A labeling tape and its preparation method

Abstract

This invention provides a labeling tape comprising: a labeling layer cured with photocurable ink, the labeling layer including a first surface; an adhesive layer including a second surface, the labeling layer being integrally embedded in the adhesive layer from the second surface, and the labeling layer and the adhesive layer being flush with the first surface and the second surface; and a substrate layer including a third surface, the labeling layer being bonded to the third surface of the substrate layer via the first surface, and the adhesive layer being bonded to the third surface of the substrate layer via the second surface. In the labeling tape provided by this invention, the application of photocurable ink enables rapid and convenient molding of the labeling layer. By adjusting the color of the photocurable ink and the thickness of the resulting coating, the display effect of the formed labeling layer can be flexibly and effectively adjusted, thereby solving the problem of the strong dependence of the display effect of laser-engraved labels on the adhesive layer.

Description

Technical Field

[0001] This invention belongs to the field of adhesive materials, specifically relating to a marking tape and its preparation method. Background Technology

[0002] With the development of the national new energy industry, the market demand for lithium batteries has surged rapidly. However, the manufacturing of lithium batteries involves many materials and processes, and current technology cannot ensure that every step and every material reaches a complete pass rate. Substandard lithium batteries pose a great safety hazard once they are put on the market. Therefore, it is necessary to trace information about lithium batteries to achieve effective management and safety identification, reduce safety risks, and realize effective traceability of information during the circulation of lithium batteries.

[0003] Currently, lithium battery manufacturers use a method of attaching identification tape with unique markings to the surface of lithium batteries to effectively trace each battery and its materials throughout the entire process. This allows them to track the entire production process of each battery using its unique markings.

[0004] Currently, laser engraving is commonly used to engrave codes onto the adhesive layer to produce identification tapes. The display quality (clarity, color, resolution, etc.) of the codes formed using this process is generally highly dependent on the material of the adhesive layer, making it difficult to flexibly adapt to different usage requirements and effectively control the display quality during production. Furthermore, the production equipment required for laser engraving is sophisticated, and the production process is complex, resulting in low production efficiency and high production costs for current identification tapes. Summary of the Invention

[0005] To optimize the display effect of labeling tape and improve its production efficiency, this paper provides a labeling tape and its preparation method.

[0006] According to a first aspect of the present invention, a labeling tape is provided, the labeling tape comprising: a labeling layer, the labeling layer being cured by photocurable ink, the labeling layer including a first surface; an adhesive layer, the adhesive layer including a second surface, the labeling layer being integrally embedded in the adhesive layer from the second surface, and the labeling layer and the adhesive layer being disposed such that the first surface and the second surface are flush; and a substrate layer, the substrate layer including a third surface, the labeling layer being laminated with the third surface of the substrate layer via the first surface, and the adhesive layer being laminated with the third surface of the substrate layer via the second surface. In the labeling tape provided by this invention, the application of photocurable ink can quickly and conveniently form the labeling layer 1. By adjusting the color of the photocurable ink and the thickness of the coating formed, the display effect of the formed labeling layer 1 can be flexibly and effectively adjusted, thereby solving the problem of the strong dependence of the display effect of the labeling code formed by laser engraving on the adhesive layer. In addition, by embedding the labeling layer entirely into the adhesive layer, the adhesive layer can provide strict protection for the labeling layer, isolating the labeling layer from external corrosive materials, so that the labeling layer can be firmly fixed to the product for a long time and maintain a clear display effect. When it is necessary to identify the labeling layer of the above-mentioned labeling tape, the side of the adhesive layer opposite to its second surface can be used as the identification surface.

[0007] Preferably, the dyne value of the third surface is ≥38 dyn / cm. The substrate layer utilizes its third surface to simultaneously bond with the marking layer and the adhesive layer. When the dyne value of the third surface meets the above range, it is beneficial to promote the simultaneous and firm bonding of the substrate layer with the marking layer and the adhesive layer.

[0008] Preferably, the substrate layer is a release film. In the labeling tape provided by the present invention, the introduction of the substrate layer serves to provide a supporting carrier for the label code and adhesive layer during the production and storage (before being attached to the product surface) of the labeling tape. By directly using the release film as the substrate layer, it can serve as the aforementioned supporting carrier. On the other hand, when the labeling tape is rolled up for later use, the release film can prevent the labeling tape, which is the inner and outer ring, from sticking together, making it easy to store. It is also easy to unwind when the labeling tape provided by the present invention is needed.

[0009] Preferably, the thickness of the marking layer is 0.2–3.5 μm. The resolution of the marking layer can be controlled by adjusting its thickness. This ensures that the resolution meets requirements while maintaining a sufficient thickness of the adhesive layer at the marking layer location. This allows the adhesive layer to provide sufficient adhesion to the marking tape and offer some protection to the marking layer. By limiting the ratio of the maximum adhesive layer thickness to the marking layer thickness, it is possible to ensure that an appropriately thick adhesive layer provides sufficient protection for the marking layer, allowing it to adhere stably to the third surface of the substrate layer over a long period without easily detaching. Furthermore, it prevents large cumulative thickness differences caused by localized spraying at single points, thus avoiding appearance defects caused by excessively thick marking tape during winding.

[0010] Preferably, the adhesive used to form the adhesive layer includes at least one of acrylic adhesive and rubber adhesive.

[0011] Preferably, the photocurable ink comprises: a photosensitive monomer, a photoinitiator, and a colorant; calculated by mass percentage, the photosensitive monomer accounts for 55-90 wt% and the photoinitiator accounts for 3.5-12 wt% in the photocurable ink; the photosensitive monomer includes at least one of a four-membered oxocyclic photosensitive monomer, a five-membered oxocyclic photosensitive monomer, and a six-membered oxocyclic photosensitive monomer. Specifically, a four-membered oxocyclic photosensitive monomer refers to a photosensitive compound containing at least one four-membered oxocyclic ring in its molecular structure, a five-membered oxocyclic photosensitive monomer refers to a photosensitive compound containing at least one five-membered oxocyclic ring in its molecular structure, and a six-membered oxocyclic photosensitive monomer refers to a photosensitive compound containing at least one six-membered oxocyclic ring in its molecular structure. The photosensitive monomers used in this invention are formulated to produce photocurable inks containing photosensitive monomers with oxygen-containing heterocyclic rings in their chemical composition. This gives the photocurable inks good chemical resistance, and in particular, excellent corrosion resistance to solvents contained in adhesives. As a result, the marking layer formed by curing the photocurable ink is not eroded by the adhesive used to prepare the adhesive layer, thus avoiding the situation where the adhesive erodes the marking layer during the incomplete curing process, resulting in a loss of the marking layer's display effect (reduced clarity).

[0012] Preferably, the photosensitive monomer comprises a four-membered oxocyclic photosensitive monomer, wherein the chemical composition of the four-membered oxocyclic photosensitive monomer conforms to the general formula, which is: Photosensitive monomers also include epoxy monomers. The chemical composition of epoxy monomers conforms to the general formula, which is:

[0013] Preferably, the four-membered oxocyclic photosensitive monomer includes at least one of 3,3'-[oxybismethylene]bis[3-ethyl]oxetane (CAS: 18934-00-4), 3-ethyl-3-[[(2-ethylhexyl)oxy]methyl]oxetane (CAS: 298695-60-0), 3,3'-[oxybismethylene]bis[3-ethyl]oxetane (CAS: 18934-00-4), 3-ethyl-3-[(epoxyethylene methoxy)methyl]oxetane (CAS: 15957-34-3), and (3-ethyl-3-oxetane)methyl isobutylene ester (CAS: 37674-57-0).

[0014] Preferably, the four-membered oxocyclic photosensitive monomer includes 3-ethyl-3-[(epoxyethylene methoxy)methyl]oxecyclobutane and (3-ethyl-3-oxecyclobutyl)methyl isobutylene ester.

