Resin precursor as well as preparation method and application thereof

Abstract

The invention discloses a resin precursor as well as a preparation method and application thereof, and belongs to the field of high polymer materials. The triptycene-containing polyimide resin is obtained through an addition polymerization reaction of at least one dianhydride with a triptycene structure, diamine with cyclohexane and a flexible branched chain structure with more than 4 carbon atoms, and diamine with a fluorenyl structure. Wherein the triptycene structure has a relatively large intramolecular cavity, and the triptycene structure is introduced into a PI skeleton, so that the polyimide film has a porous structure, the free volume and porosity of the polyimide film are improved, the dielectric constant (Dk) is reduced, and meanwhile, the solubility of polyimide resin is improved; through combination of diamine with cyclohexane and a flexible branched chain structure with more than 4 carbon atoms and diamine with a fluorenyl structure, the elongation at break of the polyimide film can be improved, and meanwhile, high glass transition temperature (Tg) and heat resistance can be kept.

Description

Technical Field

[0001] The present application relates to a resin precursor, a preparation method thereof, and an application, belonging to the field of polymer materials. Background Art

[0002] Polyimide (PI) is a class of organic polymer materials containing imide rings, which has good thermal stability, chemical stability, electrical insulation and good mechanical properties, and is widely used in various components such as passivation films, surface protection films, and interlayer insulation films of semiconductor devices.

[0003] However, the dielectric constant of traditional polyimide is relatively high (about 3.4), which is difficult to meet the requirements of next-generation semiconductor packaging materials, and it needs to be modified to have a low dielectric constant, especially in the field of 5G communication technology. With the development of microelectronic devices towards smaller size and more functions, a series of problems such as poor diffraction ability of electromagnetic wave signals, increased signal transmission attenuation, parasitic resistance effect in the circuit, and aggravated capacitance effect have emerged, which will seriously affect the use performance of electronic components. Therefore, it is urgent to develop high-performance, low-dielectric or even ultra-low-dielectric materials for 5G.

[0004] At present, porous polyimide materials can combine the excellent heat resistance, insulation and mechanical properties of polyimide materials and the many advantages of porous materials such as low dielectric constant, light weight and small density, and become high-quality materials in the fields of power electronics devices, aerospace, etc. Summary of the Invention

[0005] The present application provides a resin precursor, which is obtained by polyaddition reaction of at least one dianhydride having a triptycene structure, a diamine having a cyclohexane and a flexible branched chain structure with 4 or more carbon atoms, and a diamine having a fluorene-based structure. Among them, the triptycene structure has a large intramolecular cavity. Introducing it into the PI skeleton makes the polyimide film have a porous structure, increases its free volume and porosity, thereby reducing the dielectric constant (Dk), and at the same time improving the solubility of polyimide resins; the combination of a diamine having a cyclohexane and a flexible branched chain structure with 4 or more carbon atoms and a diamine having a fluorene-based structure can increase the elongation at break of the polyimide film while maintaining a high glass transition temperature (Tg) and heat resistance.

[0006] In the first aspect of the present application, a resin precursor is provided.

[0007] A resin precursor, the resin precursor is selected from at least one of a polyimide precursor and a polyimide;

[0008] The polyimide precursor is a polymer having a structural unit represented by the following formula (1), and the polyimide is a polymer having a structural unit represented by the following formula (2):

[0009]

[0010] X1 and X2 are each independently selected from at least one organic group containing at least one structure represented by formula (3) and simultaneously containing at least one organic group not having the structure represented by formula (3);

[0011]

[0012] Y1 and Y2 are each independently selected from derivatives obtained by removing terminal amino groups from diamine compounds, and the diamine compounds include diamine compound A having an alicyclic structure and a hydrocarbon structure with 4 or more carbon atoms and diamine compound B having a bulky fluorene group structure;

[0013] R1, R2, R3, and R4 are each independently selected from a hydrogen atom or an organic group having 1 to 10 carbon atoms.

[0014] Optionally, the organic group having the structure represented by formula (3) is derived from at least one of the dianhydride compounds represented by formula (4):

[0015]

[0016] Optionally, the organic group not having the structure represented by formula (3) is derived from at least one of the dianhydride compounds represented by formula (5):

[0017]

[0018] Optionally, the dianhydride compound having the structure represented by formula (3) accounts for 5 to 50% of the total molar amount of the dianhydride compounds, preferably 10 to 30%.

