CN109553566B - Anti-counterfeiting material with adjustable imaging waveband and preparation method and application thereof - Google Patents
Anti-counterfeiting material with adjustable imaging waveband and preparation method and application thereof Download PDFInfo
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- CN109553566B CN109553566B CN201811440243.1A CN201811440243A CN109553566B CN 109553566 B CN109553566 B CN 109553566B CN 201811440243 A CN201811440243 A CN 201811440243A CN 109553566 B CN109553566 B CN 109553566B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/60—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
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Abstract
The invention discloses an anti-counterfeiting material with adjustable imaging waveband, which has a structure shown in a general formula I or a general formula II:
in addition, the invention also discloses a preparation method and a use method of the anti-counterfeiting material. The anti-counterfeiting material prepared by the invention can finally present multi-color anti-counterfeiting marks, and the anti-counterfeiting marks can read anti-counterfeiting information only by three steps of operation, so that the anti-counterfeiting safety coefficient is extremely high, the imaging definition is high, the stability of the anti-counterfeiting marks is good, and the storage life is long.
Description
Technical Field
The invention belongs to the field of preparation and application of anti-counterfeiting materials, and particularly relates to a high-safety anti-counterfeiting material with adjustable imaging waveband, a preparation method and application thereof.
Background
At present, the era of the rapid development of science and technology, the development of high technology in all countries without residual force, and the level of science and technology becomes a standard for the strength of a country. Under the promotion of more and more technological encouragement policies of the country and the large environment of advocating technological innovation, more and more high-tech products come out and successfully enter the market. The back of each new product bears the hard work of numerous creators and producers, and more importantly, high research and development investments. However, the reality is that some lawbreakers can manufacture some pirated and counterfeit products to deceive consumers at the risk of illegal because of the huge profit margin of the high and new technology products. Such behavior not only infringes the economic interests of research and development investors, but also may jeopardize the safety of the consumers. For example, counterfeit money circulating in the market in large numbers inevitably destroys social stability, resulting in serious economic and social problems; or the fake medicine is circulated in the market, and the life and health of the patient are directly harmed. In the past decades, the anti-counterfeiting technology is rapidly developed in China, and a plurality of anti-counterfeiting technologies, including watermarking, metal wires, holograms, spectral analysis, electronic tracking and other methods, are widely popularized and applied, so that most of counterfeit and shoddy products are practically prevented from flowing into the market. However, with the familiarity of lawless persons to the method, many anti-counterfeiting technologies are cracked, and anti-counterfeiting marks are counterfeited, so that counterfeit and shoddy products can not be radically treated when entering the market, and the counterfeited anti-counterfeiting marks become the amulet of the counterfeited and shoddy products. Therefore, there is a need to develop a new anti-counterfeit material with higher security and difficult technical cracking and imitation.
Patent CN107098891A discloses a fluorescent anti-counterfeiting material based on mechanical force response, which is a microcrystalline organic dye taking N-substituted 9, 9-dimethylacridine as a substituent and spiro [ fluorene-9, 9' -xanthene ] as a core. The anti-counterfeiting material has simple imaging technical principle and is easy to steal by lawbreakers. In addition, the anti-counterfeiting mark is read by means of mechanical force, and different consumers have different degrees of mastery on the force, so that the anti-counterfeiting mark cannot be used on materials with soft texture and fragile texture.
Patent CN107502341A discloses a piezoluminescence security material, which has a significant change in luminescence color under the action of external stimuli such as external force, temperature and solvent, and can be mutually transformed. The anti-counterfeiting material has simple imaging principle and lower anti-counterfeiting safety coefficient. In addition, the reading of the anti-counterfeiting mark needs external force, temperature and solvent, and the application range of the anti-counterfeiting mark is limited.
Patent CN108102639A discloses a spin-switching controlled multiple optical signal response security material, which is obtained by mixing a spin-switching material and a luminescent material to obtain a composite material, and is characterized in that: after temperature, ultraviolet light and visible light signals are input, four color signals with obvious difference can be output. Although the anti-counterfeiting material can obtain different color signals, the preparation raw materials of the anti-counterfeiting material are expensive and difficult to obtain, so that the preparation cost of the anti-counterfeiting material is higher.
