CN109232619A - Multicolor fluorescence material based on rare earth metal organic frame and preparation method thereof and anti-counterfeiting ink application - Google Patents
Multicolor fluorescence material based on rare earth metal organic frame and preparation method thereof and anti-counterfeiting ink application Download PDFInfo
- Publication number
- CN109232619A CN109232619A CN201811305118.XA CN201811305118A CN109232619A CN 109232619 A CN109232619 A CN 109232619A CN 201811305118 A CN201811305118 A CN 201811305118A CN 109232619 A CN109232619 A CN 109232619A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- metal organic
- organic frame
- earth metal
- multicolor fluorescence
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/307—Monocyclic tricarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
The invention discloses multicolor fluorescence materials based on rare earth metal organic frame and preparation method thereof and anti-counterfeiting ink application.By rare earth nitrate solution, 1,3,5- benzenetricarboxylic acids, anhydrous sodium acetate, dehydrated alcohol, N, dinethylformamide and deionized water after mixing, are placed in baking oven at 75 DEG C and react, and take out centrifugation, with deionized water and dehydrated alcohol washing and drying, it is made after grinding.Rare earth is yttrium, terbium and europium.The materials synthesis condition is simple, light emission luminance is high, the photochromic adjusting from green to red color range may be implemented, the preset security pattern comprising a certain particular color or blend color is printed by ink-jet printer, pattern after printing is recessiveness in the sunlight, overcomes the not strong problem of the concealment occurred in anti-counterfeit printing.254nm ultraviolet lamp excitation pattern is used in fake certification, is shown preset particular color or blend color, is reached preferable antifalse effect.
Description
Technical field
The invention belongs to anti-counterfeiting ink field, in particular to a kind of multicolor fluorescence material based on rare earth metal organic frame
And preparation method thereof with anti-counterfeiting ink application.
Background technique
With the fast development of economic society, the velocity of liquid assets of the wealth of society is accelerated, for commodity money and drug etc.
It forges and personation criminal activity is becoming increasingly rampant, great property loss is caused to numerous people.25-26 days in May, 2004,
" first whole world crack down on counterfeit goods conference " is held in Brussels general headquarters of World Customs Organization.Meeting material shows that the whole world is palmed off and infringement
Commodity value is more than 600,000,000,000 dollars, is equivalent to the 7% of quantum of world trade, has become and be only second to terrorist activity, peddle poison
The big public hazards in the third place in the world of product.It palms off infringing activity and damages investment environment, inhibit the initiative spirit of people, cause government revenue stream
It loses, induces social concern.Therefore this illegal activity needs severe strike, in addition to legally providing a set of perfect system
It spends outside regulation, must also be developed in anti-counterfeiting technology.
Regulation anti-counterfeiting technology refers in China's national standard " takes, in a certain range to reach anti-fake purpose
It can accurately discern the false from the genuine and be not easy the technology for being imitated and replicating." at present common anti-fake mode be mainly physical security technology,
Including holographic false proof, radio frequency identification etc., although these technologies are difficult to replicate, antifalsification is preferable, but there is also equipment to take simultaneously
It builds and problem that maintenance cost is high, therefore the appearance of chemical anti-fake material, just overcomes this disadvantage.
For enterprise, anti-counterfeiting ink using relatively broad.And for the different function of anti-counterfeiting ink, have
The anti-counterfeiting ink of fluorescent characteristic is then most approved by industry.And for certain fluorescence falsification preventing inks, such as quantum dot, although it is sent out
Brightness is strong, but it can also show certain color in the sunlight, and the concealment as anti-fake material is then had a greatly reduced quality.This
Outside, existing many fluorescent materials for being used as anti-counterfeiting ink shine photochromic single, in long-term use under burst of ultraviolel
It is easy to be imitated, ineffective security.Therefore, it is strong and strong through excitation response to develop a kind of concealment, light emission luminance is high, and sends out
The photochromic changeable anti-fake material of light or a target constantly pursued.
