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

Abstract

This application relates to the field of polymer materials technology, and particularly to an alkali-soluble polyimide precursor, its preparation method, and a positive photosensitive resin composition. The alkali-soluble polyimide precursor comprises a polyamide ester resin, which is formed by a silanization reaction between a polyamic acid resin and a silanizing agent. The polyamic acid resin is formed by a polycondensation reaction between an acid dianhydride compound and a diamine compound, wherein the diamine compound includes siloxane-containing diamines and aromatic diamines. The aforementioned alkali-soluble polyimide precursor has a low dielectric constant. Furthermore, when the aforementioned alkali-soluble polyimide precursor is used in a positive photosensitive resin composition, it exhibits good photosensitivity, a high film removal rate after exposure and development, and a high visible light transmittance of the cured film.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to an alkali-soluble polyimide precursor, its preparation method, and a positive photosensitive resin composition. Background Technology

[0002] With the rapid development of science and technology, various electronic products and intelligent devices (such as smartphones, tablets, and ultra-thin TVs) have emerged, continuously evolving towards more intelligent content, more reliable use, and thinner and lighter designs. To achieve these requirements, more electronic circuits need to be laid out on the product chips, resulting in the design of ultra-large-scale integrated circuits. As microelectronic devices become smaller and the wiring density on chips increases, signal hysteresis caused by capacitive coupling and crosstalk between closely spaced wires significantly increases. This necessitates low-dielectric materials to meet the insulating packaging requirements of the microelectronics industry. Furthermore, low-dielectric materials are also required for dielectric films and etched barrier layers in the microelectronics industry. Other fields, such as gas separation membranes, wires, and cables, also require low-dielectric materials to meet their application needs.

[0003] Polyimide materials can be used in the aforementioned fields and have the following advantages: high heat resistance, high mechanical strength, low water absorption, good adhesion to the matrix, and resistance to chemical corrosion. However, the dielectric constant of most commercially available polyimide materials no longer meets the requirements, so developing materials with even lower dielectric constants is currently a research hotspot in the field of materials science. Summary of the Invention

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

[0005] An alkali-soluble polyimide precursor includes a polyamide ester resin, which is formed by a silanization reaction of a polyamic acid resin with a silanizing agent, and the polyamic acid resin is formed by a polycondensation reaction of an acid dianhydride compound and a diamine compound, wherein the diamine compound includes a siloxane-containing diamine and an aromatic diamine.

[0006] Compared with traditional solutions, this application has the following advantages:

[0007] This application involves a polycondensation reaction of a diamine compound, including a siloxane-containing diamine and an aromatic diamine, with an acid dianhydride compound to introduce siloxane segments into the main chain. Simultaneously, the polyamic acid generated through the polycondensation reaction undergoes a silanization reaction with a silanizing agent. Through the reaction of the silanizing agent with carboxyl groups, the carboxyl content is controlled, and siloxane is further introduced. Through this combination of methods, the alkali-soluble polyimide precursor exhibits a low dielectric constant and can be used in the microelectronics industry as a dielectric film, etching barrier layer, or encapsulation material. It can also be used as an insulating material in gas separation membranes, wires, cables, and other fields. Furthermore, when the aforementioned alkali-soluble polyimide precursor is used in a positive photosensitive resin composition, it exhibits good photosensitivity to ultraviolet light, X-rays, electron beams, or ion beams, high film removal rate after exposure and development, and high visible light transmittance of the cured film.

[0008] The polyamic acid resin is formed through a polycondensation reaction between an acid dianhydride compound and a diamine compound. Alternatively, the acid dianhydride compound can react directly with the diamine compound, or the acid dianhydride compound can first react with an alcohol to obtain a diester, and then react with the amine in the presence of a condensing agent. Another option is that the acid dianhydride compound can first react with an alcohol to obtain a diester, then the residual dicarboxylic acid is acylated, and finally reacted with an amine.

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

[0010] A solution containing a diamine compound is added to a solution containing an acid dianhydride compound, resulting in a polycondensation reaction to obtain a polyamic acid resin.

[0011] The solvent for solutions containing dianhydride compounds can be N-methylpyrrolidone (NMP), and the solvent for solutions containing diamine compounds can also be N-methylpyrrolidone (NMP).

