Irreversible temperature change product identification as well as preparation method and application thereof

By using irreversible temperature change product logos on medical product packaging, the problem that the existing technology cannot intuitively display the temperature overtemperature history and warn of potential risks is solved, and low-cost, easy-to-identify temperature monitoring and risk warnings are achieved to ensure the safety of drugs in transportation.

CN120236454APending Publication Date: 2025-07-01SHENZHEN MOFAN LABEL MATERIAL CO LTD
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Patent Information

Application Number
CN202510489759.9
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-04-17
Publication Date
2025-07-01

AI Technical Summary

Technical Problem

The prior art cannot display the temperature overtemperature history on medical product packaging at low cost and intuitively, and warn of potential risks, resulting in the risk of use of drugs due to temperature out of control during transportation.

Method used

Irreversible temperature change product identification is used, which includes superimposed PET layer, light stabilizer layer, temperature change layer and composite glue layer. The temperature change layer consists of A and B crystal violet lactone, microcapsules and solvents. The rupture temperature of the microcapsules is set to the safe use temperature of the drug, causing the release of copper ion source and combining with A and B crystal violet lactone to achieve irreversible color changes.

Benefits of technology

It realizes sensitive visualization of temperature changes, directly displays whether the drug is overheating through irreversible color changes, and provides anti-ripping and anti-counterfeiting functions to meet the requirements of low-cost, easy to identify and no need for external equipment to read.

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Abstract

The invention discloses an irreversible temperature change product identifier as well as a preparation method and application thereof, and belongs to the technical field of temperature change labels. The irreversible temperature change product mark comprises a first PET layer, a light stabilizer layer, a temperature change layer and a composite adhesive layer which are arranged in a stacked mode. The preparation raw materials of the temperature change layer comprise a temperature change component and a temperature change layer base material; the temperature change component comprises crystal violet lactone A and B, a solvent and a microcapsule; the microcapsule comprises a capsule wall and a copper ion source wrapped by the capsule wall; and the rupture temperature of the capsule wall is approximate to the safe use temperature of the irreversible temperature change product identifier. The irreversible temperature change product identification provided by the invention can effectively improve the sensitivity and visualization of temperature change. The invention further provides a preparation method and application of the irreversible temperature change product identifier.
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Description

Technical Field

[0001] The present invention relates to the technical field of temperature-changing labels, and in particular to an irreversible temperature-changing product identifier and its preparation method and application. Background Art

[0002] In medical products, many biological agents, vaccines, blood products, and some chemical drugs need to be stored and transported under strict low-temperature environments (such as 2 - 8°C or below - 20°C) to ensure their activity, safety, and effectiveness. Temperature fluctuations may cause protein denaturation, vaccine inactivation, or microbial contamination, thereby affecting the therapeutic effect and even posing safety hazards. For example, mRNA vaccines are extremely sensitive to temperature. If they are briefly over-temperature during transportation, they may lose their immunogenicity; while some biopharmaceuticals may produce irreversible degradation products after being exposed to temperatures higher than the specified temperature. Therefore, cold chain logistics is a core link in the pharmaceutical industry, and international drug regulatory agencies (such as WHO, FDA) have put forward clear requirements for temperature control, requiring full-process temperature recording and ensuring compliance with standards.

[0003] Currently, medical cold chain transportation mainly relies on temperature recorders (such as electronic data recorders) or Internet of Things devices for monitoring, but these technologies have certain limitations. Electronic recorders usually only provide historical backtracking of temperature data and cannot intuitively and real-time warn transportation personnel or end-users; while Internet of Things devices can achieve real-time alarms, but they are costly and rely on network signals, and may fail in remote areas or cross-border transportation. In addition, existing technologies mostly focus on the determination of "whether over-temperature occurs", but lack an active prompting mechanism for "the risk of the product after over-temperature". For example, brief over-temperature may not immediately damage the drug, but will significantly shorten its shelf life or reduce its efficacy, and this risk is often ignored, leading to potential safety hazards.