Metal organic frame, unique structure impart its numerous physicochemical properties, make its every field all
It is applied.Rare earth element is able to achieve shining for multiple color due to its energy level abundant, therefore has emphatically in display illumination
The effect wanted.Rare earth element is introduced in metal organic frame, is utilized " antenna effect ", the energy transmission of ligand to rare earth from
Son can generate stronger shine；In addition, by the doping of a variety of rare earth elements, may be implemented it is photochromic adjustable, this is more
Color luminescent material is used in the printing of security pattern, can reduce the possibility that anti-fake material is repeated.
In conclusion needing to develop multicolor fluorescence material the answering in anti-counterfeiting ink based on rare earth metal organic frame
With, it is weak and shine photochromic single deficiency to solve concealment in existing chemiluminescence anti-fake material, a kind of synthesis work is provided
Skill is simple, light emission luminance is strong and photochromic adjustable anti-counterfeiting ink.
Summary of the invention
It is an object of that present invention to provide a kind of multicolor fluorescence material based on rare earth metal organic frame, solution is existing not
Foot prints the preset security pattern comprising a certain particular color or blend color by ink-jet printer, after printing
Pattern be in the sunlight it is recessive, 254nm ultraviolet lamp excitation pattern is used in fake certification, shows preset particular color
Or blend color, color is adjustable in green to red color range, reaches antifalse effect.
Another object of the present invention is to provide the above-mentioned multicolor fluorescence anti-counterfeiting inks based on rare earth metal organic frame
Preparation method.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of multicolor fluorescence material based on rare earth metal organic frame, is prepared: rare earth nitrades are molten by following methods
Liquid, 1,3,5- benzenetricarboxylic acids, anhydrous sodium acetate, dehydrated alcohol, n,N-Dimethylformamide and deionized water after mixing,
It is placed in baking oven at 75 DEG C and reacts, centrifugation is taken out, and with after deionized water and dehydrated alcohol washing and drying, in agate mortar
After grinding, the multicolor fluorescence material based on rare earth metal organic frame is made.
In the above-mentioned multicolor fluorescence material based on rare earth metal organic frame, the rare earth is yttrium, terbium and europium.
In the above-mentioned multicolor fluorescence material based on rare earth metal organic frame, the preparation of the rare earth nitrate solution
Method includes the following steps: to take yttrium nitrate hexahydrate, addition deionized water dissolving constant volume；Terbium oxide powder is taken, is added appropriate
Concentrated nitric acid is stirred to after being completely dissolved, and deionized water is added and is settled to；Europium oxide powder is taken, appropriate concentrated nitric acid is added and stirs to complete
After fully dissolved, deionized water constant volume is added.
Using the anti-counterfeiting ink of the above-mentioned multicolor fluorescence material preparation based on rare earth metal organic frame, by what is matched as follows
Group is grouped as:
0.1 g of rare earth metal organic frame powder
Dehydrated alcohol 20-25mL
Ethylene glycol 20-25mL
Glycerine 1-4mL
Diethylene glycol (DEG) 1-4 mL
2 mL of sodium dodecyl sulfate solution.
The preparation method of anti-counterfeiting ink includes the following steps: each component after mixing, ultrasonic disperse, takes supernatant after centrifugation
Liquid is to get the anti-counterfeiting ink prepared to the multicolor fluorescence material based on rare earth metal organic frame.
The multicolor fluorescence, color is adjustable from green to red color range, including green, yellow, orange-yellow, orange, orange
It is red, red.
Compared with prior art, the invention has the following advantages:
The present invention provides a kind of multicolor fluorescence material based on rare earth metal organic frame and preparation method thereof and anti-counterfeiting inks
Using the materials synthesis condition is simple, and light emission luminance is high, and the photochromic adjusting from green to red color range may be implemented, pass through spray
Black printer prints the preset security pattern comprising a certain particular color or blend color, and the pattern after printing is in day
It is recessiveness under light, overcomes the not strong problem of the concealment occurred in anti-counterfeit printing.It is ultraviolet using 254nm in fake certification
Lamp excitation pattern shows preset particular color or blend color, reaches preferable antifalse effect.
