Photoresist film-forming resin raw material and preparation method thereof

Abstract

The invention relates to the field of polyacrylate photoresists, in particular to a photoresist film-forming resin raw material and a preparation method thereof.The preparation method comprises the steps that cyclopentadiene is dropwise added into a mixed solution of alpha-bromomethyl acrylate and a solvent, the temperature is controlled, a reaction is conducted for 4 h, and 5-bromodicyclohept-2-ene-5-carboxylic acid methyl ester is prepared; the preparation method comprises the following steps: adding alkali into 5-bromo dicycloheptyl-2-ene-5-carboxylic acid methyl ester, and hydrolyzing at 20-30 DEG C for 2 hours to obtain a hydrolysis product; the hydrolysis product is subjected to epoxidation and hydrolysis with hydrogen peroxide under the condition of glacial acetic acid, and 1-bromine-5-hydroxy-3-oxa-tricyclic nonyl-2-ketone is obtained; according to the method, 1-bromo-5-hydroxy-3-oxa-tricyclic nonyl-2-ketone is cyanided by cuprous cyanide to prepare the 1-cyano-5-hydroxy-3-oxa-tricyclic nonyl-2-ketone monomer, and the method has the advantages that the raw materials are convenient and easy to obtain, the route is short, the reaction conditions are relatively mild, the operation safety is relatively high, the total yield is remarkably improved, and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyacrylate photoresist, in particular to a photoresist film-forming resin raw material and preparation method. BACKGROUND

[0002] Photoresist is a kind of photosensitive film material, and is also one of the key basic materials for microfabrication technology in the photoelectric information industry. Photoresist is composed of film-forming resin, photoacid generator, solvent and some additives. As an important upstream material in the manufacturing process of semiconductor chips, display screens and the like, the photoresist market has been in a state of stable growth. In recent years, with the rapid development of large-scale and super-large scale integrated circuits, the research and development of photoresist has rapidly developed. Photoresist technology is complex, and there are many varieties. Among them, polyacrylate compounds and their derivatives are the earliest generation of 193nm photoresist film-forming resins. Acrylate compounds containing lactone structure are the most commonly used monomers in 193nm photoresist. The polar group is deprotected after exposure, and then dissolved in the developer.

[0003] Methyl acrylate (3-cyano-2-oxohexahydro-2H-3,5-bridgemethylenecyclopenta[b] furan-6-yl) is an important monomer for preparing polyacrylate photoresist, and its main intermediate is 1-cyano-5-hydroxy-3-oxatricyclic non-2-one, English name: 1-cyano-5-hydroxy-3-oxatricyclic non-2-one.

[0004] The preparation technology of 1-cyano-5-hydroxy-3-oxatricyclic non-2-one is reported in EP1930328A1 of Japan DAICEL Chemical Industry Co., Ltd. in 2005: using 2-cyano ethyl acrylate and cyclopentadiene as starting materials, then using m-chloroperbenzoic acid for oxidation, and finally using formic acid and water for hydrolysis to obtain the target product. However, in the small test verification process, the hydrolysis of formic acid is not complete, and the cyano group is changed into carboxylic acid in the hydrolysis process. In addition, due to the difficulty in impurity purification, the yield is not high. In addition, m-chloroperbenzoic acid is used in the oxidation process, which has high cost, and the by-product m-chlorobenzoic acid is difficult to remove completely, which has a great influence on the purity. Therefore, this route has high cost and is difficult to scale up production, which is the main reason for the high market price of the intermediate 1-cyano-5-hydroxy-3-oxatricyclic non-2-one. SUMMARY

[0005] The purpose of the present application is to provide a photoresist film-forming resin raw material and preparation method, and to provide a preparation method of 1-cyano-5-hydroxy-3-oxatricyclic non-2-one, which has the advantages of convenient and easy-to-obtain raw materials, short route, relatively mild reaction conditions, high operation safety, significantly improved total yield and the like.

[0006] To achieve the above objectives, the present invention provides a photoresist film-forming resin raw material and preparation method, comprising adding cyclopentadiene dropwise to a mixture of methyl α-bromoacrylate and a solvent, reacting at a controlled temperature for 4 h to prepare methyl 5-bromodicyclohept-2-ene-5-carboxylic acid; 5-Bromodicyclohepta-2-ene-5-carboxylic acid methyl ester was added to alkali and hydrolyzed at 20-30℃ for 2 h to obtain the hydrolysis product; The hydrolysis product was epoxidized and hydrolyzed with hydrogen peroxide under glacial acetic acid conditions to obtain 1-bromo-5-hydroxy-3-oxatricyclonon-2-one; The monomer of 1-cyano-5-hydroxy-3-oxatricyclonon-2-one was prepared by cyanidation of 1-bromo-5-hydroxy-3-oxatricyclonon-2-one with cuprous cyanide.

