Preparation method and application of methacrylic resin monomer containing lactone structure

Abstract

The invention discloses a preparation method of a methacrylic resin monomer containing a lactone structure, which comprises the following steps: by taking alpha-bromo-gamma-butyrolactone and sodium methacrylate as raw materials and N, N-dimethylformamide as a solvent, reacting at 80-95 DEG C, and carrying out primary filtration and filtrate concentration, concentrated solution redissolution and secondary filtration, secondary filtrate washing, liquid separation, drying and tertiary filtration to obtain the methacrylic resin monomer containing the lactone structure. The preparation method comprises the following steps: preparing a 2-carbonyl-tetrahydrofuran-3-hydroxyl-methacrylate crude product from alpha-bromo-gamma-butyrolactone and sodium methacrylate according to a molar ratio of 1: (1.3-1.5), and rectifying the crude product to obtain a 2-carbonyl-tetrahydrofuran-3-hydroxyl-methacrylate product; according to the synthetic route, the used raw materials are all products commonly used in the field of chemical engineering and are low in price, high-toxicity substances such as a polymerization inhibitor are not needed in the preparation process, and the cost of the raw materials is greatly reduced; the synthesis process route is shorter, the operation is simple, purification of an intermediate is not needed, the production process is simplified, and the product yield is also improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photoresists, and relates to a preparation method of a photoresist main resin monomer, in particular to a preparation method and application of a methacrylic resin monomer containing an internal ester structure. BACKGROUND

[0002] A photoresist refers to a corrosion-resistant film material whose solubility changes through irradiation or radiation of a light source such as ultraviolet light, excimer laser, electron beam, ion beam, X-ray, etc., and is mainly applied to microfabrication of integrated circuits and semiconductor discrete devices, manufacturing industries such as flat panel displays, LEDs, inverted packaging, magnetic heads and precision sensors.

[0003] A photoresist mainly consists of a film-forming resin, a photosensitizer, an additive and a solvent component, wherein the film-forming resin directly determines the comprehensive performance of the photoresist and is the backbone component of the photoresist. The quality of the photoresist further affects the photoetching precision and influences the performance, yield and reliability of integrated circuits. Therefore, the research on the photoresist main resin and resin monomer is also one of the hot issues in the technical field of photoresists.

[0004] A preparation method of a photoresist resin monomer containing a lactone structure is disclosed in Chinese Invention Patent Application No. 202111636003.0, and the synthetic route is as follows:

[0005]

[0006] R1 and R2 are hydrogen atoms or alkyl groups. If compound III is α-bromo-γ-butyrolactone and compound II is methacrylic acid, 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylic acid ester can be prepared (see Example 2 Step 3 of the document), which requires the addition of a polymerization inhibitor (such as p-tert-butyl catechol and hydroquinone mentioned in the specification) and catalysis by an organic base to proceed, and more importantly, the yield of the reaction is very low, only 53.3%.

[0007] Therefore, people improve on this basis, consider preparing the target monomer by two-step method, first hydrolyze the alpha-bromo-gamma-butyrolactone under alkaline conditions to obtain the corresponding hydroxyl compound, and then add methacryloyl chloride or methacrylate anhydride under the action of a polymerization inhibitor to prepare the target product. For example, in the Chinese invention patent application with the document number 202311365317.0, a preparation method of an acrylate resin monomer for 193nm photoresist is disclosed, wherein, with acrylic anhydride and 2-carbonyl-tetrahydrofuran-3-alcohol (equivalent to a hydroxyl compound) as raw materials, under the action of a polymerization inhibitor, the reaction is carried out at 110℃ for 7h to prepare 2-carbonyl-tetrahydrofuran-3-hydroxy-acrylate. The raw material 2-carbonyl-tetrahydrofuran-3-alcohol used in the reaction is not a common chemical raw material, and the cost of acrylic anhydride is higher, and the market price of 1g is about 200 yuan, and high-toxicity substances such as benzoquinone need to be added as a polymerization inhibitor in the reaction. It can be seen that the existing synthesis process of methacrylate monomers inevitably needs to add a polymerization inhibitor to limit the self-polymerization rate due to the presence of active double bonds in the target product. If alpha-bromo-gamma-butyrolactone is considered as the starting raw material, the yield of the two-step method is not high, and the purification of the intermediate (the corresponding hydroxyl compound) also needs to be carried out, and the preparation process is too complex, so the synthesis route of the prior art is not suitable for batch production.

