Preparation of high-temperature-resistant photosensitive polyimide resin and transparent film as well as surface selective metallization method and application of high-temperature-resistant photosensitive polyimide resin and transparent film

Abstract

The invention relates to the technical field of high polymer materials, in particular to preparation of high-temperature-resistant photosensitive polyimide resin and a transparent film, a surface selective metallization method of the high-temperature-resistant photosensitive polyimide resin and the transparent film and application of the high-temperature-resistant photosensitive polyimide resin and the transparent film. A polyimide film prepared from the resin has good mechanical properties, dissolvability, optical permeability, thermal stability and photosensitivity, and has the characteristic of surface selective metallization; the film can also reduce precursor metal ions of a chemical plating catalyst under the irradiation of ultraviolet light or sunlight, selective metallization of the polyimide surface is achieved, the surface roughness of a metal coating is low, the resistivity is low, and meanwhile the adhesive force between the metal coating and photosensitive polyimide is high; therefore, the composite material has wide application prospects in the fields of substrate materials of flexible electronic devices, base materials of composite current collectors in new energy soft package batteries, supercapacitors, flexible display materials and the like.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a preparation method and application of a high-temperature resistant photosensitive polyimide resin and a transparent film, and a surface selective metallization method. Background Art

[0002] Polyimide resin is an insulating material with good heat resistance, high mechanical strength and excellent comprehensive performance. Its film is widely used in flexible electronics, electrical engineering, aerospace and other industries. Polyimide surface metallization is one of the important ways to functionally modify polyimide films, but the traditional process generally uses hot pressing to composite polyimide films with copper foil, and then etches specific metal circuits through "subtractive manufacturing" to manufacture flexible circuit boards, or deposits large areas of continuous metal on the surface of polyimide films through magnetron sputtering / high-temperature evaporation, which is further used to prepare composite copper foil for flexible circuit boards or composite current collectors for new energy batteries.

[0003] However, the polyimide film copper-clad circuit boards manufactured using the above-mentioned traditional process technology often have relatively poor metal coating adhesion, rough metal coating surface, complex manufacturing process, high resistivity, high production cost and other problems, which greatly limits the further application of polyimide film in the fields of flexible electronic materials and new energy battery materials.

[0004] Therefore, it is particularly important to develop intrinsic photosensitive polyimides with surface metallization capabilities. For example, the patent technical document CN110804181B discloses a transparent photosensitive polyimide resin, a polyimide film and a preparation method thereof. The polyimide resin and film prepared by the invention are photosensitivity, can change color under ultraviolet irradiation, and have the characteristics of intuitively visually observing the photomodified area; they are colorless and transparent, and have good flexibility, and can be used to prepare circuit boards for flexible electronic devices; surface patterns can be metallized, and the metal in the resin and coating can be recovered by dissolving the film matrix later. However, due to the introduction of spiropyran photoresponsive groups, the heat resistance of the photosensitive polyimide is subject to certain limitations.

[0005] Therefore, according to the above-mentioned related technologies, it is urgent to develop a preparation method and application of a high-temperature resistant photosensitive polyimide resin and a transparent film and a surface selective metallization method thereof. Summary of the invention

[0006] In view of this, the purpose of the present invention is to propose a preparation method and application of a high temperature resistant photosensitive polyimide resin and a transparent film and a surface selective metallization method thereof, so as to solve the problems in the prior art that the metal plating surface of the polyimide film copper clad circuit board is relatively rough, the metallization process is complex, the resistivity is also high, and the adhesion with the photosensitive polyimide is relatively poor.

[0007] Based on the above purpose, the present invention provides a preparation method and application of a high temperature resistant photosensitive polyimide resin and a transparent film and a surface selective metallization method thereof.

[0008] A method for preparing a high temperature resistant photosensitive polyimide resin, wherein the molecular main chain of the high temperature resistant photosensitive polyimide resin contains an imidazole derivative structure, and the molecular side chain contains a polyphenol hydroxyl structure, that is, the high temperature resistant photosensitive polyimide resin has any one of the structures shown in formula (I), formula (II), formula (III), and formula (IV):

[0009]

[0010]

[0011] Ar0 in the structures of formula (I), formula (II), formula (III) and formula (IV) is the residue of a diprimary amine of an imidazole-derived structure;

[0012] Ar1 in the structures of formula (I), formula (II), formula (III) and formula (IV) is a dianhydride monomer residue;

[0013] Ar2 and R6 in the structures of formula (I), formula (II), formula (III) and formula (IV) are substituents on the N in the imidazole ring of Ar0;

[0014] Ar2 in the structure of formula (I) and formula (III) is an aromatic ketone derivative structure;

[0015] In the structures of formula (I), formula (II), formula (III) and formula (IV), R1, R2, R3, R4 and R5 are any one of H and OH;

[0016] R6 in the structures of formula (II) and formula (IV) is an aliphatic ketone derivative structure;

[0017] In the structures of formula (III) and formula (IV), R' is a dibasic primary amine monomer residue.

[0018] Preferably, Ar0 is any one or more residues of diprimary amine monomers of imidazole-derived structures as shown below:

[0019]

[0020] Said Where X is any one of -H, -CH3, -CF3, F, Cl, Br, and I;

[0021] Ar1 is the residue of any one or more dianhydride monomers shown in the following structures:

[0022]

[0023] The R' is the residue of any one or more diamine monomers shown in the following structures:

[0024]

[0025] Preferably, the preparation method of the high temperature resistant photosensitive polyimide resin is as follows:

[0026] Step A1. Under a dry nitrogen atmosphere, a diamine monomer and a dianhydride monomer are dissolved in an organic solvent and reacted at 0-25° C. for 6-25 hours, then a catalyst and a dehydrating agent are added, refluxed at 80-100° C. for 1-3 hours, and then refluxed at 110-120° C. for 3-6 hours, cooled to room temperature, and then poured into a precipitant 1, and then filtered, washed and dried to obtain a photosensitive polyimide resin;

[0027] Step A2. In a dry nitrogen atmosphere, dissolve the photosensitive polyimide resin in an organic solvent, add sodium hydride at 0-25°C, stir for 1-3 hours, then add a small molecule halide, react for 3-6 hours, pour into precipitant 2, filter, wash and dry to obtain a high temperature resistant photosensitive polyimide resin.

