Alkali-soluble polyimide precursor, preparation method thereof and positive photosensitive resin composition

Abstract

The invention relates to the technical field of high polymer materials, in particular to an alkali-soluble polyimide precursor, a preparation method thereof and a positive photosensitive resin composition. The alkali-soluble polyimide precursor includes a polyesteramide resin formed by a silanization reaction of a polyamic acid resin and a silanization reagent, and the polyamic acid resin is formed by a polycondensation reaction of an acid dianhydride compound and a diamine compound, the diamine compound comprises a siloxane-containing diamine and an aromatic diamine. The alkali-soluble polyimide precursor has a low dielectric constant. Meanwhile, after the alkali-soluble polyimide precursor is applied to the positive photosensitive resin composition, the photosensitivity is relatively good, the removal rate of a film layer after exposure and development is relatively high, and the visible light transmittance of the cured film layer is relatively high.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to an alkali-soluble polyimide precursor and a preparation method thereof, and a positive photosensitive resin composition. Background Art

[0002] With the rapid development of science and technology, various electronic products and intelligent devices (such as smart phones, tablets, ultra-thin TVs, etc.) have emerged, and they are constantly developing in the direction of smarter content, more reliable use, and thinner appearance. To achieve these requirements, it is necessary to layout more electronic circuits on the product chip and design integrated circuits with ultra-large scale. As microelectronic devices become smaller and smaller, the density of wiring on the chip is getting higher and higher, and the signal delay caused by capacitive coupling and cross interference between closely connected wires has increased significantly, which requires low dielectric materials to meet the insulation packaging of the microelectronics industry. In addition, dielectric films and etching barrier layers in the microelectronics industry also require low dielectric materials. In other fields, such as gas separation membranes, wires, cables, etc., low dielectric materials are also needed to meet their use needs.

[0003] Polyimide materials can be used in the above fields and have the following advantages: high heat resistance, high mechanical strength, low water absorption, good adhesion to the substrate, and chemical corrosion resistance. However, the dielectric constants of most commercial polyimide materials can no longer meet the requirements, so the development of materials with lower dielectric constants is a research hotspot in the current field of materials science. Summary of the invention

[0004] Based on this, the first aspect of the present application provides an alkali-soluble polyimide precursor, and its technical solution is as follows:

[0005] An alkali-soluble polyimide precursor comprises a polyamide ester resin, wherein the polyamide ester resin is formed by a silylation reaction between a polyamic acid resin and a silanization agent, wherein the polyamic acid resin is formed by a condensation reaction between an acid dianhydride compound and a diamine compound, wherein the diamine compound comprises a siloxane-containing diamine and an aromatic diamine.

[0006] Compared with the traditional solution, this application has the following beneficial effects:

[0007] The present application uses a diamine compound including a siloxane-containing diamine and an aromatic diamine to undergo a polycondensation reaction with an acid dianhydride compound, and introduces a siloxane segment on the main chain. At the same time, a silanization reaction of a polyamic acid generated by the polycondensation reaction and a silanization agent is performed, and the reaction of the silanization agent with a carboxyl group controls the content of the carboxyl group on the one hand, and further introduces siloxane on the other hand. Through the coordination of the above-mentioned means, the alkali-soluble polyimide precursor has a lower dielectric constant, can be used as a dielectric film, an etching barrier layer or a packaging material in the microelectronics industry, and can also be used as an insulating material in the fields of gas separation membranes, wires, cables, etc. At the same time, when the above-mentioned alkali-soluble polyimide precursor is used for a positive photosensitive resin composition, it is sensitive to ultraviolet light, X-rays, electron beams or ion beams, has good photosensitivity, has a high film removal rate after exposure and development, and has a high visible light transmittance of the cured film layer.

[0008] The polyamic acid resin is formed by polycondensation of an acid dianhydride compound and a diamine compound. The acid dianhydride compound may directly react with the diamine compound, or the acid dianhydride compound may first react with an alcohol to obtain a diester, and then react in the presence of an amine and a condensing agent. Alternatively, the acid dianhydride compound may first react with an alcohol to obtain a diester, and then the residual dicarboxylic acid may be chlorinated and then reacted with an amine.

[0009] In some embodiments, the method for preparing the polyamic acid resin comprises the following steps:

[0010] A solution containing a diamine compound is added to a solution containing an acid dianhydride compound to cause a polycondensation reaction, thereby obtaining a polyamic acid resin.

