CN108976874A - A kind of anti-fake material and preparation method thereof and the application in cigarette - Google Patents
A kind of anti-fake material and preparation method thereof and the application in cigarette Download PDFInfo
- Publication number
- CN108976874A CN108976874A CN201810907851.2A CN201810907851A CN108976874A CN 108976874 A CN108976874 A CN 108976874A CN 201810907851 A CN201810907851 A CN 201810907851A CN 108976874 A CN108976874 A CN 108976874A
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- China
- Prior art keywords
- fake material
- cigarette
- polymer support
- photosensitizer
- fake
- Prior art date
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Classifications
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- 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
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of anti-fake materials, are made of the mixing of photosensitizer iodo fluorine boron pyrylium dyes, receptor, polymer support and solvent；The polymer support is polyethylene oxide and the mixture that polymethyl methacrylate forms.The molar ratio of the photosensitizer and receptor is 1:5-20, and the quality of polymer support is 1000-3000 times by weight.The present invention also provides application of the above-mentioned anti-fake material in cigarette.Application of the above-mentioned anti-fake material in cigarette forms homogeneous up-conversion luminescence film specifically, anti-fake material can be coated on to cigarette packing box surface after drying.When irradiating the up-conversion luminescence film with green laser pen, it passes through switching mechanism on T-T annihilation, issuing, there is anti-Stokes displacement property, energy to be higher than the blue-violet light of excitation wavelength, its special luminosity is not easy to be imitated or replicate, therefore can function well as antifalse effect.
Description
Technical field
The invention belongs to field of anti-counterfeit technology, and in particular to a kind of luminous anti-fake material and preparation method thereof and in cigarette
Application.
Background technique
The profit margin of tobacco product is huge, while being related to the vital interests of numerous consumers and the finance receipts of country
Enter.Spreading unchecked for false smoke not only influences pursuit of the majority of consumers to smoking property of cigarette quality, seriously endangers the physical and mental health of consumer,
Also result in the loss of state tax revenue.It comes into the market to limit false cigarette with product, or even causes the impact to commercially available real smoke,
This just needs to increase anti-counterfeiting technology on cigarette product.Traditional anti-counterfeiting technology, such as paper line anti-counterfeiting technology, bar codes technique, two
Tieing up code technology, chemical ink anti-counterfeiting technology or texture anti-fake technology etc., (e.g., CN200510037790.1 discloses a kind of anti-fake cigarette
Target production method, it is using the plate-making of the method for hand engraving or erosion carving, and production is time-consuming and laborious, and antifalse effect is general),
Although being also able to achieve certain anti-fake purpose, technical threshold is lower, is easy to imitate.Therefore, this can not limit vacation well
The circulation of cigarette, imitated cigarette.
In order to more effectively realize the anti-fake of cigarette product, the circulation of false cigarette product is limited, is protected to greatest extent
The vital interests of consumer ensure country in the stabilization of the tax revenues of Field of Tobacco, this just needs to develop a kind of more effective
, facilitate production, while there is certain technical threshold, be difficult to imitated cigarette anti-counterfeiting technology.
Summary of the invention
Present invention aims to overcome that prior art defect, provides a kind of luminous anti-fake material, which has
Certain technical difficulty, special luminosity are not easy to be imitated or replicate, therefore can function well as antifalse effect.
Application the present invention also provides the preparation method of above-mentioned anti-fake material and in cigarette.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of anti-fake material, by T-T annihilation convert photosensitizer iodo fluorine boron pyrylium dyes (I-Bodipy),
Receptor, polymer support and solvent mixing composition；The polymer support is polyethylene oxide and polymethyl methacrylate
The mixture of composition；The structural formula of photosensitizer and receptor is as follows:
。
Specifically, the molar ratio of the photosensitizer and receptor is 1:5-20, the quality of polymer support is by weight
1000-3000 times.
Specifically, the relative molecular weight of polyethylene oxide is 50-100 ten thousand in the polymer support, polymethyl
The relative molecular weight of sour methyl esters is 8-10 ten thousand.Polyethylene oxide can be mixed with polymethyl methacrylate with arbitrary proportion, wherein
The two mass ratio is advisable with 1:2-5.
It is further preferred that the solvent can be chloroform, methylene chloride or toluene.Photosensitizer concentration probably 2.0 ×
10–5 M–1.Solvent can be added in right amount according to the concentration of photosensitizer, the addition volume of solvent is advisable in 10-20 ml.
The present invention provides the preparation methods of above-mentioned anti-fake material, by photosensitizer iodo fluorine boron pyrylium dyes, receptor
Be dissolved in solvent, be then added polymer support, mix to get.
The present invention also provides application of the above-mentioned anti-fake material in cigarette.
Application of the above-mentioned anti-fake material in cigarette, specifically, anti-fake material can be coated on to cigarette packing box surface,
Up-conversion luminescence film of the homogeneous, thickness at 0.5-1 millimeter is formed after drying.It can also be coated in up-conversion luminescence film surface
One layer of waterproofing membrane, waterproof outer film are common polythene shrink film, and thickness range is 0.1-0.2 millimeter.
