CN116144219B - Thermochromic anti-counterfeiting ink as well as preparation method and application thereof - Google Patents
Thermochromic anti-counterfeiting ink as well as preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 40
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 8
- 150000002832 nitroso derivatives Chemical class 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 229950008882 polysorbate Drugs 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- SBNOTUDDIXOFSN-UHFFFAOYSA-N 1h-indole-2-carbaldehyde Chemical compound C1=CC=C2NC(C=O)=CC2=C1 SBNOTUDDIXOFSN-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000004440 column chromatography Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000000758 substrate Substances 0.000 description 11
- 230000002441 reversible effect Effects 0.000 description 10
- -1 complexes Chemical class 0.000 description 9
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 8
- AUORDBJGOHYGKR-UHFFFAOYSA-N 3-bromo-2-nitrophenol Chemical compound OC1=CC=CC(Br)=C1[N+]([O-])=O AUORDBJGOHYGKR-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010345 tape casting Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- YNCYPMUJDDXIRH-UHFFFAOYSA-N benzo[b]thiophene-2-boronic acid Chemical compound C1=CC=C2SC(B(O)O)=CC2=C1 YNCYPMUJDDXIRH-UHFFFAOYSA-N 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PZJSZBJLOWMDRG-UHFFFAOYSA-N furan-2-ylboronic acid Chemical compound OB(O)C1=CC=CO1 PZJSZBJLOWMDRG-UHFFFAOYSA-N 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 1
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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
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention provides thermochromic anti-counterfeiting ink and a preparation method and application thereof, and belongs to the technical field of thermochromic materials. The thermochromic anti-counterfeiting ink comprises: an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component is a spiropyran structural compound, and the structural formula of the organic thermochromic component is any one of the following compounds:
. The spiropyran structure compound can generate structural color change along with temperature change, further causes the color change of the compound and realizes the anti-counterfeiting effect of the ink.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to thermochromic anti-counterfeiting ink as well as a preparation method and application thereof.
Background
Thermochromic is a reversible chemical change, i.e. when the temperature is raised to a certain range, the original color can be restored by lowering the temperature after the color of the substance is changed. The mechanism of thermochromic can be summarized as: (1) structural changes, including changes in crystal structure or lattice constant, changes in molecular structure of organic compounds, changes in geometric configuration of complexes, and the like; (2) thermal decomposition, which changes color due to new colored substances generated by the decomposition; (3) the reaction balance shifts, and a mixed system composed of two or more substances which do not have thermochromic properties by themselves shows a color change due to a chemical reaction after being heated. Among the intermolecular chemical reactions that can cause a color change are acid-base reactions, charge transfer, proton transfer, and chelation reactions, etc. Substances having thermochromic properties are referred to as thermochromic materials. Such materials can be classified according to their composition of matter: (1) thermochromic inorganic materials such as iodides, complexes, organometallic compounds, etc., the color-changing temperature is mostly above 100 ℃; (2) thermochromic organic materials such as spiropyran, fluorescent derivatives, polythiophene, liquid crystal materials and the like, and has wide color changing temperature (-100 ℃), and rich color change.
The initial application of the thermochromic material is as a temperature indicating material, which is coated on the surface of an object in special occasions where the temperature cannot be measured by a common thermometer or a thermocouple, and the temperature distribution can be indicated according to the color change of the thermochromic material. The application of the above materials in the anti-counterfeiting field has not been reported.
In view of the above, it is necessary to provide thermochromic anti-counterfeiting ink with encryption function, and a preparation method and application thereof.
Disclosure of Invention
The invention aims at solving at least one of the technical problems existing in the prior art and provides thermochromic anti-counterfeiting ink as well as a preparation method and application thereof.
In one aspect of the present invention, a thermochromic anti-counterfeit ink is provided, comprising: 1 to 3 percent of organic thermochromic component, 3 to 7 percent of surfactant, 8 to 11 percent of organic solvent and 80 to 85 percent of deionized water; wherein,,
the organic thermochromic component is a spiropyran structural compound, and the structural formula of the organic thermochromic component is any one of the following compounds:
optionally, the thermochromic anti-counterfeiting ink comprises:
2% of an organic thermochromic component;
5% of a surfactant;
10% of an organic solvent;
83% deionized water.