[0011] The solvent of the solution containing the acid dianhydride compound may be N-methylpyrrolidone (NMP), and the solvent of the solution containing the diamine compound may be N-methylpyrrolidone (NMP).

[0012] Optionally, the temperature at which the polycondensation reaction occurs is 15°C to 60°C. Optionally, the reaction procedure of the polycondensation reaction includes: reacting at 15°C to 25°C for 0.5h to 1.5h, then reacting at 40°C to 60°C for 1h to 3h, adding a solution containing a capping agent, and reacting at 40°C to 60°C for 1h to 3h. Optionally, the capping agent includes 4-aminophenol. Optionally, the solvent of the solution containing the capping agent can be N-methylpyrrolidone (NMP).

[0013] Optionally, the molar ratio of the acid dianhydride compound to the diamine compound is 1:(0.5-1.5). For example, the molar ratio is 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5.

[0014] The diamine compound includes a siloxane-containing diamine and an aromatic diamine. Optionally, the molar proportion of the siloxane-containing diamine in the diamine compound is 5%-60%. For example, the molar proportion is 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%.

[0015] Optionally, the siloxane-containing diamine includes one or more of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, 1,3-bis(p-aminophenyl)tetramethyldisiloxane, 1,3-bis(m-aminophenyl)tetramethyldisiloxane, 1,5-bis(p-aminophenyl)hexamethyltrisiloxane, 1,5-bis(m-aminophenyl)hexamethyltrisiloxane, bis(p-aminophenyl)dimethylsiloxane and bis(m-aminophenyl)dimethylsiloxane.

[0016] Optionally, the aromatic diamine includes 2,2'-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, wherein the hydrogen atoms in the aromatic ring are substituted or unsubstituted. , 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl and 9,9-bis(4-aminophenyl)fluorene. The substituent is a C1-C3 alkyl or a halogen.

[0017] Optionally, the acid dianhydride compound includes a tetracarboxylic dianhydride compound. Optionally, the tetracarboxylic dianhydride compound includes one or more of an aromatic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride. Optionally, the aromatic tetracarboxylic dianhydride includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis( 2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride. Optionally, the aliphatic tetracarboxylic dianhydride includes one or more of butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride.

[0018] Optionally, the acid dianhydride compound includes a siloxane-containing tetracarboxylic dianhydride, and the siloxane-containing tetracarboxylic dianhydride has one of the structures shown below:

[0019] .

[0020] Optionally, the molar proportion of the siloxane-containing tetracarboxylic dianhydride in the acid dianhydride compound is 0% to 100%, for example, the molar proportion is 0%, 50%, 80%, or 100%.

[0021] Wherein, polyamide ester resin is formed by silanization reaction of polyamic acid resin and silanization agent.Through silanization reaction, the silicon content and carboxyl content of polyamic acid resin can be regulated, and then the dielectric constant, alkali dissolution rate and photosensitivity of alkali-soluble polyimide precursor can be regulated.In addition, the introduction of silanization agent will not cause large fluctuations in the molecular weight of polyamic acid, and will not have a great impact on the performance of cured film.In addition, due to the relatively expensive price of siloxane-containing diamine and siloxane-containing tetracarboxylic dianhydride, it can also have a high cost performance by silanization reaction with silanization agent.Finally, silanization agent has good compatibility as a protecting group of carboxylic acid, and can be well compatible with methyl ester, ethyl ester, benzyl ester, allyl alcohol ester, etc., and the reaction conditions are mild.

[0022] The silanization reaction between the polyamide acid resin and the silanization agent can be achieved through the Mitsunobu reaction. The silanization reaction can also occur directly in the presence of an alkali agent, for example, in the presence of imidazole (weakly alkaline). In some embodiments, the preparation method of the polyamide ester resin includes the following steps:

[0023] An alkali agent and a solution containing a silanization agent are added to a reaction system containing a polyamic acid resin to cause a silanization reaction to obtain a polyamide ester resin.

[0024] The solvent of the solution containing the silanization agent may be N-methylpyrrolidone (NMP). The alkali agent may be imidazole. Optionally, the ratio of the mole number of the alkali agent to the total mole number of the acid dianhydride compound and the diamine compound is (2-4):1. For example, the ratio is 2:1, 3:1, 4:1.

