Polyimide precursor, preparation method thereof and polyimide precursor composition

Abstract

The embodiment of the invention discloses a polyimide precursor, a preparation method thereof and a polyimide precursor composition, and belongs to the technical field of polyimide, and the structural formula of the polyimide precursor is as shown in the formula I. The polyimide precursor provided by the embodiment of the invention can realize low shrinkage rate, low dielectric loss and low dielectric constant under low-temperature curing, and meets performance requirements.

Description

Technical Field

[0001] This application relates to the field of polyimide technology, specifically to a polyimide precursor and its preparation method, and a polyimide precursor composition. Background Technology

[0002] Due to its excellent mechanical and thermal properties, negative photosensitive polyimide has become one of the important raw materials in chip manufacturing and packaging. With the development of microelectronics technology towards higher integration, and the resulting development of technologies such as fan-out wafer-level packaging and 2.5D packaging, negative photosensitive polyimide materials also need to meet requirements such as low dielectric constant, low coefficient of thermal expansion, high flatness, and low curing temperature. Summary of the Invention

[0003] This application provides a polyimide precursor and its preparation method, as well as a polyimide precursor composition, aiming to solve the problems of high shrinkage rate, high dielectric loss, and high dielectric constant of polyimide during low-temperature curing.

[0004] According to a first aspect of this application, a polyimide precursor is provided, the polyimide precursor having the structural formula shown in Formula I: Formula I; in, Derived from dianhydride monomers; It is derived from diamine monomers; R1 and R2 are independently derived from alcohols, including styrene-containing alcohols; The weight-average molecular weight of the polyimide precursor is 10,000-50,000.

[0005] Optionally, the dianhydride monomer contains cyclic aliphatic groups and / or aromatic groups, and the dianhydride monomer has 6-30 carbon atoms; And / or, the dianhydride monomers include at least one of 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, m-terphenyl 3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl 3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride; And / or, the diamine monomer contains cyclic aliphatic groups and / or aromatic groups, and the dianhydride monomer has 6-30 carbon atoms; And / or, the diamine monomer includes at least one of 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide; And / or, the alcohol compounds also include at least one of alcohols containing methacrylate groups and alcohols without free radical polymerization capability, wherein the mass percentage of alcohols containing methacrylate groups is ≤50%, the mass percentage of alcohols containing styrene groups is 50%-100%, and the mass percentage of alcohols without free radical polymerization capability is ≤20%.

[0006] Optionally, the functionality of styrene-containing alcohols, methacrylate-containing alcohols, and alcohols without free radical polymerization ability is 1. And / or, alcohols containing methacrylate groups include hydroxyethyl methacrylate; And / or, styrene-containing alcohols include at least one of 4-vinylphenylmethanol, 4-vinylphenylethanol, and 4-vinylphenylpropanol; And / or, alcohols without free radical polymerization ability include at least one of ethanol, propanol, n-butanol and triethylene glycol monomethyl ether.

[0007] Optionally, the polyimide precursor has the structural formula shown in Formula II: Formula II; R3 and R4 are each independently selected from alkyl groups having 1-3 carbon atoms, and R5 is selected from substituted or unsubstituted alkyl groups. and One of them.

[0008] Alternatively, the polyimide precursor may have a structural formula as shown in any one of Formulas III-IV: Formula III; Formula IV.

[0009] According to a second aspect of this application, a method for preparing a polyimide precursor is provided, for preparing the polyimide precursor as described above, comprising: The dianhydride monomer is added to the first solvent, followed by the addition of an alcohol compound and an organic base. After reaction, a first mixture is obtained; wherein the alcohol compound includes alcohols containing styrene groups.

[0010] A condensing agent is added to the first mixture, and after reaction, a second mixture is obtained. The diamine monomer is added to a third solvent to obtain a diamine monomer solution. The diamine monomer solution is then added to a second mixture, and after reaction, a third mixture is obtained. The third mixture was filtered and dried to obtain the polyimide precursor.

[0011] Optionally, the molar ratio of dianhydride monomer, alcohol compound and diamine monomer is 1:(0.9-1.5):(0.8-1).

[0012] According to a third aspect of this application, a polyimide precursor composition is provided, comprising the polyimide precursor as described above, and / or comprising the polyimide precursor prepared by the method described above for preparing polyimide.

[0013] Optionally, the polyimide precursor composition further includes a crosslinking agent, a photoinitiator, a thermal alkali-generating agent, and a fourth solvent.

[0014] Optionally, the mass ratio of the polyimide precursor, crosslinking agent, photoinitiator, thermal alkali-generating agent, and third solvent is 100:(5-20):(1-5):(0.2-4):(100-300); And / or, the crosslinking agent includes at least one of diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and tricyclo[5.2.1.02,6]decanediethanol diacrylate; And / or, the photoinitiator includes at least one of oxime ester photoinitiators, phosphonium oxide photoinitiators, and alkyl aryl ketone photoinitiators; And / or, the heat-generating alkali agent includes at least one of DBU-phthalate, DBU-phenol salt, DBU-p-toluenesulfonate, bis(2-morpholinylethyl) ether and 1-N-BOC-morpholine; And / or, the third solvent includes at least one of N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, and ethyl lactate.