[0028] Preferably, the molar ratio of the diamine monomer, the dianhydride monomer, the catalyst and the dehydrating agent in step A1 is 0.05: 0.051-0.06: 0.11-5: 0.06-10; the mass ratio of the photosensitive polyimide resin, the organic solvent, the small molecule halide and the precipitant 2 in step A2 is 5: 100-110: 2.15-9.5: 450-500.

[0029] Preferably, the organic solvent is any one of acetone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, phenol, benzonitrile, m-cresol, p-chlorophenol, p-chloro-m-xylenol, and nitrobenzene;

[0030] The catalyst is any one or more of pyridine, benzoic acid, p-hydroxybenzoic acid, quinoline, isoquinoline, triethylamine or N,N-dimethylaniline;

[0031] The dehydrating agent is any one or more of acetic anhydride, propionic anhydride, butyric anhydride, and phthalic anhydride;

[0032] The precipitant 1 is any one of methanol, ethanol, water, or a mixed solution of multiple thereof;

[0033] The small molecule halogenated compound is any one of the halogenated aromatic or aliphatic polyphenol hydroxyl small molecules;

[0034] The precipitant 2 is a mixed solution of dilute hydrochloric acid and any one or more of methanol, ethanol and water;

[0035] The pH of the precipitant 2 is 1.0-3.5.

[0036] A method for preparing a transparent film comprises the following steps:

[0037] The high temperature resistant photosensitive polyimide resin is dissolved in a solvent, and after standing to degas, the solution is spin coated or scraped onto a clean glass plate, and dried at 95-180°C to form a film to obtain a transparent film.

[0038] Preferably, the mass ratio of the high temperature resistant photosensitive polyimide resin to the solvent is 5-15:50-120; the solvent is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, cyclopentane, butyrolactone, acetone, tetrahydrofuran, and m-cresol; and the thickness of the polyimide wet film is 20-800 μm.

[0039] A method for selectively metallizing a transparent film surface, comprising the following steps:

[0040] Method 1. Using silver nitrate aqueous solution as ink, a designed pattern is printed on the surface of a transparent photosensitive polyimide film by means of an inkjet printer, and then the film A is pretreated by irradiating it with ultraviolet light or sunlight, and then the surface is cleaned with pure water, and then immersed in a 20-80°C plating solution for 5-120 minutes, and finally washed with pure water and dried to obtain a polyimide flexible circuit board A with a metal pattern plated on the surface;

[0041] The polyimide flexible circuit board A with a metal pattern plated on the surface described in method 1 is a two-layer structure, the upper layer is a metal pattern layer, and the lower layer is a photosensitive polyimide film layer; wherein the area of ​​the metal pattern layer is smaller than the area of ​​the photosensitive polyimide film layer;

[0042] Method 2. Use a screen printing plate with a specially designed hollow pattern and solder resist ink to print a solder resist layer on the surface of a high-temperature resistant transparent film and expose the reserved circuit pattern area, then immerse it in a silver nitrate aqueous solution, then irradiate the pre-treated film B with ultraviolet light or sunlight, wash the surface with pure water, and then immerse it in a 20-80°C plating solution for 5-120 minutes, and finally wash it with pure water and dry it to obtain a polyimide flexible circuit board B with a metal pattern plated on the surface;

[0043] The polyimide flexible circuit board B with a metal pattern plated on the surface described in method 2 is a two-layer structure, the upper layer is a coplanar layer of the metal pattern and the solder mask ink pattern, and the lower layer is a photosensitive polyimide film layer; wherein the area of ​​the metal pattern layer is smaller than the area of ​​the photosensitive polyimide film layer;

[0044] Method 3: After the transparent film surface is degreased and cleaned, it is completely immersed in a silver nitrate aqueous solution, the film is irradiated with ultraviolet light or sunlight on one side or both sides, and then the surface is cleaned with pure water, and then immersed in a 20-80°C plating solution for 5-120 minutes, and then cleaned and dried with pure water to obtain a polyimide flexible copper clad laminate C with a continuous metal layer plated on the surface;

[0045] The polyimide flexible copper-clad laminate C with a continuous metal layer on the surface in method 3 is any one of a polyimide metal composite film with a metal layer on one side and a polyimide metal composite film with a metal layer on both sides;

[0046] The polyimide metal composite film with a metal layer plated on one side has a two-layer structure, the upper layer is a continuous metal layer, and the lower layer is a photosensitive polyimide layer; wherein the area of ​​the continuous metal layer is equal to the area of ​​the photosensitive polyimide film;

[0047] The polyimide metal composite film with metal layers on both sides has a three-layer structure, the upper and lower layers are continuous metal layers, and the middle layer is a photosensitive polyimide layer; wherein the area of ​​the continuous metal layer is equal to the area of ​​the photosensitive polyimide film;

[0048] Method 4. Dissolve a photosensitive polyimide resin in an organic solvent to obtain a photosensitive polyimide solution, use a dispensing printer to pattern the photosensitive polyimide solution on the surface of any polymer film, dry it at 80°C to obtain a composite photosensitive film with a photosensitive polyimide pattern on the surface, immerse the entire film in a silver nitrate aqueous solution, irradiate the film with ultraviolet light or sunlight, then wash the surface with pure water, and then immerse it in a 20-80°C plating solution for 5-120 minutes, then wash it with pure water and dry it to obtain a composite flexible circuit board D with a metal layer plated on the surface of the photosensitive polyimide pattern;

[0049] The polymer film in method 4 is any one of a polypropylene film, a polyethylene film, a polyethylene terephthalate film, a polystyrene film, and a liquid crystal polymer film;

[0050] The composite flexible circuit board D with a metal layer plated on the surface of the photosensitive polyimide pattern described in method 4 has a three-layer structure, wherein the top layer is a metal pattern layer, the middle layer is a photosensitive polyimide pattern layer, and the bottom layer is a polymer film support layer; wherein the area of ​​the metal pattern layer is equal to the area of ​​the photosensitive polyimide pattern layer and is smaller than the area of ​​the polymer film support layer.

[0051] Preferably, the concentration of the silver nitrate aqueous solution is 0.005-2.0 mol / L; the wavelength range of the ultraviolet light during the irradiation is 200-450 nm, the sunlight is full-spectrum sunlight, and the irradiation time is 1.5-60 min; the plating solution is any one of a copper plating solution, a nickel plating solution, a silver plating solution, and a gold plating solution.