[0025] Optionally, the temperature for the silanization reaction is 40° C. to 60° C. Optionally, the time for the silanization reaction is 2 h to 4 h.

[0026] Optionally, the ratio of the mole number of the silanization agent to the total mole number of the acid dianhydride compound and the diamine compound is (1-2): 1. For example, the ratio is 1:1, 1.2:1, 1.5:1, 2:1.

[0027] Optionally, the silanization agent includes one or more of 2-(trimethylsilyl)ethanol, trimethylsilyl chloride (TMSCl), triethylsilyl chloride (TBSCl), tert-butyldimethylsilyl chloride (TBSCl) and bis(trimethylsilyl)acetamide (BSA).

[0028] The introduction of the above-mentioned siloxane chain segments, in addition to reducing the dielectric constant of the resin, has good photosensitivity, high developer film removal rate and visible light transmittance, can also improve the processability of the resin, increase its adhesion to metal, silicon, ITO, and glass, and reduce internal stress. The resin has low water absorption, high atomic oxygen resistance, good solubility and gas permeability, and strong environmental durability.

[0029] The second aspect of the present application provides a method for preparing an alkali-soluble polyimide precursor, and its technical solution is:

[0030] A method for preparing an alkali-soluble polyimide precursor comprises the following steps:

[0031] Allowing an acid dianhydride compound and a diamine compound to undergo a polycondensation reaction to generate a polyamic acid resin, wherein the diamine compound comprises a siloxane-containing diamine and an aromatic diamine;

[0032] The polyamic acid resin is subjected to a silanization reaction with a silanization agent to generate a polyamide ester resin.

[0033] The specific steps of the above preparation method can be found above and will not be repeated here.

[0034] The third aspect of the present application provides a positive photosensitive resin composition, and its technical solution is as follows:

[0035] A positive photosensitive resin composition comprises the above-mentioned alkali-soluble polyimide precursor and a photosensitive compound.

[0036] Optionally, the mass percentage of the alkali-soluble polyimide precursor in the positive photosensitive resin composition is 5% to 20%, preferably 8% to 18%, preferably 10% to 15%, preferably 12% to 13%.

[0037] Optionally, the photosensitive compound is formed by bonding a compound having a naphthoquinone diazide group to a compound having a multifunctional group with an ester bond or a sulfonyl bond. From the perspective of alkali solubility and economy, the naphthoquinone diazide group includes a naphthoquinone diazide sulfonate group or a quinone diazide sulfonyl group. Optionally, the compound having a naphthoquinone diazide group includes naphthoquinone diazide-5-sulfonyl chloride. The compound having a multifunctional group includes a compound having a polyhydroxyl group or a compound having a polyamine group. Optionally, the compound having a polyhydroxyl group includes a compound having a phenolic hydroxyl group. Optionally, the phenolic hydroxyl compound includes Α,Α,Α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene. Wherein, Α,Α,Α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene can be commercially available, for example, TrisP-PA.

[0038] Optionally, the method for preparing the photosensitive compound comprises the following steps:

[0039] In the presence of triethylamine and a solvent, a compound having a naphthoquinone diazide group and a compound having a multifunctional group are mixed and stirred for reaction to obtain the photosensitive compound.

[0040] The solvent may be 1,4-dioxane.

[0041] Optionally, the temperature of the environment in which the compound having a naphthoquinone diazide group and the compound having a multifunctional group are mixed does not exceed 35° C. For example, the temperature is 35° C., 30° C., 20° C., 10° C. The temperature of the stirring reaction does not exceed 35° C. For example, the temperature is 35° C., 30° C., 20° C., 10° C. The stirring reaction time is 1 h to 3 h.

[0042] Optionally, the molar ratio of the compound having a naphthoquinone diazide group to the compound having a multifunctional group is (1-3): 1. For example, the molar ratio is 1:1, 2:1, 3:1.

[0043] Optionally, the mass percentage of the photosensitive compound in the positive photosensitive resin composition is 2% to 12%, preferably 2% to 8%, preferably 4% to 6%.

[0044] Optionally, the positive photosensitive resin composition further comprises an auxiliary agent and an organic solvent.

