CN115874490B - Multilayer anti-counterfeiting medium frame paper and preparation method thereof - Google Patents
Multilayer anti-counterfeiting medium frame paper and preparation method thereof Download PDFInfo
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- CN115874490B CN115874490B CN202211722585.9A CN202211722585A CN115874490B CN 115874490 B CN115874490 B CN 115874490B CN 202211722585 A CN202211722585 A CN 202211722585A CN 115874490 B CN115874490 B CN 115874490B
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- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
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- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 238000004026 adhesive bonding Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
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- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 claims description 3
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
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- OALHHIHQOFIMEF-UHFFFAOYSA-N 3',6'-dihydroxy-2',4',5',7'-tetraiodo-3h-spiro[2-benzofuran-1,9'-xanthene]-3-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 OALHHIHQOFIMEF-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
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- Credit Cards Or The Like (AREA)
Abstract
The invention discloses a multilayer anti-counterfeiting medium frame paper and a preparation method thereof, and relates to the technical field of anti-counterfeiting, wherein the multilayer anti-counterfeiting medium frame paper comprises a base paper layer, a glue layer, an ink identification layer, a holographic storage layer, a medium layer and a color printing layer, wherein the glue layer is obtained by coating an adhesive force organic silicon modified polyurethane adhesive and plays a role in adhesion; the ink layer uses magnetic optically variable ink as a printing identification point; the holographic storage layer takes the mark in the ink identification layer as a positioning point, and a holographic pattern is overprinted to form the holographic storage layer; the medium layer protects the holographic storage layer through a compact molecular structure, and simultaneously makes holographic patterns more colorful; the color printing layer prints color ink on the surface of the frame paper through the anti-counterfeiting ink; and the ink identification layer, the holographic storage layer and the medium layer are adhered with the base paper layer through the glue layer, and finally, color printing ink is sprayed on the transfer coating to form a color printing layer, so that the multi-layer anti-counterfeiting medium frame paper is obtained.
Description
Technical Field
The invention relates to the technical field of multilayer anti-counterfeiting medium frame paper x, in particular to multilayer anti-counterfeiting medium frame paper and a preparation method thereof.
Background
The frame paper is used for supporting and positioning paper jams of the cigarette hard box frame, and is made into a frame box after being bent, so that the frame paper is applied to traditional hard box cigarettes, plays a role in supporting cigarettes, and protects the cigarettes in the cigarette box. The existing frame paper is formed by processing single-layer white cardboard and composite aluminum foil, the aluminum foil used by the frame paper is difficult to degrade, the environmental protection performance is poor, and along with the development of the tobacco bale industry, the traditional frame paper cannot meet the decoration and anti-counterfeiting functions.
The anti-counterfeiting medium frame paper is different from the same-row product, so that the false cigarettes are prevented from being manufactured and sold, the trust degree of brands is increased, and the image of the brands is improved. The anti-counterfeiting label can effectively inhibit the occurrence of fake products in batches, and protect legal rights and interests of enterprises and consumers.
The existing anti-counterfeiting frame paper has the following defects: 1) The anti-counterfeiting is easy to manufacture; 2) Consumers cannot directly judge the authenticity from the anti-counterfeiting code, and counterfeiters often counterfeits in a mode of copying the anti-counterfeiting code in a large scale; 3) The disposable verification of the label cannot be guaranteed, and lawless persons transfer the anti-counterfeiting mark to other articles for counterfeiting.