When with green laser pen (excitation wavelength is 532 nm) irradiation up-conversion luminescence film, which passes through triple
State-triplet buries in oblivion upper switching mechanism, and issuing, there is anti-Stokes displacement property, energy to be higher than the blue-violet light of excitation wavelength
(420-520 nm of wave-length coverage).
In the present invention, photosensitizer I-Bodipy, a kind of fluorine boron pyrylium dyes of iodo, ultraviolet and visible absorption peak is 530
Near nm, there is stronger visible absorption (molar extinction coefficient 1.2 × 105 M–1cm–1), longer triplet lifetime (> 100 μ S) and higher T-T annihilation on convert quantum efficiency ( UC10% or so)；It is described by
Body/illuminator is a kind of organic aromatic molecules of high-fluorescence quantum yield, and fluorescence quantum yield is close to 100%, emission wavelength
Range is near 420-520 nm.
The anti-fake inspection method of anti-fake material of the present invention is: directly being shone using green laser pen (532 nm, 5-30 mW)
It penetrates, detect by an unaided eye the corresponding blue-violet light issued；When being not easy to detect by an unaided eye, can be detected by general fluorescence detector,
Detection wave band is 420-520 nm.
Compared to the prior art, beneficial effects of the present invention:
Anti-fake material of the present invention is simple with structure, is easy to make, while design principle is triple using complicated triplet-
State buries in oblivion upconversion luminescence mechanism, which is not easy to be replicated or imitate, therefore has good anti-fake effect.It is of the present invention
Cigarette is also relatively easy with the anti-fake check mode for the anti-fake material that shines, and easily controllable cost has good application value.
Specific embodiment
The present invention is described in further details below with reference to embodiment, but the scope of the present invention is not limited thereto.
In following embodiments, the relative molecular weight of polyethylene oxide used in polymer support is 50-100 ten thousand, is gathered
The relative molecular weight of methyl methacrylate is 8-10 ten thousand, is ordinary commercial products.
Embodiment 1
A kind of anti-fake material, by T-T annihilation convert photosensitizer iodo fluorine boron pyrylium dyes (I-Bodipy),
Receptor, polymer support and solvent mixing composition；The polymer support is polyethylene oxide and polymethyl methacrylate
The mixture of composition.
The preparation method of above-mentioned anti-fake material, specifically comprises the following steps:
1) photosensitizer I-Bodipy(0.115 mg) and (0.25 mg) are dissolved in chloroform (10ml), are configured to concentration point
It Wei 2.0 × 10-5 M-1With 1.0 × 10-4 M-1Solution (molar ratio of photosensitizer and receptor be 1:5)；
2) it is separately added into polyethylene oxide (100 mg) and polymethyl methacrylate (400 mg) into solution, is stood after shaking up
5 hours, it is sufficiently mixed polymer support and upper conversion photosensitizer, receptor to get finished product is sticky mixture (environment temperature
20 DEG C of degree).
Application of the above-mentioned anti-fake material in cigarette, specifically:
1) it is successively coated with above-mentioned anti-fake material with packing box specific position in smooth, smooth cigarette, (10- is slowly dried after coating
20 minutes), then proceed to be coated with next time, ultimately form it is homogeneous, with a thickness of 0.5 millimeter of up-conversion luminescence film；
2) waterproof membrane is coated on 2 surface of up-conversion luminescence film, waterproof membrane is the polyethylene shrink film with a thickness of 0.1 millimeter, to rise
To the effect of isolation steam.
Embodiment 2
A kind of anti-fake material, by T-T annihilation convert photosensitizer iodo fluorine boron pyrylium dyes (I-Bodipy),
Receptor, polymer support and solvent mixing composition；The polymer support is polyethylene oxide and polymethyl methacrylate
The mixture of composition.
The preparation method of above-mentioned anti-fake material, specifically comprises the following steps:
1) photosensitizer I-Bodipy(0.115 mg) and (0.50 mg) are dissolved in toluene (10ml), are configured to concentration point
It Wei 2.0 × 10-5 M-1With 2.0 × 10-4 M-1Solution (molar ratio of photosensitizer and receptor be 1:10)；
2) it is separately added into polyethylene oxide (250 mg) and polymethyl methacrylate (750 mg) into solution, is stood after shaking up
5 hours, it is sufficiently mixed polymer support and upper conversion photosensitizer, receptor to get finished product is sticky mixture (environment temperature
20 DEG C of degree).
Application of the above-mentioned anti-fake material in cigarette, specifically:
1) it is successively coated with above-mentioned anti-fake material with packing box specific position in smooth, smooth cigarette, (10- is slowly dried after coating
20 minutes), then proceed to be coated with next time, ultimately form it is homogeneous, with a thickness of 1.0 millimeters of up-conversion luminescence films；
2) waterproof membrane is coated in up-conversion luminescence film surface, waterproof membrane is the polyethylene shrink film with a thickness of 0.15 millimeter, to rise
To the effect of isolation steam.