[0019] Optionally, the diamine compound A has a cyclohexane and a flexible branched chain structure with 4 or more carbon atoms.

[0020] Optionally, the diamine compound A is selected from at least one of the compounds having the structure represented by formula (6):

[0021]

[0022] The diamine compound B is selected from at least one of the compounds having the structure represented by formula (7);

[0023]

[0024] Optionally, the diamine compound A accounts for 1 to 30% of the total molar amount of the diamine compounds, preferably, the diamine compound A accounts for 5 to 20% of the total molar amount of the diamine compounds.

[0025] In formula (1), R1 and R2 each independently represent a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R1 and R2 are introduced through an esterifying reagent.

[0026] Optionally, the weight-average molecular weight of the resin precursor is 18,000 to 22,000.

[0027] In the second aspect of the present application, a method for preparing the above-mentioned resin precursor is provided. It is obtained by a polyaddition reaction of at least a combination of a dianhydride having a triptycene structure, a diamine having a cyclohexane and a flexible branched chain structure with 4 or more carbon atoms, and a diamine containing a fluorene group structure.

[0028] The method for preparing the above-mentioned resin precursor:

[0029] a When the resin precursor is selected from polyimide precursors and R1 and R2 are hydrogen atoms, the preparation method includes:

[0030] Reacting a mixture I containing a dianhydride monomer and a diamine monomer in Reaction I to obtain a polyamic acid;

[0031] b When the resin precursor is selected from polyimide precursors and R1 and R2 are not hydrogen atoms, the preparation method includes:

[0032] Reacting a mixture II containing a polyamic acid and an esterifying reagent in Reaction II to obtain a polyamic acid ester;

[0033] c When the resin precursor is selected from polyimides, the preparation method includes:

[0034] Reacting a mixture III containing a polyamic acid, a base, and an acid anhydride in Reaction III to obtain the polyimide;

[0035] Among them, the dianhydride monomer includes a dianhydride monomer having the structure shown in formula (3) and a dianhydride monomer not having the structure shown in formula (3);

[0036] The diamine monomer includes a diamine compound A having an alicyclic structure and a hydrocarbon structure with 4 or more carbon atoms and a diamine compound B having a bulky fluorene group structure.

[0037] Optionally, the dianhydride monomer having the structure shown in formula (3) is selected from at least one of the dianhydride compounds shown in formula (4).

[0038] Optionally, the dianhydride monomer not having the structure shown in formula (3) is selected from at least one of the dianhydride compounds shown in formula (5).

[0039] Optionally, the molar ratio of the dianhydride monomer to the diamine monomer is 1:0.8 to 1.0.

[0040] Optionally, the temperature of Reaction I is 20 to 80 °C, and the time of Reaction I is 1 to 24 h;

[0041] Preferably, the temperature of Reaction I is 40 to 60 °C, and the time of Reaction I is 1 to 5 h.

[0042] Specifically, the temperature of Reaction I is 50 °C, and the time of Reaction I is 2 h.

[0043] Optionally, the esterifying reagent is selected from at least one of C1-C10 alcohol compounds, N,N-dimethylformamide dimethyl acetal (DMFDMA), and N,N-dimethylformamide diethyl acetal (DMADEA).

[0044] Optionally, the C1-C10 alcohol compounds are methanol, ethanol, n-butanol, etc.

[0045] Optionally, the molar ratio of the polyamic acid to the esterifying reagent is 1:1 to 10.

[0046] Optionally, the temperature of Reaction II is 40 to 100 °C, and the time of Reaction II is 1 to 12 h;

[0047] Preferably, the temperature of Reaction II is 40 to 60 °C, and the time of Reaction II is 1 to 5 h.

[0048] Specifically, the temperature of Reaction II is 50 °C, and the time of Reaction II is 3 h.

[0049] In this application, the polyamic acid is heated in the esterifying reagent. During this process, the carboxylic acid functional group in the polyamic acid will be converted into a carboxylic acid ester group through an esterification reaction. Among them, the esterification rate of the polyamic acid is 40 to 90%.

[0050] Optionally, the base is selected from at least one of pyridine, triethylamine, and diisopropylethylamine;

[0051] The acid anhydride is selected from at least one of acetic anhydride and trifluoroacetic anhydride.

[0052] Optionally, the molar ratio of the dianhydride monomer to the base is 1:2 to 10;

[0053] The molar ratio of the dianhydride monomer to the acid anhydride is 1:2 to 10.

