A method and system for preparing a resin material

Abstract

The present application provides a preparation method and a preparation system of a resin material, comprising the following steps: continuously feeding a monomer-containing raw material system into a first reactor for polymerization to obtain a first liquid; continuously outputting the first liquid from the first reactor, and returning part of the first liquid to the first reactor, and continuously feeding the remaining part of the first liquid into a second reactor for aging treatment, wherein the feeding amount of the monomer-containing raw material system into the first reactor is not less than the feeding amount of the remaining part of the first liquid into the second reactor, to obtain the resin material. The present application is helpful to prepare a resin with controllable molecular weight and narrow molecular weight distribution.

Description

Technical Field

[0001] This invention relates to the field of resin technology, and more specifically to a method and system for preparing resin materials. Background Technology

[0002] Photoresist, also known as photoresist, is a material used in photolithography processes such as exposure, development, etching, and resist removal to transfer the desired pattern from a photomask onto a substrate. Depending on the application, it can be categorized into semiconductor photoresist, display panel photoresist, and PCB photoresist. Semiconductor photoresist can be further classified based on the exposure wavelength, including G-line photoresist, I-line photoresist, KrF photoresist, ArF photoresist, and EUV photoresist. KrF photoresist, in particular, is composed of resin (specifically KrF resin), photoinitiator, solvent, and additives.

[0003] Traditional resin preparation processes are batch or semi-batch processes, involving the input of large quantities of raw materials in a single batch or in multiple batches. Each batch is completed once the raw materials are used up and the reaction is finished. While these batch or semi-batch processes offer large batch production volumes, their production efficiency and reaction conversion rates are low. Furthermore, the molecular weight of the resin fluctuates significantly between batches, exhibiting a wide molecular weight distribution. This fluctuation is particularly pronounced during the transition from small-scale to industrial-scale production, leading to reduced resin quality and making it unsuitable for certain requirements. For example, KrF resin prepared using batch or semi-batch processes is of low quality and cannot meet the demands for high-quality photoresists. Summary of the Invention

[0004] This invention provides a method and system for preparing resin materials, which helps to prepare resins with controllable molecular weight and narrow molecular weight distribution.

[0005] This invention provides a method for preparing a resin material, comprising the following steps: continuously feeding a monomer-containing raw material system into a first reactor for polymerization to obtain a first liquid; continuously outputting the first liquid from the first reactor, and returning a portion of the first liquid back into the first reactor, while the remaining portion of the first liquid continuously enters a second reactor for aging treatment, wherein the feed amount of the monomer-containing raw material system entering the first reactor is not less than the feed amount of the remaining portion of the first liquid entering the second reactor, thereby obtaining the resin material.

[0006] Optionally, the monomer includes one or more of aromatic olefins, p-acetoxystyrene, and acrylate monomers.

[0007] Optionally, the monomer includes p-acetoxystyrene; the method further includes: the remaining portion of the first liquid is continuously fed into a second reactor for aging treatment to obtain a second liquid; the second liquid is continuously discharged from the second reactor and continuously fed into a third reactor for deprotection reaction to obtain a third liquid; the third liquid is subjected to solid-liquid separation, and the obtained solid product is dried to obtain the resin material.

[0008] Optionally, the monomer includes one or more of aromatic olefins and acrylate monomers, and the method further includes: continuously feeding the remaining portion of the first liquid into a second reactor for aging treatment to obtain a second liquid; performing solid-liquid separation on the second liquid and drying the obtained solid product to obtain the resin material.

[0009] Optionally, the process of continuously feeding the monomer-containing raw material system into the first reactor for polymerization includes: first, introducing solvent into the first reactor until the volume of the solvent entering the first reactor accounts for a certain percentage of the volume of the first reactor, and then stopping the introduction of the solvent; wherein, 20% ≤ a ≤ 60%; and then continuously feeding the monomer-containing raw material system into the first reactor for polymerization until the volume of the first feed liquid in the first reactor accounts for a certain percentage of the volume of the first reactor, and then continuously outputting the first feed liquid from the first reactor; wherein, 80% ≤ b ≤ 100%.