Therefore, the anti-counterfeiting frame paper with the multi-layer anti-counterfeiting function has important market prospect.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a multi-layer anti-counterfeiting medium frame paper and a preparation method thereof, provides anti-counterfeiting ink and anti-counterfeiting, and solves the problems that the traditional frame paper has a simple anti-counterfeiting function, the surface layer of an anti-counterfeiting mark in the market is recycled, and the frame paper is scanned and recycled after being transferred.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: the multi-layer anti-counterfeiting medium frame paper comprises a base paper layer and a glue layer, an ink identification layer, a holographic storage layer, a medium layer and a color printing layer which are sequentially arranged on the outer surface of the base paper layer from inside to outside, wherein the base paper layer is made of fiber materials, and plays a supporting role after being folded, and the glue layer is obtained by coating an adhesive force organosilicon modified polyurethane adhesive and plays a role in adhesion; the ink layer uses magnetic optically variable ink as a printing identification point; the holographic storage layer takes the mark in the ink identification layer as a positioning point, and a holographic pattern is overprinted to form the holographic storage layer; the medium layer protects the holographic storage layer through a compact molecular structure, and simultaneously makes holographic patterns more colorful; the color printing layer prints color ink on the surface of the frame paper through the anti-counterfeiting ink; the printing ink identification layer, the holographic storage layer and the medium layer are all positioned on the transfer coating, the transfer coating is attached to the substrate layer through the glue layer to obtain the anti-counterfeiting label, the transfer coating is attached to the substrate layer through the glue layer after being separated from the substrate layer, the color printing ink is finally sprayed on the transfer coating to form the color printing layer, and the multi-layer anti-counterfeiting medium frame paper is obtained, and the substrate layer is a PET transfer film.
Preferably, the base paper layer is made of plant fiber material and has good adhesion with a glue layer, the glue layer is an organosilicon modified polyurethane adhesive, and the preparation method of the organosilicon modified polyurethane adhesive comprises the following steps: firstly, adding proper amount of polypropylene glycol and silane coupling agents with different contents into a four-neck flask, slowly dripping liquefied diphenylmethane diisocyanate into a constant pressure funnel under the condition of nitrogen environment and 75 ℃, and reacting for 3 hours to synthesize a silicon-containing NCO-terminated polyurethane prepolymer; continuously introducing nitrogen, raising the temperature to 80 ℃, sequentially adding E-51 and dibutyltin dilaurate in sequence, and reacting for 2 hours to obtain a silicon-containing polyurethane adhesive A component; the curing agent and 2,4, 6-tris (dimethylaminomethyl) phenol are used as the component B, and the components are uniformly stirred according to the proportion of 1-3:1, so as to obtain the organosilicon modified polyurethane adhesive.
Preferably, the ink identifying layer comprises a magnetic optically variable ink, the magnetic optically variable ink is covered on the base paper layer, and the method for covering the magnetic optically variable ink on the base paper layer comprises the following steps:
step S01, preparing a magnetic optically variable film: under vacuum condition, magnetic pigment is used as raw material, and optical film layer is used as cycle to deposit for 15-25 times on glass substrate, forming a cycle composite structure of multiple isolation layers and multiple magnetic optically variable films;
step S02, separating the magnetic optically variable film: after the deposition is finished, taking out the rigid substrate from the vacuum chamber, putting the rigid substrate into an ethanol solvent for demolding, and simultaneously separating the magnetic optically variable film from the isolation layer in the periodic composite structure to obtain a separated magnetic optically variable film;
step S03, crushing the magnetic optically variable film: crushing the magnetic light thinned film obtained in the step S02 to obtain a plurality of magnetic light thinned film fragments;
step S04, coating a magnetic optically variable film: and mixing the magnetic photothin film fragments with glue, and then coating the mixture on a base paper layer to obtain the ink identification layer.
Preferably, the magnetic pigment is one or a mixture of iron oxide black and iron oxide brown, and the particle size of the magnetic pigment is 10-100nm.
Preferably, the holographic storage layer comprises a photopolymer, the preparation method of the photopolymer is to utilize photo-initiator tetraiodofluorescein sodium, a co-primer agent of phenylaminoacetic acid and a cross-linking agent of N-vinyl pyrrolidone to polymerize methacrylate under the action of illumination to generate the photopolymer, then store anti-counterfeiting information in the photopolymer through a laser and setting a horizontal selection angle to obtain the holographic storage layer,
preferably, the preparation of the holographic storage layer comprises the following steps:
step S11, preparing a mixed solution: uniformly mixing a monomer, a photoinitiator, a co-primer and a cross-linking agent (40:1:2:17) according to a proportion, placing the mixture into a cassette, carrying out ultrasonic treatment for 30min, standing for 20min, and taking an upper layer liquid for waiting use;
step S12, preparing a photopolymer: preparing a sample box with three sealed surfaces and one open surface by using two clean glass sheets and three glass gaskets with the thickness of 100-300 mu m, and pouring the prepared mixed solution from the opening to obtain a photopolymer;
step S13, information storage: storing information into a photopolymer by utilizing the action of object light and reference light, emitting light beams by using a solid laser, wherein the light beams emit two light beams, namely object light and reference light, through the other end of a prism, the object light loads holographic patterns on the photopolymer under the focusing of a convex lens, a horizontal selection angle is firstly set, and then a three-dimensional image is recorded in the photopolymer under the interaction of the object light and the reference light;
and S14, bonding the photopolymer storing information with the base paper layer or the ink identification layer through glue to obtain the holographic pattern layer.