[0015] The polyimide precursor provided in this application has the structural formula shown in Formula I. It is derived from alcohol compounds, including styrene-containing alcohols, by using graft groups derived from alcohols. This significantly reduces the polarity of the polyimide precursor, decreasing the number of dipoles within the cured material and thus improving dielectric properties. Furthermore, the graft groups formed by styrene-containing alcohols possess excellent free radical polymerization activity, which helps increase the degree of crosslinking during curing. This reduces the content of components that need to be "vaporized" and "volatiled" in subsequent curing processes, lowering the generation of volatiles during curing. This, in turn, helps mitigate the increased shrinkage and decreased flatness caused by the escape of gaseous components. In other words, the polyimide precursor provided in this application can achieve low shrinkage, low dielectric loss, and low dielectric constant under low-temperature curing, meeting performance requirements. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0017] Figure 1 This is the 1H NMR spectrum of the A1 polyimide precursor in the embodiments of this application; Figure 2 This is the 1H NMR spectrum of the A2 polyimide precursor in the embodiments of this application; Figure 3 This is the 1H NMR spectrum of the A3 polyimide precursor in the embodiments of this application; Figure 4 This is the 1H NMR spectrum of the A4 polyimide precursor in the embodiments of this application; Figure 5 This is the 1H NMR spectrum of the A5 polyimide precursor in the embodiments of this application; Figure 6 This is the 1H NMR spectrum of the B1 polyimide precursor in the embodiments of this application; Figure 7 This is the 1H NMR spectrum of the B2 polyimide precursor in the embodiments of this application. Detailed Implementation

[0018] The technical solutions in the embodiments of this application are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0019] This application provides a polyimide precursor and its preparation method, a polyimide precursor composition and its application. These are described in detail below. It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of the embodiments. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative and do not impose numerical requirements or establish an order. Various embodiments of this application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that a range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a range of numbers is specified in this document, it means including any referenced numbers (fractions or integers) within the range referred to.

[0020] In a first aspect, embodiments of this application provide a polyimide precursor, the structural formula of which is shown in Formula I: Formula I; in, Derived from dianhydride monomers; It is derived from diamine monomers; R1 and R2 are independently derived from alcohols, including styrene-containing alcohols; The weight-average molecular weight of the polyimide precursor is 10,000-50,000.

[0021] Polyimide materials play a crucial role in chip packaging, providing insulation, isolation, support, and protection. To ensure these insulation and isolation functions, the cured polyimide film must possess excellent dielectric properties, namely low dielectric loss (Df) and low dielectric constant (Dk). Excellent dielectric properties can accelerate signal transmission, reduce parasitic capacitance and crosstalk, and improve the long-term reliability of devices. With the development trends of high-frequency, high-speed, high-integration, and miniaturized integrated circuits, developing polyimide materials and their resin compositions with low dielectric constant and low dielectric loss is one of the core technological directions. Low-temperature curing polyimide materials can effectively reduce the thermal budget of the process, narrow the difference in thermal expansion properties between them and copper wiring layers, thereby reducing wafer warpage and preventing chip stress concentration leading to cracking. This is also a key technological challenge in the field of next-generation chip packaging. Meanwhile, as RDL structures develop towards more layers (structures such as 3p3m, 4p4m, and 5p5m have been reported), there is also a demand for low curing shrinkage rates in polyimide curing films to achieve high flatness. This can avoid deterioration in photolithography accuracy and improve the overall stability of the process.

[0022] In related technologies, the grafting groups in polyimide precursors are usually obtained from hydroxyethyl methacrylate (HEMA) containing ester bonds, resulting in a large number of polar ester groups. This leads to poor dielectric properties of the cured polyimide precursor after curing, and large-volume ester side chains will leave during the curing process, resulting in high curing shrinkage and poor flatness after curing.

[0023] The polyimide precursor provided in this application has the structural formula shown in Formula I. By deriving its grafting groups from alcohol compounds, including styrene-containing alcohols, the polarity of the polyimide precursor can be significantly reduced, decreasing the number of dipoles within the cured material and thus improving dielectric properties. Furthermore, the grafting groups formed by styrene-containing alcohols possess excellent free radical polymerization activity, which helps to increase the degree of crosslinking during the curing process. This reduces the content of components that need to be "vaporized" and "volatiled" in subsequent curing processes, lowering the generation of volatiles during curing. This, in turn, helps to mitigate the increased shrinkage and reduced flatness caused by the escape of gaseous components. In other words, the polyimide precursor provided in this application can achieve low shrinkage, low dielectric loss, and low dielectric constant under low-temperature curing, meeting performance requirements.

[0024] By using the polyimide precursor provided in the embodiments of this application, the requirements of dielectric loss <0.015, dielectric constant <3.0, and curing shrinkage <15% can be achieved, thereby meeting the performance requirements.

