CN1237130C - Friction luminous antiforge printing ink and mfg. method thereof - Google Patents
Friction luminous antiforge printing ink and mfg. method thereof Download PDFInfo
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- CN1237130C CN1237130C CN 200410004469 CN200410004469A CN1237130C CN 1237130 C CN1237130 C CN 1237130C CN 200410004469 CN200410004469 CN 200410004469 CN 200410004469 A CN200410004469 A CN 200410004469A CN 1237130 C CN1237130 C CN 1237130C
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- Prior art keywords
- friction
- vacuum furnace
- luminous
- printing ink
- triboluminescence
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000005390 triboluminescence Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 7
- 230000001133 acceleration Effects 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000012495 reaction gas Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000010902 jet-milling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Inspection Of Paper Currency And Valuable Securities (AREA)
- Printing Methods (AREA)
Abstract
The present invention discloses a friction luminous anti-counterfeiting printing ink and a manufacture method thereof. The manufacture method comprises the steps: processing friction luminous materials into powder with the grain size no greater than 5 mu m; removing the ultraviolet fluorescence of the materials; coating the friction luminous materials in a chemical or physical mode; coating a layer of protective film made of materials with the properties of high moisture resistance and acid resistance on the surface of each grain; and putting the friction luminous materials into printing ink according to certain proportion to manufacture the anti-counterfeiting printing ink. The present invention also discloses a CVD improving method for generating a silicon dioxide film on the surface of the friction luminous material powder, which is a chemical treatment method. The friction luminous anti-counterfeiting printing ink manufactured by the method does not project fluorescence under the irradiation of ultraviolet lamps, and has the advantages of stable chemical and physical properties, and long service life. The friction luminous anti-counterfeiting printing ink can be used for printing anti-counterfeiting marks of banknotes, securities, etc.
Description
Technical Field
The invention relates to a triboluminescence anti-counterfeiting ink for printing and a manufacturing method thereof.
Background
British patent GB2232119A discloses a method for printing valuable documents by adding a triboluminescent material to printing ink in a certain proportion to form anti-counterfeiting ink. However, the friction luminescent material has orange fluorescence under an ultraviolet lamp, and bank notes and valuable documents are usually provided with a plurality of anti-counterfeiting marks, so that in order to prevent the friction luminescent material from emitting light under the ultraviolet lamp to influence the identification of other anti-counterfeiting marks such as ultraviolet and the like, a coating containing an ultraviolet absorbent is printed on the friction luminescent material, and the printing process and the printing difficulty are increased. In addition, because the humidity resistance and acid resistance of the used friction luminescent material are poor, the friction luminescent function of the material is easy to weaken or disappear under the common use condition, and the use is influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the triboluminescence anti-counterfeiting ink which does not emit ultraviolet fluorescence under the irradiation of an ultraviolet lamp and has strong moisture resistance and acid resistance. The invention further provides a method for manufacturing the triboluminescence anti-counterfeiting ink.
In order to achieve the purpose, the triboluminescence anti-counterfeiting ink comprises a triboluminescence material and ink, wherein the triboluminescence material is ZnS: Mn with the particle size not larger than 5 mu m, the triboluminescence material accounts for 15-60 wt% in the ink, and a protective film made of a material with strong moisture resistance and acid resistance is coated on the surface of the triboluminescence material particles.
Further, the protective film on the surface of the triboluminescent material is silicon dioxide.
A method for manufacturing triboluminescence anti-counterfeiting ink with a protective film made of silicon dioxide comprises the following steps:
(1) processing the triboluminescence material into powder with the diameter not more than 5 μm by using a jet milling method or a ball milling method;
(2) filling the friction luminescent material powder into a high-temperature vacuum furnace capable of vibrating at a high speed, vacuumizing the vacuum furnace to 0.1-0.28Pa, and then filling nitrogen into the vacuum furnace, wherein the input flow of the nitrogen is 80-100 ml/min;
(3) heating the vacuum furnace to 800-1000 ℃ and starting vibration with the vibration acceleration of 6-15m/s2；
(4) Then simultaneously inputting SiCl into the vacuum furnace through two pipelines4High purity gas and steamGas, SiCl4The input flow rate of the high-purity gas is 50-70ml/min, and the input flow rate of the water vapor is 70-90 ml/min;
(5) the reaction lasts for 30-120 minutes, the gas reacts on the surface of the friction luminescent material to generate a silicon dioxide film, and the chemical reaction equation is as follows: ；
(6) after the reaction is carried out for a preset time, stopping heating and vibrating, stopping inputting reaction gas, and keeping inputting nitrogen;
(7) stopping inputting nitrogen when the vacuum furnace is cooled to room temperature, putting the atmosphere into the vacuum furnace, and taking out the treated friction luminescent material;
(8) and finally, putting 15-60% of friction luminescent material by weight into the printing ink, and fully mixing to prepare the friction luminescent anti-counterfeiting ink.