[0015] Preferably, the mass ratio of 3-ethyl-3-[(epoxyethylene methoxy)methyl]oxetane:(3-ethyl-3-oxetane)methyl isobutyl ester is 18-25:8-12.

[0016] Preferably, the epoxy monomer includes at least one of the following: methyl 3,4-epoxycyclohexanecarboxylate (CAS: 41088-52-2), 3,4-epoxycyclohexylmethacrylate (CAS: 64630-63-3), 3,4-epoxycyclohexylmethylisobutylene ester (CAS: 82428-30-6), 3-epoxyethyl-7-oxabicyclo[4,1,0]heptane (CAS: 106-87-6), and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (CAS: 2386-87-0).

[0017] Preferably, the epoxy monomers include 3,4-epoxycyclohexylmethyl isobutylene ester, 3-epoxyethyl-7-oxabicyclo[4,1,0]heptane and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate.

[0018] Preferably, the mass ratio of 3,4-epoxycyclohexylmethyl isobutylene ester: 3-epoxyethyl-7-oxabicyclo[4,1,0]heptane: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate is 8-12:8-12:18-25.

[0019] Preferably, the mass ratio of the quaternary oxocyclic photosensitive monomer to the epoxy monomer is 20-30:20-40.

[0020] Preferably, the photosensitive monomer further includes acrylate monomers, including vinyl ethoxyethyl acrylate (CAS: 86273-46-3) and 1,6-hexanediol diacrylate (CAS: 13048-33-4).

[0021] Preferably, the epoxy monomer to acrylate monomer ratio is 45-55:15-25.

[0022] Preferably, the photoinitiator includes photoinitiator A, photoinitiator B, and photoinitiator C, wherein photoinitiator A is diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate (CAS: 71449-78-0), photoinitiator B is di[4-diphenylthiophenyl]sulfide dihexafluoroantimonate (CAS: 89452-37-9), and photoinitiator C is bis(4-tert-butylphenyl)iodonium hexafluorophosphate (CAS: 61358-25-6); the photoinitiator A: photoinitiator B: photoinitiator C ratio is 2-8: 2-5: 2-5.

[0023] Preferably, the photosensitizing monomer includes a six-membered oxoheterocyclic photosensitizing monomer, which includes dioxane monomers and morpholine monomers, wherein the chemical composition of the dioxane monomer conforms to the general formula, which is: The chemical composition of morpholine monomers conforms to the general formula, which is: Based on the mass ratio, the ratio of dioxane monomers to morpholine monomers is 10–20:10–20.

[0024] Preferably, the dioxane monomers mentioned above include methyl (5-ethyl-13-dioxane-5-yl) acrylate.

[0025] (CAS: 66492-51-1), the above-mentioned morpholine monomers include N-acryloylmorpholine (CAS:

[0026] 5117-12-4).

[0027] Preferably, the photosensitizing monomer further includes acrylate monomers, which include at least one of 1,6-hexanediol diacrylate (CAS: 13048-33-4), 2-ethyleneoxyethoxyethyl acrylate (CAS: 87273-46-3), 3,3,5-trimethylcyclohexyl acrylate (CAS: 86178-38-3), and ethoxyethoxyethyl acrylate (CAS: 7328-17-8). The acrylate monomers include 1,6-hexanediol diacrylate, 2-ethyleneoxyethoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, and ethoxyethoxyethyl acrylate; calculated by mass ratio, the ratio is 1,6-hexanediol diacrylate : 2-ethyleneoxyethoxyethyl acrylate : 3,3,5-trimethylcyclohexyl acrylate : ethoxyethoxyethyl acrylate.

[0028] =8~12:8~12:10~15:8~12.

[0029] Preferably, the mass ratio of the six-membered oxocyclic photosensitive monomer to the acrylate monomer is 35-45:40-50.

[0030] Preferably, the photoinitiator comprises (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0031] The photocurable ink used in this invention to form the marking layer has high photoreactivity and can rapidly cure under ultraviolet light. Applying this photocurable ink to the production of marking tape can effectively improve the production efficiency and yield rate of marking tape. The photocurable ink used in this invention to form the marking layer has excellent chemical resistance; the marking layer formed using it is not easily corroded by solvents in the adhesive or electrolyte. This effectively reduces the occurrence of corrosion of the marking layer due to contact with undried adhesive during tape production, which could lead to deterioration of the display effect. It also helps the marking tape maintain accurate and stable identification performance over a long period when used in environments where it may come into contact with electrolytes.

[0032] According to a second aspect of the present invention, a method for preparing the above-mentioned marking tape is provided, comprising the following steps:

[0033] Step 1: Spray a UV-curable ink onto the third surface of the substrate layer; Step 2: Allow the UV-curable ink to cure under light to form a marking layer on the surface of the substrate layer; Step 3: Apply adhesive to the third surface of the substrate layer, covering the marking layer; Step 4: Allow the adhesive to cure to form an adhesive layer. The method provided by this invention for preparing marking tape eliminates the need for complex and expensive production equipment, simplifies the production process, and enables efficient production of marking tape. Attached Figure Description

[0034] Figure 1 This is a schematic diagram of the structure of the labeling tape of the present invention.

[0035] In the above figures, the correspondence between each component and the figure number is as follows: 1. Identification layer, 2. Adhesive layer, 3. Substrate layer. Detailed Implementation

[0036] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0037] Example 1

[0038] In this embodiment, different photocurable inks were prepared using the formulations provided in Tables 1 and 2. In this embodiment, the specific composition of the oxygen-containing heterocyclic photosensitive monomer in the formulation used to prepare the photocurable ink was used as a variable to set up treatment groups 1A to 18A. The photocurable ink formulations used in treatment groups 1A to 17A included oxygen-containing heterocyclic photosensitive monomers, and the composition of the oxygen-containing heterocyclic photosensitive monomers included in these formulations is shown in Table 2. The photocurable ink formulation used in treatment group 18A did not include oxygen-containing heterocyclic photosensitive monomers, and its formulation composition is shown in Table 3.

[0039] Table 1. Formulation composition of UV-curable inks for treatment groups 1A to 17A

[0040]

[0041] Table 2. Composition of oxygen-containing heterocyclic photosensitive monomers used in the formulation of UV-curable inks for treatment groups 1A to 17A (parts by mass)

[0042]

[0043] In this embodiment: 3-ethyl-3-[(epoxyethylene methoxy)methyl]oxetane (CAS: 15957-34-3) was selected as the four-membered oxetine photosensitive monomer 1 in Table 2, and its structural formula is as follows: (3-Ethyl-3-oxecyclobutyl)methyl isobutylene ester (CAS: 37674-57-0) was selected as the four-membered oxecyclophotosensitive monomer 2 in Table 2, and its structural formula is as follows: 3-Ethyl-3-[[(2-ethylhexyl)oxy]methyl]oxetane (CAS: 298695-60-0) was selected as the four-membered oxetine photosensitive monomer 3 in Table 2, and its structural formula is as follows:

[0044]

[0045] In this embodiment, tetrahydrofuran acrylate (CAS: 2399-48-6) was selected as the five-membered oxocyclic photosensitive monomer in Table 2, and its structural formula is as follows:

[0046] In this embodiment, methyl acrylate (5-ethyl-13-dioxane-5-yl) acrylate (CAS: 66492-51-1) was selected as the six-membered oxocyclic photosensitive monomer in Table 2, and its structural formula is as follows:

[0047] In this embodiment: 3-epoxyethyl-7-oxabicyclo[4,1,0]heptane (CAS: 106-87-6) was selected as epoxy monomer 1 in Table 2, and its structural formula is as follows: 3,4-Epoxycyclohexylmethyl isobutylene ester (CAS: 82428-30-6) was selected as epoxy monomer 2 in Table 2, and its structural formula is as follows: 3,4-Epoxycyclohexylmethyl-3,4-Epoxycyclohexylcarboxylate (CAS: 2386-87-0) was selected as epoxy monomer 3 in Table 2, and its structural formula is as follows:

[0048] To correspond with the amount of oxygen-containing heterocyclic photosensitive monomers (105 parts) involved in the photocurable ink formulations provided in Table 1, the total amount of oxygen-containing heterocyclic photosensitive monomers used in each treatment group provided in Table 2 is 105 parts.