Patent CN107936527A discloses a wavelength-adjustable fluorescent anti-counterfeiting composite material, which is prepared by preparing different cadmium telluride quantum dot solutions and polyurethane prepolymers, finally adding the cadmium telluride quantum dot solutions into the polyurethane prepolymers under stirring for emulsification to obtain an aqueous polyurethane dispersion, placing the aqueous polyurethane dispersion at room temperature, completely volatilizing the solvent, and then drying the aqueous polyurethane dispersion in vacuum to obtain the wavelength-adjustable fluorescent anti-counterfeiting composite material. Although the anti-counterfeiting material can be used for preparing the fluorescent anti-counterfeiting material with adjustable wavelength, the imaging mode is too simple, so that the security of anti-counterfeiting contents can not be ensured.
Patent CN107310294A discloses a high-stability metal nano-cluster fluorescent anti-counterfeiting material, which is characterized in that a layer of compact barium sulfate is deposited on the surface of a metal nano-cluster composite material through a barium sulfate-coated metal nano-cluster composite material, so that the metal nano-cluster anti-counterfeiting material is protected, and the fluorescent color is kept for a long time. Although the anti-counterfeiting material has long information retention time, the preparation process is complicated, and the manufacturing cost is high. In addition, the anti-counterfeiting mark drawn by the anti-counterfeiting material has a simple imaging mode, and is not suitable for precise and expensive products.
In order to overcome the defects of the prior art, the invention provides the anti-counterfeiting material with the adjustable imaging wave band and the preparation method thereof, the anti-counterfeiting mark drawn by the anti-counterfeiting material can be imaged only through three steps of operation, and the anti-counterfeiting safety coefficient is extremely high. In addition, the anti-counterfeiting material has high imaging definition, and can be used for clearly imaging even anti-counterfeiting marks with small fonts. And secondly, different anti-counterfeiting materials prepared by changing preparation raw materials can realize multi-band imaging, present different fluorescence colors and prepare anti-counterfeiting marks with different colors and attractive appearance. Finally, through the optimization of the preparation material, the anti-counterfeiting material prepared by the invention has good stability, and the drawn anti-counterfeiting mark has long retention period and better wear resistance.
Disclosure of Invention
The invention aims to provide an anti-counterfeiting material with adjustable imaging wave band and a preparation method thereof; the invention also aims to provide a use method of the anti-counterfeiting material with adjustable imaging waveband.
The purpose of the invention is realized by the following technical scheme:
an anti-counterfeiting material with adjustable imaging waveband is structurally represented by a general formula I or a general formula II:
wherein R is1、R2、R3、R4And R5Independently selected from: H. c1-10Straight/branched alkyl, -CH ═ C (C)0-10Alkyl) (C0-10Alkyl group), C3-10Cycloalkyl, an aromatic five-membered ring group, an aromatic six-membered ring group, or R1、R2And R1And R2Nitrogen atom in between, or R4、R5And R4And R5Form C with carbon atoms in between3-8Cycloalkyl or C containing-O, -S3-8Heterocycloalkyl radical, C4-20Condensed ring alkyl, C3-7Cyclic lactam, C3-7Cyclic lactone, C3-7Cyclic ketones wherein the alkyl, alkenyl, aromatic ring may be substituted at any carbon atom or hydrogen at a carbon atom by one or two of the following groups: halogen, alkyl, -CN, -OC0-10Alkyl, -S (O) mC0-10Alkyl, -SO2N(C0-10Alkyl) (C0-10Alkyl), -N (C)0-10Alkyl) (C0-10Alkyl), -N (C)0-10Alkyl) C (═ O) (C)0-10Alkyl), -N (C)0-10Alkyl) C (═ O) O (C)0-10Alkyl), -N (C)0-10Alkyl) C (═ O) N (C)0-10Alkyl), -C (═ O) C0-10Alkyl, -C (═ O) OC0-10Alkyl, -C (═ O) N (C)0-10Alkyl) (C0-10Alkyl), -heterocycloalkyl, -N (C)0-10Alkyl) heterocycloalkyl, -N (C)0-10Alkyl) aryl, -N (C)0-10Alkyl) a heterocyclic aromatic group, an aryl group, an-N heterocyclic aromatic group, an-S heterocyclic aromatic group or an-O heterocyclic aromatic group, and m is 0, 1 or 2.