[0010] Optionally, the ratio of the volume of the first feed liquid continuously output from the first reactor returning to the first reactor to the volume of the remaining first feed liquid entering the second reactor is 2 to 50; and / or, the polymerization reaction temperature is 50 to 100°C; and / or, the residence time of the monomer-containing raw material system in the first reactor is 30 to 180 min; and / or, the monomer-containing raw material system further includes an initiator, the initiator including one or more of azobisisobutyronitrile and azobisisoheptanenitrile; and / or, the aging treatment temperature is 50 to 100°C and the time is 10 to 60 min.

[0011] Optionally, the flow rate of the second feed liquid continuously entering the third reactor is 800–1200 g / h; and / or, a neutralizing agent is continuously added to the third reactor at a flow rate of 800–1200 g / h, causing the second feed liquid to undergo the deprotection reaction to obtain the third feed liquid; the neutralizing agent includes one or more of sodium methoxide, sodium ethoxide, ethanolamine, triethylamine, and ammonia water; and / or, the temperature of the deprotection reaction is 30–60°C and the time is 10–60 min.

[0012] The present invention provides a resin material preparation system, comprising: a first reactor and a second reactor, wherein the first reactor is used for polymerization reaction and the second reactor is used for aging treatment; the first reactor is provided with a first inlet and a second outlet and a third outlet connected to the first inlet, and the second reactor is provided with a second inlet connected to the third outlet.

[0013] Optionally, the first reactor is an elliptical annular reactor, wherein the ratio of the major axis to the minor axis of the elliptical annular reactor is (1.5 to 5):1; a static mixer is provided inside the elliptical annular reactor; and / or, the second reactor is a tubular reactor.

[0014] Optionally, the reactor further includes a third reactor, a fourth reactor, and a fifth reactor; the third reactor is used for deprotection reaction, the fourth reactor is used for solid-liquid separation, and the fifth reactor is used for drying; the inlet of the third reactor is connected to the outlet of the second reactor, the inlet of the fourth reactor is connected to the outlet of the second reactor and / or the outlet of the third reactor, and the inlet of the fifth reactor is connected to the outlet of the fourth reactor; preferably, the third reactor is a tubular reactor or a batch reactor; preferably, the fourth reactor is a filtration-washing combined reactor or a batch reactor; preferably, the fifth reactor 005 includes one or more of the following: a vacuum drying oven, a freeze dryer, a vibrating dryer, a spray dryer, a single cone dryer, and a double cone dryer.

[0015] This invention provides a method and system for preparing resin materials. By continuously feeding a raw material system containing monomers into a first reactor and continuously outputting a first liquid from the first reactor, and ensuring that the amount of raw material system containing monomers entering the first reactor is not less than the amount of the remaining first liquid entering the second reactor, continuous production of resin materials is achieved. Furthermore, in the above-mentioned continuous resin material preparation system, a portion of the first liquid is returned to the first reactor, ensuring that the various components in the reaction process are more uniform, making the molecular weight of the resin material more controllable and the molecular weight distribution narrower. This effectively avoids the problem of large batch-to-batch fluctuations in the molecular weight of resin materials caused by batch and semi-batch preparation processes, thereby improving the quality of the resin material. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the process for preparing resin materials in some embodiments.

[0017] Figure label:

[0018] 001-First reactor; 002-Second reactor; 003-Third reactor; 004-Fourth reactor; 005-Fifth reactor; 101-Pump; A-Raw material system containing monomer; B-Resin material. Detailed Implementation

[0019] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below. The specific embodiments listed below are merely descriptions of the principles and features of the present invention, and the examples are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] This invention provides a method for preparing a resin material, comprising the following steps: continuously feeding a monomer-containing raw material system into a first reactor for polymerization to obtain a first liquid; continuously outputting the first liquid from the first reactor, returning a portion of the first liquid to the first reactor, and continuously feeding the remaining portion of the first liquid into a second reactor for aging treatment, wherein the feed amount of the monomer-containing raw material system entering the first reactor is not less than the feed amount of the remaining portion of the first liquid entering the second reactor, thereby obtaining a resin material.

