Anthracene skeleton compound and photoinitiator application thereof

Abstract

The invention discloses a polyhydroxy anthracene skeleton compound and a photoinitiator application thereof.The polyhydroxy anthracene skeleton compound is used as a photoinitiator precursor, the structure of the series of compounds has anisotropy, hydroxyl distribution is uniform, steric hindrance is small, and background absorption influence cannot be generated after the series of compounds are combined with a diazo naphthoquinone photosensitizer (DNQ). Therefore, the compound can be used as a novel photoinitiator, and is hopeful to emit bright colors in the field of semiconductors.

Description

Technical Field

[0001] The invention discloses a type of polyhydroxy anthracene skeleton compound and the application of a photoinitiator thereof, belonging to the technical field of photochemistry. Background Art

[0002] Photolithography technology has been very popular in the electronics industry and is a major process in the production of planar transistors and integrated circuits. As the most important part of the photolithography process, photoresists are classified from low-end to high-end in the panel and semiconductor industries. The type of photoresist and the accuracy of the photolithography machine are the main factors that determine the minimum line width of the photolithography process. The composition of G / I line photoresists includes: resin, photoinitiator, solvent and a small amount of additives. The current G / I line photolithography accuracy is limited by the photosensitivity of the photoinitiator. The photoinitiator is mainly formed by the condensation of diazonaphthoquinone photosensitizer and polyhydroxybenzene ring derivatives under alkaline conditions. Its photosensitive properties are related to the distribution position of DNQ in the molecule. The larger the interval between adjacent DNQs, the better the photosensitivity. For example, the three hydroxyl groups of ɑ,ɑ,ɑ'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (TPA) are on different benzene rings, and the photosensitivity after grafting DNQ is particularly excellent. Benzophenones and fluorenones with multiple grafting sites are also widely used. Among them, heterocyclic anthracene compounds are often used in photochemical research. Its unique six-membered ring structure has good symmetry and rigidity in space, and the hydroxyl-substitutable active sites on the benzene ring are evenly distributed and have low steric hindrance. The existing carbon-based sites can be well modified and can be used in the preparation of G / I line photoinitiators. The G / I line photoinitiators required by the semiconductor industry usually have the characteristics of high stability, multi-stage applicability, high photosensitivity, and low cost. At present, domestic semiconductor companies need this kind of domestically substituted and high-demand new product. Summary of the invention

[0003] The present invention aims to solve the problems of insufficient output of new photoinitiators and single type of precursor skeletons of new photoinitiators, proposes a synthesis method of a class of polyhydroxyanthracene skeleton compounds and photoinitiators thereof, and uses photolithography technology to complete related applications of photoinitiators.

[0004] A class of polyhydroxy anthracene skeleton compounds, the structural formulas of the compounds include the following: , ; said R 2 '、R 3 ' is phenol, R 4 '、R 5 ' is hydrogen or -OH, and not H, R 4 '、R 5 'The position is not fixed; the R 1 is selected from one of the elements N, O, S, and P, then R7 According to R 1 It optionally contains H. The reaction equation is:

[0005] Where R 1 is a heteroatom, representing one of the four elements N, O, S, and P; R 2 '、R 3 ' is a phenol group; R 4 '、R 5 ' are phenolic hydroxyl groups or hydrogen atoms on the benzene ring, R 7 is a hydrogen atom or optionally has no substituent according to the heteroatom.

[0006] Another technical solution of the present invention is to provide an anthracene skeleton compound, wherein the polyhydroxy anthracene skeleton compound is subjected to an esterification reaction with a diazonaphthoquinone compound DNQ in a solvent under alkaline conditions to generate a diazonaphthoquinone type photoinitiator, namely an anthracene skeleton compound, wherein the structural formula of the anthracene skeleton compound is: ; R 2 , R 3 for , where R 6 Selected from H and ,in, The grafting rate is 80.0-95.0%; R 4 , R 5 is hydrogen or -OR 6 , the R 4 , R 5 The position is not fixed, among which R 6 Selected from H and ,in, The grafting rate is 80.0-95.0%.