Preferably, the holographic pattern layer is used for storing anti-counterfeiting information to achieve anti-counterfeiting effect, information is stored in a sample by changing a horizontal selection angle of the solid laser, and the formula of the horizontal selection angle satisfies the following formula:wherein Δq is the full width of diffraction, Δθ is the angle between the object light and the reflection plane, θ0 and θr respectively represent the angle between the object light and the normal line and the angle between the reference light and the normal line, and d is the distance between the light source and the reflection plane.
Preferably, the dielectric layer is used for increasing the color of the pattern and is one or more of zinc sulfide, magnesium fluoride, silicon dioxide and titanium dioxide.
Preferably, the color printing layer comprises anti-counterfeiting ink, the anti-counterfeiting ink comprises three primary color fluorescent carbon dots, the preparation mode of the fluorescent carbon dots is to prepare fluorescent carbon dot powder respectively, then the fluorescent carbon dot powder is mixed with resin, a dispersing agent and a thickening agent to prepare the anti-counterfeiting ink, and the preparation mode of the three primary color fluorescent carbon dots is as follows: dissolving polyacrylamide in water or ethanol, adjusting pH=3 and pH=8 by adding hydrochloric acid, transferring the solution which is uniformly mixed by magnetic stirring into an autoclave, setting the temperature to 200 ℃ for 12 hours, collecting reaction products, centrifuging for 10 minutes at a rotating speed of 8000r/min to remove impurities, separating, purifying, drying and grinding into red fluorescent carbon dots and yellow fluorescent carbon dot powder; dissolving sodium glutamate and copper sulfate in deionized water, transferring the solution into a stainless steel autoclave, heating the stainless steel autoclave for 3 hours in a 200 ℃ oven, centrifuging the synthesized blue fluorescent carbon dot solution at 6000r/min for 10 minutes to remove large particles, filtering supernatant to remove lower liquid, dialyzing the lower liquid through a dialysis membrane for 24 hours, and then vacuum freeze-drying the inner liquid in a dialysis bag for 12 hours to obtain the blue fluorescent carbon dots.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method of making a multi-layered anti-counterfeit media framing paper, said method comprising the steps of:
step S21, preparing a resin base layer: fixing a clean and dry resin-based bottom layer on a coating machine, wherein the coating adopts an organosilicon modified polyurethane adhesive, and the resin-based bottom layer is a PET transfer film;
step S22, preparing an ink layer: firstly, preparing a magnetic optically variable film, and printing a magnetic ink identification layer on a gravure printing machine, wherein the ink uses ferroferric oxide and ferric oxide as identification media, and the ink system is acrylic acid modified resin, and the solid content of the ink is 15-20%;
step S23, preparing a holographic storage layer: firstly preparing a photopolymer, and then storing information into the photopolymer under the action of object light and reference light, wherein the holographic storage layer is positioned at the hollowed-out area or one side of the ink layer;
step S24, smearing a medium layer: plating a medium on the molding surface of the base film by using a vacuum plating mode, and performing vacuum evaporation by using a molybdenum boat heating mode to form a medium layer, wherein the plating medium has the main function of protecting the holographic pattern, so that the brightness of the holographic pattern is better;
step S25, preparing an anti-counterfeiting medium label: coating an organosilicon modified polyurethane adhesive on a resin substrate layer in a three-roller gluing mode, then attaching a transfer layer and a resin substrate layer, drying in an oven to obtain the anti-counterfeiting label, wherein the transfer layer comprises an ink identification layer, a medium layer and a holographic pattern layer, separating the resin substrate layer from the transfer layer after the transfer layer is taken out of the oven, attaching the transfer layer with the base paper layer through a glue layer,
step S26, performing color printing: and (3) spraying anti-counterfeiting ink with fluorescent carbon dots on the surface of the transfer coating obtained in the step (S25) to obtain the multi-layer anti-counterfeiting medium frame paper.
