Multi-layer composite adhesive tape and preparation method thereof

Abstract

The invention discloses a multi-layer composite adhesive tape and a preparation method thereof, and belongs to the technical field of new adhesive tape materials. The multi-layer composite adhesive tape is composed of a bottom base film layer, a lower bonding layer, a middle base film layer, an upper bonding layer and a release film layer, the modified adhesive is prepared by the following steps: fully stirring 50-60 parts by weight of polyester resin, 30-40 parts by weight of epoxy resin, 10-15 parts by weight of an auxiliary agent and 20-30 parts by weight of a solvent, adding 5-15 parts by weight of a curing agent, stirring, and filtering. The auxiliary agent contains calcium carbonate, an organic anti-aging structure, an inorganic anti-aging component, organic flame-retardant elements including nitrogen and silicon and an inorganic flame-retardant component, and the auxiliary agent has chemical action with the epoxy resin and the curing agent, so that the auxiliary agent can stably play a role, and the modified adhesive and the adhesive tape have excellent anti-aging property, flame retardance and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of new tape materials, and specifically relates to a multi-layer composite tape and a preparation method thereof. Background Art

[0002] A tape, also known as a gummed strip, adhesive tape, and tape paper, etc., is a strip-shaped artificial product with adhesiveness, which can adhere to the surface of some items and can be used to connect two different items or for the protection of a certain screen wall. A tape is composed of a base material, an adhesive, or a base material, an adhesive, and a release film, and connects two or more non-connected objects through bonding.

[0003] However, the adhesive in the tape will undergo an oxidation reaction with oxygen when exposed to air for a long time, resulting in changes in the molecular structure, a decrease in viscosity. Ultraviolet rays will also damage the molecular structure of the adhesive, leading to aging, degradation, a decrease in viscosity or even loss of viscosity, thus affecting the use. In the prior art, in order to ensure that the tape maintains its original viscosity and physical properties during long-term use and avoid problems such as performance decline, discoloration, and cracking, anti-aging agents or antioxidants are usually simply physically mixed with the remaining raw materials in the adhesive to achieve an anti-aging effect. However, since there is no interaction between the anti-aging agent or antioxidant and the remaining raw materials, with the extension of the use time, the anti-aging agent or antioxidant will gradually migrate or even escape, thus losing the anti-aging effect. Therefore, it is urgent to design a multi-layer composite tape with excellent and stable anti-aging effect. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a multi-layer composite tape and a preparation method thereof.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A multi-layer composite tape is composed of a bottom base film layer, a lower adhesive layer, a middle base film layer, an upper adhesive layer, and a release film layer.

[0007] Further, the materials of the bottom base film layer and the middle base film layer are one or several of polyethylene terephthalate film, polyimide film, polyethylene naphthalate film, polypropylene film, and polyethylene film.

[0008] Further, the thickness of the bottom base film layer and the middle base film layer is 20 - 50 μm.

[0009] Further, the lower adhesive layer is formed by curing a modified adhesive, and the thickness is 20 - 25 μm.

[0010] Further, the modified adhesive is prepared by the following steps:

[0011] Fully stir 50-60 parts of polyester resin, 30-40 parts of epoxy resin, 10-15 parts of additives and 20-30 parts of solvent by weight, finally add 5-15 parts of curing agent, stir well and filter to obtain the modified adhesive.

[0012] Furthermore, the polyester resin is one or both of polyethylene terephthalate and polybutylene terephthalate.

[0013] Furthermore, the epoxy resin is bisphenol A epoxy resin.

