractive index layer 6 For the fourthThe film thickness coefficient of the high refractive index layer, b is the film thickness coefficient of the absorption layer, c is the film thickness coefficient of the magnetic core layer, wherein 0 < a 1 ≤5、0≤a 2 ≤5、0≤a 3 ≤5、0≤a 4 ≤5、0≤a 5 ≤5、0≤a 6 B is more than or equal to 5 and less than or equal to 0 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 3, and n1 and n2 are the corresponding medium film stack periods;
the magnetic optically variable pigment has a photochromic effect under the irradiation of white light with preset intensity, wherein the preset intensity comprises at least one of ambient light intensity less than 300lx and light source intensity greater than 3000 lx.
3. The magnetic optically variable pigment of claim 1 or 2 wherein the film stack filter layer has opposed first and second major surfaces,
the first main surface and the second main surface are respectively provided with a plurality of metal nano particles so that the magnetic optically variable pigment has a symmetrical structure taking the film stack filter layer as a center, or,
and a plurality of metal nano particles are arranged on the first main surface or the second main surface.
4. The magnetic optically variable pigment according to claim 1 or 2, wherein the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer and the fourth high refractive index layer are materials having a refractive index of more than 1.65; the first low refractive index layer and the second low refractive index layer are both made of materials with refractive indexes smaller than or equal to 1.65.
5. The magnetic optically variable pigment according to claim 4, wherein the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer and the fourth high refractive index layer are the same, or,
at least two of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer, and the fourth high refractive index layer are different in material.
6. The magnetic optically variable pigment according to claim 5, wherein the materials of the first high refractive index layer, the second high refractive index layer, the third high refractive index layer and the fourth high refractive index layer comprise: at least one of lanthanum titanate, titanium pentoxide, niobium pentoxide, zinc sulfide, zinc oxide, zirconium oxide, titanium dioxide, carbon, indium oxide, indium tin oxide, tantalum pentoxide, cerium oxide, yttrium oxide, europium oxide, iron oxide, ferric oxide, hafnium nitride, hafnium carbide, hafnium oxide, lanthanum oxide, magnesium oxide, neodymium oxide, praseodymium oxide, samarium oxide, antimony trioxide, silicon carbide, silicon nitride, silicon monoxide, selenium trioxide, tin oxide, and tungsten trioxide.
7. The magnetic optically variable pigment according to claim 4, wherein the first low refractive index layer and the second low refractive index layer are made of the same material, or,
the first low refractive index layer and the second low refractive index layer are of different materials.
8. The magnetic optically variable pigment according to claim 7, wherein the materials of the first low refractive index layer and the second low refractive index layer comprise: silica, alumina, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, calcium fluoride, lithium fluoride polystyrene, polyethylene, polymethyl methacrylate, polyamideimide, polyperfluoroethylene propylene, tetrafluoroethylene, chlorotrifluoroethylene, cellulose propionate, cellulose acetate butyrate, methylpentene polymer, homo-formaldehyde, acrylic resin, nitrocellulose, ethylcellulose, polypropylene, polysulfone, polyethersulfone, mica, heterogeneous isomorphous polymer, polybutene, ionomer, acrylic copolymer, styrene butadiene, polyvinyl chloride, urea formaldehyde, styrene acrylonitrile and polycarbonate.
9. The magnetic optically variable pigment according to claim 1 or 2, wherein the material of the absorbing layer comprises: titanium, aluminum, chromium, nickel, palladium, titanium, silicon, vanadium, cobalt, iron, carbon, tin, tungsten, molybdenum, rhodium, niobium, and an alloy of at least two of these.
10. The magnetic optically variable pigment of claim 1 or 2 wherein the absorber layer has a physical thickness of from 5nm to 100nm.
11. The magnetic optically variable pigment according to claim 1 or 2, wherein the magnetic core layer has a single layer structure;
the material of the magnetic core layer comprises: an oxide of at least one of iron, cobalt, nickel, gadolinium, terbium, dysprosium, and erbium, or an alloy of at least two; or alternatively, the process may be performed,
the material of the magnetic core layer comprises: at least one of ferrosilicon, ferroaluminum, ferrosilicon aluminum, ferrosilicon chromium, and ferronickel molybdenum.
12. The magnetic optically variable pigment according to claim 1 or 2, characterized in that: the magnetic core layer is of a multi-layer structure, and the structure of the magnetic core layer is as follows: m is M 1 M 0 M 2 、M 0 M 1 M 0 、M 0 M 1 、M 1 D 1 M 0 D 2 M 2 、M 0 D 1 M 1 D 2 M 0 Or M 1 D 1 M 0 Wherein M is 0 Is a magnetic film layer, M 1 And M 2 Is a metal film layer D 1 And D 2 Is a dielectric film layer.
13. The magnetic optically variable pigment of claim 12, wherein the material of the magnetic film layer comprises: at least one of iron, cobalt, nickel, gadolinium, terbium, dysprosium, erbium, or an oxide of at least one of them, or an alloy of at least two, or the material of the magnetic film layer comprises at least one of iron-silicon alloy, iron-aluminum alloy, iron-silicon-chromium alloy, and iron-nickel-molybdenum alloy;
the material of the metal film layer comprises: at least one of aluminum, silver, gold, copper, platinum, tin, titanium, palladium, rhodium, niobium, and chromium, or an alloy of at least two thereof;
the dielectric film layer comprises the following materials: at least one of silica, alumina, magnesium fluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, neodymium fluoride, samarium fluoride, barium fluoride, and calcium fluoride.
14. The magnetic optically variable pigment according to claim 1 or 2, wherein a plurality of the metal nanoparticles are spaced apart from each other with a gap of 2nm to 1mm between the plurality of the metal nanoparticles.
15. The magnetic optically variable pigment of claim 1 or 2, wherein the material of the metal nanoparticles comprises: at least one of aluminum, silver, gold, copper, platinum, ruthenium, palladium, rhodium, cobalt, iron, nickel, lead, osmium, and iridium, or an alloy of at least two thereof.
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