CN103087555B - Microstructure metallic pigment with anti-fake function and preparation method of microstructure metallic pigment - Google Patents
Microstructure metallic pigment with anti-fake function and preparation method of microstructure metallic pigment Download PDFInfo
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- CN103087555B CN103087555B CN201210532317.0A CN201210532317A CN103087555B CN 103087555 B CN103087555 B CN 103087555B CN 201210532317 A CN201210532317 A CN 201210532317A CN 103087555 B CN103087555 B CN 103087555B
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Abstract
The invention discloses a microstructure metallic pigment with an anti-fake function and a preparation method of the microstructure metallic pigment. The microstructure metallic pigment is of a multi-layer structure with a regular three-dimensional shape, and comprises an anti-fake function layer (1); and the regular three-dimensional shape is a regular shape selected from letters, digitals or polygons, and the grain size is 10-60 microns. On the basis of giving play to the anti-fake feature formed by the special shape pattern on the microstructure metallic pigment, other anti-fake features capable of being read qualitatively are integrated on the microstructure metallic pigment to enhance the composite anti-fake level of the pigment; and meanwhile, readable information of an integrated anti-fake material can be taken as a secret key to read expanded information stored in a client or a central database.
Description
Technical field
The present invention relates to the false proof metallic pigment of microstructure and its preparation method and application scope
Background technology
Metallic pigment refer to a kind of pigment being made by metal or alloy.World's annual production reaches 7,000,000 tons, is widely used in coatings industry, and principal item has aluminium powder, copper powder, zinc powder and Stainless Steel Powder, and wherein, with the consumption maximum of aluminium powder, the consumption of copper powder is few compared with aluminium powder, and luminous reflectance intensity is also slightly poorer than aluminium powder.Aluminium powder, zinc powder and Stainless Steel Powder all have corrosion-resisting function, and aluminium powder has ornamental preferably, and anodized aluminium surface has special raster effects, and are widely used at present holographic optical change film.Metallic pigment product is widely used in coating, ink and injection molding and other industrial application.The application of metallic pigment in ink is tiny sheet metal to be replaced to pigment in traditional ink or dyestuff is formulated, the ink with the glittering raster effects of unique metal.
The application of metallic pigment in ink, not only can have the glittering raster effects of the metal of above mentioning, along with the development of every technology, and metallic pigment or the pigment that contains metal level also shows its unique antifalse effect gradually in field of anti-counterfeit technology.
Containing the anti-fraud functional pigment of having of metal level or non-metal-containing layer at home and abroad also possesses some special knowledge, the CN02808832.8 of Elex Products, Inc. has disclosed multi-layered magnetic pigments sheet and the paper tinsel that a kind of magnetosphere, reflecting layer, medium layer are composited, wherein an embodiment is that mean size is the pigment flakes of 44 microns, comprises reflecting layer (aluminium)-magnetosphere (iron)-reflecting layer (aluminium) structure.This invention emphasis is realization has distinct colors optical anti-counterfeiting function at different viewing angles or input angle material, in this invention, the magnetospheric function of pigment flakes is for providing pigment aligning in magnetic field, this invention be not taking the microstructure of material and with other antiforge functions as function priority application, pigment flakes is random irregular shape, be subject to the restriction of preparation process condition, the pigment of this invention can not be prepared into regular shape.
The CN200880119100.9 of Merck Patent GmbH provides a kind of and has been embedded in by transparent inorganic matrix and at least one anti-fake material that the particulate material in this matrix forms, in this invention, the change information of anti-fake material and product have simple corresponding relation, utilize the quantity of particle in matrix and the variation of color (under different illuminate conditions), size or scale parameter thereof, form for manufacturers, batch, the specific security pigment coding such as production cycle, marketing channel, judge accordingly the correspondence of product.Using printing and the product of the anti-fake material manufacture in this invention is simple corresponding relation, real-time information acquisition while manufacturing that the realization of this invention more depends on printing, and its application must be installed supporting collecting device hardware in the time of printing.
The research with anti-fraud functional metallic pigment is less at present, the CN201110145270.8 of Shanghai Zige Optical Membrane Material Co., Ltd. has disclosed a kind of anti-counterfeiting microstructure pigment and manufacturing process thereof, obtain the microstructure individual layer flaky aluminum pigment of particle diameter 1-200 micron, regular shape (as character pattern, geometrical shape) by mold pressing, can be used as security pigment and use.This invention utilizes the shape pattern of metallic pigment itself to form anti-counterfeiting characteristic, uses magnifying glass to observe detection, without other compound antiforge functions, can not carry out quantitative false proof discriminating, has limited the extent of spreading amd application of such anti-fake material.