[0014] Furthermore, the auxiliary agent is prepared by the following steps:

[0015] S1. Blow nitrogen gas into a dry three-necked flask for 30 minutes to expel air and moisture from the flask, then add 3,5-di-tert-butyl-4-hydroxybenzoic acid, EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), NHS (N-hydroxysuccinimide) and chloroform, stir to dissolve and then slowly add 2,2,6,6-tetramethylpiperidinamine, then heat to 65°C and keep warm for 6.5 hours. After the reaction is completed, cool to room temperature, evaporate under reduced pressure, purify by column chromatography (a mixed solvent of chloroform and ether is selected as the eluent, and the volume ratio of chloroform to ether is 9:1), and then evaporate under reduced pressure to obtain intermediate 1; the dosage ratio of 3,5-di-tert-butyl-4-hydroxycinnamic acid, 2,2,6,6-tetramethylpiperidinamine, EDC, NHS and chloroform is 25g:20mL:0.6g:0.4g:200mL;

[0016] Under the action of EDC and NHS, the molar ratio of 3,5-di-tert-butyl-4-hydroxycinnamic acid to 2,2,6,6-tetramethylpiperidinamine is controlled to be 1:1.1-1.2, then -COOH of 3,5-di-tert-butyl-4-hydroxycinnamic acid and -NH2 of 2,2,6,6-tetramethylpiperidinamine undergo amidation reaction, and the reaction equation is as follows:

[0017]

[0018] S2, nitrogen blowing dry three-necked flask for 30min to expel air and moisture in the flask, then add intermediate 1, triethylamine and chloroform, stir to dissolve, then slowly add cyanuric chloride, stir and react at room temperature for 3h after the addition is complete, cool to room temperature after the reaction is completed, then distill under reduced pressure, purify by column chromatography (eluent selects a mixed solvent of benzene and ether, the volume ratio of benzene and ether is 6:4), and finally distill under reduced pressure to obtain intermediate 2; the amount ratio of intermediate 1, cyanuric chloride, triethylamine and chloroform is 27g:13.8g:11.7mL:240mL;

[0019] Triethylamine is used as an acid-binding agent, and the molar ratio of intermediate 1 to cyanuric chloride is controlled to be 1:1.05 - 1.1. The -NH- of intermediate 1 undergoes a substitution reaction with the -Cl of cyanuric chloride, and the reaction process is as follows:

[0020]

[0021] S3. Bubble nitrogen through the dried brown three-necked flask for 30 min to expel the air and moisture in the flask. Then add resorcinol, anhydrous aluminum trichloride, and dimethyl sulfoxide. After stirring evenly, slowly add intermediate 2. Then stir and heat up to 115 °C and react at 115 °C for 12 h. After the reaction is completed, slowly pour the reaction mixture into ice water to precipitate a solid. Filter it, and then recrystallize it with an 80% methanol aqueous solution to obtain intermediate 3; the dosage ratio of intermediate 2, resorcinol, anhydrous aluminum trichloride, and dimethyl sulfoxide is 26 g:4.9 mL:7.8 g:200 mL;

[0022] Control the molar ratio of intermediate 2 to resorcinol to be 1:1.1 - 1.2. Intermediate 2 and resorcinol undergo a Friedel-Crafts acylation reaction under the catalysis of anhydrous aluminum trichloride, and the reaction process is as follows:

[0023]

[0024] S4. Bubble nitrogen through the dried three-necked flask for 30 min to expel the air and moisture in the flask. Then add intermediate 3, triethylamine, and dimethyl sulfoxide. After stirring and dissolving, slowly add 3-aminopropyltriethoxysilane. After adding, heat up to 50 °C and stir for 3 h. After the reaction is completed, first cool to room temperature, and then distill under reduced pressure to obtain intermediate 4; the dosage ratio of intermediate 3, 3-aminopropyltriethoxysilane, triethylamine, and dimethyl sulfoxide is 22 g:9 mL:5.6 mL:200 mL;

[0025] Triethylamine is used as an acid-binding agent, and the molar ratio of intermediate 3 to 3-aminopropyltriethoxysilane is controlled to be 1:1.05 - 1.1. The -Cl of intermediate 3 undergoes a substitution reaction with the -NH2 of 3-aminopropyltriethoxysilane, and the reaction process is as follows:

[0026]

