Photoinduced acid generator as well as preparation and application thereof

Abstract

The invention provides a photoacid generator as well as a preparation method and application thereof. The photoacid generator has a structure as shown in a formula (I), can improve the stability of molecules, is used for a photocuring material and can improve the stability of products, and other application performances of the molecules are not influenced.

Description

Technical Field

[0001] The present invention belongs to the field of organic chemistry, and particularly relates to a photoacid generator and a preparation method and application thereof. Background Art

[0002] Aromatic ring-containing sulfimide compounds are commonly used photoacid generators and cationic photoinitiators, which are used as photoacid generators in resist compositions for lithography used in the formation of electronic circuits such as semiconductors, or as cationic polymerization initiators in photo-curable resin compositions, coatings, paints, adhesives, inks and other photo-polymerizable compositions.

[0003] The sulfimide structure containing a naphthalene skeleton is a common photoacid generator and has a very wide range of applications, such as CN104822662A, CN107250114A, CN102712599A, etc. As a photoacid generator used in a photoresist or a cationic polymerization initiator used in a photo-curable resin composition, an adhesive, an ink, etc., light sources such as EUV, X-rays, F2, ArF, KrF, I-rays, H-rays, G-rays and other far ultraviolet rays, electron rays, radiation rays, etc. can be used. In the case of using these light sources, substances with a large absorption at a wavelength of 365 nm are dominant. In addition, from the viewpoints of countermeasures for high-precision patterning and countermeasures for shortening the process, it is desirable to make the photoresist and the cationic polymer system contain a sufficient amount of acid generator or use an acid generator with a good acid generation rate. Therefore, as an acid generator, a substance with high solubility in an organic solvent and a substance with a sufficient acid generation rate are required.

[0004] However, the stability of such products needs to be further improved. Researchers often modify the parent group of such products or modify them by linking different groups on the naphthalene ring, such as CN115745865A, CN116283945A. Such changes often require further adjustment of the formulation while increasing the cost. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a photoacid generator and a preparation method and application thereof.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] On the one hand, the present invention provides a photoacid generator, and the photoacid generator has a structure shown in formula (I):

[0008]

[0009] Among them, R1, R2, R3, R4, R5 and R6 are independently selected from hydrogen, deuterium, nitro, cyano, C1-C20 straight-chain or branched-chain alkyl, C3-C20 cycloalkyl, C2-C7 straight-chain, branched-chain or cyclic aliphatic acyl, C2-C20 straight-chain or branched-chain alkynyl, C2-C20 straight-chain or branched-chain alkenyl, C6-C10 aryl acyl, C6-C18 substituted or unsubstituted aryl, a substituent formed by interrupting C2-C20 straight-chain or branched-chain alkyl with at least one -O-, -S-, -O-CO- or -CO-O-, a substituent formed by interrupting C2-C20 straight-chain or branched-chain alkenyl with at least one -O-, -S-, -O-CO- or -CO-O-, and at least one of R1, R2, R3, R4, R5 and R6 is deuterium.

[0010] In the present invention, the inventors unexpectedly found that deuterium-substituted naphthalene ring sulfonimide compounds can improve the stability of molecules, the stability of products is improved, and other application properties of the molecules are not affected.

[0011] Preferably, the number of carbon atoms in the above groups is limited. The limited range indicates that the number of carbon atoms in the group is any integer within the limited range. For example, C2-C20 means that the number of carbon atoms can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. The limitation of the remaining carbon atom ranges has the same or similar meaning by analogy.

[0012] Preferably, R1, R2, R3, R4, R5 and R6 are independently selected from hydrogen, deuterium, nitro, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, phenyl, and at least one of R1, R2, R3, R4, R5 and R6 is deuterium.

[0013] Further preferably, the photoacid generator is selected from any one of the following compounds:

[0014]

[0015]

[0016] On the other hand, the present invention provides a preparation method of the photoacid generator as described above. The preparation method includes the following steps:

[0017] (1) Raw material a undergoes a deuteration reaction with heavy water to obtain intermediate a;

[0018] (2) Intermediate a is dehydrated to obtain intermediate b;

[0019] (3) Intermediate b undergoes an oximation reaction with hydroxylamine hydrochloride or hydroxylamine sulfate to obtain the hydroxylaminated product intermediate c;