Summary of the invention
The object of this invention is to provide one and there are anti-fraud functional microstructure metallic pigment and preparation method thereof, the anti-counterfeiting technology defect existing to overcome prior art.
Of the present invention have anti-fraud functional microstructure metallic pigment, for having the multilayered structure of three-dimensional regular shape, wherein contains antiforge function layer;
Described three-dimensional regular shape is selected from letter, numeral or Polygons regular shape, and particle diameter is 10～60 microns;
Preferably, described in there are anti-fraud functional microstructure metallic pigment, be the multilayered structure with three-dimensional regular shape of even thickness;
Preferably, the number of plies of described multilayered structure is 2～3 layers;
Preferably, the number of plies of described multilayered structure is 3 layers, and centre is antiforge function layer, and skin is metal material layer; The Thickness Ratio of antiforge function layer and metal material layer is 1:100～1:2, and the thickness error of upper and lower double layer of metal material layer is 10 nanometers;
Preferably, the number of plies of described multilayered structure is 3 layers, and centre is metal material layer, and skin is anti-fake material layer; The Thickness Ratio of anti-fake material layer and metal material layer is 1:40～2:1, and the thickness error control of two-layer anti-fake material layer is less than 5%;
Preferably, the number of plies of described multilayered structure is two-layer, and one deck is metal material layer, and one deck is anti-fake material layer, and the Thickness Ratio of antiforge function layer and metal material layer is 1:40～2:1;
When this pigment is the numeral of double-layer structure and letter shapes, comprise two kinds of situations, overlook this pigment flakes: 1) first see antiforge function layer, then see metal material layer; 2) first see metal material layer 1, then see antiforge function layer 2.
The material of antiforge function layer, is selected from fluorescent material, twilight sunset fluorescent material, metamerism filter, raman material or magnetic anti-counterfeit functional materials more than one;
Wherein, fluorescent material, preferred excitation wavelength is 254 nanometers and 365 nanometers, reflected light is scope 400-700 nanometers (can, by the long fluorescent material Mixed Pinyin of difference reflection, obtain specific emission wavelength, play better antifalse effect); Twilight sunset fluorescent material exciting light is the UV-light of 190 nanometer～400 nanometers, and wavelength of transmitted light scope is 400-1000 nanometer;
Preferably, described fluorescent material is selected from the fluorescent material such as rare earth organic complex (including but not limited to lower valency rare earth organic complex, rare earth organic polymer title complex and rare earth organic supermolecular title complex), large lopps title complex; Be alkaline earth sulfide, the aluminate etc. of activator and co-activator with rare earth lanthanide (europium, samarium, erbium, neodymium), for example ZnS, CaS, SrAl
2o
4, CaAl
2o
4, BaAl
2o
4deng;
Described twilight sunset fluorescent material is selected from silicate systems afterglow material, metallic sulfide system afterglow material, aluminates system afterglow material, can select (ZnS:Cu, Co), (SrAl
2o
4, Eu), (CaAl
2o
4: Eu, Nd), (Sr
4al
14o
25: Eu, Dy), (SrAl
2o
4: Eu, Dy), (Ca
3mgSi
2o
8: Eu, Dy) and Eu
2+, Mn
2+coactivated R
3mgSi
2o
8(R is Ca, Sr and Ba);
Described metamerism filter is selected from the large material of SPECTRAL DIVERSITY in infrared, the ultraviolet region of human eye low sensitivity and visible-range, the red material of optical filtering that for example color changes in the time that red spectral filter is observed, can select the green of novel material company limited of Yangzhou divine boat red material, the black blueness of red material, the Shanghai Lin Duoqi Chemical Industry Science Co., Ltd red material that filters that filters that filters;
Described raman material selects to have the material of obvious characteristic raman scattering spectrum, as the surface enhanced Raman spectroscopy material taking gold and silver, palladium, platinum, the nanoparticle such as silver is covered with gold leaf, platinum is covered with gold leaf as substrate, and use separately or the ratio adjusted between different raman materials obtains specific raman scattering spectrum; Magnetic anti-counterfeit functional materials chosen from Fe, neodymium iron boron, SmCo, Z 250 and all kinds of ferrite and amorphous, the soft magnetic materials such as nanocrystalline, can select Magnetic Pig.340, the Magnetic Pig.347 of BASF;