[0012] Optionally, the temperature at which the polycondensation reaction occurs is 15℃~60℃. Optionally, the reaction procedure for the polycondensation reaction includes: reacting at 15℃~25℃ for 0.5h~1.5h, then reacting at 40℃~60℃ for 1h~3h, adding a solution containing a capping agent, and reacting at 40℃~60℃ for 1h~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 ratios are 1:0.5, 1:0.8, 1:1, 1:1.2, and 1:1.5.

[0014] The aforementioned diamine compounds include siloxane-containing diamines and aromatic diamines. Optionally, the siloxane-containing diamine accounts for 5%-60% of the molar percentage in the diamine compound. For example, the molar percentages are 5%, 10%, 15%, 20%, 30%, 40%, 50%, and 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-aminobenzoylamino)-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-naphthylenediamine, 2,6-naphthylenediamine, bis(4-aminophenoxy)biphenyl, and bis[4-(4-aminophenoxy)phenyl] ether, in which the hydrogen atoms in the aromatic ring are substituted or unsubstituted. One or more of 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 group or a halogen.

[0017] Optionally, the dianhydride compound includes tetracarboxylic acid dianhydride compounds. Optionally, the tetracarboxylic acid dianhydride compound includes one or more of aromatic tetracarboxylic acid dianhydrides and aliphatic tetracarboxylic acid dianhydrides. Optionally, the aromatic tetracarboxylic acid 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( The aliphatic tetracarboxylic acid dianhydride comprises one or more of the following: 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)fluorenic acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic 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 comprises one or more of butanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride.

[0018] Optionally, the acid dianhydride compound includes a siloxane-containing tetracarboxylic dianhydride having one of the following structures:

[0019] .

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

[0021] Polyamide ester resin is formed by the silanization reaction of polyamic acid resin with a silanizing agent. Through silanization, the silicon and carboxyl content of the polyamic acid resin can be controlled, thereby regulating the dielectric constant, alkali solubility rate, and photosensitivity of the alkali-soluble polyimide precursor. Furthermore, the introduction of the silanizing agent does not cause significant fluctuations in the molecular weight of the polyamic acid, thus having little impact on the performance of the cured film. In addition, since siloxane diamines and siloxane tetracarboxylic dianhydrides are relatively expensive, silanization with a silanizing agent offers a high cost-performance ratio. Finally, the silanizing agent, as a protecting group of carboxylic acids, has excellent compatibility, being well-compatible with methyl esters, ethyl esters, benzyl esters, allyl esters, etc., and the reaction conditions are mild.

[0022] The silanization reaction of polyamic acid resin with a silanizing agent can be achieved through the Mitsunobu reaction (phototensive reaction). Alternatively, the silanization reaction can occur directly in the presence of an alkaline agent, for example, in the presence of imidazole (a weak base). In some embodiments, the preparation method of the polyamic acid resin includes the following steps:

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

[0024] The solvent for the solution containing the silanizing agent can be N-methylpyrrolidone (NMP). The alkali can be imidazole. Optionally, the ratio of the molar amount of the alkali to the total molar amount of the acid dianhydride compound and the diamine compound is (2~4):1. For example, the ratio is 2:1, 3:1, or 4:1.

[0025] Optionally, the silanization reaction occurs at a temperature of 40°C to 60°C. Optionally, the silanization reaction lasts for 2 to 4 hours.

[0026] Optionally, the ratio of the molar number of the silanizing agent to the total molar 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, or 2:1.

[0027] Optionally, the silanizing agent includes one or more of 2-(trimethylsilyl)ethanol, trimethylchlorosilane (TMSCl), triethylchlorosilane (TBSCl), tert-butyldimethylchlorosilane (TBSCl), and bis(trimethylsilyl)acetamide (BSA).

[0028] The introduction of the aforementioned siloxane segments not only reduces the dielectric constant of the resin, resulting in better photosensitivity, high film removal rate, and high visible light transmittance, but also improves the resin's processability, increases its adhesion to metals, silicon, ITO, and glass, and reduces internal stress. The resin exhibits low water absorption, high resistance to atomic oxygen, good solubility and gas permeability, and strong environmental durability.

