A high temperature resistant protective film and preparation method thereof

Abstract

The present invention discloses a high temperature resistant protective adhesive film, comprising the following raw materials in parts by weight: 20-30 parts of epoxy phenolic resin, 55-65 parts of amino-terminated hyperbranched polyimide, 8-12 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 3-5 parts of benzidine disulfonic acid, and 0.5-0.9 parts of anti-aging agent. The present invention also discloses a method for preparing the high temperature resistant protective adhesive film. The high temperature resistant protective adhesive film disclosed by the present invention has good high temperature resistance, sufficient mechanical properties and peel strength stability, good aging resistance, flame retardancy and environmental protection, high peel strength and long service life.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, and in particular to a high-temperature resistant protective adhesive film and a preparation method thereof. Background Art

[0002] Protective film is a film-like structural adhesive that acts as a fixation, shielding and protection for high temperature treatment and acid-base treatment or other special functions in the circuit board manufacturing process. This type of adhesive has the advantages of low volatility, uniform and controllable adhesive layer thickness, high strength, high toughness, high durability and high reliability, and is widely used in the protection of circuit board gold fingers, electroplating insulation or the opening process of soft and hard combination boards, aerospace and other fields.

[0003] Existing protective films have more or less the following defects: poor high temperature resistance, insufficient mechanical properties and peel strength stability, and the aging resistance, flame retardancy and environmental protection need to be further improved. To have an appropriate bonding strength, a certain thickness is required, and therefore, it is not suitable for the thinning process requirements of circuit boards.

[0004] In order to solve the above problems, Chinese invention patent application CN111139003A discloses a high-temperature resistant adhesive and a high-temperature resistant protective film formed by coating it, whose structure includes a high-temperature resistant plastic film layer (or substrate film layer), a high-temperature resistant adhesive layer (or glue layer) and a release film layer from top to bottom. The high-temperature resistant protective film of the invention can be used to protect the contact surfaces of different materials of circuit boards, such as raw copper, or the surface after roughening treatment such as brown copper, and other insulating materials such as polyimide films and insulating prepreg materials. It has high adhesion. Moreover, in the subsequent process requirements of the circuit board, such as high temperature conditions or acid-base processes, it still has good peeling strength and peeling retention. At the same time, after the process is completed, it can be easily peeled off from the surfaces of different materials without residual glue. However, its flame retardancy, aging resistance and mechanical properties still need to be further improved.

[0005] It can be seen that the art still needs a high-temperature resistant protective film and a preparation method thereof with good high-temperature resistance, sufficient mechanical properties and peel strength stability, good aging resistance, flame retardancy and environmental protection, high peel strength and long service life. Summary of the invention

[0006] The main purpose of the present invention is to provide a high-temperature resistant protective film with good high-temperature resistance, sufficient mechanical properties and peel strength stability, good aging resistance, flame retardancy and environmental protection, high peel strength and long service life, and a preparation method thereof.

[0007] To achieve the above purpose, the present invention provides a high temperature resistant protective adhesive film, characterized in that it is prepared from the following raw materials in parts by weight: 20-30 parts of epoxy phenolic resin, 55-65 parts of amino-terminated hyperbranched polyimide, 8-12 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 3-5 parts of benzidine disulfonic acid, and 0.5-0.9 parts of anti-aging agent.

[0008] Preferably, the antioxidant is at least one of antioxidant 2246-S, antioxidant 2246, antioxidant 1010, and antioxidant 1076.

[0009] Preferably, the preparation method based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer comprises the following steps: adding 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane to an organic solvent, stirring and reacting at 80-90°C for 3-5 hours, then rotary evaporating to remove the solvent, washing the product with ether 3-6 times, and finally rotary evaporating to remove the ether to obtain a 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer.

[0010] Preferably, the molar ratio of the 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and the organic solvent is 1:1:(6-10).

[0011] Preferably, the organic solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide and N-methylpyrrolidone.

[0012] Preferably, the epoxy phenolic resin is prepared according to the method of Example 1 in Chinese invention patent CN104693391B.

[0013] Preferably, there is no special requirement for the source of the amino-terminated hyperbranched polyimide. In one embodiment of the present invention, the amino-terminated hyperbranched polyimide is prepared according to the method of Example 1 in Chinese invention patent CN107789677B.

[0014] Another object of the present invention is to provide a method for preparing the high-temperature resistant protective film, which is characterized in that it includes the following steps: mixing the raw materials in parts by weight to form a mixed material, then adding the mixed material to a high-boiling point solvent, stirring evenly, and obtaining a flat film by a solvent casting method, then drying it to constant weight at 90-100°C, then soaking it in water for 1-2 hours, and then taking it out and placing it in a vacuum drying oven at 85-95°C to dry it to constant weight to obtain a high-temperature resistant protective film.

