CN107057688A - A kind of ZnO quantum dots and anti-forgery ink prepared therefrom and secure file - Google Patents

A kind of ZnO quantum dots and anti-forgery ink prepared therefrom and secure file Download PDF

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Publication number
CN107057688A
CN107057688A CN201611268174.1A CN201611268174A CN107057688A CN 107057688 A CN107057688 A CN 107057688A CN 201611268174 A CN201611268174 A CN 201611268174A CN 107057688 A CN107057688 A CN 107057688A
Authority
CN
China
Prior art keywords
quantum dot
zno quantum
ink
printing
base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611268174.1A
Other languages
Chinese (zh)
Inventor
施周
吴旺宝
郭界
陆泰伟
金劼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Banknote Printing Co Ltd
China Banknote Printing and Minting Corp
Original Assignee
Shanghai Banknote Printing Co Ltd
China Banknote Printing and Minting Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Banknote Printing Co Ltd, China Banknote Printing and Minting Corp filed Critical Shanghai Banknote Printing Co Ltd
Priority to CN201611268174.1A priority Critical patent/CN107057688A/en
Publication of CN107057688A publication Critical patent/CN107057688A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/54Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B42BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42DBOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30Identification or security features, e.g. for preventing forgery
    • B42D25/36Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378Special inks
    • B42D25/387Special inks absorbing or reflecting ultra-violet light
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/50Sympathetic, colour changing or similar inks

Abstract

The invention provides a kind of ZnO quantum dot and use anti-forgery ink and secure file made from the ZnO quantum dot, using zinc acetate and DMF as raw material, single step reaction obtains ZnO quantum dot in a heated condition, the ZnO quantum dot prepared is less than 50nm fluorescence emission peak under 325nm exciting lights in 380nm or so ultraviolet invisible area one half-peak breadth of formation.The anti-forgery ink that ZnO quantum dot addition printing is rolled into base in black adds the special glow peak of ultraviolet invisible area in the case where not influenceing the anti-counterfeiting performance of base ink, strengthens anti-counterfeiting performance.It the anti-forgery ink printing can be used to prepare secure file, increase the anti-counterfeiting performance of secure file.

