High-ultraviolet photosensitive black polyimide, preparation method and application thereof

Abstract

The application discloses a high-ultraviolet-sensitivity black polyimide and a preparation method and application thereof, and belongs to the technical field of functional polymer materials, and solves the problem that polyimides in the prior art cannot have excellent masking ability and ultraviolet photosensitivity. The structural formula of the polyimide is shown in the following formula: wherein, the structural unit A is a polyarylether or a polyarylketone; the structural unit B is a tetraphenylcyclopentadiene biphenyl; the structural unit C is diphenylamine or biphenyldiol; and n is a positive integer from 1 to 50. The application prepares the intrinsic high-ultraviolet-sensitivity black polyimide through reasonable molecular structure design of the polyimide, so that the intrinsic high-ultraviolet-sensitivity black polyimide can occur photoisomerization after exposure.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional polymer materials, and more particularly to a high-ultraviolet-sensitivity black polyimide and a preparation method and application thereof. BACKGROUND

[0002] The black polyimide is a new type of polyimide, which can sense ultraviolet light, completely absorb visible light, effectively prevent the aging of internal circuits of a circuit board caused by external visible light, and protect internal circuit design, and is widely used in the electronic field.

[0003] With the rapid development of optoelectronic devices, there is an increasing demand for photosensitive black polyimides with excellent shielding ability and high ultraviolet sensitivity. However, the existing photosensitive black polyimides have a UV cutoff wavelength of about 580 nm, which will cause a large amount of UV light to be absorbed, resulting in a greatly reduced UV exposure effect, and the photo-induced structure transformation in the exposure area is not obvious or even impossible. Further, it has poor masking ability and ultraviolet sensitivity.

[0004] Therefore, it is urgent to develop a polyimide with excellent shielding ability and high ultraviolet sensitivity. SUMMARY

[0005] The present application provides a high-ultraviolet-sensitivity black polyimide and a preparation method and application thereof, to solve the problem that the existing polyimides cannot have excellent masking ability and ultraviolet sensitivity.

[0006] In a first aspect, the present application provides a high-ultraviolet-sensitivity black polyimide, having the following structural formula: wherein the structural unit A is a polyaryl ether or a polyaryl ketone; the structural unit B is a tetraphenylcyclopentadiene biphenyl; the structural unit C is diphenylamine or biphenol; and n is a positive integer from 1 to 50.

[0007] As a possible implementation manner, the structural unit A is any one of the following groups: the structural unit B is any one of the following groups: and the structural unit C is any one of the following groups: .

[0008] As a possible implementation manner, the number average molecular weight of the high-ultraviolet-sensitivity black polyimide is 10000-30000; the structural unit C is connected to a photosensitive group through an alkane chain, and the mass percentage of the photosensitive group is 5%-15%.

[0009] As a possible implementation manner, the structural formula is selected from any one of the following: ; .

[0010] In a second aspect, the present application provides a preparation method of the high-ultraviolet photosensitive black polyimide according to any possible implementation manner of the first aspect, comprising the following steps: dissolving diamine monomers with structural unit B and photosensitive monomers with structural unit C in a polar organic solvent under the protection of inert gas, adding anhydride with structural unit A, and fully dissolving and reacting under light-proof condition to obtain a photosensitive black polyamide solution.

[0011] As a possible implementation manner, the method further comprises the following steps: coating the photosensitive black polyamide solution on a substrate, and performing photoetching on the surface thereof by using an ultraviolet light source; and performing thermal imidization to obtain a high-ultraviolet photosensitive black polyimide film.

[0012] As a possible implementation manner, the anhydride with structural unit A is any one of bis(3,4-dimethylphenyl) ketone, 4,4'-{[propane-2,2-diylbis(4,1-phenyl)]bis(oxy)}bis(1,2-dimethylbenzene); and / or, the diamine monomers with structural unit B are any one of 4,4'-{3,5-bis(4'-methyl-[1,1'-biphenyl]-4-yl)cyclopenta-2,5-dien-1,2-diyl}diphenol, 4',4'''-(4,5-diphenylcyclopenta-3,5-dien-1,3-diyl)bis(4-methyl-1,1'-biphenyl); and / or, the photosensitive diamine monomers with structural unit C are any one of 4,4',5,5'-tetramethyl-[1,1'-biphenyl]-3,3'-diol, bis(3,4-dimethylphenyl) amine.