[0027] S5. Take dry aluminum hydroxide, magnesium hydroxide, titanium dioxide, and calcium carbonate and disperse them in a mixed solution of absolute ethanol and water. Add acetic acid to adjust the pH to 4. After stirring evenly, transfer it to a three-necked flask. Disperse Intermediate 4 in dimethyl sulfoxide, stir for 15 min, and then transfer it to the above three-necked flask. After the transfer is complete, raise the temperature to 65 °C and react for 1 h. After the reaction is completed, cool it to room temperature, centrifuge, take the precipitate, ultrasonically vibrate it in absolute ethanol for 0.5 h, and finally dry it at 80 °C for 12 h to obtain the additive. The dosage ratio of aluminum hydroxide, magnesium hydroxide, titanium dioxide, calcium carbonate to Intermediate 4 is 15 g: 15 g: 20 g: 10 g: 3 g.

[0028] The silanol groups generated after the hydrolysis of Intermediate 4 will chemically react with the hydroxyl groups on the surfaces of aluminum hydroxide, magnesium hydroxide, titanium dioxide, and calcium carbonate to form stable chemical bonds. The formation of the new chemical bonds reduces the surface energy of aluminum hydroxide, magnesium hydroxide, titanium dioxide, and calcium carbonate, making them in a stable state. At the same time, the organic medium on the particle surface increases the steric resistance to aggregation between the particles. Thus, the dispersibility of aluminum hydroxide, magnesium hydroxide, titanium dioxide, and calcium carbonate is improved, that is, the dispersion degree of the additive in the modified adhesive is greatly increased.

[0029] Aluminum hydroxide and magnesium hydroxide in the additive can endow the modified adhesive with excellent flame retardancy and smoke suppression effects; titanium dioxide in the additive can endow the modified adhesive with excellent ultraviolet resistance; the fine structure and porous structure characteristics of calcium carbonate in the additive can increase the contact area between the modified adhesive and the adhered material, thereby enhancing the bonding strength of the modified adhesive. At the same time, calcium carbonate can also improve the mechanical properties and heat resistance of the modified adhesive.

[0030] The additive also contains triazine structures, hindered phenol structures, and hindered amine structures. Due to the chelate ring formed by intramolecular hydrogen bonds in the triazine structure, after absorbing ultraviolet light, the intramolecular hydrogen bonds are broken, forming an unstable high-energy ionic compound, and then releasing excess energy to restore the original low-energy stable state. Thus, it strongly absorbs ultraviolet light in the range of 280 nm - 400 nm. In addition, the triazine structure has advantages such as high efficiency, high temperature resistance, light color, and good compatibility. The hindered phenol structure can capture the free radicals generated during the oxidation process of the polymer, interrupt the free radical chain reaction, and thus prevent further oxidative degradation, improving the antioxidant ability of the modified adhesive. The hindered amine structure realizes the light protection effect, exerts the light stabilization effect, and achieves the purpose of preventing oxidation through actions such as capturing free radicals, decomposing hydroperoxides, quenching singlet oxygen, and capturing heavy metal ions. The hindered amine structure in the additive is used in combination with the hindered phenol structure and the triazine structure, showing excellent synergistic effects.

[0031] The additive contains amino groups, which can chemically react with the epoxy groups in the epoxy resin and the isocyanate groups in the curing agent. As a result, the additive can stably exist in the modified adhesive and play its role fully and stably. The organic anti-aging structures (hindered amine structure, hindered phenol structure, triazine structure) and inorganic anti-aging components (titanium dioxide) in the additive work synergistically, making the modified adhesive with the additive have excellent thermal anti-aging performance and ultraviolet anti-aging performance. It is not easy to age under the influence of factors such as heat and light, and can ensure the viscosity of the modified adhesive. The organic flame-retardant elements nitrogen and silicon (halogen-free flame-retardant elements) and inorganic flame-retardant components (aluminum hydroxide, magnesium hydroxide) in the additive work synergistically, making the modified adhesive with the additive have a highly efficient, safe and long-lasting flame-retardant and smoke-suppressing effect. The calcium carbonate in the additive makes the modified adhesive with the additive have excellent mechanical properties and heat resistance.

[0032] Further, the curing agent is one or more of toluene diisocyanate, 2,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate.

