A series of multi-benzene ring photoinitiators and their photoinitiator applications

Abstract

The application discloses a series of compounds with a multi-benzene ring hydroxyl system and application of the compounds as photoinitiators. The multi-benzene ring hydroxyl aromatic system compound of the application can be combined with diazonium naphthoquinone (DNQ) to form a photoresist which is loaded on the surface of a substrate, and the photoresist can be processed by a photoetching process to obtain a high depth gradient, thus having practical significance for becoming an I-line photoinitiator.

Description

Technical Field

[0001] This invention discloses a series of compounds with polybenzene ring hydroxyl systems and their applications as photoinitiators, belonging to the field of photochemical technology. Background Technology

[0002] Heterocyclic anthrones are frequently studied in the field of photochemistry. Aza- / oxoxanthrones are commonly used in bioactivity research. Thioxanthones, through benzene ring modification and nitrogen para-position modification, can synthesize photoinitiators with high photosensitivity. Therefore, anthrones possess excellent optical properties. Due to their structural uniqueness, they can be modified at multiple sites, thus overcoming the functional deficiencies of anthracene compounds.

[0003] G / I line photoinitiators mainly function through the reaction of a polyhydroxy framework and DNQ. Existing polyhydroxy frameworks are primarily benzophenone structures, and the tri- or tetra-hydroxy groups within these structures exhibit different effects at different stages of the photolithography process. Given the performance requirements of photoinitiators in the domestic market, domestic companies are eager to find photoinitiators that can simultaneously meet the standards of multiple process stages. However, achieving this goal will take time. Therefore, the research and industrialization of domestically produced, multifunctional novel photoinitiators is a crucial measure to promote the development of China's semiconductor industry. Summary of the Invention

[0004] This invention aims to solve the problems of scarce production of novel photoinitiators and limited types of precursor skeletons for novel photoinitiators. It proposes a series of synthesis methods for polycyclic hydroxyl system compounds and their photoinitiators, and uses photolithography technology to illustrate the functionality of the photoinitiators.

[0005] A series of compounds with polycyclic hydroxyl groups, with the following structural formula: , R2' and R3' are polyhydroxyphenols, R4' and R5' are hydrogen or -OH, and not all of them are H, and the positions of R4' and R5' are not fixed; R1 is selected from one of the elements N, O, S, and P, and R7 selectively contains H according to R1.

[0006] The polyhydroxyphenol is a phenol with at least two hydroxyl groups; when there are multiple hydroxyl groups, the positions of the hydroxyl groups are not fixed.

[0007] The polyhydroxyphenol is a phenol with two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed, such as ortho-hydroxy, para-hydroxy, or m-hydroxyphenol;

[0008] The polyhydroxyphenol is a phenol with three hydroxyl groups, and the positions of the three hydroxyl groups are not fixed, such as 1,2,3-trihydroxyphenol, 1,2,4-trihydroxyphenol, 2,3,4-trihydroxyphenol, and 1,2,5-trihydroxyphenol.

[0009] The polyhydroxyphenol is a phenol with four hydroxyl groups, and the positions of the four hydroxyl groups are not fixed, such as 1,2,3,4-tetrahydroxyphenol or 2,3,4,5-tetrahydroxyphenol.

[0010] The polyhydroxyphenol is a phenol with five hydroxyl groups.

[0011] The method for preparing the compound with polybenzene ring hydroxyl system includes the following steps:

[0012] In an organic solvent, the carbonyl group of any one of anthrone, anthrone derivatives, heterocyclic anthrones, or heterocyclic anthrone derivatives is activated using a strong acid catalyst and then undergoes an electrophilic substitution reaction with phenol to generate anthracene compounds with multiple phenolic hydroxyl groups, which are polyhydroxy heterocyclic anthracene skeleton compounds. The reaction formula is as follows: ; R2' and R3' are polyhydroxyphenols, R4' and R5' are hydrogen or -OH, and the positions of R4' and R5' are not fixed; R1 is selected from one of the elements N, O, S, and P, and R7 selectively contains H according to R1; R8 is hydrogen or hydroxyl.