[0054] Optionally, the temperature of Reaction III is 20 to 100 °C, and the time of Reaction III is 10 to 40 h;

[0055] Preferably, the temperature of Reaction III is 30 to 60 °C, and the time of Reaction III is 10 to 20 h.

[0056] Optionally, the mixture I further includes a capping agent. The capping agent is used to improve the stability of the resin.

[0057] Preferably, the end-capping agent is selected from at least one of monoamines, monoanhydrides, monocarboxylic acids, monoacyl chloride compounds, and monoactive ester compounds.

[0058] In this application, the type and amount of the selected end-capping agent can be adjusted as needed. The usage methods of the end-capping agent generally include: adding the end-capping agent simultaneously with the diamine monomer and the dianhydride monomer; adding the end-capping agent after the reaction of the diamine monomer and the dianhydride monomer; adding the diamine monomer or the dianhydride monomer after reacting the end-capping agent with the dianhydride monomer or the diamine monomer.

[0059] Optionally, after the reaction, it further includes the steps of adding water to precipitate the polymer precipitate, filtering, washing, and drying.

[0060] After the reaction is completed, the reaction solution is poured into deionized water to precipitate the polymer to obtain a white precipitate. After filtering the white precipitate and washing it three times with deionized water, it is dried under vacuum at 40-100 °C for 36-120 h to obtain the resin precursor powder.

[0061] In the third aspect of this application, a resin composition is provided.

[0062] A resin composition, the resin composition contains the above-mentioned resin precursor and an organic solvent.

[0063] Optionally, the organic solvent is selected from any one or more of polar aprotic solvents, ethers, ketones, esters, alcohols, and aromatic hydrocarbons.

[0064] Optionally, the polar aprotic solvent is selected from any one or more of N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0065] Optionally, the ketones are selected from any one or more of acetone, methyl ethyl ketone, and diisobutyl ketone.

[0066] Optionally, the ethers are selected from any one or more of tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0067] Optionally, the esters are selected from any one or more of ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, and methyl lactate.

[0068] Optionally, the alcohols are selected from any one or more of diacetone alcohol and 3-methyl-3-methoxybutanol.

[0069] Optionally, the aromatic hydrocarbons are toluene and / or xylene.

[0070] Optionally, the weight ratio of the resin precursor to the organic solvent is 100:100 to 2000; preferably, the weight ratio of the resin precursor to the organic solvent is 100:150 to 500.

[0071] Optionally, the resin composition further includes an acrylate surfactant. The acrylate surfactant is used to improve the leveling property of the adhesive liquid, prevent the generation of bubbles or stripes during coating, and avoid affecting the properties of the cured film.

[0072] Optionally, the acrylate surfactant is selected from any one or more of POLYFLOW NO.7, NO.36, NO.56, NO.77, NO.90, WS, WS-314 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), SKB-FLOW SD, SL, P90, 1358, 1392, 1460D, 90D (trade names, manufactured by SKB of Korea).

[0073] Optionally, the weight ratio of the resin precursor to the acrylate surfactant is 100:0.01 to 5.

[0074] In the fourth aspect of the present application, a polyimide film is provided.

[0075] A polyimide film, which is obtained by coating and curing the above-mentioned resin composition.

[0076] In the preparation process of the polyimide film in the present application, the substrate for coating is not particularly limited, and those skilled in the art can make conventional selections. Examples include silicon wafers, aluminum sheets, silver sheets, copper sheets, copper alloy sheets, ceramic sheets, etc. Preferred are silicon wafers (such as 4-inch silicon wafers), aluminum sheets, silver sheets, and copper sheets. The specific coating method is also not particularly limited, and examples include spraying method, spin coating method, knife coating method, etc. In the actual coating operation process, due to differences in coating methods, rotation speeds, viscosities, composition components, etc., the film thickness will also vary. The spin coating method is preferred.

[0077] In the preparation process of the polyimide film in the present application, the drying method can adopt baking operations. Specifically, an oven, a heating stage, an infrared lamp, etc. can be used for baking, and the heating stage baking is preferred. Further preferably, the drying temperature is 80 - 150 °C, and the drying time is 1 - 10 min. Further preferably, the drying temperature is 100 - 130 °C, and the drying time is 2 - 5 min. After the drying operation is completed, it is naturally cooled to 25 °C, and then the thickness of the resin film layer is measured.