(III) beneficial effects
The invention provides a multilayer anti-counterfeiting medium frame paper and a preparation method thereof, and the multilayer anti-counterfeiting medium frame paper has the following beneficial effects:
(1) The multi-layer anti-counterfeiting medium frame paper comprises an ink identification layer, a holographic storage layer and a color printing layer, wherein anti-counterfeiting ink can be implanted with anti-counterfeiting information, the anti-counterfeiting medium frame paper can simply and effectively perform true and false inquiry by using a reader, the holographic storage layer stores information in a photopolymer by changing a horizontal selection angle, the information is used for anti-counterfeiting, and finally the holographic storage layer is covered with the color ink, fluorescent carbon points in the color ink are used for anti-counterfeiting, and the multi-anti-counterfeiting function is achieved;
(2) The multi-layer anti-counterfeiting medium frame paper adopts holographic technology and color printing technology, so that the frame paper has good decorative effect, adopts multi-layer anti-counterfeiting technology, is easy to identify, is low in cost and durable, is stuck on a base paper layer through glue, changes color when being in contact with water or damp after being stuck, and is irrecoverable after being unwound.
Detailed Description
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions: the multi-layer anti-counterfeiting medium frame paper comprises a base paper layer and a glue layer, an ink identification layer, a holographic storage layer, a medium layer and a color printing layer which are sequentially arranged on the outer surface of the base paper layer from inside to outside, wherein the base paper layer is made of fiber materials, and plays a supporting role after being folded, and the glue layer is obtained by coating an adhesive force organosilicon modified polyurethane adhesive and plays a role in adhesion; the ink layer uses magnetic optically variable ink as a printing identification point; the holographic storage layer takes the mark in the ink identification layer as a positioning point, and a holographic pattern is overprinted to form the holographic storage layer; the medium layer protects the holographic storage layer through a compact molecular structure, and simultaneously makes holographic patterns more colorful; the color printing layer prints color ink on the surface of the frame paper through the anti-counterfeiting ink; the printing ink identification layer, the holographic storage layer and the medium layer are all positioned on the transfer coating, the transfer coating is attached to the substrate layer through the glue layer to obtain the anti-counterfeiting label, the transfer coating is attached to the substrate layer through the glue layer after being separated from the substrate layer, the color printing ink is finally sprayed on the transfer coating to form the color printing layer, and the multi-layer anti-counterfeiting medium frame paper is obtained, and the substrate layer is a PET transfer film.
Furthermore, the base paper layer is made of plant fiber materials and has good bonding effect with the glue layer, the glue layer is an organosilicon modified polyurethane adhesive, and the preparation method of the organosilicon modified polyurethane adhesive comprises the following steps: firstly, adding proper amount of polypropylene glycol and silane coupling agents with different contents into a four-neck flask, slowly dripping liquefied diphenylmethane diisocyanate into a constant pressure funnel under the condition of nitrogen environment and 75 ℃, and reacting for 3 hours to synthesize a silicon-containing NCO-terminated polyurethane prepolymer; continuously introducing nitrogen, raising the temperature to 80 ℃, sequentially adding E-51 and dibutyltin dilaurate in sequence, and reacting for 2 hours to obtain a silicon-containing polyurethane adhesive A component; the curing agent and 2,4, 6-tris (dimethylaminomethyl) phenol are used as the component B, and the components are uniformly stirred according to the proportion of 1-3:1, so as to obtain the organosilicon modified polyurethane adhesive.