Detailed description of the invention
Fig. 1 is color in embodiment 1 ~ 2 from green to the X of red adjustable rare earth metal organic frame multicolor fluorescence material
Ray powder diffraction pattern.The map for wherein indicating " s " is with La (BTC) 6H2The crystallography message file of O
The simulated diffraction map that (Crystallographic Information File, cif) is drawn indicates the sample difference of " a-h "
Indicate the volume ratio that feeds intake in embodiment 1 ~ 2 according to yttrium nitrate, terbium nitrate and europium nitrate solution: 3:7:0; 5:14:1; 2:7:
1; 3:14:3; 1:7:2; 1:14:5; 0:7:3;8 samples of 7:0:3.
It according to the volume ratio that feeds intake of yttrium nitrate, terbium nitrate and europium nitrate solution is the green of 3:7:0 that Fig. 2, which is in embodiment 1 ~ 2,
The scanning electron microscope image of light emitting rare earth metal organic framework materials.Amplification factor is 30,000 times, and length of the scale is in figure
1μm。
It is the launching light spectrogram of rare earth metal organic frame multicolor fluorescence material at room temperature that Fig. 3, which is in embodiment 1 ~ 2,.Swash
Hair wavelength is 300nm, and spectral region is 450 nm -750nm.Wherein, indicate that the sample of " a-h " respectively indicates in embodiment 1 ~ 2
According to the volume ratio that feeds intake of yttrium nitrate, terbium nitrate and europium nitrate solution: 3:7:0; 5:14:1; 2:7:1; 3:14:3; 1:7:
2; 1:14:5; 0:7:3;8 samples of 7:0:3.
Fig. 4 is the chromaticity coordinates figure of the rare earth metal organic frame multicolor fluorescence material of Color tunable in embodiment 1 ~ 2.Its
In, indicate that the chromaticity coordinates of " a-h " respectively indicates the body that feeds intake in embodiment 1 ~ 2 according to yttrium nitrate, terbium nitrate and europium nitrate solution
Product ratio: 3:7:0; 5:14:1; 2:7:1; 3:14:3; 1:7:2; 1:14:5; 0:7:3;The color of 8 samples of 7:0:3 is sat
Mark.
It according to the volume ratio that feeds intake of yttrium nitrate, terbium nitrate and europium nitrate solution is the green of 3:7:0 that Fig. 5, which is in embodiment 1 ~ 4,
Effect of the light emitting metal organic frame fluorescence falsification preventing ink on ink-jet printer after print pattern under 254nm ultraviolet lamp
Figure.
Fig. 6 is the Huang that volume ratio is 5:14:1 that feeds intake in embodiment 1 ~ 4 according to yttrium nitrate, terbium nitrate and europium nitrate solution
Effect of the light emitting metal organic frame fluorescence falsification preventing ink on ink-jet printer after print pattern under 254nm ultraviolet lamp
Figure.
It according to the volume ratio that feeds intake of yttrium nitrate, terbium nitrate and europium nitrate solution is the red of 7:0:3 that Fig. 7, which is in embodiment 1 ~ 4,
Effect of the light emitting metal organic frame fluorescence falsification preventing ink on ink-jet printer after print pattern under 254nm ultraviolet lamp
Figure.