[0004] Current cold chain monitoring technologies cannot intuitively and cost-effectively prompt whether a drug has experienced an over-temperature event during transportation, nor can they evaluate the specific risks caused by over-temperature to the product. Therefore, there is an urgent need to develop a new identifier that can directly display the over-temperature history on the drug packaging and warn medical staff or patients that "this product may have a risk of use due to temperature out of control", thereby avoiding ineffective treatment or adverse reactions. This identifier needs to meet requirements such as low cost, easy recognition, and no need for external device reading to adapt to the complex scenarios of the global pharmaceutical supply chain. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the prior art. For this reason, the present invention proposes an irreversible temperature-changing product identifier that can effectively improve the sensitivity and visualization to temperature changes.

[0006] The present invention also provides a preparation method for the above-mentioned irreversible temperature-changing product identifier.

[0007] The present invention also provides an application of the above irreversible temperature-changing product identification.

[0008] According to the irreversible temperature-changing product identification provided by the first aspect embodiment of the present invention, the irreversible temperature-changing product identification includes a first PET layer, a light stabilizer layer, a temperature-changing layer, and a composite adhesive layer which are superposed;

[0009] The preparation raw materials of the temperature-changing layer include a temperature-changing component and a temperature-changing layer substrate; the temperature-changing component includes methyl ethyl crystal violet lactone, a solvent, and microcapsules;

[0010] The microcapsules include a capsule wall and a copper ion source encapsulated by the capsule wall;

[0011] The rupture temperature of the capsule wall ≈ the safe use temperature of the irreversible temperature-changing product identification.

[0012] The irreversible temperature-changing product identification according to the embodiment of the present invention has at least the following beneficial effects:

[0013] The present invention defines that the melting point of the capsule wall ≈ the safe use temperature of the irreversible temperature-changing product identification; therefore, when the ambient temperature exceeds the above safe use temperature, the capsule wall ruptures, the internally encapsulated copper ion source is released, combines with methyl ethyl crystal violet lactone, and promotes it to change color, and this color change is basically irreversible, thereby realizing the irreversible temperature-changing identification of the target product.

[0014] According to some embodiments of the present invention, the thickness of the first PET layer is 12-15 μm.

[0015] According to some embodiments of the present invention, by mass, the preparation raw materials of the light stabilizer layer include:

[0016] Deionized water 30-35 parts;

[0017] Adhesive 10-15 parts;

[0018] Light stabilizer 20-35 parts.

[0019] Among them, the light stabilizer is titanium dioxide@zinc oxide core-shell nanoparticles.

[0020] The adhesive is at least one of polyurethane resin adhesive and acrylic resin adhesive. In actual production, the type of this adhesive is not strictly limited as long as it does not affect the material of the temperature-changing layer, can accommodate the light stabilizer, and can realize the bonding between the temperature-changing layer and the first PET layer.

[0021] According to some embodiments of the present invention, the thickness of the light stabilizer layer is 1-2 μm.

[0022] According to some embodiments of the present invention, the thermochromic component is present in a local area of the thermochromic layer. For example, it forms a specific shape or displays specific text.

[0023] According to some embodiments of the present invention, the mass concentration of methyl ethyl crystal violet lactone in the thermochromic component is 0.4 - 5 mg / cm 3 . For example, it can specifically be about 1 mg / cm 3 , 2 mg / cm 3 , 3 mg / cm 3 or about 4 mg / cm 3 ; Thus, the color development performance of the methyl ethyl crystal violet lactone can be better exerted; and it does not cause waste of raw material costs.

[0024] According to some embodiments of the present invention, the solvent includes at least one of polyethylene glycol, benzyl benzoate, and lauryl alcohol. The melting point of the above solvent is between 10 - 30 °C. For example, it can specifically be about 15 °C, 20 °C, or about 25 °C; Thus, by adjusting the temperature, it can be ensured that the solvent is a solid during the preparation process, which is convenient for production; and it becomes a liquid after use, enhancing the reaction between the methyl ethyl crystal violet lactone and the copper ion source.

[0025] According to some embodiments of the present invention, the copper ion source includes at least one of copper-based MOFs and copper salts.