The material of described metal material layer is selected from lower boiling metallic substance, as aluminium, magnesium, chromium, nickel etc., preferable alloy aluminium;
The preparation method with anti-fraud functional microstructure metallic pigment of the present invention, the three-decker metallic pigment manufacture craft taking centre as metal level is example, comprises the steps:
(1) select smooth substrate, on substrate, apply the glue-line of peeling off of the moldable moulding of one deck; (2) at the coating layer of peeling off glue-line surface coated and containing antiforge function material, magneticsubstance also can use the mode of evaporation to deposit to and peel off glue-line surface; (3) depositing metal layers on anti-fake material layer; (4) carry out step (2) once at metal level; (5) pass through laser ablation, obtain specific word or numeral or figure pigment, lamellar pigment is stripped down from plastic film substrate, (can vacuum separation through separating technology, also can be in liquid filtering separation) treatment zone is except being less than 10 microns and be greater than the impurity of 60 microns, obtains described have anti-fraud functional 10-60 microns of words or numeral or the false proof metallic pigment of pattern microstructure.
Wherein, the laser ablation of step (5) is method well known in the art, can be referring to the method for relevant bibliographical information.
It is only that manufacture craft order there are differences that the middle three-decker pigment for false proof layer and double-layer structure pigment are made.
The using method with anti-fraud functional microstructure metallic pigment of the present invention is as follows:
After 1%～60% the false proof metallic pigment of microstructure and 10%～90% low-melting ink vehicle, 0～50% solvent are dispersed, make the microstructure anti-forgery inks such as silk screen, photogravure, adagio, bat printing, offset printing, gravure, number.
Can detect antiforge function material by qualitative detection equipment, according to detected result, apply the identification of this security pigment, and can detect by corresponding detection by quantitative equipment, obtain quantitative information;
Described qualitative detection equipment is as FDD-300 multifunctional false-proof detector, CYI-5 multifunctional comprehensive identifier, CY-30 type bill images visualizer, and described detection by quantitative equipment is as RF-5301PC spectrograph, Thmo Scientific DXR Raman spectrometer, TD8210 soft magnetism DC test system, TD8310 permanent magnet material test macro, nominal value magnetism detector, number magnetism detector;
Set up and detect client database or central database, taking the pseudo-material quantitative information of antiforge function layer that detect as routing information (key);
Data in described client database or central database, not only comprise the routing information that detects, have the false proof man-to-man information distinguishing the true from the false, and also comprise the extend information of giving it while making database.
Can carry out identification by the qualitative detection structure to antiforge function layer, do higher level genuine/counterfeit discriminating one to one with the quantitative information reading from false proof layer, and read in client terminal or central database corresponding with it extend information as key.
The present invention is prepared and is had anti-fraud functional microstructure metallic pigment by laser etching method, the production capacity of pigment production process be improved (can multiple-layer stacked laser ablation together, spirally wound continuous laser etching).
On the basis of the anti-counterfeiting characteristic that the present invention forms at the specific shape pattern of performance microstructure metallic pigment itself, integrated other anti-counterfeiting characteristics that can qualitatively read are on such microstructure metallic pigment, strengthen the composite anti-fake rank of pigment, utilize the readable information that is integrated anti-fake material as key simultaneously, read the extend information being stored in client terminal or central database.
Brief description of the drawings
Fig. 1 be have three-dimensional regular shape 3-tier architecture there are anti-fraud functional microstructure metallic pigment.
Fig. 2 be have three-dimensional regular shape 3-tier architecture there are anti-fraud functional microstructure metallic pigment.
Fig. 3 be have three-dimensional regular shape 2 layers of structure there are anti-fraud functional microstructure metallic pigment.