[0007] The structural formula of the anthracene skeleton compound is: , R 1 is one of the elements N, O, S, and P, then the structural formula is, R 2 , R 3 for , where R 6 Selected from H and ,in, The grafting rate is 80.0-95.0%; R 4 , R 5 is hydrogen or -OR 6 , the R 4 , R 5 The position is not fixed, among which R 6Selected from H and ,in, The grafting rate is 80.0-95.0%.

[0008] The anthracene skeleton compound includes any one of the following: , where R 6 Selected from H and ,in, The grafting rate is 80.0-95.0%.

[0009] In some embodiments, taking a compound as an example, the synthesis method of the heterocyclic anthracene-based photoinitiator is as follows, taking the synthesis of compound (1) as an example: in, The grafting rate is 80.0-95.0%. Since the product obtained is a mixture, the grafting rate refers to the The synthesis process of other compounds is the same.

[0010] Based on the above synthesis process, all compounds of the present invention include anthracene skeleton compounds and heterocyclic anthracene photoinitiators, and their structures are: , where R 6 Selected from H and ,in, The grafting rate is 80.0-95.0%. Since the product obtained is a mixture, the grafting rate refers to the The amount.

[0011] Another technical solution of the present invention is to provide a method for synthesizing anthracene-based skeleton compounds, comprising the following steps: (1) In an organic solvent, the carbonyl group of anthrone is activated using a strong acid catalyst and undergoes an electrophilic substitution reaction with phenol to generate anthracene compounds with multiple phenolic hydroxyl groups; (2) Under alkaline conditions, anthracene compounds with multiple phenolic hydroxyl groups react with diazonaphthoquinone compounds DNQ in a solvent to generate diazonaphthoquinone photoinitiators.

[0012] The anthrone raw material further comprises phenol, 3-hydroxy-9H-xanthen-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:

[0013] In the method for synthesizing the polyhydroxy heterocyclic anthracene skeleton compound, the catalyst used includes one or more of β-mercaptopropionic acid, sulfuric acid, trifluoromethylsulfonic acid, trifluoromethylsulfonic anhydride, and Amberlyst-15 hydrogen-type strong acid resin.

[0014] In the method for synthesizing the polyhydroxyheterocyclic anthracene-based skeleton compound, the organic solvent used includes one or more of DMF, methanol, acetone, and phenol.

[0015] In the method for synthesizing the polyhydroxy heterocyclic anthracene skeleton compound, the molar feed ratio of the raw material anthrone to phenol is 1: 6-30, the reaction temperature is 30-120° C., and the reaction time is 12-24 h. It can be understood by those skilled in the art that in order to avoid oxidation reaction, nitrogen protection is used throughout the reaction process of the present invention.

[0016] In the heterocyclic anthracene photoinitiator synthesis method, the molar feed ratio of the raw material DNQ to the polyhydroxy heterocyclic anthracene skeleton compound is 2-5:1, the synthesis temperature is controlled at 30-35°C, the solvent is 1,4-dioxane, the catalyst is triethylamine (the dropping time is controlled at 60-65min), and the reaction time is 5-30min.

[0017] A G / I-ray photoinitiator comprises the polyhydroxy anthracene skeleton compound and anthracene photoinitiator thereof.

[0018] A photosensitive material comprises the anthracene skeleton compound.

[0019] The photosensitive material further comprises a composition formed by a phenolic resin and an organic solvent, and the organic solvent is selected from PGMEA.

[0020] The present invention applies the photosensitive material in the field of photolithography.