[0049] Table 3. Formulation composition of UV-curable inks for treatment group 18A

[0050]

[0051] When preparing the photocurable inks used in each treatment group, the materials were prepared according to the relevant contents of Tables 1 to 3. The raw materials required for each formula were mixed in the required amount and fully dispersed to obtain the photocurable inks used in Example 1.

[0052] After obtaining the UV-curable ink, each processing group further followed the steps below to complete the production of the labeling tape:

[0053] S1. A 19μm thick PET release film is used as the substrate layer 3. One surface of the substrate layer 3 is subjected to corona treatment so that the dyn value of the surface of the substrate layer 3 reaches 38dyn / cm. This surface is used as the third surface of the substrate layer 3.

[0054] S2. Set the identification image of the identification layer 1 (in this embodiment, the identification image is a QR code). Use a coding device to spray the light-curing ink prepared in this embodiment onto the third surface of the substrate layer 3, and then provide UV light to cure the light-curing ink, thereby obtaining the formed identification layer 1 (thickness of 0.3μm) and obtaining the first semi-finished product. The side of the identification layer 1 that is composite with the third surface of the substrate layer 3 is used as the first surface of the identification layer 1.

[0055] S3. Using a micro-gravure coating method, acrylic adhesive containing blue pigment is applied to the third surface of the substrate layer 3 in the first semi-finished product to cover the marking layer 1 that is composite with the substrate layer 3. Then, it is transferred to an oven to dry the solvent in the acrylic adhesive at a drying temperature of 100°C and the acrylic adhesive is cured and formed. The thickness of the coating formed after the acrylic adhesive is dried is 11μm. Then, a 25μm thick PET release film is laminated to the surface of the coating to obtain the second semi-finished product.

[0056] S4. The second semi-finished product is cured at 50±5°C for 48 hours to complete the production of the adhesive layer 2 formed by acrylic glue, and the third semi-finished product is obtained. The side of the adhesive layer 2 that is bonded to the third surface of the substrate layer 3 is used as the second surface of the adhesive layer 2.

[0057] S5. The third finished product is slit according to the required length and width, and then the release film covering the surface of the adhesive layer 2 is peeled off to obtain the finished label tape.

[0058] like Figure 1 As shown, the labeling tape obtained through the above steps includes a substrate layer 3, a labeling layer 11, and an adhesive layer 2. The substrate layer 3 is a PET release film, the labeling layer 11 is cured by the light-curing ink prepared in this embodiment, and the adhesive layer 2 is cured by acrylic adhesive. The third surface of the substrate layer 3 is simultaneously laminated with the first surface of the labeling layer 11 and the second surface of the adhesive layer 2. Furthermore, the labeling layer 11 is integrally embedded into the adhesive layer 2 from the second surface of the adhesive layer 2. In the composite structure formed by the labeling layer 11 and the adhesive layer 2, the first surface of the labeling layer 11 and the second surface of the adhesive layer 2 are flush.

[0059] Test Example 1

[0060] 1. Test Objective

[0061] The chemical resistance of the marking layer 1 formed by the different photocurable inks used in Example 1 was tested.

[0062] 2. Test Object

[0063] The first semi-finished product obtained by processing groups 1A to 18A of Example 1 during the production of labeling tape.

[0064] 3. Test Items

[0065] (1) Moisture resistance test

[0066] The test subject was placed in an insulated chamber at 28°C and 60% relative humidity for 2 hours. After removing the test subject from the insulated chamber, the identification layer 1 of the test subject was scanned using an SR-2000 barcode scanner and an SR-700 barcode scanner, and the recognition results were recorded. Then, tesa7475 tape was applied to the surface of the identification layer 1 of the test subject and left to stand for 10 minutes. Then, a puller was used to peel the tesa7475 tape off the surface of the identification layer 1 at a peeling angle of 180° and a pull force of 15N, and the ink adhesion on the tesa7475 tape was recorded. In the above test, 100 repetitions were set for each test subject, and each identification code (one identification code was set on one identification layer 1) was counted as one repetition.

[0067] (2) High temperature resistance test

[0068] The test object was placed in an insulated chamber at 130°C and 60% relative humidity for 2 hours. After removing the test object from the insulated chamber, the identification layer 1 of the test object was scanned using an SR-2000 barcode scanner and an SR-700 barcode scanner, and the recognition results were recorded. Then, tesa7475 tape was applied to the surface of the identification layer 1 of the test object and left to stand for 10 minutes. Then, a puller was used to peel the tesa7475 tape off the surface of the identification layer 1 at a peeling angle of 180° and a pull force of 15N, and the ink adhesion on the tesa7475 tape was recorded. In the above test, 100 repetitions were set for each test object, and each identification code (one identification code was set on one identification layer 1) was counted as one repetition.

[0069] (3) Solvent resistance test

[0070] At 70°C, the test objects were immersed in toluene and ethyl acetate for 2 hours respectively. After removing the test objects from the immersion solvent, the solvent on the surface of the test objects was absorbed with filter paper. The identification layer 1 of the test objects was scanned using an SR-2000 barcode scanner and an SR-700 barcode scanner, and the identification results were recorded. Then, tesa7475 tape was attached to the surface of the identification layer 1 of the test objects and left to stand for 10 minutes. Then, a puller was used to peel the tesa7475 tape off the surface of the identification layer 1 at a peeling angle of 180° and a pulling force of 15N, and the ink adhering on the tesa7475 tape was recorded. In the above test, 100 repetitions were set for each test object, and each identification code (one identification code was set on one identification layer 1) was counted as one repetition.

[0071] (4) Electrolyte resistance test

[0072] Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a volume ratio of EC:EMC:DEC = 1:1:1 to obtain an organic solvent. Then, fully dried lithium salt LiPF6 was dissolved in the organic solvent to prepare an electrolyte with a concentration of 1 mol / L. At 60°C, the test object was immersed in the electrolyte for 2 hours. After removing the test object from the immersion solvent, the electrolyte on the surface of the test object was absorbed with filter paper. The identification layer 1 of the test object was scanned using an SR-2000 barcode scanner and an SR-700 barcode scanner, and the identification results were recorded. Then, tesa7475 tape was attached to the surface of the identification layer 1 of the test object and left to stand for 10 minutes. Then, a puller was used to peel the tesa7475 tape off the surface of the identification layer 1 at a peeling angle of 180° and a pull force of 15N. The ink adhering to the tesa7475 tape was recorded. In the above test, 100 repetitions were set for each test object, and each identification code (one identification code was set on one identification layer 1) was one repetition.

[0073] 4. Data Statistics

[0074] (1) Recognition rate calculation: Recognition rate = Number of recognizable identification codes / Total number of repeated identification codes. Recognition rate rating: Recognition rate ≥ 90%, rating: Excellent; 90% > Recognition rate ≥ 80%, rating: Good; 80% > Recognition rate ≥ 60%, rating: Average; Recognition rate < 60%, rating: Poor.

[0075] (2) Decolorization rate calculation: Number of identification codes that have fallen off and adhered to the tesa7475 tape / Total number of repeated identification codes. Adhesion rating: Decolorization rate ≤ 10%, rating: Excellent; 10% < Decolorization rate ≤ 20%, rating: Good; 20% < Decolorization rate ≤ 40%, rating: Medium; Decolorization rate > 40%, rating: Poor.