Optionally, the surfactant is a nonionic surfactant; and/or the number of the groups of groups,
the organic solvent is an alkyl-containing solvent.
Optionally, the surfactant is one of glycerol, polyethylene glycol, polyoxyethylene ether, polysorbate and polyvinyl alcohol.
Optionally, the organic solvent is one of methanol, isopropanol, dichloromethane, chloroform and toluene.
In another aspect of the present invention, a method for preparing the thermochromic anti-counterfeit ink described above is provided, the method comprising:
synthesizing an organic thermochromic component;
adding the organic thermochromic component into an organic solvent, stirring, adding into deionized water, carrying out ultrasonic treatment, adding a surfactant, and stirring to obtain the thermochromic anti-counterfeiting ink.
Optionally, the synthetic organic thermochromic component comprises:
reacting 6-bromo-2-phenol with nitrite at 0 ℃ for 1-2 hours to obtain a nitroso compound;
reflux-reacting the nitroso compound with indolal at 100 ℃ for 24-48h to obtain an intermediate;
reacting the intermediate with a compound shown in any one of the following structural formulas for 12-24 hours through Suziki reaction to obtain a spiropyran structural compound; wherein, the structural formula is as follows:
in another aspect of the present invention, an application of thermochromic anti-counterfeit ink is provided, and the thermochromic anti-counterfeit ink is applied to a thin-film device.
The invention provides thermochromic anti-counterfeiting ink, a preparation method and application thereof, and the thermochromic anti-counterfeiting ink has the following advantages: the thermochromic anti-counterfeiting ink containing different spiropyran compound formulas provided by the invention has the advantages of short color changing time, stable material, simplicity in preparation, higher material yield, lower cost and the like based on that spiropyran structure compounds in the ink can change structurally along with temperature change, further cause compound color change and realize the anti-counterfeiting effect of the ink.
Drawings
FIG. 1 is a flow chart of a method for preparing thermochromic anti-counterfeit ink according to an embodiment of the present invention;
FIG. 2 is a reaction scheme showing the synthesis of a spiropyran compound of example 1 of the present invention;
FIG. 3 is a reaction scheme showing the synthesis of a spiropyran compound of example 2 of the present invention;
FIG. 4 is a reaction scheme showing the synthesis of a spiropyran compound of example 3 of the present invention;
FIG. 5 is a reaction scheme showing the synthesis of a spiropyran compound of example 4 of the present invention;
FIG. 6 is a reaction scheme showing the synthesis of a spiropyran compound of example 5 of the present invention;
FIG. 7 is a reaction scheme showing the synthesis of a spiropyran compound of example 6 of the present invention;
FIG. 8 is a reaction scheme showing the synthesis of a spiropyran compound of example 7 of the present invention;
FIG. 9 is a reaction scheme showing the synthesis of a spiropyran compound of example 8 of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of better understanding of the technical solution of the present invention to those skilled in the art. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention belong to the protection scope of the present invention.
Unless specifically stated otherwise, technical or scientific terms used herein should be defined in the general sense as understood by one of ordinary skill in the art to which this invention belongs. The use of "including" or "comprising" and the like in the present invention does not limit the shape, number, step and/or group thereof mentioned nor exclude the presence or addition of one or more other different shapes, numbers, steps and/or groups thereof.
In one aspect of the present invention, a thermochromic anti-counterfeit ink is provided, comprising: an organic thermochromic component, a surfactant, an organic solvent and deionized water; the organic thermochromic component is mainly a spiropyran structural compound, and the structural formula of the spiropyran structural compound is any one of the following structural formulas:
in order to realize the encryption function of the ink, the structure of the spiropyran compound is designed and applied to the thermochromic component of the ink, so that the ink can realize color change in the heating process, the process is reversible, and the thermochromic anti-counterfeiting function of the ink is realized.
The color change principle of the spiropyran structure compound is as follows:
the spiropyran structure compound of the invention is used as an organic thermochromic material and has the advantages of good heat sensitivity, stability, fatigue resistance and the like.
