Series of multi-benzene-ring photoinitiators and photoinitiator application thereof

Abstract

The invention discloses a series of compounds with multi-benzene-ring hydroxyl systems and photoinitiator application thereof.The multi-benzene-ring hydroxyl aromatic system compounds serve as photoinitiator precursors and can be prepared into photoresist to be loaded on the surface of a base material after being combined with diazonaphthoquinone (DNQ), and obvious high-depth-difference gradient treatment of the photoresist can be completed through a photolithography technique; the photoinitiator has the practical significance of becoming an I-line photoinitiator.

Description

Technical Field

[0001] The invention discloses a series of multi-benzene ring hydroxyl system compounds and photoinitiator applications thereof, belonging to the technical field of photochemistry. Background Art

[0002] Heterocyclic anthrone compounds are often studied in the field of photochemistry. Aza / xanthone is often used in biological activity research. Thioxanthone is synthesized into a photoinitiator with high photosensitivity through benzene ring modification and nitrogen para-position modification. Therefore, anthrone compounds have excellent optical properties. According to the structural specificity, multi-site modification can be performed to make up for the lack of functionality of anthracene compounds.

[0003] G / I line photoinitiators mainly work after the reaction of a polyhydroxy skeleton and DNQ. The existing polyhydroxy skeleton is mainly a benzophenone structure. The trihydroxy or tetrahydroxy group contained in this structure will have different effects on different photolithography process stages. In response to the performance requirements of the domestic market for photoinitiators, domestic companies very much hope to find some photoinitiators that can meet the standards of multiple process stages at the same time, but it takes time to achieve this goal. Therefore, the research and development and industrialization of domestically produced and multifunctional new photoinitiators are important measures to promote the development of the domestic semiconductor industry. Summary of the invention

[0004] The present invention aims to solve the problems of insufficient output of new photoinitiators and single type of precursor skeleton of new photoinitiators, proposes a series of synthesis methods of polyphenyl ring hydroxyl system compounds and photoinitiators thereof, and uses photolithography technology to illustrate the functionality of the photoinitiator.

[0005] A series of compounds with multiple benzene ring hydroxyl systems, the structural formula is , ; said R 2 '、R 3 ' is polyhydroxyphenol, 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 R 7 According to R 1 Optionally contains H.

[0006] The polyhydroxyphenol is a phenol having at least two hydroxyl groups. When the polyhydroxyphenol has more than one hydroxyl group, the positions of the hydroxyl groups are not fixed.

[0007] The polyhydroxy phenol is a phenol with two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed, such as o-hydroxyl, p-hydroxyl, and m-hydroxyl phenol; 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; 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 and 2,3,4,5-tetrahydroxyphenol; The polyhydroxy phenol is a phenol having five hydroxy groups.

[0008] The preparation method of the compound with multiple benzene ring hydroxyl system comprises the following steps: In an organic solvent, the carbonyl group of any one of anthrone, anthrone derivatives, heterocyclic anthrone or heterocyclic anthrone derivatives is activated by a strong acid catalyst, and then reacted with phenol for electrophilic substitution to generate an anthracene compound with multiple phenolic hydroxyl groups, i.e., a polyhydroxy heterocyclic anthracene skeleton compound. The reaction formula is as follows: ; said R 2 '、R 3 ' is polyhydroxyphenol, R 4 '、R 5 ' is hydrogen or -OH, 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 R 7 According to R 1 Optionally contains H; R 8 It is hydrogen or hydroxyl.

[0009] In some preferred embodiments, the synthesis method of the polyphenyl ring hydroxyl system compound has the reaction equation:

[0010] Where R 1 is a heteroatom, representing one of the four elements N, O, S, and P; R 2 , R 3 is a catechol group or pyrogallol; R 4 , R 5 is the phenolic hydroxyl group or hydrogen atom on the benzene ring, R 7 According to R 1 The hetero atom is optionally a hydrogen atom or has no substituent.

[0011] A novel polyphenyl ring photoinitiator is a novel polyphenyl ring photoinitiator. The polyphenyl ring hydroxyl system compound is subjected to an esterification reaction with a diazonaphthoquinone compound DNQ in a solvent under alkaline conditions to generate a diazonaphthoquinone type photoinitiator. The novel polyphenyl ring photoinitiator has the structural formula: ,or , R 1 is one of the elements N, O, S, and P, then R 7 According to R 1 Optionally contains H; Among them, R 2 , R 3 for , R 6 Selected from H, OH and ,and, The grafting rate is 75.0-85.0%; R 4 , R 5 is hydrogen, -OH, or , the R 4 , R 5 The location is not fixed, The grafting rate is 75.0-85.0%.

