A poly-p-hydroxystyrene resin, its preparation method and use

Abstract

The application discloses a kind of poly-p-hydroxystyrene resin and its preparation method and application, belong to high polymer material technical field.It uses "prepolymer synthesis-block copolymerization" step strategy, first poly-p-hydroxystyrene prepolymer solution and polyurea resin prepolymer solution are prepared respectively, then two kinds of prepolymer solution are carried out block copolymerization under the action of catalyst, and the target resin is obtained after treatment.By introducing polyurea segment into poly-p-hydroxystyrene molecular structure, the many defects of traditional poly-p-hydroxystyrene resin are effectively solved, the synergistic improvement of resin thermal stability, mechanical property, dielectric property, moisture resistance, etching resistance and dimensional stability is realized, the prepared resin has excellent film forming property, can be widely applied in semiconductor photoresist, electronic packaging and liquid crystal display orientation layer and other fields, especially outstanding in high-end electronic and flexible display scene, with significant industrial application value.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a poly-p-hydroxystyrene resin and a preparation method and application thereof. BACKGROUND

[0002] Poly-p-hydroxystyrene (PHS) resin is a functional high polymer material with high heat resistance (Tg≈150-180℃) and modifiable hydroxyl groups. The benzene ring and side chain hydroxyl groups in the molecular structure of PHS resin endow it with excellent film-forming property, chemical stability and dielectric property (Dk≈3.0). These characteristics make PHS resin irreplaceable in the fields of semiconductor photoresist (such as KrF / ArF photoetching process), liquid crystal display alignment layer (such as OLED planarization) and medical sustained-release carrier.

[0003] However, the single-structure poly-p-hydroxystyrene has obvious performance short boards, and it is difficult to meet the stringent requirements of advanced technology on the comprehensive performance of the material. First, the pure PHS resin has high brittleness, and the elongation at break is usually less than 5%. In the process of photoresist coating and device packaging, the film layer is prone to cracking, which affects the reliability of the device. Second, the surface energy of the pure PHS resin is high, and the hydrophilicity of the side chain hydroxyl group leads to the easy absorption of water vapor in the environment by the PHS film layer. Under high temperature and humidity conditions, the dielectric property decreases significantly, and the anticorrosion protection ability of the metal substrate is insufficient. In addition, the plasma etching resistance of the pure PHS resin is limited, and it is difficult to meet the requirements in advanced semiconductor processes. In the scene of 5G high-frequency chip packaging, the coefficient of thermal expansion (CTE) of the pure PHS does not match the silicon substrate (≈3ppm / ℃), and it is difficult to meet the size stability requirements.

[0004] In order to overcome these defects, the industry has tried various improvement methods. One common method is random copolymerization with other monomers, such as copolymerization with tert-butyl methacrylate (TBMA) to improve the chemical amplification effect, or copolymerization with fluorine-containing monomers to improve the etching resistance. However, these methods often lead to the decline of other properties, such as the decrease of thermal stability, phase separation problem, or the decrease of film uniformity, etc. Another method is to introduce a protecting group (such as t-BOC group) to improve photosensitivity, but this will increase the process complexity and cost, and it is easy to produce by-products when the protecting group is removed, resulting in pattern defects. In addition, there is also a strategy of nano-particle composite modification, which adjusts the coefficient of thermal expansion by adding nano-filler such as silicon dioxide and aluminum nitride, but the dispersion of nano-particles is poor, and impurities are easily introduced, which affects the electrical properties of semiconductor devices.

[0005] Therefore, it is a key to develop a poly-p-hydroxystyrene resin that takes into account multiple dimensional properties to break through the technical bottleneck. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application proposes a poly-p-hydroxystyrene resin, a preparation method and application thereof, aiming to solve at least one of the above problems. The present application introduces polyurea segments into the molecular structure of poly-p-hydroxystyrene by a "prepolymer synthesis-block copolymerization" step-by-step strategy, achieving a synergistic improvement in the heat resistance, mechanical properties, dielectric properties, etch resistance and process compatibility of the resin, and expanding its application in high-end fields.