Fig. 8 is the Huang that volume ratio is 5:14:1 that feeds intake in embodiment 1 ~ 4 according to yttrium nitrate, terbium nitrate and europium nitrate solution
Effect picture of the light emitting metal organic frame fluorescence falsification preventing ink on ink-jet printer after print pattern under fluorescent light.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
Embodiment 1: the preparation of rare earth nitrate solution:
Yttrium nitrate hexahydrate 1.9150g is weighed, deionized water stirring and dissolving is added and is settled to 50 mL；Weighing purity is
99.99% 1.8692 g of terbium oxide powder, is added appropriate concentrated nitric acid and stirs to after being completely dissolved, and deionized water is added and is settled to
50 mL；1.7596 g of europium oxide powder that purity is 99.99% is weighed, appropriate concentrated nitric acid is added and stirs to after being completely dissolved, adds
Enter deionized water and is settled to 50 mL；0.0150 g lauryl sodium sulfate powder is weighed, deionized water dissolving is added and is settled to 50
mL。
Embodiment 2: the synthesis of rare earth metal organic frame multicolor fluorescence material:
By the rare earth nitrades of 0.1 mol/L respectively according to yttrium nitrate, terbium nitrate and europium nitrate solution 3:7:0; 5:14:1; 2:
7:1; 3:14:3; 1:7:2; 1:14:5; 0:7:3;The volume ratio of 7:0:3 feeds intake, and rare earth nitrades total volume is 2.8
ML, and 1,3, the 5- benzenetricarboxylic acids of 0.08 g, the anhydrous sodium acetate of 0.025g, 8 mL dehydrated alcohols, 8 mL N, N- bis- are added
Methylformamide, 3.6 mL deionized waters after mixing, are placed in baking oven at 75 DEG C after reacting 48 h, use after taking-up
4000 rpm are centrifuged 5min, and repeatedly wash centrifugation with deionized water and dehydrated alcohol, after drying, grind in agate mortar
Afterwards, rare earth metal organic frame powder sample is obtained.
Embodiment 3: the preparation of the multicolor fluorescence anti-counterfeiting ink based on rare earth metal organic frame
0.1 g of rare earth metal organic frame powder
Dehydrated alcohol 22.5mL
Ethylene glycol 22.5mL
2.5 mL of glycerine
2.5 mL of diethylene glycol (DEG)
2 mL of sodium dodecyl sulfate solution
After mixing by raw material, it after 30 min of ultrasonic disperse, after being centrifuged 5min on centrifuge with 1000 rpm revolving speeds, takes
Clear liquid to get arrive the multicolor fluorescence anti-counterfeiting ink based on rare earth metal organic frame.
Embodiment 4: test experiments
1. for the structural property of rare earth metal organic frame in above-described embodiment 1 ~ 2, as shown in the result of Fig. 1, according to this hair
The color that bright preparation method obtains all has La (BTC) 6H from green to red adjustable rare earth metal organic frame2The knot of O
Structure (crystal structural data is included by Cambridge crystal structural data center (CCDC), and No. CCDC are as follows: 290771).
2. being 3:7:0's with the volume ratio that feeds intake in above-described embodiment 1 ~ 2 according to yttrium nitrate, terbium nitrate and europium nitrate solution
For green emission metal organic frame, pattern is as shown in the result of Fig. 2.The rare earth metal organic frame is more uniform stick
Shape structure, width are 100 ~ 200nm, and length reaches several μm.
3. the spectrum test condition of rare earth metal organic frame in embodiment 1 ~ 2.
The emission spectrum of burst of ultraviolel, using Xe lamp as excitation light source, adjusting excitation wavelength through monochromator is 300nm,
Spectrum test range is 450nm -750 nm.
4. the spectrum test result of rare earth metal organic frame in embodiment 1 ~ 2.
Fig. 3 is the launching light spectrogram of the rare earth metal organic frame fluorescent material of Color tunable in embodiment 1 ~ 2.?
Under 300nm excitation, according to the green light green emission sample that volume ratio is 3:7:0 that feeds intake of yttrium nitrate, terbium nitrate and europium nitrate solution
Product obtain several relatively narrow emission peaks that peak value is located at 541nm, belong to the f-f transition of terbium element in metal organic frame, tool
Body ownership is as follows: being belonging respectively at about 486,541,581,617 nm5D4 – 7FJThe jump of (J=6,5,4,3)
It moves.Peak value is obtained according to the red emission sample that volume ratio is 7:0:3 that feeds intake of yttrium nitrate, terbium nitrate and europium nitrate solution to be located at
Several relatively narrow emission peaks of 613nm belong to the f-f transition of europium element in metal organic frame, and specific ownership is as follows: about
Belong at 580,590,613,647,687 nm5D0 – 7FJ’The transition of (J '=0,1,2,3,4).Remaining is co-doped with
Sample then obtains belonging to the emission peak of terbium element and europium element simultaneously.