[0033] Further, the solvent is one or more of toluene, chloroform, dimethyl sulfoxide, and tetrahydrofuran.

[0034] Further, the upper adhesive layer is cured from an acrylate adhesive and has a thickness of 25 - 30 μm.

[0035] Further, the material of the release film layer is polyethylene terephthalate film.

[0036] Further, the thickness of the release film layer is 25 - 30 μm.

[0037] A preparation method of a multi-layer composite tape includes the following steps:

[0038] Corona one side of the middle base film layer, then coat the modified adhesive, cure at 60 - 120 °C to form the lower adhesive layer, and then laminate the bottom base film layer on one side of the lower adhesive layer; coat the acrylate adhesive on the release surface of the release film layer, cure at 60 - 120 °C to form the upper adhesive layer, and then laminate the upper adhesive layer on the other side of the middle base film layer and wind it up to obtain the multi-layer composite tape.

[0039] Advantages of the present invention: The additive of the present invention contains calcium carbonate, organic anti-aging structures (hindered amine structure, hindered phenol structure, triazine structure), inorganic anti-aging components (titanium dioxide), organic flame retardant elements nitrogen and silicon (halogen-free flame retardant elements), and inorganic flame retardant components (aluminum hydroxide, magnesium hydroxide). In addition, there is a chemical interaction between the additive and the epoxy resin and curing agent. Therefore, the additive can stably exist in the modified adhesive, maximizing its own function. Furthermore, the modified adhesive and multi-layer composite tape of the present invention have excellent and stable anti-thermal aging performance and anti-ultraviolet aging performance, efficient, safe and long-lasting flame retardant and smoke suppression effects, as well as excellent mechanical properties and heat resistance. Specific embodiments

[0040] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0041] Example 1, preparation of the additive, the specific steps are as follows:

[0042] S1. Nitrogen was blown into a 500 mL dry three-necked flask for 30 min to remove the air and moisture in the flask. Subsequently, 25 g of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 0.6 g of EDC, 0.4 g of NHS, and 200 mL of chloroform were added. After stirring and dissolving, 20 mL of 2,2,6,6-tetramethylpiperidinamine was slowly added, and then the temperature was raised to 65 °C and the reaction was kept for 6.5 h. After the reaction was completed, it was first cooled to room temperature, distilled under reduced pressure, and purified by column chromatography (the eluent was a mixed solvent of chloroform and ether, and the volume ratio of chloroform to ether was 9:1), and then distilled under reduced pressure to obtain intermediate 1;

[0043] S2. Nitrogen was blown into a 500 mL dry three-necked flask for 30 min to remove the air and moisture in the flask. Subsequently, 27 g of intermediate 1, 11.7 mL of triethylamine, and 240 mL of chloroform were added. After stirring and dissolving, 13.8 g of cyanuric chloride was slowly added. After the addition was completed, the reaction was stirred at room temperature for 3 h. After the reaction was completed, it was first cooled to room temperature, then distilled under reduced pressure, and purified by column chromatography (the eluent was a mixed solvent of benzene and ether, and the volume ratio of benzene to ether was 6:4). Finally, it was distilled under reduced pressure to obtain intermediate 2;

[0044] S3. Purge a 500 mL dry brown three-necked flask with nitrogen for 30 min to expel the air and moisture inside the flask. Subsequently, add 4.9 mL of resorcinol, 7.8 g of anhydrous aluminum trichloride, and 200 mL of dimethyl sulfoxide. After stirring evenly, slowly add 26 g of intermediate 2. Then, stir and heat up to 115 °C and react at 115 °C for 12 h. After the reaction is completed, slowly pour the reaction mixture into ice water to precipitate a solid. Filter it, and then recrystallize it with an 80% methanol aqueous solution to obtain intermediate 3;

[0045] S4. Purge a 500 mL dry three-necked flask with nitrogen for 30 min to expel the air and moisture inside the flask. Subsequently, add 22 g of intermediate 3, 5.6 mL of triethylamine, and 200 mL of dimethyl sulfoxide. After stirring to dissolve, slowly add 9 mL of 3-aminopropyltriethoxysilane. After adding, heat up to 50 °C and stir to react for 3 h. After the reaction is completed, first cool to room temperature, and then perform vacuum distillation to obtain intermediate 4;