[0015] Preferably, the mass ratio of the mixed material to the high boiling point solvent is (3-8):100.

[0016] Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0017] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0018] (1) The method for preparing the high temperature resistant protective film disclosed in the present invention is prepared by a solvent casting method, which reduces energy consumption, does not require special equipment, has low capital investment, simple process, convenient operation, high preparation efficiency, and is suitable for continuous large-scale production.

[0019] (2) The high temperature resistant protective film disclosed in the present invention is prepared from the following raw materials in parts by weight: 20-30 parts of epoxy phenolic resin, 55-65 parts of amino-terminated hyperbranched polyimide, 8-12 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 3-5 parts of benzidine disulfonic acid, and 0.5-0.9 parts of anti-aging agent. The raw materials cooperate with each other to make the protective film have good high temperature resistance, sufficient mechanical properties and peel strength stability, good aging resistance, flame retardancy and environmental protection, high peel strength and long service life.

[0020] (3) The high temperature resistant protective film disclosed by the present invention, the epoxy group on the epoxy phenolic resin can undergo an epoxy ring-opening reaction with the amino group on the amino-terminated hyperbranched polyimide and the benzidine disulfonic acid, and the sulfonic acid group on the benzidine disulfonic acid can undergo an ion exchange reaction with the quaternary ammonium salt based on the 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer to form an interpenetrating network structure, which effectively improves the high temperature resistance, mechanical properties and aging resistance of the film and effectively prolongs its service life. The epoxy ring-opening reaction produces more hydroxyl groups in the molecular structure of the film, which can enhance the peel strength of the film.

[0021] (4) The high temperature resistant protective film disclosed in the present invention, through the interaction and mutual influence between various raw materials, simultaneously introduces phenyl-1,3,4-oxadiazole, siloxane, polyimide, biphenyl, quaternary ammonium salt, phenolic acid, epoxy, hyperbranched, and hydroxyl structures into the film molecular structure. Under the multiple effects of electronic effect, steric effect and conjugation effect, these structures effectively improve the high temperature resistance and aging resistance, and at the same time improve the flame retardant property and bonding property; through ion exchange, chlorine is finally volatilized and removed in the form of hydrogen chloride, and the chlorine content remaining in the film is small, which effectively avoids the release of harmful smoke due to the presence of chlorine in the event of a fire, thereby improving the environmental protection and safety of the film. DETAILED DESCRIPTION

[0022] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations.

[0023] The epoxy phenolic resin in each embodiment of the present invention is prepared according to the method of Example 1 in Chinese invention patent CN104693391B; the amino-terminated hyperbranched polyimide is prepared according to the method of Example 1 in Chinese invention patent CN107789677B.

[0024] Example 1

[0025] A high-temperature resistant protective film is prepared from the following raw materials in parts by weight: 20 parts of epoxy phenolic resin, 55 parts of amino-terminated hyperbranched polyimide, 8 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 3 parts of benzidine disulfonic acid, and 0.5 parts of an anti-aging agent; the anti-aging agent is anti-aging agent 2246-S.

[0026] The preparation method based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer comprises the following steps: adding 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane to an organic solvent, stirring and reacting at 80°C for 3 hours, then removing the solvent by rotary evaporation, and evaporating with ethyl acetate. The product was washed with ether for 3 times, and the ether was finally removed by rotary evaporation to obtain a 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer; the molar ratio of the 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and the organic solvent was 1:1:6; and the organic solvent was dimethyl sulfoxide.

[0027] A method for preparing the high-temperature resistant protective adhesive film comprises the following steps: uniformly mixing the raw materials by weight to form a mixed material, then adding the mixed material to a high-boiling point solvent, stirring evenly, obtaining a flat film by a solvent casting method, then drying at 90°C to constant weight, then soaking in water for 1 hour, then taking out and placing in a vacuum drying oven at 85°C to dry to constant weight to obtain a high-temperature resistant protective adhesive film; the mass ratio of the mixed material to the high-boiling point solvent is 3:100; and the high-boiling point solvent is dimethyl sulfoxide.

[0028] Example 2

[0029] A high-temperature resistant protective adhesive film is prepared from the following raw materials in parts by weight: 23 parts of epoxy phenolic resin, 57 parts of amino-terminated hyperbranched polyimide, 9 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 3.5 parts of benzidine disulfonic acid, and 0.6 parts of an antioxidant; the antioxidant is antioxidant 2246.