[0013] In some preferred embodiments, the reaction equation for the synthesis method of the polybenzene ring hydroxyl system compound is as follows:

[0014]

[0015] R1 is a heteroatom, representing one of the four elements N, O, S, and P; R2 and R3 are catechol groups or pyrogallol; R4 and R5 are phenolic hydroxyl groups or hydrogen atoms on the benzene ring; and R7 is selectively hydrogen atoms or unsubstituted, depending on the heteroatom of R1.

[0016] A novel type of polyphenylene ring photoinitiator is generated by esterification of the aforementioned compound with a polyphenylene ring hydroxyl system and the diazonopeptidone compound DNQ in a solvent under alkaline conditions, resulting in a diazonopeptidone-type photoinitiator. The structural formula of this novel polyphenylene ring photoinitiator is as follows:

[0017] ,or If R1 is one of the elements N, O, S, and P, then R7 selectively contains H based on R1.

[0018] Among them, R2 and R3 are R6 is selected from H, OH and ,and, The grafting rate was 75.0-85.0%;

[0019] R4 and R5 are hydrogen, -OH, or... The positions of R4 and R5 are not fixed. The grafting rate is 75.0-85.0%.

[0020] The novel polyphenylene ring photoinitiator has a structural formula including any one of the following:

[0021] R6 is selected from .

[0022] The synthesis method of the polybenzene ring photoinitiator, taking the above-mentioned preferred compound (1) as an example, has the following reaction equation:

[0023] .

[0024] A method for preparing a polybenzene ring photoinitiator, characterized by comprising the following steps:

[0025] (1) In an organic solvent, the carbonyl group of any one of anthrone, anthrone derivative, heterocyclic anthrone or heterocyclic anthrone derivative is activated by a strong acid catalyst and then undergoes an electrophilic substitution reaction with a polyhydroxyphenol to generate anthracene compounds with multiple phenolic hydroxyl groups, which are polyhydroxy heterocyclic anthracene skeleton compounds.

[0026] (2) Under alkaline conditions, a polyhydroxy heterocyclic anthracene skeleton compound reacts with the diazonoquinone compound DNQ in a solvent to generate a diazonoquinone type photoinitiator, which is a polybenzene ring photoinitiator.

[0027] The structural formulas of the anthrone, anthrone derivatives, heterocyclic anthrones, or heterocyclic anthrone derivatives include: , R4' and R5' are hydrogen or -OH, and their positions are not fixed; R1 is selected from one of the elements N, O, S, and P, and R7 selectively contains H according to R1.

[0028] The polyhydroxyphenol is a phenol with at least two hydroxyl groups; when there are multiple hydroxyl groups, the positions of the hydroxyl groups are not fixed.

[0029] The polyhydroxyphenol is a phenol with two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed;

[0030] The polyhydroxyphenol is a phenol with three hydroxyl groups, and the positions of the three hydroxyl groups are not fixed;

[0031] The polyhydroxyphenol is a phenol with four hydroxyl groups, and the positions of the four hydroxyl groups are not fixed;

[0032] The polyhydroxyphenol is a phenol with five hydroxyl groups.

[0033] In the preferred embodiment, the raw materials for the synthesis method of the polyphenylene ring hydroxyl system compound include: catechol, pyrogallol, 3-hydroxy-9H-zanton-9-one, 2-hydroxyanthrone, 2,6-dihydroxyanthrone, pitavastatin impurity 75, compound (7) and compound (8), wherein the structural formulas of compound (7) and compound (8) are as follows:

[0034] .

[0035] The strong acid catalyst includes one or more of β-mercaptopropionic acid, sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, and Amberlyst-15 hydrogen-form strong acid resin.

[0036] In the method for synthesizing the polycyclic hydroxyl system compounds, the molar ratio of anthrone to catechol is 1:6, the reaction temperature is 60-120 ℃, the reaction time is 20-24 h, and the entire reaction process is under nitrogen protection.

[0037] In the method for synthesizing the polyphenylene ring hydroxyl system compounds, the molar ratio of anthrone to pyrogallol is 1:6, the reaction temperature is 60-120 ℃, the reaction time is 20-24 h, and the entire reaction process is under nitrogen protection.

[0038] In the synthesis of the novel polyphenylene ring photoinitiator, the molar ratio of the raw material DNQ to the polyphenylene ring hydroxyl system compound is 3.5-7.5:1; the reaction temperature is controlled at 30-35℃, the catalyst dropping time is controlled at 60-65min, and the reaction time is 5-30min.