[0026] According to some embodiments of the present invention, the copper ion source includes copper-based MOFs. Thus, when the solvent melts into a liquid, the copper-based MOFs can serve as a backbone support to prevent the structure of the irreversible product identification from collapsing; in addition, the copper-based MOFs material has certain microscopic characteristics whether the pore structure is unfilled or filled, which also provides another method for characterizing whether the product identification is overheated.

[0027] According to some embodiments of the present invention, the molar ratio of methyl ethyl crystal violet lactone to copper ions in the copper ion source is 1:1 - 10. For example, it can specifically be about 1:2, 1:4, 1:6, or about 1:8.

[0028] According to some embodiments of the present invention, the material of the capsule wall is poly(N-isopropylacrylamide).

[0029] According to some embodiments of the present invention, the preparation raw materials of the thermochromic component further include silica aerogel. Thus, the silica aerogel is equivalent to a heat insulation material. When the temperature briefly exceeds the safe use temperature, for example, within more than 10 s (hereinafter referred to as the temperature delay time), the silica aerogel will to a certain extent prevent the diffusion of heat and avoid the rupture of the capsule wall.

[0030] According to some embodiments of the present invention, in the temperature-changing component, the mass ratio of the silica aerogel to the methyl ethyl crystal violet lactone is 1:20 to 30. For example, it can specifically be about 1:22, 1:24, 1:26 or about 1:28. In actual production, the addition amount of the fumed silica can be adjusted according to the required temperature delay time.

[0031] According to some embodiments of the present invention, the temperature-changing layer substrate includes an acrylic resin and an isocyanate curing agent.

[0032] According to some embodiments of the present invention, by mass, the preparation raw materials of the temperature-changing layer substrate include the following components:

[0033]

[0034] Among them, the curing agent includes a TDI trimer.

[0035] According to some embodiments of the present invention, the thickness of the temperature-changing layer is 12 to 18 μm. For example, it can specifically be about 15 μm.

[0036] According to some embodiments of the present invention, by mass, the preparation raw materials of the composite adhesive layer include the following components:

[0037]

[0038] According to some embodiments of the present invention, the thickness of the composite adhesive layer is 8 to 10 μm.

[0039] According to some embodiments of the present invention, the irreversible temperature-changing product identification further includes a second PET layer, a printing layer, a covering layer, a white ink layer, a film-forming layer, an adhesive layer and a release film layer that are superimposed starting from the composite adhesive layer. When the second PET layer is torn off, the printing layer will be displayed and cannot be restored after being attached again; that is, the subsequent multiple layers defined here provide an anti-tearing and anti-counterfeiting function for the irreversible temperature-changing product identification.

[0040] Further, the thickness of the second PET layer is 20 to 30 μm; for example, it can specifically be about 25 μm.

[0041] The printing layer is arranged on the surface of the second PET layer, and the thickness ≤ 1 μm, which can be basically ignored.

[0042] According to some embodiments of the present invention, by mass, the preparation raw materials of the printing layer include the following components:

[0043] Polydimethylsiloxane 100 - 120 parts; for example, 3755 silicone oil can be specifically selected;

[0044] 8 - 10 parts of aminopropyltrimethoxysilane; for example, it can specifically be the type 708 adhesive;

[0045] 50 - 60 parts of isopropanol;

[0046] 40 - 50 parts of methyl ethyl ketone.

[0047] According to some embodiments of the present invention, by mass parts, the raw materials for preparing the covering layer include the following components:

[0048] 100 - 120 parts of acrylic resin;

[0049] 3 - 5 parts of leveling agent;

[0050] 40 - 50 parts of ethyl acetate.

[0051] Among them, the leveling agent includes hydroxypropyl methylcellulose mixed with cyclohexanone.

[0052] According to some embodiments of the present invention, the thickness of the covering layer is 0 - 1 μm.

[0053] The covering layer can effectively prevent the scratching of the printing layer and prevent the printing content from being revealed (before tearing).

[0054] According to some embodiments of the present invention, by mass parts, the raw materials for preparing the white ink layer include the following components:

[0055] 100 - 120 parts of white ink;

[0056] 45 - 50 parts of toluene;

[0057] 40 - 45 parts of ethyl acetate.

[0058] According to some embodiments of the present invention, the thickness of the white ink layer is 2 - 3 μm.