[0021] According to the inventor's research and analysis: by continuously feeding a raw material system containing monomers into the first reactor and continuously outputting the first liquid from the first reactor, and ensuring that the amount of raw material system containing monomers entering the first reactor is not less than the amount of the remaining first liquid entering the second reactor, continuous production of resin materials is achieved, which helps to improve production efficiency. In addition, under the above-mentioned continuous resin material preparation system, a portion of the first liquid is returned to the first reactor, which ensures that the various components in the reaction process are more uniform, making the molecular weight of the resin material more controllable and the molecular weight distribution narrower. This effectively avoids the problem of large batch-to-batch fluctuations in the molecular weight of resin materials caused by batch and semi-batch preparation processes, thus improving the quality of the resin material. Furthermore, traditional batch and semi-batch production processes often employ batch reactors, with large batch sizes. This leads to a large accumulation of raw materials within the batch reactor, resulting in severe backmixing, low monomer conversion efficiency, uncontrollable reaction temperature, and high energy consumption. In contrast, the resin material preparation method provided in this invention employs a multi-stage series production process, where reactants are transported step-by-step. This reduces backmixing, makes the resin's molecular weight more controllable and its molecular weight distribution narrower, and also helps improve monomer conversion rate, product yield, and production efficiency. Additionally, it offers advantages such as controllable temperature during the reaction process and lower energy consumption.

[0022] In some embodiments, the process of continuously feeding a monomer-containing feedstock system into a first reactor for polymerization includes: first, introducing a solvent (base solvent) into the first reactor until the volume of the solvent entering the first reactor accounts for a percentage of the volume of the first reactor, then stopping the solvent feeding; wherein, 20% ≤ a ≤ 60%; then, continuously feeding the monomer-containing feedstock system into the first reactor for polymerization until the volume of the first feed solution (containing resin intermediates) in the first reactor accounts for a percentage of the volume of the first reactor, then continuously discharging the first feed solution from the first reactor (i.e., continuously collecting the first feed solution from the first reactor); wherein, 80% ≤ b ≤ 100%. Exemplarily, a is a range of 20%, 30%, 40%, 50%, 60%, or any two thereof, and b is a range of 80%, 85%, 90%, 95%, 100%, or any two thereof. It is understood that when b approaches 100%, the interior of the first reactor is substantially filled with the solvent and the monomer-containing feedstock system.

[0023] The solvents mentioned above may include one or more of methanol, isopropanol, propylene glycol methyl ether acetate, and 2-butanone.

[0024] In practice, solvent (base solvent) is introduced into the first reactor until the volume of the solvent entering the first reactor is 'a' relative to the volume of the first reactor. After the solvent is stopped, the first reactor can be heated to a temperature of 50-100°C, which is not higher than the boiling point of the solvent, so that the temperature of the solvent in the first reactor reaches the temperature of the polymerization reaction.

[0025] In some embodiments, the temperature of the polymerization reaction (i.e., the temperature of the first reactor) is 50 to 100°C, for example, a range of 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or any combination thereof.

[0026] The average residence time (i.e. polymerization time) of the above-mentioned monomer-containing raw material system in the first reactor can be 30 to 180 min, for example, 30 min, 50 min, 100 min, 120 min, 150 min, 180 min or any combination thereof.

[0027] The raw material system containing monomers also includes an initiator, which may include one or more of azobisisobutyronitrile and azobisisoheptanenitrile.

