CN111192515A - A kind of temperature-sensitive irreversible intelligent fluorescent anti-counterfeiting composite coating material preparation and application method - Google Patents
A kind of temperature-sensitive irreversible intelligent fluorescent anti-counterfeiting composite coating material preparation and application method Download PDFInfo
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- CN111192515A CN111192515A CN201911317700.2A CN201911317700A CN111192515A CN 111192515 A CN111192515 A CN 111192515A CN 201911317700 A CN201911317700 A CN 201911317700A CN 111192515 A CN111192515 A CN 111192515A
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000002427 irreversible effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 230000001680 brushing effect Effects 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 3
- 239000007850 fluorescent dye Substances 0.000 claims description 15
- 230000008014 freezing Effects 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 230000002277 temperature effect Effects 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 abstract description 13
- 238000012544 monitoring process Methods 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 34
- 239000006185 dispersion Substances 0.000 description 8
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- QAKMXYFDVPDIPT-UHFFFAOYSA-N 1,1,2,3,4,5-hexakis-phenylsilole Chemical compound C1=CC=CC=C1C(C(=C([Si]1(C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=C1C1=CC=CC=C1 QAKMXYFDVPDIPT-UHFFFAOYSA-N 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229940043375 1,5-pentanediol Drugs 0.000 description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 2
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960005486 vaccine Drugs 0.000 description 1
Images
Classifications
-
- 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
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Credit Cards Or The Like (AREA)
- Measuring Temperature Or Quantity Of Heat (AREA)
Abstract
The invention discloses a preparation and application method of a temperature-sensitive irreversible intelligent fluorescent anti-counterfeiting composite coating material, which is used for determining a target temperature to be indicated; dissolving or dispersing 0.2-10 per mill w/w of fluorescent material in the basic ink to prepare the intelligent fluorescent composite coating material; after brushing a PVAL glue layer on the back of substrate paper, soaking basic ink, placing the basic ink in a low-temperature environment to solidify the basic ink, spraying a specified mark layer with the thickness of more than 1 mu m on the surface of the treated substrate paper by using an intelligent fluorescent composite coating material, placing the substrate paper sprayed with the fluorescent mark in the low-temperature environment, and observing a specific fluorescent mark after the intelligent fluorescent composite coating material is solidified; the composite coating material and the fluorescent anti-counterfeiting label product have obvious fluorescent effect in a low-temperature state, the structure of the composite coating changes after a high-temperature process, so that the fluorescent effect is weakened, and the temperature-sensitive fluorescence change process is irreversible, so that the composite coating material and the fluorescent anti-counterfeiting label product are ideal intelligent composite materials for monitoring the whole process of cold-chain transportation products.
Description
Technical Field
The invention relates to a preparation method and an application method of a temperature-sensitive irreversible intelligent fluorescent anti-counterfeiting composite coating material, which are oriented to the requirements of monitoring and managing the whole process of cold-chain storage and transportation of foods and medicines.
Background
In the increasingly developed logistics industry, cold chain storage and transportation have become an extremely important component. Based on the particularity of cold chain transportation, the fact that the transported goods are kept in a low-temperature environment all the time in the transportation process is an important factor for guaranteeing the quality of the transported goods. The traditional cold chain uses an electronic temperature sensor as a temperature label of a containerized cargo, but has the problems of high use cost, difficulty in carrying out whole-course continuous temperature detection on a single commodity from a factory to a shelf process and the like. The conventional temperature indicating label is easy to obtain and replace or change the label display. If local goods are heated in the transportation link to cause product failure, the body health is influenced, and great risks exist for special goods such as medical vaccines.
Disclosure of Invention
The invention provides an efficiency indicating material and an anti-counterfeiting label application method which are low in cost and can record whether a single product is exposed in a high-temperature environment, aiming at the problem that the whole process monitoring of the cold chain storage and transportation process is difficult to carry out on the single product, so that the whole process monitoring and management of the single product from delivery to a goods shelf to consumer application are realized.
The invention adopts the technical scheme of preparation and application of a temperature-sensitive irreversible intelligent fluorescent anti-counterfeiting composite coating material.