Embodiment 3
A kind of anti-fake material, by T-T annihilation convert photosensitizer iodo fluorine boron pyrylium dyes (I-Bodipy),
Receptor, polymer support and solvent mixing composition；The polymer support is polyethylene oxide and polymethyl methacrylate
The mixture of composition.
The preparation method of above-mentioned anti-fake material, specifically comprises the following steps:
1) photosensitizer I-Bodipy(0.115mg) and (0.25mg) are dissolved in toluene (10ml), are configured to concentration difference
It is 2.0 × 10-5 M-1With 1.0 × 10-4 M-1Solution (molar ratio of photosensitizer and receptor be 1:5)；
2) it is separately added into polyethylene oxide (150 mg) and polymethyl methacrylate (600 mg) into solution, is stood after shaking up
5 hours, it is sufficiently mixed polymer and upper conversion photosensitizer, receptor to get finished product is sticky mixture (environment temperature 20
DEG C).
Concrete application of the above-mentioned anti-fake material in cigarette, with embodiment 2.
The anti-fake inspection method of anti-fake material of the present invention is: directly being shone using green laser pen (532 nm, 5-30 mW)
It penetrates, detect by an unaided eye the corresponding blue-violet light issued；When being not easy to detect by an unaided eye, can be detected by general fluorescence detector,
Detection wave band is 420-520 nm.
It should be noted last that: technical solution of the present invention that the above embodiments are only illustrative and not limiting is any right
The equivalent replacement and do not depart from the modification of spirit and scope of the invention or locally replace that the present invention carries out, should all cover in this hair
Within bright protective scope of the claims.
Claims (9)
1. a kind of anti-fake material, which is characterized in that by photosensitizer iodo fluorine boron pyrylium dyes, receptor, polymer support and molten
Agent mixing composition；The polymer support is polyethylene oxide and the mixture that polymethyl methacrylate forms.
2. anti-fake material as described in claim 1, which is characterized in that the molar ratio of the photosensitizer and receptor is 1:5-20,
The quality of polymer support is 1000-3000 times by weight.
3. anti-fake material as described in claim 1, which is characterized in that opposite point of polyethylene oxide in the polymer support
Son amount is 50-100 ten thousand, and the relative molecular weight of polymethyl methacrylate is 8-10 ten thousand.
4. anti-fake material as described in claim 1, which is characterized in that the solvent is chloroform, methylene chloride or toluene.
5. the preparation method of any anti-fake material of Claims 1-4, which is characterized in that by photosensitizer iodo fluorine boron pyrroles
Dyestuff, receptor are dissolved in solvent, are then added polymer support, mix to get.
6. application of the anti-fake material described in claim 1 in cigarette.
7. application of the anti-fake material as claimed in claim 6 in cigarette, which is characterized in that anti-fake material is coated on cigarette packet
Mounted box surface forms homogeneous up-conversion luminescence film after drying.
8. application of the anti-fake material as claimed in claim 7 in cigarette, which is characterized in that converted in the irradiation of green laser pen
When luminescent film, anti-fake material issues, and there is anti-Stokes displacement property, energy to be higher than the blue-violet light of excitation wavelength.
9. application of the anti-fake material as claimed in claim 7 in cigarette, which is characterized in that coated in up-conversion luminescence film surface
One layer of waterproof membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810907851.2A CN108976874B (en) | 2018-08-10 | 2018-08-10 | Anti-counterfeiting material, preparation method thereof and application thereof in cigarettes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810907851.2A CN108976874B (en) | 2018-08-10 | 2018-08-10 | Anti-counterfeiting material, preparation method thereof and application thereof in cigarettes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108976874A true CN108976874A (en) | 2018-12-11 |
| CN108976874B CN108976874B (en) | 2021-02-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810907851.2A Active CN108976874B (en) | 2018-08-10 | 2018-08-10 | Anti-counterfeiting material, preparation method thereof and application thereof in cigarettes |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009070823A1 (en) * | 2007-12-07 | 2009-06-11 | Austrian Research Centers Gmbh - Arc | Printing ink, printing color and/or printing paste |
| CN105694848A (en) * | 2016-02-04 | 2016-06-22 | 苏州科技学院 | Hydrogel-based solid-state up-conversion luminescence material and preparation method thereof |
-
2018
- 2018-08-10 CN CN201810907851.2A patent/CN108976874B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009070823A1 (en) * | 2007-12-07 | 2009-06-11 | Austrian Research Centers Gmbh - Arc | Printing ink, printing color and/or printing paste |
| CN105694848A (en) * | 2016-02-04 | 2016-06-22 | 苏州科技学院 | Hydrogel-based solid-state up-conversion luminescence material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 伍晚花，等: "三重态_三重态湮灭上转换的研究进展", 《中国科学:化学》 * |
| 徐叙瑢等: "《发光材料与显示技术》", 31 January 2003 * |
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| CN108976874B (en) | 2021-02-23 |
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