[0007] The present application achieves the technical purpose by the following technical solutions:

[0008] A preparation method of a poly-p-hydroxystyrene resin, the method comprising the following steps:

[0009] Step S1, raw material preparation;

[0010] Step S2, poly-p-hydroxystyrene prepolymer synthesis, obtaining a poly-p-hydroxystyrene prepolymer solution;

[0011] Step S3, polyurea resin prepolymer synthesis, obtaining a polyurea resin prepolymer solution;

[0012] Step S4, block copolymerization reaction, adding the poly-p-hydroxystyrene prepolymer solution obtained in step S2 and the polyurea resin prepolymer solution obtained in step S3 into the same reaction kettle to obtain a block copolymerization reaction mixture;

[0013] Step S5, post-treatment of the block copolymerization reaction mixture obtained in step S4 to obtain the poly-p-hydroxystyrene resin.

[0014] Compared with the prior art, the present application has at least the following beneficial effects:

[0015] The poly-p-hydroxystyrene resin, the preparation method and application thereof provided by the application introduce polyurea segments into the molecular structure of poly-p-hydroxystyrene through a "prepolymer synthesis-block copolymerization" step-by-step strategy, effectively break through the bottleneck of single performance of traditional poly-p-hydroxystyrene resin, realize the unity of multi-dimensional performance synergistic improvement and excellent process compatibility. In terms of performance, the resin not only significantly enhances thermal stability and can withstand high-temperature processes in high-end technical scenarios, but also realizes the balance of "high strength-high toughness" mechanical properties, solving the problem of high brittleness and easy cracking of traditional resin; at the same time, it has low dielectric constant characteristics, adapts to the signal transmission demand of high-frequency electronic devices, and greatly improves the hydrophobicity, reduces the adverse effects of water vapor adsorption on dielectric properties and metal substrate protection, can also optimize the coefficient of thermal expansion to adapt to the substrate, reduce the risk of interfacial stress in the packaging process, and significantly enhance the plasma etching performance, guarantee the pattern precision and low defect rate of photolithography process. In terms of process and application, the preparation method effectively avoids problems such as phase separation and gelation, has excellent film-forming property, can be compatible with existing production processes, does not need to modify equipment, reduces the industrialization threshold, can be widely applied in the fields of semiconductor photoresist and electronic packaging materials, and also performs outstandingly in the field of liquid crystal display alignment layer, especially flexible display, can meet the performance requirements of different scenarios, and does not need to rely on expensive raw materials or complex process, has lower raw material cost, the post-processing process is environmentally friendly and has no toxic by-products, conforms to the green production trend, provides a high-performance and highly adaptive solution for the field of high-end electronic materials, and has important industrial application value. DETAILED DESCRIPTION

[0016] In order to make the purpose, technical scheme and advantages of the application clearer, further detailed description of the application will be given below in combination with examples, and the illustrative embodiments of the application and the description thereof are only used to explain the application, and do not limit the application.

[0017] Specifically, the application provides a poly-p-hydroxystyrene resin and a preparation method thereof, and the method comprises the following steps:

[0018] Step S1, raw material preparation

[0019] The p-hydroxystyrene monomer, isocyanate monomer, diamine monomer and N,N-dimethylformamide (DMF) are purified and / or dried for standby; wherein the purification and / or drying treatment comprises: the p-hydroxystyrene monomer is distilled under reduced pressure at 0.01-0.05 MPa and 80-100°C to purify, so that the purity is ≥99.5%; the isocyanate monomer is distilled under reduced pressure at 0.005-0.02 MPa and 60-80°C to purify, so that the purity is ≥99%; the diamine monomer is dried in a vacuum drying oven at 50-70°C for 2-4 hours, so that the purity is ≥99%; the N,N-dimethylformamide (DMF) is dried by molecular sieve for more than 48 hours, so that the purity is ≥99.8%;

[0020] Preferably, the isocyanate monomer is selected from one or more of TDI, MDI, HDI, IPDI, HMDI and fluorine-containing isocyanate; and the diamine monomer is preferably a polyether diamine or a diamine monomer containing a hindered amine structure such as a piperazine diamine.