[0052] A preparation method of a high-temperature resistant photosensitive polyimide resin and a transparent film and an application of a method for selectively metallizing the surface thereof. The preparation method of the high-temperature resistant photosensitive polyimide resin, the preparation method of the transparent film and the method for selectively metallizing the surface of the transparent film can all be applied to the fields of flexible electronic device substrates, flexible displays, flexible solar cells and composite current collectors for new energy batteries; the transparent film can be used to prepare copper-clad polyimide films, supercapacitor electrode sheets, solar cell electrode sheets and composite current collectors for new energy batteries.

[0053] Beneficial effects of the present invention:

[0054] The present invention provides a preparation method and application of a high temperature resistant photosensitive polyimide resin and a transparent film, and a surface selective metallization method and application thereof. The present invention prepares a high temperature resistant photosensitive polyimide resin, because its main molecular chain contains an imidazole derivative structure, and its molecular chain side chain is grafted with polyphenol hydroxyl structure molecules, which can complex silver ions and reduce silver ions to silver atoms under ultraviolet light or sunlight, thereby catalyzing metal chemical deposition, and the metallization process does not damage the film surface and does not require an adhesive layer, so the transparent film prepared by the resin has not only good photosensitivity, thermal stability and mechanical properties, The metal coating on the film has stronger adhesion to the surface of the polyimide film, the coating surface is smoother, the coating thickness is more uniform, and selective metal patterning or large-area metallization can be performed; and the preparation and metallization process of the photosensitive polyimide resin and its film are simple, with high production efficiency, low cost, and low pollution, and have huge economic benefits and environmental significance. Therefore, compared with the prior art, the transparent film prepared by the present invention has broader application prospects in the fields of substrate materials for flexible electronic devices, substrates for composite current collectors in new energy soft-pack batteries, substrates for solar cell pole pieces, and flexible display materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only for the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0056] Figure 1 This is a physical appearance diagram of a polyimide flexible circuit board with a metal pattern plated on its surface prepared in an embodiment of the present invention, wherein Figure 1 A is a physical appearance diagram of a polyimide flexible circuit board with a metal pattern plated on its surface prepared in Example 1 of the present invention; Figure 1 B is a physical appearance picture of a polyimide flexible circuit board with a metal pattern plated on the surface prepared in Example 3 of the present invention;

[0057] Figure 2 This is a Fourier transform infrared spectrum of the transparent film prepared in Example 1 of the present invention;

[0058] Figure 3 This is a thermogravimetric analysis curve of the transparent film prepared in Example 1 of the present invention;

[0059] Figure 4 The photos are before and after the cross-cut test of the metal coating on the surface of the transparent film prepared in Example 4 of the present invention. Figure 4 A is an optical photograph of the sample after 100 grids; Figure 4 B is an optical photograph of the sample surface after peeling with 3M tape; Figure 4 C is an optical photograph showing that no metal coating on the 3M tape has been peeled off;

[0060] Figure 5 This is a standard diagram for evaluating the adhesion test of the metal coating of the present invention. DETAILED DESCRIPTION

[0061] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0062] Example 1: Preparation of a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selective surface metallization thereof:

[0063] S1. In a dry nitrogen atmosphere, 0.0500 mol of 2-(4-aminophenyl)-5-aminobenzimidazole and 0.0510 mol of 4,4'-(hexafluoroisopropylene) diphthalic anhydride were dissolved in 150 mL of N,N-dimethylformamide and stirred at 0°C for 24 h, then 0.1100 mol of pyridine and 0.0600 mol of acetic anhydride were added, refluxed at 80°C for 1 h, and then refluxed at 110°C for 5 h to cool to room temperature and poured into 450 mL of methanol, and then filtered, washed and dried to obtain a photosensitive polyimide resin; the weight average molecular weight of the photosensitive polyimide resin was 2.5×10 5 g / mol, and the number average molecular weight is 1.7×10 5 g / mol;

[0064] The resulting product of the above steps is shown in the following formula:

[0065]

[0066] S2: Under a dry nitrogen atmosphere, 5 g of photosensitive polyimide resin was dissolved in 100 mL of dimethyl sulfoxide, and 1.6 g of sodium hydride was added at 0°C. After stirring for 2 h, 2.17 g of 4'-chloro-3,4-dihydroxybenzophenone was added. After reacting for 3 h, the mixture was poured into 450 mL of a mixed solution of dilute hydrochloric acid and methanol with a pH of 2, and then filtered, washed and dried to obtain a high temperature resistant photosensitive polyimide resin. The structural formula of the product obtained in the above steps is shown as follows:

[0067]

[0068] S3. 5 g of a high temperature resistant photosensitive polyimide resin was dissolved in 105 g of N, N-dimethylformamide, and the solution was spin-coated on a clean glass plate after standing for degassing, and dried at 95 ° C to obtain a transparent film having a thickness of 20 μm;

[0069] S4. Print the designed pattern on the surface of the photosensitive polyimide film in an inkjet printer with a concentration of 0.005 mol / L silver nitrate aqueous solution to obtain a pretreated film A;

[0070] S5. Dissolve 24 g of copper sulfate pentahydrate, 21 g of disodium ethylenediaminetetraacetate and 8 mg of 2,2'-bipyridine in 450 mL of deionized water to obtain a mixed solution;

[0071] S6. 8 mg of 2,2'-bipyridine, 70 mg of potassium ferrocyanide, 1 g of polyethylene glycol, 10 g of potassium sodium tartrate, 10 mL of formaldehyde solution, and 16 g of sodium hydroxide were dissolved in 475 mL of deionized water, and then 450 mL of the mixture was added and stirred to obtain a chemical plating solution;

[0072] S7. The pre-treated film A is irradiated with ultraviolet light with a wavelength range of 200 nm for 3 minutes, then washed with pure water, and then immersed in a 20° C. chemical plating solution for 5 minutes, and then washed with pure water and dried to obtain a polyimide flexible circuit board A with a metal pattern plated on the surface;

[0073] The polyimide flexible circuit board A with a metal pattern plated on the surface has a two-layer structure, the upper layer is a metal pattern layer, and the lower layer is a photosensitive polyimide film layer; wherein the area of ​​the metal pattern layer is smaller than the area of ​​the photosensitive polyimide film layer.

