A polyimide precursor resin, a polyimide material, and a preparation method and application of a photosensitive resin

Abstract

The present application relates to the technical field of polymer materials, and particularly relates to a polyimide precursor resin, a polyimide material and a preparation method and application of a photosensitive resin. The polyimide precursor resin is obtained by polycondensation of a diamine monomer and an aromatic tetracarboxylic dianhydride. By designing basic diamine monomers with different side group positions and flexible bridging groups, the free volume and degree of freedom of the polymer chain are increased, and the polymerization reaction with anhydride is more likely to occur. Compared with the polyimide material containing a nitrogen-containing heterocyclic ring in the main chain, the nitrogen-containing heterocyclic ring in the side chain is more conducive to increasing the interaction between molecules to improve the thermal stability of the material. Meanwhile, the larger side group can increase the free volume of the molecular chain and reduce the dielectric constant, which is conducive to reducing the transmission loss of the polyimide dielectric material. The prepared polyimide precursor resin can accelerate the reaction process of imidization in the process of heat curing, so that the imidization rate of the polyimide precursor resin is significantly improved at 200 DEG C.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a method for preparing and applying a polyimide precursor resin, a polyimide material, and a photosensitive resin. Background Technology

[0002] Polyimide possesses excellent high-temperature resistance, low-temperature resistance, mechanical properties, chemical resistance, and good dielectric properties, making it a crucial engineering material widely used in microelectronics and aerospace. However, the thermosetting of polyimide typically occurs at relatively high temperatures (330℃-400℃). Such high-temperature processing often leads to cracking, detachment, and recrystallization of low-melting-point solder joints in molded circuits, compromising the performance of the molded devices. Furthermore, in ultra-thin wafer devices, residual stress generated during high-temperature processing can easily cause serious problems such as warping and peeling, affecting their reliability. Moreover, when applied to the redistribution layer (RDL) of fan-out wafer packages, excessively high curing temperatures can cause a mismatch between the coefficient of thermal expansion (CTE) of the RDL layer and the epoxy molding compound (EMC) layer. Therefore, developing low-temperature curing (≤250℃) polyimide resin materials is particularly important for the semiconductor industry.

[0003] CN114249892A discloses a diamine compound with a nitrogen-containing heterocyclic main chain and the preparation of its corresponding polyimide resin. The material obtained by this invention exhibits some low-temperature curing properties; however, due to its strong structural rigidity, the highest imidization rate at 200°C in the provided examples is 72%. Its low-temperature curing effect is not yet sufficient for application requirements.

[0004] Therefore, it is very important to develop a method for preparing polyimide precursors with low-temperature curing properties. Summary of the Invention

[0005] Therefore, in view of the shortcomings of the prior art, the purpose of this invention is to provide a method for preparing polyimide precursor resin, polyimide material and photosensitive resin and their application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] This invention provides a polyimide precursor resin, which is obtained by polycondensation of a diamine monomer and an aromatic tetracarboxylic acid dianhydride;

[0008] The diamine monomer includes at least one diamine compound having a structure as shown in general formulas (1)-(3):

[0009]

[0010] Among them, in the general formulas (1), (2), and (3),

[0011] At least one of X1, X2, X3, and X4 is a nitrogen atom, and the rest are carbon atoms;

[0012] Y is any one of hydrogen, deuterium, methyl, phenyl, methoxy, trifluoromethyl, naphthyl, anthraquinone, silyl, halogen, substituted or unsubstituted C2-C10 straight-chain or branched alkyl, substituted or unsubstituted C7-C30 aryl, C2-C10 alkoxy, C1-C10 alkylamino, substituted or unsubstituted C2-C10 silyl, and substituted or unsubstituted C2-C15 nitrogen-containing heterocycles.

[0013] X is any one of -O-, -S-, -CH2-, -SiH2-, -CO-, -CO-O-, sulfone, phenyl, or C2- to C12 straight-chain or branched alkylene groups.

[0014] Furthermore, the aforementioned It is a pyrimidine ring, a pyridine ring, or a triazine.

[0015] Furthermore, Y is hydrogen, deuterium, methyl, halogen, silyl, phenyl, biphenyl, trifluoromethyl, tert-butyl, naphthyl, anthracene, ethyl, n-propyl, isopropyl, n-butyl, aldehyde, carboxyl, methoxy, ethoxy, propoxy, mercaptomethyl, mercaptoethyl, acetyl, methylamino, dimethylamino, ethylamino, propylamino, trimethylsilyl, deuterated methyl, or deuterated trimethylsilyl.

