CN111402706A - Film with rasterization encryption pattern on surface and preparation method thereof - Google Patents
Film with rasterization encryption pattern on surface and preparation method thereof Download PDFInfo
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- CN111402706A CN111402706A CN202010354354.1A CN202010354354A CN111402706A CN 111402706 A CN111402706 A CN 111402706A CN 202010354354 A CN202010354354 A CN 202010354354A CN 111402706 A CN111402706 A CN 111402706A
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000005192 partition Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229920001721 polyimide Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 229920005575 poly(amic acid) Polymers 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- -1 diphenyl diamine Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 24
- 238000005516 engineering process Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
- G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1814—Diffraction gratings structurally combined with one or more further optical elements, e.g. lenses, mirrors, prisms or other diffraction gratings
- G02B5/1819—Plural gratings positioned on the same surface, e.g. array of gratings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1842—Gratings for image generation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1847—Manufacturing methods
- G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a film with a rasterization encryption pattern on the surface, wherein the surface of the film is provided with n subareas and m rasterization encryption patterns positioned in the subareas, and each subarea is provided with at most one rasterization encryption pattern, wherein m is more than or equal to 2 and less than or equal to 180, and m is more than or equal to n; each grating encryption pattern is composed of grating lines which are periodically arranged and have the line width of 1-10 mu m and the period of 2-20 mu m. The invention also discloses a preparation method of the film with the grating encryption pattern on the surface. According to the invention, the encryption patterns with different profiles which can be superposed are prepared on the surface of the film, the encryption information of different partitions can be read out in the same area on the film by rotating different angles under the condition of fixing the incident light angle and the observation angle, and only the single encryption information corresponding to the single partition can be read out at a single angle, so that the encryption patterns have strong anti-interference capability and are convenient to read. The invention belongs to the field of preparation of anti-counterfeiting materials, and relates to an anti-counterfeiting label for preparing daily consumer goods.
Description
Technical Field
The invention belongs to the technical field of optical encryption, and is used for preparing an anti-counterfeiting material, in particular to a film with a grating encryption pattern on the surface and a preparation method thereof.
Background
With the rapid development of science and technology and the enhancement of consumer brand awareness, in order to increase the degree of identification, people increasingly attach importance to adding anti-counterfeiting marks on commodities or currency and adopt advanced processes to enhance the difficulty of counterfeiting the anti-counterfeiting marks.
At present, one of the most effective and widely applied anti-counterfeiting means is to use an optical coding encryption technology to manufacture an anti-counterfeiting mark. At present, the whole anti-counterfeiting market at home and abroad is dominated by the national industry, and meanwhile, the anti-counterfeiting mark circulated and applied in the market at the present stage has single encryption and is not easy to be identified by consumers, so that counterfeiters can be confused by just imitating the fake mark rather than the fake mark, and the existing anti-counterfeiting mark is difficult to play the real anti-counterfeiting role. In order to further increase the encryption degree of optical information and improve the security of product information, in recent years, the emerging technologies such as wavelet transform encryption systems, full-phase encryption systems using phase-contrast technology, planar integrated micro-optical device encryption systems, polarization encoding encryption systems, virtual optical encryption technology and the like gradually enter into the preparation of anti-counterfeiting marks.
In view of the above, it would be a reliable way to change the single current state of the art of current optical encryption if multiple encodable encryption methods could be utilized in conjunction with new materials.
Disclosure of Invention
The invention aims to provide a film with a rasterization encryption pattern on the surface, wherein the surface of the film is provided with the encryption patterns with different outlines, different encryption information can be read out on the film by rotating different angles under the condition of fixing an incident light angle and an observation angle, and the encryption pattern only can be used for reading single encryption information at a single angle, has strong anti-interference capability and is convenient to read.
It is still another object of the present invention to provide a method for preparing the above-mentioned thin film having a rasterized encrypted pattern on its surface.
In order to achieve the purpose, the invention adopts the following technical scheme:
a film with a surface provided with a rasterization encryption pattern, wherein the surface of the film is provided with n subareas and m rasterization encryption patterns positioned in the subareas, each subarea is provided with at most one rasterization encryption pattern, m is more than or equal to 2 and less than or equal to 180, and m is less than or equal to n;
each grating encryption pattern is composed of grating line groups formed by grating lines which are periodically arranged and have the line width of 1-10 mu m and the period of 2-20 mu m.
As a limitation: the grating lines of different grating encryption patterns are not overlapped in a cross mode in a plane, and the included angle of the extension lines of the grating lines of different grating encryption patterns is a positive integer angle which is larger than or equal to 1 degree and smaller than 180 degrees.
As a second limitation: each partition is a rectangle with the minimum side length larger than or equal to 5 mu m, and the design layout of the grating encryption pattern is divided into minimum unit pixel points by the rectangles.
As a third limitation: the film is any polymer film or metal film.