[0028] In some embodiments, the ratio (reflux ratio) of the volume of the first liquid continuously output from the first reactor and returned to the first reactor to the volume of the remaining first liquid entering the second reactor is 2 to 50, for example, a range of 2, 5, 10, 20, 30, 40, 50 or any combination thereof. By controlling the reflux ratio to meet the above range, most of the first liquid is returned to the first reactor for recycling and polymerization. This reduces material backmixing and ensures that the various components in the polymerization and aging processes are more uniform. This helps to reduce batch-to-batch fluctuations in the molecular weight of the resin material, making the molecular weight of the resin material more controllable and the molecular weight distribution narrower.

[0029] Understandably, in order to ensure the continuous operation of the resin preparation process, the amount of raw material system, including monomers, continuously added to the first reactor is not less than the amount of the remaining first liquid (output) continuously entering the second reactor.

[0030] The temperature of the aging treatment (i.e., the temperature of the second reactor) can be 50 to 100°C, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or any combination thereof. The aging treatment time (i.e., the residence time of the remaining first liquid in the second reactor) can be 10 to 60 minutes, for example, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes or any combination thereof. This helps to promote the continued polymerization reaction of unreacted monomers in the first liquid and improve the conversion rate of monomers.

[0031] The monomers mentioned above may include one or more of aromatic olefins, p-acetoxystyrene, and acrylate monomers.

[0032] Specifically, the aromatic olefins mentioned above may include styrene, and the acrylate monomers mentioned above may include tert-butyl acrylate.

[0033] In some embodiments, the monomer includes p-acetoxystyrene. When the monomer includes p-acetoxystyrene, the aged product needs to undergo a deprotection reaction to obtain a resin material. The specific process includes: the remaining portion of the first feed solution continuously enters a second reactor for aging treatment to obtain a second feed solution; the second feed solution is continuously discharged from the second reactor and continuously enters a third reactor for a deprotection reaction to obtain the resin material.

[0034] Furthermore, a neutralizing agent can be continuously added to the third reactor to cause the second feed liquid to undergo a deprotection reaction to obtain the third feed liquid. Specifically, a neutralizing agent can be continuously added to the third reactor at a flow rate of 800-1200 g / h to cause the second feed liquid to undergo a deprotection reaction to obtain the third feed liquid. The neutralizing agent can include one or more of sodium methoxide, sodium ethoxide, ethanolamine, triethylamine, and ammonia water.

[0035] The temperature of the above-mentioned deprotection reaction (i.e., the temperature of the third reactor) can be 30 to 60°C, for example, 30°C, 40°C, 50°C, 60°C or any combination thereof, and the time of the deprotection reaction (i.e., the residence time of the second feed liquid and the neutralizing agent in the third reactor) can be 10 to 60 min, for example, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min or any combination thereof.

[0036] Furthermore, the flow rate of the second feed liquid continuously entering the third reactor can be 800 to 1200 g / h, for example, 800 g / h, 900 g / h, 1000 g / h, 1100 g / h, 1200 g / h or any combination thereof.

[0037] In practice, the third feed liquid needs to be post-processed to obtain the resin material. For example, the second feed liquid is continuously output from the second reactor and continuously enters the third reactor for deprotection reaction to obtain the third feed liquid; the third feed liquid is then subjected to solid-liquid separation, and the resulting solid product is dried to obtain the resin material.

[0038] When the monomers mentioned above do not include p-acetoxystyrene, the above deprotection reaction is not required. The remaining first liquid is continuously fed into the second reactor for aging treatment to obtain the second liquid. The second liquid is then subjected to solid-liquid separation, and the resulting solid product is dried to obtain the resin material.

[0039] After performing solid-liquid separation on the third feed liquid or the second feed liquid (e.g., precipitation, filtration), the solid product is separated from the liquid phase. Further, the solid product can be washed to remove residual monomers and impurities such as metal ions, yielding a resin filter cake. This process can take 10–60 minutes. The resin filter cake is then dried to obtain the resin material.