[0016] Furthermore, the diamine monomer includes one or more of the following compounds:

[0017]

[0018]

[0019]

[0020] Furthermore, the polyimide precursor resin further includes a known diamine monomer copolymerized with the diamine monomer and an aromatic tetracarboxylic acid dianhydride; the known diamine monomer includes any one of the following compounds:

[0021]

[0022]

[0023] The aromatic tetracarboxylic acid dianhydride has the structure shown in the following formula:

[0024] Ar3 can be any one of the following groups:

[0025]

[0026] Furthermore, the preparation method includes: undergoing a polycondensation reaction between a diamine monomer and an aromatic tetracarboxylic acid dianhydride to obtain a polyimide precursor resin;

[0027] Alternatively, the polyimide precursor resin can be obtained by ternary or quaternary copolymerization of a diamine monomer, a known diamine monomer, and an aromatic tetracarboxylic acid dianhydride.

[0028] Furthermore, the temperatures for the polycondensation and copolymerization reactions are 0°C to 80°C.

[0029] The time for the polycondensation and copolymerization reactions is 1h-24h;

[0030] The polycondensation and copolymerization reactions are carried out in a protective atmosphere;

[0031] The polycondensation and copolymerization reactions are carried out in the presence of a solvent.

[0032] The present invention also provides a photosensitive resin, the photosensitive resin comprising a combination of the polyimide precursor resin and the photosensitive monomer as described above;

[0033] The photosensitive monomers include tetraethylene glycol trimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1, The following are one or more of the following: 6-hexanediol dimethacrylate, pentaerythritol trimenoate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, or N-hydroxymethylacrylamide.

[0034] The present invention also provides a polyimide material obtained by curing a polyimide precursor resin as described above.

[0035] The present invention also provides the application of the photosensitive resin as described above or the polyimide material as described above in the fields of photoresist, semiconductor devices, display devices, lighting devices and electronic packaging.

[0036] Compared with the prior art, the technical solution provided by the present invention has at least the following advantages:

[0037] This invention provides a method for preparing a polyimide precursor resin. By designing basic diamine monomers with different side group positions and flexible bridging groups, the free volume and degrees of freedom of the polymer chain are increased, making it easier to polymerize with acid anhydrides. Compared with polyimide materials with nitrogen-containing heterocycles in the main chain, nitrogen-containing heterocycles in the side chains are more conducive to increasing intermolecular interactions, thereby improving the thermal stability of the material. At the same time, larger side groups can increase the free volume of the molecular chain and reduce the dielectric constant, which is beneficial to reducing the transmission loss of polyimide dielectric materials. The prepared polyimide precursor resin can accelerate the imidization reaction process during heat curing, significantly improving the imidization rate of the polyimide precursor resin at 200°C. This achieves a near 100% imidization rate for the polyimide precursor resin. Furthermore, nitrogen-containing side groups with different substitution positions can increase hydrogen bonding between polymer molecular chains, thereby achieving high thermal stability and good mechanical properties, fully meeting the application requirements of polyimide precursor resins in the field of electronic packaging. Attached Figure Description

[0038] One or more embodiments are illustrated by way of example with reference to the accompanying drawings. These illustrations do not constitute a limitation on the embodiments, and unless otherwise stated, the figures in the drawings are not to be limited by scale.

[0039] Figure 1a This is a comparison of the ATR-FTIR spectra of the polyimide precursor resin in Example 1 cured at different temperatures;

[0040] Figure 1b A comparison of ATR-FTIR spectra of the polyimide precursor resin in Example 10 cured at different temperatures;

[0041] Figure 1c Comparison of ATR-FTIR spectra of the polyimide precursor resins in Examples 11 and 13 cured at different temperatures;

[0042] Figure 1d This is a comparison of the ATR-FTIR spectra of the polyimide precursor resin in Example 13 cured at different temperatures;

[0043] Figure 2This is a comparison chart showing the fracture stress of polyimide films obtained by curing the polyimide precursor resins from Examples 2, 6, and 8 and the PAA from Comparative Example 1 at a final curing temperature of 200°C into strips of 3mm × 5mm for testing. Detailed Implementation

[0044] As can be seen from the background technology, the main problem with the low-temperature curing polyimide and photosensitive resin reported so far is that there are few types of diamine monomers that can achieve low-temperature curing function, and most monomers will significantly reduce the thermal stability of polyimide when heat-cured at 200℃.

[0045] The purpose of this invention is to provide a method for preparing and applying polyimide precursor resin, polyimide material and photosensitive resin, so as to develop low-temperature curing polyimide material.

[0046] The present invention will now be described in detail with reference to specific embodiments.