Further, in the embodiment of the invention, the organic thermochromic component accounts for 1% -3%, the surfactant accounts for 3% -7%, the organic solvent accounts for 8% -11%, and the deionized water accounts for 80% -85%.
In a preferred embodiment of the present invention, the thermochromic anti-counterfeit ink includes: 2% of an organic thermochromic component; 5% of a surfactant; 10% of an organic solvent; 83% deionized water.
Further, in the embodiment of the present invention, the surfactant is a nonionic surfactant, for example, one of glycerin, polyethylene glycol, polyoxyethylene ether, polysorbate, and polyvinyl alcohol.
Further, in the embodiment of the present invention, the organic solvent is an alkyl-containing solvent, for example, one of methanol, isopropanol, dichloromethane and chloroform.
The thermochromic anti-counterfeiting ink provided by the invention comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water, wherein a spiropyran structure compound is adopted based on the organic thermochromic component, so that structural color change can occur along with temperature change, further the compound is caused to change color, and the anti-counterfeiting effect of the ink is realized.
As shown in fig. 1, in another aspect of the present invention, a method S100 for preparing the thermochromic anti-counterfeit ink described above is provided, which specifically includes the following steps S110 to S120:
s110, synthesizing an organic thermochromic component.
Specifically, the process for synthesizing the organic thermochromic component is as follows: reacting 6-bromo-2-phenol with nitrite at 0 ℃ for 1-2 hours to obtain a nitroso compound; reacting a nitroso compound with indolal, and carrying out reflux reaction for 24-48h at 100 ℃ to obtain an intermediate; reacting the intermediate with a compound shown in any one of the following structural formulas for 12-24 hours through Suziki reaction to obtain a spiropyran structural compound; wherein, the structural formula is as follows:
s120, adding an organic thermochromic component into an organic solvent, stirring, dropwise adding the solution into deionized water after stirring, adding a surfactant after ultrasonic treatment, and stirring to obtain the thermochromic anti-counterfeiting ink.
The preparation method of the invention is simple, the cost is lower, and the yield of the material is higher.
In another aspect of the invention, a thermochromic anti-counterfeit ink is provided, which has an encryption function and can be used in an anti-counterfeit thin-film device.
In the embodiment of the invention, the thermochromic anti-counterfeiting ink is applied to a substrate by scraping, and then dried at room temperature to obtain the thin film device.
The substrate in this embodiment is not particularly limited, and for example, a flexible substrate may be used, and polyimide or glass sheet may be used, and the thickness thereof may be 100nm to 300nm.
Further, the invention also tests the thermochromic performance of the formed thin film device, the dried thin film presents transparent color, then the thin film is heated by a blower and turns from colorless to light red, and the thin film is cooled to room temperature and then returns to colorless. That is, the color-changing anti-counterfeiting effect can be realized by heating or cooling the thin film device formed by the thermochromic anti-counterfeiting ink.
The thermochromic anti-counterfeiting ink, the preparation method and the specific application thereof are further described below with reference to a few specific examples:
example 1
The example provides thermochromic anti-counterfeiting ink which comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component adopts a spiropyran compound.
Based on the above components, the preparation process and specific application of the thermochromic anti-counterfeiting ink will be specifically given below.
1) Preparation of reversible thermochromic anti-counterfeiting ink:
to 15mL of methylene chloride solution, 70mg of the prepared spiropyran compound was added, stirring was sufficiently carried out for 2 hours, the above solution was added dropwise to 30mL of 80℃deionized water, and the solution was then sonicated with an ultrasonic machine for 20 minutes, followed by addition of 50mg/mL of polyvinyl alcohol. After the ink preparation was completed, the mixture was stirred for 1 hour.
The synthesis procedure of the spiropyran compound used in the preparation process is as follows, and the synthetic reaction formula is shown in fig. 2:
s1: a clean and dry three-necked flask with a magneton was taken, to which 0.5g of 6-bromo-2-phenol was added, followed by dissolution by addition of chloroform, to which 80mg of 90wt% aqueous sodium hydroxide solution, 0.20mL of sulfuric acid and 0.17g of sodium nitrite were added, and reacted at 0℃for 1 hour, and the product was purified by column chromatography to give 0.39g of 6-bromo-1-nitrobenzene-2-ol.