[0045] The positive photosensitive resin composition contains an organic solvent, which can be in the state of varnish, and can improve the coating property of the composition. Optionally, the organic solvent includes one or more of γ-butyrolactone, acetone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, ethyl acetate, ethyl lactate, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and diethylene glycol methyl ethyl ether. For example, it can be a mixed solvent of γ-butyrolactone and propylene glycol monomethyl ether. Among them, the mass ratio of γ-butyrolactone and propylene glycol monomethyl ether can be 1: (1~3). Optionally, the mass percentage of the organic solvent in the positive photosensitive resin composition is 75%~86%. For example, the mass percentage is 75%, 78%, 80%, 83%, and 86%.

[0046] The positive photosensitive resin composition contains an auxiliary agent to further improve the coating property of the resin composition, the bonding property with the substrate, and the thermal stability of the cured film. Optionally, the auxiliary agent includes one or more of a thermal crosslinking agent and a surfactant.

[0047] Optionally, the thermal crosslinking agent has at least one group selected from alkoxy, methylol, epoxy and oxetane. Optionally, the thermal crosslinking agent has two groups selected from alkoxy, methylol, epoxy and oxetane. Optionally, the thermal crosslinking agent has an alkoxy group. The above groups are crosslinking groups, providing better crosslinking properties. From the perspective of alkali solubility and heat resistance of the cured film, the thermal crosslinking agent optionally includes a compound having a phenolic hydroxyl group. Optionally, the thermal crosslinking agent is 1,1,1-tris(4-hydroxyphenyl)-ethane. Optionally, the thermal crosslinking agent includes a compound having a phenolic hydroxyl group and an alkoxy group. The following compounds may be cited but are not limited thereto: one or more of 4-methoxy-2,6-dimethyl-phenol, 3,5-dimethoxyphenol, 3,4,5-trimethoxyphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-6-methylphenol, 4,4'-dimethoxybiphenyl, 3,3',5,5'-tetramethoxy-4,4'-dihydroxybiphenyl, and 4-methoxytrityl alcohol. Optionally, the mass percentage of the thermal crosslinking agent in the positive photosensitive resin composition is 1% to 10%, preferably 1% to 5%.

[0048] Optionally, the surfactant includes one or more of a silicone surfactant, a fluorine surfactant, and a surfactant formed by an acrylic acid and / or methacrylic acid polymer. For example, the surfactant is a silicone surfactant KP-341. Optionally, the mass percentage of the surfactant in the positive photosensitive resin composition is 0.1% to 0.5%.

[0049] The positive photosensitive resin composition is sensitive to ultraviolet light, X-rays, electron beams or ion beams, has good photosensitivity, a high film removal rate after exposure and development, and a high visible light transmittance of the film after curing. Through photolithography technology and the positive photosensitive resin composition, the pattern can be directly transferred to the film material using a patterned mask, which can greatly shorten the process and improve production efficiency.

[0050] After the positive photosensitive resin composition is coated, it is heated to dehydrate and ring-close the alkali-soluble polyimide precursor to form a polyimide film. DETAILED DESCRIPTION

[0051] The present application will be further described in detail below in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thoroughly understood.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0053] the term

[0054] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0055] In the present application, "plurality", "multiple", "multiple times", "plurality", etc., unless otherwise specified, refer to a number greater than 2 or equal to 2. For example, "one or more" means one or greater than or equal to two.

[0056] In this application, "optionally", "optional" and "optional" refer to optional, that is, to any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0057] In this application, in the "first aspect", "second aspect", "third aspect", "fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0058] In the present application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the optional numerical distribution within the above numerical interval is deemed to be continuous and includes the two numerical endpoints of the numerical range (i.e., the minimum value and the maximum value), and every numerical value between the two numerical endpoints.

[0059] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0060] The following is further described in conjunction with specific embodiments and comparative examples. The raw materials involved in the following specific embodiments and comparative examples, unless otherwise specified, can all be commercially available, the instruments used, unless otherwise specified, can all be commercially available, and the processes involved, unless otherwise specified, are all routinely selected by those skilled in the art.

[0061] Among them, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 3,3',4,4'-diphenylether tetracarboxylic anhydride, pyromellitic anhydride, N-methylpyrrolidone (NMP), etc. were purchased from Inokai and other companies; 4-aminophenol, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and imidazole were purchased from Aladdin and other companies; naphthoquinonediazide-5-sulfonyl chloride, 1,1,1-tris(4-hydroxyphenyl)-ethane, triethylchlorosilane (TBSCl), etc. were purchased from McLean and other companies.