[0076] 5. Test Results and Analysis

[0077] The moisture resistance test results for this test example are shown in Table 4. In most of the test products provided in treatment groups 1A to 18A, ink discoloration did not occur, indicating that the tested UV-cured inks are essentially not discolored due to moisture after complete curing. On the other hand, the test products provided in treatment groups 2A to 17A were generally clearly identifiable by barcode scanners of different sizes, demonstrating good moisture resistance. Compared to the above treatment groups, some samples in treatment groups 1A and 18A showed barcode deformation after exposure to moisture, resulting in a slightly lower recognition rate for these two treatment groups compared to other treatment groups. The barcode deformation was more pronounced in the test products provided in treatment group 18A, and some samples also showed ink discoloration.

[0078] Table 4. Statistical analysis of the moisture resistance test results for Test Example 1

[0079]

[0080]

[0081] The results of the high-temperature resistance test are shown in Table 5. In the high-temperature resistance test, the test products provided by treatment groups 2A-11A and 16A exhibited excellent high-temperature resistance characteristics. These test products generally maintained a clear display effect after high-temperature treatment, were accurately identified by barcode scanners, and showed virtually no ink discoloration. While the identification codes of the test products provided by treatment groups 12A-15A and 17A generally maintained their original images after high-temperature treatment, some test products showed ink discoloration. The photocurable ink formulations used to prepare the identification layer in treatment groups 2A-11A and 16A all involved the combined use of a multi-component oxygen-containing heterocyclic photosensitive monomer (at least one of a four-membered, five-membered, or six-membered oxygen-containing heterocyclic photosensitive monomer) and epoxy monomers 2 and 3. Epoxy monomers 2 and 3 are both epoxy monomers containing ester groups in their chemical composition. However, none of the photocurable inks used to prepare the identification layer in treatments 12A-15A and 17A involved the simultaneous use of epoxy monomers. Considering the differences in high-temperature resistance test results among the treatment groups, it indicates that using epoxy monomers 2 and 3 in combination in the formulation of the photocurable ink for preparing the identification layer is beneficial for improving the high-temperature resistance of the identification layer. While the photocurable ink formulation for the identification layer in treatment group 1A also involved the combination of epoxy monomers 2 and 3, this formulation did not include a multi-component oxygen-containing heterocyclic photosensitive monomer, and it also exhibited ink discoloration after heat treatment. This suggests that the multi-component oxygen-containing heterocyclic photosensitive monomer in the photocurable inks used to prepare the identification layer in treatments 2A-11A and 16A can also improve the high-temperature resistance of the identification layer to some extent. Since the ink adhesion of the identification layer 1 prepared in treatments 1A and 18A already showed some deficiencies before testing, these deficiencies became more pronounced after high-temperature treatment.

[0082] Table 5. Statistical analysis of high temperature resistance test results for Test Example 1

[0083]

[0084] Before the solvent resistance test began, the identification codes of the test products in treatment groups 1A to 18A all had clear display effects, and the patterns between each repetition were basically consistent, indicating a high degree of consistency among identification codes made according to the same pattern. However, during the solvent resistance test, the test products in treatment groups 1A to 18A were immersed in different solvents, and the display effect of the pattern of the identification layer 1 of the test products in different treatment groups showed significant differences, as shown in Table 6.

[0085] During solvent immersion, the test products from treatment groups 1A and 18A exhibited severe ink discoloration, and the identification codes on most of the identification layers showed significant deformation and damage, rendering most of the test products from these two treatment groups unreadable after solvent immersion. A significant difference between treatment groups and other treatment groups is that neither treatment group 1A nor treatment group 18A used a multi-component oxocyclic photopolymer (at least one of a quaternary, pentagonal, or hexacyclic photopolymer). This indicates that adding a multi-component oxocyclic photopolymer to the formulation of the photopolymer ink significantly improves the solvent resistance of the identification layer formed by the photopolymer ink.

[0086] In the photocurable inks used to prepare the identification layer in treatment groups 3A to 7A, only one type of multi-membered heterocyclic photomonomer was employed. As shown in Table 6, compared to treatment groups 1A and 18A, the solvent resistance of the test products from these treatment groups was significantly improved. This further demonstrates that adding a multi-membered heterocyclic photomonomer to the formulation of photocurable inks can significantly improve the solvent resistance of the identification layer formed by the photocurable ink. However, the test products from treatment groups 3A to 7A still exhibited varying degrees of ink discoloration. The ink discoloration in the test products from treatment groups 3A to 5A was less severe, and the integrity of the identification code after solvent immersion was also higher. The difference between these treatment groups and treatment groups 6A and 7A is that the photocurable ink formulations used in treatment groups 3A to 5A contained a quaternary heterocyclic photomonomer. This indicates that among various multi-membered heterocyclic photomonomers, using a quaternary heterocyclic photomonomer to prepare photocurable inks can yield an identification layer with better solvent resistance.

[0087] The formulations used in treatment groups 8A to 10A for preparing photocurable inks all contained two quaternary oxocyclic photosensitive monomers. Among them, the test products prepared in treatment groups 8A and 9A still showed ink discoloration due to solvent immersion. However, the test product prepared in treatment group 10A basically did not show ink discoloration. This indicates that when quaternary oxocyclic photosensitive monomer 1 and quaternary oxocyclic photosensitive monomer 2 are used together in the preparation of photocurable inks, ink discoloration due to solvent immersion can be effectively prevented. However, in the photocurable ink formulation used in treatment group 10A, the mass ratio of quaternary oxoheterocyclic photomonomer 1 to quaternary oxoheterocyclic photomonomer 2 was 1:1, while in the photocurable ink formulations used in treatment groups 11A, 12A, 15A, and 17A, the mass ratio of quaternary oxoheterocyclic photomonomer 1 to quaternary oxoheterocyclic photomonomer 2 was 2:1. These treatment groups exhibited excellent solvent resistance characteristics during the solvent resistance test, with no ink discoloration and no obvious deformation of the identification layer after immersion in solvent, and they were basically able to be accurately identified.

[0088] The test products provided in treatment groups 2A, 13A, 14A, and 16A also demonstrated good solvent resistance during the solvent resistance test, without significant ink discoloration. However, compared to treatment group 11A, these treatment groups showed slight deformation after solvent immersion, resulting in slightly lower barcode scanner recognition rates. A notable difference between treatment group 11A and the others is that the formulation used to prepare the UV-curable ink does not include epoxy monomer 1. This indicates that using oxygen-containing monomer 1 in the preparation of UV-curable ink can further improve the solvent resistance of the recognition layer formed by the UV-curable ink.

[0089] Table 6. Statistical analysis of solvent resistance test results for Test Example 1

[0090]

[0091] The electrolyte resistance test results of the tested objects are shown in Table 7. The formulation design of the photocurable ink used to prepare the labeling layer 1 generally showed a consistent trend in improving the electrolyte resistance and solvent resistance of the labeling layer 1. However, the deficiencies in the formulation design made the performance defects of the labeling layer 1 more obvious in the electrolyte resistance test. Overall, most of the tested products in the group that did not use multi-membered heterocyclic photosensitive monomers in the photocurable ink used to prepare the labeling layer 1 showed significant deformation and ink discoloration after being soaked in electrolyte. The electrolyte resistance of the identification layer in the group that used photocurable ink containing multi-membered heterocyclic photosensitive monomers was significantly improved. Among them, the group that used photocurable ink formulations containing both quaternary heterocyclic photosensitive monomer 1 and quaternary heterocyclic photosensitive monomer 2 showed better electrolyte resistance.