Fig. 4 is the chromaticity coordinates figure of the rare earth metal organic frame fluorescent material of Color tunable in embodiment 1 ~ 2.Wherein, it marks
The chromaticity coordinates of bright " a-h " respectively indicates the volume ratio that feeds intake in embodiment 1 ~ 2 according to yttrium nitrate, terbium nitrate and europium nitrate solution:
3:7:0; 5:14:1; 2:7:1; 3:14:3; 1:7:2; 1:14:5; 0:7:3;The chromaticity coordinates of 8 samples of 7:0:3.Its
Color gamut changes in green between red, and changes obvious.
Fig. 5,6,7 are based on the multicolor fluorescence anti-counterfeiting ink of rare earth metal organic frame in embodiment 1 ~ 4 in inkjet printing
Effect on machine after print pattern under 254nm ultraviolet lamp.By taking green, yellow and red fluorescence anti-counterfeiting ink as an example, utilization is green
Color fluorescence falsification preventing ink printed goes out Zhongshan University's school badge pattern；Using yellow fluorescence anti-counterfeiting ink print Sun Yat-sen as and
" SunYat-sen " printed words；Pattern in 2 D code is printed using red ink.
Fig. 8 be embodiment 1 ~ 4 in based on the multicolor fluorescence anti-counterfeiting ink of rare earth metal organic frame on ink-jet printer
Effect after print pattern under fluorescent light.With the volume ratio that feeds intake according to yttrium nitrate, terbium nitrate and europium nitrate solution for 5:14:
For 1 yellow emission metal organic frame fluorescence falsification preventing ink, the pattern printed is stealth in the sunlight, is overcome well
Certain anti-counterfeiting inks concealment not strong disadvantage in the sunlight.
Claims (5)
1. a kind of multicolor fluorescence material based on rare earth metal organic frame, which is characterized in that be prepared by following methods: will
Rare earth nitrate solution, 1,3,5- benzenetricarboxylic acid, anhydrous sodium acetate, dehydrated alcohol, N,N-dimethylformamide and deionized water
After mixing, it is placed in baking oven and is reacted at 75 DEG C, take out centrifugation, and with after deionized water and dehydrated alcohol washing and drying,
After grinding in agate mortar, the multicolor fluorescence material based on rare earth metal organic frame is made.
2. as described in claim 1 based on the multicolor fluorescence material of rare earth metal organic frame, which is characterized in that
The rare earth is yttrium, terbium and europium.
3. as claimed in claim 2 based on the multicolor fluorescence material of rare earth metal organic frame, it is characterised in that the rare earth
The preparation method of nitrate solution includes the following steps: to take yttrium nitrate hexahydrate, addition deionized water dissolving constant volume；Take oxidation
Terbium powder is added appropriate concentrated nitric acid and stirs to after being completely dissolved, and deionized water constant volume is added；Europium oxide powder is taken, is added appropriate
Concentrated nitric acid is stirred to after being completely dissolved, and deionized water constant volume is added.
4. special using the anti-counterfeiting ink of the multicolor fluorescence material preparation described in claim 1 based on rare earth metal organic frame
Sign is to be grouped as by the group matched as follows:
0.1 g of rare earth metal organic frame powder
Dehydrated alcohol 20-25mL
Ethylene glycol 20-25mL
Glycerine 1-4mL
Diethylene glycol (DEG) 1-4 mL
2 mL of sodium dodecyl sulfate solution.
