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CN-119350286-B - A series of multi-benzene ring photoinitiators and photoinitiator application thereof

CN119350286BCN 119350286 BCN119350286 BCN 119350286BCN-119350286-B

Abstract

The invention discloses a series of compounds with multi-benzene ring hydroxyl system and application of photoinitiator thereof, wherein the compound with multi-benzene ring hydroxyl aromatic system is used as a precursor of the photoinitiator, and can be combined with Diazonaphthoquinone (DNQ) to prepare photoresist to be loaded on the surface of a substrate, and the photoresist can be subjected to obvious gradient treatment of the height and depth through a photoetching process, so that the compound has practical significance of becoming an I-line photoinitiator.

Inventors

  • SU PENG
  • Zhou Yueer
  • LI XIN
  • HE ZHAOBO
  • ZHOU GANGXIANG
  • WU XIANG
  • CUI HUIDONG
  • ZHANG NUONUO
  • AI QIONG
  • TAN XIAOLONG
  • HU CONG

Assignees

  • 湖北兴福电子材料股份有限公司

Dates

Publication Date
20260508
Application Date
20240912

Claims (14)

  1. 1. The multi-benzene ring photoinitiator is characterized in that a compound with a multi-benzene ring hydroxyl system is adopted to perform esterification reaction with a diazonaphthoquinone compound DNQ in a solvent under an alkaline condition to generate the diazonaphthoquinone photoinitiator, namely the multi-benzene ring photoinitiator, and the structural formula of the multi-benzene ring photoinitiator is as follows: R 1 is one of N, O, S, P elements, R 7 optionally contains H according to R 1 ; wherein R 2 、R 3 is R 6 is selected from H, OH and And, in addition, the method comprises, The grafting ratio of (2) is 75.0-85.0%; R 4 、R 5 is hydrogen, -OH, or The R 4 、R 5 position is not fixed, wherein, The grafting ratio of (2) is 75.0-85.0%.
  2. 2. The multi-benzene ring photoinitiator according to claim 1, wherein the multi-benzene ring photoinitiator is R 2 、R 3 is Wherein R 6 is selected from H, OH and , wherein, The grafting ratio of (2) is 75.0-85.0%; R 4 、R 5 is hydrogen, -OH, or The R 4 、R 5 position is not fixed, wherein, The grafting ratio of (2) is 75.0-85.0%.
  3. 3. The multi-benzene ring photoinitiator according to claim 2, wherein the structural formula of the multi-benzene ring photoinitiator comprises any one of the following: R 6 is selected from 。
  4. 4. A method for preparing the multi-benzene ring photoinitiator according to any one of claims 1 to 3, comprising the steps of: (1) Activating carbonyl of any one of anthrone, anthrone derivative, heterocyclic anthrone or heterocyclic anthrone derivative by using a strong acid catalyst in an organic solvent, and performing electrophilic substitution reaction with polyhydroxy phenol to generate an anthracene compound with a plurality of phenolic hydroxyl groups, namely a polyhydroxy heterocyclic anthracene skeleton compound; the structural formula of the anthrone, the anthrone derivative, the heterocyclic anthrone or the heterocyclic anthrone derivative comprises 、 R 4 '、R 5 'is hydrogen or-OH, the position of R 4 '、R 5 ' is not fixed, R 1 is selected from N, O, S, P elements, and R 7 selectively contains H according to R 1 ; (2) Under alkaline condition, the compound with polyhydroxy heterocyclic anthracene skeleton and the diazonaphthoquinone compound DNQ are subjected to esterification reaction in a solvent to generate the diazonaphthoquinone photoinitiator, namely the multi-benzene ring photoinitiator.
  5. 5. The method for preparing a multi-benzene ring photoinitiator according to claim 4, wherein the polyhydroxyphenol is phenol having at least 2 hydroxyl groups, and the hydroxyl groups are not fixed in position when the number of the polyhydroxyphenol is plural.
  6. 6. The method for preparing a multi-benzene ring photoinitiator according to claim 5, wherein the polyhydric phenol is phenol having two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed; the polyhydroxy phenol is phenol with three hydroxyl groups, and the positions of the three hydroxyl groups are not fixed; the polyhydroxy phenol is phenol with four hydroxyl groups, and the positions of the four hydroxyl groups are not fixed; the polyhydroxy phenol is phenol with five hydroxyl groups.
  7. 7. The method for preparing a multi-benzene ring photoinitiator according to claim 4, wherein the strong acid catalyst comprises one or more of beta-mercaptopropionic acid, sulfuric acid, trifluoromethanesulfonic anhydride and Amberlyst-15 hydrogen type strong acid resin.
  8. 8. The method for preparing a multi-benzene ring photoinitiator according to claim 4, wherein in the esterification reaction process, the molar feed ratio of the raw material DNQ to the polyhydroxy heterocyclic anthracene skeleton compound is 3.5-7.5:1, the synthesis temperature is controlled at 30-35 ℃, and the reaction time is 5-30min.
  9. 9. The method for preparing a multi-benzene ring photoinitiator according to claim 4, wherein the organic solvent in the step (1) comprises one or more of DMF and acetone; the solvent in step (2) comprises 1, 4-dioxane.
  10. 10. The method for synthesizing a multi-benzene ring photoinitiator according to claim 4, wherein during the esterification reaction in the step (2), the diazonaphthoquinone compound performs an esterification reaction of hydroxyl groups of each of a plurality of compounds of the phenolic hydroxyl group system, and the esterification reaction comprises one or more of mono-esterification, di-esterification, tri-esterification, tetra-esterification, penta-esterification, hexa-esterification, hepta-esterification, octa-esterification, nona-esterification and deca-esterification products.
  11. 11. A G/I line photoinitiator comprising a multi-benzene ring photoinitiator according to any one of claims 1 to 3.
  12. 12. A photosensitive composite film material comprising the multi-benzene ring photoinitiator according to any one of claims 1 to 3.
  13. 13. The photosensitive composite film material of claim 12, wherein the photosensitive material further comprises a combination of a phenolic resin and an organic solvent selected from the group consisting of propylene glycol methyl ether acetate PGMEA.
  14. 14. Use of the photoactive composite film material of claim 12 or 13 in the field of photolithography processes.

