CN117142988A

CN117142988A - Preparation method and application of diazonaphthoquinone sulfonate monoester compound

Info

Publication number: CN117142988A
Application number: CN202311079641.6A
Authority: CN
Inventors: 邹敏; 宋凤革; 穆亮; 陈静; 曹正; 王进
Original assignee: Shanghai Mituo Material Technology Co ltd; Anhui Mituo Material Technology Co ltd
Current assignee: Shanghai Mituo Material Technology Co ltd; Anhui Mituo Material Technology Co ltd
Priority date: 2023-08-25
Filing date: 2023-08-25
Publication date: 2023-12-01
Anticipated expiration: 2043-08-25
Also published as: CN117142988B

Abstract

The application discloses a preparation method and application of a diazonaphthoquinone sulfonic monoester compound, which belong to the technical field of organic optical function information recording materials, and comprise the steps of carrying out esterification reaction on 4-cinnamyl phenol (II) and a naphthoquinone diazide sulfonic acid derivative (M-1 and/or N-1) and obtaining the diazonaphthoquinone sulfonic monoester compound (I) through post-treatment. The post-treatment process adopts a simple and easy-to-operate method, and active carbon and a dimethylformamide catalyst are added, so that the diazonaphthoquinone sulfonate monoester compound (I) is light yellow in color, has no raw material residue, and has high product purity and metal ion content of less than 50ppb; the positive photosensitive resin composition obtained from the diazonaphthoquinone sulfonic monoester compound (I) has good quality stability and chloride ion content of less than 10ppm.

Description

Preparation method and application of diazonaphthoquinone sulfonate monoester compound

Technical Field

The application belongs to the technical field of organic light functional information recording materials, and particularly relates to a preparation method and application of a diazonaphthoquinone sulfonate monoester compound.

Background

The diazonaphthoquinone sulfonic acid monoester compound can be prepared by condensing naphthoquinone diazide sulfonyl chloride and phenol derivatives in a proper solvent, and the obtained compound has good solubility and stability and is suitable for preparing various photoresist applications such as thick film photoresist for semiconductor manufacturing. In addition, the compound can be used for a multi-layer photosensitive material on a metal support or a plastic film, and has excellent storage performance. Therefore, the compound has good application prospect in the fields of flat panel display (such as liquid crystal display, OLED display), semiconductor manufacturing process and the like.

The synthesis of this compound has been reported so far, but we have found that there are a series of problems in the synthesis process. For example, in US patent No. 3640992, the diazonaphthoquinone sulfonic acid monoester compound is obtained by a condensation reaction of 2-diazonium-1-naphthol-4-sulfonyl chloride and cumylphenol in a dioxane solvent, using sodium hydroxide as an acid-binding agent. However, the use of sodium hydroxide can cause serious reaction heat release, the temperature is not easy to control, the metal ion content is easy to exceed the standard, and the product with the metal ion content below 50ppb is not easy to obtain; in addition, naphthoquinone diazide sulfonyl chloride which is one of the raw materials also has residues, is unstable when meeting water, can be decomposed into sulfonic acid and hydrochloric acid, and can influence the quality stability of photoresist in the subsequent use process, such as the problems of increased viscosity, excessive chloride ion content and the like. In patent WO2022154020A1, 2-diazonium-1-naphthol-4-sulfonyl chloride and cumylphenol undergo condensation reaction in an acetone solvent, and although the method can effectively control metal ion pollution, the color of a reaction solution is easy to blacken, the synthesized diazonium naphthoquinone sulfonic acid monoester compound is blackish red, the color is not satisfactory, the naphthoquinone diazide sulfonyl chloride is remained, and the quality stability of photoresist is still affected. Those skilled in the art are urgent to develop a preparation method and application of diazonaphthoquinone sulfonate monoester compound to meet the existing application market and performance requirements.

Disclosure of Invention

In view of the above-mentioned shortcomings of the prior art, the present application aims to provide a preparation method of diazonaphthoquinone sulfonic acid monoester compound, which can effectively solve the problems of raw material residue, metal ion and chloride ion exceeding standard, and the obtained diazonaphthoquinone sulfonic acid monoester compound has no raw material residue, light yellow solid in color, metal ion content lower than 50ppb, chloride ion content lower than 10ppm and viscosity change rate lower than 10% when applied to a positive photosensitive resin composition.