The specific implementation of the process of preparing the "temperature efficacy indication label" can be performed in steps, and the preparation process of the result is mainly described with respect to fig. 1. The temperature efficiency indicating label comprises a PVAL adhesive layer 1, substrate paper 2, a bottom base ink layer 3 and an intelligent fluorescent anti-counterfeiting composite coating 4;
the preparation process comprises the following steps:
a. determining a target temperature to be indicated, and adopting solvents such as higher alkane (C8-18), higher alcohol and the like as base ink, wherein the target temperature is not lower than the freezing point of the adopted base ink; (the mixing ratio is adjusted according to the specific temperature)
b. Dissolving or dispersing 0.2-10 per mill w/w of fluorescent material in the basic ink to prepare the intelligent fluorescent composite coating material;
c. after brushing a PVAL glue layer on the back of substrate paper, soaking basic ink, placing the basic ink in a low-temperature environment to solidify the basic ink, spraying a specified mark layer with the thickness of more than 1 mu m on the surface of the treated substrate paper by using the intelligent fluorescent composite coating material, placing the substrate paper sprayed with the fluorescent mark in the low-temperature environment, and observing a specific fluorescent mark after the intelligent fluorescent composite coating material is solidified; (the size of the tag is sprayed on as needed).
The application process comprises the following steps:
and placing the label in an environment needing temperature indication for 2-5 minutes, observing whether the fluorescent mark changes, and judging whether the environment temperature reaches or exceeds the target temperature if the fluorescent mark changes or disappears.
The ink is not limited to alkanes and alcohols and other chemicals can be widely used.
The fluorescent material refers to organic molecules or inorganic nanoparticles with fluorescent characteristics.
The substrate paper refers to non-fluorescent paper or fabric with good stability and can not react with ink or fluorescent dye.
The temperature effect indicating label is square, round, triangular and the like.
The designated mark is a character, a figure or a special pattern.
The low-temperature environment is a low-temperature environment which is not less than 2 ℃ lower than the target temperature.
When the ambient temperature rises to the melting point of the basic ink, the basic ink on the bottom layer and the intelligent fluorescent composite coating material are mixed and diffused, so that the fluorescent material in the intelligent fluorescent composite coating material is subjected to irreversible changes such as diffusion and mixing. When the label is placed in a low-temperature environment again, the mixed basic ink cannot be separated from the fluorescence, and damaged fluorescent marks and the like cannot be recovered. Irreversible changes in the sensitivity to high temperatures can be achieved by this technique. In addition, the requirements of different corresponding temperatures are realized by adjusting the selection of the base ink; the requirement of different fluorescent colors is achieved by selecting different fluorescent dyes or multiple fluorescent dyes.
The temperature sensitive efficiency indicating label provided by the invention has the advantages of simple structure, low cost, high sensitivity and strong anti-counterfeiting property. The efficiency and the reliability of transportation goods temperature supervision are stored to the cold chain are improved.
The term "intelligent" as used herein means that the "tag" can autonomously record whether it has been exposed to high temperature and can easily read the result directly.
Drawings
Fig. 1 is a schematic cross-sectional view of a temperature performance indicator according to a first embodiment of the present invention.
In the figure: 1 is PVAL glue film, 2 is substrate paper, 3 is bottom basic printing ink layer, 4 is intelligent fluorescence anti-fake composite coating.
Fig. 2 is a photo of a temperature performance indicator label according to a first embodiment of the present invention and a change of fluorescent label during a temperature increase process.
Fig. 3 is a photo of a temperature performance indicator label according to a second embodiment of the present invention.
Detailed Description
In order to make the technical spirit and advantages of the present invention more clearly understandable to those skilled in the art and particularly to the public, the applicant shall describe in detail the following embodiments, but the description of the embodiments is not a limitation to the technical solution of the present invention, and any equivalent changes made according to the inventive concept, which are only in form and not substantial, shall be considered as the technical solution of the present invention.
The first embodiment is as follows: an elongated temperature performance indicating label with a size of 30mm gamma and 20mm is manufactured, and non-fluorescent paper, PVAL glue, tetradecane and hexaphenylsilole are selected as materials. As shown in fig. 2
And (3) label making:
1. 2-100mg of hexaphenylsilole and 10g of n-tetradecane are subjected to ultrasonic treatment at 30 ℃ for 10min to prepare the fluorescent material dispersion liquid.