[0047] Preparation Example 1

[0048] A diamine monomer, 4,4'-((4-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine, has the following structure:

[0049]

[0050] The preparation method includes the following steps:

[0051]

[0052] Weigh 8.00 g (50.31 mmol) of 2-bromopyrimidine, 8.34 g (52.83 mmol) of 2,4-difluorophenylboronic acid, and 20.86 g (150.95 mmol) of potassium carbonate into a 500 mL three-necked flask, add 208 mL of tetrahydrofuran and 71 mL of water. Stir magnetically at room temperature and purge with nitrogen for 10 min, then add 1.74 g (1.50 mmol) of tetratetraphenylphosphine palladium. The reaction mixture was then refluxed at 68 °C for 20 h. After the reaction was stopped, the mixture was allowed to cool naturally to room temperature. The organic and aqueous phases were separated by extraction with dichloromethane and saturated brine, and the solvent was removed by rotary evaporation. The crude product was subjected to column chromatography on a silica gel column using petroleum ether / ethyl acetate (8:1 v / v). After drying, 6.56 g of white crystals were obtained, with a yield of 85%.

[0053]

[0054] Weigh 8.00 g (41.63 mmol) of the first-step product, 14.478 g (104.07 mmol) of p-nitrophenol, and 14.38 g (104.07 mmol) of potassium carbonate into a 500 mL three-necked flask. Maintain a nitrogen atmosphere and add 48 mL of ultra-dry DMF. Stir and heat to 150 °C under a nitrogen atmosphere and react for 5 h. After stopping the reaction, allow the reaction system to cool naturally to room temperature. Separate the organic and aqueous phases using dichloromethane and water extraction, and remove the solvent by rotary evaporation. Analyze the crude product by column chromatography on a silica gel column using petroleum ether / ethyl acetate (4:1 v / v). Dry to give a brownish-yellow solid in 60% yield.

[0055]

[0056] Weigh 13.00 g (32.43 mmol) of the product from step two and 0.50 g of palladium on carbon into a 500 mL three-necked flask. Maintain a nitrogen atmosphere and add 100 mL of ultradry THF. Stir and heat to 68 °C under a nitrogen atmosphere. Then, slowly add 7.4 mL of hydrazine hydrate dropwise to the reaction system. After the addition is complete, react for 5 h. After stopping the reaction, allow the system to cool naturally to room temperature. Remove the palladium on carbon by filtration, and then remove the solvent by rotary evaporation. Analyze the crude product by column chromatography on a silica gel column using petroleum ether / ethyl acetate (1:1 v / v). Dry to obtain a solid in 90% yield.

[0057] The characterization results of the diamine monomer were as follows: mass spectrometry at 372.34; NMR results were as follows: 1H NMR (500MHz, Chloroform-d) δ 8.74 (d, J = 4.0Hz, 2H), 7.96 (d, J = 9.3Hz, 1H), 7.08 (t, J = 4.0Hz, 1H), 6.97 (dd, J = 9.2, 2.4Hz, 1H), 6.86–6.80 (m, 4H), 6.75–6.69 (m, 5H), 3.93 (s, 4H).

[0058] Preparation Example 2

[0059] A diamine monomer, 4,4'-((5-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine, has the following structure:

[0060]

[0061] The preparation method includes the following steps:

[0062]

[0063] The synthesis method is the same as in Preparation Example 1, except that one of the raw materials is replaced with 3,5-difluorophenylboronic acid, and the yield is 82%.

[0064]

[0065] The synthesis method is the same as in Preparation Example 1, with a yield of 77%.

[0066]

[0067] The synthesis method is the same as in Preparation Example 1, with a yield of 92%.

[0068] The characterization results of the diamine monomer were as follows: mass spectrometry at 372.51; NMR results were as follows: 1H NMR (500MHz, Chloroform-d) δ 8.67 (d, J = 4.0Hz, 2H), 7.21 (d, J = 2.1Hz, 2H), 7.08 (t, J = 4.0Hz, 1H), 6.87–6.81 (m, 4H), 6.75–6.69 (m, 4H), 6.53 (t, J = 2.2Hz, 1H), 3.93 (s, 4H).

[0069] Preparation Example 3

[0070] A diamine monomer, 4,4'-((2-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine, has the following structure:

[0071]

[0072] The preparation method includes the following steps:

[0073]

[0074] The synthesis method is the same as in Preparation Example 1, except that one of the raw materials was replaced with 2,6-difluorophenylboronic acid, and the yield was 74%.

[0075]

[0076] The synthesis method is the same as in Preparation Example 1, with a yield of 80%.

[0077]

[0078] The synthesis method was the same as in Preparation Example 1, with a yield of 95%. The characterization results of the diamine monomer were as follows: mass spectrometry at 372.94; NMR results: 1H NMR (500MHz, Chloroform-d) δ 8.67 (d, J = 3.9Hz, 2H), 7.42 (t, J = 8.0Hz, 1H), 7.08 (t, J = 4.0Hz, 1H), 7.01 (d, J = 7.9Hz, 2H), 6.88–6.82 (m, 4H), 6.75–6.69 (m, 4H), 3.93 (s, 3H).