Embodiment
Referring to Fig. 1～Fig. 3, of the present invention have anti-fraud functional microstructure metallic pigment, for having the multilayered structure of three-dimensional regular shape, wherein contains antiforge function layer 1;
Described three-dimensional regular shape is selected from letter, numeral or Polygons regular shape, and particle diameter is 10～60 microns;
Preferably, described in there are anti-fraud functional microstructure metallic pigment, be the multilayered structure with three-dimensional regular shape of even thickness;
Preferably, the number of plies of described multilayered structure is 2～3 layers;
Preferably, the number of plies of described multilayered structure is 3 layers, and centre is antiforge function layer 1, and skin is metal material layer 2; Antiforge function layer 1 is 1:100～1:2 with the Thickness Ratio of metal material layer 2, and the thickness error of upper and lower double layer of metal material layer 2 is 10 nanometers;
Preferably, the number of plies of described multilayered structure is 3 layers, and centre is metal material layer 2, and skin is anti-fake material layer 1; Anti-fake material layer 1 is 1:40～2:1 with the Thickness Ratio of metal material layer 2, and the thickness error control of two-layer anti-fake material layer 1 is less than 5%;
Preferably, the number of plies of described multilayered structure is two-layer, and one deck is metal material layer 2, and one deck is anti-fake material layer 1;
Antiforge function layer 1 is 1:40～2:1 with the Thickness Ratio of metal material layer 2;
When this pigment is the numeral of double-layer structure and letter shapes, comprise two kinds of situations, overlook this pigment flakes: 1) first see antiforge function layer 2, then see metal material layer 1; 2) first see metal material layer 1, then see antiforge function layer 2.
Embodiment 1
There are anti-fraud functional microstructure metallic pigment, be shaped as equilateral triangle, 40 microns of left and right of the length of side, three-decker, centre is metal level, and metal level adopts lower boiling aluminium, and both sides are fluorescent material layer, fluorescent material layer is that the composition of 10% fluorescent material (title complex of quinoline Féraud beautiful jade/triphenylphosphine oxide/thienyl trivalent Eu) is write gravure printing machine coating by shadow and formed by containing massfraction, and metal aluminium lamination forms by vapor deposition.Consisting of beyond fluorescent material in composition: DSM profit health resin NeoCryB-735,25%; Ethyl acetate, 40%; Butylacetate 22%; Other ink addition agents, 3%.Structural representation is as Fig. 1.
These trilateral microstructure metallic pigment, under the UV wavelength light of specifying is observed, show qualitatively luminous antiforge function, utilize RF-5301PC spectrograph quantitatively to measure fluorescence emission spectrum under the UV wavelength of specifying, in selected curve of spectrum designated wavelength range, the quantitative information of wave, wave first order derivative model parameter is as key, read built good client database or central database as path, to obtain corresponding with it extend information.
Embodiment 2
Microstructure metallic pigment, be shaped as regular equilateral triangle, 40 microns of left and right of the length of side, three-decker, centre is magnetosphere, and both sides are metal material layer, and metal level is selected metallic aluminium, form by vapor deposition, magnetosphere is that the ink composite of 25% magneticsubstance (Magnetic Pig.340) is write gravure printing machine coating or vacuum evaporation formation of deposits by shadow by containing massfraction.Consisting of beyond magneticsubstance in composition: DSM profit health resin NeoRez U-394,35%; Ethyl acetate, 18%; Butylacetate 15%; Other ink addition agents, 7%.
These trilateral microstructure metallic pigment, under the magnetic field condition of motion, observe, show and align qualitatively, utilize TD8310 magnetic material testing system, quantitatively read the information parameter that magnetic layer material comprises, the quantitative information parameters such as selected coercivity H b, residual induction Br, HCJ Hcj, as key, read client database or the central database built up, to obtain corresponding with it extend information as path.Structure is as Fig. 2.
Embodiment 3
Microstructure metallic pigment, are shaped as square, 40 microns of left and right of the length of side, double-layer structure, one side is metal level, and opposite side is burst of ultraviolel twilight sunset fluorescent material layer, and burst of ultraviolel twilight sunset fluorescent material layer is 15% burst of ultraviolel twilight sunset fluorescent material (Ca by containing massfraction
3mgSi
2o
8: Eu, Dy) composition write gravure printing machine by shadow and be coated with formation, metal level is by vacuum evaporation formation of deposits.Consisting of beyond composition medium afterglow material: DSM profit health resin NeoCryB-735,30%; Ethyl acetate, 33%; Butylacetate 19%; Other ink addition agents, 3%.