[0007] The solvent is any one of dichloromethane, dichloroethane, toluene, and tetrahydrofuran.

[0008] The temperature range of the temperature-controlled reaction is 15–40°C.

[0009] The molar ratio of cyclopentadiene to methyl α-bromoacrylate is 1:1.8 to 1:3.0.

[0010] The alkali is either sodium hydroxide or potassium hydroxide.

[0011] The reaction temperature under glacial acetic acid conditions is 60℃~70℃.

[0012] The molar ratio of the hydrolysis product to hydrogen peroxide is 1:6.0 to 1:8.5.

[0013] The reaction temperature for cyanidation with cuprous cyanide is 150°C, and the reaction time is 6-12 hours.

[0014] The 1-cyano-5-hydroxy-3-oxatricyclonon-2-one monomer is recrystallized from a 50% EA / n-heptane mixed solvent at a ratio of 1:2 to 1:4.

[0015] Secondly, the present invention also provides a photoresist film-forming resin raw material, wherein the structural formula of the photoresist film-forming resin raw material is as follows: .

[0016] This invention discloses a photoresist film-forming resin raw material and its preparation method, comprising: adding cyclopentadiene dropwise to a mixture of methyl α-bromoacrylate and a solvent, reacting at a controlled temperature for 4 h to prepare methyl 5-bromodicyclohepta-2-ene-5-carboxylate; adding methyl 5-bromodicyclohepta-2-ene-5-carboxylate to an alkali and hydrolyzing at 20-30°C for 2 h to obtain a hydrolysis product; epoxidizing and hydrolyzing the hydrolysis product with hydrogen peroxide under glacial acetic acid conditions to obtain 1-bromo-5-hydroxy-3-oxatricyclonon-2-one; and cyaniding 1-bromo-5-hydroxy-3-oxatricyclonon-2-one with cuprous cyanide to prepare a 1-cyano-5-hydroxy-3-oxatricyclonon-2-one monomer. This photoresist film-forming resin raw material and its preparation method, through a multi-step organic synthesis reaction, construct a novel monomer—1-cyano-5-hydroxy-3-oxatricyclonon-2-one—with a rigid tricyclic skeleton and containing hydroxyl and cyano functional groups. This structure has significant benefits in the field of photoresist, specifically in the following aspects: The resulting monomer contains a rigid tricyclic structure (3-oxatricyclic nonane backbone), which can significantly improve the rigidity and thermal stability of the polymer backbone. After subsequent polymerization to form a resin, it helps to improve the dimensional stability and deformation resistance of the photoresist film in high-temperature processes (such as post-baking and etching).

[0017] The hydroxyl groups (–OH) introduced into the molecule provide polar sites, enhancing the resin's solubility rate in alkaline developers (such as 2.38% TMAH aqueous solution). Unexposed areas retain low solubility due to cross-linking or hydrophobicity, resulting in high development contrast, which is beneficial for obtaining steep pattern sidewalls and fine patterns.

[0018] The tricyclic framework is rich in hydrocarbon structures and does not contain heteroatoms that are easily attacked by plasma (such as sulfur and silicon), which gives it excellent performance in CF4 / O2 or Cl2-based plasma etching.

[0019] The starting materials (cyclopentadiene and methyl α-bromoacrylate) are inexpensive and readily available; the reaction conditions for each step are mild (e.g., hydrolysis is carried out at 20-30°C, and epoxidation uses a hydrogen peroxide / glacial acetic acid system), ensuring high operational safety; the intermediates have high purity and few byproducts, making them suitable for scale-up production. Simultaneously, the use of heavy metal catalysts or highly toxic reagents is avoided (e.g., photoacid generator PAG does not participate in the synthesis of this monomer); the cyanation step uses cuprous cyanide instead of highly toxic sodium / potassium cyanide, allowing for safe conversion under strict control; the final resin contains no halogen residues (bromine atoms are replaced in the cyanation step), aligning with the trend of green electronic chemicals development. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a flowchart of a method for preparing a photoresist film-forming resin raw material according to the present invention.

[0022] Figure 2 This is the nuclear magnetic resonance spectrum of compound I in this invention.