Further, the ink identification layer comprises a magnetic optically variable ink, the magnetic optically variable ink is covered on the base paper layer, and the method for covering the magnetic optically variable ink on the base paper layer comprises the following steps:
step S01, preparing a magnetic optically variable film: under vacuum condition, magnetic pigment is used as raw material, and optical film layer is used as cycle to deposit for 15-25 times on glass substrate, forming a cycle composite structure of multiple isolation layers and multiple magnetic optically variable films;
step S02, separating the magnetic optically variable film: after the deposition is finished, taking out the rigid substrate from the vacuum chamber, putting the rigid substrate into an ethanol solvent for demolding, and simultaneously separating the magnetic optically variable film from the isolation layer in the periodic composite structure to obtain a separated magnetic optically variable film;
step S03, crushing the magnetic optically variable film: crushing the magnetic light thinned film obtained in the step S02 to obtain a plurality of magnetic light thinned film fragments;
step S04, coating a magnetic optically variable film: and mixing the magnetic photothin film fragments with glue, and then coating the mixture on a base paper layer to obtain the ink identification layer.
Further, the magnetic pigment is one or a mixture of iron oxide black and iron oxide brown, and the particle size of the magnetic pigment is 10-100nm.
Further, the holographic storage layer comprises a photopolymer, the preparation method of the photopolymer is to utilize photo-initiator tetraiodofluorescein sodium, a co-primer agent of phenylaminoacetic acid and a cross-linking agent of N-vinyl pyrrolidone to polymerize methacrylate under the action of illumination to generate the photopolymer, then the holographic storage layer is obtained by storing anti-counterfeiting information in the photopolymer through a laser and setting a horizontal selection angle,
further, the preparation of the holographic storage layer comprises the following steps:
step S11, preparing a mixed solution: uniformly mixing a monomer, a photoinitiator, a co-primer and a cross-linking agent (40:1:2:17) according to a proportion, placing the mixture into a cassette, carrying out ultrasonic treatment for 30min, standing for 20min, and taking an upper layer liquid for waiting use;
step S12, preparing a photopolymer: preparing a sample box with three sealed surfaces and one open surface by using two clean glass sheets and three glass gaskets with the thickness of 100-300 mu m, and pouring the prepared mixed solution from the opening to obtain a photopolymer;
step S13, information storage: storing information into a photopolymer by utilizing the action of object light and reference light, emitting light beams by using a solid laser, wherein the light beams emit two light beams, namely object light and reference light, through the other end of a prism, the object light loads holographic patterns on the photopolymer under the focusing of a convex lens, a horizontal selection angle is firstly set, and then a three-dimensional image is recorded in the photopolymer under the interaction of the object light and the reference light;
and S14, bonding the photopolymer storing information with the base paper layer or the ink identification layer through glue to obtain the holographic pattern layer.
Further, the holographic pattern layer is used for storing anti-counterfeiting information to achieve anti-counterfeiting effect, information is stored in a sample by changing the horizontal selection angle of the solid laser, and the formula of the horizontal selection angle meets the following conditions:wherein DeltaQ is the full width of diffraction, deltaθ is the included angle between the object light and the reflection plane, and theta0 and thetar respectively represent the included angle between the object light and the normal line and the included angle between the reference light and the normal line, and d is the included angle between the light source and the reflection planeDistance.
Further, the media have been used to increase the color of the pattern, being one or more of zinc sulfide, magnesium fluoride, silica, titanium dioxide.