5. the preparation method of anti-counterfeiting ink described in claim 4, it is characterised in that include the following steps: that each component is uniformly mixed
Afterwards, ultrasonic disperse, it is anti-fake to get preparing to the multicolor fluorescence material based on rare earth metal organic frame that supernatant is taken after centrifugation
Ink.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811305118.XA CN109232619B (en) | 2018-11-05 | 2018-11-05 | Multicolor fluorescent material based on rare earth metal organic framework, preparation method thereof and application of anti-counterfeiting ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811305118.XA CN109232619B (en) | 2018-11-05 | 2018-11-05 | Multicolor fluorescent material based on rare earth metal organic framework, preparation method thereof and application of anti-counterfeiting ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109232619A true CN109232619A (en) | 2019-01-18 |
| CN109232619B CN109232619B (en) | 2020-07-24 |
Family
ID=65076498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811305118.XA Active CN109232619B (en) | 2018-11-05 | 2018-11-05 | Multicolor fluorescent material based on rare earth metal organic framework, preparation method thereof and application of anti-counterfeiting ink |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109232619B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111077746A (en) * | 2019-12-31 | 2020-04-28 | 天津市中环天佳电子有限公司 | Rare earth spectrum traceable ink powder for golden light red printer |
| CN111398232A (en) * | 2020-04-07 | 2020-07-10 | 浙江大学 | Fluorescence detection method for concentration of ions to be detected in transformer oil |
| CN111476333A (en) * | 2020-04-02 | 2020-07-31 | 齐鲁工业大学 | L n-MOF-based multicolor heterojunction micro intelligent response photon anti-counterfeiting bar code material, device, preparation and application |
| CN111909385A (en) * | 2020-07-10 | 2020-11-10 | 浙江工业大学 | Rare earth supermolecule gel luminescent material, and preparation method and application thereof |
| CN111909028A (en) * | 2020-08-24 | 2020-11-10 | 北京石油化工学院 | Preparation method of Eu/Tb (BTC) for detecting AFB1 |
| CN112375230A (en) * | 2020-12-12 | 2021-02-19 | 四川师范大学 | Three-rare earth fluorescent sensor capable of being used for identifying human metabolites |
| CN113061368A (en) * | 2021-04-01 | 2021-07-02 | 厦门大学 | Novel fluorescent ink and preparation method and application thereof |
| CN113881285A (en) * | 2021-11-09 | 2022-01-04 | 山西聚微天成科技有限公司 | MOF fluorescent ink and application thereof in ion identification |
| CN114686208A (en) * | 2020-12-31 | 2022-07-01 | Tcl科技集团股份有限公司 | Composite reagent, anti-counterfeiting combined reagent and anti-counterfeiting method |
| RU2796682C1 (en) * | 2022-06-07 | 2023-05-29 | Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) | ORGANOMETALLIC FRAMEWORK STRUCTURE OF LANTHANUM (III) BENZENE TRICARBOXYLATE La-BTC AND METHOD OF ITS MANUFACTURING |
| WO2023185543A1 (en) * | 2022-03-28 | 2023-10-05 | 河南理工大学 | Preparation and detection methods for dual-channel visualized multicolor fluorescent probe |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045861A (en) * | 2007-04-11 | 2007-10-03 | 山东大学 | Whole color fluorescent material and preparation method thereof |
| CN102161671A (en) * | 2011-02-23 | 2011-08-24 | 中山大学 | Coordination polymer material with multistage pore passage structure and preparation method thereof |
| WO2014047729A1 (en) * | 2012-09-27 | 2014-04-03 | Queen's University At Kingston | Compounds and methods for enhancing metal luminescence that can be selectively turned off |
| CN103881471A (en) * | 2014-02-12 | 2014-06-25 | 浙江大胜达包装有限公司 | Preparation method of rare earth florescent LOGO anti-forgery ink |
| CN104327494A (en) * | 2014-09-11 | 2015-02-04 | 苏州大学 | Thermal oxidation stabilizing additive for polyamide |