[0023] Figure 3 This is the GC spectrum of compound I in this invention. Detailed Implementation

[0024] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0025] This invention provides a photoresist film-forming resin raw material and its preparation method, comprising adding cyclopentadiene dropwise to a mixture of methyl α-bromoacrylate and a solvent, reacting at a controlled temperature for 4 h to prepare methyl 5-bromodicyclohept-2-ene-5-carboxylic acid, the chemical reaction formula of which is as follows: .

[0026] Methyl 5-bromodicyclohepta-2-ene-5-carboxylic acid was added to a base and hydrolyzed at 20-30°C for 2 h to obtain the hydrolysis product. The chemical reaction formula is as follows: b) .

[0027] The hydrolysis product was epoxidized and hydrolyzed with hydrogen peroxide under glacial acetic acid conditions to obtain 1-bromo-5-hydroxy-3-oxatricyclonon-2-one, as shown in the following chemical reaction formula: c) .

[0028] The monomer of 1-cyano-5-hydroxy-3-oxatricyclonon-2-one was prepared by cyanidation of 1-bromo-5-hydroxy-3-oxatricyclonon-2-one with cuprous cyanide. The chemical reaction formula is as follows: d) .

[0029] The solvent is any one of dichloromethane, dichloroethane, toluene, and tetrahydrofuran.

[0030] The temperature range of the temperature-controlled reaction is 15–40°C.

[0031] The molar ratio of cyclopentadiene to methyl α-bromoacrylate is 1:1.8 to 1:3.0.

[0032] The alkali is either sodium hydroxide or potassium hydroxide.

[0033] The reaction temperature under glacial acetic acid conditions is 60℃~70℃.

[0034] The molar ratio of the hydrolysis product to hydrogen peroxide is 1:6.0 to 1:8.5.

[0035] The reaction temperature for cyanidation with cuprous cyanide is 150°C, and the reaction time is 6-12 hours.

[0036] The 1-cyano-5-hydroxy-3-oxatricyclonon-2-one monomer is recrystallized from a 50% EA / n-heptane mixed solvent at a ratio of 1:2 to 1:4.

[0037] This invention provides a photoresist film-forming resin raw material, the structural formula of which is: .

[0038] Example 1 Step 1: Synthesis of compound (Ⅳ) In a 500 mL three-necked flask equipped with a mechanical stirrer, thermometer, and constant-pressure dropping funnel, 126 g of dichloromethane (DCM) (approximately 94.5 mL) and 118.1 g of monomer (II) were added. The reaction system was kept at 15–20 °C, and a solution prepared by dissolving 26.4 g of monomer (III) in an appropriate amount of dichloromethane was slowly added dropwise (unless otherwise specified, the solvent is assumed to be the same system). The addition was completed within 30–45 minutes. After the addition was complete, the reaction was continued at 15–20 °C with stirring for 4 hours. After the reaction was completed, the solvent was removed by concentration under reduced pressure (-0.085 MPa, water bath temperature 35 °C) to obtain a light yellow oily compound (IV). No further purification was required, and it was directly used in the next reaction with a yield of 100% (based on monomer (II)).

[0039] Step 2: Synthesis of compound (V) 10.0 g of the obtained compound (Ⅳ) was placed in a 250 mL three-necked flask, and 12.9 g of 25% sodium hydroxide aqueous solution (containing approximately 3.23 g of NaOH, 0.081 mol) was added. The mixture was stirred and kept at 20 °C for 2 hours. After the reaction was completed, the pH of the reaction solution was carefully adjusted to 1 with 5% hydrochloric acid aqueous solution to ensure complete protonation of the target product. Subsequently, the aqueous phase was extracted twice with 50 g of ethyl acetate (EA), and the organic layers were combined. After drying with anhydrous sodium sulfate, the solvent was removed by concentration under reduced pressure to obtain a pale yellow solid or oily compound (V) in 80% yield.

[0040] Step 3: Synthesis of compound (VI) 23.0 g of compound (V) was added to a 250 mL three-necked flask, followed by 34.5 g of deionized water and 1.15 g of glacial acetic acid. The mixture was stirred and slowly heated to 70 °C, at which point the system gradually turned into a yellow turbid liquid. At this temperature, 72.1 g of 30% hydrogen peroxide (containing approximately 21.6 g of H₂O₂, 0.64 mol) was slowly added dropwise, controlling the dropping rate to avoid violent exothermic reactions. After the addition was complete, the reaction was maintained at 70 °C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted three times with 92 g of ethyl acetate (EA). The combined organic phases were dried over anhydrous magnesium sulfate and concentrated under reduced pressure (-0.085 MPa, ≤40 °C) to remove the solvent, yielding the crude compound (VI) in 85% yield.