To achieve the above and other related objects, a first aspect of the present application provides a method for preparing a diazonaphthoquinone sulfonic monoester compound, comprising: esterification reaction is carried out on 4-cinnamyl phenol (II) and a sulfonic acid derivative (M-1 and/or N-1) of naphthoquinone diazide, and diazonaphthoquinone sulfonic acid monoester compound (I) is obtained through post-treatment;

the process route is as follows:

wherein R is selected from M or N;

the chemical structure of M is as follows:

；

the chemical structure of N is as follows:

；

the chemical structure of M-1 is as follows:

；

the chemical structure of the N-1 is as follows:

；

wherein X and Y are independently selected from Cl, br or I.

Further, it is preferable that the sulfonic acid derivative of naphthoquinone diazide is 1, 2-naphthoquinone diazide-4-sulfonyl chloride (NAC-4) or 1, 2-naphthoquinone diazide-5-sulfonyl chloride (NAC-5), and the above esterifying agents may be used alone or in combination.

In a possible embodiment, the diazonaphthoquinone sulfonic acid monoester compound can be obtained by reacting 1.0 equivalent of 4-cinnamoyl phenol (II) with 1.0 equivalent of a sulfonic acid derivative of naphthoquinone diazide at 20 to 50 ℃ for 1 to 4 hours, i.e., the molar ratio of the 4-cinnamoyl phenol (II) to the sulfonic acid derivative of naphthoquinone diazide is 1.0:1.0. Alternatively, the reaction temperature may be 20 to 30 ℃,30 to 40 ℃, or 40 to 50 ℃. And further alternatively, the reaction time is 1-2 h, 2-3 h or 3-4 h.

In a possible embodiment, the esterification reaction is performed under the condition of a solvent, specifically, the solubility and the reactivity of the reactants are determined, and at least one of 1, 4-dioxane, tetrahydrofuran, diethyl ether, gamma-butyrolactone, N-methylpyrrolidone, acetone or methyl ethyl ketone is preferably selected, and the addition amount of the solvent is provided that the reaction is not affected and the solvent is environment-friendly, so long as the raw materials can be dissolved.

In a possible embodiment, the esterification reaction is carried out in the presence of a dehydrohalogenating agent; preferably, the dehydrohalogenating agent is selected from inorganic bases, organic bases, or a combination of organic and inorganic bases; still preferably, the dehydrohalogenating agent is selected from at least one of sodium carbonate, sodium bicarbonate, ethylamine, ethanolamine, diethylamine, diethanolamine, triethylamine, triethanolamine, N-dimethylaniline or pyridine. In particular, the dehydrohalogenating agent generally comprises a basic compound capable of forming a salt with HCl. Of course, the dehydrohalogenating agent may be used alone, or in combination of two or more kinds, or may be added in portions. The dehydrohalogenating agent is added in an amount of 1.0 to 3.0 equivalents, more preferably 1.1 to 1.5 equivalents, per equivalent of sulfonic acid derivative of naphthoquinone diazide, i.e. the molar ratio of sulfonic acid derivative of naphthoquinone diazide to dehydrohalogenating agent is 1.0:1.0 to 3.0, preferably 1.0:1.1 to 1.5.

In a possible embodiment, the post-processing comprises the steps of:

1) Adding hydrochloric acid into the reaction system for quenching reaction, and adjusting the pH value to be 3.0-5.0, wherein the color of the reaction solution is black;

2) After the solvent is removed under reduced pressure, adding dichloromethane to dissolve the sample, and then adding active carbon to decolorize;

3) Filtering the reaction solution to obtain filtrate;

4) Adding a catalyst and ultrapure water into the filtrate, heating to 50 ℃, and preserving heat for 2 hours;

5) And then washing with water, decompressing and desolventizing, and drying to obtain a pale yellow powder product, namely the diazonaphthoquinone sulfonate monoester compound (I).

Specifically, the addition amount of the dichloromethane is not limited, and the dichloromethane can be used only by dissolving and cleaning the sample;

the addition amount of the activated carbon is 2-10%, preferably 3-6% of the theoretical yield of the diazonaphthoquinone sulfonic acid monoester compound;

the catalyst can accelerate the decomposition rate of residual raw material naphthoquinone diazide sulfonic acid derivatives in water, thereby improving the reaction efficiency. Specifically, the catalyst is at least one of N, N-dimethylformamide and N, N-dimethylacetamide, and the addition amount of the catalyst is 1.0 to 5.0 times, preferably 1.0 to 3.0 times, the residual molar amount of NAC. The mass ratio of the catalyst to the ultrapure water is 1.0:10.0-100.0, preferably 1.0:20.0-80.