[0013] As a possible implementation manner, in terms of the molar ratio, the anhydride with structural unit A: the diamine monomers with structural unit B: the photosensitive diamine monomers with structural unit C = (10~100):(1~20):(2~50); and / or, the sum of the mass of the anhydride with structural unit A, the diamine monomers with structural unit B and the photosensitive diamine monomers with structural unit C accounts for 5%~10% of the total mass of the reaction solution; and / or, the polar organic solvent is any one of N-methyl-2-pyrrolidone, N,N-dimethylformamide, N-vinyl-2-pyrrolidone, toluene; and / or, the fully dissolving and reacting condition is that the reaction system is placed under the condition of -5~25℃, and the reaction is stirred in the dark for 12~20 h.

[0014] As a possible implementation manner, the exposure parameter of the photolithography is that the wavelength of the ultraviolet light source is 350-400 nm, and the exposure time is 5-80 s; the thermal imidization comprises the steps that under the atmosphere of inert gas, the temperature is kept at 30-50 DEG C for 30 minutes, 50-150 DEG C for 30 minutes, 150-250 DEG C for 30 minutes, and 250-400 DEG C for 40-60 minutes.

[0015] In a third aspect, the application provides an application of the high-ultraviolet photosensitive black polyimide in any of the fields of flexible OLED display, high-end CMOS image sensor packaging, satellite solar sail, high-frequency communication antenna / shielding and precision optical instrument.

[0016] The application provides a design route of the high-ultraviolet photosensitive black polyimide, and the intrinsic high-ultraviolet photosensitive black polyimide is prepared by reasonably designing a molecular structure of the polyimide, so that the intrinsic high-ultraviolet photosensitive black polyimide is subjected to photoisomerization after exposure.

[0017] The application provides a high-ultraviolet photosensitive black polyimide, the cut-off wavelength of the photosensitive black polyimide can reach 600 nm, external visible light is effectively prevented from causing photoaging of an internal structure, and the internal structure is protected from being plagiarized. BRIEF DESCRIPTION OF DRAWINGS

[0018] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description only show some embodiments of the application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0019] Figure 1 A schematic diagram of a surface mask pattern of the high-ultraviolet photosensitive black polyimide A after photolithography is provided for the embodiments of the application.

[0020] Figure 2 An infrared test diagram of the high-ultraviolet photosensitive black polyimide A is provided for the embodiments of the application.

[0021] Figure 3A synthesis route of the high-ultraviolet photosensitive black polyimide A provided by the embodiment of the present application.

[0022] Figure 4 A synthesis route of the high-ultraviolet photosensitive black polyimide B provided by the embodiment of the present application.

[0023] Figure 5 A synthesis route of the common black polyimide provided by the embodiment of the present application.

[0024] Figure 6 The ultraviolet-visible light test chart of the high-ultraviolet photosensitive black polyimide A and the common black polyimide provided by the embodiment of the present application. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application.

[0026] To solve the problem that the polyimide in the prior art cannot have excellent masking ability and ultraviolet photosensitivity, the embodiment of the present application provides a high-ultraviolet photosensitive black polyimide and a preparation method and application thereof.

[0027] The preparation method of the high-ultraviolet photosensitive black polyimide provided by the embodiment of the present application comprises the following steps: under the protection of an inert gas, a diamine monomer with a structural unit B and a photosensitive diamine monomer with a structural unit C are added into a polar organic solvent, and after stirring and dissolving, an anhydride with a structural unit A is added for continuous stirring. Then, the reaction system is placed in a water bath at-5~25℃, and the reaction is stirred in the dark for 12~20 h to obtain a photosensitive black polyimide acid solution. The obtained high-ultraviolet photosensitive black polyimide acid solution is coated on a substrate by a spin coating method, heated to remove the solvent, and exposed to ultraviolet light on the surface; and then, the high-ultraviolet photosensitive black polyimide is prepared by performing thermal imidization in stages under an inert gas atmosphere at 30~50℃ for 30 minutes, at 50~150℃ for 30 minutes, at 150~250℃ for 30 minutes, and at 250~400℃ for 40~60 minutes.