[0079] Preparation Example 4

[0080] A diamine monomer, 4,4'-((4-(pyrimidin-5-yl)-1,3-phenylene)bis(oxy))diphenylamine, has the following structure:

[0081]

[0082] The preparation method includes the following steps:

[0083]

[0084] 10 g (52.907 mmol) of 4-bromoresorcinol, 20.84 g (132.268 mmol) of p-chloronitrobenzene, and 18.34 g (132.268 mmol) of potassium carbonate were weighed and placed in a 500 mL three-necked flask. The mixture was kept under a nitrogen atmosphere, and 120 mL of ultra-dry DMF was added. The mixture was stirred and heated to 150 °C under a nitrogen atmosphere and reacted for 5 h. After the reaction was stopped, the reaction system was allowed to cool naturally to room temperature. The organic and aqueous phases were separated by extraction with dichloromethane and water. Subsequently, petroleum ether was added for recrystallization. The product was dried to give a pale yellow solid in 95% yield.

[0085]

[0086] Weigh 10.00 g (23.191 mmol) of the first-step product, 3.02 g (24.351 mmol) of 5-pyrimidineboronic acid, and 9.6 g (69.573 mmol) of potassium carbonate into a 500 mL three-necked flask, add 90 mL of tetrahydrofuran and 30 mL of water. Stir magnetically at room temperature and purge with nitrogen for 10 min, then add 1 g (0.865 mmol) of triphenylphosphine palladium. The reaction mixture was then refluxed at 68 °C for 20 h. After the reaction was stopped, the mixture was allowed to cool naturally to room temperature. The organic and aqueous phases were separated by extraction with dichloromethane and saturated brine, and the solvent was removed by rotary evaporation. The crude product was subjected to column chromatography on a silica gel column using petroleum ether / ethyl acetate (4:1 v / v). The product was dried to give a yellow solid in 80% yield.

[0087]

[0088] The synthesis method is the same as in Preparation Example 1, with a yield of 90%.

[0089] The characterization results of the diamine monomer are as follows: mass spectrometry: 371.14; NMR results: 1H NMR (500MHz, Chloroform-d) δ 8.89–8.86 (m, 3H), 7.72 (d, J = 8.4 Hz, 1H), 6.97 (dd, J = 8.4, 2.4 Hz, 1H), 6.89–6.81 (m, 4H), 6.77–6.70 (m, 5H), 3.93 (s, 4H).

[0090] Example

[0091] A method for preparing a polyimide material specifically includes the following steps:

[0092] (1) Pre-treat dianhydride and diamine to remove moisture and impurities. Then, at low temperature or room temperature, pour an appropriate amount of one or more diamines into a flask, add a polar organic solvent and mix well. Then, purge with nitrogen to keep the system under a nitrogen atmosphere. Then, add dianhydride in batches (the molar ratio of diamine to dianhydride is 0.9 to 1), with an interval of 10 to 30 minutes, and stir continuously for 5 to 24 hours to obtain polyimide precursor resin.

[0093] (2) Then, the polyimide precursor resin is evenly spread on the glass plate by spin coating or scraping, and then baked on the hot plate for a few minutes to remove some of the organic solvent.

[0094] (3) Finally, thermal imidization is carried out under nitrogen or air atmosphere, mainly by step heating, and then cooled to room temperature to obtain polyimide material.

[0095] Example 1

[0096] (1) First, the dianhydride and diamine were pretreated to remove moisture and impurities. The diamine was treated in a vacuum oven at 60°C for 3 h, and the dianhydride was treated in a vacuum oven at 160°C for 4 h. Then, at room temperature, 10 mmol of 4,4'-((4-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine (Preparation Example 1) was dissolved in an ultra-dry N,N-dimethylacetamide (DMAc) solution in a flask. Then, under a nitrogen atmosphere and ice bath conditions, pyromellitic dianhydride (PMDA, 10 mmol) was added in two portions and stirred for 24 h to obtain PAA-1 solution.

[0097] (2) Then, the polyamic acid solution is evenly spread on the glass plate by spin coating at a speed of 1000 rpm for 30 seconds. It is then baked on a hot plate at 80°C for 10 minutes to remove some of the organic solvent.

[0098] (3) Finally, thermal imidization was carried out under a nitrogen atmosphere, mainly by step heating. The heating program was 100℃ / 1 hour, 200℃ / 3 hours, and the heating rate was 5℃ / minute. Then, it was cooled to room temperature to obtain low-temperature curing polyimide PI-11. The heating program was changed to 100℃ / 1 hour, 200℃ / 1 hour, 250℃ / 2 hours, and the heating rate was 5℃ / minute. Then, it was cooled to room temperature to obtain low-temperature curing polyimide PI-12. The heating program was changed to 100℃ / 1 hour, 200℃ / 1 hour, 300℃ / 1 hour, 350℃ / 1 hour, and the heating rate was 5℃ / minute. Then, it was cooled to room temperature to obtain low-temperature curing polyimide PI-13.

