An all-optical cold chain break link tag, and a preparation method and application thereof
Photochromic film labels prepared by blending DASA-1 dye with polyurethane substrate solve the leakage risk and stability problems of existing cold chain breakage labels, enabling sensitive identification and reuse for long-term monitoring of cold chain status at ultra-low temperatures, and reducing costs.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SUN YAT SEN UNIV
- Filing Date
- 2023-12-08
- Publication Date
- 2026-05-19
AI Technical Summary
Existing cold chain breakage indicator labels have risks of leakage, high costs, insufficient sensitivity and stability, and cannot be reused, making it difficult to effectively monitor the cold chain status of goods such as vaccines in ultra-low temperature environments for a long period of time.
A purple film label prepared by blending DASA-1 dye with a polyurethane substrate utilizes the photochromic effect to change the ultraviolet-visible absorption spectrum at different temperatures, achieving a colorless to purple transition. It is attached to the surface of goods, and anti-counterfeiting information is written by light. It is also recolored when it leaves the cold chain, thus identifying cold chain breaks.
It exhibits good stability at -40℃, enabling long-term use. It is sensitive to cold chain breakage, has low cost, requires no electricity, and is reusable, reducing the difficulty and risk of use.
Smart Images
Figure CN117801501B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of cold chain transportation technology, and more specifically, to an all-optical cold chain break tag, its preparation method, and its application. Background Technology
[0002] Most vaccines require storage at extremely low temperatures (below -40°C) for long-term and long-distance cold chain preservation and transportation. While thawed vaccines can be stably stored at room temperature for 2 hours when diluted for administration, current regulatory standards prohibit refrozen transport once thawed or diluted. Therefore, an indicator that shows whether vaccine shipments have been out of the cold chain (i.e., broken) is crucial during the ultra-low temperature cold chain transportation of vaccines. Currently available smart cold chain break indicator tags still contain liquid components, leading to leakage risks and reduced reliability. Some cold chain tags still rely on chips and electrical power, increasing costs. Furthermore, many publicly available cold chain break indicator tags suffer from poor sensitivity, limited stability and reliability, and limited functionality.
[0003] Existing technology discloses a cold chain tag capable of distinguishing overheating duration, comprising a first cavity (1) and a transmission medium (2). The first cavity (1) contains a colorimetric liquid, and the transmission medium (2) is connected to the interior of the first cavity (1). The transmission medium (2) is filled with a temperature-controlled liquid. A triggering device is provided in the first cavity (1) to bring the colorimetric liquid into contact with the transmission medium (2). The melting point of the colorimetric liquid is not higher than that of the temperature-controlled liquid, and the colorimetric liquid and the temperature-controlled liquid are compatible. This cold chain tag contains liquid components, posing a risk of leakage, affecting detection stability, and cannot be recycled after being soaked in liquid. Summary of the Invention
[0004] The purpose of this invention is to overcome the shortcomings and deficiencies of existing cold chain breakage indicator tags, which have poor detection stability and cannot be recycled. This invention provides an all-optical cold chain breakage tag that can be stored for more than 90 days at a usage temperature of -40℃, has good stability, and good recyclability.
[0005] Another object of the present invention is to provide a method for preparing an all-optical cold chain breakage tag.
[0006] Another objective of this invention is to provide an application of an all-optical cold chain break tag in cold chain storage and transportation monitoring.
[0007] Another object of the present invention is to provide a cold chain preservation and transport packaging device.
[0008] The above-mentioned objective of this invention is achieved through the following technical solution:
[0009] A fully optical cold chain breakage label, wherein the fully optical cold chain breakage label is a purple film prepared by blending DASA-1 dye with a polyurethane substrate, and the structural formula of the DASA-1 dye is as follows:
[0010]
[0011] It should be noted that:
[0012] The mechanism by which the all-optical cold chain breakage tag of this invention can achieve cold chain breakage monitoring is as follows:
[0013] The DASA-1 (donor-acceptor Steinhaus adduct) dye molecule of the present invention is a photochromic dye. The polyurethane film blended with DASA-1 can change from a colored triene structure to a colorless cyclic structure under 550nm light, resulting in a change in the ultraviolet-visible absorption spectrum. The absorbance at 576nm decreases from the maximum value to the minimum value, thereby achieving the purpose of writing anti-counterfeiting information.