[0012] The structural formula of the novel polyphenyl ring photoinitiator includes any one of the following: , R 6 Selected from .

[0013] The synthesis method of the polyphenyl ring photoinitiator, taking the above preferred compound (1) as an example, the reaction equation is: .

[0014] A method for preparing a polyphenyl ring photoinitiator, characterized in that it comprises the following steps: (1) In an organic solvent, a carbonyl group of anthrone, anthrone derivative, heterocyclic anthrone or any one of heterocyclic anthrone derivatives is activated by a strong acid catalyst, and then subjected to an electrophilic substitution reaction with a polyhydroxy phenol to generate an anthracene compound with multiple phenolic hydroxyl groups, i.e., a polyhydroxy heterocyclic anthracene skeleton compound; (2) Under alkaline conditions, a polyhydroxy heterocyclic anthracene skeleton compound undergoes an esterification reaction with a diazonaphthoquinone compound DNQ in a solvent to generate a diazonaphthoquinone type photoinitiator, namely a polyphenyl ring photoinitiator.

[0015] The structural formula of the anthrone, anthrone derivative, heterocyclic anthrone or heterocyclic anthrone derivative includes , ; said R 4 '、R 5 ' is hydrogen or -OH, 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 R 7 According to R1 Optionally contains H.

[0016] The polyhydroxyphenol is a phenol having at least two hydroxyl groups. When the polyhydroxyphenol has more than one hydroxyl group, the positions of the hydroxyl groups are not fixed.

[0017] The polyhydroxy phenol is a phenol having two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having three hydroxyl groups, and the positions of the three hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having four hydroxyl groups, and the positions of the four hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having five hydroxy groups.

[0018] In a preferred embodiment, in the method for synthesizing a polyphenyl ring hydroxyl system compound, the raw materials include: catechol, pyrogallol, 3-hydroxy-9H-xanthen-9-one, 2-hydroxyanthraquinone, 2,6-dihydroxyanthraquinone, pitavastatin impurity 75, compound (7) and compound (8), wherein the structural formulas of compound (7) and compound (8) are as follows: .

[0019] 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.

[0020] In the method for synthesizing a polyphenyl ring hydroxyl system compound, the molar feed ratio of anthrone and catechol is 1:6, the reaction temperature is 60-120° C., the reaction time is 20-24 h, and nitrogen protection is used throughout the reaction process.

[0021] In the method for synthesizing a polyphenyl ring hydroxyl system compound, the molar feed ratio of the raw materials anthrone and pyrogallol is 1:6, the reaction temperature is 60-120° C., the reaction time is 20-24 h, and nitrogen protection is used throughout the reaction process.

[0022] In the synthesis of the novel polyphenyl ring photoinitiator, the molar feed ratio of the raw material DNQ to the polyphenyl ring hydroxyl system compound is 3.5-7.5:1; the reaction temperature is controlled at 30-35°C, the catalyst dropwise addition time is controlled between 60-65min, and the reaction time is 5-30min.

[0023] The organic solvent in step (1) includes one or more of DMF and acetone; The solvent in step (2) includes 1,4-dioxane.

[0024] During the esterification reaction in step (2), the diazonaphthoquinone compound realizes an esterification reaction of the hydroxyl groups of each compound in the anthracene-based compound having multiple phenolic hydroxyl groups, and the esterification reaction includes one or more of monoesterification, diesterification, triesterification, tetraesterification, pentaesterification, hexaesterification, heptaesterification, octaesterification, nonaesterification, and decaesterification products.

[0025] A G / I line photoinitiator comprises the polyphenyl ring photoinitiator.

[0026] A photosensitive composite film material comprises the polyphenyl ring photoinitiator.

[0027] The photosensitive material further comprises a composition formed by a phenolic resin and an organic solvent, and the organic solvent is selected from PGMEA.

[0028] Another technical solution of the present invention is to apply the photosensitive material in the field of photolithography.