[0059] According to some embodiments of the present invention, by mass parts, the raw materials for preparing the film-forming layer include the following components:

[0060] 100 - 120 parts of polyurethane resin mixture;

[0061] 8 - 12 parts of TDI - trimer curing agent;

[0062] 40 - 45 parts of ethyl acetate.

[0063] According to some embodiments of the present invention, the thickness of the film-forming layer is 1 - 2 μm.

[0064] According to some embodiments of the present invention, by mass parts, the raw materials for preparing the pressure - sensitive adhesive layer include the following components:

[0065] 100 - 120 parts of acrylic modified resin;

[0066] 8 - 12 parts of ethyl acetate;

[0067] 2 - 4 parts of aluminum acetylacetonate.

[0068] According to some embodiments of the present invention, the thickness of the pressure - sensitive adhesive layer is 15 - 20 μm.

[0069] According to some embodiments of the present invention, the thickness of the release film layer is 45 - 55 μm.

[0070] According to the embodiments of the second aspect of the present invention, there is provided a preparation method of the irreversible temperature - change product identification provided by the embodiments of the first aspect of the present invention. The preparation method includes the following steps:

[0071] S1. Sequentially dispose the light stabilizer layer, the temperature - change layer, and the composite adhesive layer on the surface of the first PET layer.

[0072] Since the preparation method adopts all the technical solutions of the irreversible temperature - change product identification of the above - mentioned embodiments, it has at least all the beneficial effects brought by the technical solutions of the above - mentioned embodiments.

[0073] According to some embodiments of the present invention, in step S1, the methods of disposing the light stabilizer layer, the temperature - change layer, and the composite adhesive layer respectively include coating or screen printing carried out in sequence, and subsequent drying.

[0074] Among them, the drying temperature after the temperature - change layer is disposed should be lower than the failure temperature of the temperature - change layer. The specifically selected drying methods include at least one of low - temperature vacuum drying or freeze - drying.

[0075] According to some embodiments of the present invention, the preparation method further includes the following steps:

[0076] S2. Sequentially dispose the printing layer, the covering layer, the white ink layer, and the film - forming layer on the surface of the second PET layer.

[0077] The numbering order of the above step S1 and step S2 is only for the convenience of statement and does not represent the actual execution order. In actual production, step S1 and step S2 can be carried out successively or simultaneously in parallel.

[0078] According to some embodiments of the present invention, in step S2, the method of disposing the printing layer includes at least one of coating and screen printing.

[0079] According to some embodiments of the present invention, in step S2, the methods of disposing the covering layer, the white ink layer, and the film - forming layer include coating and subsequent drying.

[0080] According to some embodiments of the present invention, the preparation method further includes the following steps:

[0081] S3. Composite the composite adhesive layer of the component obtained in step S1 with the second PET layer of the component obtained in step S2;

[0082] S4. Set the pressure-sensitive adhesive layer on the surface of the conjunctiva layer of the component obtained in step S3, and attach the release film layer on the surface of the pressure-sensitive adhesive layer.

[0083] According to some embodiments of the present invention, in step S3, the temperature of the composite is lower than the failure temperature of the temperature-changing layer. Therefore, in actual production, a low-temperature pressing method is mostly used.

[0084] According to an embodiment of the third aspect of the present invention, there is provided an application of the irreversible temperature-changing product identification provided in the first aspect of the present invention in the preservation of medical products.

[0085] Since the application adopts all the technical solutions of the irreversible temperature-changing product identification of the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments.

[0086] In the present invention, the safe use temperature of the irreversible temperature-changing product identification depends on the specific application scenario; for example, if the irreversible temperature-changing product identification is used for the labeling of a certain drug, and this drug will become ineffective when the temperature exceeds 20°C, then the safe use temperature is 20°C.

[0087] In the present invention, the rupture temperature of the capsule wall ≈ the safe use temperature of the irreversible temperature-changing product identification means that the difference between the rupture temperature of the capsule wall and the safe use temperature of the irreversible temperature-changing product identification is ±2°C.

[0088] Unless otherwise specified, the "about" in the present invention actually means that the allowable error is within the range of ±2%, for example, about 100 is actually 100 ± 2% × 100.