Preferably, said R is1And R2Independently selected from: c1-5Straight chain/branched alkyl, C3-6Cycloalkyl, or R1、R2And R1And R2Form C with a nitrogen atom in between3-8Cycloalkyl radical, C4-9Condensed ring alkyl, C3-7A cyclic lactam wherein any carbon atom or hydrogen on a carbon atom on the alkyl group may be substituted with one or two of the following groups: alkyl, -OC0-10Alkyl, aryl, -N (C)0-10Alkyl) aryl, -N-heterocyclic aryl.
More preferably, R is1And R2Independently selected from: c1-5Straight chain alkyl, or R1、R2And R1And R2Form C with a nitrogen atom in between5-7A cyclic lactam wherein any carbon atom or hydrogen on a carbon atom on the alkyl group may be substituted with one or two of the following groups: alkyl, -OC0-10Alkyl, aryl, -N (C)0-10Alkyl) aryl, -N-heterocyclic aryl.
Preferably, said R is3Selected from: c1-5Straight chain/branched alkyl, C3-8Cycloalkyl, aromatic five-membered ring group, aromatic six-membered ring group, wherein the alkyl, any carbon atom on the aromatic ring or a hydrogen on a carbon atom may be substituted by one or two of the following groups: halogen, alkyl, -CN, -OC0-10Alkyl, -N (C)0-10Alkyl) (C0-10Alkyl), -heterocycloalkyl, -N (C)0-10Alkyl) a heterocyclic aromatic group, an aryl group, an-N heterocyclic aromatic group, an-S heterocyclic aromatic group, or an-O heterocyclic aromatic group.
More preferably, R is3Selected from: c1-5Straight chain/branched alkyl, C5-8Cycloalkyl, aromatic five-membered ring group, aromatic six-membered ring group, wherein the alkyl, any carbon atom on the aromatic ring or a hydrogen on a carbon atom may be substituted by one or two of the following groups: halogen, alkyl, -OC0-10Alkyl, -heterocycloalkyl, aryl, -N-heterocycloaryl or-O-heterocycloaryl.
Preferably, said R is4And R5Independently selected from: c1-5Straight chain/branched alkyl, C3-6Cycloalkyl, aromatic five-membered ring group, aromatic six-membered ring group, or R4、R5And R4And R5Form C with carbon atoms in between3-8Cycloalkyl radical, C4-16Fused ring alkyl, wherein any carbon atom or hydrogen on a carbon atom on the alkyl group may be substituted with one or two of the following groups: alkyl, -OC0-10Alkyl, aryl, -N (C)0-10Alkyl) aryl, -N-heterocyclic aryl.
More preferably, R is4And R5Independently selected from: c1-5Straight-chain alkyl, aromatic five-membered ring group, aromatic six-membered ring group, or R4、R5And R4And R5Form C with carbon atoms in between6-8Cycloalkyl radical, C10-16Fused ring alkyl, wherein any carbon atom or hydrogen on a carbon atom on the alkyl group may be substituted with one or two of the following groups: alkyl, -OC0-10Alkyl, aryl, -N (C)0-10Alkyl) aryl, -N-heterocyclic aryl.
A preparation method of an anti-counterfeiting material with adjustable imaging waveband comprises the following steps:
(1) dissolving an N-hydroxyl compound or an oxime compound and an isocyanate compound by using solvents respectively for later use;
(2) adding the N-hydroxy compound or oxime compound solution and a catalyst into a reaction container, then dropwise adding the isocyanate compound solution, and stirring at room temperature for 5-20h at the stirring speed of 50-150 r/min;
(3) after the reaction is finished, carrying out reduced pressure distillation at the temperature of 40-50 ℃ to obtain a crude product;
(4) recrystallizing the crude product with anhydrous methanol at 50-60 deg.C to obtain white crystal;
(5) and dissolving the white crystal by using a solvent to ensure that the final concentration of the white crystal is 2-10%, adding a viscosity regulator, and stirring to prepare the anti-counterfeiting material.
Preferably, the N-hydroxy compound in step (1) is selected from: n-hydroxyphthalimide, N-hydroxypyridine-2, 3-dicarboximide, N-hydroxypyrazine-2, 3-dicarboximide, N-hydroxymaleimide, N-hydroxysuccinimide or N-hydroxy-1, 8-naphthalimide.
More preferably, the N-hydroxy compound is selected from: n-hydroxyphthalimide, N-hydroxysuccinimide or N-hydroxy-1, 8-naphthalimide.