Further, the color printing layer comprises anti-counterfeiting ink, the anti-counterfeiting ink comprises three primary color fluorescent carbon dots, the preparation mode of the fluorescent carbon dots is to prepare fluorescent carbon dot powder respectively, then the fluorescent carbon dot powder is mixed with resin, a dispersing agent and a thickening agent to prepare the anti-counterfeiting ink, and the preparation mode of the three primary color fluorescent carbon dots is as follows: dissolving polyacrylamide in water or ethanol, regulating pH=3 and pH=8 by adding hydrochloric acid, transferring the solution uniformly mixed by magnetic stirring into an autoclave, setting the temperature to 200 ℃ for 12 hours, collecting the reflected product, centrifuging at 8000r/min for 10min to remove impurities, separating, purifying, drying and grinding into red fluorescent carbon dots and yellow fluorescent carbon dot powder; dissolving sodium glutamate and copper sulfate in deionized water, transferring the solution into a stainless steel autoclave, heating for 3 hours in a 200 ℃ oven, centrifuging the synthesized blue fluorescent carbon dot solution at 6000r/min for 10 minutes to remove large particles, filtering supernatant to remove lower liquid, dialyzing the lower liquid through a dialysis membrane for 24 hours, and then vacuum freeze-drying the inner liquid in a dialysis bag for 12 hours to obtain blue fluorescent carbon dots.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions: a method of making a multi-layered anti-counterfeit media framing paper, said method comprising the steps of:
step S21, preparing a resin base layer: fixing a clean and dry resin-based bottom layer on a coating machine, wherein the coating adopts an organosilicon modified polyurethane adhesive, and the resin-based bottom layer is a PET transfer film;
step S22, preparing an ink layer: firstly, preparing a magnetic optically variable film, and printing a magnetic ink identification layer on a gravure printing machine, wherein the ink uses ferroferric oxide and ferric oxide as identification media, and the ink system is acrylic acid modified resin, and the solid content of the ink is 15-20%;
step S23, preparing a holographic storage layer: firstly preparing a photopolymer, and then storing information into the photopolymer under the action of object light and reference light, wherein the holographic storage layer is positioned at the hollowed-out area or one side of the ink layer;
step S24, smearing a medium layer: plating a medium on the molding surface of the base film by using a vacuum plating mode, and performing vacuum evaporation by using a molybdenum boat heating mode to form a medium layer, wherein the plating medium has the main function of protecting the holographic pattern, so that the brightness of the holographic pattern is better;
step S25, preparing an anti-counterfeiting medium label: coating an organosilicon modified polyurethane adhesive on a resin substrate layer in a three-roller gluing mode, then attaching a transfer layer and a resin substrate layer, drying in an oven to obtain the anti-counterfeiting label, wherein the transfer layer comprises an ink identification layer, a medium layer and a holographic pattern layer, separating the resin substrate layer from the transfer layer after the transfer layer is taken out of the oven, attaching the transfer layer with the base paper layer through a glue layer,
step S26, performing color printing: and (3) spraying anti-counterfeiting ink with fluorescent carbon dots on the surface of the transfer coating obtained in the step (S25) to obtain the multi-layer anti-counterfeiting medium frame paper.
In summary, the multi-layer anti-counterfeiting medium frame paper comprises an ink identification layer, a holographic storage layer and a color printing layer, wherein the holographic storage layer stores information in a photopolymer by changing a horizontal selection angle, the information is used for anti-counterfeiting, and finally color ink is covered on the holographic storage layer, fluorescent carbon dots in the color ink are used for anti-counterfeiting, so that the problems that the existing cigarette frame paper is simple in anti-counterfeiting technology, easy to forge and easy to transfer are solved.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The multi-layer anti-counterfeiting medium frame paper comprises a base paper layer and a glue layer, an ink identification layer, a holographic storage layer, a medium layer and a color printing layer which are sequentially arranged on the outer surface of the base paper layer from inside to outside, wherein the base paper layer is made of fiber materials and plays a supporting role after being folded, and the multi-layer anti-counterfeiting medium frame paper is characterized in that the glue layer is obtained by coating an adhesive force organic silicon modified polyurethane adhesive and plays a role of adhesion; the ink layer uses magnetic optically variable ink as a printing identification point; the holographic storage layer takes the mark in the ink identification layer as a positioning point, and a holographic pattern is overprinted to form the holographic storage layer; the medium layer protects the holographic storage layer through a compact molecular structure, and simultaneously makes holographic patterns more colorful; the color printing layer is printed with color ink on the surface of the frame paper through anti-counterfeiting ink, the color printing