[0025] For example, the weight-average molecular weight of the polyimide precursor can be 10,000, 11,000, 12,000, 13,000, 14,000, 15,000, 16,000, 17,000, 18,000, 19,000, 20,000, 21,000, 22,000, 23,000, 24,000, 25,000, 26,000, 27,000, or 28,000. 0, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, or 50000.

[0026] In some embodiments, the dianhydride monomer contains cyclic aliphatic groups and / or aromatic groups, and the dianhydride monomer has 6-30 carbon atoms.

[0027] By using dianhydride monomers that meet the above conditions, it helps to enhance the mechanical properties of polyimide precursors, balance flexibility and rigidity, and have good thermal stability. Cyclic aliphatic and aromatic groups help to reduce the dielectric constant and dielectric loss.

[0028] In some embodiments, the dianhydride monomer includes at least one selected from 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, m-terphenyl 3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl 3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride.

[0029] The aforementioned dianhydride monomers are all commercially available dianhydride monomers in the field. The materials are readily available and have low cost. Different dianhydride monomers have different molecular structures, which can flexibly adjust the structure of the polyimide molecular backbone, thereby controlling the various properties of the polyimide precursor. Those skilled in the art can select appropriate dianhydride monomers according to actual needs.

[0030] In some embodiments, the diamine monomer contains cyclic aliphatic groups and / or aromatic groups, and the dianhydride monomer has 6-30 carbon atoms.

[0031] Similarly, by satisfying the above conditions, the mechanical properties of polyimide precursors can be enhanced, balancing flexibility and rigidity, and exhibiting good thermal stability. Cyclic aliphatic and aromatic groups help reduce the dielectric constant and dielectric loss.

[0032] In some embodiments, the diamine monomer includes at least one selected from 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0033] Similarly, the diamine monomers mentioned above are all commercially available diamine monomers in the field. The materials are readily available and have low cost. Different diamine monomers have different molecular structures, which can flexibly adjust the structure of the polyimide molecular backbone, thereby controlling the various properties of the polyimide precursor. Those skilled in the art can select appropriate diamine monomers according to actual needs.

[0034] In some embodiments, the alcohol compound further includes at least one of an alcohol containing a methacrylate group and an alcohol without free radical polymerization capability, wherein the alcohol containing a methacrylate group has a mass percentage of ≤50%, the alcohol containing a styrene group has a mass percentage of 50%-100%, and the alcohol without free radical polymerization capability has a mass percentage of ≤20%.

[0035] In other words, the predominance of vinyl alcohols at low temperatures results in lower graft group morphology in the polyimide precursor, reducing the number of internal dipoles and effectively lowering dielectric loss and dielectric constant. It also provides good free radical polymerization capability, ensuring reduced feed conversion ratio, minimizing shrinkage caused by gaseous component escape, and lowering curing shrinkage to meet various performance requirements. Conversely, alcohols containing methacrylate groups and alcohols without free radical polymerization capability can adjust the dielectric properties, crosslinking degree, curing properties, and process adaptability of the polyimide precursor.

[0036] In some embodiments, the functionality of the styrene-containing alcohol, the methacrylate-containing alcohol, and the alcohol without free radical polymerization capability is 1.

[0037] By setting its functionality to 1, side reactions can be reduced, grafting effect can be guaranteed, and preparation process can be simplified.

[0038] In some embodiments, alcohols containing methacrylate groups include hydroxyethyl methacrylate (HEMA).

[0039] The carbon-carbon double bonds in hydroxyethyl methacrylate (HME) exhibit high reactivity, enabling them to participate in free radical polymerization, form cross-linked networks, and promote curing. Furthermore, HME demonstrates good compatibility, ensuring uniformity and stability of the reaction. The hydroxyl and ester groups in HME can also improve the properties of polyimide precursors.

[0040] In some embodiments, the styrene-containing alcohol includes at least one of 4-vinylphenylmethanol, 4-vinylphenylethanol, and 4-vinylphenylpropanol.

[0041] 4-Vinylphenylmethanol, 4-Vinylphenylethanol, and 4-Vinylphenylpropanol all contain styrene groups, have low polarity, and exhibit good free radical polymerization activity. They can reduce polarity while ensuring the degree of crosslinking, enabling polyimide precursors to achieve low shrinkage, low dielectric loss, and low dielectric constant under low-temperature curing, thus meeting performance requirements.

[0042] In some embodiments, alcohols without free radical polymerization capability include at least one of ethanol, propanol, n-butanol, and triethylene glycol monomethyl ether.

[0043] None of the above compounds have free radical polymerization ability, but they can adjust the flexibility of polyimide precursors, regulate the degree of crosslinking, and affect thermal properties.

[0044] In some embodiments, the polyimide precursor has the structural formula shown in Formula II: Formula II; R3 and R4 are each independently selected from alkyl groups having 1-3 carbon atoms, and R5 is selected from substituted or unsubstituted alkyl groups. and One of them.

[0045] That is, in the polyimide precursor provided in the embodiments of this application, the grafting group includes styrene group, which can take advantage of its low polarity and high free radical polymerization activity to reduce the generation of volatiles during the curing process and improve dielectric properties while ensuring the degree of crosslinking.