[0021] The performance test and evaluation of the novel heterocyclic anthracene-based photoinitiator described in the present invention are specifically as follows: The 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 photoinitiator accounted for 5.5 wt%, PGMEA accounted for 23.0%, and phenolic resin accounted for 72.0%. 10 mL of the mixture solution was dripped on an 8-inch circular substrate material, and it was evenly distributed on the substrate material into a 20 μm thick film by spin coating. The pre-baking treatment was performed, and the photolithography machine was used for exposure at a 365 nm light source, and the exposure energy was 120 mJ / cm 2, post-baking treatment, and then the material was placed in a developing tank filled with 2.38 wt% tetramethylammonium hydroxide (TMAH) for immersion and development for 20 s. After the excess developer on the surface of the material was rinsed off with ultrapure water, the height difference of the pattern was observed by a profilometer. The photosensitivity of the photoinitiator was judged by the value. The evaluation standard was: the larger the height difference of the pattern, the better the photosensitivity of the photoinitiator.

[0022] The beneficial effects of the present invention are as follows: 1. Compared with common polyhydroxy compounds such as benzophenones, fluorenones and TPA, the polyhydroxy anthracene skeleton compound of the present invention has a larger non-conjugated benzene ring system, a farther distance between hydroxyl sites, easy rotation of the carbon-carbon bonds between the benzene rings, and a molecular structure that better exposes the hydroxyl groups in space, which is conducive to grafting DNQ and easily forms an excellent photoinitiator.

[0023] 2. The anthracene-based photoinitiator of the present invention has good photosensitivity when mixed with resin and can be developed into a G / I line photoinitiator, which has great industrial value.

[0024] 2. The synthesis method of the polyhydroxyanthracene skeleton compound of the present invention is simple, with low process cost and reaction hazard risk, and has practical industrial value. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of compound (1-1).

[0026] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of compound (2-1).

[0027] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of compound (3-1).

[0028] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of compound (4-1).

[0029] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of compound (5-1).

[0030] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of compound (6-1).

[0031] Figure 7 This is a graph showing the variation of the light irradiation residual rate of six photoinitiator compounds over time. DETAILED DESCRIPTION

[0032] The present invention is further described below with reference to embodiments, but the scope of protection claimed by the present invention is not limited to the scope described in the embodiments.

[0033] The reaction raw materials of the present invention include phenol, anthrone, 3-hydroxy-9H-xanthen-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] Synthesis steps of polyhydroxy heterocyclic anthracene skeleton compounds (method 1): a. Mix the raw materials and solvent in a 250 mL flask according to the reaction ratio, and use nitrogen bubbling to expel the air in the flask; b(1). When the catalyst is β-mercaptopropionic acid and sulfuric acid: first place the mixed solution of step (a) in a 30 ℃ oil bath, add β-mercaptopropionic acid into the reaction system under nitrogen protection and react at 30 ℃ for 30 min, then slowly add sulfuric acid dropwise, 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; 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 °C), then slowly add the catalyst dropwise, and continue the reaction for 12-24 h; b(3). When the catalyst is Amberlyst-15 hydrogen-type strong acid resin: Amberlyst-15 hydrogen-type strong acid resin is added to the flask together with the raw materials and the solvent in step (a) to form a solid-liquid mixed system, and the reaction is carried out at 60-120 ℃ for 12-24 h; c. Monitor the reaction of the raw materials by thin layer chromatography (TLC), maintain a nitrogen atmosphere during the reaction process, and cool the temperature to room temperature after the reaction is completed. Add 2 times the volume of the solvent to the reaction system. After the product solid is fully separated, filter it at room temperature and rinse the solid with water at room temperature. Collect the product solid and dry it at 40°C. Finally, recrystallize it in an acetone solution to obtain a product with a purity of more than 99.00%; d. The product was subjected to HPLC (purity) and NMR tests.