[0099] Example 2

[0100] The difference between the preparation method of this embodiment and that of Example 1 is that the diamine in step (1) is replaced with a mixed diamine of 4,4'-((4-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine and 4,4'-diaminodiphenyl ether (ODA) prepared in Example 1, with a mixing molar ratio of 1:9. PAA-2 is obtained by polymerization and then cured at 200°C, 250°C and 350°C to obtain polyimides PI-21, PI-22 and PI-23, respectively.

[0101] Example 3

[0102] The difference between the preparation method of this embodiment and that of Example 1 is that the diamine in step (1) is replaced with a mixed diamine of 4,4'-((4-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine and 4,4'-diaminodiphenyl ether (ODA) prepared in Example 1, with a mixing molar ratio of 2:8. PAA-3 is obtained by polymerization and then cured at 200°C, 250°C and 350°C to obtain polyimides PI-31, PI-31 and PI-33, respectively.

[0103] Example 4

[0104] The difference between the preparation method of this embodiment and that of Example 1 is that the diamine in step (1) is replaced with a mixed diamine of 4,4'-((4-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine and 4,4'-diaminodiphenyl ether (ODA) prepared in Example 1, with a mixing molar ratio of 3:7. PAA-4 is obtained by polymerization and then cured at 200°C, 250°C and 350°C to obtain polyimides PI-41, PI-42 and PI-43, respectively.

[0105] Example 5

[0106] The difference between the preparation method of this embodiment and that of Example 1 is that the diamine in step (1) is replaced with 4,4'-((5-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine, which is polymerized with pyromellitic dianhydride (PMDA) to obtain PAA-5, and then cured at 200°C, 250°C and 350°C to obtain polyimides PI-51, PI-52 and PI-53, respectively.

[0107] Example 6

[0108] The difference between the preparation method of this embodiment and that of Example 1 is that the diamine in step (1) is replaced with 4,4'-((2-(pyrimidin-2-yl)-1,3-phenylene)bis(oxy))diphenylamine, which is polymerized with pyromellitic dianhydride (PMDA) to obtain PAA-6, and then cured at 200°C, 250°C and 350°C to obtain polyimides PI-61, PI-62 and PI-63, respectively.

[0109] Example 7

[0110] The difference between the preparation method of this embodiment and that of Example 1 is that the diamine in step (1) is replaced with 4,4'-((4-(pyrimidin-5-yl)-1,3-phenylene)bis(oxy))diphenylamine, which is polymerized with pyromellitic dianhydride (PMDA) to obtain PAA-7, and then cured at 200°C, 250°C and 350°C to obtain polyimides PI-71, PI-72 and PI-73, respectively.

[0111] Example 8

[0112] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with 3,3,4,4-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), and PAA-8 is obtained by direct polymerization. Then, the polyimides PI-81, PI-82, and PI-83 are obtained by curing at 200°C, 250°C, and 350°C, respectively.

[0113] Example 9

[0114] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), and PAA-9 is obtained by direct polymerization. Then, the polyimides PI-91, PI-92, and PI-93 are obtained by curing at 200°C, 250°C, and 350°C, respectively.

[0115] Example 10

[0116] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), and PAA-10 is obtained by direct polymerization. Then, the polyimides PI-101, PI-102, and PI-103 are obtained by curing at 200°C, 250°C, and 350°C, respectively.

[0117] Example 11

[0118] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with 4,4'-oxybisphthalic anhydride (ODPA), and PAA-11 is obtained by direct polymerization. Then, the polyimides PI-111, PI-112, and PI-113 are obtained by curing at 200°C, 250°C, and 350°C, respectively.

[0119] Example 12

[0120] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with bisphenol A type diether dianhydride (BPADA), and PAA-12 is directly polymerized to obtain PAA-12. Then, the polyimides PI-121, PI-122, and PI-123 are obtained by curing at 200°C, 250°C, and 350°C, respectively.

[0121] Example 13

[0122] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with hexafluorodianhydride (6FDA), and PAA-13 is directly polymerized to obtain PAA-13. Then, the polyimides PI-131, PI-132, and PI-133 are obtained by curing at 200°C, 250°C, and 350°C, respectively.

[0123] Example 14

[0124] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with a mixed dianhydride of hexafluorodianhydride (6FDA) and PMDA in a molar ratio of 1:9, and directly polymerized to obtain PAA-14. Then, the PAA-14 is obtained by curing at 200°C, 250°C and 350°C, respectively, to obtain polyimides PI-141, PI-142 and PI-143.