[0014] In the film matrix, DASA-1, after being heated to a temperature above -40°C, can freeze its chain segments in an environment below the glass transition temperature. This restricts the spontaneous recovery of DASA-1 from a colorless cyclic structure to a colored triene structure, thus maintaining its faded state. The colorless cyclic structure transforms into a colored chain structure, resulting in a change in the ultraviolet-visible absorption spectrum, which achieves the purpose of indicating chain breakage during cold chain transportation.
[0015] Once the label is removed from an environment above -40°C, the molecular chains of the polyurethane matrix regain fluidity, causing the colorless cyclic structure of DASA-1 to spontaneously revert to a colored triene structure. Eventually, its color will gradually recolor to a purple state. At 25°C, the entire recoloring process can be completed in as little as 17 minutes. The identification of the cold chain break time of goods is achieved by changing the ultraviolet-visible absorption spectrum of the film anti-counterfeiting label.
[0016] The all-light cold chain break label of this invention is a purple film that is flexible and can be attached to the surface of goods packaging that require cold chain transportation. It contains no liquid components and has no risk of leakage. It fades to colorless when exposed to 550nm light. The authenticity and information of the goods can be identified by the naked eye, ultraviolet-visible absorption spectrum or encrypted information recognition software (QR code recognition software).
[0017] The DASA-1 dye in the all-light cold chain chain-breaking label of the present invention is simple to prepare and has a high yield, ensuring that large-area synthesis and all-light cold chain chain-breaking label preparation can be achieved.
[0018] Furthermore, the DASA-1 dye in the all-optical cold chain chain breakage label of this invention has good fatigue resistance and is recyclable, ensuring that the all-optical cold chain chain breakage label prepared with it can be reused.
[0019] The all-optical cold chain breakage tag provided by this invention is written and read entirely by light, requiring no electrical energy, thus reducing costs and simplifying its use.
[0020] In a specific embodiment, preferably, the mass of the DASA-1 dye is 1% to 5% of the mass of the polyurethane, more preferably 4%.
[0021] Controlling the mass of DASA-1 dye to 1% to 5% of the polyurethane mass ensures that the all-light cold chain chain break label has high absorbance (light absorption performance) while preventing phase separation due to excessive DASA-1 dye loading. Excessive loading will affect the compatibility and uniformity of the two phases, and phase separation will result in the film not fading completely. The impact on fading sensitivity directly affects the sensitivity of the all-light cold chain chain break label.
[0022] Preferably, the thickness of the purple film is 0.01 to 0.03 mm, more preferably 0.020 mm.
[0023] The thickness of the purple film not only affects the fading and color development effect, i.e. the sensitivity of the all-light cold chain breakage label, but also its mechanical strength needs to be considered. If it is too thin, although it will not affect the light color recognition performance, the film will be prone to breakage. If it is too thick, the light intensity will decrease as the film thickness decreases during the light fading process, resulting in incomplete or uneven fading. Therefore, the present invention takes into account a variety of synergistic effects and preferably the thickness of the purple film is 0.01 to 0.03 mm, more preferably 0.020 mm.
[0024] This invention also specifically protects a method for preparing an all-optical cold chain break tag, comprising the following steps:
[0025] S1. Dissolve the polyurethane to obtain a stable polymer solution, add DASA-1 dye and mix and dissolve evenly to obtain a mixed solution;
[0026] S2. Pour the mixed solution into the mold, air dry it in the dark, and then peel it off from the mold to obtain a purple film, which is the all-light cold chain break label.
[0027] The solvent for the polyurethane polymer solution of the present invention is preferably tetrahydrofuran, and it is preferably dissolved by stirring at 50-65°C. The ratio of polyurethane to tetrahydrofuran is 5g:95-105mL.
[0028] This method is low-cost, simple in its synthesis steps, does not require a catalyst, and is environmentally friendly.
[0029] This invention also specifically protects the application of an all-optical cold chain break tag in cold chain storage and transportation monitoring.
[0030] The all-optical cold chain breakage label of the present invention is a flexible, recyclable, all-solid-state, simple to synthesize, low-cost, green and pollution-free, all-optical writeable, power-free, and anti-counterfeiting cold chain breakage indicator and anti-counterfeiting label, used for indicating whether goods transported in ultra-low temperature (-40℃ and below) have ever been separated from the cold chain (i.e., broken chain) and for anti-counterfeiting purposes.
[0031] In a specific embodiment, the monitoring method of the present invention can preferably be as follows: the all-optical cold chain breakage label is irradiated with 550nm light to fade to colorless, thereby writing anti-counterfeiting information, and then placed on the surface of the cold chain stored and transported goods. Once the cold chain storage and transport temperature requirements are exceeded, the all-optical cold chain breakage label is recolored and can be identified by the naked eye, ultraviolet-visible absorption spectrum, or encrypted information recognition software.