[0035] Photoinitiator synthesis steps (method 2): a. Dissolve 1.000 mmol of polyhydroxyanthracene skeleton compound and DNQ in 1,4-dioxane at a certain molar ratio and stir to dissolve at 35°C; b. After the reaction system is cooled to 30°C, slowly add triethylamine catalyst and the same volume of triethylamine solvent 1,4-dioxane (addition time is about 1 h), and keep the temperature between 30-31°C. After the addition is completed, heat to 35°C and continue the reaction for 30 min; c. Add 30% by volume of hydrochloric acid to the reaction system for quenching, filter and collect the filtrate; d. The filtrate was slowly poured into a stream containing 5 times the volume of the organic solution in ultrapure water (mixed with 30% by volume of hydrochloric acid) with vigorous mechanical stirring for pulping operation; e. Filter the mixed solution and 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.

[0036] Embodiment 1-11: Example 1-11 Compound (1-1) and Compound (1-2) were prepared, and their structural formulas were:

[0037] Compound (1-1) Preparation Method 1 was selected. The chemicals required for the preparation process include: raw materials (3-hydroxy-9H-xanthen-9-one, phenol), solvents (DMF, acetone, methanol, phenol), catalysts (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, Amberlyst-15 hydrogen-type strong acid resin) The reaction conditions of each embodiment are shown in the following table:

[0038] In Example 1-4, the solvent for the synthesis reaction of compound (1-1) was tested. It can be seen that the technical solution of the present invention can achieve a yield of more than 45%, further more than 60%, further more than 70%, and up to 86%. In Example 5-11, phenol and DMF were used as reaction solvents to compare three catalysts: trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, and Amberlyst-15 hydrogen-type strong acid resin. The reaction yield can reach up to 86% when trifluoromethanesulfonic acid is used. The NMR data results are as follows: Figure 1 shown.

[0039] Method 2 for the synthesis of compound (1-2) is selected. The drugs required for the preparation process include: raw materials (compound (1-1), DNQ), solvent (1,4-dioxane), catalyst (triethylamine). The dosage of each drug is shown in the following table:

[0040] Compound (1-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 92.3%.

[0041] Embodiment 12-13: Example 12-13 Prepare compound (2-1) and compound (2-2), the structural formulas are:

[0042] Compound (2-1) was prepared by synthetic method 1. The drugs required for the preparation process include: raw materials (Pitavalstat impurity 75, phenol), solvent (DMF), catalyst (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid).

[0043] The reaction conditions of each embodiment are shown in the following table:

[0044] In Example 12-13, the catalyst for the synthesis of compound (2-1) was screened. The results showed that the catalyst trifluoromethanesulfonic acid had the highest yield, reaching 92%. Therefore, the optimal reaction conditions for the synthesis of compound (2-1) are: based on the molar amount of the raw material pitavastatin impurity 75, the molar amount of phenol is 6eq, the molar amount of the catalyst trifluoromethanesulfonic acid is 1.2eq, the solvent is DMF, the reaction temperature is 120℃, the reaction time is 24h, the product purity is 99.18%, and the yield is 92%. The NMR test results of compound (2-1) are as follows: Figure 2 shown.

[0045] Method 2 for the synthesis of compound (2-2) is selected. The drugs required for the preparation process include: raw materials (compound (2-1), DNQ), solvent (1,4-dioxane), catalyst (triethylamine). The dosage of each drug is shown in the following table:

[0046] Compound (2-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 86.9%.

[0047] Embodiment 14: Example 14 Compound (3-1) and compound (3-2) were prepared, and the structural formula is:

[0048] Preparation of Compound (3-1) Synthesis method 1 was selected. The chemicals required for the preparation process include: raw materials (compound (7) and phenol), solvent (DMF), catalyst (trifluoromethanesulfonic acid), and the reaction conditions are:

[0049] The yield of compound (3-1) reached 85%, and the purity was 99.57% as tested by HPLC. The results of NMR data are as follows: Figure 3 shown.