[0040] The temperature for the above drying (such as baking) can be 50-100℃ and the pressure can be 0-30kPaA.

[0041] When the monomer does not include p-acetoxystyrene, the above-mentioned process of treating the first feed liquid may include: the remaining portion of the first feed liquid is continuously fed into the second reactor for aging treatment to obtain the second feed liquid; the second feed liquid is subjected to solid-liquid separation, and the obtained solid product is dried to obtain the resin material.

[0042] In some embodiments, the resin includes fluorinated krypton photoresist resin (KrF photoresist resin). A fluorinated krypton photoresist resin with good photolithographic performance can be prepared according to the above preparation method.

[0043] This invention also provides a resin material preparation system, including: a first reactor 001 and a second reactor 002, wherein the first reactor 001 is used for polymerization reaction and the second reactor 002 is used for aging treatment; the first reactor 001 is provided with a first inlet, and a second outlet and a third outlet connected to the first inlet, and the second reactor 002 is provided with a second inlet connected to the third outlet.

[0044] In some embodiments, the first reactor 001 described above is an elliptical annular reactor. Compared with a batch reactor, it helps to increase the heat transfer area and mass transfer efficiency, and also helps to increase the monomer conversion rate, thereby increasing the reaction conversion rate and production efficiency, and increasing the product yield. In addition, it has the advantages of controllable temperature during the reaction process and lower energy consumption.

[0045] Furthermore, the ratio of the major axis to the minor axis of the elliptical annular reactor can be (1.5 to 5):1, for example, 1.5:1, 2:1, 3:1, 4:1, 5:1 or any combination thereof.

[0046] Traditional resin preparation reactors (such as batch reactors) generally use mechanical stirring. The sealing of the stirring (mechanical stirring) is generally a single-end or double-end seal. During long-term use, wear of the dynamic and stationary rings in the mechanical seal structure can cause contamination inside the reactor. Leakage of the sealing liquid in double-end seals can also affect product quality.

[0047] In the above-mentioned elliptical annular reactor of the present invention, a static mixer can be provided. Using a static mixer for material mixing and mass transfer can reduce the degree of backmixing of materials, making the molecular weight of the resin material more controllable and the molecular weight distribution narrower. It also avoids the contamination of the resin caused by mechanical seal wear and leakage of sealing liquid in the mechanical stirring of the batch reactor, which helps to improve the purity of the resin.

[0048] The number of units in the static mixer within the aforementioned elliptical annular reactor can be from 1 to 1000.

[0049] Furthermore, the surface of the aforementioned elliptical annular reactor may be covered with a jacket or coil, through which a heat-conducting medium flows. Preferably, these heat-conducting media may be a mixture of water and ethylene glycol or heat-conducting oil.

[0050] The type of static mixer mentioned above can be selected from SV, SK, SX, SH or SL.

[0051] In some embodiments, the second reactor 002 is a tubular reactor (e.g., a tubular plug flow reactor) used to age the first feed liquid to improve monomer conversion rate.

[0052] Furthermore, the above-mentioned preparation system may also include a third reactor 003 for carrying out a deprotection reaction; it may also include a fourth reactor 004 for carrying out solid-liquid separation; and it may also include a fifth reactor 005 for carrying out drying.

[0053] The feed inlet of the third reactor can be connected to the discharge outlet of the second reactor, the feed inlet of the fourth reactor can be connected to the discharge outlet of the second reactor and / or the discharge outlet of the third reactor, and the feed inlet of the fifth reactor can be connected to the discharge outlet of the fourth reactor.

[0054] In some embodiments, the third reactor 003 is a tubular reactor or a batch reactor.

[0055] In some embodiments, the fourth reactor 004 includes one or more of a filtration-washing combined reactor or a batch reactor.

[0056] In some embodiments, the fifth reactor 005 may include one or more of a vacuum drying oven, a freeze dryer, a vibration dryer, a spray dryer, a single cone dryer, and a double cone dryer, in which the above-mentioned drying is performed to obtain a resin material (resin solid powder).

