A positive photosensitive polyimide resin adhesive with high resistance to damp heat and moisture, its preparation method and uses

Abstract

This patent discloses the application of a positive photosensitive resin adhesive with high resistance to damp heat. The positive photosensitive resin adhesive is composed of a phenolic hydroxyl polyamic acid ester and a mixed resin containing phenolic hydroxyl polyamide, a photoacid-generating agent, a thermotropic crosslinking agent, and a solvent. The mixed resin containing phenolic hydroxyl polyamic acid ester includes both phenolic hydroxyl polyamic acid ester and phenolic hydroxyl polyamide resin. The thermosetting resin film formed after heating and curing of this positive photosensitive resin adhesive exhibits high resistance to damp heat, as well as high strength, toughness, adhesion, and chemical resistance. Furthermore, this positive photosensitive resin adhesive has excellent photolithographic processability; the stereolithographic pattern formed after coating, exposure, development, and rinsing has high resolution and is 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 to a positive photosensitive polyimide resin liquid with high resistance to moisture and heat, its preparation method, and its uses. Background Technology

[0002] In recent years, advanced packaging technologies for high-density integrated circuits (ICs), 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 circuit layers (RDLs) need to be fabricated on the surface of the reconstructed wafer or glass substrate. Fan-out PLP uses a glass substrate with an area exceeding 600mm × 600mm, and the linewidth / spacing of the RDLs can reach 15 / 10μm or even 8 / 5μm.

[0003] As the number of metal wiring layers in RDLs increases, the overall thickness of the cured dielectric film also increases, leading to a significant increase in internal stress and causing problems such as wafer warpage, deformation, and interlayer cracking. Therefore, reducing the internal stress of the resin film during the high-temperature curing process, while ensuring high resistance to moisture and heat, high chemical resistance, and high copper adhesion, has become a problem that advanced packaging must solve.

[0004] Photosensitive polyimide (PSPI) materials mainly include negative PSPI (n-PSPI) and positive PSPI (p-PSPI). Compared with high-temperature curing (≥300℃) negative PSPI, low-temperature curing (≤230℃) positive PSPI has become a research hotspot for RDL materials used in WLP and PLP. However, existing low-temperature curing positive PSPI still lags behind negative PSPI in terms of resistance to humid heat and chemical moisture penetration.

[0005] The positive photosensitive resin compositions disclosed by Tory Industries of Japan (US8,883,391B2, etc.) use polyimide precursors containing phenolic hydroxyl groups and have a curing temperature as high as 350°C. The positive photosensitive resin compositions disclosed by Hitachi Chemical DuPont Microsystems of Japan (US2019 / 0049842A1, etc.) use polybenzoxazole precursor resins. Although the curing temperature can be reduced to 200-250°C, there is still room for improvement in terms of resistance to damp heat and chemical resistance.

[0006] To address the aforementioned problems, this invention improves heat resistance by introducing biphenyl-type polyamic acid ester precursor resin segments into the main chain structure of phenolic hydroxyl polyamic acid ester-1; subsequently, it is compounded with phenolic hydroxyl polyamide resin-2 to form a composite resin system. By utilizing the synergistic effect of the biphenyl-type resin segments and phenolic hydroxyl groups, the problem of the mutual constraint between high resistance to damp heat and high chemical resistance and high photolithography processability of positive photosensitive resins is effectively solved. Summary of the Invention

[0007] This invention discloses a positive photosensitive resin solution with high resistance to damp heat and moisture, its preparation method, and its applications. The thermosetting resin film formed after the positive photosensitive resin solution is cured by heating exhibits high resistance to damp heat and moisture, as well as high strength, toughness, adhesion, and chemical resistance. Furthermore, the resin solution possesses excellent photolithography processability; the stereolithographic pattern formed after coating, exposure, development, and rinsing has high resolution and is suitable for multilayer metal interconnect wiring in wafer-level packaging and panel-level packaging.

[0008] The positive photosensitive resin adhesive is composed of the following chemical components: (A) a mixed resin containing phenolic hydroxyl polyamide ester resin-1 and phenolic hydroxyl polyamide resin-2; (B) a photoacid generator; (C) a thermal crosslinking agent; (D) a thermal acid generator; (E) a sensitizer; (F) an organic solvent; and (G) a tackifier.

[0009] The phenolic hydroxyl-containing polyamide ester resin-1 is formed by a polycondensation reaction of biphenyl-type aromatic dianhydride, a phenolic hydroxyl-containing aromatic diamine, and a reactive end-capping agent. The biphenyl-type aromatic dianhydride 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 in any proportion. The phenolic hydroxyl-containing polyamide resin-2 is formed by a polycondensation reaction of aromatic diacyl chloride or its derivatives, a phenolic hydroxyl-containing aromatic diamine, and a reactive end-capping agent.