[0125] Example 15

[0126] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with a mixed dianhydride of hexafluorodianhydride (6FDA) and PMDA in a molar ratio of 2:8, and directly polymerized to obtain PAA-15. Then, the polyimides PI-151, PI-152, and PI-153 are obtained by curing at 200°C, 250°C, and 350°C, respectively.

[0127] Example 16

[0128] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with a mixed dianhydride of hexafluorodianhydride (6FDA) and PMDA in a molar ratio of 3:7, and PAA-16 is obtained by direct polymerization. Then, the polyimides PI-161, PI-162, and PI-163 are obtained by curing at 200°C, 250°C, and 350°C, respectively.

[0129] Example 17

[0130] The difference between the preparation method of this embodiment and that of Example 7 is that the dianhydride is replaced with a mixed dianhydride of hexafluorodianhydride (6FDA), DSDA and PMDA in a molar ratio of 1:1:8, and directly polymerized to obtain PAA-17. Then, it is cured at 200°C, 250°C and 350°C to obtain polyimides PI-171, PI-172 and PI-173, respectively.

[0131] Example 18

[0132] The preparation method of this embodiment differs from that of Example 7 in that the dianhydride is replaced with a mixed dianhydride of hexafluorodianhydride (6FDA), DSDA and PMDA in a molar ratio of 2:1:7. PAA-18 is obtained by direct polymerization and then cured at 200°C, 250°C and 350°C to obtain polyimides PI-181, PI-182 and PI-183, respectively.

[0133] Comparative Example 1

[0134] The difference between the preparation method of this embodiment and that of Example 1 is that the diamine in step (1) is replaced with 4,4'-diaminodiphenyl ether, which is polymerized with acid anhydride 4,4'-oxybisphthalic anhydride (ODPA) to obtain PAA-0, and then cured at 200℃, 250℃ and 350℃ to obtain polyimides PI-01, PI-02 and PI-03, respectively.

[0135] Application Example 1

[0136] A method for preparing a photosensitive resin specifically includes the following steps:

[0137] 200 mL of N,N-dimethylacetamide was added to dilute the polyimide precursor resin PAA-2350 g (solid content 15%) provided in Example 2. Then, 7.5 mL of trifluoroacetic anhydride was slowly added under a nitrogen atmosphere, and the temperature was raised to 50 °C for 2 h. Afterwards, 15 g of hydroxyethyl methacrylate was added and stirred overnight at 50 °C. The resulting product was precipitated in methanol, filtered, and dried to obtain a grayish-yellow solid, which is the photosensitive resin 1. A photoresist was prepared using the above photosensitive resin, with the following specific formulation: 1.0 parts by weight of photosensitive resin, 0.03 parts by weight of tetraethylmielone, 0.06 parts by weight of o-chlorohexaaryldiimidazole, 0.02 parts by weight of 2-mercaptobenzoxazole, and 30 parts by weight of N-methylpyrrolidone. The photolithographic performance of the photoresist was tested under a UV exposure machine (EVG610) with an exposure dose of 370 mJ / cm². 2The development time was 20 seconds (using developer KS5400), resulting in a pattern with a linewidth / spacing of 15 μm. The pattern was then examined using a scanning electron microscope (SEM, NanoSEM 450).

[0138] Application Example 2

[0139] A method for preparing a photosensitive polyimide resin specifically includes the following steps:

[0140] PMDA (0.05 mol), HEA (0.1 mol), and a small amount of polymerization inhibitor were added to a mixed solvent of 45 mL sulfolane and 0.3 mL pyridine. The mixture was reacted at 55–60 °C for 12 h, then cooled to room temperature. 7.5 mL (0.103 mol) of SOCl2 was slowly added dropwise while maintaining the temperature below 25 °C for 4 h. The system was then evacuated under a vacuum of 13.33 Pa to remove residual gases such as HCl and SO2, as well as unreacted SOCl2. The temperature was then lowered to -15 °C to allow the reaction mixture to solidify. Under stirring, a solution of 0.05 mol of 4,4'-((4-(pyrimidin-5-yl)-1,3-phenylene)bis(oxy))diphenylamine (Preparation Example IV), 230 mL of DMAc, and 5 mL of pyridine was added to the reaction system, and the temperature was maintained at approximately -5 °C for 3.5 h. The reaction mixture was poured into 2L of methanol in a thin stream, and stirred, soaked, dried under vacuum, and washed several times. It was then soaked in deionized water, dried under vacuum, and vacuum dried at 40℃ for 24 hours to obtain photosensitive resin 2. The photoresist was prepared using the above photosensitive resin, with the following specific formula: 1.0 parts by weight of photosensitive resin, 0.03 parts by weight of tetraethylmielone, 0.06 parts by weight of o-chlorohexaaryldiimidazole, 0.02 parts by weight of 2-mercaptobenzoxazole, and 30 parts by weight of N-methylpyrrolidone. The photolithographic performance of the photoresist was tested using an ultraviolet lithography machine (EVG610) with an exposure dose of 370 mJ / cm². 2 The development time was 20 seconds (using developer KS5400), resulting in a pattern with a linewidth / spacing of 15 μm. The pattern was then examined using a scanning electron microscope (SEM, NanoSEM 450).