Description

A series of multi-benzene ring photoinitiators and photoinitiator application thereof Technical Field The invention discloses a series of hydroxyl system compounds with multiple benzene rings and application of photoinitiators thereof, belonging to the technical field of photochemistry. Background Heterocyclic anthracenone compounds are often more widely studied in the photochemical field. The aza/xanthone is commonly used in the aspect of biological activity research, and the thioxanthone is synthesized into a photoinitiator with high photosensitivity through benzene ring modification and nitrogen para-modification, so that the anthrone compound has excellent optical properties, can carry out multi-site modification according to structural specificity, and can finish the defect of lack of functionality of the anthrone compound. The G/I line photoinitiator mainly comprises a polyhydroxy skeleton and DNQ which react, the prior polyhydroxy skeleton is mainly provided with a benzophenone structure, the trihydroxy or tetrahydroxy carried by the structure has different effects on different photoetching process stages, and domestic enterprises are very hoped to find out some photoinitiators which can meet a plurality of process section standards at the same time according to the performance requirements of the domestic market, but the aim is to realize the aim in a time, so that the research and development and industrialization of domestic and multifunctional novel photoinitiators are important measures for promoting the development of the domestic semiconductor industry. Disclosure of Invention The invention provides a series of multi-benzene ring hydroxyl system compounds and a method for synthesizing the photoinitiator by solving the problems of the lack of production of the novel photoinitiator and single type of a novel photoinitiator precursor skeleton, and the functional description of the photoinitiator by utilizing a photoetching technology. A series of compounds with multi-benzene ring hydroxyl system have the structural formula、R 2'、R3 ' is polyhydroxy phenol, R 4'、R5 ' is hydrogen or-OH, and is not H at the same time, the position of R 4'、R5 ' is not fixed, R 1 is selected from one of N, O, S, P elements, and R 7 selectively contains H according to R 1. The polyhydroxyphenol is phenol with at least 2 hydroxyl groups, and when the polyhydroxyphenol is a plurality of polyhydroxyphenols, the positions of the hydroxyl groups are not fixed. The polyhydroxy phenol is phenol with two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed, such as ortho-hydroxyl, para-hydroxyl and meta-hydroxyl phenol; The polyhydroxy phenol is phenol with three hydroxyl groups, and the positions of the three hydroxyl groups are not fixed, such as 1,2, 3-trihydroxy phenol, 1,2, 4-trihydroxy phenol, 2,3, 4-trihydroxy phenol and 1,2, 5-trihydroxy phenol; the polyhydroxy phenol is phenol with four hydroxyl groups, and the positions of the four hydroxyl groups are not fixed, such as 1,2,3, 4-tetrahydroxy phenol and 2,3,4, 5-tetrahydroxy phenol; the polyhydroxy phenol is phenol with five hydroxyl groups. The preparation method of the compound with the multi-benzene ring hydroxyl system comprises the following steps: In an organic solvent, activating carbonyl groups of any one of anthrone, anthrone derivatives, heterocyclic anthrone or heterocyclic anthrone derivatives by using a strong acid catalyst, and performing electrophilic substitution reaction with phenol to generate an anthracene compound with a plurality of phenolic hydroxyl groups, namely a polyhydroxy heterocyclic anthracene skeleton compound, wherein the reaction formula is as follows: ; r 2'、R3 ' is polyhydroxy phenol, R 4'、R5 ' is hydrogen or-OH, the position of R 4'、R5 ' is not fixed, R 1 is selected from one of N, O, S, P elements, R 7 selectively contains H according to R 1, and R 8 is hydrogen or hydroxyl. In some preferred embodiments, the synthetic method of the multi-benzene ring hydroxyl system compound comprises the following reaction equations: Wherein R 1 is heteroatom, represents one of N, O, S, P elements, R 2、R3 is catechol group or pyrogallol, R 4、R5 is phenolic hydroxyl group or hydrogen atom on benzene ring, R 7 is hydrogen atom or no substituent according to heteroatom of R 1. The novel multi-benzene ring photoinitiator is prepared by adopting the compound with the multi-benzene ring hydroxyl system to perform esterification reaction with a diazonaphthoquinone compound DNQ in a solvent under an alkaline condition, and the diazonaphthoquinone photoinitiator is generated, namely the novel multi-benzene ring photoinitiator, and the structural formula of the novel multi-benzene ring photoinitiator is as follows: Or (b) R 1 is one of N, O, S, P elements, R 7 optionally contains H according to R 1; wherein R 2、R3 is R 6 is selected from H, OH andAnd, in addition, the method comprises,The grafting ratio of (2) is 75.0-85.0%; R 4、R5 is