Preferably, the oxime compound is selected from: benzophenone oxime, furildioxime, bis (2-thiophene) methoxime, cyclooctanone oxime or cyclopentadecanone oxime.
More preferably, the oxime compound is selected from: benzophenone oxime, cyclooctanone oxime or cyclopentadecanone oxime.
Preferably, the isocyanate-based compound is selected from: methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate and the like, benzyl isocyanate, furfuryl isocyanate, t-butyl isocyanate, naphthalene diisocyanate, isopropyl isocyanate, phenyl isocyanate, cyclopentyl isocyanate, allyl isocyanate, cyclohexyl isocyanate, cycloheptyl isocyanate, p-chlorophenyl isocyanate, m-tolyl isocyanate, o-tolylisocyanate, p-tolylisocyanate, 2-chloroethyl isocyanate, 2-bromoethyl isocyanate or 2-phenylethyl isocyanate.
More preferably, the isocyanate-based compound is selected from: methyl isocyanate, propyl isocyanate, benzyl isocyanate, phenyl isocyanate, naphthalene diisocyanate, cyclopentyl isocyanate, allyl isocyanate, p-chlorobenzene isocyanate or 2-bromoethyl isocyanate.
Preferably, the catalyst in step (2) is selected from: one or more of triethylamine, triethylene diamine, tetramethyl ethylene diamine and tetramethyl propylene diamine.
More preferably, the catalyst is triethylamine.
Preferably, the solvent in step (5) is selected from: one or more of ethanol, tetrahydrofuran, propylene glycol methyl ether acetate and ethyl acetate.
More preferably, the solvent is ethanol.
Preferably, the viscosity modifier in step (5) is selected from: one or more of polyvinyl butyral (PVB), a copolymer of binary vinyl chloride and vinyl acetate, a copolymer of ternary vinyl chloride and vinyl acetate, and a copolymer of quaternary vinyl chloride and vinyl acetate, wherein the mass fraction of the viscosity regulator is 2-7%, and the ultrasonic time is 30-40 min.
More preferably, the viscosity modifier is PVB.
A use method of an anti-counterfeiting material with adjustable imaging waveband comprises the following steps:
(1) drawing an anti-counterfeiting mark: writing or spraying the anti-counterfeiting material on the surface of an object needing anti-counterfeiting, and preparing an anti-counterfeiting mark after the solvent is volatilized;
(2) and (3) imaging light treatment: exposing the anti-counterfeiting mark under an ultraviolet lamp of 254nm for 1-6 min;
(3) imaging chemical treatment: spraying or wiping the fluorescent color developing agent on the anti-counterfeiting mark;
(4) reading anti-counterfeiting information: the anti-counterfeiting mark is irradiated by an ultraviolet lamp with the wavelength of 400nm, and the anti-counterfeiting information can be read.
Preferably, the drawing mode of the anti-counterfeiting material in the step (1) is handwriting or printer spraying and the like.
The surface of the object needing anti-counterfeiting is any non-fluorescent substrate, such as paper base, plastic, glass, metal and the like.
Preferably, the fluorescent color developer in step (3) is selected from: one or more of fluorescamine, fluorescamine diacetate, fluorescein-5-maleimide, fluorescein chloride, 5-carboxyfluorescein succinimidyl ester and 6-carboxyfluorescein succinimidyl ester.
More preferably, the fluorescent color developer is dissolved in cyclohexane/acetone (v cyclohexane/v acetone ═ 4:1 to 5:1) to prepare a solution having a concentration of 1 to 15 mmol/L.
The application of the anti-counterfeiting material with adjustable imaging waveband in drawing the anti-counterfeiting mark is preferable, the anti-counterfeiting material is suitable for products needing higher anti-counterfeiting coefficient, and the products are selected from the following components: drugs, wines, tobacco, cosmetics, publications, mechanical products, chemical products, and the like.
The anti-counterfeiting material with the adjustable imaging waveband provided by the invention has the following beneficial effects: 1, the anti-counterfeiting mark drawn by the anti-counterfeiting material can be imaged only through three steps of operation, and the anti-counterfeiting safety coefficient is extremely high; 2, the anti-counterfeiting material has high imaging definition, and even the anti-counterfeiting mark with small font can be imaged clearly; 3, multi-band imaging can be realized by changing the preparation raw materials, different fluorescent colors are presented, and anti-counterfeiting marks with different colors and attractive appearance are prepared; 4, through the optimization of the preparation material, the anti-counterfeiting material prepared by the invention has good stability, and the drawn anti-counterfeiting mark has long retention period and better wear resistance.