[0092] Table 7. Statistical analysis of electrolyte resistance test results for Test Example 1

[0093]

[0094]

[0095] Based on the results of the moisture resistance test, high temperature resistance test, solvent resistance test, and electrolyte resistance test in this test example, it can be seen that the test product provided by treatment group 11A in Example 1 has the best overall performance. No obvious deformation of the identification code or discoloration of the identification code ink was observed in the different tests conducted in this test example. Before and after the test, the identification layer has a clear display effect and can be accurately identified by barcode scanners of different specifications.

[0096] Example 2

[0097] In the test results of Test Example 1, the labeling layer 1 of the labeling tape prepared by treatment group 11A of Example 1 was found to have the best chemical resistance. Based on this, this example uses treatment group 11A of Example 1 as a reference and sets treatment groups 1B to 6B to prepare labeling tape. The formulations of the labeling layer 1 used to prepare the labeling tape are different for different treatment groups. For details, please refer to Table 8. The photocurable ink formulation of treatment group 1B is consistent with that of treatment group 11A of Example 1.

[0098] Table 8. Formulation composition of the photocurable ink in Example 2 (parts by weight)

[0099]

[0100]

[0101] When preparing the photocurable inks used in each treatment group, prepare the materials according to the relevant contents in Table 8, mix the raw materials required for each formula in the required amount, disperse them fully, and obtain the photocurable inks.

[0102] Each processing group used the photocurable inks prepared according to Table 8 and further followed the labeling tape preparation method provided in Example 1 to complete the preparation of the labeling tapes. Except for the different photocurable inks used, the other materials and operations involved in the preparation of the labeling tapes were consistent with those in Example 1.

[0103] Test Example 2

[0104] 1. Test Objective

[0105] The chemical resistance of the marking layer 1 formed by the different photocurable inks used in Example 2 was tested.

[0106] 2. Test Object

[0107] The first semi-finished product obtained by processing groups 1B to 6B of Example 2 during the production of labeling tape.

[0108] 3. Test Items

[0109] (1) Moisture resistance test

[0110] The procedure is consistent with the moisture resistance test in Test Example 1, and will not be repeated here.

[0111] (2) High temperature resistance test

[0112] The high-temperature resistance test procedure is consistent with that of Test Example 1, and will not be repeated here.

[0113] (3) Solvent resistance test

[0114] The solvent resistance test procedure is consistent with that in Test Example 1, and will not be repeated here.

[0115] (4) Electrolyte resistance test

[0116] The electrolyte resistance test procedure is consistent with that of Test Example 1, and will not be repeated here.

[0117] 4. Data Statistics

[0118] The data statistics operations are consistent with those in Test Example 1, and will not be repeated here.

[0119] 5. Test Results and Analysis

[0120] The test results for this test example are shown in Tables 9-12. As can be seen from the results presented in Tables 9, 11, and 12, all the test subjects in this test example exhibited good moisture resistance, solvent resistance, and electrolyte resistance. During the temperature resistance, solvent resistance, and electrolyte resistance tests, no significant deformation of the identification code or large-scale ink discoloration was observed. However, in the high-temperature resistance test, the test products provided by each treatment group showed significant differences. The main difference between the test subjects in this test example lies in the type of acrylate monomer in the UV-curable ink formulation used to prepare the identification layer 1. Treatment groups 4B, 5B, and 6B used vinyl ethoxyethyl acrylate, 1,6-hexanediol diacrylate, and 2-ethyleneoxyethoxyethyl acrylate as acrylate monomers in their UV-curable ink formulations, respectively. After high-temperature treatment, the test products provided by these three treatment groups all showed discoloration of the identification layer ink, and the identification code was also slightly deformed. The photocurable inks used in treatment groups 2B and 3B each contained two types of acrylate monomers: a combination of vinyl ethoxyethyl acrylate and 2-ethyleneoxyethoxyethyl acrylate (treatment group 2B), and a combination of 1,6-hexanediol diacrylate and 2-ethyleneoxyethoxyethyl acrylate. However, compared to treatment groups using single-component acrylate monomers, the high-temperature resistance of the test products provided by treatment groups 2B and 3B was not significantly improved. Compared to treatment groups 2B-6B, the recognition layer of treatment group 1B showed significantly superior high-temperature resistance. After high-temperature treatment, the test products in this group showed virtually no deformation or ink discoloration. The photocurable ink formulation used in treatment group 1B contained vinyl ethoxyethyl acrylate and 1,6-hexanediol diacrylate as acrylate monomers. This indicates that using a combination of vinyl ethoxyethyl acrylate and 1,6-hexanediol diacrylate as acrylate monomers in the photocurable ink formulation for forming the layer is beneficial to the high-temperature resistance of the recognition layer formed by the photocurable ink.

[0121] Table 9. Statistical analysis of the moisture resistance test results for Test Example 2

[0122]

[0123]

[0124] Table 10. Statistical analysis of high temperature resistance test results for Test Example 2

[0125]

[0126] Table 11. Statistical analysis of solvent resistance test results for Test Example 2

[0127]

[0128] Table 12. Statistical analysis of electrolyte resistance test results for Test Example 2

[0129]

[0130]

[0131] Example 3

[0132] In the test results of Test Example 1, the labeling layer 1 of the labeling tape prepared by treatment group 11A of Example 1 was found to have the best chemical resistance. Based on this, this example uses the photocurable ink formulation used in treatment group 11A of Example 1 as a reference, and sets up treatment groups 1C to 8C to prepare photocurable inks. The types and proportions of photocuring agents in the formulations used to prepare the labeling layer 1 of the labeling tape are different in different treatment groups. For details, please refer to Table 13. The photocurable ink formulation of treatment group 1C is consistent with that of treatment group 11A of Example 1.

[0133] Table 13. Formulation composition of the photocurable ink in Example 3 (parts by weight)

[0134]

[0135]

[0136] Each processing group used the photocurable ink prepared according to Table 13, and further used the photocurable ink of this embodiment to conduct photocuring speed tests according to the following steps:

[0137] Referring to the QB / T2826-2006 standard, the UV-curable inks prepared by treatment groups 1C to 7C were sprayed onto PET release films with a surface dyn value of 38 dyn / cm. The amount of UV-curable ink sprayed was sufficient to form a layer thickness of 0.3 μm. Then, a small UV curing machine (BLTUV type, UV light main peak of 365 nm) was used to irradiate the marking layer 1 formed by the UV-curable ink to cure it and form marking layer 1. At the same time, a stopwatch was used to time the process. Then, the tail of a paperclip was used to forcefully scratch the edge of the marking layer 1 to check whether there were ink traces left on the blank part of the edge of marking layer 1. At the same time, the marking layer 1 was touched with a finger to judge its dryness.

[0138] In the photocuring speed test set in this embodiment, 10 replicates were set for each type of photocurable ink, and each identification code (one identification code is set on one identification layer) constitutes one replicate. The photocuring time applied to each type of photocurable ink is the average of the photocuring time of the corresponding 10 replicate samples.