[0057] like Figure 1As shown, in some embodiments, a raw material system A containing monomers is continuously fed into a first reactor 001 for polymerization to obtain a first liquid. The first liquid is continuously discharged from the first reactor 001, and a portion of the first liquid is returned to the first reactor 001 under the drive of pump 101. The remaining portion of the first liquid is continuously fed into a second reactor 002 for aging treatment to obtain a second liquid. The second liquid is continuously discharged from the second reactor 002 and continuously fed into a third reactor 003 for deprotection reaction to obtain a third liquid. The third liquid is continuously discharged from the third reactor 003 and continuously fed into a fourth reactor 004 for solid-liquid separation to obtain a solid product. The solid product is continuously discharged from the fourth reactor 004 and continuously fed into a fifth reactor 005 for drying to obtain resin material B.

[0058] Understandably, the amount of the remaining first liquid continuously entering the second reactor 002 or the amount of the second liquid continuously entering the third reactor 003 is the actual output of the first reactor 001.

[0059] Compared with batch and semi-batch production processes carried out in a batch reactor, the resin material preparation system provided in this embodiment of the invention connects multiple reactors in series to form a multi-stage series production process that can be used for continuous production of resin materials. The reactants are transported step by step in the production process, which can reduce backmixing of materials, make the molecular weight of the resin more controllable and the molecular weight distribution narrower, and also help to improve the conversion rate of monomers, increase the yield of products and production efficiency. In addition, it also has the advantages of controllable temperature in the reaction process and lower energy consumption.

[0060] The present invention will be further described below through specific embodiments and comparative examples. Unless otherwise specified, the reagents, materials and instruments used below are all conventional reagents, materials and instruments, all of which are commercially available, and the reagents and materials involved can also be synthesized by conventional synthetic methods.

[0061] The main raw material information is as follows:

[0062] Styrene, Wanhua Chemical Group Co., Ltd., purity ≥99.5%.

[0063] Para-acetoxystyrene, China Energy Conservation Wanrun Co., Ltd., electronic grade G3.

[0064] tert-butyl acrylate, Ningbo Microchip Electronics Co., Ltd., purity ≥99.5%.

[0065] Methanol / isopropanol / propylene glycol methyl ether acetate / ammonia, Jiangyin Jianghua Microelectronics Materials Co., Ltd., electronic grade G3.

[0066] Azobisisobutyronitrile / Azobisisoheptanenitrile, Shanghai Aladdin Biochemical Technology Co., Ltd., purity ≥99.5%.

[0067] Sodium methoxide / sodium ethanol / ethanolamine / methanolamine, Jiangsu Kemio Chemical Co., Ltd., purity ≥99.5%.

[0068] Example 1

[0069] This embodiment provides a method for preparing a resin, including the following steps:

[0070] Methanol (solvent) is introduced into the first reactor until the volume of methanol entering the first reactor accounts for a percentage of the reactor's volume (a = 50%). After stopping the methanol introduction, the first reactor is heated to 62°C. Then, a methanol solution of styrene, p-acetoxystyrene, and azobisisobutyronitrile (the azobisisobutyronitrile methanol solution contains 20 wt% azobisisobutyronitrile) is continuously added to the first reactor at flow rates of 1000 g / h, 400 g / h, and 250 g / h (the monomer, initiator, and their inflow rates into the first reactor). The polymerization reaction yields the first feed solution. Once the volume of the first feed solution in the first reactor reaches b (b = 100%), the first feed solution is continuously discharged from the first reactor. Simultaneously, a methanol solution (monomer and initiator solution) of styrene, p-acetoxystyrene, and azobisisobutyronitrile is added to the first reactor at a flow rate of 2000 g / h (the rate at which raw materials are added to the first reactor) according to the aforementioned material mass ratio. Methanol is also added to the first reactor at a flow rate of 2000 g / h (the rate at which raw materials are added to the first reactor).