Description

A kind of ZnO quantum dot and anti-forgery ink prepared therefrom and secure file
Technical field
The present invention relates to field of anti-counterfeit technology, more particularly to a kind of preparation method of ZnO quantum dot, a kind of anti-forgery ink with And the secure file being printed as using anti-forgery ink.
Background technology
In current anti-counterfeit field, Antiforge fluorescent ink is weighed very much because of its false proof disguised and printability as a kind of The security element wanted, is widely used in bank note, passport, stamp, valuable money and all kinds of antifalsification labels.Current fluorescence Fluorescent material in ink is generally organic-fuel or fluorescent material, it is advantageous that the number when fluorescent material in ink is higher When, fluorescent brightness is brighter under uviol lamp.And developing rapidly with fluorescent material, regions of fluorescence emissions can be from visible region Extend to region of ultra-red.But its inferior position is also clearly, traditional its fluorescence emission peak half-peak breadth of fluorescent material is wider, and colourity is not It is pure, easily copied by colorant match, and half-peak breadth is wider is unfavorable for machine-readable discrimination;Single fluorescent material is easily authenticated;Furthermore, it is assorted Fluorescent material is easy to buy and prepared, and substantially reduces imitation difficulty, and this causes its antiforge function to be reduced.
Quanta point material is as a kind of state-of-the art fluorescent material, compared with conventional fluorescent material, with obviously Advantage, has extensive research in fluorescence falsification preventing field.The material of traditional quantum dot, the quantum such as CdTe, CdSe and CdS Point material has high fluorescence efficiency, and color can regulate and control from green with size changes to red.But for antifalse effect, utilize The characteristic that quanta point material lights in visibility region, the characteristics of luminescence difference of this and conventional fluorescent material is less, thus false proof Performance difference is also little.
To sum up, it is necessary to find a kind of fluorescent material for being conducive to machine-readable discrimination and being lighted in black light region, peace is realized The manufacture of whole file, improves antiforge function.
The content of the invention
To solve the above problems, the invention provides a kind of ZnO quantum dot, under 325nm exciting lights, in 380nm or so Ultraviolet invisible area one half-peak breadth of formation be less than 50nm fluorescence emission peak, the luminescence feature peak is different from any at present A kind of fluorescent material, distinguishes beneficial to machine-readable, improves antiforge function.
The purpose of the present invention is achieved through the following technical solutions:
A kind of ZnO quantum dot, is that raw material passes through one-step method in a heated condition with zinc acetate and DMF (dimethylformamide) ZnO quantum dot is made in reaction, and obtained ZnO quantum dot is under 325nm exciting lights, in 380nm or so ultraviolet invisible area Domain forms the fluorescence emission peak that a half-peak breadth is less than 50nm.
Further, the one-step method specifically includes following steps:(1) it is (1-2) by mass ratio:100 zinc acetate and DMF solution is mixed, and stirring 10-30min dissolves zinc acetate at 25-35 DEG C of temperature, and reaction temperature then is promoted into 90- 110 DEG C and keep 5-10h, you can form ZnO quantum dot;(2) ZnO quantum dot is centrifuged, dried, obtain powdered ZnO quantum Point.
Another object of the present invention is to provide a kind of anti-forgery ink, the anti-forgery ink in printing with base ink by being added Enter above-mentioned ZnO quantum dot mixed rolling to form, ZnO quantum dot and printing are black in mass ratio (1-3) with base:(9-7) is mixed.
Further, the printing is offset printing base ink, carved gravure base ink, varnish or gloss oil with base ink.
Further, the printing base ink is common base ink or fluorescent base ink, when printing is that fluorescent base is black with base ink, The fluorescent base ink has different fluorescence emission wavelengths, the ZnO quantum dot of addition under same exciting light from ZnO quantum dot Have no effect on the anti-counterfeiting performance of original printing base ink.
Another object of the present invention is to provide to be printed with a kind of secure file, the secure file to prevent using above-mentioned The security pattern of pseudo- ink printing.
The beneficial effects of the present invention are:(1) the reaction generation ZnO quantum dot (reaction using zinc acetate in DMF solvent The visible under type 1 of equation), it is different from the ZnO quantum dot that at present conventional alcohol method prepares and (generally requires 3-4 step Prepare), and this preparation method is simple, process stabilizing, the obtained ZnO amounts in wide temperature range and wider reaction time range Son point can produce the characteristic peak of half-peak breadths of the 380nm or so less than 50nm under 325nm exciting lights;
Zn(Ac)2·2H2O+(CH3)2NC(O)H→ZnO+(Ac)2CHN(CH3)2+2H2O ... ... formulas 1
(2) it is located at visible region at present, with common fluorescent material and invariably more at the fluorescent characteristics peak of most ZnO quantum dots Together, ZnO quantum dot produces fluorescent characteristics peak and is different from any fluorescent material at present and made from this preparation method, adds The anti-forgery ink of ZnO quantum dot made from this preparation method or the fluorescent characteristics peak of secure file are located at 380nm invisible area Domain, outward appearance does not develop the color, and improves anti-counterfeiting performance.
Brief description of the drawings
The fluorescent effect spectrogram that the secure file of Fig. 1 embodiment of the present invention 3 is produced under 325nm exciting lights.
Embodiment
Principle below in conjunction with specific embodiment for the present invention is further elaborated.
Embodiment 1
10g zinc acetates and 1000ml DMF solutions are taken, 10min is stirred at 25 DEG C dissolves zinc acetate, then will reaction Temperature is promoted to 90 DEG C and kept for 5 hours, obtains white ZnO quantum dot precipitation.About 3g is obtained after centrifugation, 50 DEG C of dry 2h ZnO quantum dot white powder.
The above-mentioned quantum dot powder of 3g and 7g offset printing base ink is taken to be mixed and made into the offset ink containing quantum dot.
Above-mentioned offset ink is printed into specific pattern and forms a kind of secure file, this secure file is in nothing under natural light Color, under 325nm exciting light, does not develop the color in appearance, but from fluorescing frequencies, in 380nm or so ultraviolet invisible area Domain forms the fluorescence emission peak that a half-peak breadth is less than 50nm, and this is different from any fluorescent material at present, so as to form anti- Pseudo- effect.
Embodiment 2
10g zinc acetates and 900ml DMF solutions are taken, 30min is stirred at 30 DEG C dissolves zinc acetate, then will reaction temperature Degree is promoted to 95 DEG C and kept for 8 hours, obtains white ZnO quantum dot precipitation.About 3g is obtained after centrifugation, 50 DEG C of dry 2h ZnO quantum dot white powder.
The above-mentioned quantum dot powder of 3g and 7g offset printing red fluorescence base ink is taken to be mixed and made into the offset ink containing quantum dot.
Above-mentioned offset ink is printed into specific pattern and forms a kind of secure file, this secure file is in nothing under natural light Color, under 325nm exciting light, does not show red fluorescence in appearance, but from fluorescing frequencies, except occurring in 700nm or so Fluorescence peak, while in 380nm or so fluorescence emission peak of one half-peak breadth of ultraviolet invisible area formation less than 50nm, this area Not in current any fluorescent material, so as to form antifalse effect.
Embodiment 3
20g zinc acetates and 2200ml DMF solutions are taken, 20min is stirred at 35 DEG C dissolves zinc acetate, then will reaction Temperature is promoted to 105 DEG C and kept for 10 hours, obtains white ZnO quantum dot precipitation.Obtained about after centrifugation, 50 DEG C of dry 2h 6g ZnO quantum dot white powders.
The above-mentioned quantum dot powder of 3g and 7g offset printings varnish or mill base is taken to be mixed and made into the offset ink containing quantum dot, the oil After ink is by offset printing, obtained secure file is detected by Fluoromax-4 XRFs, can read Fig. 1 institutes The fluorescent effect shown, can effectively be different from conventional fluorescent ink.