[0028] The anhydride with the structural unit A: the diamine monomer with the structural unit B: the photosensitive diamine monomer with the structural unit C = (10~100):(1~20):(2~50) in terms of the substance amount ratio.

[0029] The total mass of the anhydride having the structural unit A, the diamine monomer having the structural unit B and the photosensitive diamine monomer having the structural unit C accounts for 5% to 10% of the total mass of the reaction solution.

[0030] The polar organic solvent is selected from any one of N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N-vinyl-2-pyrrolidone and toluene.

[0031] The technical solutions of the present application will be further described below in combination with specific examples.

[0032] Example 1

[0033] This example provides a preparation experiment of high-ultraviolet photosensitive black polyimide.

[0034] The diamine monomer 4'',4'''''-(4,5-diphenylcyclopenta-3,5-diene-1,3-diyl)bis([1,1':4',1''-terphenyl]-4-amine) 205.30 g and the photosensitive diamine monomer 110.01 g were mixed and added to a device with a stirrer, the reaction system was placed in an ice water bath at 0℃, then 771.7 g of N-methyl pyrrolidone (NMP) was added, and the diamine monomer was stirred until it was completely dissolved. 351.91 g of 5,5'-carbonylbis(isobenzofuran-1,3-dione) was added to the reaction system in three times, each time interval being 20 min, and the reaction was carried out in an inert gas atmosphere for 12 h in the dark to obtain a high-ultraviolet photosensitive black polyamic acid solution A. After filtering and defoaming, the photosensitive black polyamic acid solution A was coated on a substrate by spin coating. The coated substrate was placed on a heating table at 80℃ for 3 h to evaporate the solvent, and a black polyimide film A was obtained. The photosensitive black polyimide film A was exposed to a 350 nm ultraviolet light source for 10 s. The results are shown in Figure 1 It can be seen from Figure 1 that the pattern can be clearly observed on the film after ultraviolet mask exposure.

[0035] Then the exposed photosensitive black polyimide film A was placed in an inert gas atmosphere and kept at 50℃ for 30 min, 100℃ for 30 min, 250℃ for 30 min and 400℃ for 60 min to perform thermal imidization in stages, and a high-ultraviolet photosensitive black polyimide A was prepared. The high-ultraviolet photosensitive black polyimide A was tested by infrared, and the results are shown in Figure 2 .

[0036] The synthesis route of this example is shown in Figure 3 .

[0037] Example 2

[0038] The present embodiment provides a preparation experiment of a high-ultraviolet photosensitive black polyimide.

[0039] The diamine monomer 4,4'-[3,5-bis(4'-amino-[1,1'-biphenyl]-4-yl)cyclopenta-2,5-diene-1,2-diyl]diphenol 77.90 g and the photosensitive diamine monomer 277.03 g were mixed and added to a device with a stirrer, the reaction system was placed in an ice water bath at 5°C, then 1110.50 g of N,N-dimethylformamide (DMF) was added, and the stirring was continued until the diamine monomer was completely dissolved. 757.70 g of 5,5'-[(propane-2,2-diylbis[4,1-phenylene])bis(oxy)]bis(isobenzofuran-1,3-dione) was added to the reaction system in three portions, with an interval of 5 min each time, and the reaction was carried out under an inert gas atmosphere and in the dark for 15 h to obtain a high-ultraviolet photosensitive black polyamic acid solution B. After filtering and defoaming, the photosensitive black polyamic acid solution B was coated on a substrate by spin coating. The coated substrate was placed on a heating table at 50°C for 2 h to evaporate the solvent, obtaining a black polyimide film B. The photosensitive black polyimide film B was exposed to a 400 nm ultraviolet light source for 70 s, and then was kept at 50°C for 30 min, 150°C for 30 min, 250°C for 30 min, and 400°C for 60 min under an inert gas atmosphere to perform thermal imidization in stages, obtaining a high-ultraviolet photosensitive black polyimide film B.

[0040] The synthetic route of the present embodiment is shown in Figure 4

[0041] Example 3

[0042] The present embodiment provides a preparation experiment of a high-ultraviolet photosensitive black polyimide.