[0071] A portion of the first feed solution is returned to the first reactor, while the remaining portion continuously enters the second reactor for aging treatment. The residence time (residence time or duration of aging treatment) of the reaction solution in the second reactor is 1 hour. The ratio of the volume of the first feed solution returned to the first reactor to the volume of the remaining portion entering the second reactor (reflux ratio) is 5:1. The residence time (average residence time of polymerization reaction) of the reaction solution in the first reactor is 30 minutes, i.e., the polymerization reaction temperature is 62°C and the time is 30 minutes, thus obtaining the second feed solution.

[0072] The second feed solution is continuously output from the second reactor, and the second feed solution and sodium methoxide (neutralizing agent) are continuously fed into the third reactor at a flow rate of 800 g / h to carry out the deprotection reaction. The temperature of the deprotection reaction in the third reactor is 45℃, and the residence time of the reaction solution (i.e. the deprotection reaction time) is 30 min, thus obtaining the third feed solution.

[0073] The third feed liquid is continuously output from the third reactor and continuously fed into the fourth reactor for precipitation and washing for 60 minutes to obtain KrF resin filter cake;

[0074] The KrF resin filter cake was continuously discharged from the fourth reactor and continuously fed into the fifth reactor for drying at 65°C and 10 kPaA to obtain resin (resin solid).

[0075] The reactor is a first elliptical annular reactor with a major axis to minor axis ratio of 2:1. A static mixer of type SK is installed inside the elliptical annular reactor. The second reactor is a tubular reactor. The third reactor is a tubular reactor. The fourth reactor is a batch reactor. The fifth reactor is a single cone dryer.

[0076] Comparative Example 1

[0077] This comparative example provides a method for preparing a resin, comprising the following steps:

[0078] Add 2000g of methanol to a 10L glass reactor and heat the glass reactor to 62℃ using an oil bath.

[0079] Add 1000g of styrene, 400g of p-acetoxystyrene, and 300g of azobisisobutyronitrile in methanol (where the mass percentage of azobisisobutyronitrile is 20wt%) to a 5L narrow-mouthed glass bottle, stir and mix evenly to obtain a monomer mixture.

[0080] The monomer mixture was added dropwise to the glass reactor described above. After 3 hours of dropwise addition and 5 hours of heat preservation, a resin intermediate was obtained. Then, the glass reactor was cooled to 45°C, 800 mg of sodium methoxide was added, and after 5 hours of reaction, a mixed solution was obtained. The mixed solution was added dropwise to a mixture of methanol and water, a precipitate was formed, and the precipitate was filtered to obtain a filter cake.

[0081] The filter cake was dried in a vacuum drying oven to obtain KrF resin.

[0082] Referring to the process of Example 1, the resins of Examples 2 to 10 and Comparative Example 2 were prepared. The first reactor and the ratio of the long axis to the short axis, the type of static mixer, the second reactor, the third reactor, the fourth reactor, the fifth reactor, the solvent, a and b, the monomer and its flow rate into the first reactor, the initiator and its flow rate into the first reactor are summarized in Table 1. The flow rate of raw materials added to the first reactor, the temperature and time of the polymerization reaction, the temperature and time of the aging treatment, the reflux ratio, the flow rate of the second feed liquid and the neutralizing agent into the third reactor, the temperature and time of the deprotection reaction, the precipitation washing time, the drying temperature and pressure, etc. are summarized in Table 2. Other conditions are kept the same as in Example 1.

[0083] Table 1

[0084]

[0085]

[0086] Table 2

[0087]

[0088] Test case

[0089] The following parameters of the resins in the above embodiments and comparative examples were tested:

[0090] Molecular weight (Mw) and molecular weight distribution of the resin: The molecular weight (Mw) and molecular weight distribution of the resin were determined by gel permeation chromatography (GPC). A Shimadzu LC-ADXR-2 chromatograph was used. The standard was polystyrene (PS), prepared as a 1% (w / w) polystyrene THF solution using tetrahydrofuran (THF) as the solvent. The test temperature was 35℃, and the flow rate of the standard was 1 mL / min. Specific results are shown in Table 3.