Drawings
FIG. 1 is a flow chart of anti-counterfeit mark imaging.
FIG. 2 is an image of the anti-counterfeit mark.
FIG. 3 is an image of the anti-counterfeit mark.
FIG. 4 is a diagram showing the effect of multi-color fluorescence, wherein 1-blue, 2-green, 3-yellow, and 4-red.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 preparation and imaging of Security Material 1
Preparing the anti-counterfeiting material: dissolving 4 parts of propyl isocyanate and 3.5 parts of N-hydroxysuccinimide by using 50 parts of anhydrous tetrahydrofuran and 10 parts of anhydrous tetrahydrofuran respectively for later use, adding an N-hydroxysuccinimide solution and 0.2 part of catalyst triethylamine into a single-neck flask, dropwise adding the propyl isocyanate solution, stirring at room temperature for 7 hours after dropwise adding, and stirring at the speed of 100 r/min.
After the reaction is finished, carrying out reduced pressure distillation at 40 ℃ to obtain a crude product; the crude product was recrystallized from anhydrous methanol at 60 ℃ to obtain white crystals with a yield of about 80%.
The white crystals were added to ethyl acetate in an amount of 5% by mass, and PVB in an amount of 2% by mass was added to ethyl acetate to adjust the viscosity. And (4) performing ultrasonic treatment for 30min until the anti-counterfeiting material is completely dissolved, wherein the obtained solution is the anti-counterfeiting material 1.
Drawing the anti-counterfeiting mark: writing or spraying the anti-counterfeiting information on the surfaces of paper base, plastics, glass and metal, completing the drawing process of the anti-counterfeiting mark after ethyl acetate is completely volatilized, and at the moment, the anti-counterfeiting mark is invisible under naked eyes.
And (3) information imaging process: exposing the anti-counterfeiting mark under an ultraviolet lamp of 254nm for 5min, wherein the anti-counterfeiting mark is still invisible; then 6mmol/L fluorescamine solution is coated on the anti-counterfeiting mark, and the anti-counterfeiting mark is invisible under naked eyes after 10 seconds; finally, the anti-counterfeiting information of blue fluorescence can be seen by irradiating with an ultraviolet lamp with the wavelength of 400 nm. The reading process of the anti-counterfeiting information is shown in figure 1.
Example 2 preparation and imaging of security material 2
Preparing the anti-counterfeiting material: dissolving 5 parts of naphthalene diisocyanate and 4.5 parts of N-hydroxyphthalimide respectively by using 60 parts of anhydrous tetrahydrofuran and 10 parts of anhydrous tetrahydrofuran for later use, adding N-hydroxyphthalimide solution and 0.25 part of catalyst triethylamine into a single-neck flask, dropwise adding the naphthalene diisocyanate solution, stirring at room temperature for 15 hours after dropwise adding, and stirring at the speed of 50 r/min.
After the reaction is finished, carrying out reduced pressure distillation at 40 ℃ to obtain a crude product; the crude product was recrystallized from anhydrous methanol at 60 ℃ to obtain white crystals with a yield of about 83%.
The white crystals were added to ethyl acetate in an amount of 5% by mass, and a vinylchloride-vinyl acetate copolymer was added to ethyl acetate in an amount of 5% by mass to adjust the viscosity. And (4) performing ultrasonic treatment for 30min until the anti-counterfeiting material is completely dissolved, wherein the obtained solution is the anti-counterfeiting material 2.
Drawing the anti-counterfeiting mark: writing or spraying the anti-counterfeiting information on the surfaces of paper base, plastics, glass and metal, completing the drawing process of the anti-counterfeiting mark after ethyl acetate is completely volatilized, and making the anti-counterfeiting mark invisible under naked eyes.
And (3) information imaging process: exposing the anti-counterfeiting mark under an ultraviolet lamp of 254nm for 5min, wherein the anti-counterfeiting mark is still invisible; then coating 10mmol/L fluorescamine solution on the anti-counterfeiting mark, and waiting for 10s until the anti-counterfeiting mark is invisible to naked eyes; finally, the anti-counterfeiting information of green fluorescence can be seen by irradiating with an ultraviolet lamp with the wavelength of 400 nm.