[0046] In some embodiments, the polyimide precursor has a structural formula as shown in any one of Formulas III-IV: Formula III; Formula IV.

[0047] The polyimide precursor provided in this application embodiment has a grafted group of vinylphenyl group, which can significantly reduce the polarity of the polyimide precursor while ensuring the degree of crosslinking in the later curing process, reduce the number of dipoles inside the cured material, thereby improving the dielectric properties, and can reduce the content of components that need to be "vaporized" and "volatile" in the subsequent curing process, reducing the generation of volatiles during the curing process, thereby helping to improve the increase in shrinkage and decrease in flatness caused by the escape of gas components.

[0048] Secondly, embodiments of this application provide a method for preparing a polyimide precursor, used to prepare the polyimide precursor as described above, comprising: The dianhydride monomer is added to the first solvent, followed by the addition of an alcohol compound and an organic base. After the reaction, the first mixture is obtained. A condensing agent is added to the first mixture, and after reaction, a second mixture is obtained. The diamine monomer is added to the second solvent to obtain a diamine monomer solution. The diamine monomer solution is then added to the second mixture, and after reaction, a third mixture is obtained. The third mixture was filtered and dried to obtain the polyimide precursor.

[0049] The method for preparing the polyimide precursor provided in this application has all the beneficial effects of the polyimide precursor as described above, and will not be repeated here. Furthermore, the method for preparing the polyimide precursor provided in this application is simple, uses mild reaction conditions, and uses readily available raw materials, which helps reduce preparation costs and is suitable for large-scale production applications.

[0050] It is understood that the preparation method of the polyimide precursor provided in the embodiments of this application is not intended to limit the polyimide precursor described above. Without creative effort, those skilled in the art can also use other preparation methods to obtain the polyimide precursor provided in the embodiments of this application.

[0051] For example, the organic base may be at least one of pyridine, triethylamine, N,N-diisopropylethylamine, 1,8-diazabicycloundec-7-ene, 1,4-diazabicyclo[2,2,2]octane and pyrrole.

[0052] In some embodiments, the molar ratio of dianhydride monomer, alcohol compound and diamine monomer is 1:(0.9-1.5):(0.8-1).

[0053] By keeping the molar ratio of dianhydride monomer, alcohol compound, and diamine monomer within the above range, the reaction can proceed in an orderly manner, ensuring the efficiency of the polycondensation reaction and simplifying the difficulty of process control.

[0054] For example, the first solvent, the second solvent, and the third solvent can all be γ-butyrolactone (GBL). GBL is a polar aprotic solvent that can effectively dissolve the raw materials in the process of preparing polyimide precursors. Its molecular structure is stable, which can reduce the generation of side reactions and ensure the stability of the reaction process.

[0055] Taking the polyimide precursor shown in Formula III as an example, the preparation method can be as follows: (1) 103g of 4,4'-oxobisphthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 89g of (4-vinylphenyl)methanol was added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 67g of 4,4'-diaminodiphenyl ether (ODA) was added to 300 mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an ODA solution. The ODA solution was then added to the second mixture and reacted for 6 hours. After the reaction was completed, 20 mL of ethanol was added as a quencher and reacted for 2 hours to obtain the third mixture. (4) The third mixture is filtered, the filtrate is collected, methanol is added to the filtrate to precipitate lumpy solids, the lumpy solids are collected and refrigerated for 12 hours, then 800 mL of GBL is added and stirred. After it is completely dissolved, water is added dropwise to precipitate white flocculent substances. After filtration and drying, the corresponding polyimide precursor is obtained with a weight-average molecular weight of about 20,000.

[0056] Taking the polyimide precursor shown in Formula IV as an example, the preparation method can be as follows: (1) 103g of 4,4'-oxobisphthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 89g of (4-vinylphenyl)methanol was added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 71 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB) was added to 300 mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an ODA solution. The ODA solution was then added to the second mixture and reacted for 6 h. After the reaction was completed, 20 mL of ethanol was added as a quencher and reacted for 2 h to obtain the third mixture. (4) The third mixture is filtered, the filtrate is collected, methanol is added to the filtrate to precipitate blocky solids, the blocky solids are collected and refrigerated for 12 hours, then 800 mL of GBL is added and stirred. After it is completely dissolved, water is added dropwise to precipitate white flocculent substances. After filtration and drying, the corresponding polyimide precursor is obtained with a weight-average molecular weight of about 21,000.

[0057] Thirdly, embodiments of this application provide a polyimide precursor composition, comprising the polyimide precursor as described above, and / or comprising the polyimide precursor prepared by the method described above for preparing polyimide.

[0058] The polyimide precursor composition provided in this application has all the beneficial effects of the polyimide precursor as described above, which will not be repeated here.

[0059] In some embodiments, the polyimide precursor composition further includes a crosslinking agent, a photoinitiator, a thermal alkali-generating agent, and a third solvent.