[0043] ​A mixture of 17.3 g of diamine monomer N1-(4-aminophenyl)-N1- phenylbenzene-1,4-diamine and 111.5 g of photosensitive diamine monomer was added into a device equipped with mechanical stirring, the reaction system was placed in a 20 °C water bath, and then 1756.5 g of N,N-dimethylformamide (DMF) was added into the device, and the diamine monomers were stirred until completely dissolved. Then 108 g of 2,3,6,7-naphthalene tetracarboxylic dianhydride was added into the reaction solution at one time, and the reaction was continuously stirred for 24 h under inert gas protection to obtain a photosensitive black polyamic acid solution. The photosensitive black polyamic acid solution was filtered and defoamed at room temperature and in the dark, and then was coated on a substrate by a doctor blade method. The substrate was placed in a blast heating device and subjected to solvent evaporation at 60 °C for 2 h to obtain a photosensitive black polyimide film. The black polyimide film was subjected to imidization by stepwise heating at 80 °C for 60 min, 150 °C for 60 min, and 280 °C for 120 min under an inert gas atmosphere to obtain a common black polyimide with self-supporting property.

[0044] The synthetic route of the present example is shown in Figure 5

[0045] The high-ultraviolet photosensitive black polyimide A and the common black polyimide prepared in Example 1 were subjected to ultraviolet-visible light test, and the results are shown in Figure 6 Figure 6 It can be seen that the absorbance of the high-ultraviolet photosensitive black polyimide A in the ultraviolet region is more than 40% higher than that of the common photosensitive black polyimide.

[0046] Although the preferred embodiments of the present application have been described, those skilled in the art who have the benefit of the present disclosure can make additional changes and modifications to these embodiments without departing from the spirit and scope of the present application. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of the present application.

[0047] Obviously, various modifications and changes can be made to the present application by those skilled in the art without departing from the spirit and scope of the present application. Thus, it is intended that the present application embrace all such modifications and changes and, accordingly, the appended claims are intended to cover all such modifications and changes as falling within the scope of the present application.​​

Claims

1. A method for preparing a black polyimide with high UV sensitivity, characterized in that, The method comprises the following steps: dissolving diamine monomers with structural unit B and photosensitive diamine monomers with structural unit C in a polar organic solvent under inert gas protection, adding anhydride with structural unit A, and fully dissolving and reacting under light-proof condition to obtain a photosensitive black polyamide solution; coating the photosensitive black polyamide solution on a substrate, and performing photoetching on the surface thereof by using a UV light source; and performing thermal imidization to obtain the high-UV photosensitive black polyimide; The anhydride having structural unit A is any one of , . and / or the diamine monomer having structural unit B is any one of , . and / or the photoreactive diamine monomer having structural unit C is any one of , .

2. The production method according to claim 1, characterized by, the anhydride with structural unit A: the diamine monomers with structural unit B: the photosensitive diamine monomers with structural unit C = (10-100):(1-20):(2-50) in terms of the mass ratio; and / or the total mass of the anhydride with structural unit A, the diamine monomers with structural unit B and the photosensitive diamine monomers with structural unit C accounts for 5%-10% of the total mass of the reaction solution; and / or the polar organic solvent is any one of N-methyl-2-pyrrolidone, N,N-dimethylformamide, N-vinyl-2-pyrrolidone and toluene; and / or the fully dissolving and reacting condition is that the reaction system is placed under the condition of-5-25℃, and the reaction is stirred in the dark for 12-20 h.

3. The preparation method according to claim 1, characterized in that, the exposure parameter of the photoetching is that the wavelength of the UV light source is 350-400 nm, and the exposure time is 5-80 s; the thermal imidization comprises the following steps: keeping at 30-50℃ for 30 min, 50-150℃ for 30 min, 150-250℃ for 30 min and 250-400℃ for 40-60 min under inert gas atmosphere.

4. The method of claim 1, wherein, the number average molecular weight of the high-UV photosensitive black polyimide is 10000-30000.

5. A high-UV sensitive black polyimide, characterized by, which is prepared by the preparation method in any one of claims 1-4.

6. Application of the high-UV photosensitive black polyimide in claim 5 in any one of the following fields: flexible OLED display, high-end CMOS image sensor packaging, satellite solar sail, high-frequency communication antenna / shielding and precision optical instrument.

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