These microstructure metallic pigment, under the UV wavelength light source of specifying after certain hour, there is twilight sunset phenomenon towards viewer's pigment in twilight sunset material one side, detect by Quantaurus-Tan high precision fluorescence lifetime measurement system, can obtain the quantitative factor information in fluorescence emission spectral curve, the twilight sunset life-span etc. of twilight sunset material, read client database or the central database built up as path, to obtain corresponding with it extend information.Structure is as Fig. 3.
Embodiment 4
Microstructure metallic pigment, be shaped as alphabetical O, 20 microns of left and right of long shaft external diameter, 10 microns of left and right of internal diameter, three-decker, centre is metal level, both sides are Raman subject matter layer, select Single Walled Carbon Nanotube as subject matter, and subject matter material layer is by being that the ink composite of 10% this subject matter is write gravure printing machine by shadow and is coated with formation containing massfraction, metal level is selected metallic aluminium, forms by vapor deposition.Consisting of beyond composition medium afterglow material: DSM profit health resin NeoCryB-735,25%; Ethyl acetate, 40%; Butylacetate 22%; Other ink addition agents, 3%.
These O shape microstructure metallic pigment, use Thmo Scientific DXR Raman spectrometer, obtain Raman spectrogram, Raman collection of illustrative plates is used to Lorentz curve matching swarming, obtain the frequency peak corresponding with carbon nanotube diameter, read client database or the central database built up taking frequency as quantitative factor information as path, to obtain corresponding with it extend information.
Embodiment 5
Microstructure metallic pigment, are shaped as square, 40 microns of left and right of the length of side, and double-layer structure, a side is metal level, and opposite side is magnetic material layer, and the manufacture craft of metallic substance and magneticsubstance and each layer is identical with example 2.Structural representation is as Fig. 3.Consisting of beyond magneticsubstance in composition: DSM profit health resin NeoCryB-735,35%; Ethyl acetate, 18%; Butylacetate 15%; Other ink addition agents, 7%.
These square microstructure metallic pigment, under the magnetic field condition of motion, observe, show and align qualitatively, utilize TD8310 magnetic material testing system, quantitatively read the information parameter that magnetic layer material comprises, the quantitative information parameters such as selected coercivity H b, residual induction Br, HCJ Hcj, as key, read client database or the central database built up, to obtain corresponding with it extend information as path.
Claims (5)
1. there are anti-fraud functional microstructure metallic pigment, it is characterized in that, for thering is the multilayered structure of three-dimensional regular shape, wherein contain anti-fake material layer (1); Described three-dimensional regular shape is selected from letter, numeral or Polygons regular shape, and particle diameter is 10～60 microns;
The number of plies of described multilayered structure is 3 layers, and centre is anti-fake material layer (1), and skin is metal material layer (2);
Anti-fake material layer (1) is 1:100～1:2 with the Thickness Ratio of metal material layer (2), and the thickness error of upper and lower double layer of metal material layer (2) is 10 nanometers.
2. there are anti-fraud functional microstructure metallic pigment, it is characterized in that, for thering is the multilayered structure of three-dimensional regular shape, wherein contain anti-fake material layer (1); Described three-dimensional regular shape is selected from letter, numeral or Polygons regular shape, and particle diameter is 10～60 microns; The number of plies of described multilayered structure is 3 layers, and centre is metal material layer (2), and skin is anti-fake material layer (1);
Anti-fake material layer (1) is 1:40～2:1 with the Thickness Ratio of metal material layer (2), and the thickness error control of two-layer anti-fake material layer (1) is less than 5%.
3. there are anti-fraud functional microstructure metallic pigment, it is characterized in that, for thering is the multilayered structure of three-dimensional regular shape, wherein contain anti-fake material layer (1); Described three-dimensional regular shape is selected from letter, numeral or Polygons regular shape, and particle diameter is 10～60 microns; The number of plies of described multilayered structure is two-layer, and one deck is metal material layer (2), and one deck is anti-fake material layer (1);
Antiforge function layer (1) is 1:40～2:1 with the Thickness Ratio of metal material layer (2).
4. according to the anti-fraud functional microstructure metallic pigment that have described in claim 1～3 any one, it is characterized in that, the material of described anti-fake material layer, be selected from fluorescent material, metamerism filter, raman material or magnetic anti-counterfeit functional materials more than one, the material of described metal material layer is metallic aluminium.