[0139] Table 14 shows the statistical results of the photocuring speed of the photocurable inks in treatment groups 1C to 3C of this embodiment. The photocurable ink formulations used in treatment groups 4C to 6C all contained only one photoinitiator, and the photocuring speeds of the photocurable inks prepared in these three treatment groups were significantly lower. However, the photocurable ink used in treatment group 7C included di[4-diphenylthiophenyl]sulfide dihexafluoroantimonate and bis(4-tert-butylphenyl)iodonium hexafluorophosphate. Compared to treatment groups 1C to 3C, the photocuring time of the photocurable ink used in treatment group 7C was significantly shortened. This indicates that the combined use of the two photoinitiators can improve the photocuring speed of the photocurable ink containing the photosensitive monomer used in Example 3. Based on the combination of di[4-diphenylthiophenyl]sulfide dihexafluoroantimonate and bis(4-tert-butylphenyl)iodonium hexafluorophosphate, treatment groups 1C and 8C respectively used diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide in combination with the above two photoinitiators to form three-component composite photoinitiators. However, the photocuring speeds of the two three-component composite photoinitiators differed significantly. Compared with the photocuring speed of treatment group 7C, the photocuring speed of treatment group 1C was significantly faster, while the photocuring speed of treatment group 8C was slower. The curing speed was somewhat reduced, indicating that not all photoinitiators, when combined with di[4-diphenylthiophenyl]sulfide dihexafluoroantimonate and bis(4-tert-butylphenyl)iodonium hexafluorophosphate to form a three-component composite photoinitiator, can further improve the photocuring speed of the photocurable ink containing the photosensitive monomer used in Example 3. However, the combination of diphenyl-(4-phenylthiophenyl)sulfide dihexafluoroantimonate with di[4-diphenylthiophenyl]sulfide dihexafluoroantimonate and bis(4-tert-butylphenyl)iodonium hexafluorophosphate can effectively improve the photocuring speed of the photocurable ink containing the photosensitive monomer used in Example 3.

[0140] Table 14. Statistical results of the photocuring time of the photocurable ink in Example 3

[0141]

[0142] Example 4

[0143] In this embodiment, different photocurable inks were prepared using the formulations provided in Tables 15 and 16. In this embodiment, the specific composition of the oxygen-containing heterocyclic photosensitive monomer in the formulation used to prepare the photocurable ink was used as a variable to set up treatment groups 1D to 8D. The photocurable ink formulations used in treatment groups 1D to 7D included oxygen-containing heterocyclic photosensitive monomers, and the composition of the oxygen-containing heterocyclic photosensitive monomers included in these formulations is shown in Table 16. The photocurable ink formulation used in treatment group 8D did not include oxygen-containing heterocyclic photosensitive monomers, and its formulation composition is shown in Table 17.

[0144] Table 15. Formulation composition of UV-curable inks for treatment groups 1D to 7D

[0145]

[0146]

[0147] Table 16. Composition of oxygen-containing heterocyclic photosensitive monomers used in the formulation of UV-curable inks for treatment groups 1D to 7D (parts by mass)

[0148]

[0149] In this embodiment, (3-ethyl-3-oxecyclobutyl)methyl isobutylene ester (CAS: 37674-57-0) was selected as the four-membered oxecyclophotosensitive monomer in Table 16, and its structural formula is as follows:

[0150] In this embodiment, tetrahydrofuran acrylate (CAS: 2399-48-6) was selected as the five-membered oxocyclic photosensitive monomer in Table 16, and its structural formula is as follows:

[0151] In this embodiment, methyl acrylate (5-ethyl-13-dioxane-5-yl) acrylate (CAS: 66492-51-1) was selected as the six-membered oxoheterocyclic photosensitive monomer 1 in Table 16, and its structural formula is as follows: N-Acryloylmorpholine (CAS: 5117-12-4) was selected as the six-membered oxocyclic photosensitizer 2 in Table 16, and its structural formula is as follows:

[0152] To correspond with the amount (40 parts) of oxygen-containing heterocyclic photosensitive monomers involved in the photocurable ink formulations provided in Table 15, the total amount of oxygen-containing heterocyclic photosensitive monomers used in each treatment group provided in Table 16 is 40 parts.

[0153] Table 17. Formulation composition of UV-curable inks for treatment group 8D

[0154]

[0155]

[0156] When preparing the photocurable inks used in each treatment group, the materials were prepared according to the relevant contents of Tables 15 to 17. The raw materials required for each formula were mixed in the required amount and fully dispersed to obtain the photocurable inks used in Example 4.

[0157] Furthermore, each processing group completed the labeling tape according to the manufacturing method of the labeling tape provided in Example 1. Except for the difference in the photocurable ink used, the other materials and operations involved in the preparation of the labeling tape were consistent with those in Example 1.

[0158] Test Example 3

[0159] 1. Test Objective

[0160] The chemical resistance of the marking layer 1 formed by the different photocurable inks used in Example 4 was tested.

[0161] 2. Test Object

[0162] The first semi-finished product obtained by processing groups 1D to 8D of Example 4 during the production of labeling tape.

[0163] 3. Test Items

[0164] (1) Moisture resistance test

[0165] The procedure is consistent with the moisture resistance test in Test Example 1, and will not be repeated here.

[0166] (2) High temperature resistance test

[0167] The high-temperature resistance test procedure is consistent with that of Test Example 1, and will not be repeated here.

[0168] (3) Solvent resistance test

[0169] The solvent resistance test procedure is consistent with that in Test Example 1, and will not be repeated here.

[0170] (4) Electrolyte resistance test

[0171] The electrolyte resistance test procedure is consistent with that of Test Example 1, and will not be repeated here.

[0172] 4. Data Statistics

[0173] The data statistics operations are consistent with those in Test Example 1, and will not be repeated here.

[0174] 5. Test Results and Analysis

[0175] The moisture resistance test results for this test example are shown in Table 18. In most of the test products provided in treatment groups 1D to 8D, ink discoloration did not occur, indicating that the tested UV-cured inks are essentially not discolored due to moisture after complete curing. On the other hand, the test products provided in treatment groups 1D to 7D were generally clearly identifiable by barcode scanners of different sizes, demonstrating good moisture resistance. Compared to the above treatment groups, some samples in treatment group 8D showed deformation of the identification code after exposure to moisture, resulting in a slightly lower recognition rate for the test products in this treatment group compared to the other treatment groups.

[0176] Table 18. Statistical analysis of the moisture resistance test results for Test Example 3

[0177]

[0178] The high-temperature resistance test results of this test example are shown in Table 19. The identification layer of the test product provided by test group 8D showed significant deformation and ink discoloration after high-temperature treatment, resulting in a significantly lower identification code recognition rate compared to other treatment groups. Except for test group 8D, the test products provided by other treatment groups participating in this test example all exhibited good high-temperature resistance. After high-temperature treatment, the test products provided by treatment groups 1D to 7D did not show ink discoloration. Among them, the identification codes of the test products provided by treatment groups 5D to 7D did not show significant deformation after high-temperature treatment. Therefore, the test products provided by these treatment groups can be accurately identified by different types of barcode scanners. The photocurable ink formulations used by these treatment groups all contain two oxygen-containing heterocyclic photosensitive monomers. This proves that, compared to using only one oxygen-containing heterocyclic photosensitive monomer to prepare photocurable inks, using two oxygen-containing heterocyclic photosensitive monomers in combination to prepare photocurable inks is beneficial to improving the high-temperature resistance of photocurable inks.

[0179] Table 19. Statistical analysis of high temperature resistance test results for Test Example 3

[0180]

[0181] Before the solvent resistance test, the identification codes of the test products in treatment groups 1D to 8D all had clear display effects, and the patterns between each repetition were basically consistent. The identification codes made according to the same pattern had high consistency. However, during the solvent resistance test, the test products in treatment groups 1D to 8D were immersed in different solvents. The display effect of the pattern of the identification layer 1 of the products in different treatment groups showed obvious differences, as shown in Table 20.

[0182] During solvent immersion, the test products provided by treatment group 8D exhibited severe ink discoloration, and the identification codes on most of the identification layers showed significant deformation and damage, rendering most of the test products from treatment group 8D unreadable after solvent immersion. Regarding the formulation used to prepare the UV-curable ink, a difference from other treatment groups is that treatment group 8D did not use the oxygen-containing heterocyclic photosensitive monomer from Example 4. Based on the lowest solvent resistance test rating among all test products, this indicates that adding the oxygen-containing heterocyclic photosensitive monomer to the formulation used in Example 4 for preparing the UV-curable ink can effectively improve the solvent resistance of the product's identification layer.