As a fourth limitation: the grating line group is composed of a convex grating line and a concave grating line, the line widths of the convex grating line and the concave grating line are both 1-10 mu m, and the adjacent convex grating line and the concave grating line form a grating line group with a two-dimensional concave-convex structure, the depth difference of the two-dimensional concave-convex structure is less than or equal to 100 nm.
The preparation method of the film with the rasterization encryption pattern on the surface comprises the following steps:
firstly, adding a photosensitive diphenyl diamine monomer, 4' -diaminodiphenyl ether and anhydrous N, N-diethylacetamide into a container, and then mechanically stirring at 5-10 ℃ until all solids are dissolved to obtain a material A;
secondly, adding pyromellitic dianhydride into the material A under the protection of inert gas, and stirring and reacting for 8-24 hours at the temperature of 0-10 ℃ to obtain a photosensitive polyamic acid solution;
thirdly, spin-coating the photosensitive polyamic acid solution on a substrate, placing the substrate in vacuum, and performing thermal imidization to obtain a photosensitive polyimide film with the thickness of 3-300 mu m;
fourthly, exposing the design layout on the surface of the photosensitive polyimide film, then immersing the exposed photosensitive polyimide film into a methanol solution containing copper sulfate for development operation, and finally adsorbing metal copper ions deposited on an exposure area and a non-exposure area to form the rasterization encryption pattern, thus obtaining the film with the rasterization encryption pattern on the surface;
the design layout is provided with a grating structure corresponding to the grating encryption pattern.
The grating line group is limited to be composed of a convex grating line and a concave grating line, the line widths of the convex grating line and the concave grating line are both 1-10 mu m, and the adjacent convex grating line and the concave grating line form a grating line group with a two-dimensional concave-convex structure, the depth difference of which is less than or equal to 100 nm; the fourth step is carried out according to the following steps:
placing a photosensitive polyimide film in a maskless ultraviolet exposure machine;
exposing a design layout with multiple digital superposition in a direct-writing exposure mode on the surface of the photosensitive polyimide film, wherein the exposure wavelength is 365nm, and the exposure time of a single pixel point is 30-300 ms;
(III) immersing the exposed photosensitive polyimide film into a methanol solution containing copper sulfate for development operation, and forming the grating encryption pattern formed by a grating line group with a two-dimensional concave-convex structure with the depth difference less than or equal to 100nm by adsorbing metal copper ions deposited in an exposure area and an unexposed area to obtain the film with the grating encryption pattern on the surface;
the design layout of the rasterization encryption pattern is divided into minimum unit pixel points by the rectangle, and the minimum side length of the rectangle is more than or equal to 5 mu m.
The second limitation is that the copper sulfate concentration in the copper sulfate-containing methanol solution is 5 to 10 g/L.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) according to the method provided by the invention, the encryption patterns with different profiles which can be superposed can be prepared on the surface of the thin film, the encryption information of different partitions can be read out in the same area on the thin film by rotating different angles under the condition of fixing the incident light angle and the observation angle, and the single angle can only read the single encryption information corresponding to the single partition, so that the encryption pattern has strong anti-interference capability and convenient reading, meanwhile, the decryption pattern has extremely high viewing effect, and the method is very suitable for preparing the anti-counterfeiting mark of daily consumer goods;
(2) the grating lines of different grating encryption patterns are not overlapped in a cross mode in a plane, and the included angle of the extension lines of the grating lines of different grating encryption patterns is a positive integer angle which is larger than or equal to 1 degree and smaller than 180 degrees, so that 180 different grating encryption patterns can be manufactured, the anti-counterfeiting level is high, and the anti-counterfeiting effect can be effectively prevented.
The invention is suitable for the technical field of preparation of anti-counterfeiting materials.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
fig. 1 and 2 are diagrams of a photosensitive polyimide film containing a rasterized encryption pattern in example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the present invention.
EXAMPLE 1A film having a rasterized encrypted pattern on its surface
The surface of the film with the rasterization encryption patterns in the embodiment is provided with n subareas and m rasterization encryption patterns positioned in the subareas, wherein each subarea is provided with at most one rasterization encryption pattern, m is more than or equal to 2 and less than or equal to 180, and m is more than or equal to n.
Each grating encryption pattern is composed of grating line groups formed by grating lines which are periodically arranged and have the line width of 1-10 mu m and the period of 2-20 mu m. The grating line group consists of a convex grating line and a concave grating line, the line widths of the convex grating line and the concave grating line are both 1-10 mu m, and the adjacent convex grating line and the concave grating line form a grating line group with a two-dimensional concave-convex structure, wherein the depth difference of the two-dimensional concave-convex structure is less than or equal to 100 nm.