[0074] Example 2: Preparation of a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selective surface metallization thereof:

[0075] S1. Under a dry protective atmosphere, 0.04 mol of 2-(4-aminophenyl)-5-aminobenzimidazole, 0.01 mol of 1,1-bis(4-aminophenyl)cyclohexane and 0.055 mol of 4,4'-(hexafluoroisopropylene)diphthalic anhydride were dissolved in 180 mL of phenol and stirred at 10 ° C for 24.5 h, then 0.12 mol of triethylamine and 0.065 mol of butyric anhydride were added, refluxed at 90 ° C for 2 h, and then refluxed at 115 ° C for 3 h to cool to room temperature and poured into 480 mL of ethanol, and then filtered, washed and dried to obtain a photosensitive polyimide resin;

[0076] The structural formula of the product obtained in the above steps is shown below:

[0077]

[0078] S2. Under a dry protective atmosphere, 5 g of photosensitive polyimide resin was dissolved in 105 mL of phenol, 1.65 g of sodium hydride was added at 10 ° C, and 1.64 g of 3,4-dihydroxy-2'-chloroacetophenone was added after stirring for 2.5 h. After reacting for 5 h, it was poured into 480 mL of a mixed solution of dilute hydrochloric acid and ethanol with a pH of 2.1, and then filtered, washed and dried to obtain a high temperature resistant photosensitive polyimide resin;

[0079] The structural formula of the product obtained in the above steps is shown below:

[0080]

[0081] S3. 5 g of a high temperature resistant photosensitive polyimide resin was dissolved in 110 g of N, N-dimethylacetamide, and the solution was scraped onto a clean glass plate after standing for degassing, and dried at 130 ° C to obtain a transparent film having a thickness of 400 μm;

[0082] S4. Print the designed pattern on the surface of the photosensitive polyimide film in an inkjet printer with a 1.0 mol / L aqueous silver nitrate solution to obtain a pretreated film A;

[0083] S5. Dissolve 24.5 g of copper sulfate pentahydrate, 21 g of disodium ethylenediaminetetraacetate and 8 mg of 2,2'-bipyridine in 480 mL of deionized water to obtain a mixed solution;

[0084] S6. 8 mg of 2,2'-bipyridine, 70 mg of potassium ferrocyanide, 1 g of polyethylene glycol, 10 g of potassium sodium tartrate, 10 mL of formaldehyde solution, and 16 g of sodium hydroxide were dissolved in 490 mL of deionized water, and then 480 mL of the mixture was added and stirred to obtain a chemical plating solution;

[0085] S7. Pre-treating the film A by irradiating the film with ultraviolet light of wavelength range 365 nm for 30 min, then washing with pure water, and then immersing the film in a 50° C. chemical plating solution for 60 min, and then washing with pure water and drying to obtain a polyimide flexible circuit board A with a metal pattern plated on the surface;

[0086] The polyimide flexible circuit board A with a metal pattern plated on the surface has a two-layer structure, the upper layer is a metal pattern layer, and the lower layer is a photosensitive polyimide film layer; wherein the area of ​​the metal pattern layer is smaller than the area of ​​the photosensitive polyimide film layer.

[0087] Example 3: Preparation of a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selective surface metallization thereof:

[0088] S1. Under a dry protective atmosphere, 0.04 mol of 2-(4-aminophenyl)-5-aminobenzimidazole, 0.01 mol of 2,2'-bis(trifluoromethyl)diaminobiphenyl and 0.06 mol of 4,4'-(hexafluoroisopropylene)diphthalic anhydride were dissolved in 200 mL of m-cresol and stirred at 25° C. for 25 h, then 5 mol of quinoline and 10 mol of phthalic anhydride were added, refluxed at 100° C. for 3 h, then refluxed at 120° C. for 6 h, cooled to room temperature, poured into 500 mL of water, filtered, washed and dried to obtain a photosensitive polyimide resin;

[0089] The structural formula of the product obtained in the above steps is shown below:

[0090]

[0091] S2. Under a dry protective atmosphere, 5 g of photosensitive polyimide resin was dissolved in 110 mL of N-methylpyrrolidone, 1.7 g of sodium hydride was added at 25 ° C, and 9.5 g of 4'-chloro-3,4-dihydroxybenzophenone was added after stirring for 3 h. After reacting for 6 h, it was poured into 500 mL of a mixed solution of dilute hydrochloric acid and water with a pH of 2.2, and then filtered, washed and dried to obtain a high temperature resistant photosensitive polyimide resin;

[0092] The structural formula of the product obtained in the above steps is shown below:

[0093]

[0094] S3. 15 g of a high temperature resistant photosensitive polyimide resin was dissolved in 120 g of sulfolane, and the solution was spin-coated on a clean glass plate after standing for degassing, and dried at 180 ° C to obtain a transparent film having a thickness of 800 μm;

[0095] S4. Using a screen printing plate with a specifically designed hollow pattern and solder resist ink, a solder resist layer is printed on the surface of the high temperature resistant photosensitive polyimide film and a reserved circuit pattern area is exposed, and then immersed in a 2 mol / L silver nitrate aqueous solution to obtain a pretreated film B;

[0096] S5. Dissolve 25 g of copper sulfate pentahydrate, 21 g of disodium ethylenediaminetetraacetate and 8 mg of 2,2'-bipyridine in 500 mL of deionized water to obtain a mixed solution;

[0097] S6. 8 mg of 2,2'-bipyridine, 70 mg of potassium ferrocyanide, 1 g of polyethylene glycol, 10 g of potassium sodium tartrate, 10 mL of formaldehyde solution, and 16 g of sodium hydroxide were dissolved in 500 mL of deionized water, and then 500 mL of the mixture was added and stirred to obtain a chemical plating solution;

[0098] S7. Pre-treating the film B by irradiating it with ultraviolet-near ultraviolet light with a wavelength range of 450 nm for 60 minutes, then washing it with pure water, and then immersing it in a chemical plating solution at 80° C. for 120 minutes, and then washing it with pure water and drying it to obtain a polyimide flexible circuit board B with a metal pattern plated on the surface;

[0099] The polyimide flexible circuit board B with a metal pattern on the surface is a two-layer structure, the upper layer is a coplanar layer of the metal pattern and the solder mask ink pattern, and the lower layer is a photosensitive polyimide film layer; wherein the area of ​​the metal pattern layer is smaller than the area of ​​the photosensitive polyimide film layer.