[0008] In order to reduce the production cost of the main body resin of the photoresist raw material, according to the basic principle, a more suitable raw material and synthesis route can be found, and a synthesis route and preparation method of such methacrylic acid monomer containing lactone ring which is simple and easy to operate, has lower raw material cost and is suitable for batch production can be developed. SUMMARY

[0009] The purpose of the present application is to develop a methacrylate resin monomer containing a lactone ring which is simple and easy to operate, has lower raw material cost and is suitable for batch production, to develop a one-step synthesis route, to improve the yield of the product by optimizing the process, and the target product of the present application contains a lactone ring, which can be used as a monomer for preparing a photoresist main body resin.

[0010] The technical scheme adopted by the present application provides a preparation method of a methacrylic resin monomer containing an internal ester structure, and the key lies in that the preparation method is to use alpha-bromo-gamma-butyrolactone and sodium methacrylate as raw materials, use N,N-dimethylformamide as a solvent, react at 80-95 DEG C, and then prepare 2-carbonyl-tetrahydrofuran-3-hydroxyl-methacrylate crude product through one-time filtration and filtrate concentration, concentration liquid redissolution and two-time filtration, two-time filtrate water washing, liquid separation, drying and three-time filtration, and then obtain 2-carbonyl-tetrahydrofuran-3-hydroxyl-methacrylate product through rectification of the crude product, and the molar ratio of the alpha-bromo-gamma-butyrolactone to the sodium methacrylate is 1:1.3-1.5, and the synthesis route of the preparation method is as follows:

[0011]

[0012] Further, the reaction time is 1-3 hours, and stirring is needed during the reaction, and the stirring frequency is controlled to be 60-100 r / min.

[0013] Specifically, the used solvent for the concentration liquid redissolution operation is dichloromethane, and the amount of the dichloromethane used is 2-3 times the volume of the concentrated liquid.

[0014] More specifically, the two-time filtrate water washing operation also needs to first adjust the pH value of the two-time filtrate to 7.0-7.8.

[0015] Preferably, the amount of the N,N-dimethylformamide used is 800-1000 mL per mole of alpha-bromo-gamma-butyrolactone.

[0016] Preferably, activated carbon or silica gel can also be added during the one-time filtration and filtrate concentration operation, and the amount of the activated carbon or silica gel added is 5 g per 100 mL of N,N-dimethylformamide.

[0017] The application of the preparation method of the methacrylic resin monomer containing the internal ester structure lies in that the 2-carbonyl-tetrahydrofuran-3-hydroxyl-methacrylate product can be used to prepare a 193 nm photoresist main body resin.

[0018] Compared with the prior art, the present application has the following beneficial effects:

[0019] The present application uses alpha-bromo-gamma-butyrolactone and sodium methacrylate as raw materials, uses N,N-dimethylformamide as a solvent, and then obtains 2-carbonyl-tetrahydrofuran-3-hydroxyl-methacrylate product through one-step synthesis reaction and subsequent purification steps such as three-time filtration, water washing, liquid separation and drying.

[0020] The one-step synthesis route of this invention uses raw materials that are commonly used in the chemical industry and are inexpensive. During the preparation process, highly toxic substances such as polymerization inhibitors are not required, significantly reducing raw material costs. The one-step synthesis process is shorter, simpler to operate, eliminates the need for intermediate purification, simplifies the production process, and improves product yield.

[0021] More importantly, this invention can prepare high-purity monomers with a purity of 99.9% for use in the synthesis of photoresist base resins, meeting the purity requirements of raw materials in the electrochemical field. When resin samples were prepared from the monomer samples of this invention, the destructive strength of the resin samples was found to be improved, indicating higher adhesion. It is evident that this invention improves the purity of the resin monomers, which helps to improve the adhesion of the corresponding resin products, thereby affecting the adhesion of the photoresist. Attached Figure Description

[0022] Figure 1 This is the NMR spectrum of sample 1 prepared in this invention.