The grating lines of different grating encryption patterns are not overlapped in a cross mode in a plane, and the included angle of the extension lines of the grating lines of different grating encryption patterns is a positive integer angle which is larger than or equal to 1 degree and smaller than 180 degrees.
Each partition is a rectangle with the minimum side length more than or equal to 5 mu m, and the design layout of the rasterization encryption pattern is divided into minimum unit pixel points by the rectangles.
For convenience of understanding, this embodiment will be described by taking as an example that the film used is a photosensitive polyimide film. In order to better show the encryption effect, the present embodiment performs a raster encoding design on the number "8" in the digifacenide font. After the graph 8 is subjected to rectangular segmentation, four adjacent rectangles capable of forming a 'tian' shape are selected as basic points, and for the convenience of subsequent description, each rectangle contained in the 'tian' shape is named clockwise from the upper left position as a starting point: upper left subregion, upper right subregion, lower left subregion. The multi-digital superposition encryption is realized by arranging the grating encryption patterns formed by encoding grating line groups in different directions in the four subareas, the line widths of the convex grating lines and the concave grating lines are both 1.5 mu m, and the period is 3 mu m. And adjacent convex grating lines and concave grating lines form a grating line group with a two-dimensional concave-convex structure, and the depth difference of the grating line group is less than or equal to 50 nm.
Wherein, the angles between the directions of the grating lines filled in the upper left subarea, the upper right subarea, the lower right subarea and the lower left subarea and the positive direction of the x-axis in the plane are 0 degree, 45 degree, 90 degree and 135 degree in sequence. The rasterized encryption patterns corresponding to the upper left partition, the upper right partition, the lower right partition and the lower left partition are basic light encryption coding units of Digifacenide fonts of '1', '2', '3' and '4' in sequence. When the encrypted pattern is observed, the incidence angle is selected under the fixed white light, and then the encrypted information in different partitions on the film can be read in sequence under different rotation angles by rotating the film. Fig. 1 and 2 are schematic diagrams of the photosensitive polyimide film containing the rasterized encryption pattern according to the present embodiment, wherein fig. 1 shows the result of the observation angle being changed without changing the position of the film, wherein the film is placed in a culture dish with a diameter of 3.5 marked with an AB arrow having an included angle of 90 degrees, and fig. 2 shows that the encryption pattern can be sequentially read by rotating the film clockwise without moving the culture dish and the observation angle. The arrows in fig. 1 and 2 designate horizontal and vertical directions for reference in the digital interpretation direction.
For convenience of description, this embodiment is exemplified by four partitions and four rasterization encryption patterns, and in practice, in practical use, n partitions may be disposed on the surface of each photosensitive polyimide film according to needs, one rasterization encryption pattern may be disposed in each partition, or no rasterization encryption pattern may be disposed, the total number of rasterization encryption patterns should not exceed 180, and the number of partitions is not less than the number of rasterization encryption patterns. The grating lines of different grating encryption patterns are not overlapped in a cross mode in a plane, and the included angle of the extension lines of the grating lines of different grating encryption patterns is a positive integer angle which is larger than or equal to 1 degree and smaller than 180 degrees. The line width of the grating lines and the period of the grating line group can be selected within a specified range according to actual needs.
In this embodiment, the film used may also be a metal film or any other polymer film.
Example 2 method for preparing a thin film having a rasterized encrypted pattern on its surface
This example was used to prepare example 1, following the following sequence of steps:
firstly, 100mol of photosensitive diphenyl diamine monomer, 100mol of 4, 4' -diaminodiphenyl ether and 1570.5Kg of anhydrous N, N-diethyl acetamide are added into a container, and then the mixture is put into a reactor1Mechanically stirring at 5 ℃ until all solids are dissolved to obtain a material A;
secondly, adding 190mol of pyromellitic dianhydride into the material A under the protection of inert gas and adding the mixture into the mixture T2Reaction t is stirred in the environment of 0 DEG C1=12h, obtaining a photosensitive polyamic acid solution;
thirdly, spin-coating the photosensitive polyamic acid solution on a flat and clean glass substrate, and performing thermal imidization in a vacuum oven to obtain the product with the thickness of h1A photosensitive polyimide film of =100 um;
fourthly, placing the photosensitive polyimide film in a maskless ultraviolet exposure machine;
(II) exposing a design layout with multiple digital superposition in a direct-writing exposure mode on the surface of the photosensitive polyimide film, wherein the exposure wavelength is 365nm, and the exposure time of a single pixel point is t2=30ms；
Thirdly, the exposed photosensitive polyimide film is immersed into a methanol solution with copper sulfate concentration of 5 g/L for development operation, and finally, the metal copper ions adsorbed and deposited on the exposed area and the unexposed area form a film with the depth difference of h2And (3) obtaining the film with the rasterized encryption pattern on the surface, wherein the rasterized encryption pattern is formed by the raster lines of the two-dimensional concave-convex structure with the thickness of 50 nm.