[0060] Crosslinking agents can form a three-dimensional network structure of polyimide precursors through chemical bonding, ensuring the mechanical and heat resistance properties of the cured product. Photoinitiators can generate active free radicals under specific light conditions, initiating crosslinking reactions and achieving photosensitive curing. Thermally generated alkali agents can produce alkaline substances upon heating and decomposition, accelerating the crosslinking reaction and ensuring crosslinking and curing efficiency.

[0061] In some embodiments, the mass ratio of polyimide precursor, crosslinking agent, photoinitiator, thermal alkali-generating agent and third solvent is 100:(5-20):(1-5):(0.2-4):(100-300).

[0062] By ensuring that the mass ratios of the components are within the above range, excellent mechanical properties, thermal stability, suitable dielectric properties, and process compatibility can be guaranteed.

[0063] In some embodiments, the crosslinking agent includes at least one of diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and tricyclo[5.2.1.02,6]decanediethanol diacrylate.

[0064] The aforementioned crosslinking agent enables the polyimide precursor assembly to crosslink and form a three-dimensional network structure, improving mechanical properties, thermal stability, and chemical stability, while also regulating flexibility. This results in a cured product with excellent mechanical properties, thermal stability, and chemical stability, meeting application requirements.

[0065] In some embodiments, the photoinitiator includes at least one of oxime ester photoinitiators, phosphonooxy photoinitiators, and alkylaryl ketone photoinitiators.

[0066] Oxime ester photoinitiators possess deep curing capabilities, which helps improve curing uniformity and reduces oxygen inhibition, thereby increasing curing efficiency. Phosphine oxide photoinitiators have broad absorption spectra and high activity, expanding the application range of photocuring technology and improving curing efficiency. Alkyl aryl ketone photoinitiators are low-cost, have good solubility, and help form stable systems, ensuring curing efficiency and reducing costs.

[0067] In some embodiments, the thermal alkali-generating agent includes at least one of DBU-phthalate, DBU-phenol salt, DBU-p-toluenesulfonate, bis(2-morpholinylethyl) ether, and 1-N-BOC-morpholine.

[0068] The aforementioned heat-generating alkali agent can release alkali under suitable temperature conditions, promoting the curing of polyimide precursors.

[0069] In some embodiments, the third solvent includes at least one of N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, and ethyl lactate.

[0070] N-Methylpyrrolidone (NMP) is a highly polar aprotic solvent with strong dissolving power. It is also chemically stable and temperature resistant, ensuring process reliability. Ethyl lactate (EL) has broad-spectrum solubility, guaranteeing effective dissolution and dispersion.

[0071] Fourthly, embodiments of this application also provide the application of the polyimide precursors as described above, and / or the polyimide precursor compositions as described above, in the field of electronic materials.

[0072] The applications provided in this application have all the beneficial effects of the polyimide precursors described above, and will not be repeated here.

[0073] For example, the polyimide precursor composition provided in the embodiments of this application can be applied to the field of chip packaging technology, which can achieve low-temperature curing, ensure low dielectric loss, low dielectric constant and low shrinkage, and significantly improve packaging quality and stability.

[0074] The embodiments of this application are further illustrated below with reference to specific examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. Experimental methods in the following embodiments that do not specify specific conditions are generally performed according to the conditions recommended by the manufacturer.

[0075] Polyimide precursors A1, A2, A3, A4, A5, B1, and B2 were prepared respectively.

[0076] The preparation method of polyimide precursor A1 is as follows: (1) 103g of 4,4'-oxobisphthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 89g of (4-vinylphenyl)methanol was added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 67g of 4,4'-diaminodiphenyl ether (ODA) was added to 300 mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an ODA solution. The ODA solution was then added to the second mixture and reacted for 6 hours. After the reaction was completed, 20 mL of ethanol was added as a quencher and reacted for 2 hours to obtain the third mixture. (4) The third mixture was filtered, the filtrate was collected, methanol was added to the filtrate to precipitate lumpy solids, the lumpy solids were collected and refrigerated for 12 hours, then 800 mL of GBL was added and stirred. After complete dissolution, water was added dropwise to precipitate white flocculent substances. The mixture was filtered and dried to obtain polyimide precursor A1, with a weight-average molecular weight of approximately 20,000. The structural formula is shown in Figure A1, and its proton NMR spectrum is shown in Figure A1. Figure 1 As shown: A1; In A1, all R bases are .

[0077] The preparation method of polyimide precursor A2 is as follows: (1) 103g of 4,4'-oxophthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 87g of hydroxyethyl methacrylate (HEMA) was added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 67g of 4,4'-diaminodiphenyl ether (ODA) was added to 300 mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an ODA solution. The ODA solution was then added to the second mixture and reacted for 6 hours. After the reaction was completed, 20 mL of ethanol was added as a quencher and reacted for 2 hours to obtain the third mixture. (4) The third mixture was filtered, the filtrate was collected, methanol was added to the filtrate to precipitate lumpy solids, the lumpy solids were collected and refrigerated for 12 hours, then 800 mL of GBL was added and stirred. After complete dissolution, water was added dropwise to precipitate white flocculent substances. The mixture was filtered and dried to obtain polyimide precursor A2, with a weight-average molecular weight of approximately 21,000. The structural formula is shown in Figure A2, and its proton NMR spectrum is shown in Figure A2. Figure 2 As shown: A2; In A2, all R bases are .