[0046] S5. Disperse 15 g of dry aluminum hydroxide, 15 g of magnesium hydroxide, 20 g of titanium dioxide, and 10 g of calcium carbonate in a mixed solution of 180 mL of absolute ethanol and 100 mL of water. Add acetic acid to adjust the pH to 4. After stirring evenly, transfer it to a three-necked flask; Disperse 3 g of intermediate 4 in 25 mL of dimethyl sulfoxide, stir for 15 min, and then transfer it to the above three-necked flask. After transferring, heat up to 65 °C and react for 1 h. After the reaction is completed, cool to room temperature, centrifuge, take the precipitate, ultrasonically vibrate it in absolute ethanol for 0.5 h, and finally dry it at 80 °C for 12 h to obtain the additive.

[0047] Example 2. To prepare the modified adhesive, the specific steps are as follows:

[0048] Stir 50 parts of polybutylene terephthalate, 30 parts of bisphenol A epoxy resin, 10 parts of the additive prepared in Example 1, and 20 parts of toluene by weight. Finally, add 5 parts of toluene diisocyanate, stir well and filter to obtain the modified adhesive.

[0049] Example 3. To prepare the modified adhesive, the specific steps are as follows:

[0050] Stir 55 parts of polyethylene terephthalate, 36 parts of bisphenol A epoxy resin, 13 parts of the additive prepared in Example 1, 18 parts of chloroform, and 10 parts of tetrahydrofuran by weight. Finally, add 6 parts of 2,4-diphenylmethane diisocyanate and 6 parts of hexamethylene diisocyanate, stir well and filter to obtain the modified adhesive.

[0051] Example 4. To prepare the modified adhesive, the specific steps are as follows:

[0052] Mix 60 parts of polyethylene terephthalate, 40 parts of bisphenol A epoxy resin, 15 parts of the auxiliary agent prepared in Example 1, and 30 parts of dimethyl sulfoxide by weight, stir well, and finally add 9 parts of isophorone diisocyanate and 6 parts of xylylene diisocyanate, stir well and filter to obtain the modified adhesive.

[0053] Example 5, prepare a modified adhesive, and the specific steps are as follows:

[0054] Keep the remaining steps unchanged, and only replace the auxiliary agent in Example 2 with 2.38 parts of aluminum hydroxide, 2.38 parts of magnesium hydroxide, 3.17 parts of titanium dioxide, 1.59 parts of calcium carbonate, 0.16 part of antioxidant 1010, 0.16 part of light stabilizer 944, and 0.16 part of ultraviolet absorber UV-531 to obtain the modified adhesive.

[0055] Example 6, prepare a modified adhesive, and the specific steps are as follows:

[0056] Keep the remaining steps unchanged, and only remove the auxiliary agent in Example 2 to obtain the modified adhesive.

[0057] Example 7, prepare a multi-layer composite tape, and the specific steps are as follows:

[0058] Corona one side of the middle base film layer (polypropylene film, thickness 20 μm), then coat the modified adhesive prepared in Example 2, cure at 60 °C to form a lower adhesive layer (thickness 20 μm), and then laminate the bottom base film layer (polypropylene film, thickness 20 μm) on one side of the lower adhesive layer; coat an acrylate adhesive on the release surface of the release film layer (polyethylene terephthalate film, thickness 25 μm), cure at 60 °C to form an upper adhesive layer (thickness 25 μm), and then laminate the upper adhesive layer on the other side of the middle base film layer (polypropylene film, thickness 20 μm) and wind it up to obtain the multi-layer composite tape.