2. And (4) brushing PVAL glue on one side of the non-fluorescent paper and drying. The non-fluorescent paper after being painted is cut into strips with the x of 30mm and the x of 20mm, and the non-painted surface is coated with tetradecane. After absorbing the excessive n-tetradecane by using filter paper, the treated fluorescence-free paper is frozen at the temperature of minus 20 ℃ for 10 min.
3. And taking out the fluorescent-free paper. Dipping the fluorescent material dispersion liquid by a cotton swab, drawing lines on the non-fluorescent paper at equal intervals, and immediately freezing the non-fluorescent paper at-20 ℃ for 10min after drawing. The temperature performance indication label can be obtained.
The label is used: when in use, the temperature efficiency indicating label is attached to a product package stored in a cold chain, and is placed in an environment of 2 ℃ for refrigeration, and fluorescent marks with equal intervals can be observed by using an ultraviolet lamp for irradiation. If the product is taken out from the refrigerated environment and placed in a room temperature environment (20 ℃), the tetradecane on the label is dissolved and mixed with the fluorescent material, so that the fluorescent material is fully diffused, and the fluorescent label cannot be shown by the irradiation of an ultraviolet lamp at the moment, thereby indicating that the product is exposed in an environment higher than the specified storage temperature, the product efficiency cannot be ensured and the product cannot be used. When the label which loses the fluorescent mark is frozen again, the fluorescent mark can not be recovered because the diffused fluorescent material can not be gathered again, namely, the process of disappearance of the fluorescent mark is irreversible, so that whether the product is invalid or not can be effectively indicated.
Example two: a round temperature efficiency indicating label with the size of phi 15mm is manufactured, and the material selected is non-fluorescent paper, PVAL glue, n-tetradecane and hexaphenylsilole. As shown in fig. 3
And (3) label making:
1. 2-100mg of hexaphenylsilole and 10g of n-tetradecane are subjected to ultrasonic treatment at 30 ℃ for 10min to prepare the fluorescent material dispersion liquid.
2. And (4) brushing PVAL glue on one side of the non-fluorescent paper and drying. Cutting the non-fluorescent paper after being brushed with the glue into a round label with the size of phi 15mm, and coating tetradecane on the surface without being brushed with the glue. After absorbing the excessive n-tetradecane by using filter paper, the treated fluorescence-free paper is frozen at the temperature of minus 20 ℃ for 10 min.
3. And taking out the fluorescent-free paper. Dipping a cotton swab into the fluorescent material dispersion liquid, drawing a 'number matching' mark on the non-fluorescent paper, and immediately freezing the non-fluorescent paper at-20 ℃ for 10min after drawing. The temperature performance indication label can be obtained.
The label is used: when in use, the temperature efficiency indicating label is attached to a product package stored in a cold chain, and is placed in a 2 ℃ environment for refrigeration, and the 'number matching' fluorescent label can be observed by irradiating with an ultraviolet lamp. If the product is removed from the refrigerated environment and placed in a room temperature environment (20℃), the tetradecane on the label dissolves and mixes with the fluorescent material, causing the AIEgens to diffuse, at which time the fluorescent label cannot be revealed by irradiation with an ultraviolet lamp, thereby indicating that the product has been exposed to temperatures above the specified storage temperature, and that the product is unusable because of its effectiveness. When the label which loses the fluorescent mark is frozen again, the fluorescent mark can not be recovered because the diffused fluorescent material can not be gathered again, namely, the process of disappearance of the fluorescent mark is irreversible, so that whether the product is invalid or not can be effectively indicated.
Example three: an elongated temperature efficiency indicating label with the size of 30mm gamma and 20mm is manufactured, and non-fluorescent paper, PVAL glue, tetradecane and tetraphenyl ethylene are selected as materials.
And (3) label making:
1. 2-100mg of tetraphenylethylene and 10g of n-tetradecane are subjected to ultrasonic treatment at 30 ℃ for 10min to prepare a fluorescent material dispersion liquid.