[0010] The preparation method of the phenolic hydroxyl-containing polyaminate resin-1 is as follows: Aromatic dianhydride-1 is reacted with a fatty alcohol under heating conditions via esterification to generate an aromatic diacid diester; then reacted with thionyl chloride to generate an aromatic diester diacyl chloride; then reacted with an imidazole-based nitrogen-containing organic base to generate an aromatic diester diimidazolium salt compound; finally, reacted with a phenolic hydroxyl-containing aromatic diamine in an organic solvent under the presence of a reactive end-capping agent via polycondensation to generate a phenolic hydroxyl-containing polyaminate resin solution; the resin is precipitated in a poor solvent, separated, thoroughly washed, and then heated and vacuum dried to obtain the phenolic hydroxyl-containing polyaminate resin (PAE-1) with a number average molecular weight of 1.0 × 10⁻⁶. 4 Up to 3.0×10 4 .

[0011] The preparation method of the phenolic hydroxyl-containing polyamide resin-2 is as follows: An aromatic diacid is reacted with thionyl chloride to generate an aromatic diacyl chloride; then, it is reacted with an imidazole-based nitrogen-containing organic base to generate an aromatic diimidazolium salt compound; next, it is reacted with a phenolic hydroxyl-containing aromatic diamine in an organic solvent in the presence of a reactive end-capping agent via a condensation reaction to generate a phenolic hydroxyl-containing polyamide resin solution; the resin is precipitated in a poor solvent, separated, thoroughly washed, and then heated and vacuum dried to obtain the phenolic hydroxyl-containing polyamide resin (PAE-2) with a number-average molecular weight of 1.0 × 10⁻⁶. 4 Up to 3.0×10 4 .

[0012] The weight ratio of the phenolic hydroxyl polyamide ester resin-1 to the phenolic hydroxyl polyamide resin-2 is 99:1 to 50:50.

[0013] The photoacid-producing agents include diazonoquinone compounds, iodonium salt compounds, and sulfonium salt compounds. The thermal crosslinking agents refer to compounds that can undergo crosslinking reactions under heating conditions or under the action of Lewis acids, including compounds containing epoxy groups, compounds containing hydroxymethyl or alkoxymethyl groups, etc. The thermally induced acid-producing agents refer to compounds that can produce strong acids upon heating, with a thermal decomposition initiation temperature of 150℃-250℃. The sensitizers include compounds containing phenolic hydroxyl, hydroxyl, or carboxyl groups. The organic solvents include N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, ethyl acetate, cyclopentanone, cyclohexanone, etc. The tackifiers include silane coupling agents such as γ-aminopropyltrimethoxysilane and γ-glycidyl etheroxypropyltrimethoxysilane.

[0014] The method for preparing the resin solution of this invention is as follows:

[0015] In a Class 1000 cleanroom equipped with a yellow light source, 100 parts by weight of phenolic hydroxyl polyamide resin (A), 3-40 parts by weight of photoacid-generating agent (B), 3-40 parts by weight of thermal crosslinking agent (C), 0.1-20 parts by weight of thermalacid-generating agent (D), 3-40 parts by weight of sensitizer (E), and 3-40 parts by weight of tackifier (G) were added in batches to an organic solvent (F) under stirring to form a homogeneous solution. After filtration, the solution was packaged to obtain a positive photosensitive resin solution with a solid content of 15-45 wt.% and a solution viscosity of 500-4000 mPa·s at room temperature.

[0016] The positive photosensitive resin solution described in this invention is suitable for fabricating dielectric insulating films for multilayer metal interconnect circuits (RDLs) on the surface of 12-inch silicon wafers or large-area glass substrates. The photolithography patterning process includes: 1) coating; 2) pre-baking (80-150℃); 3) exposure; 4) development and rinsing (2.38% TMAH aqueous developer); 5) heat curing (180-230℃); 6) forming conductive copper lines through copper electroplating and etching. Repeating the above steps can form a multilayer RDL structure.

[0017] The beneficial effects of this invention are as follows:

[0018] The 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

[0019] Figure 1 The chemical structure of phenolic hydroxyl polyamide ester resin-1 is shown.

[0020] Figure 2 The chemical structure of phenolic hydroxyl polyamide ester resin-2 is shown. Detailed Implementation

[0021] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, all materials and reagents used are commercially available.

[0022] 1. Comprehensive performance evaluation method:

[0023] The performance of the positive photosensitive resin liquid was evaluated using the following evaluation method:

[0024] 1) 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.

[0025] The photolithography resolution is evaluated by observing the three-dimensional pattern under an optical microscope: if the uniformity of the thickness (8.0 μm) of the cured resin film after curing is ≤0.5%, the resolution of each raised strip pattern and through hole is ≤5.0 µm, and the patterns are cleanly developed without any foreign matter residue, the photolithography processability is rated as "excellent"; if the uniformity of the thickness of the cured film is 0.51-0.99%, the resolution of each pattern is ≤10 µm, and the patterns are cleanly developed without any foreign matter residue, the photolithography processability is rated as "good"; if the uniformity of the thickness of the cured film is ≥1.0%, the pattern resolution is ≥15 µm, the patterns are not cleanly developed, and there is foreign matter residue, the photolithography processability is rated as "poor".