[0030] The preparation method based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer comprises the following steps: adding 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane to an organic solvent, stirring and reacting at 83° C. for 3.5 hours, then removing the solvent by rotary evaporation, and washing with ether. The product is washed four times, and finally the ether is removed by rotary evaporation to obtain a 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer; the molar ratio of the 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and the organic solvent is 1:1:7; the organic solvent is N,N-dimethylformamide.

[0031] A method for preparing the high-temperature resistant protective adhesive film comprises the following steps: uniformly mixing the raw materials by weight to form a mixed material, then adding the mixed material to a high-boiling point solvent, stirring evenly, obtaining a flat film by a solvent casting method, then drying at 93°C to constant weight, then soaking in water for 1.2 hours, then taking out and placing in a vacuum drying oven at 87°C to dry to constant weight to obtain a high-temperature resistant protective adhesive film; the mass ratio of the mixed material to the high-boiling point solvent is 4:100; and the high-boiling point solvent is N,N-dimethylformamide.

[0032] Example 3

[0033] A high-temperature resistant protective adhesive film is prepared from the following raw materials in parts by weight: 25 parts of epoxy phenolic resin, 60 parts of amino-terminated hyperbranched polyimide, 10 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 4 parts of benzidine disulfonic acid, and 0.7 parts of an anti-aging agent; the anti-aging agent is anti-aging agent 1010.

[0034] The preparation method based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer comprises the following steps: adding 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane to an organic solvent, stirring and reacting at 85° C. for 4 hours, then removing the solvent by rotary evaporation, and washing with ether. The product is washed 5 times, and finally the ether is removed by rotary evaporation to obtain a 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer; the molar ratio of the 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and the organic solvent is 1:1:8; the organic solvent is N-methylpyrrolidone.

[0035] A method for preparing the high-temperature resistant protective adhesive film comprises the following steps: uniformly mixing the raw materials by weight to form a mixed material, then adding the mixed material to a high-boiling point solvent, stirring evenly, obtaining a flat film by a solvent casting method, then drying at 95°C to constant weight, then soaking in water for 1.5 hours, then taking out and placing in a vacuum drying oven at 90°C to dry to constant weight to obtain a high-temperature resistant protective adhesive film; the mass ratio of the mixed material to the high-boiling point solvent is 5.5:100; and the high-boiling point solvent is N,N-dimethylacetamide.

[0036] Example 4

[0037] A high-temperature resistant protective adhesive film is prepared from the following raw materials in parts by weight: 28 parts of epoxy phenolic resin, 63 parts of amino-terminated hyperbranched polyimide, 11 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 4.5 parts of benzidine disulfonic acid, and 0.8 parts of an antioxidant; the antioxidant is a mixture of antioxidant 2246-S, antioxidant 2246, antioxidant 1010, and antioxidant 1076 in a mass ratio of 1:2:2:1.

[0038] The preparation method based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer comprises the following steps: adding 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane to an organic solvent, stirring and reacting at 88° C. for 4.5 hours, then rotary distilling to remove the solvent, washing the product with ether for 6 times, and finally rotary distilling to remove the ether to obtain Based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer; the molar ratio of the 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and organic solvent is 1:1:9.5; the organic solvent is a mixture of dimethyl sulfoxide, N,N-dimethylformamide and N-methylpyrrolidone in a mass ratio of 2:3:1.

[0039] A method for preparing the high-temperature resistant protective adhesive film comprises the following steps: uniformly mixing the raw materials by weight to form a mixed material, then adding the mixed material to a high-boiling point solvent, stirring evenly, obtaining a flat film by a solvent casting method, then drying at 98°C to constant weight, then soaking in water for 1.8 hours, then taking out and placing in a vacuum drying oven at 93°C to dry to constant weight to obtain a high-temperature resistant protective adhesive film; the mass ratio of the mixed material to the high-boiling point solvent is 7:100; the high-boiling point solvent is a mixture of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone in a mass ratio of 1:3:2:2.

[0040] Example 5

[0041] A high-temperature resistant protective adhesive film is prepared from the following raw materials in parts by weight: 30 parts of epoxy phenolic resin, 65 parts of amino-terminated hyperbranched polyimide, 12 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 5 parts of benzidine disulfonic acid, and 0.9 parts of an anti-aging agent; the anti-aging agent is anti-aging agent 1076.

[0042] The preparation method based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer comprises the following steps: adding 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane to an organic solvent, stirring and reacting at 90° C. for 5 hours, then removing the solvent by rotary evaporation, and purging with ether. The product is washed 6 times, and finally the ether is removed by rotary evaporation to obtain a polymer based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane; the molar ratio of the 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and the organic solvent is 1:1:10; and the organic solvent is dimethyl sulfoxide.