[0050] Method 2 for the synthesis of compound (3-2) was selected. The drugs required for the preparation process include: raw materials (compound (3-1), DNQ), solvent (1,4-dioxane), catalyst (triethylamine). The dosage of each drug is shown in the following table:

[0051] Compound (3-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 82.4%.

[0052] Embodiment 15: Example 15 Compound (4-1) and compound (4-2) were prepared, and the structural formula is:

[0053] Preparation of compound (4-1) Synthesis method 1 was selected. The drugs required for the preparation process include: raw materials (compound (8) and phenol), solvent (DMF), catalyst (trifluoromethanesulfonic acid), and the reaction conditions are:

[0054] The yield of compound (4-1) reached 91%, and the purity was 99.52% as tested by HPLC. The results of NMR data are as follows: Figure 4 shown.

[0055] Method 2 for the synthesis of compound (4-2) was selected. The drugs required for the preparation process include: raw materials (compound (4-1), DNQ), solvent (1,4-dioxane), catalyst (triethylamine). The dosage of each drug is shown in the following table:

[0056] Compound (4-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 83.2%.

[0057] Embodiment 16-19: Example 16-19 Prepare compound (5-1) and compound (5-2), the structural formula is:

[0058] Compound (5-1) was prepared by synthetic method 1. The chemicals required for the preparation process include: raw materials (2-hydroxyanthraquinone, phenol), solvents (DMF, phenol), and catalysts (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid).

[0059] The reaction conditions of each embodiment are shown in the following table:

[0060] Examples 16-19 screened the solvent and catalyst for the synthesis reaction of compound (5-1). During the test, phenol and DMF were used as solvents to screen β-mercaptopropionic acid and two catalysts, sulfuric acid and trifluoromethanesulfonic acid. The results showed that when DMF was used as the solvent and trifluoromethanesulfonic acid was used as the catalyst, the reaction yield could reach a maximum of more than 60%, and further more than 70%, and up to 88%. At the same time, the optimal conditions for the synthesis of compound (5-1) were: based on the molar amount of the raw material 2-hydroxyanthraquinone, the molar amount of phenol was 6eq, the molar amount of the catalyst trifluoromethanesulfonic acid was 1.2eq, the solvent was DMF, the reaction temperature was 120°C, the reaction time was 24 h, the product purity was 99.48%, the yield was 88%, and the nuclear magnetic resonance test results were as follows: Figure 5 shown.

[0061] Method 2 for the synthesis of compound (5-2) is selected. The drugs required for the preparation process include: raw materials (compound (5-1), DNQ), solvent (1,4-dioxane), catalyst (triethylamine). The dosage of each drug is shown in the following table:

[0062] Compound (5-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 82.8%.

[0063] Embodiment 20-22: Example 20-22 Prepare compound (6-1) and compound (6-2), the structural formula is:

[0064] The preparation of compound (6-1) selected synthesis method 1. The chemicals required for the preparation process include: raw materials (2,6-dihydroxyanthraquinone, phenol), solvents (DMF, phenol), and catalysts (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid).

[0065] The reaction conditions of each embodiment are shown in the following table:

[0066] In Example 20-22, the solvent and catalyst were screened for the synthesis of compound (6-1). The reaction solvents were DMF and phenol, and the reactivity with β-mercaptopropionic acid, sulfuric acid and trifluoromethanesulfonic acid was compared respectively. The results showed that DMF as a solvent was beneficial to the reaction, and the reaction effect was better when trifluoromethanesulfonic acid was the catalyst, with a yield of more than 60%, further reaching more than 70%, and up to 76%. Therefore, the optimal reaction conditions for the synthesis of compound (6-1) are: based on the molar amount of the raw material 2,6-dihydroxyanthraquinone, the molar amount of phenol is 6eq, the molar amount of the catalyst trifluoromethanesulfonic acid is 1.2eq, the solvent is DMF, the reaction temperature is 120°C, the reaction time is 24 h, the product purity is 99.28%, the yield is 76%, and the nuclear magnetic resonance test results are as follows: Figure 6 shown.