[0029] The second aspect of this application provides a method for preparing an alkali-soluble polyimide precursor, the technical solution of which is as follows:

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

[0031] A polycondensation reaction is carried out between an acid dianhydride compound and a diamine compound to generate a polyamic acid resin, wherein the diamine compound includes siloxane-containing diamines and aromatic diamines;

[0032] The polyamic acid resin is subjected to a silanization reaction with a silanizing 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] A third aspect of this application provides a positive photosensitive resin composition, the technical solution of which is as follows:

[0035] A positive photosensitive resin composition comprising, as described above, an alkali-soluble polyimide precursor and a photosensitive compound.

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

[0037] Optionally, the photosensitive compound is formed by a compound having a diazidonaphthoquinone group bonded by an ester bond or a sulfonyl bond to a compound having multiple functional groups. For alkali solubility and economy, the diazidonaphthoquinone group includes a diazidoquinone sulfonate group or a diazidoquinone sulfonyl group. Optionally, the compound having a diazidonaphthoquinone group includes diazidonaphthoquinone-5-sulfonyl chloride. The compound having multiple functional groups includes a compound having multiple hydroxyl groups or a compound having multiple amine groups. Optionally, the compound having multiple hydroxyl groups includes a compound having a phenolic hydroxyl group. Optionally, the phenolic hydroxyl compound includes A,A,A'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene. A,A,A'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene may be commercially available, for example, TrisP-PA.

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

[0039] In the presence of triethylamine and a solvent, a compound having a diazidonaphthoquinone group and a compound having multiple functional groups are mixed and stirred to obtain the photosensitive compound.

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

[0041] Optionally, the ambient temperature for mixing compounds having a diazidonaphthoquinone group and compounds having multiple functional groups does not exceed 35°C. For example, temperatures of 35°C, 30°C, 20°C, and 10°C. The temperature for the stirred reaction does not exceed 35°C. For example, temperatures of 35°C, 30°C, 20°C, and 10°C. The stirring reaction time is 1 to 3 hours.

[0042] Optionally, the molar ratio of the compound having a diazidonaphthoquinone group to the compound having multiple functional groups is (1~3):1. For example, the molar ratio is 1:1, 2:1, or 3:1.

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

[0044] Optionally, the positive photosensitive resin composition also includes additives and organic solvents.

[0045] The positive photosensitive resin composition contains an organic solvent, which can be in a varnish state and improve the coatability 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. The mass ratio of γ-butyrolactone to propylene glycol monomethyl ether can be 1:(1~3). Optionally, the organic solvent in the positive photosensitive resin composition has a mass percentage of 75%~86%. For example, the mass percentages are 75%, 78%, 80%, 83%, and 86%.

[0046] The positive photosensitive resin composition contains additives that can further improve the coatability of the resin composition, its adhesion to the substrate, and the thermal stability of the cured film. Optionally, the additives include one or more of thermal crosslinking agents and surfactants.

[0047] Optionally, the thermal crosslinking agent has at least one group selected from alkoxy, hydroxymethyl, epoxy, and oxetyl. Optionally, the thermal crosslinking agent has two groups selected from alkoxy, hydroxymethyl, epoxy, and oxetyl. Optionally, the thermal crosslinking agent has an alkoxy group. These groups are crosslinking-compatible groups, providing better crosslinking properties. Considering alkali solubility and the 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 both phenolic hydroxyl and alkoxy groups. Examples, but not limited to, the following compounds: one or more of 4-methoxy-2,6-dimethylphenol, 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-methoxytriphenylmethyl alcohol. Optionally, the thermal crosslinking agent is present in the positive photosensitive resin composition at a mass percentage of 1% to 10%. Preferably, it is 1% to 5%.

[0048] Optionally, the surfactant includes one or more of the following: silicone surfactants, fluorinated surfactants, and surfactants formed from acrylic and / or methacrylic polymers. For example, the surfactant is silicone surfactant KP-341. Optionally, the surfactant is present in the positive photosensitive resin composition at a mass percentage of 0.1% to 0.5%.

[0049] The aforementioned positive photosensitive resin composition is sensitive to light such as ultraviolet light, X-rays, electron beams, or ion beams, exhibiting good photosensitivity. It also demonstrates a high film removal rate after exposure and development, and high visible light transmittance after curing. Using photolithography and the aforementioned positive photosensitive resin composition, patterns can be directly transferred onto the film material using a patterned photomask, significantly shortening the process and improving production efficiency.