[0032] In practical applications, the cold chain storage and transportation temperature of this invention is ≤-40℃.
[0033] In practical applications, the identification of whether a product has been removed from the cold chain storage and transportation temperature is preferably achieved by increasing the intensity of ultraviolet-visible absorption light at 576 nm.
[0034] The cold chain preservation and transportation monitoring of the present invention can cover various products that require cold chain preservation and transportation at specific low temperatures, especially vaccine products.
[0035] The present invention also specifically protects a cold chain preservation and transport packaging device, wherein the device is provided with the all-light cold chain break label.
[0036] Compared with the prior art, the beneficial effects of the present invention are:
[0037] In the all-light cold chain breakage label of this invention, the DASA-1 dye molecule is a photochromic dye. The polyurethane film blended with DASA-1 can change from a colored triene structure to a colorless cyclic structure under 550nm light, resulting in a change in the ultraviolet-visible absorption spectrum. The absorbance at 576nm drops from its maximum value to its minimum value, achieving the purpose of writing anti-counterfeiting information. In an environment above -40°C, when the polymer is below the glass transition temperature, the chain molecular segments freeze, and the colorless cyclic structure changes into a colored chain structure, resulting in a change in the ultraviolet-visible absorption spectrum. Finally, its color will gradually recolor to a purple state, achieving the purpose of cold chain transportation breakage indication.
[0038] The all-light cold chain break label of the present invention can complete the entire recoloring process in as little as 17 minutes at 25°C. It is flexible and can be attached to the surface of goods packaging that need to be transported by cold chain. It does not contain liquid components and has no risk of leakage. The DASA-1 dye in the all-light cold chain break label has good fatigue resistance and is recyclable, ensuring that the all-light cold chain break label prepared with it can be reused. Attached Figure Description
[0039] Figure 1 Images show the actual storage times of the cold chain breakage label at different operating temperatures.
[0040] Figure 2 Absorption spectrum of the all-light cold chain broken label after being stored at a usage temperature of -40℃ for 90 days.
[0041] Figure 3 For all-light cold chain broken labels, store at different temperatures for 1 / 2 / 3 days. Figure 1 This is a diagram illustrating the use of the cold chain breakage label.
[0042] Figure 4 The results are from the cyclic stability test of the all-optical cold chain broken tag.
[0043] Figure 5 This is a schematic diagram illustrating the use of the all-optical cold chain breakage indicator and anti-counterfeiting label.
[0044] Figure 6 The images show actual products of the all-light cold chain breakage indicator and anti-counterfeiting label, stored for different times at temperatures of -78℃ and room temperature of 25℃.
[0045] Figure 7 Images of the all-light cold chain breakage indicator and anti-counterfeiting label at different storage times at room temperature (25°C).
[0046] Figure 8 Absorption spectra of the all-optical cold chain breakage indicator and anti-counterfeiting label at different storage times under use temperature of -78℃ and room temperature of 25℃.
[0047] Figure 9 Absorption spectra of the all-optical cold chain breakage indicator and anti-counterfeiting label at different storage times under use temperature of -40℃ and room temperature of 25℃. Detailed Implementation
[0048] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.
[0049] Example 1
[0050] A fully optical cold chain break tag, comprising a purple film prepared by blending DASA-1 dye molecules with a polyurethane substrate, the purple film having a thickness of 0.02 mm, and the structural formula of the DASA-1 dye molecule as follows:
[0051]
[0052] The DASA-1 dye accounts for 4% of the mass of the polyurethane.
[0053] The preparation method of the above-mentioned all-optical cold chain break tag includes the following steps:
[0054] 5 g of polyurethane was dissolved in 100 mL of tetrahydrofuran, and the resulting mixture was stirred at 60 °C to obtain a stable polymer solution. Subsequently, 45 mg of DASA-1 powdered photochromic agent was mixed with 90 mL of polymer solution, and the resulting mixture was transferred using a pipette and repeatedly extruded using the pipette to ensure complete dissolution of the dye powder.
[0055] 90 mL of the mixture solution was poured onto a PTFE substrate with an inverted mold measuring 30 cm × 30 cm × 1 cm. The film was allowed to air dry in the dark and then peeled off from the PTFE substrate to obtain a freestanding and flexible polymer film with an average thickness of 0.020 mm, which was then cut and used as a fully optical cold chain disconnection label.