The purity of the fully esterified diazonaphthoquinone sulfonate monoester compound provided by the application can reach more than 99.5%, no raw material residue exists, the content of metal ions is lower than 50ppb, and the fully esterified diazonaphthoquinone sulfonate monoester compound is light yellow solid powder. The method can be applied to positive photoresist or photoresist, particularly various photoresist applications such as thick film photoresist for semiconductor manufacturing, and multi-layer photosensitive materials on metal supports or plastic films, and has good application prospects in the fields of flat panel displays (such as liquid crystal displays, OLED displays), semiconductor manufacturing processes and the like.

The second aspect of the present application provides a positive photosensitive resin composition obtained by:

dissolving alkali-soluble resin and the diazonaphthoquinone sulfonic monoester compound in an active diluent, stirring and dissolving at a certain temperature, and filtering the solution by a filter with the pore diameter of 0.2 mu m to obtain the positive photosensitive resin composition. The dissolution temperature is not particularly limited and may be 0 to 40 ℃, and the filtration apparatus is a conventional filter.

Specifically, the alkali-soluble resin is exemplified by phenolic resin. The mass ratio of the alkali-soluble resin to the diazonaphthoquinone sulfonic monoester compound is 100:1-50. The reactive diluent is Propylene Glycol Monomethyl Ether Acetate (PGMEA). The amount of the reactive diluent to be used is usually in the range of 70 to 1900 parts by mass relative to 100 parts by mass of the alkali-soluble resin.

The preparation method and the application of the diazonaphthoquinone sulfonic monoester compound have the main beneficial effects that: 1) The product has no raw material residue, high purity, metal ion content lower than 50ppb and light yellow powder color, and meets the technical index requirements of the application of the semiconductor photoresist material; 2) The post-treatment method of the diazonaphthoquinone sulfonate monoester compound is simple and easy to operate, safe and environment-friendly; 3) The positive photosensitive resin composition containing the diazonaphthoquinone sulfonic monoester compound has good room temperature storage stability, and the chloride ion content is less than 10ppm.

Detailed Description

Other advantages and effects of the present application will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present application with reference to specific examples. The application may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present application.

Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present application may be used to practice the present application according to the knowledge of one skilled in the art and the description of the present application.

Example 1

Into a 1L four-necked flask, 40.00g of 4-cinnamylphenol, 49.61g of 2-diazonium-1-naphthol-4-sulfonyl chloride (NAC-4 for short) and 638.98g of acetone were charged, and the mixture was refluxed by opening a condenser, followed by stirring and clearing at 40 ℃. To this was added dropwise 20.56g of Triethylamine (TEA) at a constant rate over 30 minutes. After the completion of the dropwise addition, the mixture was stirred at 40℃for another 30 minutes, then 4.01g of 37wt% aqueous hydrochloric acid solution was added to the reaction mixture to adjust the pH, and then the reaction mixture was cooled at room temperature. The residual amount of NAC-4 in the reaction solution at this time was 5.2% as measured by high performance liquid chromatography.

The post-treatment comprises the following steps: 1) Adding hydrochloric acid into the reaction system to quench reaction, wherein the color of the reaction solution is black; 2) After the solvent is removed under reduced pressure, adding dichloromethane to dissolve the sample, and then adding active carbon to decolorize; 3) Filtering the reaction solution to obtain filtrate; 4) Adding a catalyst N, N-dimethylformamide and ultrapure water into the filtrate, heating to 50 ℃, and preserving heat for 2 hours; 5) And then washing with water, decompressing and desolventizing, and drying to obtain a pale yellow powder product, namely the diazonaphthoquinone sulfonate monoester compound. Wherein the addition amount of the activated carbon is 2% of the theoretical yield of the diazonaphthoquinone sulfonic acid monoester compound; the catalyst was added in an amount 1.0 times the residual molar amount of NAC. The mass ratio of the N, N-dimethylformamide catalyst to the ultrapure water was 1.0:20.

The results of the tests for metal ion content in the product, product purity, NAC residual amount, and apparent color are shown in table 1.

Example 2

In comparison with example 1, the procedure was exactly the same as in example 1 except that the starting material 2-diazonium-1-naphthol-4-sulfonyl chloride (abbreviated as NAC-4) was changed to 2-diazonium-1-naphthol-5-sulfonyl chloride (abbreviated as NAC-5).