[0039] The organic solvent in step (1) includes one or more of DMF and acetone;

[0040] The solvent in step (2) includes 1,4-dioxane.

[0041] In the esterification reaction process described in step (2), the diazonoquinone compound realizes the esterification reaction of the hydroxyl groups of each compound in the anthracene series of multiple phenolic hydroxyl groups. The esterification reaction includes one or more of the following products: monoesterification, dieesterification, trimesterification, tetraesterification, pentaesterification, hexaesterification, heptaesterification, octaesterification, nonaesterification, and decaesterification.

[0042] A G / I line photoinitiator, comprising the aforementioned polybenzene ring photoinitiator.

[0043] A photosensitive composite thin film material, comprising the aforementioned polyphenylene ring photoinitiator.

[0044] The photosensitive material also includes a composition formed by phenolic resin and an organic solvent, wherein the organic solvent is selected from PGMEA.

[0045] Another technical solution of the present invention is the application of the aforementioned photosensitive material in the field of photolithography.

[0046] The performance testing and evaluation of the novel polybenzene ring photoinitiator are as follows:

[0047] A photoinitiator was dissolved in propylene glycol methyl ether acetate (PGMEA), and then mixed with phenolic resin (molecular weight 4500-5400) to form a solution. The mixture contained 5.5 wt% photoinitiator, 23.0% PGMEA, and 72.0% phenolic resin. 10 mL of the mixture was dropped onto an 8-inch circular substrate and spin-coated to a uniform thickness of 20 μm. After pre-baking, the film was exposed using a photolithography machine at a 365 nm light source with an exposure energy of 120 mJ / cm². 2 After post-baking, the material is immersed in a developing tank containing 2.38 wt% tetramethylammonium hydroxide (TMAH) for 20 seconds. After rinsing off excess developer from the material surface with ultrapure water, the height difference of the pattern is observed using a profilometer. The quality of the photosensitivity of the photoinitiator is judged by the value of this value. The evaluation standard is: the larger the height difference of the pattern, the better the photosensitivity of the photoinitiator.

[0048] The beneficial effects of this invention are as follows:

[0049] 1. This invention synthesizes a polyphenyl ring hydroxyl system compound and its photoinitiator. By utilizing the multiple benzene ring hydroxyl groups on polyhydroxyphenol, the active sites for grafting with DNQ are reasonably increased, which greatly enhances the photosensitivity of the photoinitiator. The synthesized photoinitiator, when combined with resin, exhibits excellent ultraviolet irradiation reactivity, and clear patterns can be obtained through a simple photolithography process.

[0050] 2. The synthesis method of the polybenzene ring hydroxy aromatic system compounds and their photoinitiators of the present invention is simple, with low process cost and low reaction risk, and has practical industrialization value. Attached Figure Description

[0051] Figure 1 The image shows the 1H NMR spectrum of compound (1-1).

[0052] Figure 2 The image shows the 1H NMR spectrum of compound (2-1).

[0053] Figure 3 The image shows the 1H NMR spectrum of compound (3-1).

[0054] Figure 4 The image shows the 1H NMR spectrum of compound (4-1).

[0055] Figure 5The image shows the 1H NMR spectrum of compound (5-1).

[0056] Figure 6 The image shows the 1H NMR spectrum of compound (6-1).

[0057] Figure 7 The graph shows the change in the residual rate of six photoinitiator compounds under light irradiation over time. Detailed Implementation

[0058] The present invention will be further illustrated below with reference to the embodiments, but the scope of protection of the present invention is not limited to the scope described in the embodiments.

[0059] The raw materials used in the embodiments of the present invention include catechol, pyrogallol, 3-hydroxy-9H-zanton-9-one, 2-hydroxyanthrone, 2,6-dihydroxyanthrone, pitavastatin impurity 75, compound (7) and compound (8), wherein the structural formulas of compound (7) and compound (8) are as follows:

[0060] .

[0061] Synthetic steps of polyhydroxy heterocyclic anthracene skeleton compounds (Method 1):

[0062] a. Mix the raw materials with the solvent in the reaction ratio in a 250 mL flask and purge the air in the flask with nitrogen bubbling.