| CN106905534A (en) * | 2017-01-17 | 2017-06-30 | 浙江大学 | A kind of substep preparation method and application of high stable rare earth organic framework materials |
| CN108410266A (en) * | 2018-03-09 | 2018-08-17 | 南开大学 | A kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials |
-
2018
- 2018-11-05 CN CN201811305118.XA patent/CN109232619B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045861A (en) * | 2007-04-11 | 2007-10-03 | 山东大学 | Whole color fluorescent material and preparation method thereof |
| CN102161671A (en) * | 2011-02-23 | 2011-08-24 | 中山大学 | Coordination polymer material with multistage pore passage structure and preparation method thereof |
| WO2014047729A1 (en) * | 2012-09-27 | 2014-04-03 | Queen's University At Kingston | Compounds and methods for enhancing metal luminescence that can be selectively turned off |
| CN103881471A (en) * | 2014-02-12 | 2014-06-25 | 浙江大胜达包装有限公司 | Preparation method of rare earth florescent LOGO anti-forgery ink |
| CN104327494A (en) * | 2014-09-11 | 2015-02-04 | 苏州大学 | Thermal oxidation stabilizing additive for polyamide |
| CN106905534A (en) * | 2017-01-17 | 2017-06-30 | 浙江大学 | A kind of substep preparation method and application of high stable rare earth organic framework materials |
| CN108410266A (en) * | 2018-03-09 | 2018-08-17 | 南开大学 | A kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials |
Non-Patent Citations (2)
| Title |
|---|
| N. KERBELLEC等: "An Unprecedented Family of Lanthanide-Containing Coordination Polymers with Highly Tunable Emission Properties", 《INORGANIC CHEMISTRY》 * |
| 王道龙: "羧酸类金属—有机框架的合成、表征、荧光研究与机械化学活性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111077746A (en) * | 2019-12-31 | 2020-04-28 | 天津市中环天佳电子有限公司 | Rare earth spectrum traceable ink powder for golden light red printer |
| CN111476333A (en) * | 2020-04-02 | 2020-07-31 | 齐鲁工业大学 | L n-MOF-based multicolor heterojunction micro intelligent response photon anti-counterfeiting bar code material, device, preparation and application |
| CN111476333B (en) * | 2020-04-02 | 2023-06-13 | 齐鲁工业大学 | Ln-MOF-based multicolor heterojunction miniature intelligent response photon anti-counterfeiting bar code material, device, preparation and application |
| CN111398232B (en) * | 2020-04-07 | 2021-07-16 | 浙江大学 | Fluorescence detection method for concentration of ions to be detected in transformer oil |
| CN111398232A (en) * | 2020-04-07 | 2020-07-10 | 浙江大学 | Fluorescence detection method for concentration of ions to be detected in transformer oil |
| CN111909385A (en) * | 2020-07-10 | 2020-11-10 | 浙江工业大学 | Rare earth supermolecule gel luminescent material, and preparation method and application thereof |
| CN111909385B (en) * | 2020-07-10 | 2022-04-08 | 浙江工业大学 | Rare earth supermolecule gel luminescent material, and preparation method and application thereof |
| CN111909028B (en) * | 2020-08-24 | 2022-11-29 | 北京石油化工学院 | Preparation method of Eu/Tb (BTC) for detecting AFB1 |
| CN111909028A (en) * | 2020-08-24 | 2020-11-10 | 北京石油化工学院 | Preparation method of Eu/Tb (BTC) for detecting AFB1 |
| CN112375230B (en) * | 2020-12-12 | 2022-07-29 | 四川师范大学 | Three-rare earth fluorescent sensor capable of being used for identifying metabolites of human body |
| CN112375230A (en) * | 2020-12-12 | 2021-02-19 | 四川师范大学 | Three-rare earth fluorescent sensor capable of being used for identifying human metabolites |
| CN114686208A (en) * | 2020-12-31 | 2022-07-01 | Tcl科技集团股份有限公司 | Composite reagent, anti-counterfeiting combined reagent and anti-counterfeiting method |
| CN113061368A (en) * | 2021-04-01 | 2021-07-02 | 厦门大学 | Novel fluorescent ink and preparation method and application thereof |
| CN113881285A (en) * | 2021-11-09 | 2022-01-04 | 山西聚微天成科技有限公司 | MOF fluorescent ink and application thereof in ion identification |