[0067] Method 2 for the synthesis of compound (6-2) is selected. The drugs required for the preparation process include: raw materials (compound (6-1), DNQ), solvent (1,4-dioxane), catalyst (triethylamine). The dosage of each drug is shown in the following table:

[0068] Compound (6-2) is a mixture, the solid color is yellow, and the DNQ grafting rate is 84.9%.

[0069] Embodiment 23: a. The photoinitiator compound (1-2), compound (2-2), compound (3-2), compound (4-2), compound (5-2), and compound (6-2) of the present invention were dissolved in acetonitrile to prepare samples with a concentration of 0.0378 g / L, and the samples were numbered (1-2), (2-2), (3-2), (4-2), (5-2), and (6-2); b. Set the wavelength of the UV light source to 365 nm and the light intensity to 10 mW / cm 2 ; c. Irradiate (1-2), (2-2), (3-2), (4-2), (5-2), and (6-2) under ultraviolet light source respectively, detect the ultraviolet spectrum of the sample solution every 10 seconds, and record the highest peak absorbance greater than 300 nm. The highest peak absorbance of each sample is normalized and plotted into a linear relationship diagram between time and residual rate, as shown in the figure. Figure 7 shown.

[0070] observe Figure 7For each curve, the larger the slope within the same time period, the stronger the photosensitivity. After 20 s of light irradiation, the residual rates of compositions (5-2) and (6-2) were significantly lower than those of compositions (1-2), (2-2), (3-2), and (4-2), indicating that compositions (5-2) and (6-2) have stronger photosensitivity.

[0071] Embodiment 24: a. Weigh 5.000 g of each of compounds (1-2), (2-2), (3-2), (4-2), (5-2), and (6-2) and mix with 20.000 g of phenolic resin and 65.000 g of organic solvent PGMEA to prepare a photosensitive composition, which are numbered as compositions (1-2), (2-2), (3-2), (4-2), (5-2), and (6-2); b. The six compositions in a were subjected to photolithography processes under the same conditions, the process flow including: spin coating, pre-baking, exposure, post-baking, and development, and the process parameters of the process are shown in the table:

[0072] c. The height difference of the film covered by each group of substrates is tested by profilometer, and the test results are shown in the table:

[0073] It is obvious that the height difference of compositions (1-2), (2-2), (3-2), (4-2), (5-2), and (6-2) is large, and all have photosensitivity. Among them, composition (3-2), composition (1-2), composition (5-2), and composition (6-2) have more specific photosensitivity than (1-2) and (4-2), and the above examples prove that compound (6-2) and compound (5-2) have significantly higher photosensitivity than other compounds and can be used as photoinitiators.

[0074] It should be noted that the embodiments of the present invention have better practicability and do not impose any form of limitation on the present invention. Any technician familiar with the field may use the technical content disclosed above to change or modify it into an equivalent effective embodiment. However, any modification 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 are still within the scope of the technical solution of the present invention.

Claims

1. A polyhydroxy anthracene skeleton compound, characterized in that: The structural formula of the compound includes the following: , ; R2' and R3' are phenol, R4' and R5' are hydrogen or -OH, and they are not H at the same time, 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.

2. The method for preparing a polyhydroxy anthracene skeleton compound according to claim 1, characterized in that: The steps include: In an organic solvent, the carbonyl group of anthrone is activated by a strong acid catalyst and undergoes an electrophilic substitution reaction with phenol to generate anthracene compounds with multiple phenolic hydroxyl groups, namely, polyhydroxy anthracene skeleton compounds. The reaction formula is as follows: R2' and R3' are phenol, R4' and R5' are hydrogen or -OH, and are not H at the same time, 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.