[0029] The performance test and evaluation of the novel polyphenyl ring photoinitiator 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.

[0030] The beneficial effects of the present invention are as follows: 1. The present invention synthesizes a polyphenyl ring hydroxyl system compound and a photoinitiator thereof, and utilizes the multiple benzene ring hydroxyl groups of polyhydroxyphenol to reasonably increase the active sites for grafting with DNQ, thereby greatly enhancing the photosensitivity of the photoinitiator; the synthesized photoinitiator has excellent ultraviolet light irradiation reactivity after being combined with a resin, and a clear pattern can be obtained through a simple photolithography process.

[0031] 2. The synthesis method of the polyphenyl ring hydroxy aromatic system compound and the photoinitiator thereof of the present invention is simple, the process cost and the risk of reaction hazard are low, and it has practical industrial value. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of compound (1-1).

[0033] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of compound (2-1).

[0034] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of compound (3-1).

[0035] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of compound (4-1).

[0036] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of compound (5-1).

[0037] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of compound (6-1).

[0038] Figure 7 This is a graph showing the variation of the light irradiation residual rate of six photoinitiator compounds over time. DETAILED DESCRIPTION

[0039] 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.

[0040] The raw materials used in the examples of the present invention include catechol, pyrogallol, 3-hydroxy-9H-xanthen-9-one, 2-hydroxyanthraquinone, 2,6-dihydroxyanthraquinone, pitavastatin impurity 75, compound (7) and compound (8), wherein the structural formulas of compound (7) and compound (8) are as follows: .

[0041] 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 hours; 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.

[0042] 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 (addition time is about 1 h), keep the temperature between 30-31°C, and after the addition is complete, raise the temperature to 35°C and continue the reaction for 30 minutes; 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.

[0043] Embodiment 1-4: Example 1-4 Prepare compounds (1-1) and (1-2), the structural formulas of which are:

[0044] Preparation of compound (1-1) Select synthesis method 1. The drugs required for the preparation process include: raw materials (3-hydroxy-9H-xanthen-9-one, catechol), solvent (DMF), catalyst (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:

[0045] Example 1-4 tested the catalysts for the synthesis reaction of compound (1-2). This experiment tested four catalysts: β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, and Amberlyst-15 hydrogen-type strong acid resin, and found that all catalysts had good catalytic effects. NMR data such as Figure 1 shown.

[0046] 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:

[0047] Compound (1-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 82.6%.

[0048] Embodiment 5-6: Example 5-6 Prepare compound (2-1) and compound (2-2), the structural formulas are:

[0049] Preparation of compound (2-1) Select synthesis method 1. The drugs required for the preparation process include: raw materials (Pitavalstat impurity 75, catechol), solvent (acetone), catalyst (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid) The reaction conditions of each embodiment are shown in the following table:

[0050] Example 5-6 screened the catalyst for the synthesis of compound (2-1). The results showed that the catalyst trifluoromethanesulfonic acid could promote the reaction, and the yield was above 67%, and more preferably 86%. Figure 2 shown.

[0051] 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:

[0052] Compound (2-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 78.4%.

[0053] Embodiment 7: Example 7 Compound (3-1) and compound (3-2) were prepared, and the structural formula was:

[0054] Preparation of Compound (3-1) Synthesis method 1 was selected. The chemicals required for the preparation process include: raw materials (compound (7) and catechol), solvent (acetone), catalyst (trifluoromethanesulfonic acid), and the reaction conditions are:

[0055] The yield of compound (3-1) reached 92%, and the purity was 99.26% after HPLC test. The results of NMR data are as follows: Figure 3 shown.

[0056] 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:

[0057] Compound (3-2) is a mixture, the solid color is yellow, and the DNQ grafting rate is 77.2%.

[0058] Embodiment 8: Example 8 Compound (4-1) and compound (4-2) were prepared, and the structural formula was:

[0059] Preparation of compound (4-1) Synthesis method 1 was selected. The chemicals required for the preparation process include: raw materials (compound (8) and catechol), solvent (acetone), catalyst (trifluoromethanesulfonic acid), and the reaction conditions are:

[0060] The yield of compound (4-1) reached 89%, and the purity was 99.23% as tested by HPLC. The results of NMR data are as follows: Figure 4 shown.

[0061] 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:

[0062] Compound (4-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 76.8%.