[0059] Example 8, prepare a multi-layer composite tape, and the specific steps are as follows:

[0060] Corona one side of the middle base film layer (polyimide film, thickness 50 μm), then coat the modified adhesive prepared in Example 3, cure at 120 °C to form a lower adhesive layer (thickness 25 μm), and then laminate the bottom base film layer (polyimide film, thickness 50 μm) on one side of the lower adhesive layer; coat an acrylate adhesive on the release surface of the release film layer (polyethylene terephthalate film, thickness 30 μm), cure at 120 °C to form an upper adhesive layer (thickness 30 μm), and then laminate the upper adhesive layer on the other side of the middle base film layer (polyimide film, thickness 50 μm) and wind it up to obtain the multi-layer composite tape.

[0061] Example 9, prepare a multi-layer composite tape, and the specific steps are as follows:

[0062] One side of the middle base film layer (polyethylene terephthalate film with a thickness of 30 μm) was corona treated, and then the modified adhesive prepared in Example 4 was coated and cured at 80°C to form a lower adhesive layer (with a thickness of 24 μm). Then, a bottom base film layer (polyethylene terephthalate film with a thickness of 30 μm) was laminated on one side of the lower adhesive layer; on the release surface of the release film layer (polyethylene terephthalate film with a thickness of 28 μm), an acrylate adhesive was coated and cured at 80°C to form an upper adhesive layer (with a thickness of 28 μm). Then, the upper adhesive layer was laminated on the other side of the middle base film layer (polyethylene terephthalate film with a thickness of 30 μm), and the product was wound up to obtain a multi-layer composite tape.

[0063] Comparative Example 1, preparing a multi-layer composite tape, the specific steps are as follows:

[0064] The remaining steps remained unchanged, and only the modified adhesive in Example 7 was replaced with the modified adhesive prepared in Example 5 to prepare a multi-layer composite tape.

[0065] Comparative Example 2, preparing a multi-layer composite tape, the specific steps are as follows:

[0066] The remaining steps remained unchanged, and only the modified adhesive in Example 7 was replaced with the modified adhesive prepared in Example 6 to prepare a multi-layer composite tape.

[0067] Performance testing

[0068] (1) Heat aging performance test

[0069] The multi-layer composite tape products prepared in Examples 7-9 and Comparative Examples 1-2 were stretched by 200% and semi-lap wound around the connector assembly, and then placed in a room temperature environment for 7 days (moisture curing time). After that, they were placed in a 160°C air circulation oven for one week, and then taken out to observe the surface cracking phenomenon and the change in the adhesiveness of the adhesive layer.

[0070] (2) UV aging performance test

[0071] The multi-layer composite tape products prepared in Examples 7-9 and Comparative Examples 1-2 were stretched by 200% and semi-lap wound around the connector assembly, and then under the conditions of room temperature, a vertical irradiation distance of 20 cm, and a 30 W UV lamp, they were subjected to UV aging for one week. After that, they were taken out to observe the surface cracking phenomenon and the change in the adhesiveness of the adhesive layer.

[0072] (3) Flame retardancy test

[0073] The oxygen index test was carried out with reference to GB / T 2406-2009, and the vertical burning rating test was carried out with reference to UL94-2013.

[0074] The test results of all items are shown in the following table:

[0075]

[0076] "-" indicates no combustion rating.

[0077] In the description of the specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean 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.