[0041] Step 4: Synthesis of target compound (Ⅰ) 15.0 g of compound (VI), 45 g of N,N-dimethylformamide (DMF), 5.0 g of cuprous cyanide (CuCN), and 1.3 g of cuprous iodide (CuI) were sequentially added to a 250 mL three-necked flask. The mixture was heated to 150 °C under nitrogen protection and stirred for 5 hours. After the reaction was complete, most of the DMF was recovered by hot vacuum distillation. The residue was cooled and extracted three times with 60 g of ethyl acetate (EA). The combined organic phases were dried over anhydrous magnesium sulfate and concentrated to dryness under reduced pressure. 24 g of a 1:1 (v / v) mixture of ethyl acetate and n-heptane was added to the residue, and the mixture was heated to dissolve. The mixture was then slowly cooled to room temperature, precipitating white or off-white crystals. After filtration and drying, the target compound (I) was obtained in 80% yield with a gas chromatographic (GC) purity of 98%–99%.

[0042] Example 2

[0043] Step 1: Synthesis of compound (Ⅳ) (toluene system) Toluene was used instead of dichloromethane as the reaction solvent. 189 g of toluene (approximately 210 mL) and 118.1 g of monomer (II) were added to a 500 mL three-necked flask. The temperature was controlled at 15–20 °C, and 26.4 g of monomer (III) solution (dissolved in a small amount of toluene) was added dropwise. After the addition was complete, the reaction continued for 4 hours. The post-treatment was the same as step 1 in Example 1, and the mixture was concentrated under reduced pressure to obtain compound (IV) in 85% yield. The results indicate that while the toluene system is feasible, the yield is slightly lower than that of the dichloromethane system, possibly due to its lower polarity and poorer solubility for intermediates.

[0044] Step 2: Alkaline hydrolysis reaction (KOH instead of NaOH) Hydrolysis was performed using 18.2 g of 25% potassium hydroxide solution (containing approximately 4.55 g of KOH, 0.081 mol) instead of sodium hydroxide. All other operating conditions remained unchanged. Post-treatment yielded compound (V) with a yield of 75%, slightly lower than the NaOH system. This is presumably due to the larger radius of the K⁺ ion, which may have affected phase transfer efficiency or increased side reactions.

[0045] Step 3: Oxidation reaction (increase the amount of hydrogen peroxide) The amount of hydrogen peroxide was increased to 82.5 g (containing approximately 24.8 g of H2O2, 0.73 mol), and the other conditions were the same as in step 3 of Example 1. The product yield remained at 85%, indicating that increasing the oxidant dosage within this range did not significantly improve the yield, but may increase the safety redundancy of the reaction.

[0046] Step 4: Crystallization Optimization During the crystallization stage, 36 g of a mixed solvent of EA and n-heptane (volume ratio 1:1) was used, and the yield of the target compound (Ⅰ) was 71%, with a GC purity of 98%–99%. The decrease in yield may be related to the influence of trace impurities introduced into the KOH system on the efficiency of subsequent coupling reactions.

[0047] Example 3 Step 1: High loading reaction (dichloroethane system) Using 126 g of 1,2-dichloroethane (DCE) as solvent, the amount of monomer (II) was increased to 196.8 g (approximately 1.67 times that of Example 1), while monomer (III) remained at 26.4 g. The reaction was carried out at 15–20 °C for 4 hours, and post-treatment yielded compound (IV) in 95% yield. This indicates that DCE has good solubility and reaction compatibility, making it suitable for high-concentration reactions.

[0048] The operating conditions for steps 2–4 are basically the same as in Example 1, except that the amount of hydrogen peroxide is increased to 100.1 g (containing approximately 30.0 g of H2O2, or 0.88 mol). The final yield of the target compound (Ⅰ) is 72%, with a GC purity of 98%–99%. The slight decrease in yield may be due to increased side reactions or decreased stability of intermediates at high concentrations.

[0049] Example 4 Step 1: High Load Capacity + DCM System 196.8 g of monomer (II) (high loading) was added to 126 g of dichloromethane, followed by the dropwise addition of 26.4 g of monomer (III), under the same reaction conditions. Compound (IV) was obtained in a yield as high as 99%, demonstrating that DCM can maintain excellent reaction efficiency even under high concentration conditions.