[0100] Example 4: Preparation of a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selective surface metallization thereof:

[0101] S1. Under a dry protective atmosphere, 0.04 mol of 2-(4-aminophenyl)-5-aminobenzimidazole, 0.01 mol of 2,2'-bis(trifluoromethyl)diaminobiphenyl and 0.06 mol of 4,4'-(hexafluoroisopropylene)diphthalic anhydride were dissolved in 200 mL of nitrobenzene and stirred at 25° C. for 25 h, then 5 mol of isoquinoline and 10 mol of propionic anhydride were added, refluxed at 100° C. for 3 h, then refluxed at 120° C. for 6 h, cooled to room temperature, poured into 500 mL of water, filtered, washed and dried to obtain a photosensitive polyimide resin;

[0102] The structural formula of the product obtained in the above steps is shown below:

[0103]

[0104] S2. Under a dry protective atmosphere, 5 g of photosensitive polyimide resin was dissolved in 110 mL of N-methylpyrrolidone, 1.7 g of sodium hydride was added at 25 ° C, and 9.5 g of 4'-chloro-3,4-dihydroxybenzophenone was added after stirring for 3 h. After reacting for 6 h, it was poured into 500 mL of a mixed solution of dilute hydrochloric acid and water with a pH of 2.2, and then filtered, washed and dried to obtain a high temperature resistant photosensitive polyimide resin;

[0105] The structural formula of the product obtained in the above steps is shown below:

[0106]

[0107] S3. 15 g of a high temperature resistant photosensitive polyimide resin was dissolved in 120 g of tetrahydrofuran, and the solution was spin-coated on a clean glass plate after standing for degassing, and dried at 180 ° C to obtain a transparent film having a thickness of 800 μm;

[0108] S4. Dissolve 25 g of copper sulfate pentahydrate, 21 g of disodium ethylenediaminetetraacetate and 8 mg of 2,2'-bipyridine in 500 mL of deionized water to obtain a mixed solution;

[0109] S5. 8 mg of 2,2'-bipyridine, 70 mg of potassium ferrocyanide, 1 g of polyethylene glycol, 10 g of potassium sodium tartrate, 10 mL of formaldehyde solution, and 16 g of sodium hydroxide were dissolved in 500 mL of deionized water, and then 500 mL of the mixture was added and stirred to obtain a chemical plating solution;

[0110] S6. After the transparent film surface is degreased and cleaned, it is completely immersed in a 2 mol / L silver nitrate aqueous solution, the film is irradiated with sunlight on one side for 1.5 min, and then the surface is washed with pure water, and then immersed in a 20° C. chemical plating solution for 5 min, and then washed with pure water and dried to obtain a polyimide flexible copper clad laminate C with a continuous metal layer plated on one side;

[0111] The polyimide metal composite film of the polyimide flexible copper-clad laminate C with a continuous metal layer plated on one side has a two-layer structure, the upper layer is a continuous metal layer, and the lower layer is a photosensitive polyimide layer; wherein the area of ​​the continuous metal layer is equal to the area of ​​the photosensitive polyimide film;

[0112] Example 5: Preparation of a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selective surface metallization thereof:

[0113] S1. Under a dry protective atmosphere, 0.04 mol of 2-(4-aminophenyl)-5-aminobenzimidazole, 0.01 mol of 2,2'-bis(trifluoromethyl)diaminobiphenyl and 0.06 mol of 4,4'-(hexafluoroisopropylene)diphthalic anhydride were dissolved in 200 mL of benzonitrile and stirred at 25°C for 25 h, then 5 mol of triethylamine and 10 mol of butyric anhydride were added, refluxed at 100°C for 3 h, and then refluxed at 120°C for 6 h to room temperature, then poured into 500 mL of water, filtered, washed and dried to obtain a photosensitive polyimide resin;

[0114] The structural formula of the product obtained in the above steps is shown below:

[0115]

[0116] S2. Under a dry protective atmosphere, 5 g of photosensitive polyimide resin was dissolved in 110 mL of acetone, 1.7 g of sodium hydride was added at 25 ° C, and 9.5 g of 4'-chloro-3,4-dihydroxybenzophenone was added after stirring for 3 h. After reacting for 6 h, it was poured into 500 mL of a mixed solution of dilute hydrochloric acid and water with a pH of 2.2, and then filtered, washed and dried to obtain a high temperature resistant photosensitive polyimide resin;

[0117] The structural formula of the product obtained in the above steps is shown below:

[0118]

[0119] S3. 15 g of a high temperature resistant photosensitive polyimide resin was dissolved in 120 g of N, N-dimethylformamide, and the solution was spin-coated on a clean glass plate after standing for degassing, and dried at 180 ° C to obtain a transparent film having a thickness of 800 μm;

[0120] S4. Dissolve 25 g of copper sulfate pentahydrate, 21 g of disodium ethylenediaminetetraacetate and 8 mg of 2,2'-bipyridine in 500 mL of deionized water to obtain a mixed solution;

[0121] S5. 8 mg of 2,2'-bipyridine, 70 mg of potassium ferrocyanide, 1 g of polyethylene glycol, 10 g of potassium sodium tartrate, 10 mL of formaldehyde solution, and 16 g of sodium hydroxide were dissolved in 500 mL of deionized water, and then 500 mL of the mixture was added and stirred to obtain a chemical plating solution;

[0122] S6. After the transparent film surface is degreased and cleaned, it is completely immersed in a 2 mol / L silver nitrate aqueous solution, the film is irradiated with sunlight on both sides for 60 minutes, and then the surface is washed with pure water, and then immersed in an 80°C chemical plating solution for 120 minutes, and then washed with pure water and dried to obtain a polyimide flexible copper clad laminate C with continuous metal layers on both sides;

[0123] The polyimide metal composite film of the polyimide flexible copper-clad laminate C with continuous metal layers on both sides is a three-layer structure, wherein the upper and lower layers are both continuous metal layers, and the middle layer is a photosensitive polyimide layer; wherein the area of ​​the continuous metal layer is equal to the area of ​​the photosensitive polyimide film;