layer comprises the anti-counterfeiting ink, the anti-counterfeiting ink comprises three primary color fluorescent carbon dots, the fluorescent carbon dots are prepared by respectively preparing fluorescent carbon dot powder, then the fluorescent carbon dot powder is mixed with resin, a dispersing agent and a thickening agent to prepare the anti-counterfeiting ink, and the three primary color fluorescent carbon dots are prepared by the following steps: dissolving polyacrylamide in water or ethanol, adjusting pH=3 and pH=8 by adding hydrochloric acid, transferring the solution which is uniformly mixed by magnetic stirring into an autoclave, setting the temperature to 200 ℃ for 12 hours, collecting reaction products, centrifuging for 10 minutes at a rotating speed of 8000r/min to remove impurities, separating, purifying, drying and grinding into red fluorescent carbon dots and yellow fluorescent carbon dot powder; dissolving sodium glutamate and copper sulfate in deionized water, transferring the solution into a stainless steel autoclave, heating the stainless steel autoclave for 3 hours in a 200 ℃ oven, centrifuging the synthesized blue fluorescent carbon dot solution at 6000r/min for 10 minutes to remove large particles, filtering supernatant to remove lower liquid, dialyzing the lower liquid through a dialysis membrane for 24 hours, and then vacuum freeze-drying the inner liquid in a dialysis bag for 12 hours to obtain blue fluorescent carbon dots; the printing ink identification layer, the holographic storage layer and the medium layer are all positioned on the transfer coating, the transfer coating is attached to the substrate layer through the glue layer to obtain the anti-counterfeiting label, the transfer coating is attached to the substrate layer through the glue layer after being separated from the substrate layer, the color printing ink is finally sprayed on the transfer coating to form the color printing layer, and the multi-layer anti-counterfeiting medium frame paper is obtained, and the substrate layer is a PET transfer film.
2. The multi-layered anti-counterfeiting medium framing paper according to claim 1, wherein: the base paper layer is made of plant fiber materials and has good bonding effect with the glue layer, the glue layer is an organosilicon modified polyurethane adhesive, and the preparation method of the organosilicon modified polyurethane adhesive comprises the following steps: firstly, adding proper amount of polypropylene glycol and silane coupling agents with different contents into a four-neck flask, slowly dripping liquefied diphenylmethane diisocyanate into a constant pressure funnel under the condition of nitrogen environment and 75 ℃, and reacting for 3 hours to synthesize a silicon-containing NCO-terminated polyurethane prepolymer; continuously introducing nitrogen, raising the temperature to 80 ℃, sequentially adding E-51 and dibutyltin dilaurate in sequence, and reacting for 2 hours to obtain a silicon-containing polyurethane adhesive A component; the curing agent and 2,4, 6-tris (dimethylaminomethyl) phenol are used as the component B, and the components are uniformly stirred according to the proportion of 1-3:1, so as to obtain the organosilicon modified polyurethane adhesive.
3. The multi-layered anti-counterfeiting medium framing paper according to claim 1, wherein: the ink identification layer comprises magnetic optically variable ink which is covered on the base paper layer, and the method for covering the base paper layer with the magnetic optically variable ink comprises the following steps:
step S01, preparing a magnetic optically variable film: under vacuum condition, magnetic pigment is used as raw material, and optical film layer is used as cycle to deposit for 15-25 times on glass substrate, forming a cycle composite structure of multiple isolation layers and multiple magnetic optically variable films;
step S02, separating the magnetic optically variable film: after the deposition is finished, taking out the rigid substrate from the vacuum chamber, putting the rigid substrate into an ethanol solvent for demolding, and simultaneously separating the magnetic optically variable film from the isolation layer in the periodic composite structure to obtain a separated magnetic optically variable film;
step S03, crushing the magnetic optically variable film: crushing the magnetic light thinned film obtained in the step S02 to obtain a plurality of magnetic light thinned film fragments;
step S04, coating a magnetic optically variable film: and mixing the magnetic photothin film fragments with glue, and then coating the mixture on a base paper layer to obtain the ink identification layer.
4. The multi-layered anti-counterfeiting medium framing paper according to claim 1, wherein: the magnetic pigment is one or a mixture of iron oxide black and iron oxide brown, and the particle size of the magnetic pigment is 10-100nm.
5. The multi-layered anti-counterfeiting medium framing paper according to claim 1, wherein: the holographic storage layer comprises a photopolymer, wherein the preparation method of the photopolymer is to utilize photo-initiator tetrachloro-tetraiodo-fluorescein sodium, a co-primer agent of phenylaminoacetic acid and a cross-linking agent of N-vinyl pyrrolidone to polymerize methacrylate under the action of illumination to generate the photopolymer, and then store anti-counterfeiting information in the photopolymer through a laser and setting a horizontal selection angle to obtain the holographic storage layer.