S2: to 50mL of acetonitrile solution, 0.76mL of indolal compound and 6-bromo-1-nitrophenyl-2-ol were added, respectively, and the mixture was refluxed under vacuum for 24 hours. After the completion of the reaction, purification by column chromatography gave 0.59g of 8 '-bromo-1, 3, 3-trimethylspiro [ indoline-2, 3' -heptane naphthalene [2, 1-b ] [1, 4] oxazine ].
S3: 0.59g of the product of the previous step was reacted with 1.45g of 2-boracic acid benzene by Suziki reaction to obtain 1.01g of the final product.
2) Preparation of a thin film device: the ink prepared above was knife coated on a flexible polyimide substrate, followed by drying at room temperature.
3) Film thermochromic performance test:
the dried film appeared transparent, and then heated by a blower until the temperature reached 80 ℃, the film turned from colorless to pale white, and the film was cooled to room temperature and recovered to colorless.
Example 2
The example provides thermochromic anti-counterfeiting ink which comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component adopts a spiropyran compound.
Based on the above components, the preparation process and specific application of the thermochromic anti-counterfeiting ink will be specifically given below.
1) Preparation of reversible thermochromic anti-counterfeiting ink:
adding 75mg of the prepared spiropyran compound into 15mL of chloroform solution, fully stirring for 2 hours, dropwise adding the solution into 20mL of deionized water at 80 ℃, then carrying out ultrasonic treatment on the solution for 20 minutes by using an ultrasonic machine, and then adding 60mg/mL of polyoxyethylene ether. After the ink preparation was completed, the mixture was stirred for 1 hour.
The synthesis procedure of the spiropyran compound used in the preparation process is as follows, and the synthetic reaction formula is shown in fig. 3:
s1: a clean and dry three-necked flask with a magneton was taken, to which 0.5g of 6-bromo-2-phenol was added, followed by dissolution by addition of chloroform, to which 90mg of 90wt% aqueous sodium hydroxide solution, 0.16ml of sulfuric acid and 0.16g of sodium nitrite were added, and reacted at 0℃for 1 hour, and the product was purified by column chromatography to give 0.41g of 6-bromo-1-nitrobenzene-2-ol.
S2: to 50mL of acetonitrile solution, 1.01mL of indolal compound and 6-bromo-1-nitrophenyl-2-ol were added, respectively, and the mixture was refluxed under vacuum for 24 hours. After the completion of the reaction, the mixture was purified by column chromatography to obtain 1.32g of 8 '-bromo-1, 3, 3-trimethylspiro [ indoline-2, 3' -naphthalenenonane [2, 1-b ] [1, 4] oxazine ].
S3: 1.32g of the product of the previous step was reacted with 1.32g of naphthalene 2-borate by Suziki reaction to obtain 0.81g of the final product.
2) Preparation of a thin film device:
the ink prepared above was knife coated on a flexible polyimide substrate, followed by drying at room temperature.
3) Film thermochromic performance test:
the dried film appeared transparent, and then heated by a blower until the temperature reached 80 ℃, the film turned from colorless to pale white, and the film was cooled to room temperature and recovered to colorless.
Example 3
The example provides thermochromic anti-counterfeiting ink which comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component adopts a spiropyran compound.
Based on the above components, the preparation process and specific application of the thermochromic anti-counterfeiting ink will be specifically given below.
1) Preparation of reversible thermochromic anti-counterfeiting ink:
to 15mL of methylene chloride solution, 75mg of the prepared spiropyran compound was added, and stirring was sufficiently carried out for 2 hours, and then the above solution was added dropwise to 20mL of 80℃deionized water, after which the solution was sonicated with an ultrasonic machine for 20 minutes, and then 60mg/mL of polyvinyl alcohol was added. After the ink preparation was completed, the mixture was stirred for 1 hour.