2. And (4) brushing PVAL glue on one side of the non-fluorescent paper and drying. The non-fluorescent paper after being painted is cut into strips with the x of 30mm and the x of 20mm, and the non-painted surface is coated with tetradecane. After absorbing the excessive n-tetradecane by using filter paper, the treated fluorescence-free paper is frozen at the temperature of minus 20 ℃ for 10 min.
3. And taking out the fluorescent-free paper. Dipping the fluorescent material dispersion liquid by a cotton swab, drawing lines on the non-fluorescent paper at equal intervals, and immediately freezing the non-fluorescent paper at-20 ℃ for 10min after drawing. The temperature performance indication label can be obtained.
The label is used: when in use, the temperature efficiency indicating label is attached to a product package stored in a cold chain, and is placed in an environment of 2 ℃ for refrigeration, and fluorescent marks with equal intervals can be observed by using an ultraviolet lamp for irradiation. If the product is taken out from the refrigerated environment and placed in a room temperature environment (20 ℃), the tetradecane on the label is dissolved and mixed with the fluorescent material, so that the fluorescent material is fully diffused, and the fluorescent label cannot be shown by the irradiation of an ultraviolet lamp at the moment, thereby indicating that the product is exposed in an environment higher than the specified storage temperature, the product efficiency cannot be ensured and the product cannot be used. When the label which loses the fluorescent mark is frozen again, the fluorescent mark can not be recovered because the diffused fluorescent material can not be gathered again, namely, the process of disappearance of the fluorescent mark is irreversible, so that whether the product is invalid or not can be effectively indicated.
Example four: an elongated temperature efficiency indicating label with a size of 30mm gamma and 20mm is manufactured, and non-fluorescent paper, PVAL glue, 1, 5-pentanediol and hexa-phenyl silole are selected as materials.
And (3) label making:
1. 2-100mg of hexaphenyl silole and 10g of 1, 5-pentanediol were subjected to ultrasonic treatment at 30 ℃ for 10min to prepare a fluorescent material dispersion.
2. And (4) brushing PVAL glue on one side of the non-fluorescent paper and drying. The non-fluorescent paper after being painted is cut into strips with the x of 30mm and the x of 20mm, and the non-painted surface is coated with tetradecane. After absorbing the excessive n-tetradecane by using filter paper, the treated fluorescence-free paper is frozen at the temperature of minus 40 ℃ for 10 min.
3. And taking out the fluorescent-free paper. Dipping the fluorescent material dispersion liquid by a cotton swab, drawing lines on the non-fluorescent paper at equal intervals, and immediately freezing the non-fluorescent paper at-40 ℃ for 10min after drawing. The temperature performance indication label can be obtained.
The label is used: when in use, the temperature efficiency indicating label is attached to a product package stored in a cold chain, and is frozen at the temperature of minus 20 ℃, and fluorescent marks with equal distance can be observed by using an ultraviolet lamp for irradiation. If the product is taken out from the freezing environment and placed in the cold storage environment (2 ℃), the 1, 5-pentanediol on the label is dissolved and mixed with the fluorescent material, so that the fluorescent material is fully diffused, and the fluorescent label cannot be shown by the irradiation of an ultraviolet lamp at the moment, so that the condition that the product is exposed in the environment higher than the specified storage temperature is indicated, the product efficiency cannot be ensured, and the product cannot be used. When the label which loses the fluorescent mark is frozen again, the fluorescent mark can not be recovered because the diffused fluorescent material can not be gathered again, namely, the process of disappearance of the fluorescent mark is irreversible, so that whether the product is invalid or not can be effectively indicated.
Claims (8)
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Cited By (1)
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CN113409678A (en) * | 2021-07-23 | 2021-09-17 | 上海东蕴实业有限公司 | Novel fluorescent label material |
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CN209641217U (en) * | 2019-04-03 | 2019-11-15 | 无锡群欢包装材料有限公司 | A kind of combined type anti-counterfeit printing label |
CN110229558A (en) * | 2019-06-19 | 2019-09-13 | 重庆展印包装印刷有限公司 | A kind of frozen product temperature monitoring method |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113409678A (en) * | 2021-07-23 | 2021-09-17 | 上海东蕴实业有限公司 | Novel fluorescent label material |
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