Example 3 preparation and imaging of security Material 3
Preparing the anti-counterfeiting material: dissolving 5 parts of 2-chloroethyl isocyanate and 4 parts of benzophenone oxime by 55 parts of anhydrous tetrahydrofuran and 15 parts of anhydrous tetrahydrofuran respectively for later use, adding an N-hydroxysuccinimide solution and 0.2 part of catalyst triethylamine into a single-neck flask, dropwise adding a propyl isocyanate solution, stirring at room temperature for 10 hours after dropwise adding, and stirring at the speed of 150 r/min.
After the reaction is finished, carrying out reduced pressure distillation at 40 ℃ to obtain a crude product; the crude product was recrystallized from anhydrous methanol at 60 ℃ to obtain white crystals with a yield of about 79%.
The white crystals were added to ethanol in an amount of 5% by mass, and PVB in an amount of 7% by mass was added to ethanol to adjust the viscosity. And (4) performing ultrasonic treatment for 30min until the anti-counterfeiting material is completely dissolved, wherein the obtained solution is the anti-counterfeiting material 3.
Drawing the anti-counterfeiting mark: writing or spraying the anti-counterfeiting information on the surfaces of paper base, plastics, glass and metal, completing the drawing process of the anti-counterfeiting mark after the ethanol is completely volatilized, and making the anti-counterfeiting mark invisible under naked eyes.
And (3) information imaging process: exposing the anti-counterfeiting mark under an ultraviolet lamp of 254nm for 5min, wherein the anti-counterfeiting mark is still invisible; then coating a 3mmol/L fluorescamine solution on the anti-counterfeiting mark, and waiting for 10s until the anti-counterfeiting mark is invisible under naked eyes; finally, the anti-counterfeiting information of the red fluorescence can be seen by irradiating the anti-counterfeiting information with an ultraviolet lamp with the wavelength of 400 nm.
EXAMPLE 4 preparation and imaging of the Security Material 4
Preparing the anti-counterfeiting material: dissolving 4.5 parts of phenyl isocyanate and 4 parts of cyclooctanone oxime by respectively using 40 parts of anhydrous tetrahydrofuran and 10 parts of anhydrous tetrahydrofuran for later use, adding an N-hydroxysuccinimide solution and 0.15 part of catalyst triethylamine into a single-neck flask, dropwise adding a propyl isocyanate solution, stirring at room temperature for 20 hours after dropwise adding, and stirring at the speed of 120 r/min.
After the reaction is finished, carrying out reduced pressure distillation at 40 ℃ to obtain a crude product; the crude product was recrystallized from anhydrous methanol at 60 ℃ to obtain white crystals with a yield of about 82%.
The white crystal is added into a mixed solvent of propylene glycol methyl ether acetate and ethyl acetate in an amount of 5 mass percent, and a ternary vinyl chloride-vinyl acetate copolymer in an amount of 4 mass percent is added into the solvent to adjust the viscosity. And (4) performing ultrasonic treatment for 30min until the anti-counterfeiting material is completely dissolved, wherein the obtained solution is the anti-counterfeiting material 4.
Drawing the anti-counterfeiting mark: the anti-counterfeiting information is drawn on paper base, plastic, glass and metal in an ink-jet printing or writing mode, after the solvent is completely volatilized, the drawing process of the anti-counterfeiting mark is finished, and at the moment, the hand-drawn anti-counterfeiting mark is invisible under naked eyes.
And (3) information imaging process: exposing the anti-counterfeiting mark under an ultraviolet lamp of 254nm for 5min, wherein the anti-counterfeiting mark is still invisible; then coating 9mmol/L fluorescamine solution on the anti-counterfeiting mark, and waiting for 10s until the anti-counterfeiting mark is invisible to naked eyes; finally, the anti-counterfeiting information of yellow fluorescence can be seen by irradiating with an ultraviolet lamp with the wavelength of 400 nm.
EXAMPLE 5 drawing of a multicolor Security feature
The security materials prepared in examples 1-4 were each drawn on a paper substrate, one dot for each material. Exposing the drawn pattern under an ultraviolet lamp of 254nm for 5min, then coating a fluorescamine solution of 6mmol/L on the anti-counterfeiting mark, waiting for 10s, and finally irradiating with an ultraviolet lamp of 400nm to respectively see 4 fluorescent color dots of blue, green, yellow and red, as shown in figure 4. Therefore, the anti-counterfeiting material prepared by the invention can also be used for preparing patterns with different colors and more beautiful appearance as anti-counterfeiting marks.