[0021] Step S2, synthesis of poly-p-hydroxystyrene prepolymer

[0022] A certain amount of p-hydroxystyrene monomer purified in step S1 (the molar amount is denoted as n) is added to a reaction kettle, then DMF dried in step S1 is added to the reaction kettle, and the amount is adjusted to ensure that the mass fraction of p-hydroxystyrene monomer in the total solution in the reaction kettle is 15-25%; then, an initiator such as azobisisobutyronitrile (AIBN) is added to the reaction kettle, and the amount of AIBN is 0.5-1% of the mass of p-hydroxystyrene monomer; under the protection of nitrogen, the reaction system in the reaction kettle is heated to 60-80°C at a stirring speed of 200-300 r / min, and reacted for 4-6 hours, to obtain a poly-p-hydroxystyrene prepolymer solution;

[0023] In this step, when the reaction system in the reaction kettle is heated to 60-80°C, the initiator azobisisobutyronitrile (AIBN) is first decomposed to generate isobutyronitrile radicals and nitrogen, and the reaction equation is exemplarily as follows:

[0024] ;

[0025] Subsequently, the generated isobutyronitrile radicals can initiate the opening of the double bond on the p-hydroxystyrene monomer to form a linear polymer chain through radical polymerization, thereby obtaining a poly-p-hydroxystyrene prepolymer, and the reaction equation is exemplarily as follows:

[0026] ;

[0027] Wherein, Ph represents a benzene ring, and x represents the polymerization degree of the poly-p-hydroxystyrene prepolymer; wherein, the number average molecular weight of the poly-p-hydroxystyrene prepolymer obtained in step S2 is controlled to be 5000-8000 Da.

[0028] Step S3, synthesis of polyurea resin prepolymer

[0029] In another reaction kettle, the isocyanate monomer after drying in step S1 (molar amount is denoted as m) and DMF solvent are added, so that the mass ratio of the isocyanate monomer is 20-30%

isocyanate monomer / (isocyanate monomer + DMF)

[0030] Wherein, R is a polyether main chain or a main chain containing a hindered amine structure, y represents the number of repetitions of the corresponding group, and M is a simplified form of the corresponding group in the polyurea resin prepolymer; wherein, the number average molecular weight of the polyurea resin prepolymer obtained in step S3 is controlled to be 3000-6000 Da.

[0031] Step S4, block copolymerization reaction

[0032] The poly-p-hydroxystyrene prepolymer solution obtained in step S2 and the polyurea resin prepolymer solution obtained in step S3 are added into the same reaction kettle, stirring is carried out under the protection of nitrogen at a speed of 200-300 r / min, the temperature is raised to 50-70℃, and dibutyltin dilaurate (DBTDL) is added into the same reaction kettle while stirring, the addition amount of the DBTDL is 0.1-0.3% of the total mass of the poly-p-hydroxystyrene prepolymer solution and the polyurea resin prepolymer solution in the same reaction kettle, and the reaction is carried out for 6-8 hours, and a block copolymerization reaction mixture is obtained.

[0033] In this step, the reaction equation of the poly-p-hydroxystyrene prepolymer and the polyurea resin prepolymer is exemplarily as follows:

[0034] .

[0035] Wherein, “ ” represents an omitted p-hydroxystyrene group, " indicates the unshown block. It should be noted that the actual product molecular structure after block copolymerization is a network structure due to the molecular structure limitation of the urea-based material, and the above reaction equation is only a schematic drawing and does not represent the actual structure. During the block copolymerization reaction, dibutyltin dilaurate as an organic catalyst can ensure that the block copolymerization reaction rate is maintained at 0.05-0.15 L•mol -1 -1 interval, ensuring that the chain growth reaction selectivity is ≥90% and inhibiting the homopolymerization side reaction.

[0036] Step S5, post-treatment

[0037] The solution after the reaction of step S4 is poured into 10-15 times the volume of methanol for precipitation, and the precipitate is collected by filtration, washed with methanol for multiple times, and the precipitate is placed in a vacuum drying oven at 40-60°C for drying for 12-24 hours to a constant weight, to obtain a block copolymer solid, which is dissolved in propylene glycol methyl ether acetate (PGMEA) to prepare a solution with a mass fraction of 10-15%, filtered through a 0.2 μm polytetrafluoroethylene (PTFE) filter membrane to obtain the final resin product.

[0038] Preferably, in the preparation method, the ratio of the molar amount n of the hydroxystyrene monomer to the molar amount m of the isocyanate monomer is controlled to be n:m=(6~10):1.