[0050] Next steps The amount of hydrogen peroxide was further increased to 113.6 g (containing approximately 34.1 g of H2O2, 1.00 mol), and the crystallization solvent was increased to 48 g of EA / n-heptane. The final yield of the target compound (Ⅰ) was 70%, with a GC purity of 99%. Despite the excess oxidant, the yield did not increase significantly; in fact, it decreased slightly, suggesting a risk of over-oxidation or byproduct formation. Increasing the amount of crystallization solvent helped improve product purity, but had a limited impact on the yield.

[0051] Structural confirmation of compound (I) The target compound (Ⅰ) was analyzed by ¹H-NMR using a Bruker AC 400 nuclear magnetic resonance spectrometer. The specific method was as follows: approximately 50 mg of sample was dissolved in 1 mL of deuterated chloroform (CDCl3), with tetramethylsilane (TMS) as an internal standard. Test conditions: room temperature, scan range 0–10 ppm.

[0052] ¹H-NMR (400 MHz, CDCl3) δ (ppm):4.52–4.54 (m, 1H, –CH–), 3.69–3.73 (m, 2H, –OCH2–), 2.54–2.55 (m, 1H, –CH–), 2.29–2.35 (m, 2H, –CH2–), 2.13–2.16 (m, 1H, –CH–), 1.85–1.88 (m, 1H, –CH–).

[0053] Spectral data and target structure 1-cyano-5-hydroxy-3-oxatricyclic [4.3.0.0², 4 The results showed a high degree of similarity to nonan-2-one, and combined with the GC purity (≥98%), the obtained product was confirmed to be the target compound (Ⅰ).

[0054] The above description discloses only one preferred embodiment of the present invention, and should not be construed as limiting the scope of the present invention. Those skilled in the art will understand that all or part of the processes of the above embodiments can be implemented, and equivalent changes made in accordance with the claims of the present invention are still within the scope of the invention.

Claims

1. A method for preparing a photoresist film-forming resin raw material, characterized in that, include: Cyclopentadiene was added dropwise to a mixture of methyl α-bromoacrylate and solvent, and the reaction was carried out at a controlled temperature for 4 h to prepare methyl 5-bromodicyclohepta-2-ene-5-carboxylic acid. 5-Bromodicyclohepta-2-ene-5-carboxylic acid methyl ester was added to alkali and hydrolyzed at 20-30℃ for 2 h to obtain the hydrolysis product; The hydrolysis product was epoxidized and hydrolyzed with hydrogen peroxide under glacial acetic acid conditions to obtain 1-bromo-5-hydroxy-3-oxatricyclonon-2-one; The monomer of 1-cyano-5-hydroxy-3-oxatricyclonon-2-one was prepared by cyanidation of 1-bromo-5-hydroxy-3-oxatricyclonon-2-one with cuprous cyanide.

2. The method for preparing a photoresist film-forming resin raw material as described in claim 1, characterized in that, The solvent is any one of dichloromethane, dichloroethane, toluene, and tetrahydrofuran.

3. The method for preparing a photoresist film-forming resin raw material as described in claim 2, characterized in that, The temperature range of the temperature-controlled reaction is 15–40°C.

4. The method for preparing a photoresist film-forming resin raw material as described in claim 3, characterized in that, The molar ratio of cyclopentadiene to methyl α-bromoacrylate is 1:1.8 to 1:3.

0.

5. The method for preparing a photoresist film-forming resin raw material as described in claim 4, characterized in that, The alkali is either sodium hydroxide or potassium hydroxide.

6. The method for preparing a photoresist film-forming resin raw material as described in claim 5, characterized in that, The reaction temperature under glacial acetic acid conditions is 60℃~70℃.

7. The method for preparing a photoresist film-forming resin raw material as described in claim 6, characterized in that, The molar ratio of the hydrolysis product to hydrogen peroxide is 1:6.0 to 1:8.

5.

8. The method for preparing a photoresist film-forming resin raw material as described in claim 7, characterized in that, The reaction temperature for cyanidation with cuprous cyanide is 150°C, and the reaction time is 6-12 hours.

9. The method for preparing a photoresist film-forming resin raw material as described in claim 8, characterized in that, The 1-cyano-5-hydroxy-3-oxatricyclonon-2-one monomer is recrystallized from a 50% EA / n-heptane mixed solvent at a ratio of 1:2 to 1:

4.

10. A photoresist film-forming resin raw material, prepared by the preparation method of the photoresist film-forming resin raw material according to any one of claims 1 to 9, characterized in that, The structural formula of the photoresist film-forming resin raw material is: 。

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