[0078] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the specific embodiments described or use similar ways to substitute, as long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. A multi-layer composite tape, characterized in that, It is composed of a bottom base film layer, a lower adhesive layer, a middle base film layer, an upper adhesive layer and a release film layer; the lower adhesive layer is cured from a modified adhesive, and the thickness is 20 - 25μm; the modified adhesive is prepared by the following steps: fully stir 50 - 60 parts by weight of polyester resin, 30 - 40 parts by weight of epoxy resin, 10 - 15 parts by weight of additives and 20 - 30 parts by weight of solvent, and finally add 5 - 15 parts by weight of curing agent, fully stir and filter to obtain the modified adhesive; The additives are prepared by the following steps: S1. After blowing nitrogen into the flask, add 3,5 - di - tert - butyl - 4 - hydroxybenzoic acid, EDC, NHS and chloroform, stir and slowly add 2,2,6,6 - tetramethylpiperidineamine, heat up to 65°C and react for 6.5h, cool, distill under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain intermediate 1; S2. After blowing nitrogen into the flask, add intermediate 1, triethylamine and chloroform, stir and add cyanuric chloride, react at room temperature for 3h, cool, distill under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain intermediate 2; S3. After blowing nitrogen into the flask, add resorcinol, anhydrous aluminum trichloride and dimethyl sulfoxide, stir and add intermediate 2, heat up to 115°C and react for 12h, after the reaction is completed, pour the reaction mixture into ice water, precipitate solids, filter, and recrystallize to obtain intermediate 3; S4. After blowing nitrogen into the flask, add intermediate 3, triethylamine and dimethyl sulfoxide, stir and add 3 - aminopropyltriethoxysilane, heat up to 50°C and react for 3h, cool, distill under reduced pressure to obtain intermediate 4; S5. Take aluminum hydroxide, magnesium hydroxide, titanium dioxide, calcium carbonate and disperse them in a mixed solution of absolute ethanol and water, adjust the pH to 4 with acetic acid and transfer it to a flask; disperse intermediate 4 in dimethyl sulfoxide, stir and transfer it to the above - mentioned flask, heat up to 65°C and react for 1h, cool, centrifuge, take the precipitate and ultrasonically vibrate it in absolute ethanol for 0.5h, and dry to obtain the additives.

2. The multi-layer composite tape according to claim 1, characterized in that, The dosage ratios of 3,5 - di - tert - butyl - 4 - hydroxycinnamic acid, 2,2,6,6 - tetramethylpiperidineamine, EDC, NHS and chloroform in step S1 are 25g:20mL:0.6g:0.4g:200mL; the dosage ratios of intermediate 1, cyanuric chloride, triethylamine and chloroform in step S2 are 27g:13.8g:11.7mL:240mL; the dosage ratios of intermediate 2, resorcinol, anhydrous aluminum trichloride and dimethyl sulfoxide in step S3 are 26g:4.9mL:7.8g:200mL; the dosage ratios of intermediate 3, 3 - aminopropyltriethoxysilane, triethylamine and dimethyl sulfoxide in step S4 are 22g:9mL:5.6mL:200mL; the dosage ratios of aluminum hydroxide, magnesium hydroxide, titanium dioxide, calcium carbonate and intermediate 4 in step S5 are 15g:15g:20g:10g:3g.

3. The multi-layer composite tape according to claim 1, characterized in that, The materials of the bottom base film layer and the middle base film layer are one or more of polyethylene terephthalate film, polyimide film, polyethylene naphthalate film, polypropylene film, polyethylene film, and the thickness of the bottom base film layer and the middle base film layer is 20 - 50μm.

4. The multi-layer composite tape according to claim 1, wherein, The polyester resin is one or two of polyethylene terephthalate and polybutylene terephthalate.

5. A multi-layer composite tape according to claim 1, characterized in that, The epoxy resin is bisphenol A epoxy resin.

6. The multi-layer composite tape according to claim 1, wherein The curing agent is one or several of toluene diisocyanate, 2,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate.

7. The multi-layer composite tape according to claim 1, wherein The solvent is one or several of toluene, chloroform, dimethyl sulfoxide, and tetrahydrofuran.

8. The multi-layer composite tape according to claim 1, characterized in that, The upper adhesive layer is cured from an acrylate adhesive and has a thickness of 25 - 30 μm.

9. The multi-layer composite tape according to claim 1, characterized in that, The material of the release film layer is a polyethylene terephthalate film, and the thickness of the release film layer is 25 - 30 μm.

10. The preparation method of a multi-layer composite tape according to claim 1, characterized in that, It includes the following steps: Corona one side of the middle base film layer, then coat a modified adhesive, cure at 60 - 120 °C to form a lower adhesive layer, and then laminate the bottom base film layer on one side of the lower adhesive layer; coat an acrylate adhesive on the release surface of the release film layer, cure at 60 - 120 °C to form an upper adhesive layer, and then laminate the upper adhesive layer with the other side of the middle base film layer and wind it up to obtain a multi-layer composite tape.

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