[0124] Example 6: Preparation of a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selective surface metallization thereof:

[0125] S1. Under a dry protective atmosphere, 0.04 mol of 2-(4-aminophenyl)-5-aminobenzimidazole, 0.01 mol of 2,2'-bis(trifluoromethyl)diaminobiphenyl and 0.06 mol of 4,4'-(hexafluoroisopropylene)diphthalic anhydride were dissolved in 200 mL of m-cresol and stirred at 25° C. for 25 h, then 5 mol of isoquinoline and 10 mol of acetic anhydride were added, refluxed at 100° C. for 3 h, then refluxed at 120° C. for 6 h, cooled to room temperature, poured into 500 mL of water, filtered, washed and dried to obtain a photosensitive polyimide resin;

[0126] The structural formula of the product obtained in the above steps is shown below:

[0127]

[0128] S2. Under a dry protective atmosphere, 5 g of photosensitive polyimide resin was dissolved in 110 mL of acetone, 1.7 g of sodium hydride was added at 25 ° C, and 9.5 g of 4'-chloro-3,4-dihydroxybenzophenone was added after stirring for 3 h. After reacting for 6 h, it was poured into 500 mL of a mixed solution of dilute hydrochloric acid and water with a pH of 2.2, and then filtered, washed and dried to obtain a high temperature resistant photosensitive polyimide resin;

[0129] The structural formula of the product obtained in the above steps is shown below:

[0130]

[0131] S3. Dissolve 25 g of copper sulfate pentahydrate, 21 g of disodium ethylenediaminetetraacetate and 8 mg of 2,2'-bipyridine in 500 mL of deionized water to obtain a mixed solution;

[0132] S4. 8 mg of 2,2'-bipyridine, 70 mg of potassium ferrocyanide, 1 g of polyethylene glycol, 10 g of potassium sodium tartrate, 10 mL of formaldehyde solution, and 16 g of sodium hydroxide were dissolved in 500 mL of deionized water, and then 500 mL of the mixture was added and stirred to obtain a chemical plating solution;

[0133] S5. Dissolve the photosensitive polyimide resin in an organic solvent to obtain a photosensitive polyimide solution, use a dispensing printer to pattern the photosensitive polyimide solution on the surface of the polymer film, dry it at 80°C to obtain a composite photosensitive film with a photosensitive polyimide pattern, immerse it in a silver nitrate aqueous solution, irradiate the film with ultraviolet light or sunlight, wash the surface with pure water, and then immerse it in an 80°C chemical plating solution for 120 minutes, then wash it with pure water and dry it to obtain a composite flexible circuit board D with a metal layer plated on the surface of the photosensitive polyimide pattern;

[0134] The polymer film is any one of a polypropylene film, a polyethylene film, a polyethylene terephthalate film, a polystyrene film, and a liquid crystal polymer film;

[0135] The composite flexible circuit board D having a metal layer plated on the surface of the photosensitive polyimide pattern has a three-layer structure, wherein the top layer is the metal pattern layer, the middle layer is the photosensitive polyimide pattern layer, and the bottom layer is the polymer film support layer; wherein the area of ​​the metal pattern layer is equal to the area of ​​the photosensitive polyimide pattern layer and is smaller than the area of ​​the polymer film support layer.

[0136] Comparative Example 1: Preparation of a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selective surface metallization thereof (no polyphenol hydroxyl grafts on the molecular chain):

[0137] S1. In a dry nitrogen atmosphere, 0.0520 mol of 2-(4-aminophenyl)-5-aminobenzimidazole and 0.0530 mol of 4,4'-(hexafluoroisopropylene) diphthalic anhydride were dissolved in 150 mL of an organic solvent and stirred at 0°C for 24 h, then 0.1100 mol of pyridine and 0.0600 mol of acetic anhydride were added, refluxed at 80°C for 1 h, and then refluxed at 110°C for 5 h to cool to room temperature, poured into 450 mL of methanol, and then filtered, washed and dried to obtain a photosensitive polyimide resin; the weight average molecular weight of the photosensitive polyimide resin was 2.6×10 5 g / mol, and the number average molecular weight is 1.8×10 5 g / mol;

[0138] The resulting product of the above steps is shown in the following formula:

[0139]

[0140] S2. 12 g of a high temperature resistant photosensitive polyimide resin was dissolved in 105 g of N, N-dimethylformamide, and the solution was spin-coated on a clean glass plate after standing for degassing, and dried at 95 ° C to obtain a transparent film having a thickness of 25 μm;

[0141] S3. After the transparent film surface is degreased and cleaned, it is immersed in a 0.005 mol / L aqueous silver nitrate solution to obtain a pretreated film C;

[0142] S4. Dissolve 24 g of copper sulfate pentahydrate, 21 g of disodium ethylenediaminetetraacetate and 8 mg of 2,2'-bipyridine in 450 mL of deionized water to obtain a mixed solution;

[0143] S5. 8 mg of 2,2'-bipyridine, 70 mg of potassium ferrocyanide, 1 g of polyethylene glycol, 10 g of potassium sodium tartrate, 10 mL of formaldehyde solution, and 16 g of sodium hydroxide were dissolved in 475 mL of deionized water, and then 450 mL of the mixture was added and stirred to obtain a chemical plating solution;

[0144] S6. The pretreated film C was irradiated with ultraviolet light with a wavelength of 254 nm on one side for 3 minutes, then washed with pure water, and then immersed in a 20° C. chemical plating solution for 5 minutes. After being washed with pure water and dried, a polyimide flexible copper clad laminate C with a continuous metal layer plated on one side was obtained.