[0078] The preparation method of polyimide precursor A3 is as follows: (1) 103g of 4,4'-oxophthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 22.3g of (4-vinylphenyl)methanol and 65.2g of hydroxyethyl methacrylate (HEMA) were added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 67g of 4,4'-diaminodiphenyl ether (ODA) was added to 300 mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an ODA solution. The ODA solution was then added to the second mixture and reacted for 6 hours. After the reaction was completed, 20 mL of ethanol was added as a quencher and reacted for 2 hours to obtain the third mixture. (4) The third mixture was filtered, the filtrate was collected, methanol was added to the filtrate to precipitate lumpy solids, the lumpy solids were collected and refrigerated for 12 hours, then 800 mL of GBL was added and stirred. After complete dissolution, water was added dropwise to precipitate white flocculent substances. The mixture was filtered and dried to obtain polyimide precursor A3, with a weight-average molecular weight of approximately 20,000. The structural formula is shown in Figure A3, and its proton NMR spectrum is shown in Figure A3. Figure 3 As shown: A3; In A3, the R basis is or ,and and The molar ratio is 3:1.

[0079] The preparation method of polyimide precursor A4 is as follows: (1) 103g of 4,4'-oxophthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 44.5g of (4-vinylphenyl)methanol and 43.5g of hydroxyethyl methacrylate (HEMA) were added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 67g of 4,4'-diaminodiphenyl ether (ODA) was added to 300 mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an ODA solution. The ODA solution was then added to the second mixture and reacted for 6 hours. After the reaction was completed, 20 mL of ethanol was added as a quencher and reacted for 2 hours to obtain the third mixture. (4) The third mixture was filtered, the filtrate was collected, methanol was added to the filtrate to precipitate lumpy solids, the lumpy solids were collected and refrigerated for 12 hours, then 800 mL of GBL was added and stirred. After complete dissolution, water was added dropwise to precipitate white flocculent substances. The mixture was filtered and dried to obtain polyimide precursor A4, with a weight-average molecular weight of approximately 20,000. The structural formula is shown in Figure A4, and its proton NMR spectrum is shown in Figure A4. Figure 4 As shown: A4; In A4, the R basis is or ,and and The molar ratio is 1:1.

[0080] The preparation method of polyimide precursor A5 is as follows: (1) 103g of 4,4'-oxophthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 66.7g of (4-vinylphenyl)methanol and 22.2g of hydroxyethyl methacrylate (HEMA) were added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 67g of 4,4'-diaminodiphenyl ether (ODA) was added to 300 mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an ODA solution. The ODA solution was then added to the second mixture and reacted for 6 hours. After the reaction was completed, 20 mL of ethanol was added as a quencher and reacted for 2 hours to obtain the third mixture. (4) The third mixture was filtered, the filtrate was collected, methanol was added to the filtrate to precipitate lumpy solids, the lumpy solids were collected and refrigerated for 12 hours, then 800 mL of GBL was added and stirred. After complete dissolution, water was added dropwise to precipitate white flocculent substances. The mixture was filtered and dried to obtain polyimide precursor A4, with a weight-average molecular weight of approximately 20,000. Its structural formula is shown in A5, and its proton NMR spectrum is shown in [image missing]. Figure 5 As shown: A5; In A5, the R basis is or ,and and The molar ratio is 1:3.

[0081] The preparation method of polyimide precursor B1 is as follows: (1) 103g of 4,4'-oxobisphthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 89g of (4-vinylphenyl)methanol was added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 71g of 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB) was added to 300mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an mTB solution. The mTB solution was then added to the second mixture and reacted for 6h. After the reaction was completed, 20mL of ethanol was added as a quencher and reacted for 2h to obtain the third mixture. (4) The third mixture was filtered, the filtrate was collected, methanol was added to the filtrate to precipitate lumpy solids, the lumpy solids were collected and refrigerated for 12 hours, then 800 mL of GBL was added and stirred. After complete dissolution, water was added dropwise to precipitate white flocculent substances. The mixture was filtered and dried to obtain polyimide precursor B1, with a weight-average molecular weight of approximately 21,000. The structural formula is shown in Figure B1, and its proton NMR spectrum is shown in Figure B1. Figure 6 As shown: B1.

[0082] The preparation method of polyimide precursor B2 is as follows: (1) 103g of 4,4'-oxophthalic anhydride (ODPA) was added to 200mL of γ-butyrolactone (GBL), then 87g of hydroxyethyl methacrylate (HEMA) was added, and then 53g of pyridine was slowly added dropwise. The mixture was reacted at room temperature for 16h to obtain the first mixture. (2) 137g of dicyclohexylcarbodiimide (DCC) was added to 100mL of γ-butyrolactone (GBL) to obtain a DCC solution. The DCC solution was then added to the first mixture and stirred for 2h to obtain a second mixture. (3) 71 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB) was added to 300 mL of γ-butyrolactone (GBL) under a nitrogen atmosphere to obtain an ODA solution. The ODA solution was then added to the second mixture and reacted for 6 h. After the reaction was completed, 20 mL of ethanol was added as a quencher and reacted for 2 h to obtain the third mixture. (4) The third mixture was filtered, the filtrate was collected, methanol was added to the filtrate to precipitate lumpy solids, the lumpy solids were collected and refrigerated for 12 hours, then 800 mL of GBL was added and stirred. After complete dissolution, water was added dropwise to precipitate white flocculent substances. The mixture was filtered and dried to obtain polyimide precursor B2, with a weight-average molecular weight of approximately 20,000. The structural formula of B2 is shown in the figure. Its proton NMR spectrum is shown in the figure. Figure 7 As shown: B2.