[0089] Unless otherwise specified, "between... and..." in the present invention includes the values, for example, "between 2 and 3" includes the endpoint values 2 and 3.

[0090] Other features and advantages of the present invention will be described in the subsequent specification, and, in part, will be obvious from the specification, or will be understood by implementing the present invention. Brief Description of the Drawings

[0091] The above and / or additional aspects and advantages of the present invention will become obvious and easy to understand from the description of the embodiments in conjunction with the following drawings, wherein:

[0092] Figure 1It is a schematic structural diagram of the irreversible temperature-changing product identification obtained in Embodiment 1 of the present invention.

[0093] Figure 2 It is the apparent diagram after setting the printing layer in step S2 of Embodiment 1 of the present invention.

[0094] Figure 3 It is a photo of the color (left) of the temperature-changing component used in Embodiment 1 of the present invention at 4°C (right) and 40°C. Detailed implementation manners

[0095] The following will clearly and completely describe the concept of the present invention and the technical effects generated in combination with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts shall fall within the scope of protection of the present invention.

[0096] In the description of the present invention, the description referring to terms such as "one embodiment", "some embodiments", "schematic embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0097] Embodiment 1

[0098] In this example, an irreversible temperature-changing product identification was prepared, and the schematic structural diagram of the obtained product is as Figure 1 shown, including a release film layer with a thickness of 50 μm, an adhesive layer with a thickness of 18 μm, a caking layer with a thickness of 1.5 μm, a white ink layer with a thickness of 2.5 μm, a covering layer with a thickness of 0.5 μm, a printing layer with a thickness that can be almost ignored, a second PET layer with a thickness of 25 μm, a composite adhesive layer with a thickness of 9 μm, a temperature-changing layer with a thickness of 15 μm, a light stabilizer layer with a thickness of 1.5 μm, and a first PET layer with a thickness of 14 μm, which are superimposed. The preparation method of the above irreversible temperature-changing product identification includes the following steps:

[0099] S1. A light stabilizer layer, a temperature-changing layer and a composite adhesive layer are sequentially arranged on the surface of the first PET layer. Among them,

[0100] The preparation method of the light stabilizer layer is the coating method;

[0101] The preparation method of the temperature-variable layer is to mix the temperature-variable components evenly and then heat them to 10-15 °C for solvent dissolution; the substrate with a light stabilizer layer is cold-treated at a temperature of about 8 °C. The paste-like temperature-variable components are printed on the surface of the substrate to form a mark with a specific shape (such as the word "RISK"); due to the temperature difference, after coating, the temperature-variable components become solid.

[0102] After that, the coating method is adopted to coat the temperature-variable layer substrate at other positions of the light-stable layer, and then vacuum drying is carried out below 20 °C.

[0103] The setting method of the composite adhesive layer is coating, and the drying method is vacuum drying below 20 °C.

[0104] The temperature-variable components are composed of methyl ethyl crystal violet lactone, polyethylene glycol 600 (melting point about 22 °C) and microcapsules; among them,

[0105] In the temperature-variable components, the mass concentration of methyl ethyl crystal violet lactone is 3mg / cm 3 .

[0106] The microcapsules are composed of a capsule wall made of poly(N-isopropylacrylamide) (LCST = 32 °C) and Cu3(BTC)2 included therein in a mass ratio of 1:4.

[0107] The molar ratio of methyl ethyl crystal violet lactone to copper ions in Cu3(BTC)2 is 1:5;

[0108] The balance of the temperature-variable components is polyethylene glycol 600.

[0109] S2. An imprinting layer (the appearance of the obtained product is as Figure 2 shown), a covering layer, a white ink layer and a film-forming layer are sequentially arranged on the surface of the second PET layer.

[0110] The setting method of the imprinting layer is screen printing.

[0111] The setting methods of the covering layer, the white ink layer and the film-forming layer are coating;

[0112] The drying temperature in this step is 60-80 °C. Any temperature within this range is acceptable and will not have an obvious impact on the performance of the product.

[0113] S3. The composite adhesive layer of the component obtained in step S1 is laminated with the second PET layer of the component obtained in step S2; the lamination temperature is between 10-15 °C.