[0145] Comparative Example 2: Preparation of a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selective surface metallization thereof (few polyphenol hydroxyl grafts on the molecular chain):

[0146] S1. In a dry nitrogen atmosphere, 0.0500 mol of 2-(4-aminophenyl)-5-aminobenzimidazole and 0.0510 mol of 3,3',4,4'-dibenzophenonetetracarboxylic dianhydride were dissolved in 150 mL of an organic solvent and stirred at 0°C for 24 h, then 0.1100 mol of pyridine and 0.0600 mol of propionic anhydride were added, refluxed at 80°C for 1 h, and then refluxed at 110°C for 5 h to cool to room temperature, poured into 450 mL of methanol, and then filtered, washed and dried to obtain a photosensitive polyimide resin; the weight average molecular weight of the photosensitive polyimide resin was 2.45×10 5 g / mol, and the number average molecular weight is 1.67×10 5 g / mol;

[0147] The resulting product of the above steps is shown in the following formula:

[0148]

[0149] S2: Under a dry nitrogen atmosphere, 5 g of photosensitive polyimide resin was dissolved in 100 mL of dimethyl sulfoxide, 1.6 g of sodium hydride was added at 0°C, and 0.05 g of 4'-chloro-3,4-dihydroxybenzophenone was added after stirring for 2 hours. After reacting for 3 hours, the mixture was poured into 450 mL of a mixed solution of dilute hydrochloric acid and methanol with a pH of 2, and then filtered, washed and dried to obtain a high temperature resistant photosensitive polyimide resin; the structural formula of the product obtained in the above steps is shown as follows:

[0150]

[0151] S3. 5 g of a high temperature resistant photosensitive polyimide resin was dissolved in 105 g of N, N-dimethylformamide, and the solution was spin-coated on a clean glass plate after standing for degassing, and dried at 95 ° C to obtain a transparent film having a thickness of 20 μm;

[0152] S4. After the transparent film surface is degreased and cleaned, it is immersed in a 0.005 mol / L aqueous silver nitrate solution to obtain a pretreated film C;

[0153] S5. Dissolve 24 g of copper sulfate pentahydrate, 21 g of disodium ethylenediaminetetraacetate and 8 mg of 2,2'-bipyridine in 450 mL of deionized water to obtain a mixed solution;

[0154] S6. 8 mg of 2,2'-bipyridine, 70 mg of potassium ferrocyanide, 1 g of polyethylene glycol, 10 g of potassium sodium tartrate, 10 mL of formaldehyde solution, and 16 g of sodium hydroxide were dissolved in 475 mL of deionized water, and then 450 mL of the mixture was added and stirred to obtain a chemical plating solution;

[0155] S7. The film C is pretreated by irradiating one side with ultraviolet light with a wavelength range of 200 nm for 3 minutes, then washed with pure water, and then immersed in a 20°C chemical plating solution for 5 minutes. After being washed with pure water and dried, a polyimide flexible copper clad laminate C with a continuous metal layer plated on one side is obtained.

[0156] Performance Test:

[0157] The infrared spectrum of the transparent film prepared in Example 1 was measured by Fourier transform infrared spectrometer (FTIR, Nico-leti S50 model), with a resolution of 4 cm -1 , range is 4000-400cm -1 , the scanning times are 32 times, the test results are as attached Figure 2 As shown;

[0158] Determination of thermal stability:

[0159] The thermal stability of the samples was tested by a thermogravimetric analyzer (TGA, NETZSCH-Libra / 209F3), with a sample mass of 5-10 mg, a temperature range of 30-800° C., a purge gas of nitrogen, and a heating rate of 10° C. / min. The glass transition temperature (° C.) of the transparent films prepared in Examples 1 to 6 and Comparative Examples 1 to 2 was measured by this method.

[0160] Tensile strength test

[0161] Referring to GB / T1040.3-2006 "Test for tensile properties of plastics", a strip sample with a width of 15 mm, a length of 150 mm and parallel markings with an interval of 50 mm in the middle was prepared by a cutting method, and the tensile strength (MPa) of the transparent films prepared in Examples 1 to 6 and Comparative Examples 1 and 2 was tested using a universal material testing machine (Instron 6800, Instron) at a speed of 10 mm / min;

[0162] Determination of water absorption:

[0163] According to the ASTM-D570 "Test for Water Absorption of Plastics" standard, three test strips with a length of 5 cm and a width of 1 cm were taken, and the length, width, thickness and mass of the dry film were measured and recorded under standard atmospheric pressure; the strips were immersed in deionized water at 23°C for 24 hours, and the length, width, thickness and mass of the wet film were measured and recorded; the water absorption rate was the ratio of the difference between the mass of the wet film and the mass of the dry film to the mass of the dry film; an electronic balance (FA1104N, Shanghai Minqiao) was used to test the transparent films prepared in Examples 1 to 6 and Comparative Examples 1 to 2, and the average value of the water absorption rate of the samples in each Example and Comparative Example 3 was calculated as the water absorption rate (%) of the transparent film;

[0164] Metal coating adhesion test:

[0165] Refer to the national standard GB / T 9286-2021 "Paint and varnish - cross-cut test", cut three metallized polyimide film samples with a side length of 5 cm, use a special knife to cut the metal layer on the surface of the film horizontally and vertically at a spacing of 1 mm, and draw 100 square grids with a side length of 1 mm. All cuts should penetrate the surface of the substrate, but the substrate should not be cut off. Finally, use a special tape to test the adhesion of the metal coating, and evaluate the adhesion results of the metal coating and the photosensitive polyimide surface according to the test standard. The evaluation standard is as shown in the attached Figure 5 As shown;

[0166] The measurement results are shown in Table 1;

[0167] Table 1

[0168]

[0169] Data Analysis:

[0170] It can be seen from Examples 1 to 6 in Table 1 that the transparent film prepared by the present invention has good thermal stability and mechanical properties, high light transmittance and low water absorption, and the adhesion between the metal coating and the substrate reaches the highest level of ISO standards, and the coating adhesion is excellent; it can be seen from Comparative Examples 1 and 2 that the transparent photosensitive polyimide resin prepared by the present invention, if not grafted with small molecule halides or the grafting amount is insufficient, its film is also photosensitivity and surface metallization can be achieved, but the adhesion of the metal coating is slightly poor.

[0171] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0172] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A high temperature resistant photosensitive polyimide resin, characterized in that: The molecular structure of the high temperature resistant photosensitive polyimide resin is any one of the structures shown in formula (I), formula (II), formula (III) and formula (IV): Ar0 in the structures of formula (I), formula (II), formula (III) and formula (IV) is the residue of a diprimary amine of an imidazole-derived structure; Ar1 in the structures of formula (I), formula (II), formula (III) and formula (IV) is a dianhydride monomer residue; Ar2 and R6 in the structures of formula (I), formula (II), formula (III) and formula (IV) are substituents on the N in the imidazole ring of Ar0; Ar2 in the structure of formula (I) and formula (III) is an aromatic ketone derivative structure; In the structures of formula (I), formula (II), formula (III) and formula (IV), R1, R2, R3, R4 and R5 are any one of H and OH; R6 in the structures of formula (II) and formula (IV) is an aliphatic ketone derivative structure; In the structures of formula (III) and formula (IV), R' is a dibasic primary amine monomer residue.