[0062] Comparative Example 1

[0063] This comparative example provides an alkali-soluble polyimide precursor and a preparation method thereof, the steps are as follows:

[0064] Under a dry nitrogen stream, 31.0 g (0.10 mole) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. 48.36 g (0.08 mole) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP) and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mole) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, an organic reagent was added dropwise over 10 minutes, and the organic reagent was obtained by adding 28.6 g (0.24 mole) of N,N-dimethylformamide dimethyl acetal (reacted with carboxyl groups to control the carboxyl content) to 50 g of NMP. After the addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the target alkali-soluble polyimide precursor (a-1).

[0065] Comparative Example 2

[0066] This comparative example provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as comparative example 1, except that a silanization agent is added, and the steps are as follows:

[0067] Under a dry nitrogen stream, 31.0 g (0.10 mole) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. 48.36 g (0.08 mole) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP) and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mole) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mole) of imidazole was added to the reaction solution, and a silanization agent solution was added, which was obtained by adding 36.17 g (0.24 mole) of triethylsilyl chloride (TBSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble polyimide precursor (a-2).

[0068] Example 1

[0069] This embodiment provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as Comparative Example 2, except that a siloxane-containing diamine is added, and the steps are as follows:

[0070] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a terminal blocking agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole was added to the reaction solution, and a silanization agent solution was added, wherein the silanization agent solution was obtained by adding 36.17 g (0.24 mol) of triethylsilyl chloride (TBSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble polyimide precursor (A-1).

[0071] Example 2

[0072] This embodiment provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as that of Embodiment 1, except that the types of the acid dianhydride compound and the aromatic diamine are different. The steps are as follows:

[0073] Under a dry nitrogen stream, 21.8 g (0.10 mole) of pyromellitic dianhydride was dissolved in 500 g of NMP. 15.00 g (0.075 mole) of diphenyl ether diamine (ODA), 1.24 g (0.005 mole) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mole) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mole) of imidazole was added to the reaction solution, and a silanizing agent solution was added, which was obtained by adding 36.17 g (0.24 mole) of triethylsilyl chloride (TBSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the target alkali-soluble polyimide precursor (A-2).

[0074] Example 3

[0075] This embodiment provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as that of Embodiment 1, except that the type of siloxane diamine is different. The steps are as follows:

[0076] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP), 1.38 g (0.005 mol) of 1,3-bis(4-aminobutyl)tetramethyldisilane and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole was added to the reaction solution, and a silanization agent solution was added, wherein the silanization agent solution was obtained by adding 36.17 g (0.24 mol) of triethylsilyl chloride (TBSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble polyimide precursor (A-3).

[0077] Example 4

[0078] This embodiment provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as that of Embodiment 1, except that the type and molar amount of the siloxane diamine are different. The steps are as follows:

[0079] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. 45.35 g (0.074 mol) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP), 1.66 g (0.006 mol) of 1,3-bis(4-aminobutyl)tetramethyldisilane and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole was added to the reaction solution, and a silanization agent solution was added, wherein the silanization agent solution was obtained by adding 36.17 g (0.24 mol) of triethylsilyl chloride (TBSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble polyimide precursor (A-4).

[0080] Example 5

[0081] This embodiment provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as that of Embodiment 1, except that the type of silanization agent is different. The steps are as follows:

[0082] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a terminal blocking agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole was added to the reaction solution, and a silanization agent solution was added, wherein the silanization agent solution was obtained by adding 26.07 g (0.24 mol) of trimethylsilyl chloride (TMSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble polyimide precursor (A-5).

[0083] Example 6

[0084] This embodiment provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as that of Embodiment 1, except that the type and molar amount of the silanization agent are different. The steps are as follows:

[0085] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a terminal blocking agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole was added to the reaction solution, and a silanization agent solution was added, wherein the silanization agent solution was obtained by adding 28.25 g (0.26 mol) of trimethylsilyl chloride (TMSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble polyimide precursor (A-6).