[0114] S4. An adhesive layer is arranged on the surface of the film-forming layer of the component obtained in step S3, and a release film layer is attached to the surface of the adhesive layer.

[0115] The preparation raw materials of the above layers are shown in Table 1.

[0116] Table 1 Raw materials for preparing each layer in Example 1

[0117]

[0118]

[0119] The titanium dioxide@zinc oxide core-shell nanoparticles in Table 1 were customized from Xianfeng Nano, with a D50 particle size of 65 nm and an average shell thickness of 8 nm.

[0120] Example 2

[0121] In this example, an irreversible thermochromic product identification was prepared. The specific difference from Example 1 is as follows:

[0122] In step S1, the thermochromic component further includes silica aerogel. The mass ratio of silica aerogel to methyl ethyl crystal violet lactone is 1:25. The silica aerogel was purchased from Xianfeng Nano, with the model number XFI03 7631-86-9.

[0123] Example 3

[0124] In this example, an irreversible thermochromic product identification was prepared. The specific difference from Example 1 is as follows:

[0125] Calculated according to the amount of substance of copper, Cu3(BTC)2 in step S1 was replaced with an equal amount of copper sulfate.

[0126] Comparative Example 1

[0127] In this example, an irreversible thermochromic product identification was prepared. The specific difference from Example 1 is as follows:

[0128] Calculated according to the amount of substance of metal, Cu3(BTC)2 in step S1 was replaced with an equal amount of zinc-containing MOF material Zn-ZIF-62.

[0129] Comparative Example 2

[0130] In this example, an irreversible thermochromic product identification was prepared. The specific difference from Example 1 is as follows:

[0131] The capsule wall was replaced with traditional polylactic acid (the thermosensitive temperature is about 80 °C).

[0132] Comparative Example 3

[0133] In this example, an irreversible thermochromic product identification was prepared. The specific difference from Example 1 is as follows:

[0134] The solvent in step S1 was replaced with an equal mass of natural wax (melting at about 60 °C).

[0135] Test Example

[0136] This example tests the performance of the irreversible temperature change product marking obtained in the embodiment and the comparative example, as follows:

[0137] Appearance of the temperature-change components in the original temperature-change layer: visual inspection;

[0138] Transfer from a 4°C environment to a 35°C environment, measure the time required for the temperature-dependent component to change color, and visually observe the color after the change;

[0139] The labels after the color change were transferred from a 35°C environment to a 4°C environment to observe whether the color was restored.

[0140] Peel off the second PET layer to see if the text on the printed layer is visible, and see if it can be re-laminated in place.

[0141] The above test results are shown in Table 2.

[0142] Table 2 Performance results of the irreversible temperature change product identification obtained in the examples and comparative examples

[0143] Number Original Color Color Change Time Color after Transformation Whether to Restore Second PET Layer Example 1 Light Blue 5s Blue-Violet No Display Text / Non-Reattachable Example 2 Light Blue 12s Blue-Violet No Display Text / Non-Reattachable Example 3 Light Blue 3s Blue-Violet No Display Text / Non-Reattachable Comparative Example 1 Greyish White / Almost No Transformation / Display Text / Non-Reattachable Comparative Example 2 Light Blue 5s Blue-Violet Yes Display Text / Non-Reattachable Comparative Example 3 Light Blue / Almost No Transformation / Display Text / Non-Reattachable

[0144] Regarding the original color in the logo of irreversible temperature-changing products, alpha-beta crystal violet lactone is basically a colorless sample at low temperature and without external interference; therefore, the original color is mostly the color displayed by copper ions (or other ions in the comparative example) through the capsule wall, so the color is very light, and due to the layer-by-layer wrapping, it appears grayish ( Figure 3 on the right).