[0020] (4) The hydroxylaminated product intermediate c undergoes an esterification reaction with sulfonic anhydride (R3-SO2)2O or sulfonyl chloride R3-SO2-Cl to obtain the target compound, and the reaction process is as follows:

[0021]

[0022] Wherein R1', R2', R3', R4', R5' and R6' are independently selected from hydrogen, nitro, cyano, C1-C 20 linear or branched alkyl, C3-C20 cycloalkyl, C2-C7 linear, branched or cyclic aliphatic acyl, C2-C20 linear or branched alkynyl, C2-C20 linear or branched alkenyl, C6-C10 aryl acyl, C6-C18 substituted or unsubstituted aryl, C2-C20 linear or branched alkyl interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, C2-C20 linear or branched alkenyl interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, and at least one of R1', R2', R3', R4', R5' and R6' is hydrogen.

[0023] Preferably, the molar ratio of the raw material a to heavy water in step (1) is 1:5 - 300, such as 1:5, 1:10, 1:20, 1:30, 1:50, 1:80, 1:100, 1:150, 1:200, 1:250 or 1:300.

[0024] Preferably, the deuteration reaction in step (1) is carried out in the presence of a mixed solvent, and the mixed solvent is a mixed solvent of isopropyl alcohol and decalin.

[0025] Preferably, the deuteration reaction in step (1) is carried out in the presence of a catalyst. Preferably, the catalyst is selected from Pt / C.

[0026] Preferably, the temperature of the deuteration reaction in step (1) is 80 - 130 °C, such as 80 °C, 90 °C, 100 °C, 110 °C, 120 °C or 130 °C, and the reaction time is 12 - 48 h, such as 12 h, 15 h, 18 h, 20 h, 24 h, 28 h, 30 h, 33 h, 36 h, 40 h, 44 h or 48 h.

[0027] Preferably, the dehydration in step (2) is carried out in the presence of a dehydrating agent.

[0028] Preferably, the dehydrating agent is selected from acetic anhydride.

[0029] Preferably, the temperature of the dehydration in step (2) is 60 - 150 °C, such as 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C or 150 °C, and the time is 1 - 3 h, such as 1 h, 1.5 h, 2 h, 2.5 h or 3 h.

[0030] Preferably, the molar ratio of intermediate b to hydroxylamine hydrochloride or hydroxylamine sulfate in step (3) is 0.8:1.5 - 1.5:0.8, such as 0.8:1.5, 0.8:1.3, 0.8:1.2, 0.8:1, 0.8:0.8, 1:0.8, 1.2:0.8, 1.5:0.8, 1:1, 1.2:1, 1:1.2, 1:1.5, 1.5:1, etc.

[0031] Preferably, the oximation reaction in step (3) is carried out in a solvent, and the solvent is selected from dimethylformamide.

[0032] Preferably, the oximation reaction in step (3) is carried out in the presence of a basic substance, and the basic substance is preferably sodium hydroxide or potassium hydroxide.

[0033] Preferably, the oximation reaction in step (3) is carried out at room temperature, and the reaction time is 2 - 5 h, such as 2 h, 3 h, 4 h or 5 h.

[0034] Preferably, after the oximation reaction in step (3) is completed, hydrochloric acid is added for acidification to obtain intermediate c.

[0035] Preferably, the molar ratio of the hydroxylaminated product intermediate c to sulfonic anhydride or sulfonyl chloride in step (4) is 0.9 - 2:2 - 0.9, such as 0.9:2, 1:0.9, 1.2:0.9, 1.5:0.9, 1.8:0.9, 2:0.9, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 1:1.5, 1.2:1.8, 1.5:2, 2:1.8, 2:1.5, 2:1.2, etc.

[0036] Preferably, the solvent for the esterification reaction in step (4) is any one or a combination of at least two of ethanol, dimethyl sulfoxide, toluene, dichloromethane, ethyl acetate or chloroform

[0037] Preferably, the temperature of the esterification reaction in step (4) is -5 to 5 °C, such as -5 °C, -3 °C, -2 °C, 0 °C, 1 °C, 2 °C, 3 °C, 4 °C or 5 °C, and the reaction time is 0.5 - 3 h, such as 0.5 h, 0.8 h, 1 h, 2 h or 3 h.

[0038] On the other hand, the present invention provides an acid generation method, which is to irradiate the photoacid generator as described above with actinic energy rays.