[0039] Example One

[0040] ​The poly-p-hydroxystyrene resin of the first embodiment is prepared by the above preparation method, wherein, in the preparation process, the isocyanate monomer is MDI, and the diamine monomer is selected from polyether diamine (specifically, Jeffamine ED-600 series polyether amine purchased from HUNTSMAN company in the United States); in step S2, the amount of p-hydroxystyrene monomer is 6 mol, and after adding DMF, the mass fraction of p-hydroxystyrene monomer in the total solution in the reaction kettle is 20%, the amount of AIBN is 0.7% of the mass of p-hydroxystyrene monomer, under the protection of nitrogen, the stirring speed is 200 r / min, and the stirring is carried out at 70°C for 5 h; in step S3, the amount of MDI is 1 mol, the mass fraction of MDI in DMF is 25%, under the protection of nitrogen, the stirring speed is 200 r / min, the temperature is raised to 50°C, and the DMF solution containing polyether diamine monomer is slowly added, the mass fraction of polyether diamine monomer in the DMF solution containing polyether diamine monomer is 20%, the adding time is 1 h, after the adding is completed, the reaction is continued for 2 h, and a polyurea resin prepolymer solution is obtained, in this process, the molar ratio of MDI to polyether diamine monomer is controlled to be 1.05:1; in step S4, under the protection of nitrogen, the stirring speed is 200 r / min, the temperature is raised to 70°C, the amount of DBTDL added is 0.2%, and the reaction is carried out for 8 h; in step S5, the solution after step S4 is poured into 10 times the volume of methanol for precipitation, the precipitate is placed in a 60°C vacuum drying oven for drying for 12 h to constant weight, a solution with a mass fraction of 15% is prepared, and then filtered through a 0.2 μm polytetrafluoroethylene (PTFE) filter membrane.

[0041] Example two

[0042] The difference between example two and example one is only that the amount of p-hydroxystyrene monomer in step S2 is 8 mol.

[0043] Example three

[0044] The difference between example three and example one is only that the amount of p-hydroxystyrene monomer in step S2 is 10 mol.

[0045] Comparative example one

[0046] The difference between comparative example one and example one is only that the amount of p-hydroxystyrene monomer in step S2 is 4 mol.

[0047] Comparative example two

[0048] The difference between comparative example two and example one is only that the amount of p-hydroxystyrene monomer in step S2 is 15 mol.

[0049] Comparative example three

[0050] Comparative Example 3 differs from Example 1 in that steps S3 and S4 are not involved, i.e., after obtaining the poly-p-hydroxystyrene prepolymer solution, the solution after reaction is directly precipitated by pouring into 10 times volume of methanol, and the precipitate is dried in a vacuum oven at 60°C for 12 hours to constant weight, then a resin solution with a mass fraction of 15% is prepared, and then filtered with a 0.2 μm polytetrafluoroethylene (PTFE) filter membrane. That is, a pure poly-p-hydroxystyrene resin is prepared without polyurea prepolymer preparation and block copolymerization reaction.

[0051] Comparative Example 4

[0052] Comparative Example 4 refers to Example 1, and differs from Example 1 in that it does not contain steps S2 to S4 in Example 1, but the substances used in steps S2 to S4 (p-hydroxystyrene monomer, DMF, AIBN, MDI, polyether diamine monomer, etc.) are weighed in equal mass and directly mixed, stirred at a speed of 200 r / min, and warmed to 60°C for 8 hours. Then, purification and preparation of the resin solution are performed according to step S5 of Example 1.

[0053] Comparative Example 5

[0054] Comparative Example 5 refers to Example 1, and differs from Example 1 in that the p-hydroxystyrene monomer is mixed with t-butyl methacrylate (TBMA) at a molar ratio of 6:1, then AIBN (0.7% of the mass of the p-hydroxystyrene monomer) and DMF (20% of the total monomer mass) are added, and the mixture is reacted at 70°C and 200 r / min for 5 hours. The post-treatment is the same as step S5 of Example 1.

[0055] Comparative Example 6

[0056] The pure PHS resin of Comparative Example 3 is mixed with t-BOC anhydride at a mass ratio of 10:3, and reacted at 60°C for 4 hours under catalysis of pyridine. The post-treatment is the same as step S5 of Example 1.

[0057] Performance Test

[0058] The performance test includes testing of the following parameters:

[0059] Glass transition temperature (Tg): using a differential scanning calorimeter (DSC), with a heating rate of 10°C / min, in a nitrogen atmosphere;

[0060] Tensile properties: using a universal testing machine, with a tensile rate of 5 mm / min, and a sample size of 10 mm x 4 mm x 0.2 mm;

[0061] Dielectric constant: using an impedance analyzer, with a test frequency of 1 MHz, at room temperature;

[0062] Water contact angle: using contact angle measuring instrument, deionized water titration, test 5 times to take the average value;