[0141] Table 1

[0142] Example 1 PAA-1 95％ 97％ Example 2 PAA-2 93％ 97％ Example 3 PAA-3 92％ 96％ Example 4 PAA-4 97％ 99％ Example 5 PAA-5 96％ 98％ Example 6 PAA-6 94％ 96％ Example 10 PAA-10 94％ 99％ Example 11 PAA-11 93％ 97％ Example 13 PAA-13 95％ 98％ Comparative Example 1 PAA-01 82％ 86％

[0143] Table 2

[0144]

[0145]

[0146] Figure 1 shows the polyimide films cured at different endpoint curing temperatures, as measured by an Attenuated Total Reflectance Fourier Transform Infrared Spectrometer (ATR-FTIR, Vertex 70). Figure 1a , Figure 1b , Figure 1c and Figure 1d The images show a comparison of the ATR-FTIR spectra of the polyimide precursor resins from Examples 1, 10, 11, and 13 cured at different temperatures. The imidization rate was calculated by comparing the peak areas of the CN stretching vibration peak of the polyimide ring and the CC stretching vibration peak of the benzene ring in the infrared spectra. Using this ratio obtained at 350°C as a reference, the calculation formula is: Imidization Degree(ID) = (S... C-N / S C-C ) T / (S C-N / S C-C ) 350 S C-N S represents the peak area of ​​CN stretching vibration. C-C The peak area represents the C-C stretching vibration. The results of the imidization rate test are shown in Table 1. The results indicate that, compared to the polyimide precursor resin PAA-01 obtained in Comparative Example 1 without the addition of the diamine monomer provided by this invention, the polyimide precursor resins PAA-1 to PAA-13 obtained by copolymerization or direct polymerization of the diamine monomer provided by this invention all achieved imidization rates of over 90% at 200°C and 250°C.

[0147] Appendix Figure 2 The mechanical properties of the polyimide film were obtained using a dynamic mechanical thermal analyzer (TA, DMAQ800). Polyimide films obtained by curing the polyimide precursor resins from Examples 2, 6, and 8, and the PAA from Comparative Example 1, at a final curing temperature of 200°C, were cut into 3mm × 5mm strips for testing. The resulting fracture stress comparison diagram is shown below. Figure 2 As shown. From Figure 2As can be seen from the results, the polyimide film formed by curing the polyimide precursor resin provided in Example 2 at 200°C has an elongation at break of 21%, a breaking stress of 160 MPa, and a Young's modulus of 3.05 GPa. Compared with the polyimide film formed by curing at 200°C in Comparative Example 1, which has an elongation at break of 12%, a breaking stress of 141 MPa, and a Young's modulus of 2.80 GPa, the mechanical properties are significantly improved. The polyimide films formed by curing the polyimide precursor resins provided in Examples 4, 6, and 7 at 200°C also have better mechanical properties than the polyimide film in Comparative Example 1. This also proves that the polyimide film formed by curing the polyimide precursor obtained using a flexible diamine monomer with a pyrimidine ring in the side group at low temperature has better mechanical properties than the polyimide film formed by curing ordinary polyimide precursor resin without nitrogen at low temperature.

[0148] Table 2 summarizes the thermal and mechanical properties of the polyimide precursor resins prepared in Examples 1, 2, 3, 6, 7, 12, 15, 17, and Comparative Example 1. Data comparison shows that the polyimide films formed by curing the polyimide precursor resins in the examples provided by this invention at 200°C have better thermal and mechanical properties than the polyimide films obtained by polymerization using known diamines ODA and dianhydrides ODPA in the comparative example. This indicates that diamine compounds containing pyrimidine rings in the side groups can both improve the imidization rate during low-temperature curing and ensure good thermal and mechanical stability of the film. It can be seen that designing N-containing heterocycles such as pyridine and pyrimidine at the side group positions can prevent the reduction of benzene ring density in the main chain, thereby effectively protecting the excellent thermal stability inherent in polyimide itself. Moreover, compared to other low-temperature curing diamine monomers, introducing N-containing heterocycles and flexible bridging groups at different side group positions can also enhance the hydrogen bonding between polymer molecular chains, further improving the thermal properties of the polyimide material.