[0091] Test results

[0092] Table 3. Molecular weight (Mw) and molecular weight distribution of the resins

[0093]

[0094]

[0095] By comparing Examples 1, 2, 3 and Comparative Example 1, it can be seen that the KrF resin obtained by the continuous preparation process of the present invention has controllable molecular weight and a narrower molecular weight distribution, which is beneficial to improving photolithography performance.

[0096] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a resin material, characterized in that, Includes the following steps: The raw material system containing monomers is continuously fed into the first reactor for polymerization to obtain the first feed liquid; The first liquid feed is continuously output from the first reactor, and a portion of the first liquid feed is returned to the first reactor. The remaining portion of the first liquid feed is continuously fed into the second reactor for aging treatment to obtain the resin material. The feed amount of the monomer-containing raw material system entering the first reactor is not less than the feed amount of the remaining portion of the first liquid feed entering the second reactor. The ratio of the volume of the portion of the first liquid feed continuously output from the first reactor that returns to the first reactor to the volume of the remaining portion of the first liquid feed entering the second reactor is 2 to 50.

2. The method for preparing the resin material according to claim 1, characterized in that, The monomers include one or more of aromatic olefins, p-acetoxystyrene, and acrylate monomers.

3. The method for preparing the resin material according to claim 2, characterized in that, The monomer includes p-acetoxystyrene; the method further includes: The remaining portion of the first liquid is continuously fed into the second reactor for aging treatment to obtain the second liquid. The second feed solution is continuously output from the second reactor and continuously enters the third reactor for deprotection reaction to obtain the third feed solution; The third liquid is subjected to solid-liquid separation, and the resulting solid product is dried to obtain the resin material.

4. The method for preparing the resin material according to claim 2, characterized in that, The monomer includes one or more of aromatic olefins and acrylate monomers, and the method further includes: The remaining portion of the first liquid is continuously fed into the second reactor for aging treatment to obtain the second liquid. The second liquid material is subjected to solid-liquid separation, and the resulting solid product is dried to obtain the resin material.

5. The method for preparing the resin material according to claim 1, characterized in that, The process of continuously feeding the monomer-containing raw material system into the first reactor for polymerization includes: First, solvent is introduced into the first reactor until the volume of the solvent entering the first reactor accounts for a certain percentage (a) of the total volume of the first reactor, at which point the introduction of solvent is stopped; wherein, 20% ≤ a ≤ 60%; The monomer-containing raw material system is continuously fed into the first reactor for polymerization until the volume of the first liquid in the first reactor is b, and then the first liquid is continuously discharged from the first reactor; wherein, 80%≤b≤100%.

6. The method for preparing the resin material according to claim 1, characterized in that, The polymerization reaction is carried out at a temperature of 50~100℃; And / or, the residence time of the raw material system containing monomers in the first reactor is 30~180 min; And / or, the monomer-containing raw material system further includes an initiator, the initiator including one or more of azobisisobutyronitrile and azobisisoheptanenitrile; And / or, the aging treatment is performed at a temperature of 50~100℃ for a time of 10~60min.

7. The method for preparing the resin material according to claim 3, characterized in that, The second feed liquid continuously enters the third reactor at a flow rate of 800~1200 g / h; And / or, a neutralizing agent is continuously added to the third reactor at a flow rate of 800-1200 g / h, causing the second feed liquid to undergo the deprotection reaction to obtain the third feed liquid; the neutralizing agent includes one or more of sodium methoxide, sodium ethoxide, ethanolamine, triethylamine, and ammonia water; And / or, the deprotection reaction is carried out at a temperature of 30-60°C for a time of 10-60 min.

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