The design layout is provided with a grating structure corresponding to the grating encryption pattern, the design layout is divided into minimum unit pixel points by a rectangle, and the minimum side length of the rectangle is L =5 μm.
In the above process, the chemical structure of the photosensitive biphenyldiamine used for preparing the photosensitive polyimide is as follows:
EXAMPLES 3 to 6A method for preparing a thin film having a rasterized encryption pattern on the surface thereof
Examples 3-6 were prepared substantially the same as example 2, except for the differences in the specific parameters, as shown in table 1 below:
TABLE 1 parameters for examples 3-6
Claims (8)
1. A film having a rasterized encrypted pattern on a surface thereof, wherein: the surface of the film is provided with n subareas and m rasterization encryption patterns positioned in the subareas, and each subarea is provided with at most one rasterization encryption pattern, wherein m is more than or equal to 2 and less than or equal to 180, and m is more than or equal to n;
each grating encryption pattern is composed of grating line groups formed by grating lines which are periodically arranged and have the line width of 1-10 mu m and the period of 2-20 mu m.
2. A film having a surface with a rasterized encrypted pattern according to claim 1, characterized in that: the grating lines of different grating encryption patterns are not overlapped in a cross mode in a plane, and the included angle of the extension lines of the grating lines of different grating encryption patterns is a positive integer angle which is larger than or equal to 1 degree and smaller than 180 degrees.
3. A film having a surface with a rasterized encrypted pattern according to claim 1 or 2, characterized in that: each partition is a rectangle with the minimum side length larger than or equal to 5 mu m, and the design layout of the grating encryption pattern is divided into minimum unit pixel points by the rectangles.
4. A film having a surface with a rasterized encrypted pattern according to claim 1 or 2, characterized in that: the film is any polymer film or metal film.
5. A film having a surface with a rasterized encrypted pattern according to claim 1 or 2, characterized in that: the grating line group is composed of a convex grating line and a concave grating line, the line widths of the convex grating line and the concave grating line are both 1-10 mu m, and the adjacent convex grating line and the concave grating line form a grating line group with a two-dimensional concave-convex structure, the depth difference of the two-dimensional concave-convex structure is less than or equal to 100 nm.
6. A method of producing a film having a rasterized encrypted pattern on its surface according to any one of claims 1 to 5, characterized in that the following steps are carried out in the following order:
firstly, adding a photosensitive diphenyl diamine monomer, 4' -diaminodiphenyl ether and anhydrous N, N-diethylacetamide into a container, and then mechanically stirring at 5-10 ℃ until all solids are dissolved to obtain a material A;
secondly, adding pyromellitic dianhydride into the material A under the protection of inert gas, and stirring and reacting for 8-24 hours at the temperature of 0-10 ℃ to obtain a photosensitive polyamic acid solution;
thirdly, spin-coating the photosensitive polyamic acid solution on a substrate, placing the substrate in vacuum, and performing thermal imidization to obtain a photosensitive polyimide film with the thickness of 3-300 mu m;
fourthly, exposing the design layout on the surface of the photosensitive polyimide film, then immersing the exposed photosensitive polyimide film into a methanol solution containing copper sulfate for development operation, and finally adsorbing metal copper ions deposited on an exposure area and a non-exposure area to form the rasterization encryption pattern, thus obtaining the film with the rasterization encryption pattern on the surface;
the design layout is provided with a grating structure corresponding to the grating encryption pattern.
7. The method for preparing a film with a rasterized encrypted pattern on the surface according to claim 6, wherein the grating line group consists of a convex grating line and a concave grating line, the line widths of the convex grating line and the concave grating line are both 1-10 μm, and the adjacent convex grating line and the concave grating line form a grating line group with a two-dimensional concave-convex structure with the depth difference of less than or equal to 100 nm; the fourth step is carried out according to the following steps:
placing a photosensitive polyimide film in a maskless ultraviolet exposure machine;
exposing a design layout with multiple digital superposition in a direct-writing exposure mode on the surface of the photosensitive polyimide film, wherein the exposure wavelength is 365nm, and the exposure time of a single pixel point is 30-300 ms;
(III) immersing the exposed photosensitive polyimide film into a methanol solution containing copper sulfate for development operation, and forming the grating encryption pattern formed by a grating line group with a two-dimensional concave-convex structure with the depth difference less than or equal to 100nm by adsorbing metal copper ions deposited in an exposure area and an unexposed area to obtain the film with the grating encryption pattern on the surface;
the design layout of the rasterization encryption pattern is divided into minimum unit pixel points by the rectangle, and the minimum side length of the rectangle is more than or equal to 5 mu m.
8. The method for preparing a film with a rasterized encrypted pattern on the surface according to claim 6 or 7, wherein the concentration of copper sulfate in the methanol solution containing copper sulfate is 5-10 g/L.
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