[0023] Figure 2 This is the mass spectrum of sample 1 prepared according to the present invention.

[0024] Figure 3 This is the gas chromatogram of sample 1 prepared according to the present invention. Detailed Implementation

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] Unless otherwise specified in the examples, the procedures can be followed according to conventional conditions; unless the manufacturers of the reagents or instruments used are specified, they are all conventional products that can be purchased commercially.

[0027] Example 1

[0028] The preparation method of methacrylic resin monomers containing lactone structures includes the following specific steps:

[0029] S1, Synthesis reaction

[0030] 165 kg of α-bromo-γ-butyrolactone and 151.3 kg of sodium methacrylate (molar ratio 1:1.4) were added to 900 L of N,N-dimethylformamide. The mixture was stirred at a frequency of 80 r / min. The reaction vessel was heated to 90 °C and stirred continuously for 2 h to obtain a reaction solution containing the target product 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate.

[0031] S2, Primary filtration and filtrate concentration

[0032] The reaction solution was filtered and concentrated under reduced pressure to obtain 300L of concentrated solution.

[0033] S3, Concentrate Redissolution and Secondary Filtration

[0034] The concentrate was dissolved again in 900L of dichloromethane, and the solution was filtered twice to obtain a secondary filtrate.

[0035] S4. Secondary filtrate washing and separation

[0036] Wash the secondary filtrate twice with purified water, let it stand, separate the liquid, and retain the lower organic phase.

[0037] S5, drying and triple filtration, distillation

[0038] Magnesium sulfate was added for drying, and the mixture was filtered three times to obtain a crude sample. The crude sample was then distilled, and the fraction collected at 78–84 °C was used to obtain product sample 1.

[0039] Example 2

[0040] The preparation method of methacrylic resin monomers containing lactone structures includes the following specific steps:

[0041] S1, Synthesis reaction

[0042] 165 kg of α-bromo-γ-butyrolactone and 140.5 kg of sodium methacrylate (molar ratio 1:1.3) were added to 800 L of N,N-dimethylformamide. The mixture was stirred at a frequency of 60 r / min. The reaction vessel was heated to 95 °C and stirred continuously for 1 h to obtain a reaction solution containing the target product 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate.

[0043] S2, Primary filtration and filtrate concentration

[0044] Filter the reaction solution. Before filtration, add 40 kg of activated carbon and concentrate under reduced pressure to obtain 400 L of concentrated solution.

[0045] S3, Concentrate Redissolution and Secondary Filtration

[0046] The concentrate was dissolved again in 800L of dichloromethane, and the solution was filtered twice to obtain a secondary filtrate.

[0047] S4. Secondary filtrate washing and separation

[0048] The secondary filtrate was washed three times with purified water, and after standing, the lower organic phase was separated.

[0049] S5, drying and triple filtration, distillation

[0050] Magnesium sulfate was added for drying, and the sample was filtered three times to obtain a crude sample. The crude sample was then distilled, and the fraction collected at 78–84 °C was used to obtain product sample 2.

[0051] Example 3

[0052] The preparation method of methacrylic resin monomers containing lactone structures includes the following specific steps:

[0053] S1, Synthesis reaction

[0054] 165 kg of α-bromo-γ-butyrolactone and 162.1 kg of sodium methacrylate (molar ratio 1:1.5) were added to 1000 L of N,N-dimethylformamide. The mixture was stirred at a frequency of 100 r / min. The reaction vessel was heated to 95 °C and stirred continuously for 1 h to obtain a reaction solution containing the target product 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate.

[0055] S2, Primary filtration and filtrate concentration

[0056] Filter the reaction solution. Before filtration, 50 kg of silica gel can be added, and the solution can be concentrated under reduced pressure to obtain 400 L of concentrated solution.

[0057] S3, Concentrate Redissolution and Secondary Filtration

[0058] The concentrate was dissolved again in 1000L of dichloromethane, and the solution was filtered twice to obtain a secondary filtrate.

