A positive photosensitive polyimide resin glue with high toughness, and a preparation method and use thereof

Abstract

This invention discloses a method for preparing and using a high-strength and tough positive photosensitive resin adhesive. In a Class 1000 cleanroom equipped with a yellow light source, 100 parts by weight of component (A), 3-40 parts by weight of component (B), 3-40 parts by weight of component (C), 0.1-20 parts by weight of component (D), 3-40 parts by weight of component (E), and 3-40 parts by weight of component (G) are added in batches to component (F) under stirring to form a homogeneous solution. After filtration, the solution is dispensed to obtain a positive photosensitive resin adhesive with a solid content of 15-45 wt.% and a viscosity of 500-4000 mPa·s at room temperature. After coating, exposure, development, and curing, the resulting resin film exhibits high strength and toughness, high heat resistance, high adhesion, and high chemical resistance, making it suitable for multilayer metal interconnect wiring in wafer-level packaging and panel-level packaging.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically disclosing a high-strength and tough positive photosensitive polyimide resin liquid, its preparation method and uses, which is suitable for multilayer metal interconnect wiring in wafer-level packaging and panel-level packaging. Background Technology

[0002] In recent years, advanced packaging technologies for high-density integrated circuits, including wafer-level packaging (WLP) and panel-level packaging (PLP), have developed rapidly. In the manufacturing process of fan-out WLP / PLP, multiple layers of metal interconnect circuits (RDLs) need to be fabricated on the surface of the reconstructed wafer or glass substrate. As the number of RDLs increases, the overall thickness of the cured dielectric film increases, leading to a significant increase in internal stress, often causing problems such as warping, deformation, and interlayer cracking. Therefore, improving the strength and toughness of the resin film has become a crucial challenge that must be addressed.

[0003] Positive photosensitive polyimide (PSPI) materials mainly include two types: negative PSPI and positive PSPI. Based on different curing temperatures, they are further divided into high-temperature curing (≥300°C) and low-temperature curing (≤230°C). Compared with low-temperature curing negative PSPI, low-temperature curing positive PSPI still has a significant gap in terms of resistance to humid heat and chemical moisture penetration.

[0004] In the prior art, Tory Industries, Inc. of Japan (US 10,908,500 B2) disclosed a photosensitive resin composition containing a polybenzoxazole precursor resin, which is formed by the condensation polymerization of an aromatic diacid and its derivatives with a phenolic hydroxyl aromatic diamine and a fatty ether chain diamine, and the curing temperature is 170-250°C. o C. Hitachi Chemical DuPont Microsystems Co., Ltd. (US 2019 / 0049842 A1, US 2018 / 0074403 A1) disclosed a positive photosensitive resin composition comprising a polybenzoxazole precursor resin, a crosslinking agent, a photosensitizing agent, and an organic solvent. The precursor resin is formed by a polycondensation reaction of a phenolic hydroxyl aromatic diamine and an aliphatic diacid, and is suitable for multi-chip FOWLP packaging. Summary of the Invention

[0005] This invention discloses a positive photosensitive resin liquid with high strength and toughness. The resin film formed after the liquid is coated into a film, pre-baked, exposed, developed, rinsed, and cured by heating (180-230°C) has high strength and toughness, high resistance to damp heat, high resistance to chemical corrosion and high copper surface adhesion, and is suitable for multilayer metal interconnect wiring in advanced packaging of high-density integrated circuits.

[0006] The positive photosensitive resin adhesive comprises the following chemical components: (A) a mixed resin containing phenolic hydroxyl polyaminate resin-1 (PAE-1) and phenolic hydroxyl polyaminate resin-2 (PAE-2); (B) a photoacid-generating agent; (C) a thermal crosslinking agent; (D) a thermal acid-generating agent; (E) a sensitizer; (F) an organic solvent; (G) a tackifier; and optionally, a carboxyl-containing organic compound. The weight ratio of PAE-1 to PAE-2 is from 99:1 to 50:50.

[0007] PAE-1 is formed by a polycondensation reaction of aromatic dianhydride-1, a phenolic hydroxyl-containing aromatic diamine, and a reactive end-capping agent; PAE-2 is formed by a polycondensation reaction of aromatic dianhydride-2, a phenolic hydroxyl-containing aromatic diamine, and a reactive end-capping agent.

[0008] The aromatic dianhydride-1 includes 2,3,2',3'-biphenyltetracarboxylic dianhydride (23BPDA), 2,3',3,4'-biphenyltetracarboxylic dianhydride (34BPDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (44BPDA), and mixtures thereof; the aromatic dianhydride-2 includes 2,3,2',3'-diphenylethertetracarboxylic dianhydride (23ODPA), 2,3',3,4'-diphenylethertetracarboxylic dianhydride (34ODPA), 3,3',4,4'-diphenylethertetracarboxylic dianhydride (44ODPA), and mixtures thereof in any proportion.

[0009] The phenolic hydroxyl-containing aromatic diamines include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (3HFAP), 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane (4HFAP), 2,2-bis(3-amino-4-hydroxyphenyl)propane (3-BAPP), bis(4-amino-3-hydroxyphenyl)methane (4BAPP), 2,2'-bis[N-(3-aminobenzoamido)-3-amino-4-hydroxyphenyl]hexafluoropropane (3HFHA), 2,2'-bis[N-(4-aminobenzoamide)-3-amino-4-hydroxyphenyl]hexafluoropropane (4HFHA), and siloxane-containing diamines, as well as mixtures thereof in any proportion.

[0010] The reactive end-capping agent includes maleic anhydride, 4-aminobenzocyclobutene, 4-vinylaniline, norbornene, allylamine, anhydrides or amines containing ethynyl or phenylethynyl groups, and mixtures thereof in any proportion.

[0011] The photoacid-producing agent includes diazonoquinone compounds, iodonium salt compounds, and sulfonium salt compounds. The thermal crosslinking agent includes compounds containing epoxy groups and / or compounds containing hydroxymethyl or alkoxymethyl groups. The thermal acid-producing agent is a compound that can produce a strong acid upon heating and has a thermal decomposition initiation temperature of 150℃-250℃. The sensitizer includes compounds containing phenolic hydroxyl, hydroxyl, or carboxyl groups. The tackifier includes silane coupling agents containing amino, epoxy, vinyl, mercapto, or isocyanate groups.

[0012] The preparation methods of PAE-1 and PAE-2 include: esterifying aromatic dianhydrides with fatty alcohols under heating conditions to generate aromatic diacid diesters; reacting them with thionyl chloride to generate aromatic diester diacyl chlorides; reacting them with imidazole-based nitrogen-containing organic bases to generate aromatic diester diimidazolium salts; and then polycondensing them with phenolic hydroxyl-containing aromatic diamines in an organic solvent in the presence of a reactive end-capping agent; precipitating the reaction solution in a poor solvent, separating, thoroughly washing, heating, and vacuum drying to obtain GPC with a molecular weight of 1.0 × 10⁻⁶. 4 Up to 3.0×10 4 The resin.

[0013] The present invention also provides a method for preparing the positive photosensitive resin solution: In a Class 1000 cleanroom equipped with a yellow light source, 100 parts by weight of mixed resin (A), 3-40 parts by weight of photoacid generator (B), 3-40 parts by weight of thermal crosslinking agent (C), 0.1-20 parts by weight of thermalacid generator (D), 3-40 parts by weight of sensitizer (E), and 3-40 parts by weight of tackifier (G) are added in batches to an organic solvent (F) under stirring to form a homogeneous solution. After filtration, the solution is packaged to obtain a positive photosensitive resin solution with a solid content of 15-45 wt.% and a viscosity of 500-4000 mPa·s at room temperature.

[0014] The present invention also provides the application of the adhesive in multilayer metal interconnect wiring for wafer-level packaging and panel-level packaging, including: spin coating or inkjet printing the adhesive into a film, pre-baking, exposure, development and rinsing, and then heating and curing at 180-230°C to form a resin three-dimensional pattern, and then forming conductor copper lines through electroplating and etching processes, and repeating the above process to form a multilayer RDL structure.

[0015] The beneficial effects of this invention are as follows:

[0016] The high-strength and tough positive photosensitive resin liquid disclosed in this invention can form a liquid film of uniform thickness on the surface of a 12-inch silicon wafer through a spin coating process. The resin three-dimensional pattern formed after photolithography processes such as pre-baking, exposure, and development has high photolithographic resolution and excellent photolithographic processability. The resin film formed after low-temperature curing (180-230℃) has the characteristics of high resistance to damp heat, high resistance to chemical corrosion and high copper surface adhesion, and is suitable for manufacturing multilayer metal interconnect circuit layers for advanced packaging such as high-density integrated circuit wafer-level packaging. Attached Figure Description

[0017] Figure 1 The chemical structure diagram of phenolic hydroxyl polyamide ester resin-1 is shown.

[0018] Figure 2 This is the chemical structure diagram of phenolic hydroxyl polyamide ester resin-2. Detailed Implementation

[0019] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0020] 1. Comprehensive performance evaluation method:

[0021] The performance of the positive photosensitive resin liquid was evaluated using the following evaluation method:

[0022] 1) Film toughness: A positive photosensitive resin solution is spin-coated onto the surface of a 12-inch silicon wafer to form a uniformly thick film; at 120°C... o After baking at C for 3 minutes, the surface was exposed to UV light (i and g lines) without a mask. It was then developed by spraying or immersion with an aqueous developer (2.38% TMAH), rinsed with ultrapure water, and cured in a nitrogen-protected oven at 150°C. o C / 1h, 200 o C / 1h, 230 o(C / 1h). A silicon wafer with a cured film on its surface was immersed in 47% HF for 5-10 minutes, then rinsed with water to obtain a cured resin film with a thickness of 8.0 µm. The cured resin film was cut into strips 1.0 cm wide and 9.0 cm long, and the mechanical properties of the film were tested using a tensile testing machine. The testing rate was 50 mm / min, with 7 strips per group. The 5 highest values ​​were averaged to obtain the tensile strength and elongation at break. If the tensile strength of the prepared cured resin film is ≥150 MPa and the elongation at break is ≥60%, it is rated as "Excellent"; if the tensile strength of the prepared cured resin film is ≥150 MPa and the elongation at break is in the range of 31-49%, it is rated as "Good"; if the tensile strength of the prepared cured resin film is ≥150 MPa and the elongation at break is ≤30%, it is rated as "Poor".

[0023] 2) Photolithography processability: A positive photosensitive resin liquid is spin-coated onto the surface of a 12-inch silicon wafer to form a liquid film of uniform thickness; at 100-110... o After baking at C for 1-3 minutes, place a mask on its surface and expose it with ultraviolet lamps (i and g lines); develop it with an aqueous developer (2.38% TMAH) by spraying or immersion, rinse with ultrapure water, and then heat-cur it in a nitrogen-protected oven at 150°C. o C / 1h, 200 o C / 1h, 230 o C / 1h) was used to obtain a stereolithographic pattern of cured resin with a thickness of 8.0 μm.

[0024] The photolithography processability is evaluated by observing the three-dimensional pattern under an optical microscope: if the thickness uniformity of the cured resin film after curing is ≤0.5%, the resolution of each raised strip pattern and through hole is ≤5.0µm, and the patterns are cleanly developed without foreign matter residue, the photolithography resolution is rated as "excellent"; if the thickness uniformity of the cured film is 0.51-0.99%, the resolution of each pattern is 5.1-9.9µm, and the patterns are cleanly developed without foreign matter residue, the photolithography resolution is rated as "good"; if the thickness uniformity of the cured film is ≥1.0%, the resolution of the pattern is ≥10.0µm, and the patterns are not cleanly developed with foreign matter residue, the photolithography resolution is rated as "poor".

[0025] 3) Resistance to damp heat: A liquid adhesive film is formed by spin-coating a positive photosensitive resin solution onto the surface of a 12-inch silicon wafer; 120 o After baking at C for 3 minutes, the surface was exposed to UV light (i and g lines) without a mask. It was then developed by spraying or immersion with an aqueous developer (2.38% TMAH), rinsed with ultrapure water, and cured in a nitrogen-protected oven at 150°C.o C / 1h, 200 o C / 1h, 230 o C / 1h), a cured resin film is formed on the substrate surface; the substrate is then placed in 120 o After steaming in a pressure cooker at C / 2 atm for 100 hours, it was then cooled to room temperature of -260°C. o C. Three thermal cycling shock tests; using FIB (fiber optic lithography), the longitudinal section of the copper-tin bumps covering the resin film was cut open, and the interface morphology between the copper-tin bumps and the resin film was observed using an optical microscope. If no cracking or voids were found at the interface between the copper-tin bumps and the cured resin, it was rated as "Excellent"; if a small amount of cracking or voids were found at the interface between the copper-tin bumps and the cured resin, it was rated as "Good"; if a large number of cracks or voids were found at the interface between the copper-tin bumps and the cured resin, it was rated as "Poor".

[0026] 4) Chemical resistance: The photolithographic 3D pattern of the heat-cured resin was subjected to 100°C in a caustic solution (1 wt.% potassium hydroxide + 39 wt.% 3-methoxy-3-methyl-1-butanol + 60 wt.% dimethyl sulfoxide (DMSO)). o After soaking in C for 1 hour, the film was washed with water and air-dried. The chemical resistance of the cured resin film was evaluated by measuring the change in film thickness and observing it under an optical microscope: if the thickness change of the cured resin film after soaking was within ±1% and no cracks or defects were produced, it was rated as "excellent"; if the thickness change of the cured resin film after soaking was within ±3% and no cracks or defects were produced, it was rated as "good"; if the thickness change of the cured resin film after soaking exceeded ±5% or cracks or defects were produced, it was rated as "poor".

[0027] 5) Adhesion to copper surfaces: Positive photosensitive resin is spin-coated onto the surface of a 12-inch silicon wafer to form a uniformly thick film; at 100-110... o After baking at C for 1-3 minutes, expose the surface with ultraviolet lamps (i and g lines) without placing a mask; develop with aqueous developer (2.38% TMAH) by spraying or immersion, rinse with ultrapure water, and then heat-cur in a nitrogen-protected oven at 150°C. o C / 1h, 200 o C / 1h, 230 o (C / 1h) to obtain a cured resin film with a thickness of 10-12µm. The adhesion between the film and copper was evaluated using a cross-cut test: "Excellent" was defined as 0 cross-cuts of film with no cross-cuts peeled off; "Good" was defined as 1-10 cross-cuts of film with no cross-cuts peeled off; and "Poor" was defined as more than 11 cross-cuts of film with no cross-cuts peeled off.

[0028] 6) Overall performance evaluation: If all indicators are "excellent", the overall performance evaluation is "excellent"; if any one indicator is "good", the overall performance evaluation is "good"; if any one indicator is "poor", the overall performance evaluation is "poor".

[0029] 2. Example of synthesis of phenolic hydroxyl resin

[0030] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. Unless otherwise specified, the reaction temperatures in the following examples were all conducted at room temperature.

[0031] PAE-1-1 to PAE-11

[0032] Resin Synthesis Example 1

[0033] In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and nitrogen protection device, 29.42 g (0.10 mol.) of 2,3,2',3'-biphenyltetracarboxylic dianhydride (33BPDA), 9.20 g (0.20 mol. Mw=46.02) of ethanol, 15.82 g (0.20 mol.) of pyridine, and 129 g of N-methylpyrrolidone (NMP) were added. The mixture was stirred at room temperature for 6 h to produce the corresponding diethyl aromatic diacid ester. The product was then reacted with 23.79 g of SOCl2 at 0-10 °C for 2 h, followed by a reaction at room temperature for 4 h to produce a solution of the corresponding 33BPDA diethyl diacid chloride.

[0034] In a 1L three-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and nitrogen protection device, 36.62 g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) and 158 g of NMP were added and stirred until dissolved to form a homogeneous transparent solution (3HFAP / NMP); the 33BPDA diethyl dichlorodimethyl ... 1.00 g of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (4MSiNA) was added to phthalic anhydride and stirred for 1 h. The reaction solution was poured into 5 L of deionized water, the solid precipitated, filtered, and dried under vacuum to obtain primary polyamic acid ester resin (PAE-1-1). This solution was dissolved in tetrahydrofuran to form a solution, and residual metal or non-metal ions were removed by adsorption with anionic and cationic resins to obtain high-purity phenolic hydroxyl-containing polyamic acid ester resin solid (abbreviated as: PAE1-1-1: 33BPDA-3HFAP).

[0035] Resin Synthesis Example 2

[0036] In Resin Synthesis Example 1, 29.42 g (0.10 mol.) 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA) was replaced with 29.42 g (0.10 mol.) 2,3',3,4'-biphenyltetracarboxylic dianhydride (34BPDA), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-2: 34BPDA-3HFAP).

[0037] Resin Synthesis Example 3

[0038] In Resin Synthesis Example 1, 29.42 g (0.10 mol.) 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA) was replaced with 29.42 g (0.10 mol.) 3,3',4,4'-biphenyltetracarboxylic dianhydride (44BPDA), while keeping everything else the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-3:44BPDA-3HFAP).

[0039] Resin Synthesis Example 4

[0040] In Resin Synthesis Example 1, 29.42 g (0.10 mol.) 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA) was replaced with a mixture of 14.71 g (0.05 mol.) 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA) and 14.71 g (0.05 mol.) 2,3',3,4'-biphenyltetracarboxylic dianhydride (34BPDA), while other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-4: 33BPDA / 34BPDA(1 / 1)-3HFAP).

[0041] Resin Synthesis Example 5

[0042] In Resin Synthesis Example 1, 29.42 g (0.10 mol.) 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA) was replaced with a mixture of 14.71 g (0.05 mol.) 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA) and 14.71 g (0.05 mol.) 3,3',4,4'-biphenyltetracarboxylic dianhydride (44BPDA), while all other conditions remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-5: 33BPDA / 44BPDA(1 / 1)-3HFAP).

[0043] Resin Synthesis Example 6

[0044] In Resin Synthesis Example 1, 29.42 g (0.10 mol.) 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA) was replaced with a mixture of 14.71 g (0.05 mol.) 2,3',3,4'-biphenyltetracarboxylic dianhydride (34BPDA) and 14.71 g (0.05 mol.) 3,3',4,4'-biphenyltetracarboxylic dianhydride (44BPDA), while all other conditions remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-6: 34BPDA / 44BPDA(1 / 1)-3HFAP).

[0045] Resin Synthesis Example 7

[0046] In Resin Synthesis Example 2, 36.62 g (0.10 mol.) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) was replaced with 36.62 g (0.10 mol.) 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane (abbreviated as: 4HFAP, Mw=366.17), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-7: 34BPDA-4HFAP).

[0047] Resin Synthesis Example 8

[0048] In Resin Synthesis Example 2, 36.62 g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) was replaced with 60.43 g (0.10 mol.) of 2,2'-bis[N-(3-aminobenzoamide)-3-amino-4-hydroxyphenyl]hexafluoropropane (abbreviated as: 3HFHA, Mw=604.32), with all other parameters remaining the same, to obtain a high-purity phenolic hydroxyl polyaminate resin solid (abbreviated as: PAE1-1-8:34BPDA-3HFHA).

[0049] Resin Synthesis Example 9

[0050] In Resin Synthesis Example 2, 36.62 g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) was replaced with 60.43 g (0.10 mol.) of 2,2'-bis[N-(4-aminobenzoylamino)-3-amino-4-hydroxyphenyl]hexafluoropropane (abbreviated as: 4HFHA, Mw=604.32), with all other parameters remaining the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-9:34BPDA-4HFHA).

[0051] Resin Synthesis Example 10

[0052] In Resin Synthesis Example 2, 36.62 g (0.10 mol.) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) was replaced with 25.82 g (0.10 mol.) 2,2-bis(3-amino-4-hydroxyphenyl)propane (abbreviated as: 3-HHAP, Mw=258.17), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-10:34BPDA-3HHAP).

[0053] Resin Synthesis Example 11

[0054] In Resin Synthesis Example 2, 36.62 g (0.10 mol.) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) was replaced with 25.82 g (0.10 mol.) 2,2-bis(4-amino-3-hydroxyphenyl)propane (abbreviated as: 4-HHAP, Mw=258.17), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-11:34BPDA-4HHAP).

[0055] PAE-2-1

[0056] Resin Synthesis Example 12

[0057] In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and nitrogen protection device, 31.02 g (0.10 mol.) of 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride (44ODPA), 9.20 g (0.20 mol.) of ethanol, 15.82 g (0.20 mol.) of pyridine, and 129 g of N-methylpyrrolidone (NMP) were added. The mixture was stirred at room temperature for 6 h to produce the corresponding diethyl aromatic diacid ester. The product was then reacted with 23.79 g of SOCl2 at 0-10 °C for 2 h, followed by a reaction at room temperature for 4 h to produce a solution of the corresponding 44ODPA diethyl diacyl chloride.

[0058] In a 1L three-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and nitrogen protection device, 36.62 g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) and 158 g of NMP were added and stirred until dissolved to form a homogeneous transparent solution (3HFAP / NMP); the 44ODPA diethyl dichlorodimethyl ... 1.00 g of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (4MSiNA) was added to phthalic anhydride and stirred for 1 h. The reaction solution was poured into 5 L of deionized water, the solid precipitated, filtered, and dried under vacuum to obtain primary polyamic acid ester resin (PAE-2-1). This solution was dissolved in tetrahydrofuran to form a solution, and residual metal or non-metal ions were removed by adsorption with anionic and cationic resins to obtain high-purity phenolic hydroxyl-containing polyamic acid ester resin solid (abbreviated as: PAE-2-1: 44ODPA-3HFAP).

[0059] Resin Synthesis Example 13

[0060] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride (44ODPA) was replaced with 31.02 g (0.10 mol.) 2,2,3',3'-diphenyl ether tetracarboxylic dianhydride (33ODPA), while keeping all other parameters the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE-2-2:33ODPA-3HFAP).

[0061] Resin Synthesis Example 14

[0062] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride (44ODPA) was replaced with 31.02 g (0.10 mol.) 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (34ODPA), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE-2-3:34ODPA-3HFAP).

[0063] Resin Synthesis Example 15

[0064] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride (44ODPA) was replaced with a mixture of 15.51 g (0.05 mol.) 2,2,3',3'-diphenyl ether tetracarboxylic dianhydride (33ODPA) and 15.51 g (0.05 mol.) 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride (44ODPA), while other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE-2-4:33ODPA / 44ODPA(1 / 1)-3HFAP).

[0065] Resin Synthesis Example 16

[0066] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride (44ODPA) was replaced with a mixture of 15.51 g (0.05 mol.) 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (34ODPA) and 15.51 g (0.05 mol.) 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride (44ODPA), otherwise the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE-2-5: 34ODPA / 44ODPA(1 / 1)-3HFAP).

[0067] Resin Synthesis Example 17

[0068] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 3,3,4',4'-diphenyl ether tetracarboxylic dianhydride (44ODPA) was replaced with a mixture of 15.51 g (0.05 mol.) 2,2,3',3'-diphenyl ether tetracarboxylic dianhydride (33ODPA) and 15.51 g (0.05 mol.) 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (34ODPA), otherwise the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE-2-6: 33ODPA / 34ODPA(1 / 1)-3HFAP).

[0069] 3. Positive photosensitive resin solution

[0070] Examples 1-6 and Comparative Examples 1-2

[0071] Example 1

[0072] In a cleanroom equipped with a yellow light, 50g of phenolic hydroxyl polyamide ester resin-1 (PAE-1-1) prepared in Resin Synthesis Example 1 and 50g of phenolic hydroxyl polyamide resin-2 (PAE-2-1) prepared in Resin Synthesis Example 12 were weighed and dissolved in 100g of γ-butyrolactone solvent to form a homogeneous solution. Then, 10g of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone-5-sulfonate (photoacid-generating agent), 5.0g of p-toluenesulfonic acid-2-methoxyethyl ester (thermal acid-generating agent), 5.0g of 2,2-bis(4-hydroxyphenyl)propane (sensitizer), 4.0g of 2,2-bis(4-epoxypropoxyphenyl)propane (thermal crosslinking agent), and 5.0g of γ-aminopropyltriethoxysilane (adhesive agent) were added sequentially. The mixture was stirred at room temperature for 1 hour to obtain a positive resin composition solution. When the solid content was 35wt.%, the solution viscosity was 1500. mPa.s.

[0073] The above-mentioned positive resin solution is uniformly coated onto the surface of a 12-inch silicon wafer or a large-area glass substrate using a spin coating process; at a temperature of 100-110°C... o After baking at C for 1-3 minutes, place a mask on its surface and expose it with ultraviolet lamps (i and g lines); spray develop it with a tetramethylammonium hydroxide alkaline aqueous solution (2.38% TMAH), rinse with deionized ultrapure water, and then heat-cur it in a nitrogen-protected forced-air oven (150°C). o C / 1h, 200 o C / 1h, 220 o (C / 1h) to obtain a stereolithographic pattern formed by a thermosetting resin film.

[0074] The prepared positive photosensitive resin solution was evaluated for performance using the above evaluation method. The evaluation results are as follows: ① Film toughness: tensile strength is 155 MPa, elongation at break is 66%, rated as "excellent"; ② Photolithography processability: film thickness uniformity is 0.47%, photolithography resolution is 4.6 μm, rated as "excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "excellent"; ④ Resistance to chemical etching: film thickness change rate is 0.62%, no microcracks or defects were observed, rated as "excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result is 0 / 100, rated as "excellent"; ⑥ Comprehensive performance evaluation: all indicators are excellent, rated as "excellent".

[0075] Example 2

[0076] In Example 1, PAE-1-1 was replaced with PAE-1-2, while other aspects remained the same, to obtain a positive photosensitive resin solution. The performance of the positive photosensitive resin solution was evaluated using the above evaluation method. The evaluation results were as follows: ① Film toughness: tensile strength was 157 MPa, elongation at break was 67%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.64%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0077] Example 3

[0078] In Example 1, PAE-1-1 was replaced with PAE-1-3, while other aspects remained the same, resulting in a positive photosensitive resin solution. The performance of this solution was evaluated using the aforementioned evaluation method. The results were as follows: ① Film toughness: tensile strength was 159 MPa, elongation at break was 68%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.75%, photolithography resolution was 7.5 μm, rated as "Good"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.56%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Overall performance evaluation: one indicator was "Good", rated as "Good".

[0079] Example 4

[0080] In Example 1, PAE-1-1 was replaced with PAE-1-4, while other aspects remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Film toughness: tensile strength was 156 MPa, elongation at break was 64%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.44%, photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.67%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0081] Example 5

[0082] In Example 1, PAE-1-1 was replaced with PAE-1-5, while other aspects remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Film toughness: tensile strength was 152 MPa, elongation at break was 65%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.43%, photolithography resolution was 4.5 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.64%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0083] Example 6

[0084] In Example 1, PAE-1-1 was replaced with PAE-1-6, while other aspects remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Film toughness: tensile strength was 153 MPa, elongation at break was 64%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.48%, photolithography resolution was 4.4 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.66%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0085] Comparative Example 1

[0086] PAE-2-1 was removed from Example 1, while all other parameters remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the aforementioned evaluation method, and the results were as follows: ① Film toughness: tensile strength was 156 MPa, elongation at break was 46%, rated as "Good"; ② Photolithography processability: film thickness uniformity was 0.46%, photolithography resolution was 4.7 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.64%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 8 / 100, rated as "Good"; ⑥ Overall performance evaluation: two indicators were good, rated as "Good".

[0087] Comparative Example 2

[0088] PAE-1-1 was removed from Example 1, while all other parameters remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Film toughness: tensile strength was 135 MPa, elongation at break was 36%, rated as "Good"; ② Photolithography processability: film thickness uniformity was 0.70%, photolithography resolution was 8.2 μm, rated as "Good"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.67%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 9 / 100, rated as "Good"; ⑥ Overall performance evaluation: two indicators were good, rated as "Good".

[0089] Table 1 compares the effects of changes in the main chain structure of the PAE-1 series resins (PAE-1-1, 1-2, 1-3, 1-4, 1-5, 1-6) on the overall performance of the prepared positive photosensitive resins when the weight ratio of the PAE-1 series resins (PAE-1) and PAE-2 series resins (PAE-2-1) in Examples 1-6 is 1:1. The results show that the positive photosensitive resin solution formed by thoroughly mixing PAE-1-1 or PAE-1-2, PAE-1-4, PAE-1-5, PAE-1-6 with PAE-2-1 in a 1:1 weight ratio, with components such as photoacidifiers, thermal crosslinking agents, and tackifiers, exhibits excellent overall performance, and its overall performance is rated as "excellent". The overall performance evaluation of the positive photosensitive resin solution prepared by combining PAE-1-3 and PAE-2-1 in a 1:1 weight ratio was "good". In contrast, when the phenolic hydroxyl polyaminate resin (PAE-1-1) or the phenolic hydroxyl polyaminate resin (PAE-2-1) is only a single component resin, rather than a mixed resin formed by the two, the overall performance evaluation of the prepared positive photosensitive resin solution is "good or poor".

[0090] Table 1 Comparison of results between Examples 1-6 and Comparative Examples 1-2

[0091] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 PAE-1 PAE-1-133BPDA-3HFAP PAE-1-234BPDA-3HFAP PAE-1-344BPDA3HFAP PAE-1-433BPDA / 34BPDA(1 / 1)-3HFAP PAE-1-533BPDA / 44BPDA(1 / 1)-3HFAP PAE-1-634BPDA / 44BPDA(1 / 1)-3HFAP PAE-1-133BPDA-3HFAP -- PAE-2 PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP Solid content of adhesive (wt.%) 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 Adhesive viscosity, mPa·s (23℃) 1500±100 1500±100 1500±100 1500±100 1500±100 1500±100 1500±100 1500±100 Curing temperature (°C) 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h ①Film strength, tensile strength / elongation 155MPa / 66% excellent 157MPa / 67% excellent 159MPa / 68% excellent 156MPa / 64% excellent 152MPa / 65% excellent 153MPa / 64% excellent 156MPa / 46% good 135MPa / 36% good ②Film thickness uniformity / photolithography resolution in photolithography process 0.47% / 4.6μm Excellent 0.47% / 4.6μm Excellent 0.75% / 7.5μm fine 0.44% / 4.6μm Excellent 0.43% / 4.5μm Excellent 0.48% / 4.4μm Excellent 0.46% / 4.7μm Excellent 0.7% / 8.2μm fine ③ Resistance to damp heat No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent ④ Chemical corrosion resistance film thickness change rate / microcracks or defects 0.62% / No microcracks or defects / Excellent 0.64% / No microcracks or defects / Excellent 0.56% / No cracks or minor defects / Excellent 0.67% / No microcracks or defects / Excellent 0.64% / No microcracks or defects / Excellent 0.66% / No microcracks or defects / Excellent 0.64% / No microcracks or defects / Excellent 0.67% / No microcracks or defects / Excellent ⑤ Copper adhesion / 100-cross test 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 8 / 100 good 9 / 100 good ⑥ Comprehensive performance evaluation excellent excellent good excellent excellent excellent good good

[0092] Example 7

[0093] In Example 1, PAE-1-1 was replaced with PAE-1-7, while other aspects remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Film toughness: tensile strength was 150 MPa, elongation at break was 66%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.44%, photolithography resolution was 4.7 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.82%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0094] Example 8

[0095] In Example 1, PAE-1-1 was replaced with PAE-1-8, while other aspects remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Film toughness: tensile strength was 157 MPa, elongation at break was 67%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0096] Example 9

[0097] In Example 1, PAE-1-1 was replaced with PAE-1-9, while other aspects remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method. The evaluation results were as follows: ① Film toughness: tensile strength was 159 MPa, elongation at break was 66%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.43%, photolithography resolution was 4.5 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.76%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0098] Example 10

[0099] In Example 1, PAE-1-1 was replaced with PAE-1-10, while other aspects remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Film toughness: tensile strength was 157 MPa, elongation at break was 64%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.45%, photolithography resolution was 7.6 μm, rated as "Good"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.72%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Overall performance evaluation: one indicator was good, rated as "Good".

[0100] Example 11

[0101] PAE-1-1 in Example 1 was replaced with PAE-1-11, while other aspects remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Film toughness: tensile strength was 152 MPa, elongation at break was 65%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, photolithography resolution was 8.5 μm, rated as "Good"; ③ Resistance to damp heat: many microcracks or defects were observed, rated as "Poor"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Overall performance evaluation: one indicator was poor, rated as "Poor".

[0102] Comparative Example 3

[0103] PAE-2-1 was removed from Example 8, while all other parameters remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the aforementioned evaluation method, and the results were as follows: ① Film toughness: tensile strength was 156 MPa, elongation at break was 46%, rated as "Good"; ② Photolithography processability: film thickness uniformity was 0.45%, photolithography resolution was 4.7 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 8 / 100, rated as "Good"; ⑥ Overall performance evaluation: two indicators were good, rated as "Good".

[0104] Comparative Example 4

[0105] PAE-2-1 was removed from Example 9, while all other parameters remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the aforementioned evaluation method, and the results were as follows: ① Film toughness: tensile strength was 125 MPa, elongation at break was 36%, rated as "Good"; ② Photolithography processability: film thickness uniformity was 1.10%, photolithography resolution was 8.2 μm, rated as "Poor"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.77%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 9 / 100, rated as "Good"; ⑥ Overall performance evaluation: one indicator was poor, rated as "Poor".

[0106] Table 2 Comparison of results from Examples 7-11

[0107] Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 3 Comparative Example 4 PAE-1 PAE-1-734BPDA-4HFAP PAE-1-834BPDA-3HFHA PAE-1-934BPDA-4HFHA PAE-1-1034BPDA-3HHAP PAE-1-1134BPDA-4HHAP PAE-1-834BPDA-3HFHA PAE-1-934BPDA-4HHAP PAE-2 PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP PAE-2-144ODPA-3HFAP -- -- Solid content of adhesive (wt.%) 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 Adhesive viscosity, mPa·s (23℃) 1500±100 1500±100 1500±100 1500±100 1500±100 1500±100 1500±100 Curing temperature (°C) 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h ①Film strength, tensile strength / elongation 150MPa / 66% excellent 157MPa / 67% excellent 159MPa / 66% excellent 157MPa / 64% excellent 152MPa / 65% excellent 156MPa / 46% good 125MPa / 36% good ②Film thickness uniformity / photolithography resolution in photolithography process 0.44% / 4.7μm Excellent 0.47% / 4.6μm Excellent 0.43% / 4.5μm Excellent 0.45% / 7.6μm fine 0.47% / 8.5μm fine 0.45% / 4.7μm Excellent 1.1% / 8.2μm difference ③ Resistance to damp heat excellent excellent excellent excellent Difference excellent excellent ④ Chemical corrosion resistance film thickness change rate / microcracks or defects 0.82% / No microcracks or defects / Excellent 0.74% / No microcracks or defects / Excellent 0.76% / No cracks or minor defects / Excellent 0.72% / No microcracks or defects / Excellent 0.74% / No microcracks or defects / Excellent 0.74% / No microcracks or defects / Excellent 0.77% / No microcracks or defects / Excellent ⑤ Copper adhesion / 100-cross test 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 8 / 100 good 9 / 100 good ⑥ Comprehensive performance evaluation excellent excellent excellent good Difference good Difference

[0108] Table 2 compares the effects of different molecular structures of the phenolic hydroxyl-containing polyaminate resin-1 series resins (PAE-1) and phenolic hydroxyl-containing polyaminate resin-2 (PAE-2-1) used in the PAE-1 series resins (PAE-1-7, PAE-1-8, PAE-1-9) on the overall performance of the prepared positive photosensitive resins when the weight ratio of PAE-1 to PAE-2-1 is 1:1. The results show that the positive photosensitive resin solution formed by thoroughly mixing the mixed resin of PAE-1-7 or PAE-1-8, PAE-1-9 and PAE-2-1 in a 1:1 weight ratio with photoacidifiers, thermal crosslinking agents, thermal acidifiers, and tackifiers exhibits excellent overall performance, and its overall performance is rated as "excellent". The overall performance evaluation of the positive photosensitive resin solution prepared by compounding PAE-1-10 or PAE-1-11 with PAE-2-1 in a 1:1 weight ratio was "good or poor". In contrast, when the phenolic hydroxyl polyaminate resin (PAE-1-8 or PAE-1-9) is only a single component, rather than a mixed resin formed with PAE-2-1, the overall performance evaluation of the prepared positive photosensitive resin solution is also "good or poor".

[0109] Example 12

[0110] In Example 2, PAE-2-1 was replaced with PAE-2-2, while other aspects remained the same, to obtain a positive photosensitive resin solution. The performance of the positive photosensitive resin solution was evaluated using the above evaluation method. The evaluation results were as follows: ① Film toughness: tensile strength was 155 MPa, elongation at break was 66%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.44%, photolithography resolution was 7.7 μm, rated as "Good"; ③ Resistance to damp heat: a small number of microcracks or defects were observed, rated as "Good"; ④ Resistance to chemical etching: film thickness change rate was 0.82%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: two indicators were good, rated as "Good".

[0111] Example 13

[0112] In Example 2, PAE-2-1 was replaced with PAE-2-3, while other aspects remained the same, resulting in a positive photosensitive resin solution. The performance of the positive photosensitive resin solution was evaluated using the above evaluation method. The evaluation results were as follows: ① Film toughness: tensile strength was 157 MPa, elongation at break was 67%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0113] Example 14

[0114] In Example 2, PAE-2-1 was replaced with PAE-2-4, while other aspects remained the same, to obtain a positive photosensitive resin solution. The performance of the positive photosensitive resin solution was evaluated using the above evaluation method. The evaluation results were as follows: ① Film toughness: tensile strength was 159 MPa, elongation at break was 66%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.73%, photolithography resolution was 4.5 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.76%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0115] Example 15

[0116] In Example 2, PAE-2-1 was replaced with PAE-2-5, while other aspects remained the same, resulting in a positive photosensitive resin solution. The performance of the positive photosensitive resin solution was evaluated using the above evaluation method. The evaluation results were as follows: ① Film toughness: tensile strength was 167 MPa, elongation at break was 68%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.45%, photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.72%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0117] Example 16

[0118] In Example 2, PAE-2-1 was replaced with PAE-2-6, while other aspects remained the same, resulting in a positive photosensitive resin solution. The performance of the positive photosensitive resin solution was evaluated using the above evaluation method. The evaluation results were as follows: ① Film toughness: tensile strength was 152 MPa, elongation at break was 65%, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, photolithography resolution was 4.5 μm, rated as "Excellent"; ③ Resistance to damp heat: many microcracks or defects were observed, rated as "Poor"; ④ Resistance to chemical etching: film thickness change rate was 0.74%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Overall performance evaluation: one indicator was poor, rated as "Poor".

[0119] Comparative Example 5

[0120] PAE-1-2 was removed from Example 13, while all other parameters remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the aforementioned evaluation method, and the results were as follows: ① Film toughness: tensile strength was 156 MPa, elongation at break was 46%, rated as "Good"; ② Photolithography processability: film thickness uniformity was 0.45%, photolithography resolution was 4.7 μm, rated as "Excellent"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 8 / 100, rated as "Good"; ⑥ Overall performance evaluation: two indicators were good, rated as "Good".

[0121] Comparative Example 6

[0122] PAE-1-2 was removed from Example 15, while all other parameters remained the same, resulting in a positive photosensitive resin solution. Its performance was evaluated using the aforementioned evaluation method, and the results were as follows: ① Film toughness: tensile strength was 125 MPa, elongation at break was 36%, rated as "Good"; ② Photolithography processability: film thickness uniformity was 1.10%, photolithography resolution was 8.2 μm, rated as "Poor"; ③ Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.77%, no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 9 / 100, rated as "Good"; ⑥ Overall performance evaluation: one indicator was poor, rated as "Poor".

[0123] Table 3 Comparison of results from Examples 12-16

[0124] Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 5 Comparative Example 6 PAE-1 PAE-1-234BPDA-3HFAP PAE-1-234BPDA-3HFAP PAE-1-234BPDA-3HFAP PAE-1-234BPDA-3HFAP PAE-1-234BPDA-3HFAP -- -- PAE-2 PAE-2-233ODPA-3HFAP PAE-2-334ODPA-3HFAP PAE-2-433ODPA / 44ODPA(1 / 1)-3HFAP PAE-2-534ODPA / 44ODPA-(1 / 1)-3HFAP PAE-2-633ODPA / 34ODPA-(1 / 1)-3HFAP PAE-2-334ODPA-3HFAP PAE-2-534ODPA / 44ODPA-(1 / 1)-3HFAP Solid content of adhesive (wt.%) 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 35±2.0 Adhesive viscosity, mPa·s (23°C) 1500±100 1500±100 1500±100 1500±100 1500±100 1500±100 1500±100 Curing temperature (°C) 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h ①Film strength, tensile strength / elongation 155MPa / 66% excellent 157MPa / 67% excellent 159MPa / 66% excellent 157MPa / 68% excellent 152MPa / 65% excellent 156MPa / 46% good 125MPa / 36% good ②Film thickness uniformity / photolithography resolution in photolithography process 0.44% / 4.7μm Excellent 0.47% / 4.6μm Excellent 0.73% / 4.5μm Excellent 0.45% / 4.6μm Excellent 0.47% / 4.5μm Excellent 0.45% / 4.7μm Excellent 1.1% / 8.2μm difference ③ Resistance to damp heat No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent No microcracks or defects / excellent ④ Chemical corrosion resistance film thickness change rate / microcracks or defects 0.82% / No microcracks or defects / Excellent 0.74% / No microcracks or defects / Excellent 0.76% / No cracks or minor defects / Excellent 0.72% / No microcracks or defects / Excellent 0.74% / No microcracks or defects / Excellent 0.74% / No microcracks or defects / Excellent 0.77% / No microcracks or defects / Excellent ⑤ Copper adhesion / 100-cross test 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 0 / 100 Excellent 8 / 100 good 9 / 100 good ⑥ Comprehensive performance evaluation All indicators are excellent / excellent. All indicators are excellent / excellent. All indicators are excellent / excellent. All indicators are excellent / excellent. All indicators are excellent / excellent. 2 indicators are good / good 1 indicator difference / difference

[0125] Table 3 compares the effects of different molecular structures of aromatic tetracarboxylic dianhydrides (33-ODPA, 34-ODPA, 44-ODPA, and their 1:1 weight ratio) on the overall performance of the prepared positive photosensitive resins when the weight ratio of PAE-2 series resins (PAE-2-2, 2-3, 2-4, 2-5, 2-6) is 1:1. The results show that the positive photosensitive resin solution formed by thoroughly mixing PAE-2-2, or PAE-2-3, PAE-2-4, PAE-2-5, PAE-2-6, and PAE-1-2 in a 1:1 weight ratio with other components such as photoacidifiers, thermal crosslinking agents, and tackifiers, exhibits excellent overall performance, and its overall performance is rated as "excellent". In contrast, when the phenolic hydroxyl polyamide resin (PAE-2-3 or PAE-2-5) is only a single component, rather than a mixed resin formed with PAE-1-2, the overall performance evaluation of the prepared positive photosensitive resin solution is "good or poor".

[0126] This invention discloses a high-strength and tough positive photosensitive resin liquid, its preparation method, and its application. The positive photosensitive polyimide resin liquid is characterized by high photolithographic resolution and excellent photolithographic processability. The liquid film formed by coating is subjected to pre-baking, exposure, development, rinsing, and heat curing (180-230°C). o C) High-quality three-dimensional photolithography patterns can be formed after the resin film is cured by heating. It has the characteristics of high resistance to damp heat, high resistance to chemical immersion, and high copper surface adhesion, and is suitable for multilayer metal interconnect wiring in advanced packaging of high-density integrated circuits.

Claims

1. A high-strength and tough positive photosensitive polyimide resin adhesive, composed of the following components: (A) A mixed resin containing phenolic hydroxyl polyaminate resin-1 and phenolic hydroxyl polyaminate resin-2; (B) Photoacid-producing agents; (C) Thermal crosslinking agent; (D) Thermotropic acid-producing agents; (E) Sensitive agents; (F) Organic solvents; (G) Adhesives; wherein: The phenolic hydroxyl polyamic acid ester resin-1 is formed by a polycondensation reaction of aromatic dianhydride-1, phenolic hydroxyl aromatic diamine, and a reactive end-capping agent; The phenolic hydroxyl polyamic acid ester resin-2 is formed by a polycondensation reaction of aromatic dianhydride-2, phenolic hydroxyl aromatic diamine, and a reactive end-capping agent.

2. The positive photosensitive polyimide resin solution according to claim 1, wherein: The weight ratio of the phenolic hydroxyl polyamide ester resin-1 to the phenolic hydroxyl polyamide ester resin-2 is 99:1 to 50:

50.

3. The positive photosensitive polyimide resin liquid according to claim 1, wherein: The preparation method of the phenolic hydroxyl polyamate resin-1 includes: Aromatic dianhydride-1 was esterified with a fatty alcohol under heating to form an aromatic diacid diester; then reacted with thionyl chloride to form an aromatic diester diacyl chloride; subsequently reacted with an imidazole-based nitrogen-containing organic base to form an aromatic diester diimidazolium salt compound; and then reacted with a phenolic hydroxyl-containing aromatic diamine in an organic solvent in the presence of a reactive end-capping agent for polycondensation; the reaction solution was precipitated in a poor solvent, and after separation, washing, and drying, GPC with a molecular weight of 1.0 × 10⁻⁶ was obtained. 4 ~3.0×10 4 The resin.

4. The positive photosensitive polyimide resin adhesive according to claim 1, wherein: The preparation method of the phenolic hydroxyl polyamate resin-2 includes: Aromatic dianhydride-2 was esterified with a fatty alcohol under heating to form an aromatic diacid diester; then reacted with thionyl chloride to form an aromatic diester diacyl chloride; subsequently reacted with an imidazole-based nitrogen-containing organic base to form an aromatic diester diimidazolium salt compound; and then reacted with a phenolic hydroxyl-containing aromatic diamine in an organic solvent in the presence of a reactive end-capping agent for polycondensation; the reaction solution was precipitated in a poor solvent, and after separation, washing, and drying, GPC with a molecular weight of 1.0 × 10⁻⁶ was obtained. 4 ~3.0×10 4 The resin.

5. The positive photosensitive polyimide resin liquid according to claim 3 or 4, wherein: The aromatic dianhydride-1 includes: 2,3,2',3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and mixtures thereof in any proportion; The aromatic dianhydride-2 includes: 2,3,2',3'-diphenyl ether tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and mixtures thereof in any proportion; The phenolic hydroxyl-containing aromatic diamine includes: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)methane, 2,2'-bis[N-(3-aminobenzoamido)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2'-bis[N-(4-aminobenzoamide)-3-amino-4-hydroxyphenyl]hexafluoropropane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, 1,3-bis(3-aminophenoxy)tetramethyldisiloxane, 1,3-bis(4-aminophenoxy)tetramethyldisiloxane, and mixtures thereof in any proportion; The reactive end-capping agent includes: maleic anhydride, 4-aminobenzocyclobutene, 4-vinylaniline, norbornene, allylamine, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-ethynylaniline, 3-ethynylaniline, 3-phenylethynylaniline, 4-phenylethynylaniline, 4-(4-aminophenylethynyl)phenylethynyl, 4-[(trimethylsilyl)ethynyl]aniline, 4-(4-amino-phenyl)-2-methyl-but-3-yn-2-ol, (E)-3-aminocinnamic acid, propargylamine, and mixtures thereof in any proportion; The organic solvents include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolium ketone, dimethyl sulfoxide, ethyl acetate, butyl acetate, tetrahydrofuran, cyclopentanone, cyclohexanone, and mixtures thereof in any proportion. The undesirable solvents include: deionized water, methanol, ethanol, hexane, toluene, and mixtures thereof in any proportion.

6. The positive photosensitive polyimide resin liquid according to claim 1, wherein: The photoacid-producing agent includes one or more of the following: diazonoquinone compounds, iodonium salt compounds, and sulfonium salt compounds; The thermal crosslinking agent includes: compounds containing epoxy groups and / or compounds containing hydroxymethyl or alkoxymethyl groups; The thermogenic acid-producing agent is a compound that can produce a strong acid upon heating and has a thermal decomposition initiation temperature of 150℃-250℃, including one or more of the following: alkyl sulfonic acid, perfluoroalkyl sulfonic acid or its salts, diaryliodomonium salt, trialkylsulfonium salt or ester compound; The sensitizer includes compounds containing phenolic hydroxyl, hydroxyl, or carboxyl groups; The adhesive aid includes: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyl ether oxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 2-cyanoethyltrimethoxysilane, 3-isocyanate-based trimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and mixtures thereof in any proportion.

7. The positive photosensitive polyimide resin liquid according to claim 1, wherein: The positive photosensitive resin solution also includes a carboxyl-containing organic compound, which is one or more carboxylic acid compounds containing 2 to 16 carbon atoms.

8. A method for preparing a positive photosensitive polyimide resin liquid according to any one of claims 1 to 7, comprising: In a Class 1000 cleanroom equipped with a yellow light source, 100 parts by weight of component (A), 3-40 parts by weight of component (B), 3-40 parts by weight of component (C), 0.1-20 parts by weight of component (D), 3-40 parts by weight of component (E), and 3-40 parts by weight of component (G) are added to component (F) in batches under stirring to form a homogeneous solution. After filtration, the solution is dispensed to obtain a positive photosensitive resin liquid with a solid content of 15-45 wt.% and a viscosity of 500-4000 mPa·s at room temperature.

9. The application of a positive photosensitive polyimide resin according to any one of claims 1 to 7 in multilayer metal interconnect wiring for wafer-level packaging and panel-level packaging.

10. The application according to claim 9, comprising: The positive photosensitive resin solution is formed into a liquid film by spin coating on the wafer surface or inkjet printing on a large-area glass substrate surface; Pre-baking at 80-150°C; exposure using a UV light source transmitted through a photomask template; The resin is developed using 2.38% TMAH aqueous developer and rinsed with ultrapure water; it is then heated and cured under nitrogen protection to form a three-dimensional resin pattern; a continuous conductive copper layer is formed by electroplating copper, and then etched to form conductive copper lines; the above process is repeated to form a multilayer RDL structure.

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