[0050] After coating with the above-mentioned positive photosensitive resin composition and heating, the alkali-soluble polyimide precursor is dehydrated and ring-closed to form a polyimide film. Detailed Implementation

[0051] The present application will be further described in detail below with reference to specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0052] Unless otherwise defined, 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. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0053] the term

[0054] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0055] In this application, the terms "multiple", "various", "multiple times", "multi-dimensional", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more or more.

[0056] In this application, the terms "optionally," "optionally," and "optional" refer to options that are optional, meaning they can be selected from either "with" or "without." If multiple "optional" options appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "optional" option is independent.

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

[0058] In this application, numerical intervals (i.e. numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the above-mentioned numerical intervals are considered continuous, and include the two numerical endpoints (i.e., the minimum value and the maximum value) of the numerical range, as well as every value between the two numerical endpoints.

[0059] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0060] The following description is further illustrated with specific embodiments and comparative examples. Unless otherwise specified, the raw materials involved in the following specific embodiments and comparative examples are all commercially available. Unless otherwise specified, the instruments used are all commercially available. Unless otherwise specified, the processes involved are conventionally selected by those skilled in the art.

[0061] Among them, 2,2-bis[3-(3-aminobenzoylamino)-4-hydroxyphenyl]hexafluoropropane, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride, and N-methylpyrrolidone (NMP) were purchased from companies such as Inokai; 4-aminophenol, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and imidazole were purchased from companies such as Aladdin; and diazidonaphthoquinone-5-sulfonyl chloride, 1,1,1-tris(4-hydroxyphenyl)-ethane, and triethylchlorosilane (TBSCl) were purchased from companies such as Maclean.

[0062] Comparative Example 1

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

[0064] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. Then, 48.36 g (0.08 mol) of 2,2-bis[3-(3-aminobenzoylamino)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP) and 50 g of NMP were added, and the mixture was reacted at 20 °C for 1 hour, followed by a reaction 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, an organic reagent, obtained by adding 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal (reacting with carboxyl groups to control carboxyl content) to 50 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, 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 its preparation method, which is basically the same as that of Comparative Example 1, with the main difference being the addition of a silanizing agent. The steps are as follows:

[0067] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. Then, 48.36 g (0.08 mol) of 2,2-bis[3-(3-aminobenzoylamino)-4-hydroxyphenyl]hexafluoropropane (m-6FDAP) and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour, followed by a reaction 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 reaction was carried out at 50 °C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole was added to the reaction solution, along with a silanizing agent solution prepared by adding 36.17 g (0.24 mol) of triethylchlorosilane (TBSCl) to 50 g of NMP. After addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using 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 its preparation method, which is basically the same as Comparative Example 2, the main difference being the addition of a siloxane-containing diamine. The steps are as follows:

[0070] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. Then, 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzoylamino)-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, and the mixture was reacted at 20 °C for 1 hour, followed by a reaction 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, along with a silanizing agent solution prepared by adding 36.17 g (0.24 mol) of triethylchlorosilane (TBSCl) to 50 g of NMP. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3 L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using 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 its preparation method, which is basically the same as that in Example 1, the main difference being the different types of acid dianhydride compound and aromatic diamine. The steps are as follows:

[0073] Under a dry nitrogen stream, 21.8 g (0.10 mol) of pyromellitic dianhydride was dissolved in 500 g of NMP. Then, 15.00 g (0.075 mol) of diphenyl ether diamine (ODA), 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour, followed by a reaction 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 reaction was carried out at 50 °C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole and a silanizing agent solution were added to the reaction solution. The silanizing agent solution was prepared by adding 36.17 g (0.24 mol) of triethylchlorosilane (TBSCl) to 50 g of NMP. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, 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 its preparation method, which is basically the same as that in Example 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'-diphenyl ether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. Then, 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzoylamino)-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, and the mixture was reacted at 20 °C for 1 hour, followed by a reaction 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, along with a silanizing agent solution prepared by adding 36.17 g (0.24 mol) of triethylchlorosilane (TBSCl) to 50 g of NMP. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3 L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using 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 its preparation method, which is basically the same as that in Example 1, except that the type and molar amount of 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'-diphenyl ether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. Then, 45.35 g (0.074 mol) of 2,2-bis[3-(3-aminobenzoylamino)-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, and the mixture was reacted at 20 °C for 1 hour, followed by a reaction 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, along with a silanizing agent solution prepared by adding 36.17 g (0.24 mol) of triethylchlorosilane (TBSCl) to 50 g of NMP. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3 L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using 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 its preparation method, which is basically the same as that in Example 1, except that the type of silanizing 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'-diphenyl ether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. Then, 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzoylamino)-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, and the mixture was reacted at 20 °C for 1 hour, followed by a reaction 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, along with a silanizing agent solution prepared by adding 26.07 g (0.24 mol) of trimethylchlorosilane (TMSCl) to 50 g of NMP. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3 L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using 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 its preparation method, which is basically the same as that in Example 1, except that the type and molar amount of the silanizing 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'-diphenyl ether tetracarboxylic dianhydride (ODPA) was dissolved in 500 g of NMP. Then, 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzoylamino)-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, and the mixture was reacted at 20 °C for 1 hour, followed by a reaction 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, along with a silanizing agent solution prepared by adding 28.25 g (0.26 mol) of trimethylchlorosilane (TMSCl) to 50 g of NMP. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3 L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using 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 its preparation method, which is basically the same as that in Example 1. The main difference is that the types or molar amounts of siloxane diamine, silanizing agent, acid dianhydride compound, and aromatic diamine are different. The steps are as follows:

[0088] Under a dry nitrogen stream, 21.8 g (0.10 mol) of pyromellitic dianhydride was dissolved in 500 g of NMP. Then, 15.00 g (0.075 mol) of diphenyl ether diamine (ODA), 1.38 g (0.005 mol) of 1,3-bis(4-aminobutyl)tetramethyldisilane, and 50 g of NMP were added, and the reaction was carried out at 20 °C for 1 hour, followed by a reaction 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 reaction was carried out at 50 °C for 2 hours. Then, 34.04 g (0.5 mol) of imidazole was added to the reaction solution, along with a silanizing agent solution prepared by adding 28.25 g (0.26 mol) of trimethylchlorosilane (TMSCl) to 50 g of NMP. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, 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 its preparation method, which is basically the same as that in Example 1, except that a siloxane-containing tetracarboxylic acid dianhydride is added. The steps are as follows:

[0091] Under a dry nitrogen stream, 42.65 g (0.10 mol) of PADS (a siloxane-containing tetracarboxylic acid dianhydride) was dissolved in 500 g of NMP. Then, 45.35 g (0.075 mol) of 2,2-bis[3-(3-aminobenzoylamino)-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, and the mixture was reacted at 20 °C for 1 hour, followed by a reaction 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, along with a silanizing agent solution prepared by adding 36.17 g (0.24 mol) of triethylchlorosilane (TBSCl) to 50 g of NMP. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3 L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried using 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 its preparation method, the steps of which 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 diazidonaphthoquinone-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and allowed to return to room temperature. A triethylamine solution was added dropwise to the system without raising the temperature above 35°C; the triethylamine solution was obtained by adding 15.18 g of triethylamine to 50 g of 1,4-dioxane. After addition, the mixture was stirred at 30°C for 2 hours. The reaction mixture was filtered, and the filtrate was added to water. The precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain the photosensitive compound.

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

[0097] Referring to Table 1, the alkali-soluble polyimide precursor (A), photosensitive compound (B), and thermal crosslinking agent 1,1,1-tris(4-hydroxyphenyl)-ethane (D) in the mass percentages shown in Table 1 were 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. The mixture was then filtered through a 0.22 μm polytetrafluoroethylene filter head to obtain a positive photosensitive resin composition.

[0098] Examples 16-21

[0099] Examples 16-21 provide a positive photosensitive resin composition and its preparation method, the steps of which are as follows:

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

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

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

[0103] Table 1

[0104]

[0105] Table 2

[0106]

[0107] test

[0108] The positive photosensitive resin compositions of the above examples and comparative examples were coated onto an 8-inch wafer using spin coating and baked at 120°C for 3 minutes on a hot plate to create a pre-baked film with a thickness of 4.0 μm. Then, using an i-line lithography machine, through a mask patterned with 5 μm contact holes, an exposure was performed at 100 mJ / cm². 2 ~600mJ / cm 2 Exposure was performed using the specified exposure level. After exposure, development was carried out for 2 minutes using a 2.38 wt% tetramethylammonium hydroxide aqueous solution (TMAH, manufactured by Suzhou Jingrui), followed by rinsing with distilled water and spin drying to obtain the pattern. The pattern was then cured in a nitrogen-filled oven at 250℃ for 2 hours to obtain the cured film.