Claims (6)

1. a kind of ZnO quantum dot, using zinc acetate and DMF as raw material in a heated condition, reacted by one-step method and ZnO quantum be made Point, obtained ZnO quantum dot is under 325nm exciting lights, in 380nm or so ultraviolet invisible area one half-peak breadth of formation Fluorescence emission peak less than 50nm.
2. a kind of ZnO quantum dot according to claim 1, it is characterised in that the one-step method comprises the following steps:(1) It is (1-2) by mass ratio:100 zinc acetate and DMF solution mixing, stirring 10-30min makes zinc acetate at 25-35 DEG C of temperature Dissolving, is then promoted to 90-110 DEG C by reaction temperature and keeps 5-10h, you can form ZnO quantum dot;(2) by ZnO quantum dot Centrifuge, dry, obtain powdered ZnO quantum dot.
3. a kind of anti-forgery ink, it is characterised in that the anti-forgery ink in printing with base ink by being added such as claim 1 institute The ZnO quantum dot mixed rolling stated is formed, and ZnO quantum dot and printing are black in mass ratio (1-3) with base:(9-7) is mixed.
4. a kind of anti-forgery ink according to claim 3, it is characterised in that the printing is offset printing base ink, carving with base ink Carve gravure base ink, varnish or gloss oil.
5. a kind of anti-forgery ink according to claim 3, it is characterised in that the printing base ink is black or glimmering for common base Light base ink, when printing is that fluorescent base is black with base ink, the fluorescent base ink has not under same exciting light with ZnO quantum dot Same fluorescence emission wavelengths.
6. a kind of secure file, it is characterised in that have on the secure file using anti-as described in claim any one of 3-5 The security pattern of pseudo- ink printing.
CN201611268174.1A 2016-12-31 2016-12-31 A kind of ZnO quantum dots and anti-forgery ink prepared therefrom and secure file Pending CN107057688A (en)

Priority Applications (1)

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CN201611268174.1A CN107057688A (en) 2016-12-31 2016-12-31 A kind of ZnO quantum dots and anti-forgery ink prepared therefrom and secure file

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611268174.1A CN107057688A (en) 2016-12-31 2016-12-31 A kind of ZnO quantum dots and anti-forgery ink prepared therefrom and secure file

Publications (1)

Publication Number Publication Date
CN107057688A true CN107057688A (en) 2017-08-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111055609A (en) * 2019-12-26 2020-04-24 上海印钞有限公司 Anti-counterfeiting self-identification method based on transparent window

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008141067A1 (en) * 2007-05-09 2008-11-20 Hewlett-Packard Development Company, L.P. Printed security mark

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008141067A1 (en) * 2007-05-09 2008-11-20 Hewlett-Packard Development Company, L.P. Printed security mark

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李酽: "升温速率对氧化锌空心微球形貌及性能的影响", 《化工新型材料》 *
王玲玲: "ZnO纳米材料的水热/溶剂热合成与物性研究", 《中国博士论文全文数据库》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111055609A (en) * 2019-12-26 2020-04-24 上海印钞有限公司 Anti-counterfeiting self-identification method based on transparent window

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Application publication date: 20170818