[0056] Figure 1 Images showing the shelf life of all-light cold chain breakage labels at different operating temperatures. Figure 1 As can be seen, under ultra-low temperature conditions of -40℃, it remains colorless for more than 40 minutes. At temperatures above -40℃, such as 0℃, color begins to appear after 15 minutes, and a clear color is visible after 40 minutes. At 10℃, color begins to appear after 5-10 minutes, and a clear color is visible after 15 minutes. At temperatures above 25℃, a clear color appears after 5 minutes. This demonstrates that the all-optical cold chain breakage tag of this invention has sensitive temperature monitoring capabilities.
[0057] The all-light cold chain breakage label was stored at -40℃ for 90 days, and its absorption spectrum was measured. Figure 2 The image shows the absorption spectrum of a fully optical cold chain broken label after being stored at -40℃ for 90 days. Figure 2 As can be seen, the absorption spectrum of the all-light cold chain broken label after 90 days of storage at -40℃ is basically unchanged from the initial value, indicating good stability.
[0058] The absorption spectra of the all-optical cold chain disconnection tags after being stored at different temperatures for 1–3 days are shown below. Figure 3 As shown: Absorption spectra of all-optical cold chain broken labels after storage at different temperatures for 1 / 2 / 3 days. Figure 3 It can be seen that the absorption spectral intensity did not change significantly after 3 days at -40℃, while it began to change on the second day at -20℃. At -12℃ and -5℃, significant changes in the absorption spectrum occurred from the beginning, especially at -5℃, where the change was the most significant. Figure 3The results demonstrate that the all-light cold chain breakage label of the present invention exhibits good stability of the fading film at -40°C within a short period (3 days).
[0059] Figure 4 The cyclic stability test results for the all-optical cold chain broken label are the changes in absorbance at 576nm of the film during each of 500 light fading / heat recovery cycles. Figure 4 The results show the absorbance retention of the all-light cold chain broken label after multiple use cycles, demonstrating good recyclability.
[0060] Example 2
[0061] A fully optical cold chain break tag, comprising a purple film prepared by blending DASA-1 dye molecules with a polyurethane substrate, the purple film having a thickness of 0.02 mm, and the structural formula of the DASA-1 dye molecule as follows:
[0062]
[0063] The DASA-1 dye is 1% of the mass of the polyurethane.
[0064] The preparation method of the above-mentioned all-optical cold chain break tag is the same as that in Example 1.
[0065] Example 3
[0066] A fully optical cold chain break tag, comprising a purple film prepared by blending DASA-1 dye molecules with a polyurethane substrate, the purple film having a thickness of 0.01 mm, and the DASA-1 dye molecule having the following structural formula:
[0067]
[0068] The DASA-1 dye accounts for 4% of the mass of the polyurethane.
[0069] The preparation method of the above-mentioned all-optical cold chain break tag is the same as that in Example 1.
[0070] Example 4
[0071] The application of the all-optical cold chain breakage tag of Examples 1-3 in the monitoring of vaccine cold chain storage and transportation is illustrated in the following diagram. Figure 5 As shown:
[0072] The all-optical cold chain breakage label is bleached to colorless under 550nm light to write anti-counterfeiting information. It is then placed on the surface of cold chain stored and transported goods. Once the cold chain storage and transport temperature requirements are removed, the all-optical cold chain breakage label is recolored and can be identified by the naked eye, ultraviolet-visible absorption spectrum, or encrypted information recognition software.
[0073] All-light cold chain broken label anti-counterfeiting information writing
[0074] The all-optical cold chain break label is placed under a 550nm light source (light power density: 60mw / cm2). By using a photomask, pattern information encoding containing anti-counterfeiting encryption information is achieved. After irradiating with the 550nm light source for 6 seconds, the anti-counterfeiting information of the all-optical cold chain break label is written.
[0075] Full-light cold chain broken label breakage detection
[0076] Using ultraviolet-visible absorption spectroscopy, the absorbance at 576 nm of the all-optical cold chain disconnection label, after being stored at the operating temperature (≤ -40℃) for a certain period of time (≤ 90 days), was measured. This absorbance was compared with the absorbance of the all-optical cold chain disconnection label before entering the operating temperature after information was written, and also compared with the absorption spectrum of the all-optical cold chain disconnection label during its natural recovery process at 25℃. This allows the determination of the disconnection time of the all-optical cold chain disconnection label. If the absorbance of the all-optical cold chain disconnection label at 576 nm is less than the absorbance before entering the operating temperature, it indicates that the all-optical cold chain disconnection label has been out of the operating temperature.