Effect example 1 evaluation of security of forgery-preventing material
A: the anti-counterfeiting material 1 prepared in example 1 is used as an experimental material to draw an anti-counterfeiting mark with a specific pattern. Exposing the anti-counterfeiting mark under an ultraviolet lamp at 254nm for 5min, then coating a 6mmol/L fluorescamine solution on the anti-counterfeiting mark, and waiting for 10s, wherein the anti-counterfeiting mark is invisible under naked eyes.
B: the anti-counterfeiting material 1 prepared in example 1 is used as an experimental material to draw an anti-counterfeiting mark with a specific pattern. Exposing the anti-counterfeiting mark under an ultraviolet lamp of 254nm for 5min, and irradiating with an ultraviolet lamp of 400nm, wherein the anti-counterfeiting mark is invisible under naked eyes.
C: the anti-counterfeiting material 1 prepared in example 1 is used as an experimental material to draw an anti-counterfeiting mark with a specific pattern. 6mmol/L fluorescamine solution is coated on the anti-counterfeiting mark, the time is waited for 10s, and then the anti-counterfeiting mark is irradiated by an ultraviolet lamp with the wavelength of 400nm, and the anti-counterfeiting mark cannot be seen under the naked eye.
D: the anti-counterfeiting material 1 prepared in example 1 is used as an experimental material to draw an anti-counterfeiting mark with a specific pattern. Exposing the anti-counterfeiting mark under an ultraviolet lamp with the wavelength of 254nm for 5min, then coating 6mmol/L fluorescamine solution on the anti-counterfeiting mark, waiting for 10s, and finally irradiating by using an ultraviolet lamp with the wavelength of 400nm to see the anti-counterfeiting information of blue fluorescence.
According to the four-step verification results, the anti-counterfeiting material prepared by the invention can read anti-counterfeiting information only by 254nm ultraviolet exposure, fluorescent color developing agent color development and 400nm ultraviolet irradiation, and the anti-counterfeiting information cannot be read normally without one step or by reversing the sequence of the three steps. Therefore, the anti-counterfeiting material prepared by the invention has higher anti-counterfeiting coefficient, which is equivalent to three insurance on anti-counterfeiting information, and the rings are buckled with each other, so that the information can not be read if any ring is lacked. The anti-counterfeiting technology is not easy to crack and copy by lawless persons, and provides safety guarantee for some important information or products.
Effect example 2 evaluation of the definition of a forgery-preventing Material
Generally, the viscosity regulator is added into most anti-counterfeiting materials to keep the stability of the anti-counterfeiting mark, so that the anti-counterfeiting material presents unclear patterns and fuzzy boundaries when being used for drawing patterns with small shapes or characters with small fonts, and the precision degree of the anti-counterfeiting mark is reduced, thereby limiting the use of the anti-counterfeiting material. To demonstrate that the anti-counterfeiting material prepared by the invention is still applicable even when smaller precise patterns are prepared, the inventor writes 'A' from big to small on a paper base, wherein the smallest 'A' is a small six-character, then exposes the paper base for 5min under an ultraviolet lamp at 254nm, then coats a fluorescent amine solution at a concentration of 6mmol/L, waits for 10s, and irradiates the paper base with an ultraviolet lamp at a concentration of 400 nm. The resulting image, as shown in FIG. 3, is clearly recognizable even for "A" with a six-minus letter number. The experiment shows that the anti-counterfeiting material prepared by the invention has higher imaging definition and is suitable for preparing some precise anti-counterfeiting marks with smaller patterns.
Effect example 3 evaluation of stability of forgery preventing Material
The anti-counterfeiting materials prepared in examples 1 to 4 were drawn into anti-counterfeiting marks with specific patterns, and the water resistance, alkali resistance, acid resistance, salt spray resistance, aging resistance and wear resistance of the anti-counterfeiting marks were respectively detected, and the detection results are shown in table 1.
Water resistance: the temperature and humidity of the preservation environment of the anti-counterfeiting mark are 25 ℃/45%, water is sprayed to the anti-counterfeiting mark every 24 hours, and the water spraying amount is 0.5-1mL each time. And detecting the imaging condition of the anti-counterfeiting mark after 20 days.