After the friction luminescent material is processed to be below 5 mu m, the fluorescence intensity of the friction luminescent material under the irradiation of an ultraviolet lamp is only 10 percent of the original fluorescence intensity, the fluorescence intensity is extremely weak and can be ignored, the interference on ultraviolet identification can be avoided, an ultraviolet absorbent coating does not need to be printed, and meanwhile, a silicon dioxide film with stable physical and chemical properties is coated on the surface of the friction luminescent material, so that the moisture resistance and the acid resistance of the friction luminescent material are improved, and the service life of the friction luminescent material is greatly prolonged.
The specific implementation mode is as follows:
example 1
Firstly, processing the friction luminescent material into powder with the particle size of less than 5 mu m by adopting a jet milling method or a ball milling method so as to remove the ultraviolet fluorescence characteristic of the material; then, filling the friction luminescent material powder into a high-temperature vacuum furnace capable of vibrating at a high speed, vacuumizing the vacuum furnace to 0.1Pa, and then filling nitrogen, wherein the input flow of the nitrogen is 80 ml/min; heating the vacuum furnace to 800 ℃, and starting vibration with the vibration acceleration of 6m/s2(ii) a Then simultaneously inputting SiCl into the vacuum furnace through two pipelines4High purity gas and water vapor, SiCl4The input flow rate of the high-purity gas is 50ml/min, and the input flow rate of the water vapor is 70 ml/min; the reaction lasts for 30 minutes, the waste gas is discharged after purification treatment, and after the preset time, the heating, the vibration and the input of reaction gas are stopped, and the input of nitrogen is kept; naturally cooling to room temperature, stopping inputting nitrogen, putting into the atmosphere, and taking out the treated friction luminescent material; and finally, putting 15% of friction luminescent material into the printing ink by weight, and fully mixing to prepare the friction luminescent anti-counterfeiting ink.
Example 2
Putting the friction luminescent material powder with the grain diameter of 5 mu m or less than 5 mu m into a high-temperature vacuum furnace; vacuumizing to 0.2Pa, wherein the flow rate of nitrogen is 120 ml/min; heating to 900 ℃; starting vibration with a vibration acceleration of 10m/s2(ii) a Re-input SiCl4High purity gas and water vapor, SiCl4The flow rates of the high purity gas and the water vapor were 60ml/min and 80ml/min, respectively, and the reaction was continued for 75 minutes. 35 percent of friction luminescent material is put into printing ink by weight to prepare the friction luminescent anti-counterfeiting ink.
Example 3
Putting friction luminescent material powder with particle size of 5 μm or less than 5 μm into a high temperature vacuum furnace, vacuumizing to 0.28Pa, nitrogen flow of 150ml/min, heating to 1000 deg.C, and vibrating at vibration acceleration of 16m/s2Then inputting SiCl4High purity gas and water vapor, SiCl4The flow rates of the high purity gas and the water vapor were 70ml/min and 90ml/min, respectively, and the reaction was continued for 120 minutes. 60% by weight of triboluminescent material is addedAdding the mixture into printing ink to prepare the tribo-luminescent anti-counterfeiting ink.
In the above embodiment, the higher the degree of vacuum in the furnace, i.e. the higher the nitrogen concentration, the more stable the chemical reaction environment, the higher the vibration acceleration, the more sufficient the contact between the surface of the friction luminescent material particles and the reaction gas is, the better the quality of the silicon dioxide film generated by the reaction of the gas on the powder surface is, and the uniform and firm coating of the film layer can be obtained by determining the duration of the reaction according to the required film thickness.
Example 4
Stirring the suspension of aluminum isopropoxide at 80 ℃ for 30 minutes, adding a small amount of nitric acid (the nitric acid is a catalyst for forming gel), boiling for 24 hours to form a slightly turbid solution, adding ZnS: Mn powder with the particle size of not more than 5 mu m, evaporating for 30 minutes under stirring to form a gel, drying the gel at 110 ℃ for 24 hours to form ZnS: Mn powder with an aluminum oxide film coated on the surface, and putting 40% by weight of friction luminescent material into printing ink to prepare the friction luminescent anti-counterfeiting ink.