[0078] During the preparation of the polyimide film in this application, the temperature of the curing operation is 300 - 400 °C, preferably 350 °C. This heat treatment usually selects a staged temperature increase and maintains a certain time at different temperatures or selects a continuous temperature increase within a certain temperature range. For example, a heat treatment method of performing heat treatment for 30 minutes at 150 °C, 250 °C, and 350 °C respectively, or a method of continuously increasing the temperature from room temperature to 350 °C, etc. Inert gases such as nitrogen and argon are often used during curing. As a specific application example, first, control the oxygen content in the oven cavity to be reduced to below 50 ppm, then start heating to 150 °C and keep it constant for 30 minutes, then heat to 250 °C and keep it constant for 30 minutes, then heat to 350 °C and keep it constant for 1 hour, and then cool to room temperature to finally obtain a cured film.

[0079] In the fifth aspect of this application, there is provided an application of at least one of the above resin, the above resin composition, and the above polyimide film in the manufacture of semiconductor components.

[0080] The application of the above-mentioned resin precursor, the above-mentioned resin composition, and the above-mentioned polyimide film in the manufacture of semiconductor components.

[0081] Optionally, the semiconductor component includes the above polyimide film.

[0082] The beneficial effects that this application can produce include:

[0083] The resin precursor provided in this application is obtained by polyaddition reaction of at least one dianhydride having a triptycene structure, a diamine having a cyclohexane and a flexible branched chain structure with 4 or more carbon atoms, and a fluorene-based diamine. Since the triptycene group itself contains micropores, when introduced into the resin skeleton, it will make the resin molecular chain segments stack more loosely, enhancing the solubility of the PI resin; the composition containing this resin can obtain a polyimide film with a porous structure through thermal curing. This cured film has properties such as low dielectric constant, high Tg, high heat resistance, and high mechanical strength, and is used as a surface protective film, an interlayer dielectric or insulating layer for semiconductor components, and an insulating layer for protecting circuit board lines. Description of the Drawings

[0084] Figure 1 It is a thermogravimetric curve graph of the polyimide film obtained by curing at 350 °C for Example 1 and Comparative Example 2. Detailed Description of the Embodiments

[0085] The following details this application with reference to the embodiments, but this application is not limited to these embodiments.

[0086] Unless otherwise specified, the raw materials in the embodiments of this application are all purchased through commercial channels.

[0087] Unless otherwise specified, the test methods are all conventional methods, and the instrument settings are all the settings recommended by the manufacturer.

[0088] In the examples, the structural formulas / names of the compounds used are shown in Table 1.

[0089] Table 1

[0090]

[0091]

[0092] Synthesis Example 1

[0093] Synthesis of polyimide C-1:

[0094] Under a nitrogen stream, 24.82 g (0.08 mol) of ODPA, 7.89 g (0.02 mol) of S-1, and 100 g of N-methylpyrrolidone (NMP) were successively added to a 500 mL three-necked flask equipped with a stirrer, a dropping funnel, and a thermometer, and stirred to dissolve to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was taken, and 8.025 g (0.015 mol) of A-1, 28.53 g (0.075 mmol) of B-1, and 100 g of NMP were successively added, and stirred to dissolve to obtain a diamine solution. The diamine solution was added dropwise to the above dianhydride solution. After the addition was completed, the reaction was carried out at room temperature for 1 h, and then at 50 °C for 2 h. After the reaction was completed, 2.18 g (0.02 mol) of 3-aminophenol as a capping agent was added, and the reaction was carried out at 50 °C for 2 h. Then 22.46 g (0.22 mol) of acetic anhydride and 17.40 g (0.22 mol) of pyridine were added, and the reaction was carried out at 50 °C for 12 h.

[0095] The obtained reaction solution was added to 5 L of deionized water to precipitate a polymer precipitate. After the obtained precipitate was filtered out, it was washed three times repeatedly with deionized water and vacuum dried at 50 °C for 72 h to obtain a polymer powder, that is, polyimide C-1. The molecular weight of the polymer powder was measured by gel permeation chromatography (converted with standard polystyrene), and the weight average molecular weight (Mw) was 18,000 - 22,000.