[0059] S4. Secondary filtrate washing and separation

[0060] Wash the secondary filtrate twice with purified water, let it stand, separate the liquid, and retain the lower organic phase.

[0061] S5, drying and triple filtration, distillation

[0062] Magnesium sulfate was added for drying, and the sample was filtered three times to obtain a crude sample. The crude sample was then distilled, and the fraction collected at 78–84 °C was used to obtain product sample 3.

[0063] Comparative Example 1

[0064] The implementation method is the same as in Example 1, except that "S3, resolution of concentrate and secondary filtration" are not performed. Instead, the concentrate is washed with purified water and subsequent steps are performed to prepare control product 1.

[0065] Comparative Example 2

[0066] The implementation method is the same as in Example 1, except that in the process of "S4, secondary filtrate washing and separation", only one washing with purified water is performed, and subsequent steps are performed to prepare control product 2.

[0067] Comparative Example 3

[0068] The implementation method is the same as in Example 1, except that when carrying out "S1, Synthesis Reaction", N,N-dimethylformamide is not used as the reaction solvent, but an equal volume of tetrahydrofuran is used, and subsequent steps are carried out to prepare control product 3.

[0069] Analysis and Testing

[0070] The samples prepared in this invention were analyzed by 1H NMR and HPLC-MS / MS, confirming that the obtained sample structure conforms to the characteristics of 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate and that no polymerization of the target product occurred. In the preparation method of this invention, suitable starting materials and synthetic routes were selected, and the target product could be prepared without the addition of polymerization inhibitors. Some of the test spectra are shown in the appendix. Figure 1 and attached Figure 2 The structural formula is:

[0071]

[0072] The purity of the samples and reference standards was determined by high-performance gas chromatography (HPLC). The results are shown in Tables 1 and 2, and some test chromatograms are shown in the appendix. Figure 3 .

[0073] The product and its reference standard were weighed, and the yield was calculated using the following formula. The results are shown in Table 1.

[0074] The formula for calculating product yield is:

[0075] Product yield = Actual weight (g) of the obtained sample or reference standard / Theoretical yield (g) calculated based on the amount of α-bromo-γ-butyrolactone used × 100%.

[0076] Table 1: Summary of Sample and Reference Standard Yield and Purity Test Results

[0077] Sample No. Product Yield (%) Product Purity (%) Sample 1 95.1 99.72 Sample 2 94.6 99.90 Sample 3 94.2 99.86 Control 1 96.9 92.36 Control 2 97.1 90.45 Control 3 94.8 85.13

[0078] As shown in Table 1, the purity of the product prepared by this invention can reach over 99.7%. Adding activated carbon or silica gel before the first filtration to adsorb impurities such as sodium bromide further increases the purity to approximately 99.9%. Omitting the filtration or washing steps in this invention, while increasing the product yield, will negatively impact the product purity to some extent. Furthermore, the synthesis reaction of this invention needs to be carried out in a suitable solvent.

[0079] Table 2: Gas chromatogram peaks of sample 1

[0080]

[0081] As can be seen from the results in Table 2, the sample prepared by this invention has fewer types of impurities, with only two impurity peaks. This indicates that the synthetic route of this invention is more reasonable, the main reaction is more complete, and there are fewer by-products, which reduces the difficulty of subsequent purification steps such as filtration.

[0082] Elemental analysis was performed on the product samples, and the results are shown in Table 3.

[0083] Table 3: Summary Table of Elemental Analysis Results of Samples

[0084] Test Items (ppb) Sample 1 Sample 2 Sample 3 Potassium 13 8 8 Sodium 14 8 11 Calcium 62 37 46 Magnesium 0 0 1 Aluminum 0 0 0 Manganese 1 0 1 Iron 1 0 0 Cobalt 1 1 1 Nickel 1 0 1 Copper 1 1 1 Zinc 14 5 8 Barium 1 0 0 Lead 1 0 0 Cadmium 1 1 1 Chromium 0 0 0 Arsenic 0 0 0 Sum of Elemental Impurities 111 61 79

[0085] As shown in Table 3, the main elemental impurities in the samples prepared by this invention are calcium, accounting for 50%–60% of the total elemental impurities, followed by sodium, potassium, and zinc. Adding activated carbon or silica gel during the first filtration can reduce the variety and total amount of elemental impurities in the product.