6. The multi-layered anti-counterfeiting medium framing paper according to claim 1, wherein: the preparation of the holographic storage layer comprises the following steps:
step S11, preparing a mixed solution: uniformly mixing a monomer, a photoinitiator, a co-primer and a cross-linking agent (40:1:2:17) according to a proportion, placing the mixture into a cassette, carrying out ultrasonic treatment for 30min, standing for 20min, and taking an upper layer liquid for waiting use;
step S12, preparing a photopolymer: preparing a sample box with three sealed surfaces and one open surface by using two clean glass sheets and three glass gaskets with the thickness of 100-300 mu m, and pouring the prepared mixed solution from the opening to obtain a photopolymer;
step S13, information storage: storing information into a photopolymer by utilizing the action of object light and reference light, emitting light beams by using a solid laser, wherein the light beams emit two light beams, namely object light and reference light, through the other end of a prism, the object light loads holographic patterns on the photopolymer under the focusing of a convex lens, a horizontal selection angle is firstly set, and then a three-dimensional image is recorded in the photopolymer under the interaction of the object light and the reference light;
and S14, bonding the photopolymer storing information with the base paper layer or the ink identification layer through glue to obtain the holographic pattern layer.
7. A multi-layered security media framing paper according to claim 3, wherein: the holographic pattern layer is used for storing anti-counterfeiting information to achieve anti-counterfeiting effect, information is stored in a sample by changing the horizontal selection angle of the solid laser, and the formula of the horizontal selection angle meets the following conditions:wherein DeltaQ is the full width of diffraction, deltaθ is the angle between the object light and the reflection plane, and Deltaθ 0 And theta r The included angle between the object light and the normal line and the included angle between the reference light and the normal line are respectively shown, and d is the distance between the light source and the reflecting surface.
8. The multi-layered anti-counterfeit media frame paper of claim 1, wherein said media layer is used to increase the color of the pattern and is one or more of zinc sulfide, magnesium fluoride, silicon dioxide, and titanium dioxide.
9. The method for preparing the multi-layer anti-counterfeiting medium frame paper according to any one of claims 1 to 8, wherein the method comprises the following steps of: the method comprises the following steps:
step S21, preparing a resin base layer: fixing a clean and dry resin-based bottom layer on a coating machine, wherein the coating adopts an organosilicon modified polyurethane adhesive, and the resin-based bottom layer is a PET transfer film;
step S22, preparing an ink layer: firstly, preparing a magnetic optically variable film, and printing a magnetic ink identification layer on a gravure printing machine, wherein the ink uses ferroferric oxide and ferric oxide as identification media, and the ink system is acrylic acid modified resin, and the solid content of the ink is 15-20%;
step S23, preparing a holographic storage layer: firstly preparing a photopolymer, and then storing information into the photopolymer under the action of object light and reference light, wherein the holographic storage layer is positioned at the hollowed-out area or one side of the ink layer;
step S24, smearing a medium layer: plating a medium on the molding surface of the base film by using a vacuum plating mode, and performing vacuum evaporation by using a molybdenum boat heating mode to form a medium layer, wherein the plating medium has the main function of protecting the holographic pattern, so that the brightness of the holographic pattern is better;
step S25, preparing an anti-counterfeiting medium label: coating an organosilicon modified polyurethane adhesive on a resin substrate layer in a three-roller gluing mode, then attaching a transfer layer and a resin substrate layer, drying in an oven to obtain the anti-counterfeiting label, wherein the transfer layer comprises an ink identification layer, a medium layer and a holographic pattern layer, separating the resin substrate layer from the transfer layer after the transfer layer is taken out of the oven, attaching the transfer layer with the base paper layer through a glue layer,
step S26, performing color printing: and (3) spraying anti-counterfeiting ink with fluorescent carbon dots on the surface of the transfer coating obtained in the step (S25) to obtain the multi-layer anti-counterfeiting medium frame paper.
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