[0096] Synthesis Example 2

[0097] Synthesis of polyimide precursor C-2:

[0098] Under a nitrogen stream, 24.82 g (0.08 mol) of ODPA, 7.89 g (0.02 mol) of S-1, and 100 g of N-methylpyrrolidone (NMP) were successively added to a 500 mL three-necked flask equipped with a stirrer, a dropping funnel, and a thermometer, and stirred to dissolve to obtain a dianhydride solution. Take another three-necked flask equipped with a stirrer, and successively add 8.025 g (0.015 mol) of A-1, 28.53 g (0.075 mmol) of B-1, and 100 g of NMP, and stir to dissolve to obtain a diamine solution. The diamine solution was added dropwise to the above dianhydride solution. After the addition was completed, the reaction was carried out at room temperature for 1 h, and then at 50 °C for 2 h. After the reaction was completed, 2.18 g (0.02 mol) of 3-aminophenol as a capping agent was added, and the reaction was carried out at 50 °C for 2 h. Then, a solution obtained by diluting 23.83 g (0.2 mol) of N,N-dimethylformamide dimethyl acetal with 45.00 g of NMP was dropped in, and after the addition was completed, the reaction was carried out at 50 °C for 3 h. After the reaction was completed, the reaction solution was poured into 3 L of deionized water, and a white precipitate of the polymer was precipitated. After filtration, it was washed three times with deionized water, placed in a vacuum oven, and dried at 80 °C for 72 h to obtain a polyimide precursor C-2. The molecular weight of the polymer powder was measured by gel permeation chromatography (GPC, Shimadzu LC-20AD) through standard polystyrene conversion, and the weight average molecular weight (Mw) was 18,000 - 22,000.

[0099] Synthesis Examples 3 - 18

[0100] The synthesis preparation methods of other resins were the same as those of Synthesis Example 1, except that the monomer compositions and ratios were different, as shown in Table 2 below.

[0101] Table 2

[0102]

[0103]

[0104] Example 1

[0105] In a three-necked flask equipped with stirring, resin C-1 (10.00 g) was dissolved in NMP (20.00 g). After the resin was fully dissolved, surfactant NO.77 (0.01 g) was added, and stirring was continued until it was completely dispersed and uniform. It was filtered through a 1.0 μm filter membrane to obtain resin composition D-1.

[0106] Examples 2 - 14, Comparative Examples 1 - 4

[0107] The preparation methods of other resin compositions were the same as those of Example 1, except that the synthesized resins were different.

[0108] The effects of the resins and resin compositions were evaluated according to the following methods, and the evaluation results are shown in Tables 3 and 4.

[0109] (1) Resin solubility

[0110] The solubility of the resin is measured by its solubility in organic solvents. Weigh 100 g of N-methylpyrrolidone (NMP), tetrahydrofuran (THF), and dimethyl sulfoxide (DMSO) into beakers respectively, and place them in a water bath to keep the temperature constant at 25°C. Continuously weigh a certain amount of resin and put it into the above solvents respectively to stir and dissolve until the solution reaches a saturated state. The total mass of the added resin is the solubility of the resin in the solvent, and the unit is recorded as g / 100 g.

[0111] (2) Film-forming property

[0112] Use a spin coater to coat the resin composition solution onto a 4-inch silicon substrate, and place it on a heating table for soft baking at 120°C for 3 minutes to obtain a resin film with a film thickness of 10 - 20 μm.

[0113] Then place it in a vacuum and oxygen-free oven (Zhenping Technology Co., Ltd., MOLZK-32D1) for heat treatment. The specific process of heat treatment is as follows: First, control the oxygen content in the oven cavity to be reduced to below 50 ppm, then start heating to 150°C and keep it constant for 30 minutes, then heat up to 250°C and keep it constant for 30 minutes, then heat up to 350°C and keep it constant for 1 hour, and then cool down to room temperature to finally obtain a cured film.

[0114] Place the silicon wafer with the resin cured film in a hydrofluoric acid solution to etch and remove the film from the silicon wafer.

[0115] The specific evaluation criteria are as follows:

[0116] "Excellent": Film formed, does not break when folded;

[0117] "Good": Film formed, partially breaks when folded;

[0118] "Poor": Unable to form a film, in a fragmented state.

[0119] In addition, when the film-forming property is "poor", it is impossible to conduct tests on the dielectric constant, glass transition temperature, and elongation at break.

[0120] (2) Dielectric constant

[0121] Refer to the national standard GB / T 31838.6-2021 Dielectric and resistive properties of solid insulating materials. Use a DMS2000 high and low temperature dielectric impedance temperature spectrum analyzer to measure the dielectric constant of the obtained cured film at 25°C, and record the value at a frequency of 1 MHz.