[0086] Application Effects and Analysis

[0087] The sample 2 prepared in this invention and commercially available 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate (purity 99.3%) were used to prepare methacrylic resin samples and reference standards. The performance of the prepared resin samples and reference standards was tested.

[0088] The adhesion of samples and controls was determined using a tensile testing method. Samples and controls were applied to flat plates with a uniform surface structure (two coats) with uniform thickness. After the coatings dried, the test specimens were bonded to the coating surface using an adhesive (using the minimum amount of adhesive). After the adhesive cured, the bonded test assembly was placed on a tensile testing machine, and a tensile stress was applied upwards in a direction perpendicular to the coating plane. This stress was steadily increased at a rate of 0.5 MPa / s. The tensile force required to break the adhesion between the coating and the flat plate was measured.

[0089] The formula for calculating the destructive strength is: Destructive strength = Destructive force / Column area. Each sample is tested 6 times, and the average value is taken.

[0090] The results are shown in Table 4.

[0091] Table 4: Performance test results of resin samples and reference standards

[0092]

[0093] As shown in Table 4, when the product sample prepared according to this invention is used as raw material to further prepare the corresponding resin sample, the resulting resin sample can withstand higher destructive strength, indicating that the resin sample of this invention has higher adhesion. This invention improves the purity of the resin monomer, which helps to improve the adhesion of the corresponding resin product, and thus affects the adhesion of the photoresist. In the field of photoresist technology, the adhesion of photoresist characterizes the strength of photoresist adhesion to the substrate. Insufficient adhesion of photoresist will lead to pattern deformation on the silicon wafer surface, and is one of the important evaluation indicators of photoresist performance.

Claims

1. A method for preparing a methacrylic resin monomer containing a lactone structure, characterized in that, The preparation method uses α-bromo-γ-butyrolactone and sodium methacrylate as raw materials, and N,N-dimethylformamide as solvent, reacting at 80℃~95℃. After one filtration and filtrate concentration, redissolving the concentrate and second filtration, washing the second filtrate with water, separation, drying, and three filtrations, crude 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate is obtained. The crude product is then distilled to obtain the 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate product. The molar ratio of α-bromo-γ-butyrolactone to sodium methacrylate is 1:1.3~1.

5. The synthetic route of the preparation method is as follows:

2. The method for preparing a methacrylic resin monomer containing a lactone structure according to claim 1, characterized in that, The reaction time is 1 to 3 hours, and stirring is required during the reaction. The stirring frequency is controlled at 60 to 100 r / min.

3. The method for preparing a methacrylic resin monomer containing a lactone structure according to claim 1, characterized in that, In the resolution operation of the concentrate, the solvent used is dichloromethane, and the amount of dichloromethane used is 2 to 3 times the volume of the concentrate.

4. The method for preparing a methacrylic resin monomer containing a lactone structure according to claim 1, characterized in that, The secondary filtrate washing operation requires adjusting the pH value of the secondary filtrate to 7.0-7.

8.

5. The method for preparing a methacrylic resin monomer containing a lactone structure according to claim 1, characterized in that, The amount of N,N-dimethylformamide used is 800 mL to 1000 mL of N,N-dimethylformamide per mole of α-bromo-γ-butyrolactone.

6. The method for preparing a methacrylic resin monomer containing a lactone structure according to claim 1, characterized in that, During the primary filtration and filtrate concentration operations, activated carbon or silica gel may be added, with the addition amount being 5g of activated carbon or silica gel per 100mL of N,N-dimethylformamide.

7. The application of the method for preparing a methacrylic resin monomer containing a lactone structure according to any one of claims 1 to 6, characterized in that, The 2-carbonyl-tetrahydrofuran-3-hydroxy-methacrylate product can be used to prepare the main resin for 193nm photoresist.

Images