[0183] By comparing the solvent resistance test results of treatment groups 1D to 4D, treatment group 4D, which contains N-acryloylmorpholine in its UV-curable ink formulation, showed the best overall solvent resistance test results. Based on this, treatment groups 5D to 7D used different oxygen-containing heterocyclic photosensitive monomers compounded with N-acryloylmorpholine as two-component compounded oxygen-containing heterocyclic photosensitive monomers in the formulation of UV-curable inks. Compared to the treatment group whose UV-curable ink formulation contained only one type of oxygen-containing heterocyclic photosensitive monomer, the solvent resistance of treatment groups 5D to 7D was improved to varying degrees. Among them, the test products provided by treatment groups 5D and 6D still showed some ink discoloration in the solvent resistance test, while the test product provided by treatment group 7D achieved the best level of solvent resistance in this test example. Its identification layer had a clear display effect before and after immersion in solvent and could be identified by different types of barcode scanners. In addition, there was basically no discoloration of the identification layer ink after immersion in solvent. This shows that, based on the UV-curable ink formulation system used in Example 4, the use of (5-phenyl-13-dioxane-5-yl)methyl acrylate and N-acryloylmorpholine as a two-component compound oxygen-containing heterocyclic photosensitive monomer in the formulation of UV-curable ink is beneficial to obtaining UV-curable ink with excellent solvent resistance.

[0184] Table 20. Statistical analysis of solvent resistance test results for Test Example 3

[0185]

[0186] The electrolyte resistance test results of the test subjects are shown in Table 21. The formulation design of the photocurable ink used to prepare the labeling layer 1 generally shows a consistent trend in improving the electrolyte resistance and solvent resistance of the labeling layer 1. Overall, based on the photocurable ink formulation system used in Example 4, the use of oxygen-containing heterocyclic photosensitive monomers in the preparation of the photocurable ink is beneficial to improving the electrolyte resistance of the labeling layer 1 cured by the photocurable ink. Among the test products in this test example, the test product provided by treatment group 7D has the best electrolyte resistance. After immersion in electrolyte, the clarity and integrity of the identification layer pattern of the test product provided by treatment group 7D did not show any significant decrease, and it could be identified by different types of barcode scanners without any discoloration of the identification layer ink.

[0187] Table 21. Statistical analysis of electrolyte resistance test results for Test Example 3

[0188]

[0189] Example 5

[0190] In the test results of Test Example 3, the labeling layer 1 of the labeling tape prepared by treatment group 7D of Example 4 was found to have the best chemical resistance. Based on this, this example uses treatment group 7D of Example 4 as a reference and sets treatment groups 1E to 6E to prepare labeling tape. The formulations of the labeling layer 1 used to prepare the labeling tape are different for different treatment groups. For details, please refer to Table 22. The photocurable ink formulation corresponding to treatment group 1E is consistent with that of treatment group 7D of Example 4.

[0191] Table 22. Formulation composition of the photocurable ink in Example 5 (parts by weight)

[0192]

[0193]

[0194] Test Example 4

[0195] 1. Test Objective

[0196] The chemical resistance of the marking layer 1 formed by the different photocurable inks used in Example 5 was tested.

[0197] 2. Test Object

[0198] The first semi-finished product obtained by processing groups 1E to 6E of Example 5 during the production of labeling tape.

[0199] 3. Test Items

[0200] (1) Moisture resistance test

[0201] The procedure is consistent with the moisture resistance test in Test Example 1, and will not be repeated here.

[0202] (2) High temperature resistance test

[0203] The high-temperature resistance test procedure is consistent with that of Test Example 1, and will not be repeated here.

[0204] (3) Solvent resistance test

[0205] The solvent resistance test procedure is consistent with that in Test Example 1, and will not be repeated here.

[0206] (4) Electrolyte resistance test

[0207] The electrolyte resistance test procedure is consistent with that of Test Example 1, and will not be repeated here.

[0208] 4. Data Statistics

[0209] The data statistics operations are consistent with those in Test Example 1, and will not be repeated here.

[0210] 5. Test Results and Analysis

[0211] The test results for this test example are shown in Tables 23-26. As can be seen from the test results presented in Tables 23, 25, and 26, all the test subjects in this test example exhibited good moisture resistance, solvent resistance, and electrolyte resistance. No significant deformation of the identification code or large-scale ink discoloration was observed during the temperature resistance, solvent resistance, and electrolyte resistance tests. However, compared with other treatment groups, the solvent resistance and electrolyte resistance test results for treatment group 2E were slightly insufficient. This is because the UV-curable ink formulation used in this treatment group does not contain 3,3,5-trihexylcyclohexyl acrylate. This indicates that, based on the UV-curable ink formulation system used in Example 5, using 3,3,5-trihexylcyclohexyl acrylate as the acrylate monomer in the formulation can improve the solvent resistance and high-temperature resistance of the identification layer formed by the UV-curable ink.

[0212] On the other hand, the test products provided by each treatment group showed significant differences in high-temperature resistance testing. The main difference between the test subjects in this test example lies in the type of acrylate monomers in the UV-curable ink formulation used to prepare the label layer 1. Treatment group 3E used a UV-curable ink containing only 3,3,5-trihexylcyclohexyl acrylate, and the test product provided by treatment group 3E showed significant ink discoloration during the high-temperature resistance test. Compared to treatment group 3E, treatment groups 4E to 6E used different types of acrylate monomers combined with 3,3,5-trihexylcyclohexyl acrylate as compound acrylate monomers in the preparation of the UV-curable ink formulation. The high-temperature resistance properties of the test products provided by these treatment groups were slightly improved. The UV-curable ink formulation used in treatment group 2E did not include 3,3,5-trihexylcyclohexyl acrylate. Instead, it used a three-component blend of 1,6-hexanediol diacrylate, 2-ethyleneoxyethoxyethyl acrylate, and ethoxyethoxyethyl acrylate. The marking layer 1 formed by this UV-curable ink exhibited good high-temperature resistance, but color fading still occurred during the high-temperature resistance test. In contrast, the UV-curable ink formulation used in treatment group 1E included four acrylate monomers: 3,3,5-trihexylcyclohexyl acrylate, 1,6-hexanediol diacrylate, 2-ethyleneoxyethoxyethyl acrylate, and ethoxyethoxyethyl acrylate. The blending of these four acrylate monomers further improved the high-temperature resistance of the identification layer formed by the UV-curable ink. The identification layer of treatment group 1E showed virtually no color fading during the high-temperature resistance test.

[0213] Table 23. Statistical analysis of the moisture resistance test results for Test Example 4

[0214]

[0215]

[0216] Table 24. Statistical analysis of high temperature resistance test results for Test Example 4

[0217]

[0218] Table 25. Statistical analysis of solvent resistance test results for Test Example 4

[0219]

[0220] Table 26. Statistical analysis of electrolyte resistance test results for Test Example 4

[0221]

[0222] Example 6

[0223] Based on the test results of Test Examples 1 to 5 above, it was found that the photocurable inks used in Treatment Group 11A of Example 1 and Treatment Group 7D of Example 4 both have excellent chemical resistance. In this example, the above two photocurable inks are used to make the label tape. Furthermore, in this example, commercially available photocurable ink (French Dolby Starflex ink) is used in the production of the label tape.

[0224] Using the three different UV-curable inks mentioned above, prepare the marking tapes according to the following steps:

[0225] S1. A 19μm thick PET release film is used as the substrate layer. One surface of the substrate layer is corona treated to make the dyn value of that surface of the substrate layer reach 38 dyn / cm. This surface is used as the third surface of the substrate layer.