[0077] Figure 6 The images show actual photos of the all-light cold chain broken label at different storage times under operating temperatures of -78℃ and room temperature of 25℃. As can be seen from the images, at low temperatures below -40℃ and -78℃, the all-light cold chain broken label maintains the transition from a colored triene structure to a colorless cyclic structure, and the anti-counterfeiting part appears colorless. However, at room temperature above 25℃, in just 17 minutes, the DASA-1 in the film matrix undergoes a colorless cyclic structure to a colored chain structure, and the entire all-light cold chain broken label appears purple to the naked eye.
[0078] Figure 7 These are actual images of the cold chain breakage label at different times under room temperature.
[0079] Figure 8 Absorption spectra of the all-light cold chain broken label at different storage times under operating temperatures of -78℃ and 25℃ were obtained. Figure 8 It can be seen from this:
[0080] When the film is exposed to light until it completely fades, it recovers its color to its pre-light-exposure color after 17 minutes at room temperature (25°C for example). After fading again upon light exposure, the film shows no color change after one hour at -78°C. However, when placed back at room temperature (25°C), a change in absorbance (color recovery) occurs within 3 minutes. Repeating this -78°C / 25°C cycle until the film color is completely restored to its pre-light-exposure color demonstrates that the film does not change color when stored at its operating temperature of -78°C, but immediately changes color upon being placed at room temperature (25°C). After a certain period (less than 17 minutes), returning it to -78°C stops the color change. This comparison of color changes at -78°C and 25°C after light fading demonstrates that the film can repeatedly undergo storage cycles at operating temperatures of -78°C and 25°C without loss of quality.
[0081] Figure 9 Absorption spectra of the all-light cold chain broken label at different storage times at -40℃ and room temperature (25℃) were obtained. Figure 9 It can be seen that:
[0082] When the film is exposed to light until it is completely faded, it recovers its color to its pre-light-exposure color after 17 minutes at room temperature (25°C for example). After further light exposure, the film shows no color change after one hour at -40°C. However, when placed back at room temperature (25°C), a change in absorbance (color recovery) occurs within 3 minutes. Repeating this -40°C / 25°C cycle until the film color is completely restored to its pre-light-exposure color demonstrates that the film does not change color when stored at its operating temperature of -40°C, but immediately changes color when placed at room temperature (25°C). After a certain period (less than 17 minutes), returning it to -40°C stops the color change. This comparison of color changes at -40°C and 25°C after light fading demonstrates that the film can repeatedly undergo storage cycles at operating temperatures of -40°C and 25°C without loss of quality.
[0083] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.
Claims
1. A fully optical cold chain breakage label, characterized in that, The all-optical cold chain breakage label is a purple film prepared by blending DASA-1 dye with a polyurethane substrate. The structural formula of the DASA-1 dye is as follows: 。 2. The all-optical cold chain breakage label as described in claim 1, characterized in that, The DASA-1 dye is 1% to 5% of the mass of the polyurethane.
3. The all-optical cold chain breakage label as described in claim 1, characterized in that, The thickness of the purple film is 0.01~0.03mm.
4. A method for preparing the all-optical cold chain break tag according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Dissolve the polyurethane to obtain a stable polymer solution, add DASA-1 dye and mix and dissolve evenly to obtain a mixed solution; S2. Pour the mixed solution into the mold, air dry it in the dark, and then peel it off from the mold to obtain a purple film, which is the all-light cold chain break label.
5. The application of the all-optical cold chain breakage tag as described in any one of claims 1 to 3 in cold chain preservation and transportation monitoring.
6. The application as described in claim 5, characterized in that, The monitoring method is as follows: the all-optical cold chain breakage label is irradiated with 550 nm light to fade to colorless, thereby writing anti-counterfeiting information. It is then placed on the surface of the cold chain stored and transported goods. Once the cold chain storage and transport temperature requirements are exceeded, the all-optical cold chain breakage label is recolored and can be identified by the naked eye, ultraviolet-visible absorption spectrum, or encrypted information recognition software.
7. The application as described in claim 5, characterized in that, The cold chain storage and transportation temperature is ≤-40℃.
8. The application as described in claim 6, characterized in that, The identification is based on the increase in the intensity of ultraviolet-visible absorption light at 576 nm.
9. The application as described in claim 5, characterized in that, The cold chain storage and transportation monitoring refers to the monitoring of vaccine cold chain storage and transportation.
10. A cold chain preservation and transport packaging device, characterized in that, The device is equipped with the all-optical cold chain breakage label as described in any one of claims 1 to 3.