Example 5
Adding ZnS: Mn powder with the particle size not larger than 5 mu m into a solution of 2.5% of high molecular polymer (polymethacrylic acid, polyvinyl pyrimidine and derivatives, polyethyleneimine, polyethylene oxide and the like), stirring the mixture for 60 minutes to ensure that the ZnS: Mn powder is wetted, filtering, drying a filter cake at 140 ℃ for a period of time to obtain the ZnS: Mn powder with the surface coated with the high molecular film, and adding 35% of friction luminescent material by weight into printing ink to prepare the friction luminescent anti-counterfeiting ink.
Claims (3)
1. The triboluminescence anti-counterfeiting ink is characterized in that the triboluminescence material is ZnS: Mn with the particle size of not more than 5 mu m, the triboluminescence material accounts for 15-60 wt% in the ink, and the surface of the triboluminescence material particle is coated with a protective film made of a material with high moisture resistance and acid resistance.
2. The triboluminescent security ink according to claim 1, wherein the protective film on the surface of the triboluminescent material is silica.
3. A method of making the triboluminescent security ink of claim 2, comprising the steps of:
(1) processing the triboluminescence material into powder with the diameter not more than 5 μm by using a jet milling method or a ball milling method;
(2) filling the friction luminescent material powder into a high-temperature vacuum furnace capable of vibrating at a high speed, vacuumizing the vacuum furnace to 0.1-0.28Pa, and then filling nitrogen into the vacuum furnace, wherein the input flow of the nitrogen is 80-100 ml/min;
(3) heating the vacuum furnace to 800-1000 ℃ and starting vibration with the vibration acceleration of 6-15m/s2；
(4) Then simultaneously inputting SiCl into the vacuum furnace through two pipelines4High purity gas and water vapor, SiCl4The input flow rate of the high-purity gas is 50-70ml/min, and the input flow rate of the water vapor is 70-90 ml/min;
(5) the reaction lasts for 30-120 minutes, the gas reacts on the surface of the friction luminescent material to generate a silicon dioxide film, and the chemical reaction equation is as follows: ；
(6) after the reaction is carried out for a preset time, stopping heating and vibrating, stopping inputting reaction gas, and keeping inputting nitrogen;
(7) stopping inputting nitrogen when the vacuum furnace is cooled to room temperature, putting the atmosphere into the vacuum furnace, and taking out the treated friction luminescent material;
(8) and finally, putting 15-60% of friction luminescent material by weight into the printing ink, and fully mixing to prepare the friction luminescent anti-counterfeiting ink.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410004469 CN1237130C (en) | 2004-02-27 | 2004-02-27 | Friction luminous antiforge printing ink and mfg. method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410004469 CN1237130C (en) | 2004-02-27 | 2004-02-27 | Friction luminous antiforge printing ink and mfg. method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1560147A CN1560147A (en) | 2005-01-05 |
| CN1237130C true CN1237130C (en) | 2006-01-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410004469 Expired - Fee Related CN1237130C (en) | 2004-02-27 | 2004-02-27 | Friction luminous antiforge printing ink and mfg. method thereof |
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| Country | Link |
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| CN (1) | CN1237130C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010026627A1 (en) * | 2010-07-09 | 2012-01-12 | Giesecke & Devrient Gmbh | Alkali metal and alkaline earth metal niobates and tantalates as security feature substances |
| CN114276719A (en) * | 2021-11-19 | 2022-04-05 | 苏州美盈森环保科技有限公司 | Mechanoluminescence anti-counterfeiting ink, preparation method and application |
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- 2004-02-27 CN CN 200410004469 patent/CN1237130C/en not_active Expired - Fee Related
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| CN1560147A (en) | 2005-01-05 |
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| C06 | Publication | ||
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Inst. of Printing Science, Peolpe's Bank of China Assignor: China banknote printing and Minting Corporation Contract fulfillment period: 2008.11.11 to 2013.11.10 contract change Contract record no.: 2008110000159 Denomination of invention: Friction luminous antiforge printing ink and mfg. method thereof Granted publication date: 20060118 License type: Exclusive license Record date: 2008.12.5 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.11.11 TO 2013.11.10; CHANGE OF CONTRACT Name of requester: PEOPLE'S BANK OF CHINA SCIENCE PRINTING TECHNOLOGY Effective date: 20081205 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060118 Termination date: 20170227 |
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| CF01 | Termination of patent right due to non-payment of annual fee |