Alkali resistance: the temperature and humidity of the preservation environment of the anti-counterfeiting mark are 25 ℃/45%, alkaline water (0.1M NaOH) is sprayed to the anti-counterfeiting mark every 24 hours, and the amount of the alkaline water sprayed each time is 0.5-1 mL. And detecting the imaging condition of the anti-counterfeiting mark after 20 days.
Acid resistance: the temperature and humidity of the preservation environment of the anti-counterfeiting mark are 25 ℃/45 percent, and acid water (0.1M H) is sprayed on the anti-counterfeiting mark every 24 hours2SO4) The amount of acid water sprayed is 0.5-1mL each time. And detecting the imaging condition of the anti-counterfeiting mark after 20 days.
Salt spray resistance: the temperature and humidity of the preservation environment of the anti-counterfeiting mark are 25 ℃/45%, salt water (0.1M NaCl) is sprayed to the anti-counterfeiting mark every 24 hours, and the amount of the salt water sprayed each time is 0.5-1 mL. And detecting the imaging condition of the anti-counterfeiting mark after 20 days.
Aging resistance: the temperature and humidity of the preservation environment of the anti-counterfeiting mark are 25 ℃/45%, and the anti-counterfeiting mark is irradiated by a xenon lamp for 15min every 24 h. And detecting the imaging condition of the anti-counterfeiting mark after 20 days.
Wear resistance: the temperature and humidity of the preservation environment of the anti-counterfeiting mark are 25 ℃/45%, and the anti-counterfeiting mark is wiped by cotton cloth every 24 hours. And detecting the imaging condition of the anti-counterfeiting mark after 20 days.
TABLE 1 stability test results for anti-counterfeiting materials
According to the stability detection result, the anti-counterfeiting material prepared by the invention has excellent water resistance, acid and alkali resistance, salt spray resistance and aging resistance, so that the anti-counterfeiting mark prepared by the anti-counterfeiting material has good stability and long storage life.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (2)
1. A use method of an anti-counterfeiting material with adjustable imaging waveband comprises the following steps:
(1) drawing an anti-counterfeiting mark: writing or spraying the anti-counterfeiting material on the surface of an object needing anti-counterfeiting, and preparing an anti-counterfeiting mark after the solvent is volatilized;
(2) and (3) imaging light treatment: exposing the anti-counterfeiting mark under an ultraviolet lamp of 254nm for 1-6 min;
(3) imaging chemical treatment: coating the fluorescent color developing agent on the anti-counterfeiting mark;
(4) reading anti-counterfeiting information: irradiating the anti-counterfeiting mark by using a 400nm ultraviolet lamp to read anti-counterfeiting information;
the preparation method of the anti-counterfeiting material comprises the following steps:
(1) respectively dissolving an N-hydroxyl compound and an isocyanate compound by using a solvent for later use, wherein the N-hydroxyl compound is N-hydroxyphthalimide, and the isocyanate compound is naphthalene diisocyanate;
(2) adding an N-hydroxy compound and a catalyst into a reaction container, then dropwise adding an isocyanate compound solution, and stirring at room temperature for 5-20h at the stirring speed of 50-150 r/min; the catalyst is triethylamine;
(3) after the reaction is finished, carrying out reduced pressure distillation at the temperature of 40-50 ℃ to obtain a crude product;
(4) recrystallizing the crude product with anhydrous methanol at 50-60 deg.C to obtain white crystal;
(5) and dissolving the white crystal by using a solvent to ensure that the final concentration of the white crystal is 2-10%, adding a viscosity regulator, and stirring to prepare the anti-counterfeiting material.
2. The use method according to claim 1, wherein the anti-counterfeiting material in the step (1) is drawn by handwriting or printer spraying; the fluorescent color developing agent in the step (3) is selected from: one or more of fluorescamine, fluorescamine diacetate, fluorescein-5-maleimide, fluorescein chloride, 5-carboxyfluorescein succinimidyl ester and 6-carboxyfluorescein succinimidyl ester.
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Non-Patent Citations (2)
| Title |
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| Study on Synthesis and Photochemical Behavior of Carbamate Photobase Generators for Fluorescence Imaging;Lanlan Liu,等;《J. APPL. POLYM. SCI》;20141230;第131卷(第22期);第41058/1-41058/7 * |
| 双波段写入多色荧光阵列的构筑及调控机理研究;刘兰兰;《北京化工大学博士研究生学位论文》;20141230;第二章 * |
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