[0039] Non-limitingly, the actinic energy rays can be electromagnetic waves in the visible light region (visible light), electromagnetic waves in the ultraviolet light region (ultraviolet rays), electromagnetic waves in the infrared light region (infrared rays), and electromagnetic waves in the non-visible region such as X-rays, etc. However, more preferably, the actinic energy rays are actinic energy rays with wavelengths between 300 - 450 nm in the near ultraviolet light region and the visible light region, and particularly preferably actinic energy rays with wavelengths of 365 nm (I-line) and 385 nm.

[0040] On the other hand, the present invention provides the application of the photoacid generator as described above in a resist film, a liquid resist, a negative resist, a positive resist, a resist for MEMS (Micro-Electro-Mechanical Systems), and a material for stereolithography or microstereolithography.

[0041] In the present invention, as a photoacid generator in a resist composition, the photoacid generator can be prepared together with a resin having an acid dissociable group to be used as a resist in semiconductor lithography.

[0042] On the other hand, the present invention provides a resist composition, which comprises the photoacid generator as described above.

[0043] On the other hand, the present invention provides the application of the photoacid generator as described above in a photocurable material.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] The photoacid generator of the present invention is a deuterium-substituted naphthalene ring-containing sulfonimide compound, which can improve the stability of the molecule. When used in a photocurable material, it can improve the stability of the product, and other application properties of the molecule are not affected. Detailed Embodiments

[0046] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0047] Preparation Example 1

[0048]

[0049] Dissolve 13.6 g of 4-butyl-1,8-naphthalenedicarboxylic acid in a mixed solution of 272 mL of D2O, 27.2 mL of IPA (isopropanol), and 544 mL of decalin. Then add 5.7 g of 5% Pt / C catalyst. Stir the mixed solution in a high-pressure reactor at 100 °C for 24 hours, and then cool it to room temperature. Add dichloromethane to the mixed solution, separate the organic layer, and dry and concentrate the separated organic layer using MgSO4. After adding IPA to the remaining solution, filter the precipitated substance to obtain 11.9 g of deuterated 4-butyl-1,8-naphthalenedicarboxylic acid.

[0050] Add 11.09 g of 4-butyl-1,8-pentadeuteronaphthalenedicarboxylic acid and 49 g of acetic anhydride to a 250 mL four-necked flask. Stir and heat the external oil bath to 70 °C, keep stirring for 2 h, stop stirring when the system in the middle control no longer changes, and cool down to 10 - 20 °C. Cool the reacted solution to below 5 °C in an ice-water bath and let it stand in the ice-water bath to precipitate 5.82 g of the product.

[0051] Add 5.55 g of 4-butyl-1,8-pentadeuteronaphthalenedicarboxylic anhydride obtained above and 30 g of dimethylformamide to a 250 ml four-necked flask. Add 16.68 g of hydroxylamine hydrochloride at room temperature, dropwise add 2.00 g of 48% aqueous sodium hydroxide solution, and stir for 3 hours. Add 20.0 g of water and 0.30 g of 35% hydrochloric acid thereto, and stir for another 1 hour. Filter and extract the precipitate, wash it with a mixture of methanol and water, and then conduct vacuum drying at 45 °C to obtain 5.15 g of the hydroxyimide body.

[0052] Add 18.9 g of chloroform and 1.26 g of pyridine to 2.74 g of the hydroxyimide body obtained above. Cool it in an ice-water bath to 0 - 3 °C with an internal temperature of 0 - 2 °C, and start to dropwise add 3.72 g of trifluoromethanesulfonic anhydride. After the addition is complete, keep stirring for 1 hour. Add 20 g of water to the reaction solution, wash the oil phase obtained by oil-water separation twice with 0.5% aqueous sodium hydroxide solution and once with 3% hydrochloric acid, and then wash it five times with water. Dissolve the solid obtained by concentrating the organic phase in chloroform by heating, add methanol to the filtrate obtained after filtration for crystallization. Filter and extract the obtained crystals, and conduct vacuum drying at 45 °C to obtain 3.09 g of light yellow crystals, namely the target compound 1.

[0053] The structure of compound 1 was confirmed by mass spectrometry: MS (m / Z): 406 (M + H) + 。

[0054] Furthermore, referring to the method of Example 1, different starting material compound a was used to prepare compounds 2 - 11 with different structures, as shown in Table 1.