[0063] b(1). When the catalyst is β-mercaptopropionic acid and sulfuric acid: First, place the mixed solution from step (a) in a 30 ℃ oil bath, add β-mercaptopropionic acid to the reaction system under nitrogen protection, and react at 30 ℃ for 30 min. Then, slowly add sulfuric acid. After the addition is complete, raise the reaction temperature to 60-120 ℃ (depending on the type of solvent) and continue the reaction for 12-24 h.

[0064] b(2). When the catalyst is trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride: raise the temperature of the mixed solution in step (a) to the reaction temperature (60-120 ℃), then slowly add the catalyst dropwise and continue the reaction for 12-24 h;

[0065] b(3). When the catalyst is Amberlyst-15 hydrogen-form strong acid resin: Amberlyst-15 hydrogen-form strong acid resin is added to the flask together with the raw materials and solvent in step (a) to form a solid-liquid mixture system, and reacted in an environment of 60-120 ℃ for 12-24 h;

[0066] c. Monitor the reaction of the raw materials by thin-layer chromatography (TLC). Maintain a nitrogen atmosphere during the reaction. After the reaction is completed, lower the temperature to room temperature and add room temperature water with a solvent volume of 2 times. After the product solid is extracted, filter it at room temperature and wash the solid with room temperature water. Collect the product solid and dry it at 40 °C. Finally, recrystallize it in acetone solution to obtain a product with a purity of over 99.00%.

[0067] d. Perform HPLC (purity) and NMR tests on the product.

[0068] Photoinitiator synthesis steps (Method 2):

[0069] a. Dissolve 1,000 mmol of a polyhydroxyanthracene skeleton compound and DNQ in 1,4-dioxane at a specific molar ratio, and stir until dissolved at 35 °C;

[0070] b. After the reaction system is cooled to 30 ℃, the same volume of solvent as the triethylamine catalyst and triethylamine is slowly added dropwise (the addition time is about 1 h), and the temperature is maintained between 30-31 ℃. After the addition is completed, the temperature is raised to 35 ℃ and the reaction is continued for 30 min.

[0071] c. Add 30% hydrochloric acid (by volume) to the reaction system to quench the reaction, filter and collect the filtrate;

[0072] d. Slowly pour the filtrate in a flowing manner into ultrapure water containing 5 times the volume of the organic solution (mixed with 30% hydrochloric acid by volume), while vigorously stirring, to perform a pulping operation;

[0073] e. Filter the mixed solution by suction, wash the solid product with ultrapure water until the pH value of the filtrate is greater than 6, collect the solid, and dry it at 40°C.

[0074] Examples 1-4:

[0075] Examples 1-4 show the preparation of compounds (1-1) and (1-2), with the following structural formulas:

[0076]

[0077] Compound (1-1) was prepared by synthetic method one. The reagents required for the preparation process include: raw materials (3-hydroxy-9H-thion-9-one, catechol), solvent (DMF), and catalyst (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, Amberlyst-15 hydrogen-form strong acid resin).

[0078] The reaction conditions for each embodiment are shown in the table below:

[0079]

[0080] Examples 1-4 tested catalysts for the synthesis reaction of compounds (1-2). Four catalysts were tested: β-mercaptopropionic acid, sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, and Amberlyst-15 hydrogen-form strong acid resin. All catalysts showed good catalytic performance. NMR data are shown below. Figure 1 As shown.

[0081] The synthesis of compound (1-2) is performed using method two. The reagents required for the preparation process include: raw materials (compound (1-1), DNQ), solvent (1,4-dioxane), and catalyst (triethylamine). The amounts of each reagent are shown in the table below.

[0082]

[0083] Compounds (1-2) are a mixture, with a bright yellow solid color and a DNQ grafting rate of 82.6%.

[0084] Examples 5-6:

[0085] Examples 5-6 show the preparation of compounds (2-1) and (2-2), with the following structural formulas:

[0086]

[0087] Compound (2-1) was prepared by synthetic method one. The reagents required for the preparation process included: raw materials (pitavatine impurity 75, catechol), solvent (acetone), and catalysts (β-mercaptopropionic acid, sulfuric acid, and trifluoromethanesulfonic acid).

[0088] The reaction conditions for each embodiment are shown in the table below:

[0089]

[0090] Examples 5-6 screened catalysts for the synthesis of compound (2-1). The results showed that trifluoromethanesulfonic acid promoted the reaction, achieving a yield of over 67%, with further optimized yields reaching 86%. NMR data are shown below. Figure 2 As shown.