The synthesis procedure of the spiropyran compound used in the preparation process is as follows, and the synthetic reaction formula is shown in fig. 4:
s1: a clean and dry three-necked flask with a magneton was taken, to which 0.5g of 6-bromo-2-phenol was added, followed by dissolution by addition of chloroform, to which 90mg of 90wt% aqueous sodium hydroxide solution, 0.16ml of sulfuric acid and 0.16g of sodium nitrite were added, and reacted at 0℃for 1 hour, and the product was purified by column chromatography to give 0.41g of 6-bromo-1-nitrobenzene-2-ol.
S2: to 50ml of acetonitrile solution, 1.01ml of indolal compound and 6-bromo-1-nitrophenyl-2-ol were added, respectively, and the mixture was refluxed under vacuum for 24 hours. After the completion of the reaction, purification by column chromatography gave 1.39g of 8 '-bromo-1, 3, 3-trimethylspiro [ indoline-2, 3' -anthracenenonane [2, 1-b ] [1, 4] oxazine ].
S3: 1.39g of the product of the previous step was reacted with 1.35g of naphthalene 2-borate by Suziki reaction to obtain 0.91g of the final product.
2) Preparation of a thin film device:
the ink prepared above was knife coated on a flexible polyimide substrate, followed by drying at room temperature.
3) Film thermochromic performance test:
the dried film appeared transparent, and then heated by a blower, and when the temperature reached 80 ℃, the film turned from colorless to white, and after cooling to room temperature, the film was restored to colorless.
Example 4
The example provides thermochromic anti-counterfeiting ink which comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component adopts a spiropyran compound.
Based on the above components, the preparation process and specific application of the thermochromic anti-counterfeiting ink will be specifically given below.
1) Preparation of reversible thermochromic anti-counterfeiting ink:
to 10mL of the isopropanol solution, 75mg of the prepared spiropyran compound was added, stirring was carried out for 2 hours, the above solution was added dropwise to 25mL of 80℃deionized water, the solution was then sonicated with an ultrasonic machine for 20 minutes, and then 60mg/mL of polysorbate was added. After the ink preparation was completed, the mixture was stirred for 1 hour.
The synthesis procedure of the spiropyran compound used in the preparation process is as follows, and the synthetic reaction formula is shown in fig. 5:
s1: a clean and dry three-necked flask with a magneton was taken, to which 0.5g of 6-bromo-2-phenol was added, followed by dissolution by addition of chloroform, to which 90mg of 90wt% aqueous sodium hydroxide solution, 0.16ml of sulfuric acid and 0.16g of sodium nitrite were added, and reacted at 0℃for 1 hour, and the product was purified by column chromatography to give 0.41g of 6-bromo-1-nitrobenzene-2-ol.
S2: to 50ml of acetonitrile solution, 0.85ml of indolal compound and 6-bromo-1-nitrophenyl-2-ol were added, respectively, and the mixture was refluxed under vacuum for 24 hours. After the completion of the reaction, purification by column chromatography gave 0.51g of 8 '-bromo-1, 3, 3-trimethylspiro [ indoline-2, 3' -naphthalenenonane [2, 1-b ] [1, 4] oxazine ].
S3: 0.51g of the product of the previous step was reacted with 2.19g of benzothiophene 2-boronic acid by Suziki reaction to give 1.07g of the final product.
2) Preparation of a thin film device:
the ink prepared above was knife coated on a glass substrate, followed by drying at room temperature.
3) Film thermochromic performance test:
the dried film appeared transparent, and then heated by a blower, and when the temperature reached 80 ℃, the film changed from colorless to pale red, and after cooling to room temperature, the film was restored to colorless.
Example 5
The example provides thermochromic anti-counterfeiting ink which comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component adopts a spiropyran compound.
Based on the above components, the preparation process and specific application of the thermochromic anti-counterfeiting ink will be specifically given below.
1) Preparation of reversible thermochromic anti-counterfeiting ink:
to 10mL of toluene solution, 75mg of the prepared spiropyran compound was added, stirring was carried out for 2 hours, the above solution was added dropwise to 25mL of 80℃deionized water, and the solution was sonicated with an ultrasonic machine for 20 minutes, followed by addition of 60mg/mL of polyvinyl alcohol. After the ink preparation was completed, the mixture was stirred for 1 hour.