[0055] Table 1

[0056]

[0057]

[0058] Performance Evaluation

[0059] The performance evaluations were separately carried out on Compound 1, Compound 6, Comparative Example 1, and Comparative Example 2. The evaluation indices included molar extinction coefficient, solubility, resist hardening property, and chemical stability.

[0060]

[0061] (1) Product solubility

[0062] 1.0000 g of the photoacid generator compound was separately taken and added to solvents (butyl acetate, cyclohexanone, and PMA) at 25 °C until the compound in each test tube was completely dissolved and clarified. The mass of the organic solvent used was recorded, and the solubility was expressed by the following formula.

[0063] Solubility = 1 g / mass of solvent × 100

[0064] The evaluation results are listed in Table 2.

[0065] (2) Hardening property of the resist

[0066] A resin solution of 75 parts of p-hydroxystyrene resin (MarukaLINKER S-2P by Maruzen Chemical Co., Ltd. of Japan), 25 parts of melamine curing agent (Benno Biotechnology Co., Ltd.), 1 part of photoacid generator, and 200 parts of propylene glycol monomethyl ether acetate (PGMEA) was coated on a glass substrate (diameter 10 cm) using a spin coater under the condition of 100 rpm / 10 s. Then, vacuum drying was carried out at 25 °C for 5 min, and then drying was carried out on a hot plate at 80 °C for 3 min to form a resist film with a thickness of about 3 μm. The resist film was exposed using an ultraviolet irradiation device (IWATA UV-100D) equipped with a filter. The cumulative exposure amount was measured at a wavelength of 365 nm. Then, post-exposure baking (PEB) was carried out for 10 min using a dryer at 120 °C, and then, it was developed by immersing in 0.5% potassium hydroxide for 30 s, and immediately washed with water and dried. A shape measurement microscope (Keyence VK-8500) was used to measure the film thickness of the resist. Based on the lowest exposure amount at which the change in the film thickness of the resist before and after development was within 10%, the resist hardening property was evaluated according to the following criteria.

[0067] ⊙: The lowest exposure amount is 200 mJ / cm 2 The following;

[0068] ○: The lowest exposure amount is greater than 200 mJ / cm2 and below 250 mJ / cm 2 ;

[0069] ×: The minimum exposure dose is greater than 250 mJ / cm 2 .

[0070] The evaluation results are listed in Table 2.

[0071] (3) Chemical stability

[0072] In the formulated composition containing a photoacid generator, a variety of additives are included to achieve the storage stability of the composition and meet the conditions of subsequent processes. This requires that the photoacid generator not only does not affect the additives in the composition, but also stably exists therein and does not undergo any chemical reactions. Using triethylamine as the additive to be investigated, with an addition amount of 10% photoacid generator (w / w), it is dissolved in PGMEA together with the photoacid generator, sealed and stored at room temperature for 336 h, and the storage stability of the photoacid generator is investigated by HPLC method.

[0073] The results are classified as follows:

[0074] ◎ - HPLC content ≥ 98.00%;

[0075] ○ - HPLC content 90.00 - 98.00%;

[0076] × - HPLC content < 90.00%.

[0077] The evaluation results are listed in Table 2.

[0078] Table 2

[0079]

[0080] As shown in Table 1 and Table 2, the deuterated naphthalene ring-based sulfonimide photoacid generator of the present invention is the same as Comparative Example 1 and Comparative Example 2 in terms of light absorption ability, solubility, and resist hardening property. However, the photoacid generator of the present invention has better chemical stability and has more advantages over the comparative example when applied in various fields.

[0081] The applicant declares that the present invention uses the above embodiments to illustrate the photoacid generator of the present invention, its preparation method and application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A photoacid generator, characterized in that, The photoacid generator has the structure shown in formula (I): Wherein, R1, R2, R3, R4, R5 and R6 are independently selected from hydrogen, deuterium, nitro group, cyano group, C1-C20 straight-chain or branched-chain alkyl group, C3-C20 cycloalkyl group, C2-C7 straight-chain, branched-chain or cyclic aliphatic acyl group, C2-C20 straight-chain or branched-chain alkynyl group, C2-C20 straight-chain or branched-chain alkenyl group, C6-C10 aryl acyl group, C6-C18 substituted or unsubstituted aryl group, a substituent formed by interrupting a C2-C20 straight-chain or branched-chain alkyl group with at least one -O-, -S-, -O-CO- or -CO-O-, a substituent formed by interrupting a C2-C20 straight-chain or branched-chain alkenyl group with at least one -O-, -S-, -O-CO- or -CO-O-, and at least one of R1, R2, R3, R4, R5 and R6 is deuterium.