2. The high temperature resistant photosensitive polyimide resin according to claim 1, characterized in that: Ar0 is any one or more residues of diprimary amine monomers of imidazole-derived structures as shown below: Said Where X is any one of -H, -CH3, -CF3, F, Cl, Br, and I; Ar1 is the residue of any one or more dianhydride monomers shown in the following structures: The R' is the residue of any one or more diamine monomers shown in the following structures:

3. A method for preparing a high temperature resistant photosensitive polyimide resin, characterized in that: The preparation method of the high temperature resistant photosensitive polyimide resin is as follows: Step A1. Under a dry nitrogen atmosphere, a diamine monomer and a dianhydride monomer are dissolved in an organic solvent and reacted at 0-25° C. for 6-25 hours, then a catalyst and a dehydrating agent are added, refluxed at 80-100° C. for 1-3 hours, and then refluxed at 110-120° C. for 3-6 hours, cooled to room temperature, and then poured into a precipitant 1, and then filtered, washed and dried to obtain a photosensitive polyimide resin; Step A2. In a dry nitrogen atmosphere, dissolve the photosensitive polyimide resin in an organic solvent, add sodium hydride at 0-25°C, stir for 1-3 hours, then add a small molecule halide, react for 3-6 hours, pour into precipitant 2, filter, wash and dry to obtain a high temperature resistant photosensitive polyimide resin.

4. The method for preparing the high temperature resistant photosensitive polyimide resin according to claim 3, characterized in that: The molar ratio of the diamine monomer, the dianhydride monomer, the catalyst and the dehydrating agent in step A1 is 0.05: 0.051-0.06: 0.11-5: 0.06-10; the mass ratio of the photosensitive polyimide resin, the organic solvent, the small molecule halide and the precipitant 2 in step A2 is 5: 100-110: 2.15-9.5: 450-500.

5. The method for preparing the high temperature resistant photosensitive polyimide resin according to claim 3, characterized in that: The organic solvent is any one of acetone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, phenol, benzonitrile, m-cresol, p-chlorophenol, p-chloro-m-xylenol, and nitrobenzene; The catalyst is any one or more of pyridine, benzoic acid, p-hydroxybenzoic acid, quinoline, isoquinoline, triethylamine or N,N-dimethylaniline; The dehydrating agent is any one or more of acetic anhydride, propionic anhydride, butyric anhydride, and phthalic anhydride; The precipitant 1 is any one of methanol, ethanol, water, or a mixed solution of multiple thereof; The small molecule halogenated compound is any one of the halogenated aromatic or aliphatic polyphenol hydroxyl small molecules; The precipitant 2 is a mixed solution of dilute hydrochloric acid and any one or more of methanol, ethanol and water; The pH of the precipitant 2 is 1.0-3.

5.

6. A method for preparing a transparent film, characterized in that: The following steps are involved: The high temperature resistant photosensitive polyimide resin is dissolved in a solvent, and after standing to degas, the solution is spin coated or scraped onto a clean glass plate, and dried at 95-180°C to form a film to obtain a transparent film.

7. The method for preparing a transparent film according to claim 6, characterized in that: The mass ratio of the high temperature resistant photosensitive polyimide resin to the solvent is 5-15:50-120; the solvent is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, cyclopentane, butyrolactone, acetone, tetrahydrofuran, and m-cresol; the thickness of the polyimide wet film is 20-800 μm.

8. A method for selectively metallizing a transparent film surface, characterized in that: The following steps are involved: Step B1-1. Using an aqueous silver nitrate solution as ink, a designed pattern is printed on the surface of a transparent photosensitive polyimide film by means of an inkjet printer to obtain a pretreated film A; Step B1-2. Use a screen printing plate with a specially designed hollow pattern and solder resist ink to print a solder resist layer on the surface of the high temperature resistant transparent film and expose the reserved circuit pattern area, and then immerse it in a silver nitrate aqueous solution to obtain a pretreated film B; Step B1-3. After the transparent film surface is degreased and cleaned, it is completely immersed in a silver nitrate aqueous solution to obtain a pretreated film C; Step B1-4. Dissolve the photosensitive polyimide resin in an organic solvent to obtain a photosensitive polyimide solution, use a dispensing printer to pattern the photosensitive polyimide solution on the surface of any polymer film, dry at 80°C to obtain a composite photosensitive film having a photosensitive polyimide pattern on the surface, and immerse all of it in a silver nitrate aqueous solution to obtain a pretreated film D; Step B2. After the film is pretreated by irradiating with ultraviolet light or sunlight, the surface is cleaned with pure water, and then immersed in a 20-80°C plating solution for 5-120 minutes, and then cleaned with pure water and dried to obtain a polyimide flexible circuit board or a flexible copper-clad laminate with a metal pattern on the surface; The pre-treated film in step B2 is any one of pre-treated films A, B, C, and D.

9. The method for metal patterning on a transparent film surface according to claim 8, characterized in that: The concentration of the silver nitrate aqueous solution is 0.005-2.0 mol / L; the wavelength range of the ultraviolet light during the irradiation is 200-450 nm, the sunlight is full-spectrum sunlight, and the irradiation time is 1.5-60 min; the plating solution is any one of a copper plating solution, a nickel plating solution, a silver plating solution, and a gold plating solution.

10. A method for preparing a high temperature resistant photosensitive polyimide resin and a transparent film and a method for selectively metallizing the surface thereof according to any one of claims 1 to 9, characterized in that: The preparation method of the high temperature resistant photosensitive polyimide resin, the preparation method of the transparent film and the method of selectively metallizing the surface of the transparent film can be applied to the fields of flexible electronic device substrates, flexible displays, flexible solar cells and composite current collectors for new energy batteries; The transparent film can be used to prepare copper-clad polyimide films, supercapacitor electrodes, solar cell electrodes and composite current collectors for new energy batteries.

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