[0145] Regarding the color after the transformation and whether the color will fade, the present invention has found that the combination of methyl ethyl crystal violet lactone and copper ions will show a blue to purple color ( Figure 3 left side); the contrast is obvious, it can be clearly distinguished, and it will not fade. In Comparative Example 1, the color change of zinc ions to methyl and ethyl crystal violet lactone is not obvious, and the sample as a whole will have a very slight light blue tone, but it is very light and difficult to distinguish by visual inspection. In Comparative Example 2, at this temperature, the copper ions in the capsule wall will not be released, but under the action of the solvent and the carboxyl group of polylactic acid, the methyl and ethyl crystal violet lactone is partially ring-opened and will show a bluish purple color, but this color will disappear with changes in temperature, etc., and the test temperature of the present invention is relatively low, and the color is very light and difficult to distinguish by visual inspection. In Comparative Example 3, natural wax does not melt under the test conditions of the present invention, and copper ions and methyl and ethyl crystal violet lactone are wrapped and fixed, and can hardly contact, and thus no color change reaction can occur.

[0146] Regarding the time taken for color change, in Examples 1 to 3, Example 3 took the shortest time. The reason is that copper ions are in a free state and are more likely to act on methyl ethyl crystal violet lactone. Therefore, this time is close to the time required for the irreversible thermochromic product label temperature to rise to the ambient temperature. In Example 1, the time taken was slightly longer because it also took some time for methyl ethyl crystal violet lactone and the solvent to diffuse into the copper-based MOF material. In Example 2, the time taken further increased because silica aerogel has a certain inhibitory and regulating effect on temperature diffusion, thus prolonging the time required for the irreversible thermochromic product label temperature to rise to the ambient temperature. In actual production, the amount of silica aerogel can be adjusted according to needs, thereby adjusting the color change time.

[0147] In summary, the irreversible thermochromic product label provided by the present invention can sensitively achieve irreversible color change, and the color change temperature is relatively low, and it is expected to find wide applications in the fields of medical supplies storage, transportation, etc.

[0148] The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various changes can be made without departing from the spirit of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. An irreversible temperature change product label, characterized in that: The irreversible temperature-changing product identification comprises a first PET layer, a light stabilizer layer, a temperature-changing layer and a composite adhesive layer which are stacked and arranged; The raw materials for preparing the temperature-variable layer include a temperature-variable component and a temperature-variable layer substrate; the temperature-variable component includes methyl and ethyl crystal violet lactone, a solvent, and microcapsules; The microcapsule comprises a capsule wall and a copper ion source wrapped by the capsule wall; The rupture temperature of the capsule wall is ≈ the safe use temperature indicated on the label of the irreversible temperature change product.

2. The irreversible temperature change product identification according to claim 1, characterized in that: The material of the capsule wall is poly (N-isopropylacrylamide).

3. The irreversible temperature change product identification according to claim 1, characterized in that: The copper ion source includes at least one of copper-based MOFs and copper salts.

4. The irreversible temperature change product identification according to claim 1, characterized in that: The solvent includes at least one of polyethylene glycol, benzyl benzoate and lauryl alcohol.

5. The irreversible temperature change product identification according to claim 1, characterized in that: The temperature-variable layer substrate comprises acrylic resin and isocyanate curing agent.

6. The irreversible temperature change product identification according to claim 1, characterized in that: The mass concentration of the methyl and ethyl crystal violet lactone in the temperature-dependent component is 0.4-5 mg / cm 3 ; Preferably, the molar ratio of the methyl and ethyl crystal violet lactone to the copper ions in the copper ion source is 1:1~10.

7. The irreversible temperature change product identification according to claim 1, characterized in that: The raw materials for preparing the temperature-dependent component also include silica aerogel; preferably, in the temperature-dependent component, the mass ratio of the silica aerogel to the methyl and ethyl crystal violet lactone is 1:20-30.

8. The irreversible temperature change product label according to any one of claims 1 to 7, characterized in that: The irreversible temperature-changing product label also includes a second PET layer, a printing layer, a covering layer, a white ink layer, a conjunctiva layer, a self-adhesive layer and a release film layer which are stacked and arranged starting from the composite adhesive layer.

9. A method for preparing an irreversible temperature-changing product label according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: S1. The light stabilizer layer, the temperature-variable layer and the composite adhesive layer are sequentially arranged on the surface of the first PET layer.

10. Use of the irreversible temperature-changing product label according to any one of claims 1 to 7 in the storage of medical products.