[0226] S2. Set the identification image of the identification layer 1 (in this embodiment, the identification image is a QR code). Use a coding device to spray the light-curing ink prepared in this embodiment onto the third surface of the substrate layer, and then provide UV light to cure the light-curing ink, thereby obtaining the formed identification layer 1 and obtaining the first semi-finished product. The side of the identification layer 1 that is composite with the third surface of the substrate layer is used as the first surface of the identification layer 1.

[0227] S3. Using a micro-gravure coating method, acrylic adhesive containing blue pigment is applied to the third surface of the substrate layer in the first semi-finished product to cover the marking layer 1 that is composite with the substrate layer. Then, it is transferred to an oven to dry the solvent in the acrylic adhesive at a drying temperature of 100°C and the acrylic adhesive is cured and formed. The thickness of the coating formed after the acrylic adhesive is dried is 11μm. Then, a 25μm thick PET release film is laminated to the surface of the coating to obtain the second semi-finished product.

[0228] S4. The second semi-finished product is cured at 50±5°C for 48 hours to complete the production of the adhesive layer formed by acrylic glue, and the third semi-finished product is obtained. The side of the adhesive layer that is bonded to the third surface of the substrate layer is used as the second surface of the adhesive layer.

[0229] S5. The third finished product is slit according to the required length and width, and then the release film covering the adhesive layer is peeled off to obtain the finished label tape.

[0230] During the preparation of the labeling tape, the thickness of the labeling layer 1 formed by the UV-curable ink is determined based on the preset resolution of the labeling layer 1. The treatment group that prepared the labeling tape using the UV-curable ink provided in Treatment Group 11A of Example 1 is designated as a treatment; the treatment group that prepared the labeling tape using the UV-curable ink provided in Treatment Group 7D of Example 4 is designated as a treatment; and the treatment group that prepared the labeling tape using commercially available UV-curable ink (brand name...) is designated as a treatment.

[0231] The resolution of the marking tapes produced in this embodiment is shown in Table 27. Among the three types of marking tapes produced in this embodiment, compared with the marking tapes produced by the treatment process, the marking layer 1 of the marking tapes produced by the treatment process and the treatment process is significantly thinner under the same resolution level. Under the condition that the marking layer 1 thickness is the same, the marking tapes produced by the treatment process and the treatment process have a clearer display effect.

[0232] Table 27. Correspondence between the resolution of the marking tape prepared in Example 6 and the thickness of marking layer 1

[0233]

[0234] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention, but such modifications or substitutions are all within the scope of protection of the present invention.

Claims

1. A labeling tape, characterized in that, The labeling tape includes: A labeling layer, formed by curing with photocurable ink, comprising a first surface, wherein the photocurable ink comprises: a photosensitive monomer, a photoinitiator, and a colorant; by mass percentage, the photosensitive monomer accounts for 55-90 wt%, and the photoinitiator accounts for 3.5-12 wt%; the photosensitive monomer comprises epoxy monomers and acrylate monomers, and at least one of four-membered oxocyclic photosensitive monomers, five-membered oxocyclic photosensitive monomers, and six-membered oxocyclic photosensitive monomers; the epoxy monomer comprises methyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethacrylate, 3,4-epoxycyclohexylmethylisobutylene ester, 3-epoxyethyl-7-oxabicyclo[4,1,0]heptane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylmethyl At least one of the following esters; the four-membered oxetine photosensitive monomer includes at least one of 3-ethyl-3-[(epoxyethylene methoxy)methyl]oxetane, (3-ethyl-3-oxetane)methyl isobutylene ester, and 3-ethyl-3-[[(2-ethylhexyl)oxy]methyl]oxetane; the five-membered oxetine photosensitive monomer includes tetrahydrofuran acrylate; the six-membered oxetine photosensitive monomer includes (5-ethyl-13-dioxane-5-yl)methyl acrylate. An adhesive layer, the adhesive layer including a second surface, the marking layer being integrally embedded in the adhesive layer from the second surface, and the marking layer and the adhesive layer being disposed such that the first surface and the second surface are flush; A substrate layer, the substrate layer including a third surface, the marking layer being laminated with the third surface of the substrate layer via the first surface, and the adhesive layer being laminated with the third surface of the substrate layer via the second surface.

2. The labeling tape as described in claim 1, characterized in that: The photosensitive monomer includes the four-membered oxygen heterocyclic photosensitive monomer.

3. The labeling tape as described in claim 2, characterized in that: The four-membered oxocyclic photosensitive monomer includes 3-ethyl-3-[(epoxyethylene methoxy)methyl]oxecyclobutane and (3-ethyl-3-oxecyclobutyl)methyl isobutylene ester.

4. The labeling tape as described in claim 3, characterized in that: The mass ratio of 3-ethyl-3-[(epoxyethylene methoxy)methyl]oxetane to (3-ethyl-3-oxetane)methyl isobutylene ester is 18~25:8~12.

5. The labeling tape as described in claim 1, characterized in that: The epoxy monomers include 3,4-epoxycyclohexylmethyl isobutylene ester, 3-epoxyethyl-7-oxabicyclo[4,1,0]heptane and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate.

6. The marking tape as described in claim 5, characterized in that: The mass ratio of the 3,4-epoxycyclohexylmethyl isobutylene ester to the 3-epoxyethyl-7-oxabicyclo[4,1,0]heptane to the 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate is 8~12:8~12:18~25.

7. The labeling tape as described in claim 2, characterized in that: The mass ratio of the quaternary oxocyclic photosensitive monomer to the epoxy monomer is 20-30:20-40.

8. The labeling tape as described in claim 1, characterized in that: The acrylate monomers include at least one of vinyl ethoxyethyl acrylate and 1,6-hexanediol diacrylate.

9. The labeling tape as described in claim 1, characterized in that: The photoinitiator includes photoinitiator A, photoinitiator B and photoinitiator C, wherein photoinitiator A is diphenyl-(4-phenylthio)phenylsulfonium hexafluoroantimonate, photoinitiator B is di[4-diphenylthiophenyl]sulfide dixafluoroantimonate, and photoinitiator C is bis(4-tert-butylphenyl)iodonium hexafluorophosphate; The photoinitiator A : photoinitiator B : photoinitiator C is calculated by mass ratio as 2~8 : 2~5 : 2~5.

10. The marking tape as described in claim 1, characterized in that: The photosensitive monomer includes the six-membered oxygen heterocyclic photosensitive monomer.

11. The marking tape as described in claim 10, characterized in that: The acrylate monomers include at least one selected from 1,6-hexanediol diacrylate, 2-ethyleneoxyethoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate and ethoxyethoxyethyl acrylate.

12. The marking tape as described in claim 11, characterized in that: The acrylate monomers include the 1,6-hexanediol diacrylate, the 2-ethyleneoxyethoxyethyl acrylate, the 3,3,5-trimethylcyclohexyl acrylate, and the ethoxyethoxyethyl acrylate. The mass ratio of 1,6-hexanediol diacrylate to 2-ethyleneoxyethoxyethyl acrylate to 3,3,5-trimethylcyclohexyl acrylate to ethoxyethoxyethyl acrylate is 8~12:8~12:10~15:8~12.

13. The marking tape as described in claim 11, characterized in that: The mass ratio of the six-membered oxocyclic photosensitive monomer to the acrylate monomer is 35~45:40~50.

14. The method for preparing the labeling tape according to any one of claims 1 to 13, characterized in that, Includes the following steps: Step 1: Spray the UV-curable ink onto the third surface of the substrate layer; Step two, the photocurable ink is cured and molded under light to form the marking layer on the surface of the substrate layer; Step 3: Apply adhesive to the third surface of the substrate layer and cover the marking layer with the adhesive; Step four: Allow the adhesive to cure and solidify to form the adhesive layer.

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