[0063] Coefficient of thermal expansion (CTE): the resin solution of each example and the comparative example was mixed with aluminum nitride filler (particle size 50-100 nm) at a mass ratio of 70:30 to prepare an electronic packaging adhesive, and then a thermal mechanical analyzer (TMA) was used to measure the coefficient of thermal expansion at a temperature range of 25-150°C and a heating rate of 5°C / min;

[0064] Film forming property and phase separation: an optical microscope was used to observe the uniformity of the film surface (100 times magnification);

[0065] Photolithography defect rate: the resin solution of each example and the comparative example was mixed with 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine (photoinitiator) and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate (crosslinking agent) at a mass ratio of 85:10:5 to prepare a photoresist solution, and then a scanning electron microscope was used to observe the number of defects of a 36 nm line width pattern;

[0066] Plasma etching loss rate: the photoresist solution was prepared according to the photolithography defect rate test, and then an inductively coupled plasma etching machine was used, CF4 / O2=3:1, power 300W, to calculate the mass loss per unit time;

[0067] The test results are as follows:

[0068]

[0069] As can be seen from the above table, the Tg values (162-174℃) of Examples 1-3 are significantly higher than those of Comparative Examples, among which Example 2 reaches 174℃, which is 23℃ higher than that of Comparative Example 3 of pure PHS resin and 14℃ higher than that of Comparative Example 6 of PHS resin protected by t-BOC, which is due to the rigid network formed by the polyurea hard segment and the benzene ring of PHS in the block structure, which has much better thermal stability than single protective group modification (Comparative Example 6) or random copolymer structure (Comparative Example 5). In terms of mechanical properties, the tensile strength (21-28MPa) and elongation at break (84-158%) of the examples are overall superior to those of the comparative examples, for example, the elongation at break (132%) of Example 2 is 33 times that of pure PHS (4%) and 16.5 times that of PHS resin protected by t-BOC, and this "high strength-high toughness" balance may be due to the synergistic effect of "PHS hard segment providing rigid support-polyurea soft segment providing elastic cushioning" in the block structure, while the comparative examples generally have the defects of "embrittlement" or "insufficient strength" due to the lack of such structure. In terms of thermal expansion performance improvement, after being compounded with aluminum nitride filler, the CTE values (14-19ppm / ℃) of the examples are significantly lower than those of the comparative examples (24-37ppm / ℃), and the CTE of Example 2 (14ppm / ℃) is the lowest, which is more compatible with the silicon substrate (3ppm / ℃), which is crucial for electronic packaging, as it can reduce the interfacial stress and cracking risk caused by mismatched expansion during thermal cycling. In addition, the dielectric constant of the examples is lower than that of the comparative examples, and the dielectric constant of Example 2 is the lowest, which meets the requirements of high-frequency electronic devices for low-dielectric materials. Water contact angle tests show that the hydrophobicity of the examples is significantly better than that of pure PHS, which is due to the non-polar polyether structure of the polyurea segment, which reduces water molecule adsorption and avoids dielectric loss in high-frequency signal transmission, especially suitable for 5G radio frequency devices and high-density packaging. For film forming quality, the examples all show "excellent" without gel or phase separation; Comparative Example 1 (n:m=4:1) causes gel due to excessive polyurea, and Comparative Example 4 (direct mixing) causes serious phase separation due to disordered reaction, which proves that stepwise block copolymerization is the key to ensuring film forming property. In addition, when the resin material of the present application is prepared into photoresist, the photoetching defect rate (0.01-0.03 / μm²) of the examples is significantly lower than that of the comparative examples, and the plasma etching loss rate (0.28-0.33% / min) is only about 1 / 9 of that of pure PHS (2.9% / min), which has excellent photoetching performance.

[0070] It should be further explained that the poly-p-hydroxystyrene resin of the present application not only can be applied in the field of electronic packaging materials and semiconductor photoresists, but also has significant application potential in the field of liquid crystal display alignment layer, etc. Its high Tg (162-174℃) can withstand the high temperature process (such as annealing process) of liquid crystal display device; excellent film forming uniformity (no phase separation) can ensure the smooth surface of the alignment layer and reduce the arrangement defects of liquid crystal molecules; moderate hydrophobicity (96-109°) can regulate the pre-tilt angle of liquid crystal molecules and optimize the display contrast; and the low dielectric constant property is helpful to reduce the driving voltage of display panel and improve the energy efficiency. Compared with the traditional polyimide alignment material, the resin of the present application has both moisture resistance and process compatibility, and in the bending durability test in the flexible display field, the sample of Example Two still maintains more than 85% of the initial performance after 100,000 times of bending, which is much better than the polyimide material (50-60%), showing the technical advantage of cross-field application.