Example 3

In comparison with example 1, the procedure was exactly as in example 1 except that the starting material 2-diazonium-1-naphthol-4-sulfonyl chloride (abbreviated as NAC-4) was replaced by a mixture of 2-diazonium-1-naphthol-4-sulfonyl chloride (abbreviated as NAC-4) and 2-diazonium-1-naphthol-5-sulfonyl chloride (abbreviated as NAC-5) in a molar ratio of 1:1.

Example 4

In comparison with example 1, the procedure was exactly the same as in example 1 except that the acetone solvent was changed to 1, 4-dioxane.

Example 5

The temperature of the esterification reaction was 50 ℃ compared to example 1; the esterification reaction time is 1h, and the post-treatment comprises the following steps: 1) Adding hydrochloric acid into the reaction system to quench reaction, and adjusting the pH value to 5.0, wherein the color of the reaction solution is black; 2) After the solvent is removed under reduced pressure, adding dichloromethane to dissolve the sample, and then adding active carbon to decolorize; 3) Filtering the reaction solution to obtain filtrate; 4) Adding a catalyst N, N-dimethylformamide and ultrapure water into the filtrate, heating to 50 ℃, and preserving heat for 2 hours; 5) And then washing with water, decompressing and desolventizing, and drying to obtain a pale yellow powder product, namely the diazonaphthoquinone sulfonate monoester compound. Wherein the addition amount of the activated carbon is 10% of the theoretical yield of the diazonaphthoquinone sulfonic acid monoester compound; the catalyst was added in an amount 5.0 times the residual molar amount of NAC, the mass ratio of N, N-dimethylformamide catalyst to ultrapure water was 1.0:100, and the rest of the procedure was exactly the same as in example 1.

Example 6

The temperature of the esterification reaction was 20 ℃ compared to example 1; the esterification reaction time is 4h, and the post-treatment comprises the following steps: 1) Adding hydrochloric acid into the reaction system to quench reaction, and adjusting the pH value to 4.0, wherein the color of the reaction solution is black; 2) After the solvent is removed under reduced pressure, adding dichloromethane to dissolve the sample, and then adding active carbon to decolorize; 3) Filtering the reaction solution to obtain filtrate; 4) Adding a catalyst N, N-dimethylformamide and ultrapure water into the filtrate, heating to 50 ℃, and preserving heat for 2 hours; 5) And then washing with water, decompressing and desolventizing, and drying to obtain a pale yellow powder product, namely the diazonaphthoquinone sulfonate monoester compound. Wherein the addition amount of the activated carbon is 6% of the theoretical yield of the diazonaphthoquinone sulfonic acid monoester compound; the catalyst was added in an amount 3.0 times the residual molar amount of NAC, the mass ratio of N, N-dimethylformamide catalyst to ultrapure water was 1.0:10, and the rest of the procedure was exactly the same as in example 1.

Comparative example 1

The procedure was exactly the same as in example 1, except that no activated carbon was added as in example 1.

Comparative example 2

In comparison with example 1, the procedure was exactly the same as in example 1, except that N, N-dimethylformamide was not added.

Comparative example 3

The procedure was exactly as in example 1, except that the triethylamine was replaced with sodium hydroxide and no N, N-dimethylformamide was added thereto, as in example 1.

TABLE 1 Performance index of diazonaphthoquinone sulfonate monoester compound

Note that: ND indicates undetected.

Application example 1

The compound prepared in example 1 and a phenolic resin were dissolved in 200 parts by mass of propylene glycol methyl ether acetate at 30 ℃, the compound prepared in example 1, the phenolic resin and the propylene glycol methyl ether acetate were mixed and dissolved in a mass ratio of 3:10:100, and then filtered through a 0.2 μm filter to prepare a positive photosensitive resin composition.

The positive photosensitive resin composition obtained was left at room temperature for 3 days as a sample immediately after adjustment, and then, left at room temperature for 4 weeks as a sample after 4 weeks, and then, the viscosity index and the chloride ion content of the sample were measured. The test results are shown in Table 2.

Application example 2

The compound prepared in comparative example 2 and a phenolic resin were dissolved in 200 parts by mass of propylene glycol methyl ether acetate at 30℃and the compound prepared in example 1, the phenolic resin and propylene glycol methyl ether acetate were mixed in a mass ratio of 3:10:100, and the mixture was stirred and dissolved, and then filtered through a 0.2 μm filter to prepare a positive photosensitive resin composition. The viscosity index and the chloride ion content of the sample were measured in the same manner as in application example 1, and the test results are shown in Table 2.