The synthesis procedure of the spiropyran compound used in the preparation process is as follows, and the synthetic reaction formula is shown in fig. 6:
s1: a clean and dry three-necked flask with a magneton was taken, to which 0.5g of 6-bromo-2-phenol was added, followed by dissolution by addition of chloroform, to which 90mg of 90wt% aqueous sodium hydroxide solution, 0.16mL of sulfuric acid and 0.16g of sodium nitrite were added, and reacted at 0℃for 1 hour, and the product was purified by column chromatography to give 0.41g of 6-bromo-1-nitrobenzene-2-ol.
S2: to 50mL of acetonitrile solution, 0.77mL of indolal compound and 6-bromo-1-nitrophenyl-2-ol were added, respectively, and the mixture was refluxed under vacuum for 24 hours. After the completion of the reaction, the mixture was purified by column chromatography to obtain 0.70g of 8 '-bromo-1, 3, 3-trimethylspiro [ indoline-2, 3' -napthone [2, 1-b ] [1, 4] oxazine ].
S3: 0.70g of the product of the previous step was reacted with 2.06. 2.06 g benzofuran 2-boronic acid by Suziki reaction to give 0.91g of the final product.
2) Preparation of a thin film device:
the ink was prepared by knife coating onto a glass substrate and then dried at room temperature.
3) Film thermochromic performance test:
the dried film appeared transparent, and then heated by a blower, and when the temperature reached 80 ℃, the film changed from colorless to pale red, and after cooling to room temperature, the film was restored to colorless.
Example 6
The example provides thermochromic anti-counterfeiting ink which comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component adopts a spiropyran compound.
Based on the above components, the preparation process and specific application of the thermochromic anti-counterfeiting ink will be specifically given below.
1) Preparation of reversible thermochromic anti-counterfeiting ink:
to 10mL of methylene chloride solution, 75mg of the prepared spiropyran compound was added, stirring was sufficiently carried out for 2 hours, the above solution was added dropwise to 25mL of 80℃deionized water, and the solution was then sonicated with an ultrasonic machine for 20 minutes, followed by addition of 60mg/mL of polyvinyl alcohol. After the ink preparation was completed, the mixture was stirred for 1 hour.
The synthesis procedure of the spiropyran compound used in the preparation process is as follows, and the synthetic reaction formula is shown in fig. 7:
s1: a clean and dry three-necked flask with a magneton was taken, to which 0.5g of 6-bromo-2-phenol was added, followed by dissolution by addition of chloroform, to which 90mg of 90wt% aqueous sodium hydroxide solution, 0.16mL of sulfuric acid and 0.16g of sodium nitrite were added, and reacted at 0℃for 1 hour, and the product was purified by column chromatography to give 0.41g of 6-bromo-1-nitrobenzene-2-ol.
S2: to 50mL of acetonitrile solution, 0.77mL of indolal compound and 6-bromo-1-nitrophenyl-2-ol were added, respectively, and the mixture was refluxed under vacuum for 24 hours. After the completion of the reaction, the mixture was purified by column chromatography to obtain 0.70g of 8 '-bromo-1, 3, 3-trimethylspiro [ indoline-2, 3' -napthone [2, 1-b ] [1, 4] oxazine ].
S3: 0.70g of the product of the previous step was reacted with 3.41g of thiophene 2-boronic acid by Suziki reaction to give 0.66g of the final product.
2) Preparation of a thin film device:
the ink was prepared by knife coating onto a flexible polyimide substrate and then dried at room temperature.
3) Film thermochromic performance test:
the dried film appeared transparent, and then heated by a blower, and when the temperature reached 80 ℃, the film turned from colorless to pale yellow, and the film was cooled to room temperature and recovered to colorless.
Example 7
The example provides thermochromic anti-counterfeiting ink which comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component adopts a spiropyran compound.
Based on the above components, the preparation process and specific application of the thermochromic anti-counterfeiting ink will be specifically given below.