[0063] Embodiment 9-13: Example 9-13 Prepare compound (5-1) and compound (5-2), the structural formulas are:

[0064] Preparation of compound (5-1) Synthesis method 1 was selected. The chemicals required for the preparation process include: raw materials (2-hydroxyanthraquinone, catechol), solvents (acetone, DMF), 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:

[0065] Examples 9-13 screened the solvents and catalysts for the synthesis reaction of compound (5-1). The test process screened two solvents (DMF and acetone) and four catalysts (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, Amberlyst-15 hydrogen-type strong acid resin). The results showed that acetone had a better reaction effect as a solvent, and the reaction yield was relatively high when the catalyst was β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid. The yield can reach more than 70%, more preferably more than 80%, and more preferably more than 90%. NMR data such as Figure 5 shown.

[0066] 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:

[0067] Compound (5-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 78.5%.

[0068] Embodiment 14-15: Example 14-15 Prepare compound (6-1) and compound (6-2), the structural formulas are:

[0069] Preparation of compound (6-1) Select synthesis method 1. The chemicals required for the preparation process include: raw materials (2,6-dihydroxyanthraquinone, catechol), solvent (acetone), catalyst (β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid) The reaction conditions of each embodiment are shown in the following table:

[0070] In Example 14-15, the catalysts used in the synthesis of compound (6-1) were compared. The two catalysts were β-mercaptopropionic acid and sulfuric acid, trifluoromethanesulfonic acid. It was found that both catalysts could achieve good catalytic effects, with a yield of more than 80%. The NMR data are as follows Figure 6 shown.

[0071] Method 2 for the synthesis of compound (6-2) 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:

[0072] Compound (6-2) is a mixture, the solid color is bright yellow, and the DNQ grafting rate is 78.3%.

[0073] Embodiment 16: Example 16 Compound (7-1) and compound (7-2) were prepared, and their structural formulas were:

[0074] Compound (7-1) was prepared by synthetic method 1. The chemicals required for the preparation process included: raw materials (compound (7), pyrogallol), solvent (acetone), and catalyst (trifluoromethanesulfonic acid).

[0075] The reaction conditions of each embodiment are shown in the following table:

[0076] The yield of compound (7-1) reached 75%, and the purity was 99.19% as tested by HPLC.

[0077] Method 2 for the synthesis of compound (7-2) is selected. The drugs required for the preparation process include: raw materials (compound (7-1), DNQ), solvent (1,4-dioxane), catalyst (triethylamine). The dosage of each drug is shown in the following table:

[0078] Compound (7-2) is a mixture, the solid color is yellow, and the DNQ grafting rate is 78.9%.

[0079] Embodiment 17: 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), (6-2), and (7-2) respectively; 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), (6-2), and (7-2) under ultraviolet light, 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.

[0080] observe Figure 7 For 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 (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.

[0081] Embodiment 18: a. Weigh 5.000 g of each of compounds (1-2), (2-2), (3-2), (4-2), (5-2), (6-2), and (7-2) 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), (6-2), and (7-2); 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:

[0082] 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:

[0083] It can be seen that the height difference of these compounds of the present invention is all above 6 μm, among which composition (6-2)>composition (5-2)>composition (1-2) even reaches above 11 μm, showing significant photosensitivity.

[0084] 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 series of compounds with multiple benzene ring hydroxyl systems, characterized in that: The structural formula is , ; 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.

2. The compound with multiple benzene ring hydroxyl system according to claim 1, characterized in that: The polyhydroxyphenol is a phenol having at least two hydroxyl groups. When the polyhydroxyphenol has more than one hydroxyl group, the positions of the hydroxyl groups are not fixed.

3. The compound with multiple benzene ring hydroxyl system according to claim 2, characterized in that: The polyhydroxy phenol is a phenol having two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having three hydroxyl groups, and the positions of the three hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having four hydroxyl groups, and the positions of the four hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having five hydroxy groups.

4. The method for preparing a multi-benzene ring hydroxyl system compound according to claim 2, characterized in that: The steps include: In an organic solvent, the carbonyl group of any one of anthrone, anthrone derivatives, heterocyclic anthrone or heterocyclic anthrone derivatives is activated by a strong acid catalyst, and then reacted with phenol for electrophilic substitution to generate an anthracene compound with multiple phenolic hydroxyl groups, i.e., a polyhydroxy heterocyclic anthracene skeleton compound. 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.