[0086] Example 7

[0087] This embodiment provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as that of Embodiment 1, except that the types or molar amounts of the siloxane diamine, the silanization agent, the acid dianhydride compound and the aromatic diamine are different. The steps are as follows:

[0088] Under a dry nitrogen stream, 21.8 g (0.10 mole) of pyromellitic dianhydride was dissolved in 500 g of NMP. 15.00 g (0.075 mole) of diphenyl ether diamine (ODA), 1.38 g (0.005 mole) of 1,3-bis(4-aminobutyl)tetramethyldisilane and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mole) of 4-aminophenol as a capping agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mole) of imidazole was added to the reaction solution, and a silanization agent solution was added, which was obtained by adding 28.25 g (0.26 mole) of trimethylchlorosilane (TMSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the target alkali-soluble polyimide precursor (A-7).

[0089] Example 8

[0090] This embodiment provides an alkali-soluble polyimide precursor and a preparation method thereof, which is basically the same as that of Embodiment 1, except that a siloxane-containing tetracarboxylic dianhydride is added, and the steps are as follows:

[0091] Under a dry nitrogen stream, 42.65 g (0.10 mol) of PADS (containing siloxane tetracarboxylic dianhydride) was dissolved in 500 g of NMP. 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 50 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a terminal blocking agent and 5 g of NMP were added, and the mixture was reacted at 50°C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole was added to the reaction solution, and a silanization agent solution was added, wherein the silanization agent solution was obtained by adding 36.17 g (0.24 mol) of triethylsilyl chloride (TBSCl) to 50 g of NMP. After the addition was completed, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water 3 times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble polyimide precursor (A-8).

[0092] Comparative Examples 3-4 and Examples 9-15

[0093] Comparative Examples 3-4 and Examples 9-15 provide a positive photosensitive resin composition and a preparation method thereof, the steps are as follows:

[0094] Step 1: Preparation of photosensitive compounds

[0095] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of naphthoquinone diazide-5-sulfonyl chloride are dissolved in 450 g of 1,4-dioxane and returned to room temperature. Triethylamine solution is added dropwise thereto in such a manner that the temperature in the system does not reach above 35°C, wherein the triethylamine solution is obtained by adding 15.18 g of triethylamine to 50 g of 1,4-dioxane. After the addition, stir at 30°C for 2 hours. The reaction system is filtered, and the filtrate is put into water. Then, the precipitate is collected by filtration. The precipitate is dried using a vacuum dryer to obtain a photosensitive compound.

[0096] Step 2: Preparation of positive photosensitive resin composition

[0097] Referring to Table 1, an alkali-soluble polyimide precursor (A), a photosensitive compound (B) and a thermal crosslinking agent 1,1,1-tris(4-hydroxyphenyl)-ethane (D) in the mass percentages shown in Table 1 are dissolved in a solvent (C) composed of propylene glycol monomethyl ether (PGME) and γ-butyrolactone (GBL), with or without the addition of surfactant KP-341, and then filtered with a filter head made of 0.22 μm polytetrafluoroethylene to obtain a positive photosensitive resin composition.

[0098] Examples 16-21

[0099] Embodiment 16-21 provides a positive photosensitive resin composition and a preparation method thereof, and the steps are as follows:

[0100] Step 1 is the same as step 1 of Example 9.

[0101] Step 2: Preparation of positive photosensitive resin composition

[0102] Referring to Table 2, an alkali-soluble polyimide precursor (A), a photosensitive compound (B) and a thermal crosslinking agent 1,1,1-tris(4-hydroxyphenyl)-ethane (D) in the mass percentages shown in Table 2 are dissolved in a solvent (C) composed of propylene glycol monomethyl ether (PGME) and γ-butyrolactone (GBL), and then filtered with a filter head made of 0.22 μm polytetrafluoroethylene to obtain a positive photosensitive resin composition.

[0103] Table 1

[0104]

[0105] Table 2

[0106]

[0107] test

[0108] The positive photosensitive resin composition of the above-mentioned embodiment and comparative example was coated on an 8-inch wafer by spin coating and baked on a hot plate at 120°C for 3 minutes to prepare a pre-baked film with a film thickness of 4.0 μm. Then, an exposure machine (i-line photolithography machine) was used to expose the positive photosensitive resin composition through a mask with a pattern of 5 μm contact holes at a rate of 100 mJ / cm 2 ~600mJ / cm 2 After exposure, a 2.38 wt% tetramethylammonium hydroxide aqueous solution (TMAH, manufactured by Suzhou Jingrui) was used for development for 2 min, and then rinsed with distilled water and dried to obtain a pattern. The pattern was then treated in a nitrogen-filled oven at 250°C for 2 h to obtain a cured film.