1) Preparation of reversible thermochromic anti-counterfeiting ink:
to 10mL of methylene chloride solution, 75mg of the prepared spiropyran compound was added, stirring was sufficiently carried out for 2 hours, the above solution was added dropwise to 25mL of 80℃deionized water, and the solution was then sonicated with an ultrasonic machine for 20 minutes, followed by addition of 60mg/mL of polyvinyl alcohol. After the ink preparation was completed, the mixture was stirred for 1 hour.
The synthesis procedure of the spiropyran compound used in the preparation process is as follows, and the synthetic reaction formula is shown in fig. 8:
s1: a clean and dry three-necked flask with a magneton was taken, to which 0.5g of 6-bromo-2-phenol was added, followed by dissolution by addition of chloroform, to which 90mg of 90wt% aqueous sodium hydroxide solution, 0.16mL of sulfuric acid and 0.16g of sodium nitrite were added, and reacted at 0℃for 1 hour, and the product was purified by column chromatography to give 0.41g of 6-bromo-1-nitrobenzene-2-ol.
S2: to 50mL of acetonitrile solution, 0.77mL of indolal compound and 6-bromo-1-nitrophenyl-2-ol were added, respectively, and the mixture was refluxed under vacuum for 24 hours. After the completion of the reaction, the mixture was purified by column chromatography to obtain 0.70g of 8 '-bromo-1, 3, 3-trimethylspiro [ indoline-2, 3' -napthone [2, 1-b ] [1, 4] oxazine ].
S3: 0.70g of the product of the previous step was reacted with 3.69g of furan 2-boronic acid by Suziki reaction, yielding 0.77g of the final product.
2) Preparation of a thin film device:
the ink was prepared by knife coating onto a flexible polyimide substrate and then dried at room temperature.
3) Film thermochromic performance test:
the dried film appeared transparent, and then heated by a blower until the temperature reached 80 ℃, the film changed from colorless to red, and the film was cooled to room temperature and recovered to colorless.
Example 8
The example provides thermochromic anti-counterfeiting ink which comprises an organic thermochromic component, a surfactant, an organic solvent and deionized water; wherein the organic thermochromic component adopts a spiropyran compound.
Based on the above components, the preparation process and specific application of the thermochromic anti-counterfeiting ink will be specifically given below.
1) Preparation of reversible thermochromic anti-counterfeiting ink:
to 10mL of methanol solution, 75mg of the prepared spiropyran compound was added, stirring was carried out for 2 hours, the above solution was added dropwise to 25mL of 80℃deionized water, and the solution was sonicated with an ultrasonic machine for 20 minutes, followed by addition of 60mg/mL of glycerol. After the ink preparation was completed, the mixture was stirred for 1 hour.
The synthetic procedure of the spiropyran compound used in the preparation process is as follows, and the synthetic reaction formula is shown in fig. 9:
s1: a clean and dry three-necked flask with a magneton was taken, to which 0.5g of 6-bromo-2-phenol was added, followed by dissolution by addition of chloroform, to which 90mg of 90wt% aqueous sodium hydroxide solution, 0.16ml of sulfuric acid and 0.16g of sodium nitrite were added, and reacted at 0℃for 1 hour, and the product was purified by column chromatography to give 0.41g of 6-bromo-1-nitrobenzene-2-ol.
S2: to 50mL of acetonitrile solution, 0.77mL of indolal compound and 6-bromo-1-nitrophenyl-2-ol were added, respectively, and the mixture was refluxed under vacuum for 24 hours. After the completion of the reaction, the mixture was purified by column chromatography to obtain 0.70g of 8 '-bromo-1, 3, 3-trimethylspiro [ indoline-2, 3' -napthone [2, 1-b ] [1, 4] oxazine ].
S3: 0.70g of the product of the previous step was reacted with 5.01g of tetraphenyl 2-boronic acid by Suziki reaction to obtain 1.62g of the final product.
2) Preparation of a thin film device:
the ink was prepared by knife coating onto a glass substrate and then dried at room temperature.