[0109] Sensitivity test

[0110] Using a microscope (Olympus), the developed pattern obtained by the above method was observed at 20x magnification. The minimum required exposure for the contact hole opening diameter to reach 8 μm was determined and used as the sensitivity. A complete pattern was obtained with an exposure of 150 mJ, and a complete pattern was obtained with an exposure of 250 mJ, which was classified as B. 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 measured using a step profiler (Bruker model). The film loss was obtained by subtracting the film thickness after development from the film thickness before development, and 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 meter (Zhongke Micro-Nano Precision Instruments Co., Ltd., model: GCSTD-D). The frequency range was 1Hz to 1000Hz, and the average dielectric constant measured within this frequency range was taken as the dielectric constant value of the cured film. The results are recorded in Table 3.

[0115] Determination of sulfur residue

[0116] The sulfur content of the cured film was determined using an elemental analyzer (Euro Vector, model: EA3000), and the ratio of sulfur mass to the total cured film mass was calculated. The results are recorded in Table 3. Higher residual sulfur content leads to greater corrosivity to operating devices and reduces their lifespan.

[0117] Visible light transmittance measurement

[0118] The transmittance of the cured film in the visible light wavelength range (400nm~760nm) was measured using a UV-Vis spectrophotometer (Shimadzu Corporation, model: UV-2600i), with the same glass as the substrate 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, diamine compounds containing siloxanes and diamine compounds containing aromatic diamines undergo a polycondensation reaction with acid dianhydride compounds to introduce siloxane segments into the main chain. At the same time, the polyamic acid generated by the polycondensation reaction undergoes a silanization reaction with a silanizing agent to further introduce siloxane while controlling the content of carboxyl groups. 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, various diamines containing siloxanes, diamine compounds of aromatic diamines, acid dianhydrides, and silanizing reagents are all beneficial to improving the film removal rate during development and increasing the dielectric constant and transmittance of the cured film.

[0124] 3) According to Examples 9-15, the changes in the content of alkali-soluble polyimide precursor, photosensitive compound, and other substances in the positive photosensitive resin composition affect the developing effect, the dielectric constant of the cured film, and the transmittance. In particular, according to Example 11, the amount of photosensitive compound can directly affect the photosensitivity of the composition. As the amount of photosensitive compound increases, the photosensitivity is improved.

[0125] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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 embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. An alkali-soluble polyimide precursor, characterized in that, The invention includes a polyamide ester resin, which is formed by a silanization reaction of a polyamic acid resin with a silanizing agent. The silanizing agent includes one or more of 2-(trimethylsilyl)ethanol, trimethylchlorosilane, triethylchlorosilane, tert-butyldimethylchlorosilane, and bis(trimethylsilyl)acetamide. The polyamic acid resin is formed by a polycondensation reaction of an acid dianhydride compound and a diamine compound. The diamine compound includes siloxane-containing diamines and aromatic diamines. The molar percentage of the siloxane-containing diamine in the diamine compound is 5%-60%. The ratio of the molar number of the silanizing agent to the total molar number of the acid dianhydride compound and the diamine compound is (1~2):

1.

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 any one of claims 1 to 2, characterized in that, The aromatic diamines include 2,2'-bis[3-(3-aminobenzoylamino)-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-naphthylenediamine, 2,6-naphthylenediamine, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] ether, 2, One or more of 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.

4. The alkali-soluble polyimide precursor according to any one of claims 1 to 2, characterized in that, The acid dianhydride compounds include tetracarboxylic acid dianhydride compounds.

5. The alkali-soluble polyimide precursor according to claim 4, characterized in that, The tetracarboxylic dianhydrides include one or more of aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.

6. The alkali-soluble polyimide precursor according to claim 5, characterized in that, The aromatic tetracarboxylic acid dianhydrides include 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, One or more of the following: 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)fluorenic dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic 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.