[0109] Sensitivity test

[0110] The pattern after development obtained by the above method was observed at a magnification of 20 times using a microscope (manufactured by Olympus), and the minimum exposure required when the opening diameter of the contact hole reached 8 μm was obtained, which was used as the sensitivity. A was determined to be A when a complete pattern was obtained at an exposure of 150 mJ, and B was determined to be B when a complete pattern was obtained at an exposure of 250 mJ. Grade A indicates better photosensitivity. The results are recorded in Table 3.

[0111] Membrane loss test

[0112] The film thickness before and after development was tested using a step profiler (manufactured by Bruker). The film loss was obtained by subtracting the film thickness after development from the film thickness before development. The results are recorded in Table 3. The greater the film loss, the higher the film removal rate and the better the development effect.

[0113] Determination of dielectric constant

[0114] The dielectric constant of the cured film was measured using a dielectric constant tester (China Science Micro-Nano Precision Instrument Co., Ltd., model: GCSTD-D), with a frequency selection range of 1 Hz to 1000 Hz, and the average value of the dielectric constant measured within the frequency range was the dielectric constant value of the cured film. The results are recorded in Table 3.

[0115] Determination of residual sulfur

[0116] The sulfur content of the cured film was measured using an element analyzer (Euro Vector, model: EA3000), and the ratio of the mass of sulfur element to the total amount of the cured film was calculated. The results are recorded in Table 3. The more sulfur element residue there is, the more corrosive it is to the running device, and the shorter the service life of the device.

[0117] Visible light transmittance measurement

[0118] The transmittance of the cured film in the visible light wavelength range (400nm~760nm) was measured using an ultraviolet-visible spectrophotometer (Shimadzu Corporation, model: UV-2600i), and the same glass as the substrate was used as a reference sample. The results are recorded in Table 3.

[0119] Table 3

[0120]

[0121] From the above, we can see that:

[0122] 1) According to Comparative Examples 3, 4 and Example 9, a diamine compound containing a siloxane-containing diamine and an aromatic diamine reacts with an acid dianhydride compound to introduce a siloxane segment on the main chain. At the same time, the polyamic acid generated by the condensation reaction reacts with a silanization agent to further introduce siloxane while controlling the content of the carboxyl group. The combination of the two methods can significantly improve the film removal rate during development, and improve the dielectric constant and transmittance of the cured film.

[0123] 2) According to Examples 9-21, alkali-soluble polyimide precursors prepared from various siloxane-containing diamines, diamine compounds of aromatic diamines, acid dianhydride compounds, and silanization agents are all beneficial for improving the film removal rate during development, and improving the dielectric constant and transmittance of the cured film.

[0124] 3) According to the records in Examples 9-15, changes in the content of alkali-soluble polyimide precursors, photosensitive compounds and other substances in the positive photosensitive resin composition have an impact on the development effect, the dielectric constant and transmittance of the cured film. Among them, according to the records in Example 11, the amount of the photosensitive compound can directly affect the photosensitivity of the composition. As the amount of the photosensitive compound increases, the photosensitivity increases.

[0125] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0126] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. An alkali-soluble polyimide precursor, characterized in that: The invention comprises a polyamide ester resin, wherein the polyamide ester resin is formed by a silylation reaction between a polyamic acid resin and a silanization agent, wherein the polyamic acid resin is formed by a condensation reaction between an acid dianhydride compound and a diamine compound, wherein the diamine compound comprises a siloxane-containing diamine and an aromatic diamine.

2. The alkali-soluble polyimide precursor according to claim 1, characterized in that The siloxane-containing diamine includes one or more of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, 1,3-bis(p-aminophenyl)tetramethyldisiloxane, 1,3-bis(m-aminophenyl)tetramethyldisiloxane, 1,5-bis(p-aminophenyl)hexamethyltrisiloxane, 1,5-bis(m-aminophenyl)hexamethyltrisiloxane, bis(p-aminophenyl)dimethylsiloxane and bis(m-aminophenyl)dimethylsiloxane.