[0083] Example 1 Under constant temperature and humidity (24℃, 50%RH) and yellow light conditions, 30.0g of N-methylpyrrolidone (NMP) solvent, 3.0g of ethyl lactate (EL) solvent, 1.2g of tricyclic [5.2.1.02,6]decanediethanol diacrylate (CAS No.: 42594-17-2), 0.2g of oxime ester photoinitiator TR-PBG-345 (Qiangli New Materials), and 0.06g of thermal alkali-generating agent DBU-phthalate (CAS No.: 97884-98-5) were added sequentially to a 100mL HDPE bottle. The mixture was stirred with a magnetic stirrer and allowed to dissolve completely within 3 hours. Then, 12g of powdered A1 polyimide precursor was added, the bottle was sealed, and the mixture was shaken overnight on a shaker. After confirming uniform resin dissolution, the mixture was pressure filtered through a 1μm filter membrane to obtain the polyimide precursor composition.

[0084] Example 2 The difference between this embodiment and Embodiment 1 is that the A1 polyimide precursor is replaced with an equal amount of the A3 polyimide precursor, while all other conditions remain the same as in Embodiment 1.

[0085] Example 3 The difference between this embodiment and Embodiment 1 is that the A1 polyimide precursor is replaced with an equal amount of A4 polyimide precursor, while all other conditions remain the same as in Embodiment 1.

[0086] Example 4 The difference between this embodiment and Embodiment 1 is that the A1 polyimide precursor is replaced with an equal amount of A5 polyimide precursor, while all other conditions remain the same as in Embodiment 1.

[0087] Example 5 The difference between this embodiment and Example 1 is that tricyclo[5.2.1.02,6]decanediethanol diacrylate is replaced with an equal amount of 1,6-hexanediol diacrylate (CAS: 13048-33-4), while all other conditions remain the same as in Example 1.

[0088] Example 6 The difference between this embodiment and Embodiment 1 is that the A1 polyimide precursor is replaced with an equal amount of the B1 polyimide precursor, while all other conditions remain the same as in Embodiment 1.

[0089] Example 7 The difference between this embodiment and Example 1 is that the 12g of A1 polyimide precursor in Example 1 is replaced with a combination of 6g of A1 polyimide precursor and 6g of B1 polyimide precursor, while all other conditions remain the same as in Example 1.

[0090] Comparative Example 1 The difference between this comparative example and Example 1 is that the A1 polyimide precursor is replaced with an equal amount of A2 polyimide precursor, while all other conditions remain the same as in Example 1.

[0091] Comparative Example 2 The difference between this comparative example and Example 1 is that the A1 polyimide precursor is replaced with an equal amount of the B2 polyimide precursor, while all other conditions remain the same as in Example 1.

[0092] The polyimide precursor compositions prepared in Examples 1-7 and Comparative Examples 1-2 were spin-coated onto 6-inch silicon wafers using a spin coater (WS-650Mz-8NPPB, MYCRO) at a spin speed of 1000 rpm for 30 seconds. A pre-baking process was performed at 100°C for 240 seconds using a hot plate. The thickness of the pre-baked film was measured using an optical film thickness gauge, and the silicon wafers were exposed to 500 mJ at the I-line using an EVG lithography machine. Then, a temperature-programmed curing oven (HCM-500D, Shanghai Silicon Power Electronics) was used to heat the wafers at 200°C for 2 hours under a nitrogen atmosphere (oxygen content less than 20 ppm) to obtain the 6-inch silicon wafers and the cured film on them. The cured film thickness was measured again using an optical film thickness gauge. The formula for calculating the curing shrinkage rate is: Cured film retention rate (%) = Cured film thickness / Pre-baked film thickness × 100%.

[0093] The aforementioned six-inch silicon wafer and its accompanying cured film were immersed in a 5% HF aqueous solution for 10 minutes. After rinsing with high-purity water, the cured film was peeled off from the silicon substrate and placed in an oven at 130°C for static heating to fully remove the moisture adsorbed by the cured film. The film sample was then placed in a resonant cavity, and the dielectric constant and dielectric loss at 10 GHz were measured using a broadband dielectric impedance spectrometer.

[0094] Dielectric loss and dielectric constant were measured using CONCEPT 40 under 10G conditions.