Application example 3

The compound prepared in example 1 and a phenolic resin were dissolved in 200 parts by mass of propylene glycol methyl ether acetate at 30 ℃, the compound prepared in example 1, the phenolic resin and the propylene glycol methyl ether acetate were mixed and dissolved in a mass ratio of 1:100:1000, and then filtered through a 0.2 μm filter to prepare a positive photosensitive resin composition. The viscosity index and the chloride ion content of the sample were measured in the same manner as in application example 1, and the test results are shown in Table 2.

Application example 4

The compound prepared in example 1 and a phenolic resin were dissolved in 200 parts by mass of propylene glycol methyl ether acetate at 30 ℃, the compound prepared in example 1, the phenolic resin and the propylene glycol methyl ether acetate were mixed and dissolved in a mass ratio of 5:10:100, and then filtered through a 0.2 μm filter to prepare a positive photosensitive resin composition. The viscosity index and the chloride ion content of the sample were measured in the same manner as in application example 1, and the test results are shown in Table 2.

TABLE 2 Performance index of Positive photosensitive resin composition after 4 weeks at room temperature

The rate of change of the 4-week viscosity at room temperature was determined by the following formula:

[ (viscosity of sample after 4 weeks) - (viscosity of sample immediately after adjustment) ]/(viscosity of sample immediately after adjustment) ×100%.

Claims

1. A preparation method of diazonaphthoquinone sulfonate monoester compound is characterized in that the preparation synthetic route is as follows:

；

the method specifically comprises the following steps: A. esterification reaction: esterification of 4-cinnamylphenol (II) with sulfonic acid derivatives of naphthoquinone diazide (M-1 and/or N-1) in a solvent; B. the post-treatment process is as follows: 1) Adding hydrochloric acid into the reaction system for quenching reaction, and adjusting the pH value to be 3.0-5.0, wherein the color of the reaction solution is black; 2) After the solvent is removed under reduced pressure, adding dichloromethane to dissolve the sample, and then adding active carbon to decolorize; 3) Filtering the reaction solution to obtain filtrate; 4) Adding a catalyst and ultrapure water into the filtrate, heating to 50 ℃, and preserving heat for 2 hours; 5) And washing with water, decompressing to remove the organic solvent, and drying to obtain a pale yellow powder product, namely the diazonaphthoquinone sulfonate monoester compound (I).

2. The method for producing a diazonaphthoquinone sulfonic acid monoester compound according to claim 1, wherein the sulfonic acid derivative of naphthoquinone diazide is one or two of 1, 2-naphthoquinone diazide-4-sulfonyl chloride and 1, 2-naphthoquinone diazide-5-sulfonyl chloride.

3. The method for producing a diazonaphthoquinone sulfonic acid monoester compound according to claim 1, wherein the molar ratio of 4-cinnamoyl phenol (II) to the sulfonic acid derivative of naphthoquinone diazide is 1.0:1.0.

4. The method for producing a diazonaphthoquinone sulfonic acid monoester compound according to claim 1, wherein the solvent is at least one selected from the group consisting of 1, 4-dioxane and acetone.

5. The method for producing a diazonaphthoquinone sulfonic acid monoester compound according to claim 1, wherein the esterification reaction is performed in the presence of a dehydrohalogenating agent; the dehydrohalogenation reagent is triethylamine, and the esterification reaction temperature is 20-50 ℃; the esterification reaction time is 1-4 h.

6. The method for preparing a diazonaphthoquinone sulfonic acid monoester compound according to claim 1, wherein the addition amount of the activated carbon is 2% -10% of the theoretical yield of the diazonaphthoquinone sulfonic acid monoester compound.

7. The method for producing a diazonaphthoquinone sulfonic acid monoester compound according to claim 1, wherein the catalyst is N, N-dimethylformamide; the addition amount of the catalyst is 1.0-5.0 times of the residual molar amount of the sulfonic acid derivative of the naphthoquinone diazide, and the mass ratio of the catalyst to the ultrapure water is 1.0:10-100.

8. A positive photosensitive resin composition comprising an alkali-soluble resin and the diazonaphthoquinone sulfonic monoester compound according to claim 1.

9. The positive photosensitive resin composition of claim 8, wherein the alkali-soluble resin is a phenolic resin; the positive photosensitive resin composition further comprises a solvent, wherein the solvent is propylene glycol monomethyl ether acetate; the mass ratio of the alkali-soluble resin to the diazonaphthoquinone sulfonic monoester compound is 100:1-50.

10. Use of the diazonaphthoquinone sulfonic monoester compound prepared by the preparation method according to claims 1 to 7 or the photosensitive resin composition according to claims 8 to 9 in positive photoresist.