3. The alkali-soluble polyimide precursor according to claim 2, characterized in that: The molar proportion of the siloxane-containing diamine in the diamine compound is 5%-60%.

4. The alkali-soluble polyimide precursor according to claim 1, characterized in that: The silylating agent includes one or more of 2-(trimethylsilyl)ethanol, trimethylsilyl chloride, triethylsilyl chloride, tert-butyldimethylsilyl chloride and bis(trimethylsilyl)acetamide.

5. The alkali-soluble polyimide precursor according to claim 4, characterized in that: The ratio of the molar number of the silanization agent to the total molar number of the acid dianhydride compound and the diamine compound is (1-2):

1.

6. The alkali-soluble polyimide precursor according to any one of claims 1 to 5, characterized in that Includes at least one of the following features: (1) The aromatic diamines include 2,2'-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, One or more of 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl and 9,9-bis(4-aminophenyl)fluorene; wherein the substituent is a C1-C3 alkyl group or a halogen; (2) The acid dianhydride compound includes a tetracarboxylic dianhydride compound; optionally, the tetracarboxylic dianhydride compound includes one or more of an aromatic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride; optionally, the aromatic tetracarboxylic dianhydride includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane Dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl} one or more of fluorene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; optionally, the aliphatic tetracarboxylic acid dianhydride includes one or more of butanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride.

7. The alkali-soluble polyimide precursor according to any one of claims 1 to 5, characterized in that The acid dianhydride compound includes a siloxane-containing tetracarboxylic dianhydride, and the siloxane-containing tetracarboxylic dianhydride has one of the following structures: 。 8. A method for preparing an alkali-soluble polyimide precursor, characterized in that: The following steps are involved: Allowing an acid dianhydride compound and a diamine compound to undergo a polycondensation reaction to generate a polyamic acid resin, wherein the diamine compound comprises a siloxane-containing diamine and an aromatic diamine; The polyamic acid resin is subjected to a silanization reaction with a silanization agent to generate a polyamide ester resin.

9. A positive photosensitive resin composition, characterized in that: Comprising the alkali-soluble polyimide precursor according to any one of claims 1 to 7 and a photosensitive compound; Optionally, the photosensitive compound is formed by bonding a compound having a naphthoquinone diazide group to a compound having a multifunctional group through an ester bond or a sulfonyl bond, and the compound having a multifunctional group includes a compound having a multihydroxyl group or a compound having a multiamine group; Optionally, the naphthoquinone diazide group includes a quinone diazide sulfonate group or a quinone diazide sulfonyl group; Optionally, the compound having a naphthoquinone diazide group includes naphthoquinone diazide-5-sulfonyl chloride; Optionally, the compound having a multihydroxyl group includes a phenolic hydroxyl compound; Optionally, the phenolic hydroxyl compound includes Α,Α,Α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene; Optionally, the molar ratio of the compound having a naphthoquinone diazide group to the compound having a multifunctional group is (1-3): 1; Optionally, the mass percentage of the alkali-soluble polyimide precursor in the positive photosensitive resin composition is 5% to 20%; preferably 8% to 18%; preferably 10% to 15%; preferably 12% to 13%; Optionally, the mass percentage of the photosensitive compound in the positive photosensitive resin composition is 2% to 12%, preferably 4% to 6%.

10. The positive photosensitive resin composition according to claim 9, characterized in that: It also includes an auxiliary agent and an organic solvent; optionally, the organic solvent includes one or more of γ-butyrolactone, acetone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, ethyl acetate, ethyl lactate, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and diethylene glycol methyl ethyl ether; optionally, the mass percentage of the organic solvent in the positive photosensitive resin composition is 75% to 86%; optionally, the auxiliary agent includes one or more of a thermal crosslinking agent and a surfactant; optionally, the thermal crosslinking agent includes a compound having a phenolic hydroxyl group; optionally, the mass percentage of the thermal crosslinking agent in the positive photosensitive resin composition is 1% to 10%; optionally, the surfactant includes one or more of a silicone surfactant, a fluorine surfactant, and a surfactant formed by an acrylic acid and / or methacrylic acid polymer; Optionally, the mass percentage of the surfactant in the positive photosensitive resin composition is 0.1% to 0.5%.

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