[0043] A method for preparing the high-temperature resistant protective adhesive film comprises the following steps: uniformly mixing the raw materials by weight to form a mixed material, then adding the mixed material to a high-boiling point solvent, stirring evenly, obtaining a flat film by a solvent casting method, then drying to constant weight at 100°C, then soaking in water for 2 hours, then taking out and placing in a vacuum drying oven at 95°C to dry to constant weight to obtain a high-temperature resistant protective adhesive film; the mass ratio of the mixed material to the high-boiling point solvent is 8:100; and the high-boiling point solvent is N-methylpyrrolidone.

[0044] Comparative Example 1

[0045] The present invention provides a high temperature resistant protective adhesive film, the formula and preparation method of which are similar to those of Example 1, except that no 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer is added.

[0046] Comparative Example 2

[0047] The present invention provides a high temperature resistant protective adhesive film, the formula and preparation method of which are similar to those of Example 1, except that no benzidine disulfonic acid is added.

[0048] In order to further illustrate the beneficial technical effects of the high temperature resistant protective films made by various embodiments of the present invention, relevant performance tests were conducted on the high temperature resistant protective films made by Examples 1-5 and Comparative Examples 1-2. The test results are shown in Table 1. The test method is as follows: the average peel strength of the honeycomb drum is tested according to GB / T-1457-2005 and tested at 25°C; the honeycomb drum is composed of a metal honeycomb core that meets the BMS4-40-N specification and a 0.5 mm thick 2024T3 aluminum panel; the tensile shear strength at 25°C is tested according to GB / T 7124-1986, and the high temperature tensile shear strength is tested according to GJB444-1988; the tensile shear specimen is an aluminum alloy LY12CZ specimen that has been chemically oxidized; wherein the heat aging experiment is based on the retention rate of the tensile shear strength of each product after being placed at 250°C for 1000 hours and then cooled to 25°C, and compared with the initial value of the tensile shear strength at 25°C, and the larger the value, the better the heat aging resistance.

[0049] Table 1

[0050] project Average roller peel strength 25℃ shear strength 250℃ shear strength Heat aging resistance unit N mm / mm MPa MPa % Example 1 98.3 32.5 21.9 90.5 Example 2 99.6 33.1 23.7 91.2 Example 3 102.1 34.0 25.2 91.7 Example 4 103.6 35.1 27.0 92.6 Example 5 105.0 35.8 28.7 93.2 Comparative Example 1 89.6 25.1 12.5 78.3 Comparative Example 2 92.2 26.7 15.3 81.6

[0051] As can be seen from Table 1, the high temperature resistant protective film disclosed in the embodiment of the present invention has better high temperature resistance and heat aging resistance than the comparative example product, and has high peel strength, which is the result of the synergistic effect of the components; the addition of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer and benzidine disulfonic acid is beneficial to improving the above properties.

[0052] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention. The scope of protection claimed by the present invention is defined by the attached claims and their equivalents.

Claims

1. A high temperature resistant protective film, characterized in that: The invention is prepared from the following raw materials in parts by weight: 20-30 parts of epoxy phenolic resin, 55-65 parts of amino-terminated hyperbranched polyimide, 8-12 parts of 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer, 3-5 parts of benzidine disulfonic acid, and 0.5-0.9 parts of anti-aging agent; The preparation method based on 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer comprises the following steps: adding 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane to an organic solvent, stirring and reacting at 80-90° C. for 3-5 hours, and then removing the solvent by rotary evaporation. The invention relates to a method for preparing a 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer. The method comprises the steps of: adding a 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole to a 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer; and washing the product with ether for 3-6 times. Finally, the ether is removed by rotary evaporation to obtain a 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole / 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane polymer. The molar ratio of the 2,5-bis(diethylamino)phenyl-1,3,4-oxadiazole, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane and the organic solvent is 1:1:(6-10).

2. The high temperature resistant protective film according to claim 1, characterized in that: The antioxidant is at least one of antioxidant 2246-S, antioxidant 2246, antioxidant 1010, and antioxidant 1076.

3. The high temperature resistant protective film according to claim 1, characterized in that: The organic solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide and N-methylpyrrolidone.

4. A method for preparing a high temperature resistant protective film according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: mixing the raw materials uniformly by weight to form a mixed material, then adding the mixed material into a high boiling point solvent, stirring uniformly, obtaining a flat film by a solvent casting method, then drying at 90-100° C. to constant weight, then soaking in water for 1-2 hours, taking out and placing in a vacuum drying oven at 85-95° C. to dry to constant weight, and obtaining a high temperature resistant protective adhesive film.

5. The method for preparing a high temperature resistant protective film according to claim 4, characterized in that: The mass ratio of the mixed material to the high boiling point solvent is (3-8):100; the high boiling point solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.