[0091] The synthesis of compound (2-2) is performed using method two. The reagents required for the preparation process include: raw materials (compound (2-1), DNQ), solvent (1,4-dioxane), and catalyst (triethylamine). The amounts of each reagent are shown in the table below.

[0092]

[0093] Compound (2-2) is a mixture, the solid is bright yellow, and the DNQ grafting rate is 78.4%.

[0094] Example 7:

[0095] Example 7 prepared compounds (3-1) and (3-2) with the following structural formulas:

[0096]

[0097] Compound (3-1) was prepared using synthetic method one. The reagents required for the preparation process included: raw materials (compound (7) and catechol), solvent (acetone), and catalyst (trifluoromethanesulfonic acid). The reaction conditions were as follows:

[0098]

[0099] The yield of compound (3-1) reached 92%, and the purity was 99.26% as determined by HPLC. The NMR data are as follows: Figure 3 As shown.

[0100] The synthesis of compound (3-2) is performed using method two. The reagents required for the preparation process include: raw materials (compound (3-1), DNQ), solvent (1,4-dioxane), and catalyst (triethylamine). The amounts of each reagent are shown in the table below.

[0101]

[0102] Compound (3-2) is a mixture, the solid is yellow in color, and the DNQ grafting rate is 77.2%.

[0103] Example 8:

[0104] Example 8 prepared compounds (4-1) and (4-2) with the following structural formulas:

[0105]

[0106] Compound (4-1) was prepared by synthetic method one. The reagents required for the preparation process included: raw materials (compound (8) and catechol), solvent (acetone), catalyst (trifluoromethanesulfonic acid), and reaction conditions as follows:

[0107]

[0108] The yield of compound (4-1) reached 89%, and the purity was 99.23% as determined by HPLC. The NMR data are as follows: Figure 4 As shown.

[0109] The synthesis of compound (4-2) is performed using method two. The reagents required for the preparation process include: raw materials (compound (4-1), DNQ), solvent (1,4-dioxane), and catalyst (triethylamine). The amounts of each reagent are shown in the table below.

[0110]

[0111] Compound (4-2) is a mixture, the solid is bright yellow, and the DNQ grafting rate is 76.8%.

[0112] Examples 9-13:

[0113] Examples 9-13 prepared compounds (5-1) and (5-2), with the following structural formulas:

[0114]

[0115] Compound (5-1) was prepared by synthetic method one. The reagents required for the preparation process include: raw materials (2-hydroxyanthraquinone, catechol), solvent (acetone, DMF), and catalyst (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, Amberlyst-15 hydrogen-form strong acid resin).

[0116] The reaction conditions for each embodiment are shown in the table below:

[0117]

[0118] Examples 9-13 screened solvents and catalysts for the synthesis of compound (5-1). Two solvents (DMF and acetone) and four catalysts (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, and Amberlyst-15 hydrogen-form strong acid resin) were screened. The results showed that acetone was the most effective solvent, and the reaction yield was relatively high when β-mercaptopropionic acid and sulfuric acid or trifluoromethanesulfonic acid were used as catalysts. The yield could reach over 70%, with further optimization reaching over 80%, and even further optimization reaching over 90%. NMR data are shown below. Figure 5 As shown.

[0119] The synthesis of compound (5-2) is performed using method two. The reagents required for the preparation process include: raw materials (compound (5-1), DNQ), solvent (1,4-dioxane), and catalyst (triethylamine). The amounts of each reagent are shown in the table below.

[0120]

[0121] Compound (5-2) is a mixture; the solid is bright yellow in color, and the DNQ grafting rate is 78.5%.

[0122] Examples 14-15:

[0123] Examples 14-15 show the preparation of compounds (6-1) and (6-2), with the following structural formulas:

[0124]

[0125] Compound (6-1) was prepared by synthetic method one. The reagents required for the preparation process included: raw materials (2,6-dihydroxyanthraquinone, catechol), solvent (acetone), and catalysts (β-mercaptopropionic acid, sulfuric acid, and trifluoromethanesulfonic acid).