[0122] (3) Glass transition temperature test

[0123] Place the silicon wafer with the cured film in a hydrofluoric acid solution to etch and remove the film from the silicon wafer. Use a mold to cut the obtained cured film into sample strips that meet the test requirements (length < 3 cm, width < 8 mm).

[0124] Refer to the national standard GB / T 36800.2-2018 Plastics - Thermomechanical analysis (TMA) - Part 2: Determination of linear thermal expansion coefficient and glass transition temperature, and use a thermomechanical analyzer TMA 450 (TA Instruments, USA) to test the glass transition temperature and thermal expansion coefficient (temperature range 30 - 150 °C).

[0125] (4) Heat resistance test

[0126] Generally, the 5% thermal weight loss temperature is used to measure the heat resistance of the material. Fill 10 mg of different cured films into aluminum standard containers respectively, and use a thermogravimetric analyzer (model: TGA55, manufacturer: TA Instruments) for determination. Test conditions: Heat from room temperature to 600 °C at a heating rate of 10 °C / min.

[0127] Among them, Figure 1 Figure 14 is the thermogravimetric curve of the polyimide film obtained by curing at 350 °C in Example 1 and Comparative Example 2.

[0128] (5) Elongation at break test

[0129] Use a dynamic thermomechanical analyzer DMA850 (TA Instruments, USA) to test the elongation at break of the sample strips. Tensile force range 0 - 18 N, rate: 3 N / min; temperature range: 30 - 400 °C, rate: 3 °C / min.

[0130] Table 3

[0131]

[0132] Table 4

[0133]

[0134]

[0135] From the solubility data of the resins in Table 3 in NMP, THF, and DMSO, it can be seen that the introduction of the triptycene structure into the resin backbone can significantly enhance the solubility of the PI resin; from the evaluation data of the cured films of each resin composition in Table 4, the cured film of the resin containing the triptycene structure has a low dielectric constant. In particular, by comparing Example 1 with Comparative Examples 1 and 4, it can be seen that the introduction of the triptycene structure can significantly reduce the dielectric constant of the cured film. By comparing Example 1 with Comparative Examples 2 and 3, it can be seen that the introduction of diamines containing a cyclohexane and a flexible branched chain structure with 4 or more carbon atoms can significantly increase the elongation at break of the resin cured film, but it will cause a decrease in Tg and thermal weight loss. The composition composed of a resin having a triptycene structure, a cyclohexane and a flexible branched chain structure with 4 or more carbon atoms, and a fluorene structure is thermally cured to obtain a porous polyimide film, which has properties such as low dielectric property, high Tg, high heat resistance, and high mechanical strength, and is used for the surface protective film of semiconductor components, the interlayer dielectric or insulating layer, and the insulating layer for protecting the circuit board lines.

[0136] As described above, only several embodiments of the present application are provided, and no any form of limitation is imposed on the present application. Although the present application is disclosed with preferred embodiments as above, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, makes some changes or modifications by using the disclosed technical content, which are all equivalent to equivalent embodiments and all fall within the scope of the technical solution.

Claims

1. A resin precursor, characterized in that, The resin precursor is selected from at least one of a polyimide precursor and a polyimide; The polyimide precursor is a polymer having a structural unit represented by the following formula (1), and the polyimide is a polymer having a structural unit represented by the following formula (2): X1 and X2 are each independently selected from at least one organic group containing at least one structure represented by the formula (3) and simultaneously containing at least one organic group not having the structure represented by the formula (3); Y1 and Y2 are each independently selected from derivatives obtained by removing terminal amino groups from diamine compounds, and the diamine compounds include diamine compound A having an alicyclic structure and a hydrocarbon structure with 4 or more carbon atoms and diamine compound B having a bulky fluorene group structure; R1, R2, R3, and R4 are each independently selected from a hydrogen atom or an organic group having 1 to 10 carbon atoms.