5. A novel polyphenyl ring photoinitiator, characterized in that: The polyphenyl ring hydroxyl system compound according to any one of claims 1 to 3 is subjected to an esterification reaction with a diazonaphthoquinone compound DNQ in a solvent under alkaline conditions to generate a diazonaphthoquinone type photoinitiator, which is a novel polyphenyl ring photoinitiator. The structural formula of the novel polyphenyl ring photoinitiator is: , R1 is one of the elements N, O, S, and P, then R7 selectively contains H according to R1; Among them, R2 and R3 are , R6 is selected from H, OH and ,and, The grafting rate is 75.0-85.0%; R4, R5 are hydrogen, -OH, or , the positions of R4 and R5 are not fixed, wherein, The grafting rate is 75.0-85.0%.

6. The novel polyphenyl ring photoinitiator according to claim 5, characterized in that: ; R2, R3 are , wherein R6 is selected from H, OH and ,in, The grafting rate is 75.0-85.0%; R4, R5 are hydrogen, -OH, or , the positions of R4 and R5 are not fixed, wherein, The grafting rate is 75.0-85.0%.

7. The novel polyphenyl ring photoinitiator according to claim 5, characterized in that: The structural formula of the novel polyphenyl ring photoinitiator includes any one of the following: , R6 is selected from .

8. A method for preparing a polyphenyl ring photoinitiator, characterized in that: The steps include: (1) In an organic solvent, a carbonyl group of anthrone, anthrone derivative, heterocyclic anthrone or any one of heterocyclic anthrone derivatives is activated by a strong acid catalyst, and then subjected to an electrophilic substitution reaction with a polyhydroxy phenol to generate an anthracene compound with multiple phenolic hydroxyl groups, i.e., a polyhydroxy heterocyclic anthracene skeleton compound; (2) Under alkaline conditions, a polyhydroxy heterocyclic anthracene skeleton compound undergoes an esterification reaction with a diazonaphthoquinone compound DNQ in a solvent to generate a diazonaphthoquinone type photoinitiator, namely a polyphenyl ring photoinitiator.

9. The method for preparing a polyphenyl ring photoinitiator according to claim 8, characterized in that: The structural formula of anthrone, anthrone derivative, heterocyclic anthrone or heterocyclic anthrone derivative includes , ; 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.

10. The method for preparing a polyphenyl ring photoinitiator according to claim 8, characterized in that: The polyhydroxyphenol is a phenol having at least two hydroxyl groups. When the polyhydroxyphenol has more than one hydroxyl group, the positions of the hydroxyl groups are not fixed.

11. The multi-benzene ring hydroxyl system compound according to claim 10, characterized in that: The polyhydroxy phenol is a phenol having two hydroxyl groups, and the positions of the two hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having three hydroxyl groups, and the positions of the three hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having four hydroxyl groups, and the positions of the four hydroxyl groups are not fixed; The polyhydroxy phenol is a phenol having five hydroxy groups.

12. The method for preparing a polyphenyl ring photoinitiator according to claim 8, 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.

13. The method for preparing a polyphenyl ring photoinitiator according to claim 8, characterized in that: During the esterification reaction, 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°C, and the reaction time is 5-30min.

14. The method for preparing a polyphenyl ring photoinitiator according to claim 8, 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.

15. The method for synthesizing a polyphenyl ring photoinitiator according to claim 8, characterized in that: During the esterification reaction in step (2), the diazonaphthoquinone compound realizes an esterification reaction of the hydroxyl groups of each compound in the compounds of the multiple phenolic hydroxyl systems, and the esterification reaction includes one or more of monoesterification, diesterification, triesterification, tetraesterification, pentaesterification, hexaesterification, heptaesterification, octaesterification, nonaesterification, and decaesterification products.

16. A G / I line photoinitiator, characterized in that: The invention comprises the polyphenyl ring photoinitiator as described in any one of claims 5 to 7.

17. A photosensitive composite film material, characterized in that: The invention comprises the polyphenyl ring photoinitiator as described in any one of claims 5 to 7.

18. The photosensitive composite thin film material according to claim 17, 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.

19. Use of the photosensitive material according to claim 18 or 19 in the field of photolithography.

Images