[0071] The above detailed description further explains the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A process for the preparation of a poly-p-hydroxystyrene resin, characterized in that, The method comprises the following steps: Step S1, raw material preparation; Step S2, synthesis of poly-p-hydroxystyrene prepolymer to obtain a poly-p-hydroxystyrene prepolymer solution; Step S3, synthesis of polyurea resin prepolymer to obtain a polyurea resin prepolymer solution; Step S4, block copolymerization reaction, the poly-p-hydroxystyrene prepolymer solution obtained in step S2 and the polyurea resin prepolymer solution obtained in step S3 are added into the same reaction kettle to obtain a block copolymerization reaction mixture; Step S5, post-treatment of the block copolymerization reaction mixture obtained in step S4 to obtain the poly-p-hydroxystyrene resin.

2. The method for preparing poly(p-hydroxystyrene) resin as described in claim 1, characterized in that, In step S2, the molecular formula of the poly-p-hydroxystyrene prepolymer is: ， wherein Ph represents a benzene ring, and x represents the polymerization degree of the poly-p-hydroxystyrene prepolymer.

3. The method for preparing poly(p-hydroxystyrene) resin as described in claim 1, characterized in that, Step S2 comprises: taking the p-hydroxystyrene monomer purified in step S1 and adding it into a reaction kettle; then, adding the dried DMF in step S1 into the reaction kettle to ensure that the mass percentage of the p-hydroxystyrene monomer in the total solution in the reaction kettle is 15-25%; then, adding azobisisobutyronitrile into the reaction kettle, the amount of which accounts for 0.5-1% of the mass of the p-hydroxystyrene monomer; stirring at a speed of 200-300 r / min under nitrogen protection and heating the reaction system in the reaction kettle to 60-80°C; and reacting for 4-6 hours to obtain the poly-p-hydroxystyrene prepolymer solution.

4. The method for preparing poly(p-hydroxystyrene) resin as described in claim 3, characterized in that, Step S3 comprises: In another reaction kettle, the isocyanate monomer and the DMF solvent dried in step S1 are added to make the mass percentage of the isocyanate monomer 20-30%; then, stirring at a speed of 150-250 r / min under nitrogen protection and heating to 40-60°C; then, slowly adding the DMF solution containing the diamine monomer, the mass percentage of the diamine monomer in the solution being 10-20%; controlling the molar ratio of the isocyanate monomer to the diamine monomer to be 1.05:1 to 1.10:1; controlling the dropping time to be 1-2 hours; and continuing to react for 2-3 hours after the dropping is completed to obtain the polyurea resin prepolymer solution.

5. The method for preparing poly(p-hydroxystyrene) resin as described in claim 4, characterized in that, The isocyanate monomer is selected from one or more of TDI, MDI, HDI, IPDI, HMDI and fluorine-containing isocyanate.

6. The method for preparing poly(p-hydroxystyrene) resin as described in claim 4, characterized in that, The diamine monomer is a polyether diamine monomer or a diamine monomer containing a hindered amine structure.

7. The method for preparing poly(p-hydroxystyrene) resin as described in claim 1, characterized in that, Step S4 comprises: adding the poly-p-hydroxystyrene prepolymer solution obtained in step S2 and the polyurea resin prepolymer solution obtained in step S3 into the same reaction kettle; stirring at a speed of 200-300 r / min under nitrogen protection and heating to 50-70°C; adding dibutyltin dilaurate into the same reaction kettle while stirring, the amount of which accounts for 0.1-0.3% of the total mass of the poly-p-hydroxystyrene prepolymer solution and the polyurea resin prepolymer solution in the same reaction kettle; and reacting for 6-8 hours to obtain the block copolymerization reaction mixture.

8. A method for preparing a poly(p-hydroxystyrene) resin according to any one of claims 1-7, characterized in that, The ratio of the molar amount n of the p-hydroxystyrene monomer to the molar amount m of the isocyanate monomer is controlled to be n:m=(6-10):

1.

9. A poly-p-hydroxystyrene resin material produced by the production method according to any one of claims 1 to 8.

10. Use of the poly-p-hydroxystyrene resin material according to claim 9 for photoresists, electronic packaging, and / or liquid crystal display alignment layers.

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