[0149] Through Examples 1 to 18 and Comparative Example 1, it was found that the direct polymerization or copolymerization of the novel diamine monomer with known diamine monomers and aromatic tetracarboxylic dianhydrides resulted in an imidization rate of over 90% even under curing at 200°C, achieving low-temperature curing performance. The polyimide film prepared by this process exhibited a decomposition temperature (5% thermal weight loss) above 450°C and a glass transition temperature above 350°C, demonstrating good thermal stability. Its elongation at break was above 15%, tensile strength above 150 MPa, and Young's modulus above 3.0 GPa, also exhibiting good mechanical properties. Furthermore, its dielectric constant was below 3.2, superior to commercial Kapton films, indicating significant potential for application in the microelectronics field. The condensation and copolymerization reactions can be collectively referred to as polymerization reactions.

[0150] Those skilled in the art will understand that the above embodiments are specific examples of implementing this application, and in practical applications, various changes in form and detail can be made without departing from the spirit and scope of this application. Any person skilled in the art can make their own modifications and alterations without departing from the spirit and scope of this application; therefore, the scope of protection of this application should be determined by the scope defined in the claims.

Claims

1. A polyimide precursor resin, characterized in that, The polyimide precursor resin is obtained by polycondensation of a diamine monomer and an aromatic tetracarboxylic acid dianhydride. The diamine monomer includes at least one diamine compound having a structure as shown in general formulas (1)-(3): , , Among them, in the general formulas (1), (2), and (3), At least one of X1, X2, X3, and X4 is a nitrogen atom, and the rest are carbon atoms; Y is any one of hydrogen, deuterium, methyl, phenyl, methoxy, trifluoromethyl, naphthyl, anthracene, silyl, halogen, substituted or unsubstituted C2~C10 straight-chain or branched alkyl, substituted or unsubstituted C7~C30 aryl, C2~C10 alkoxy, C1~C10 alkylamino, substituted or unsubstituted C2~C10 silyl, and substituted or unsubstituted C2~C15 nitrogen-containing heterocycles. X is any one of -O-, -S-, -CH2-, -SiH2-, -CO-, -CO-O-, sulfone, phenyl, or C2~C12 straight-chain or branched alkylene groups.

2. The polyimide precursor resin according to claim 1, characterized in that, The It is a pyrimidine ring, a pyridine ring, or a triazine.

3. The polyimide precursor resin according to claim 1, characterized in that, The Y is biphenyl, tert-butyl, ethyl, n-propyl, isopropyl, n-butyl, aldehyde, carboxyl, methoxy, ethoxy, propoxy, mercaptomethyl, mercaptoethyl, acetyl, methylamino, dimethylamino, ethylamino, propylamino, trimethylsilyl, deuterated methyl, or deuterated trimethylsilyl.

4. The polyimide precursor resin according to claim 3, characterized in that, The diamine monomer includes one or more of the following compounds: 。 5. The polyimide precursor resin according to claim 1, characterized in that, The polyimide precursor resin further includes a known diamine monomer copolymerized with the diamine monomer and an aromatic tetracarboxylic acid dianhydride; the known diamine monomer includes at least one of the following compounds: ； The aromatic tetracarboxylic acid dianhydride has the structure shown in the following formula: Ar3 can be any one of the following groups: .

6. A method for preparing the polyimide precursor resin as described in claim 1, characterized in that, The preparation method includes: undergoing a polycondensation reaction between a diamine monomer and an aromatic tetracarboxylic acid dianhydride to obtain a polyimide precursor resin; Alternatively, the polyimide precursor resin can be obtained by ternary or quaternary copolymerization of a diamine monomer, a known diamine monomer, and an aromatic tetracarboxylic acid dianhydride.

7. The method for preparing the polyimide precursor resin according to claim 6, characterized in that, The temperatures for the polycondensation and copolymerization reactions are 0℃-80℃; The time for the polycondensation and copolymerization reactions is 1h-24h; The polycondensation and copolymerization reactions are carried out in a protective atmosphere; The polycondensation and copolymerization reactions are carried out in the presence of a solvent.

8. A photosensitive resin, characterized in that, The photosensitive resin comprises a combination of a polyimide precursor resin and a photosensitive monomer as described in any one of claims 1-5; The photosensitive monomers include tetraethylene glycol trimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1, The following are one or more of the following: 6-hexanediol dimethacrylate, pentaerythritol trimenoate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, or N-hydroxymethylacrylamide.

9. A polyimide material, characterized in that, The polyimide material is obtained by curing the polyimide precursor resin as described in any one of claims 1-5.

10. The application of a photosensitive resin as described in claim 8 or a polyimide material as described in claim 9 in the fields of photoresist, semiconductor devices, display devices, lighting devices, and electronic packaging.

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