3) Film thermochromic performance test:
the dried film appeared transparent, and then heated by a blower, and when the temperature reached 80 ℃, the film turned from colorless to white, and after cooling to room temperature, the film was restored to colorless.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Claims (8)
1. A thermochromic anti-counterfeit ink, comprising: 1 to 3 percent of organic thermochromic component, 3 to 7 percent of surfactant, 8 to 11 percent of organic solvent and 80 to 85 percent of deionized water; wherein,,
the organic thermochromic component is a spiropyran structural compound, and the structural formula of the organic thermochromic component is any one of the following compounds:
2. the thermochromic anti-counterfeit ink of claim 1, wherein the thermochromic anti-counterfeit ink comprises:
2% of an organic thermochromic component;
5% of a surfactant;
10% of an organic solvent;
83% deionized water.
3. The thermochromic anti-counterfeit ink of claim 1 or 2, wherein the surfactant is a nonionic surfactant; and/or the number of the groups of groups,
the organic solvent is an alkyl-containing solvent.
4. The thermochromic anti-counterfeit ink according to claim 3, wherein the surfactant is one of glycerin, polyethylene glycol, polyoxyethylene ether, polysorbate, and polyvinyl alcohol.
5. The thermochromic anti-counterfeit ink of claim 3, wherein the organic solvent is one of methanol, isopropanol, methylene chloride, chloroform and toluene.
6. A method of preparing the thermochromic anti-counterfeit ink of any one of claims 1 to 5, comprising:
synthesizing an organic thermochromic component;
adding the organic thermochromic component into an organic solvent, stirring, adding into deionized water, carrying out ultrasonic treatment, adding a surfactant, and stirring to obtain the thermochromic anti-counterfeiting ink.
7. The method of claim 6, wherein the synthetic organic thermochromic component comprises:
reacting 6-bromo-2-phenol with nitrite at 0 ℃ for 1-2 hours to obtain a nitroso compound;
reflux-reacting the nitroso compound with indolal at 100 ℃ for 24-48h to obtain an intermediate;
reacting the intermediate with a compound shown in any one of the following structural formulas for 12-24 hours through Suziki reaction to obtain a spiropyran structural compound; wherein, the structural formula is as follows:
8. the application of thermochromic anti-counterfeiting ink, which is characterized in that the thermochromic anti-counterfeiting ink as claimed in any one of claims 1 to 5 is applied to a thin film device.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1405701A (en) * | 1973-09-13 | 1975-09-10 | Pilot Ink Co Ltd | Thermochromic materials |
| WO2002008821A1 (en) * | 2000-07-12 | 2002-01-31 | Skyrad Ltd. | Thermochromic composition |
| CN114456643A (en) * | 2021-12-26 | 2022-05-10 | 西北工业大学 | Photo-thermal double-response color-changing ink based on triaryl ethylene system, and preparation method and application thereof |
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| CN1064046C (en) * | 1997-11-12 | 2001-04-04 | 南开大学戈德防伪技术公司 | Photochromic spiro-compound and its preparation |
| JP4568027B2 (en) * | 2003-07-17 | 2010-10-27 | パイロットインキ株式会社 | Photochromic material |
| JP2009270033A (en) * | 2008-05-09 | 2009-11-19 | Matsui Shikiso Chem Co Ltd | Reversible thermochromic marking pen oil-based ink |
| CN107099282A (en) * | 2017-05-19 | 2017-08-29 | 成都新柯力化工科技有限公司 | A kind of preparation method of spiro-pyrans/metatitanic acid composite photochromic film |
| CN107686687A (en) * | 2017-10-30 | 2018-02-13 | 上海幂方电子科技有限公司 | Thermochromic ink and preparation method thereof |
| CN114583052B (en) * | 2022-02-21 | 2024-09-20 | 西北工业大学 | Thermochromic material organic field effect transistor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1405701A (en) * | 1973-09-13 | 1975-09-10 | Pilot Ink Co Ltd | Thermochromic materials |
| WO2002008821A1 (en) * | 2000-07-12 | 2002-01-31 | Skyrad Ltd. | Thermochromic composition |
| CN114456643A (en) * | 2021-12-26 | 2022-05-10 | 西北工业大学 | Photo-thermal double-response color-changing ink based on triaryl ethylene system, and preparation method and application thereof |
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