2. The photoacid generator according to claim 1, wherein R1, R2, R3, R4, R5 and R6 are independently selected from hydrogen, deuterium, nitro, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, phenyl, and at least one of R1, R2, R3, R4, R5 and R6 is deuterium.

3. The photoacid generator according to claim 1 or 2, wherein The photoacid generator is selected from any one of the following compounds:

4. The preparation method of the photoacid generator according to any one of claims 1-3, characterized in that The preparation method includes the following steps: (1) Raw material a reacts with heavy water in a deuteration reaction to obtain intermediate a; (2) Intermediate a is dehydrated to obtain intermediate b; (3) Intermediate b undergoes an oximation reaction with hydroxylamine hydrochloride or hydroxylamine sulfate to obtain an oximation product intermediate c; (4) The oximation product intermediate c undergoes an esterification reaction with sulfonic anhydride (R3-SO2)2O or sulfonyl chloride R3-SO2-Cl to obtain the target compound, and the reaction process is as follows: wherein R1', R2', R3', R4', R5' and R6' are independently selected from hydrogen, nitro, cyano, a C1-C 20 linear or branched alkyl group, a C3-C20 cycloalkyl group, a C2-C7 linear, branched or cyclic aliphatic acyl group, a C2-C20 linear or branched alkynyl group, a C2-C20 linear or branched alkenyl group, a C6-C10 aryl acyl group, a C6-C18 substituted or unsubstituted aryl group, a substituent formed by interrupting a C2-C20 linear or branched alkyl group with at least one -O-, -S-, -O-CO- or -CO-O-, a substituent formed by interrupting a C2-C20 linear or branched alkenyl group with at least one -O-, -S-, -O-CO- or -CO-O-, and at least one of R1', R2', R3', R4', R5' and R6' is hydrogen.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the raw material a and heavy water in step (1) is 1:5 - 300; Preferably, the deuteration reaction in step (1) is carried out in the presence of a mixed solvent, and the mixed solvent is a mixed solvent of isopropanol and decalin; Preferably, the deuteration reaction in step (1) is carried out in the presence of a catalyst. Preferably, the catalyst is selected from Pt / C. Preferably, the temperature of the deuteration reaction in step (1) is 80 - 130 °C, and the reaction time is 12 - 48 h Preferably, the dehydration in step (2) is carried out in the presence of a dehydrating agent. Preferably, the dehydrating agent is selected from acetic anhydride. Preferably, the temperature of the dehydration in step (2) is 60 - 150 °C, and the time is 1 - 3 h.

6. The preparation method according to claim 4 or 5, characterized in that The molar ratio of intermediate b and hydroxylamine hydrochloride or hydroxylamine sulfate in step (3) is 0.8:1.5 - 1.5:0.8; Preferably, the oximation reaction in step (3) is carried out in a solvent, and the solvent is selected from dimethylformamide. Preferably, the oximation reaction in step (3) is carried out in the presence of a basic substance. Preferably, the basic substance is sodium hydroxide or potassium hydroxide. Preferably, the oximation reaction in step (3) is carried out at room temperature, and the reaction time is 2 - 5 h; Preferably, after the oximation reaction in step (3) is completed, hydrochloric acid is added for acidification to obtain intermediate c. Preferably, the molar ratio of the oximation product intermediate c and sulfonic anhydride or sulfonyl chloride in step (4) is 0.9 - 2:2:0.9; Preferably, the solvent for the esterification reaction in step (4) is any one or a combination of at least two of ethanol, dimethyl sulfoxide, toluene, dichloromethane, ethyl acetate or chloroform; Preferably, the temperature of the esterification reaction in step (4) is -5 to 5 °C, and the reaction time is 0.5 - 3 h.

7. A method for producing an acid, characterized in that, The method is to perform active energy ray irradiation on the photoacid generator according to any one of claims 1 - 3.

8. Use of the photoacid generator according to any one of claims 1 - 3 in a resist film, a liquid resist, a negative resist, a positive resist, a resist for microelectromechanical systems, a material for stereolithography or microstereolithography.

9. A resist composition, characterized in that, The resist composition comprises the photoacid generator according to any one of claims 1 - 3.

10. Use of the photoacid generator according to any one of claims 1 - 3 in a photocurable material.

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