[0126] The reaction conditions for each embodiment are shown in the table below:

[0127]

[0128] Examples 14-15 compared catalysts used in the synthesis of compound (6-1) with β-mercaptopropionic acid and sulfuric acid / trifluoromethanesulfonic acid. Both catalysts achieved good catalytic performance, with yields exceeding 80%. NMR data are shown below. Figure 6 As shown.

[0129] The synthesis of compound (6-2) is performed using method two. The reagents required for the preparation process include: raw materials (compound (5-1), DNQ), solvent (1,4-dioxane), and catalyst (triethylamine). The amounts of each reagent are shown in the table below.

[0130]

[0131] Compound (6-2) is a mixture, with a bright yellow solid color and a DNQ grafting rate of 78.3%.

[0132] Example 16:

[0133] Example 16: Compounds (7-1) and (7-2) were prepared, with the following structural formulas:

[0134]

[0135] Compound (7-1) was prepared by synthetic method one. The reagents required for the preparation process include: raw materials (compound (7), pyrogallol), solvent (acetone), and catalyst (trifluoromethanesulfonic acid).

[0136] The reaction conditions for each embodiment are shown in the table below:

[0137]

[0138] The yield of compound (7-1) reached 75%, and the purity was 99.19% as determined by HPLC.

[0139] The synthesis of compound (7-2) is performed using method two. The reagents required for the preparation process include: raw materials (compound (7-1), DNQ), solvent (1,4-dioxane), and catalyst (triethylamine). The amounts of each reagent are shown in the table below.

[0140]

[0141] Compound (7-2) is a mixture, the solid is yellow in color, and the DNQ grafting rate is 78.9%.

[0142] Example 17:

[0143] a. The photoinitiator compounds (1-2), (2-2), (3-2), (4-2), (5-2), and (6-2) of the present invention were dissolved in acetonitrile to prepare samples with a concentration of 0.0378 g / L, and were numbered (1-2), (2-2), (3-2), (4-2), (5-2), (6-2), and (7-2), respectively.

[0144] b. Set the wavelength of the ultraviolet light source to 365 nm and the light intensity to 10 mW / cm². 2 ;

[0145] c. Irradiate (1-2), (2-2), (3-2), (4-2), (5-2), (6-2), and (7-2) respectively under a UV light source. Detect the UV spectrum of the sample solution every 10 s, and record the highest peak absorbance greater than 300 nm. Normalize the highest peak absorbance of each sample and plot a linear relationship between time and residual rate, as shown in the figure. Figure 7 As shown.

[0146] observe Figure 7 For each curve, the greater the slope within the same time period, the stronger the photosensitivity. When the light irradiation is 20 s, the residual rates of compositions (1-2), (5-2), and (6-2) are significantly lower than those of compositions (2-2), (3-2), (4-2), and (7-2), indicating that compositions (1-2), (5-2), and (6-2) have strong photosensitivity and can be used as photoinitiator materials.

[0147] Example 18:

[0148] a. Weigh out 5.000 g of each of compounds (1-2), (2-2), (3-2), (4-2), (5-2), (6-2), and (7-2), respectively, and mix them with 20.000 g of phenolic resin and 65.000 g of organic solvent PGMEA to prepare photosensitive compositions, which are numbered as compositions (1-2), (2-2), (3-2), (4-2), (5-2), (6-2), and (7-2), respectively;

[0149] b. Perform photolithography on the six compositions in a under the same conditions. The process flow includes: spin coating, pre-baking, exposure, post-baking, and development. The process parameters are shown in the table below.

[0150]

[0151] c. The height difference of the film covering each group of substrates was detected using a profilometer. The detection results are shown in the table below:

[0152]

[0153] It can be seen that the height difference of these compounds of the present invention is greater than 6 μm, and the difference between composition (6-2) > composition (5-2) > composition (1-2) is even greater than 11 μm, showing significant photosensitivity.

[0154] It should be noted that the embodiments of the present invention have better implementability and are not intended to limit the present invention in any way. Any person skilled in the art may use the above-disclosed technical content to change or modify it into equivalent effective embodiments. However, any modifications or equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A class of polyphenylene ring photoinitiators, characterized in that, An esterification reaction is performed between a compound with a polyphenylene ring hydroxyl system and a diazonopeptidone compound DNQ in a solvent under alkaline conditions to generate a diazonopeptidone-type photoinitiator, namely a polyphenylene ring photoinitiator. The structural formula of the polyphenylene ring photoinitiator is as follows: If R1 is one of the elements N, O, S, and P, then R7 selectively contains H based on R1. Among them, R2 and R3 are R6 is selected from H, OH and ,and, The grafting rate was 75.0-85.0%; R4 and R5 are hydrogen, -OH, or... The positions of R4 and R5 are not fixed. The grafting rate is 75.0-85.0%.