| WO2023185543A1 (en) * | 2022-03-28 | 2023-10-05 | 河南理工大学 | Preparation and detection methods for dual-channel visualized multicolor fluorescent probe |
| RU2796682C1 (en) * | 2022-06-07 | 2023-05-29 | Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) | ORGANOMETALLIC FRAMEWORK STRUCTURE OF LANTHANUM (III) BENZENE TRICARBOXYLATE La-BTC AND METHOD OF ITS MANUFACTURING |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109232619B (en) | 2020-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109232619A (en) | Multicolor fluorescence material based on rare earth metal organic frame and preparation method thereof and anti-counterfeiting ink application | |
| Liu et al. | Simultaneously excited downshifting/upconversion luminescence from lanthanide‐doped core/shell fluoride nanoparticles for multimode anticounterfeiting | |
| Meruga et al. | Security printing of covert quick response codes using upconverting nanoparticle inks | |
| Yao et al. | Preparation and RGB upconversion optic properties of transparent anti-counterfeiting films | |
| CN1333021C (en) | Photosensitive optically variable ink heterogeneous compositions for ink jet printing | |
| CN108410266A (en) | A kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials | |
| EP3390066B1 (en) | Security element formed from at least two materials present in partially overlapping areas, articles carrying the security element, and authentication methods | |
| Baride et al. | A NIR-to-NIR upconversion luminescence system for security printing applications | |
| CN103436093B (en) | Anti-counterfeiting stamp-pad ink and preparation method thereof | |
| AU2005261944B2 (en) | Valuable document | |
| CN108192602A (en) | It is a kind of with room temperature phosphorimetry property without metal-containing polymer carbon dots, preparation method and applications | |
| CN103087555B (en) | Microstructure metallic pigment with anti-fake function and preparation method of microstructure metallic pigment | |
| CN105885845B (en) | Silk-screen printing rare earth up-conversion luminescence ink and preparation method thereof and Application in Anti-counterfeiting | |
| Li et al. | Dual-mode luminescent multilayer core-shell UCNPs@ SiO2@ TEuTbB nanospheres for high-level anti-counterfeiting and recognition of latent fingerprints | |
| Zhao et al. | Spectral pure RGB up-conversion emissions in self-assembled Gd2O3: Yb3+, Er3+/Ho3+/Tm3+ 3D hierarchical architectures | |
| CN104846698A (en) | Ultraviolet double-wave excitation fluorescent transparent invisible anti-fake nano-paper preparation method | |
| CN115991993B (en) | Sodium lutetium gallium germanium garnet-based green light fluorescent powder for anti-counterfeiting and preparation method thereof | |
| US20070044679A1 (en) | White-fluorescent anti-stokes compositions and methods | |
| CN108656783B (en) | A kind of security article and its detection method and detection system | |
| Chandana et al. | Simple fabrication of novel Sm3+ doped BaGd2ZnO5 nanophosphors for flexible displays, improved data security applications, and solid-state lighting applications | |
| Girisha et al. | Stimuli-responsive color-tunable BaLa2ZnO5: Bi3+ phosphor for the encryption and authentication of security patterns and latent fingerprint detection | |
| CN110330969A (en) | A kind of multicolor fluorescence carbon quantum dot and preparation method thereof and the application in Antiforge fluorescent ink | |
| Zhang et al. | Multi-mode optical coded patterns enabled by upconversion nanoparticles and photonic crystals | |
| CN110399904A (en) | A kind of emission spectrum method for reconstructing based on full-color fluorescence printing | |
| CN111607395B (en) | Long-afterglow nano particle with fluorescence encryption anti-counterfeiting characteristic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |