A photo-induced acid-generating curing type polyimide and its preparation method and photo-induced acid-generating curing type photoresist

Abstract

The present disclosure provides a photo-induced acid-generating curing polyimide, a preparation method thereof, and a photo-induced acid-generating curing photoresist. The general structural formula of the photo-induced acid-generating curing polyimide is as follows: The photo-induced acid-generating curing polyimide provided in the embodiment of the present disclosure has a high film retention rate. When it is prepared into a chemically amplified negative photoresist, the obtained pattern has a high resolution.

Description

Technical Field

[0001] The present invention relates to the field of photolithography and development, and in particular to a photo-induced acid-generating curing polyimide and a preparation method thereof, and a photo-induced acid-generating curing photoresist. Background Art

[0002] Polyimide (PI) is a type of aromatic heterocyclic compound containing an imide ring in the main chain, which is obtained by polycondensation of diamine and dibasic acid anhydride. Since polyimide has good high temperature resistance, low temperature resistance, good mechanical properties, insulation properties and dielectric properties, it is widely used in coatings, adhesives, engineering plastics and photoresists, and is an indispensable and important material at present. However, the application of ordinary polyimide in the field of photolithography is relatively cumbersome. In order to simplify the process and improve the yield rate, researchers have developed photosensitive polyimide (PSPI) with direct photolithography function.

[0003] Photosensitive polyimide can spontaneously form patterns and eventually remain on electronic devices as a polyimide film. Therefore, the advantages of PSPI are not only reflected in the excellent performance of polyimide, but also in the simplification of the pattern formation process.

[0004] The current photosensitive polyimide has a problem of relatively low film retention rate during the curing process after cross-linking.

[0005] Public Content

[0006] In order to solve the problems of the prior art, the embodiments of the present disclosure provide a photo-induced acid-generating curing polyimide and a preparation method thereof and a photo-induced acid-generating curing photoresist. The technical solution is as follows:

[0007] In one aspect, the present disclosure provides a photo-induced acid-generating curable polyimide, the general structural formula of the photo-induced acid-generating curable polyimide is as follows:

[0008]

[0009] wherein Ar1 is selected from at least one of a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride and a tetravalent organic group derived from aromatic tetracarboxylic dianhydride;

[0010] Ar3 is At least one of;

[0011] Ar2 is at least one of a divalent organic group of an aromatic diamine and Ar3.

[0012] Specifically, Ar1 is at least one of the following groups:

[0013]

[0014] Specifically, the divalent organic group of the aromatic diamine includes:

[0015]

[0016]

[0017] On the other hand, the present disclosure provides a method for preparing a photo-induced acid-generating curable polyimide, comprising the following steps:

[0018] In the presence of a non-protonic polar solvent and an inert gas atmosphere, a dianhydride monomer and a diamine monomer are subjected to a ring-opening polymerization reaction, wherein the molar ratio of the dianhydride monomer to the diamine monomer is 1:(0.9-1.1), and the diamine monomer comprises: a diamine monomer A, to obtain a polymer precursor;

[0019] Under the inert gas atmosphere, the polymer precursor and the end-capping agent are subjected to an end-capping reaction, wherein the molar ratio of the polymer precursor to the end-capping agent is 1:(2-2.4), to obtain a prepolymer polyamic acid;

[0020] In the presence of an ionic liquid, the prepolymer polyamic acid is subjected to a thermal imidization reaction to obtain the photo-induced acid-generating curing polyimide;

[0021] The dianhydride monomer is at least one of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride;

[0022] The diamine monomer A is at least one of the following diamine structural formulas:

[0023]

[0024] The dianhydride monomer is at least one of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride;

[0025] The diamine monomer A is at least one of the following diamine structural formulas:

[0026]

[0027] Specifically, the aprotic polar solvent is at least one of N-methylpyrrolidone and dimethylacetamide (DMAc).

[0028] Specifically, the dianhydride monomer is at least one of the following dianhydride structural formulas:

[0029]

[0030] Specifically, the diamine monomer further comprises: a diamine monomer B, the molar ratio of the diamine monomer A to the diamine monomer B is 1:(0-4), and the diamine monomer B is at least one of the following aromatic diamine structural formulas:

[0031]

[0032] Specifically, the temperature of the cyclopolymerization reaction and the end-capping reaction is 25-30°C, and the temperature of the thermal imidization reaction is 160-170°C.

[0033] On the other hand, an embodiment of the present disclosure provides a photo-initiated acid-generating curing photoresist, comprising the following components in parts by weight: 10 to 35 parts of photo-initiated acid-generating curing polyimide, 0.5 to 6 parts of a cross-linking agent, 0.5 to 5 parts of a photo-initiated acid generator, and 65 to 90 parts of a non-protonic polar solvent.

[0034] Specifically, the light-initiated acid-generating curing type photoresist further includes a sensitizer, and the mass fraction of the sensitizer is 0.05 to 1.5 parts.

[0035] Furthermore, the cross-linking agent is 2,6-bis(hydroxymethyl)-p-cresol.

[0036] Furthermore, the photoinitiator acid generator is at least one of PTMA, PAG-2 and PAG108.

[0037] Further, the sensitizer is at least one of photoinitiator 819, photoinitiator 2829, photoinitiator-819DW, photoinitiator Darocur-4265, photoinitiator Darocur BP, photoinitiator Darocur MBF and photoinitiator Darocur TPO.

[0038] Furthermore, the aprotic polar solvent is at least one of N-methylpyrrolidone and dimethylacetamide.

[0039] The technical solution provided by the embodiment of the present disclosure has the following beneficial effects: the photo-induced acid-generating curable polyimide provided by the embodiment of the present disclosure has a high film retention rate during the curing process after cross-linking, and is prepared into a chemically amplified negative photoresist, and the obtained pattern has a high resolution. In addition, its cross-linking method determines that it has higher heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present disclosure. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0041] Figure 1 This is a comparison chart of infrared spectra of the prepolymer polyamic acid PAA and the photo-initiated acid-generating curing polyimide provided in Example 1 of the present disclosure;

[0042] Figure 2 It is a comparison diagram of the TG spectrum and the DTG spectrum of the photo-induced acid-generating curing polyimide provided in Example 1 of the present disclosure;

[0043] Figure 3 is a DSC spectrum of the photo-induced acid-generating curing polyimide provided in Example 1 of the present disclosure;

[0044] Figure 4 is an enlarged view of the light-triggered acid-generating curing type photoresist mask provided in the tenth embodiment of the present disclosure;

[0045] Figure 5 is an enlarged view of the photo-induced acid-generating curing type photoresist provided in the tenth embodiment of the present disclosure after photolithography;

[0046] Figure 6 yes Figure 5 A partial enlarged view of . DETAILED DESCRIPTION

[0047] In order to make the objectives, technical solutions and advantages of the present disclosure more clear, the embodiments of the present disclosure will be further described in detail below with reference to the accompanying drawings.

[0048] Embodiment 1

[0049] The embodiment of the present invention provides a method for preparing a photo-induced acid-generating curing polyimide, and the specific preparation method is as follows:

[0050] S1. In the presence of a non-protonic polar solvent and an inert gas atmosphere, a dianhydride monomer, a diamine monomer A and a diamine monomer B are subjected to a ring-opening polymerization reaction to obtain a polymer precursor; the molar ratio of the diamine monomer A and the diamine monomer B to the dianhydride monomer is 1:1.

[0051] Specifically, the aprotic polar solvent can be at least one of N-methylpyrrolidone (NMP) and dimethylacetamide. In this embodiment, the aprotic polar solvent is N-methylpyrrolidone. The diamine monomer A is 4,4'-SBAP, the diamine monomer B is 4,4'-ODA, and the dianhydride monomer is BPADA.

[0052] Specifically, under nitrogen protection, 30 mL of anhydrous NMP and 5 mmol of 4,4'-ODA were added to a flask and stirred until 4,4'-ODA was completely dissolved. Then, 10 mmol of 4,4'-SBAP and 10 mmol of BTDA were added to the flask. The mixture was stirred and reacted at room temperature (25°C) for 3 hours. After the reaction was completed, a polymer precursor was obtained.

[0053] S2, under nitrogen atmosphere, 10 mmol of polymer precursor and 20 mmol of maleic anhydride were subjected to a capping reaction at 25° C. for 3 h to obtain a prepolymer polyamic acid PAA;

[0054] S3. In the presence of an ionic liquid, the prepolymer polyamic acid PAA is subjected to a thermal imidization reaction to obtain a photo-induced acid-generating curing polyimide.

[0055] Specifically, the ionic liquid is 1,3-bis(2-methoxy-2-oxoethyl)imidazolium tetrafluoroborate.

[0056] Specifically, 30 mL of ionic liquid 1,3-bis(2-methoxy-2-oxyethyl)imidazolium tetrafluoroborate, 14 mL of xylene and 0.1 g of hydroquinone were added to 20 mmol of prepolymer polyamic acid PAA, and the mixture was reacted at 165° C. for 5 h for dehydration and thermal imidization to obtain a mixture, ethanol (detergent) was added to the mixture to obtain a precipitate, the precipitate was filtered to obtain a filter cake, and the filter cake was dried at a constant temperature at 100° C. to obtain the final product, i.e., photo-initiated acid-curing polyimide.

[0057] The prepolymer polyamic acid PAA and the photo-induced acid-curing polyimide were compared by infrared spectroscopy. The comparison results are as follows: Figure 1 As shown. Figure 1 It can be seen that 1720cm -1 The absorption peak of C=O symmetric stretching vibration at 1238cm -1 The stretching vibration peak of the CN bond at is significantly enhanced, which shows that the partial cyclization of the polyamic acid is successful.

[0058] The specific reaction process is as follows:

[0059]

[0060] The structure of the photo-induced acid-generating curable polyimide obtained in this embodiment is as follows:

[0061]

[0062] Where Ar1 is Ar2 is Ar3 is

[0063] The photo-induced acid-curing polyimide PSPI prepared in this example was subjected to thermogravimetric analysis. The obtained TG spectrum and DTG spectrum are as follows: Figure 2 As shown by Figure 2It can be seen that before 100°C, the photo-induced acid-generating curable polyimide prepared in this embodiment has a small weight loss, which is caused by the volatilization of residual ethanol; the weight loss at 180-432°C is caused by the continued imidization of incompletely cyclized PAA; the light-induced acid-generating curable polyimide prepared in this embodiment begins to decompose at 460°C, and when the temperature is 540°C, the decomposition rate reaches the maximum, and when the temperature rises to 800°C, there is still a 46% residual carbon rate, which shows that the light-induced acid-generating curable polyimide prepared in this embodiment has good heat resistance.

[0064] The photo-induced acid-curing polyimide PSPI prepared in this example was subjected to differential scanning calorimetry analysis, and the resulting DSC spectrum is shown in FIG. Figure 3 As shown by Figure 3 It can be seen that the glass transition temperature of the photo-induced acid-generating curable polyimide prepared in this embodiment is 204° C. It can be seen that the photo-induced acid-generating curable polyimide obtained in this embodiment has good heat resistance.

[0065] Embodiment 2

[0066] The difference between this embodiment and the first embodiment is that the diamine monomer A used in the embodiment of the present invention is 4,4'-SBAP, the diamine monomer B is 3,3'-DABP, and the dianhydride monomer is BTDA. Under the protection of argon, 30 mL of anhydrous NMP and 9 mmol of 3,3'-DABP are added to a flask, and stirred until 3,3'-DABP is completely dissolved. Then, 9 mmol of 4,4'-SBAP is added to the flask, and then 20 mmol of BTDA is added. The reaction is stirred at 30° C. for 3 hours. After the reaction is completed, a polymer precursor is obtained.

[0067] Under an argon atmosphere, 20 mmol of the polymer precursor and 48 mmol of maleic anhydride were subjected to a capping reaction at 30° C. to obtain a prepolymer polyamic acid PAA.

[0068] To 20 mmol of prepolymer polyamic acid PAA, 30 mL of ionic liquid 1,3-bis(2-methoxy-2-oxyethyl)imidazolium tetrafluoroborate, 14 mL of xylene and 0.1 g of hydroquinone were added, and the mixture was reacted at 165° C. for 5 h for dehydration and thermal imidization to obtain a mixture. Ethanol (detergent) was added to the mixture to obtain a precipitate. The precipitate was filtered to obtain a filter cake. The filter cake was dried at a constant temperature at 100° C. to obtain the final product, i.e., a photo-initiated acid-generating curing polyimide.

[0069] The specific reaction process is as follows:

[0070]

[0071] The structure of the photo-induced acid-generating curable polyimide PSPI obtained in this embodiment is as follows:

[0072]

[0073] Where Ar1 is Ar2 is Ar3 is

[0074]

[0075] Embodiment 3

[0076] The difference between this embodiment and the first embodiment is that the diamine monomer A used in the embodiment of the present invention is 4,4'-SBAP, the diamine monomer B is m-BAPP, and the dianhydride monomer is BTDA. Under the protection of argon, 30 mL of anhydrous DMAc and 11 mmol of m-BAPP are added to a flask, and stirred until the m-BAPP is completely dissolved. Then, 11 mmol of 4,4'-SBAP is added to the flask, and then 20 mmol of BTDA is added. The reaction is stirred at 30° C. for 3 hours. After the reaction is completed, a polymer precursor is obtained.

[0077] Under an argon atmosphere, 20 mmol of the polymer precursor and 48 mmol of maleic anhydride were subjected to a capping reaction at 30° C. to obtain a prepolymer polyamic acid PAA.

[0078] To 20 mmol of prepolymer polyamic acid PAA, 30 mL of ionic liquid 1,3-bis(2-methoxy-2-oxyethyl)imidazolium tetrafluoroborate, 14 mL of xylene and 0.1 g of hydroquinone were added, and the mixture was reacted at 160° C. for 5 h for dehydration and thermal imidization to obtain a mixture. Ethanol (detergent) was added to the mixture to obtain a precipitate. The precipitate was filtered to obtain a filter cake. The filter cake was dried at a constant temperature at 100° C. to obtain the final product, i.e., a photo-initiated acid-generating curing polyimide.

[0079] The specific reaction process is as follows:

[0080]

[0081] The structure of the photoinduced acid-generating PSPI obtained in this example is as follows:

[0082]

[0083] Where Ar1 is Ar2 is Ar3 is

[0084]

[0085] Embodiment 4

[0086] The difference between this embodiment and the first embodiment is that the diamine monomer A used in the embodiment of the present invention is BHAPP, the diamine monomer B is TFMODA, and the dianhydride monomers are CBDA and BPADA. Under nitrogen protection, 30 mL of anhydrous NMP and 16 mmol of TFMODA are added to a flask, and stirred until TFMODA is completely dissolved. Then, 4 mmol of BHAPP is added to the flask, and then 10 mmol of CBDA and 10 mmol of BPADA are added. The reaction is stirred at 30° C. for 3 hours. After the reaction is completed, a polymer precursor is obtained.

[0087] Under a nitrogen atmosphere, 20 mmol of the polymer precursor and 48 mmol of maleic anhydride were subjected to a capping reaction at 30° C. to obtain a prepolymer polyamic acid PAA.

[0088] To 20 mmol of polyamic acid PAA, 30 mL of ionic liquid 1,3-bis(2-methoxy-2-oxyethyl)imidazolium tetrafluoroborate, 14 mL of xylene and 0.1 g of hydroquinone were added, and the mixture was reacted at 170° C. for 5 h for dehydration and thermal imidization to obtain a mixture. Ethanol (detergent) was added to the mixture to obtain a precipitate. The precipitate was filtered to obtain a filter cake. The filter cake was dried at a constant temperature at 100° C. to obtain the final product, i.e., a photo-initiated acid-generating curing polyimide.

[0089] The specific reaction process is as follows:

[0090]

[0091] The structure of the photo-induced acid-generating curable polyimide PSPI obtained in this embodiment is as follows:

[0092]

[0093] Where Ar1 is Ar2 is Ar3 is

[0094] Embodiment 5

[0095] The difference between this embodiment and the first embodiment is that the diamine monomer A used in the embodiment of the present invention is 4,4'-DABP and 4,6-DAOL, the diamine monomer B is TFMB, and the dianhydride monomers are CBDA and H-PMDA. Under nitrogen protection, 30 mL of anhydrous DMAc and 12 mmol of TFMB are added to a flask, and stirred until TFMB is completely dissolved. Then, 4 mmol of 4,6-DAOL and 4 mmol of 4,4'-DABP are added to the flask, and then 10 mmol of CBDA and 10 mmol of H-PMDA are added. The reaction is stirred at 30° C. for 3 hours. After the reaction is completed, a polymer precursor is obtained.

[0096] Under nitrogen atmosphere, 20 mmol of the polymer precursor was subjected to end-capping reaction with 48 mmol of maleic anhydride at 30° C. to obtain a prepolymer polyamic acid PAA.

[0097] To 20 mmol of polyamic acid PAA, 30 mL of ionic liquid 1,3-bis(2-methoxy-2-oxyethyl)imidazolium tetrafluoroborate, 14 mL of xylene and 0.1 g of hydroquinone were added, and the mixture was reacted at 165° C. for 5 h for dehydration and thermal imidization to obtain a mixture. Ethanol (detergent) was added to the mixture to obtain a precipitate. The precipitate was filtered to obtain a filter cake. The filter cake was dried at a constant temperature at 100° C. to obtain the final product, i.e., photo-initiated acid-generating curing polyimide.

[0098] The specific reaction process is as follows:

[0099]

[0100] The structure of the photo-induced acid-generating curable polyimide PSPI obtained in this embodiment is as follows:

[0101]

[0102] Where Ar1 is Ar2 is Ar3 is

[0103] Embodiment 6

[0104] The difference between this embodiment and the first embodiment is that the diamine monomer A used in the embodiment of the present invention is 6FAP, the diamine monomer B is TFMB, the dianhydride monomers are CBDA, H-PMDA and 6FDA. Under nitrogen protection, 30 mL of anhydrous NMP and 10 mmol of TFMB are added to a flask, stirred until TFMB is completely dissolved, and then 10 mmol of 6FAP is added to the flask, and then 6 mmol of CBDA, 6 mmol of H-PMDA and 8 mmol of 6FDA are added. The reaction is stirred at 30° C. for 3 hours. After the reaction is completed, a polymer precursor is obtained.

[0105] Under an argon atmosphere, 20 mmol of the polymer precursor and 48 mmol of maleic anhydride were subjected to a capping reaction at 30° C. to obtain a prepolymer polyamic acid PAA.

[0106] To 20 mmol of polyamic acid PAA, 30 mL of ionic liquid 1,3-bis(2-methoxy-2-oxyethyl)imidazolium tetrafluoroborate, 14 mL of xylene and 0.1 g of hydroquinone were added, and the mixture was reacted at 165° C. for 5 h for dehydration and thermal imidization to obtain a mixture. Ethanol (detergent) was added to the mixture to obtain a precipitate. The precipitate was filtered to obtain a filter cake. The filter cake was dried at a constant temperature at 100° C. to obtain the final product, i.e., photo-initiated acid-generating curing polyimide.

[0107] The specific reaction process is as follows:

[0108]

[0109] The structure of the photo-induced acid-generating curable polyimide PSPI obtained in this embodiment is as follows:

[0110]

[0111] Where Ar1 is Ar2 is Ar3 is

[0112] Embodiment 7

[0113] The difference between this embodiment and the first embodiment is that the diamine monomer A used in the embodiment of the present invention is 4,4'-SBAP, the diamine monomer B is m-BAPP, and the dianhydride monomers are PMDA and BTDA. Under nitrogen protection, 30 mL of anhydrous DMAc and 12 mmol of m-BAPP are added to a flask and stirred until the m-BAPP is completely dissolved. Then, 8 mmol of 4,4'-SBAP is added to the flask, and then 4 mmol of PMDA and 16 mmol of BTDA are added. The reaction is stirred at 30° C. for 3 hours. After the reaction is completed, a polymer precursor is obtained.

[0114] Under a nitrogen atmosphere, 20 mmol of the polymer precursor and 48 mmol of maleic anhydride were subjected to a capping reaction at 30° C. to obtain a prepolymer polyamic acid PAA.

[0115] To 20 mmol of polyamic acid PAA, 30 mL of ionic liquid 1,3-bis(2-methoxy-2-oxyethyl)imidazolium tetrafluoroborate, 14 mL of xylene and 0.1 g of hydroquinone were added, and the mixture was reacted at 165° C. for 5 h for dehydration and thermal imidization to obtain a mixture. Ethanol (detergent) was added to the mixture to obtain a precipitate. The precipitate was filtered to obtain a filter cake. The filter cake was dried at a constant temperature at 100° C. to obtain the final product, i.e., photo-initiated acid-generating curing polyimide.

[0116] The specific reaction process is as follows:

[0117]

[0118] The structure of the photo-induced acid-generating curable polyimide PSPI obtained in this embodiment is as follows:

[0119]

[0120] Where Ar1 is Ar2 is Ar3 is

[0121] Embodiment 8

[0122] The difference between this embodiment and the first embodiment is that the diamine monomer A used in the embodiment of the present invention is 4,4'-DABP and 4,6-DAOL, the diamine monomer B is TFMB, and the dianhydride monomers are NTDA and ODPA. Under nitrogen protection, 30 mL of anhydrous NMAc and 12 mmol of TFMB are added to a flask, and stirred until TFMB is completely dissolved. Then, 4 mmol of 4,4'-DABP and 4 mmol of 4,6-DAOL are added to the flask, and then 10 mmol of NTDA and 10 mmol of ODPA are added. The reaction is stirred at 30°C for 3 hours. After the reaction is completed, a polymer precursor is obtained.

[0123] Under a nitrogen atmosphere, 20 mmol of the polymer precursor and 48 mmol of maleic anhydride were subjected to a capping reaction at 30° C. to obtain a prepolymer polyamic acid PAA.

[0124] To 20 mmol of polyamic acid PAA, 30 mL of ionic liquid 1,3-bis(2-methoxy-2-oxyethyl)imidazolium tetrafluoroborate, 14 mL of xylene and 0.1 g of hydroquinone were added, and the mixture was reacted at 165° C. for 5 h for dehydration and thermal imidization to obtain a mixture. Ethanol (detergent) was added to the mixture to obtain a precipitate. The precipitate was filtered to obtain a filter cake. The filter cake was dried at a constant temperature at 100° C. to obtain the final product, i.e., photo-initiated acid-generating curing polyimide.

[0125] The specific reaction process is as follows:

[0126]

[0127] The structure of the photo-induced acid-generating curable polyimide PSPI obtained in this embodiment is as follows:

[0128]

[0129] Where Ar1 is Ar2 is , Ar3 is

[0130] Embodiment 9

[0131] The difference between this embodiment and the first embodiment is that the diamine monomer A used in the embodiment of the present invention is 4,4'-SBAP, and the dianhydride monomer is DSDA. Under nitrogen protection, 30 mL of anhydrous NMP and 20 mmol of 4,4'-SBAP are added to a flask, stirred until 4,4'-SBAP is completely dissolved, and then 20 mmol of DSDA is added to the flask. The reaction is stirred at 30°C for 3 hours. After the reaction is completed, a polymer precursor is obtained.

[0132] Under a nitrogen atmosphere, 20 mmol of the polymer precursor and 48 mmol of maleic anhydride were subjected to a capping reaction at 30° C. to obtain a prepolymer polyamic acid PAA.

[0133] The specific reaction formula is as follows:

[0134]

[0135] The structure of the photo-induced acid-generating curable polyimide PSPI obtained in this embodiment is as follows:

[0136]

[0137] Where Ar1 is Ar2 is Ar3 is

[0138] The light-initiated acid-generating curable polyimide PSPI obtained in the above-mentioned Examples 1 to 9 was subjected to a heat resistance test. The test results are shown in Table 2.

[0139] Table 2 shows heat resistance

[0140]

[0141] It can be seen from Table 2 that the photo-induced acid-generating curable polyimide obtained in Examples 1 to 9 has good heat resistance.

[0142] Embodiment 10

[0143] The present embodiment provides a photo-induced acid-generating curable photoresist, comprising the following components in parts by weight: 10 to 35 parts of photo-induced acid-generating curable polyimide, 0.5 to 6 parts of a cross-linking agent, 0.5 to 5 parts of a photo-induced acid generator, and 65 to 90 parts of aprotic polar solvent.

[0144] Specifically, the light-initiated acid-generating curing type photoresist further includes a sensitizer, and the mass fraction of the sensitizer is 0.05 to 1.5 parts.

[0145] Specifically, a crosslinking agent 2,6-bis(hydroxymethyl)-p-cresol was added to the photo-induced acid-generating curable polyimide prepared in Examples 1 to 9, respectively, and the mixture was stirred and dissolved. After the mixture was completely dissolved, a mixed solution was obtained. The mixed solution was added to a brown vial, and then a photo-induced acid generator was added to obtain a photo-induced acid-generating curable photoresist. The specific amount and type of photo-induced acid generator are shown in Table 1.

[0146] Table 1 shows the combinations of different photo-induced acid-generating curing polyimides and photo-induced acid generators.

[0147]

[0148]

[0149] The photo-induced acid-curing photoresist was coated on the glass plate, and then the glass plate was placed on a heating table at 80°C for 10 minutes to remove the solvent and form a dry film. After covering with a mask, it was sent into a UV curing machine for curing for 10 seconds and then taken out. The glass plate was placed on a heating table at 120°C and baked for 30 minutes and then removed. After the glass plate was cooled, it was developed with a 5% tetramethylammonium hydroxide aqueous solution.

[0150] The pattern of the mask of the photo-induced acid-curing type photoresist prepared by the photo-induced acid-curing type polyimide provided in Example 1 is as follows: Figure 4 As shown, the pattern after photolithography of the photo-induced acid-curing photoresist is as follows Figure 5 and Figure 6 As shown by Figure 4 , Figure 5 and Figure 6 It can be seen that after a series of photolithography operations, the PSPI obtained in this embodiment can obtain a relatively clear photolithography pattern.

[0151] After the photo-induced acid-generating curable photoresist is developed, it is further imidized to obtain a photo-induced acid-generating curable photoresist film. The film retention rate of the photo-induced acid-generating curable photoresist film is tested, and the film retention rate is shown in Table 2.

[0152] Film retention rate measurement method: Use a step profiler to measure the film thickness before and after imidization, and then divide the film thickness before imidization by the film thickness after imidization to obtain the film retention rate, as shown in Table 3.

[0153] Table 3 shows the film retention rate

[0154]

[0155]

[0156] It can be seen from Table 3 that the photo-induced acid-generating curing type photoresist film prepared by the photo-induced acid-generating curing type polyimide obtained in Examples 1 to 9 has a high film retention rate. This is because the PSPI linked by the cross-linking agent 2,6-bis(hydroxymethyl)-p-cresol has higher stability during the imidization process, and the molecular chain is not easy to break, which makes the film retention rate of the photo-induced acid-generating curing type photoresist film higher.

[0157] The above description is only an optional embodiment of the present disclosure and is not intended to limit the present disclosure. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present disclosure shall be included in the protection scope of the present disclosure.

Claims

1. A method for preparing a photo-induced acid-generating curable polyimide, characterized in that: The steps include: In the presence of a non-protonic polar solvent and an inert gas atmosphere, a dianhydride monomer and a diamine monomer are subjected to a ring-opening polymerization reaction, wherein the temperature of the ring-opening polymerization reaction is 25-30° C., the time of the ring-opening polymerization reaction is 3 hours, the molar ratio of the dianhydride monomer to the diamine monomer is 1:(0.9-1.1), and the diamine monomer includes: a diamine monomer A, to obtain a polymer precursor; Under the inert gas atmosphere, the polymer precursor and the end-capping agent are subjected to an end-capping reaction, the molar ratio of the polymer precursor to the end-capping agent is 1:(2-2.4), the temperature of the end-capping reaction is 25-30° C., and the time of the end-capping reaction is 3 hours, to obtain a prepolymer polyamic acid; In the presence of an ionic liquid, the ionic liquid is 1,3-bis(2-methoxy-2-oxyethyl) imidazole tetrafluoroborate, the prepolymer polyamic acid is subjected to a thermal imidization reaction, the temperature of the thermal imidization reaction is 160-170° C., the time of the thermal imidization reaction is 5 hours, and the photo-initiated acid-generating curing polyimide is obtained; The dianhydride monomer is at least one of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride; The diamine monomer A is at least one of the following diamine structural formulas: The general structural formula of the photo-induced acid-generating curing polyimide is as follows: n is the degree of polymerization, wherein Ar1 is selected from at least one of a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride and a tetravalent organic group derived from aromatic tetracarboxylic dianhydride; Ar3 is At least one of; Ar2 is at least one of a divalent organic group of an aromatic diamine and Ar3.

2. The preparation method according to claim 1, characterized in that: Ar1 is at least one of the following groups:

3. The preparation method according to claim 1, characterized in that: The divalent organic group of the aromatic diamine includes:

4. The preparation method according to claim 1, characterized in that: The aprotic polar solvent is at least one of N-methylpyrrolidone and dimethylacetamide.

5. The preparation method according to claim 1, characterized in that: The diamine monomer further comprises: a diamine monomer B, the molar ratio of the diamine monomer A to the diamine monomer B is 1:(0-4), and the diamine monomer B is at least one of the following aromatic diamine structural formulas:

6. A photo-induced acid-generating curing photoresist, characterized in that: The method comprises the following components in parts by mass: 10 to 35 parts of a photo-induced acid-generating curable polyimide prepared by the method for preparing a photo-induced acid-generating curable polyimide according to any one of claims 1 to 3, 0.5 to 6 parts of a crosslinking agent, 0.5 to 5 parts of a photo-induced acid generator, and 65 to 90 parts of a non-protonic polar solvent.

7. The photo-induced acid-generating curing type photoresist according to claim 6, characterized in that: The light-initiated acid-generating curing type photoresist further includes a sensitizer, and the mass proportion of the sensitizer is 0.05 to 1.5 parts.

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