2. The polyphenylene ring photoinitiator according to claim 1, characterized in that, Polyphenyl ring photoinitiator is R2 and R3 are R6 is selected from H, OH and ,in, The grafting rate was 75.0-85.0%; R4 and R5 are hydrogen, -OH, or... The positions of R4 and R5 are not fixed. The grafting rate is 75.0-85.0%.

3. The polyphenylene ring photoinitiator according to claim 2, characterized in that, The structural formula of the polybenzene ring photoinitiator includes any one of the following: R6 is selected from .

4. A method for preparing the polyphenylene ring photoinitiator according to any one of claims 1-3, characterized in that, Includes the following steps: (1) In an organic solvent, the carbonyl group of any one of anthrone, anthrone derivative, heterocyclic anthrone or heterocyclic anthrone derivative is activated by a strong acid catalyst and then undergoes an electrophilic substitution reaction with a polyhydroxyphenol to generate anthracene compounds with multiple phenolic hydroxyl groups, which are polyhydroxy heterocyclic anthracene skeleton compounds. The structural formulas of anthrones, anthrone derivatives, heterocyclic anthrones, or heterocyclic anthrone derivatives include: , R4' and R5' are hydrogen or -OH, and their positions are not fixed; R1 is selected from one of the elements N, O, S, and P, and R7 selectively contains H according to R1; (2) Under alkaline conditions, a polyhydroxy heterocyclic anthracene skeleton compound reacts with the diazonoquinone compound DNQ in a solvent to generate a diazonoquinone type photoinitiator, which is a polybenzene ring photoinitiator.

5. The method for preparing the polybenzene ring photoinitiator according to claim 4, characterized in that, The polyhydroxyphenol is a phenol with at least two hydroxyl groups; when there are multiple hydroxyl groups, the positions of the hydroxyl groups are not fixed.

6. The method for preparing the polybenzene ring photoinitiator according to claim 5, characterized in that, The polyhydroxyphenol is a phenol with two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed; The polyhydroxyphenol is a phenol with three hydroxyl groups, and the positions of the three hydroxyl groups are not fixed; The polyhydroxyphenol is a phenol with four hydroxyl groups, and the positions of the four hydroxyl groups are not fixed; The polyhydroxyphenol is a phenol with five hydroxyl groups.

7. The method for preparing the polybenzene ring photoinitiator according to claim 4, characterized in that, The strong acid catalyst includes one or more of β-mercaptopropionic acid, sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, and Amberlyst-15 hydrogen-form strong acid resin.

8. The method for preparing the polybenzene ring photoinitiator according to claim 4, characterized in that, During the esterification reaction, the molar 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 5-30 min.

9. The method for preparing the polybenzene ring photoinitiator according to claim 4, characterized in that, The organic solvent in step (1) includes one or more of DMF and acetone; The solvent in step (2) includes 1,4-dioxane.

10. The method for synthesizing the polybenzene ring photoinitiator according to claim 4, characterized in that, In the esterification reaction process described in step (2), the diazonoquinone compound realizes the esterification reaction of the hydroxyl groups of each compound in the multiple phenolic hydroxyl system. The esterification reaction includes one or more of the following products: monoesterification, dieesterification, trimesterification, tetraesterification, pentaesterification, hexaesterification, heptaesterification, octaesterification, nonaesterification, and decaesterification.

11. A G / I line photoinitiator, characterized in that, Includes the polybenzene ring photoinitiator according to any one of claims 1-3.

12. A photosensitive composite thin film material, characterized in that, Includes the polybenzene ring photoinitiator according to any one of claims 1-3.

13. The photosensitive composite thin film material according to claim 12, characterized in that, The photosensitive material also includes a composition formed of phenolic resin and an organic solvent, wherein the organic solvent is selected from propylene glycol methyl ether acetate (PGMEA).

14. The application of the photosensitive composite thin film material according to claim 12 or 13 in the field of photolithography.

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