[0095] The test results are shown in Table 1: Table 1

[0096] As can be seen from Table 1, compared with Comparative Examples 1-2, the polyimide precursors in Examples 1-7 of this application can significantly improve the cured film retention rate, dielectric constant, and dielectric loss, producing unexpected technical effects. This is mainly because the grafting groups of the polyimide precursors used in Examples 1-7 contain styrene groups, which can significantly reduce the polarity of the polyimide precursor, reduce the number of dipoles inside the cured material, thereby improving dielectric properties. Furthermore, it has excellent free radical polymerization activity, which helps to increase the degree of crosslinking during the curing process, reduces the content of components that need to be "vaporized" and "volatile" in subsequent curing processes, and reduces the generation of volatiles during curing, thus helping to improve the increased shrinkage and reduced flatness caused by the escape of gaseous components.

[0097] The foregoing has provided a detailed description of a polyimide precursor and its preparation method, as well as a polyimide precursor composition and its application, provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A polyimide precursor, characterized in that, The structural formula of the polyimide precursor is shown in Formula I: Formula I; in, Derived from dianhydride monomers; It is derived from a diamine monomer; R1 and R2 are independently derived from alcohols, including styrene-containing alcohols; The weight-average molecular weight of the polyimide precursor is 10,000-50,000.

2. The polyimide precursor according to claim 1, characterized in that, The dianhydride monomer contains cyclic aliphatic groups and / or aromatic groups, and the dianhydride monomer has 6-30 carbon atoms. And / or, the dianhydride monomer comprises at least one of 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, m-terphenyl 3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl 3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride; And / or, the diamine monomer contains cyclic aliphatic groups and / or aromatic groups, and the dianhydride monomer has 6-30 carbon atoms; And / or, the diamine monomer comprises at least one selected from 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide; And / or, the alcohol compound further includes at least one of an alcohol containing a methacrylate group and an alcohol without free radical polymerization capability, wherein the mass percentage of the alcohol containing the methacrylate group is ≤50%, the mass percentage of the alcohol containing the styrene group is 50%-100%, and the mass percentage of the alcohol without free radical polymerization capability is ≤20%.

3. The polyimide precursor according to claim 2, characterized in that, The functionality of the styrene-containing alcohol, the methacrylate-containing alcohol, and the alcohol without free radical polymerization ability is all 1. And / or, the alcohol containing the methacrylate group includes hydroxyethyl methacrylate; And / or, the styrene-containing alcohol includes at least one of 4-vinylphenylmethanol, 4-vinylphenylethanol, and 4-vinylphenylpropanol; And / or, the alcohols without free radical polymerization capability include at least one of ethanol, propanol, n-butanol, and triethylene glycol monomethyl ether.

4. The polyimide precursor according to any one of claims 1-3, characterized in that, The structural formula of the polyimide precursor is shown in Formula II: Formula II; R3 and R4 are each independently selected from alkyl groups having 1-3 carbon atoms, and R5 is selected from substituted or unsubstituted alkyl groups. and One of them.

5. The polyimide precursor according to claim 4, characterized in that, The structural formula of the polyimide precursor is shown in any one of Formulas III-IV: Formula III; Formula IV.

6. A method for preparing a polyimide precursor, used to prepare the polyimide precursor as described in any one of claims 1-5, characterized in that, include: A dianhydride monomer is added to a first solvent, followed by the addition of an alcohol compound and an organic base. After reaction, a first mixture is obtained; wherein the alcohol compound includes styrene-containing alcohols. A condensing agent is added to the first mixture, and after reaction, a second mixture is obtained; The diamine monomer is added to the second solvent to obtain a diamine monomer solution. The diamine monomer solution is then added to the second mixture, and after reaction, a third mixture is obtained. The third mixture was filtered and dried to obtain a polyimide precursor.

7. The method for preparing the polyimide precursor according to claim 6, characterized in that, The molar ratio of the dianhydride monomer, the alcohol compound, and the diamine monomer is 1:(0.9-1.5):(0.8-1).

8. A polyimide precursor composition, characterized in that, Includes the polyimide precursor as described in any one of claims 1-5, and / or includes the polyimide precursor prepared by the method for preparing the polyimide precursor as described in any one of claims 6-7.

9. The polyimide precursor composition according to claim 8, characterized in that, The polyimide precursor composition further includes a crosslinking agent, a photoinitiator, a thermal alkali-generating agent, and a third solvent.

10. The polyimide precursor composition according to claim 9, characterized in that, The mass ratio of the polyimide precursor, the crosslinking agent, the photoinitiator, the thermal alkali-generating agent, and the third solvent is 100:(5-20):(1-5):(0.2-4):(100-300); And / or, the crosslinking agent comprises at least one of diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and tricyclo[5.2.1.02,6]decanediethanol diacrylate; And / or, the photoinitiator includes at least one of oxime ester photoinitiators, phosphonium oxide photoinitiators, and alkyl aryl ketone photoinitiators; And / or, the heat-generating alkali agent comprises at least one of DBU-phthalate, DBU-phenol salt, DBU-p-toluenesulfonate, bis(2-morpholinylethyl) ether and 1-N-BOC-morpholine; And / or, the third solvent includes at least one of N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, and ethyl lactate.

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