7. The alkali-soluble polyimide precursor according to claim 5, characterized in that, The aliphatic tetracarboxylic dianhydride includes one or more of butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride.

8. The alkali-soluble polyimide precursor according to any one of claims 1 to 2, characterized in that, The acid dianhydride compound includes a siloxane-containing tetracarboxylic dianhydride, which has one of the following structures: 。 9. A method for preparing an alkali-soluble polyimide precursor according to any one of claims 1 to 8, characterized in that, Includes the following steps: A polycondensation reaction is carried out between an acid dianhydride compound and a diamine compound to generate a polyamic acid resin, wherein the diamine compound includes siloxane-containing diamines and aromatic diamines; The polyamic acid resin is subjected to a silanization reaction with a silanizing agent to generate a polyamide ester resin.

10. A positive photosensitive resin composition, characterized in that, Includes the alkali-soluble polyimide precursor and photosensitive compound as described in any one of claims 1 to 8.

11. The positive photosensitive resin composition according to claim 10, characterized in that, The photosensitive compound is formed by a compound having a diazidonaphthoquinone group bonded by an ester bond or a sulfonyl bond to a compound having multiple functional groups, the compound having multiple functional groups including compounds having multiple hydroxyl groups or compounds having multiple amine groups.

12. The positive photosensitive resin composition according to claim 11, characterized in that, The diazidoquinone group includes a diazidoquinone sulfonate group or a diazidoquinone sulfonyl group.

13. The positive photosensitive resin composition according to claim 11, characterized in that, The compounds having a diazidonaphthoquinone group include diazidonaphthoquinone-5-sulfonyl chloride.

14. The positive photosensitive resin composition according to claim 11, characterized in that, The compounds having multiple hydroxyl groups include phenolic hydroxyl compounds.

15. The positive photosensitive resin composition according to claim 14, characterized in that, The phenolic hydroxyl compounds include A,A,A'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene.

16. The positive photosensitive resin composition according to claim 11, characterized in that, The molar ratio of the compound having a diazido-naphthoquinone group to the compound having multiple functional groups is (1~3):

1.

17. The positive photosensitive resin composition according to claim 11, characterized in that, The alkali-soluble polyimide precursor is present in the positive photosensitive resin composition at a mass percentage of 5% to 20%.

18. The positive photosensitive resin composition according to claim 17, characterized in that, The alkali-soluble polyimide precursor is present in the positive photosensitive resin composition at a mass percentage of 8% to 18%.

19. The positive photosensitive resin composition according to claim 18, characterized in that, The alkali-soluble polyimide precursor is present in the positive photosensitive resin composition at a mass percentage of 10% to 15%.

20. The positive photosensitive resin composition according to claim 19, characterized in that, The alkali-soluble polyimide precursor is present in the positive photosensitive resin composition at a mass percentage of 12% to 13%.

21. The positive photosensitive resin composition according to claim 11, characterized in that, The photosensitive compound is present in the positive photosensitive resin composition at a mass percentage of 2% to 12%.

22. The positive photosensitive resin composition according to claim 21, characterized in that, The photosensitive compound is present in the positive photosensitive resin composition at a mass percentage of 4% to 6%.

23. The positive photosensitive resin composition according to claim 11, characterized in that, It also includes additives and organic solvents.

24. The positive photosensitive resin composition according to claim 23, characterized in that, 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.

25. The positive photosensitive resin composition according to claim 23, characterized in that, The organic solvent in the positive photosensitive resin composition is 75% to 86% by mass.

26. The positive photosensitive resin composition according to claim 23, characterized in that, The additives include one or more of thermal crosslinking agents and surfactants.

27. The positive photosensitive resin composition according to claim 26, characterized in that, The thermal crosslinking agent includes compounds having phenolic hydroxyl groups.

28. The positive photosensitive resin composition according to claim 26, characterized in that, The thermal crosslinking agent is present in the positive photosensitive resin composition at a mass percentage of 1% to 10%.

29. The positive photosensitive resin composition according to claim 26, characterized in that, The surfactant includes one or more of the following: organosilicon surfactants, fluorinated surfactants, and surfactants formed from acrylic and / or methacrylic polymers.

30. The positive photosensitive resin composition according to claim 26, characterized in that, The surfactant is present in the positive photosensitive resin composition at a mass percentage of 0.1% to 0.5%.

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