3. A class of anthracene skeleton compounds, characterized in that: The polyhydroxy anthracene skeleton compound of claim 1 is subjected to an esterification reaction with a diazonaphthoquinone compound DNQ in a solvent under alkaline conditions to generate a diazonaphthoquinone type photoinitiator, namely an anthracene skeleton compound, wherein the structural formula of the anthracene skeleton compound is: ; R2, R3 are , wherein R6 is selected from H and ,in, The grafting rate is 80-95%; R4 and R5 are hydrogen or -OR6, and the positions of R4 and R5 are not fixed, wherein R6 is selected from H ,in, The grafting rate is 80.0-95.0%%.

4. The anthracene skeleton compound according to claim 3, characterized in that: The structural formula of the anthracene skeleton compound is: , R1 is one of N, O, S, P elements, then R7 contains H selectively according to R1, R2, R3 are , wherein R6 is selected from H and ,in, The grafting rate is 80.0-95.0%; R4 and R5 are hydrogen or -OR6, and the positions of R4 and R5 are not fixed, wherein R6 is selected from H and ,in, The grafting rate is 80.0-95.0%.

5. The anthracene skeleton compound according to claim 4, characterized in that: The anthracene skeleton compound includes any one of the following: , wherein R6 is selected from H and ,in, The grafting rate is 80.0-95.0%.

6. A method for synthesizing anthracene-based skeleton compounds, characterized in that: The steps include: (1) In an organic solvent, the carbonyl group of anthrone is activated using a strong acid catalyst and undergoes an electrophilic substitution reaction with phenol to generate anthracene compounds with multiple phenolic hydroxyl groups; (2) Under alkaline conditions, anthracene compounds with multiple phenolic hydroxyl groups react with diazonaphthoquinone compounds DNQ in a solvent to generate diazonaphthoquinone photoinitiators.

7. The method for synthesizing anthracene-based skeleton compounds according to claim 6, characterized in that: The anthrone is replaced by anthrone derivative, heterocyclic anthrone or heterocyclic anthrone derivative; The anthrone derivative structural formula is , heterocyclic anthrone selected from , heterocyclic anthrone derivatives selected from ; The R4' and R5' are hydrogen or -OH, and are not H at the same time, and the positions of R4' and R5' are not fixed; the R1 is selected from one of the elements N, O, S, and P, and R7 selectively contains H according to R1; the reaction formula is as follows: R2' and R3' are phenol.

8. The method for synthesizing anthracene-based skeleton compounds according to claim 7, 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-type strong acid resin.

9. The method for synthesizing anthracene-based skeleton compounds according to claim 6, characterized in that: During the esterification reaction, the molar feed ratio of the raw material DNQ to the polyhydroxy heterocyclic anthracene skeleton compound is 2-5:1, the synthesis temperature is controlled at 30-35°C, and the reaction time is 5-30min.

10. The method for synthesizing anthracene-based skeleton compounds according to claim 6, characterized in that: The organic solvent in step (1) includes one or more of DMF, methanol, acetone, and phenol; The solvent in step (2) includes 1,4-dioxane.

11. The method for synthesizing anthracene-based skeleton compounds according to claim 6, characterized in that: During the esterification reaction in step (2), the diazonaphthoquinone compound realizes an esterification reaction of the hydroxyl groups of each of the anthracene compounds having multiple phenolic hydroxyl groups, and the esterification reaction includes one or more of monoesterification, diesterification, triesterification, tetraesterification, pentaesterification, and hexaesterification products.

12. A G / I line photoinitiator, characterized in that: It includes the anthracene skeleton compound described in any one of claims 3 to 5.

13. A photosensitive material, characterized in that: It includes the anthracene skeleton compound described in any one of claims 3 to 5.

14. The photosensitive material according to claim 13, characterized in that: The photosensitive material further comprises a composition formed by a phenolic resin and an organic solvent, and the organic solvent is selected from propylene glycol methyl ether acetate PGMEA.

15. Use of the photosensitive material according to claim 13 or 14 in the field of photolithography.

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