2. The resin precursor according to claim 1, wherein The organic group having the structure represented by the formula (3) is derived from at least one of the dianhydride compounds represented by the formula (4): Preferably, the organic group not having the structure represented by the formula (3) is derived from at least one of the dianhydride compounds represented by the formula (5): Preferably, the dianhydride compound having the structure represented by the formula (3) accounts for 5 to 50% of the total molar amount of the dianhydride compounds, preferably 10 to 30%; Preferably, the diamine compound A has a cyclohexane and a flexible branched chain structure with 4 or more carbon atoms; Preferably, the diamine compound A is selected from at least one of the compounds having the structure represented by the formula (6): The diamine compound B is selected from at least one of the compounds having the structure represented by the formula (7); Preferably, the diamine compound A accounts for 1 to 30% of the total molar amount of the diamine compounds, and preferably, the diamine compound A accounts for 5 to 20% of the total molar amount of the diamine compounds.

3. The resin precursor according to claim 1, wherein the resin precursor has a weight average molecular weight of 18,000 to 22,000.

4. A method for preparing the resin precursor according to any one of claims 1 to 3, characterized in that a When the resin precursor is selected from a polyimide precursor and R1 and R2 are hydrogen atoms, the preparation method includes: Reacting a mixture I containing a dianhydride monomer and a diamine monomer in reaction I to obtain a polyamic acid; b When the resin precursor is selected from a polyimide precursor and R1 and R2 are not hydrogen atoms, the preparation method includes: Reacting a mixture II containing a polyamic acid and an esterifying reagent in reaction II to obtain a polyamic acid ester; c When the resin precursor is selected from a polyimide, the preparation method includes: Reacting a mixture III containing a polyamic acid, a base, and an acid anhydride in reaction III to obtain the polyimide; wherein the dianhydride monomer includes a dianhydride monomer having the structure represented by the formula (3) and a dianhydride monomer not having the structure represented by the formula (3); The diamine monomer includes diamine compound A having an alicyclic structure and a hydrocarbon structure with 4 or more carbon atoms and diamine compound B having a bulky fluorene group structure.

5. The preparation method according to claim 4, wherein the dianhydride monomer having the structure represented by the formula (3) is selected from at least one of the dianhydride compounds represented by the formula (4); Preferably, the dianhydride monomer not having the structure shown in formula (3) is selected from at least one of the dianhydride compounds shown in formula (5); Preferably, the molar ratio of the dianhydride monomer to the diamine monomer is 1:0.8 - 1.0; Preferably, the temperature of reaction I is 20 - 80 °C, and the time of reaction I is 1 - 24 h; Preferably, the temperature of reaction I is 40 - 60 °C, and the time of reaction I is 1 - 5 h; Preferably, the esterifying reagent is selected from at least one of C1-C10 alcohol compounds, N,N-dimethylformamide dimethyl acetal, and N,N-dimethylformamide dimethyl ethyl acetal; Preferably, the molar ratio of the polyamic acid to the esterifying reagent is 1:1 - 10; Preferably, the temperature of reaction II is 40 - 100 °C, and the time of reaction II is 1 - 12 h; Preferably, the temperature of reaction II is 40 - 60 °C, and the time of reaction II is 1 - 5 h; Preferably, the base is selected from at least one of pyridine, triethylamine, and diisopropylethylamine; The acid anhydride is selected from at least one of acetic anhydride and trifluoroacetic anhydride; Preferably, the molar ratio of the dianhydride monomer to the base is 1:2 - 10; The molar ratio of the dianhydride monomer to the acid anhydride is 1:2 - 10; Preferably, the temperature of reaction III is 20 - 100 °C, and the time of reaction III is 10 - 40 h; Preferably, the temperature of reaction III is 30 - 60 °C, and the time of reaction III is 10 - 20 h.

6. The preparation method according to claim 4, characterized in that the mixture I further comprises a capping agent; Preferably, the capping agent is selected from at least one of monoamines, monoanhydrides, monocarboxylic acids, monochloroacyl compounds, and monoactive ester compounds.

7. A resin composition, characterized in that the resin composition contains the resin precursor according to any one of claims 1 - 3 and an organic solvent.

8. The resin composition according to claim 7, wherein The weight ratio of the resin precursor to the organic solvent is 100:100 - 2000; Preferably, the weight ratio of the resin precursor to the organic solvent is 100:150 - 500; Preferably, the resin composition further comprises an acrylate surfactant; Preferably, the weight ratio of the resin precursor to the acrylate surfactant is 100:0.01 - 5.

9. A polyimide film, characterized in that, The polyimide film is obtained by coating and curing the resin composition according to any one of claims 7 - 8.

10. Use of the resin precursor according to any one of claims 1 - 3, the resin composition according to any one of claims 7 - 8, and the polyimide film according to claim 9 in manufacturing semiconductor elements.

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