5. the preparation method with anti-fraud functional microstructure metallic pigment according to claim 2, is characterized in that, comprises the steps:
(1) select smooth substrate, on substrate, apply the glue-line of peeling off of the moldable moulding of one deck; (2), at the coating layer of peeling off glue-line surface coated and containing antiforge function material, magneticsubstance uses the mode of evaporation to deposit to and peels off glue-line surface; (3) depositing metal layers on anti-fake material layer; (4) carry out step (2) once at metal level; (5) by laser ablation, obtain specific word or numeral or figure pigment, lamellar pigment is stripped down from plastic film substrate, through separating technology, there are anti-fraud functional microstructure metallic pigment described in acquisition.
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| CN103468056B (en) * | 2013-08-07 | 2016-03-30 | 中钞油墨有限公司 | Anti-forgery ink composition and method of making the same containing fine structure material |
| CN104710877B (en) * | 2013-12-16 | 2017-04-05 | 中国人民银行印制科学技术研究所 | A kind of anti-forgery ink |
| CN105086514B (en) * | 2014-05-21 | 2017-06-30 | 中钞特种防伪科技有限公司 | A kind of method for manufacturing optically variable pigments |
| CN104789000B (en) * | 2015-03-11 | 2017-07-18 | 中钞油墨有限公司 | The high yield preparation method of micro-structural security pigment |
| CN105303393A (en) * | 2015-12-05 | 2016-02-03 | 深圳市天兴诚科技有限公司 | Anti-fake method |
| CN107499015A (en) * | 2017-08-30 | 2017-12-22 | 郑州华美彩印纸品有限公司 | A kind of electrochemical aluminum foil |
| CN111695658B (en) * | 2019-03-12 | 2024-03-29 | 上海交通大学 | Anti-counterfeiting method based on PUF, PUF anti-counterfeiting label and preparation method thereof |
| CN111546805B (en) * | 2020-04-28 | 2021-05-25 | 中山大学 | Material capable of preparing holographic color pattern and preparation method and application thereof |
| CN111709507B (en) * | 2020-06-14 | 2021-09-28 | 北京化工大学 | Multilayer color code micro-marker capable of coding information and preparation method thereof |
| CN114891367A (en) * | 2021-01-26 | 2022-08-12 | 中钞特种防伪科技有限公司 | Flaky optical pigment, preparation method thereof and anti-counterfeiting element |
| CN114103538B (en) * | 2021-10-12 | 2022-10-14 | 维达力实业（赤壁）有限公司 | Coating film and powder with prefabricated structure and preparation method thereof |
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| US6643001B1 (en) * | 1998-11-20 | 2003-11-04 | Revco, Inc. | Patterned platelets |
| ES2462369T3 (en) * | 2000-01-21 | 2014-05-22 | Jds Uniphase Corporation | Optically variable safety devices |
| US20020160194A1 (en) * | 2001-04-27 | 2002-10-31 | Flex Products, Inc. | Multi-layered magnetic pigments and foils |
| CN1552589B (en) * | 2003-05-29 | 2010-05-05 | 中国科学院光电技术研究所 | Continuous microlens array amplifying displaying antifogery method |
| CN1741095A (en) * | 2005-07-14 | 2006-03-01 | 中国科学院光电技术研究所 | The minitype false proof sheet metal that contains microfilm of characters |
| DE102010047250A1 (en) * | 2009-12-04 | 2011-06-09 | Giesecke & Devrient Gmbh | Security element, value document with such a security element and manufacturing method of a security element |
| CN102585577B (en) * | 2011-01-17 | 2014-12-31 | 汕头市龙华珠光颜料有限公司 | Waterproof pigment, preparation method and application thereof |
| CN102269927B (en) * | 2011-05-31 | 2012-12-12 | 上海紫格光学薄膜材料有限公司 | Anti-counterfeiting microstructure pigment and manufacturing process thereof |
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Address after: 288 Xiuyan Road, Pudong New Area, Shanghai, 201315 Patentee after: CHINA BANKNOTE INK Co.,Ltd. Patentee after: China Banknote Printing and Minting Group Co.,Ltd. Address before: 288 Xiuyan Road, Pudong New Area, Shanghai, 201315 Patentee before: CHINA BANKNOTE INK Co.,Ltd. Patentee before: CHINA BANKNOTE PRINTING AND MINTING Corp. |
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