[0026] 2) Thin film mechanical properties: A positive photosensitive resin solution was spin-coated onto the surface of a 12-inch silicon wafer to form a uniformly thick film; at 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). The silicon wafer with the film is immersed in 47% HF for 5-10 minutes, then rinsed with water to obtain a polyimide film with a thickness of 10-12 µm. The polyimide film is cut into strips 1.0 cm wide and 9.0 cm long, and the mechanical properties of the film are tested using a tensile testing machine. The testing rate is 50 mm / min, with 7 strips per group. The 5 highest values ​​are averaged to obtain the tensile strength and elongation at break. If the tensile strength of the prepared polyimide film is ≥100 MPa and the elongation at break is ≥40%, it is rated as "Excellent"; if the tensile strength of the prepared polyimide film is ≥100 MPa and the elongation at break is 21-39%, it is rated as "Good"; if the tensile strength of the prepared polyimide film is ≤100 MPa and the elongation at break is ≤20%, it is rated as "Poor".

[0027] 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, 230o 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 few cracks or voids were found at the interface between the copper-tin bumps and the cured resin, it was rated as "Good"; if many cracks or voids were found at the interface between the copper-tin bumps and the cured resin, it was rated as "Poor".

[0028] 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 less than ±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 the range of ±1.1-±3.0% and no cracks or defects were produced, it was rated as "good"; if the thickness change of the cured resin film after soaking exceeded ±3.0%, or cracks or defects were produced, it was rated as "poor".

[0029] 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 to ultraviolet light (i and g lines) without placing a mask; develop with an aqueous developer (2.38% TMAH) by spraying or immersion, rinse with ultrapure water, and then cure 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.

[0030] 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".

[0031] 2. Example of synthesis of phenolic hydroxyl resin

[0032] PAE-1-1 to PAE-11

[0033] Resin Synthesis Example 1

[0034] 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 (33-BPDA), 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 diethyl diacid chloride of 33-BPDA.

[0035] 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).

[0036] Resin Synthesis Example 2

[0037] 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).

[0038] Resin Synthesis Example 3

[0039] 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).

[0040] Resin Synthesis Example 4

[0041] 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 all other conditions remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-4: 33BPDA / 34BPDA(1 / 1)-3HFAP).

[0042] Resin Synthesis Example 5

[0043] 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 parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-5: 33BPDA / 44BPDA(1 / 1)-3HFAP).

[0044] Resin Synthesis Example 6

[0045] 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).

[0046] Resin Synthesis Example 7

[0047] 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).

[0048] Resin Synthesis Example 8

[0049] 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).

[0050] Resin Synthesis Example 9

[0051] 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).

[0052] Resin Synthesis Example 10

[0053] 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).

[0054] Resin Synthesis Example 11

[0055] 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).

[0056] PAE-2-1

[0057] Resin Synthesis Example 12

[0058] 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.) 4,4'-diphenyl ether dicarboxylic acid (44OPA, Mw-258.15) and 23.79 g SOCl2 were added. The reaction was carried out at 0-10 °C for 2 h and at room temperature for 4 h to produce the corresponding 44OPA diacyl chloride solution.

[0059] In a 1L three-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and nitrogen protection device, add 36.62g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) and 158g of [unclear text - likely a continuation of the previous sentence]. NMP was stirred until dissolved to form a homogeneous, transparent solution (3HFAP / NMP); the 44OPA diacyl chloride solution prepared above was added dropwise to the 3HFAP / NMP solution over 0.5 h; then, the reaction was allowed to proceed at room temperature for 10 h; next, 1.48 g (0.10 mol.) phthalic anhydride and 1.00 g 1,3-bis(3-aminopropyl)tetramethyldisiloxane (4MSiNA) were added, and stirring was continued for 1 h; the reaction solution was poured into 5 L of deionized water, the solid precipitated, filtered, and vacuum dried to obtain a phenolic hydroxyl polyamide resin (PAE-2-1). This 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 a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE1-2-1: 44OPA-3HFAP).

[0060] Resin Synthesis Example 13

[0061] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 4,4'-diphenyl ether dicarboxylic acid (44OPA, Mw-258.15) was replaced with 31.02 g (0.10 mol.) 3,3'-diphenyl ether dicarboxylic acid (33OPA, Mw-258.15), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE1-2-2: 33OPA-3HFAP).

[0062] Resin Synthesis Example 14

[0063] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 4,4'-diphenyl ether dicarboxylic acid (44OPA, Mw-258.15) was replaced with 31.02 g (0.10 mol.) 3,4'-diphenyl ether dicarboxylic acid (34OPA, Mw-258.15), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE1-2-3: 34OPA-3HFAP).

[0064] Resin Synthesis Example 15

[0065] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 4,4'-diphenyl ether dicarboxylic acid (44OPA, Mw-258.15) was replaced with 15.53 g (0.05 mol.) 3,4'-diphenyl ether dicarboxylic acid (33OPA, Mw-258.15) and 15.53 g (0.05 mol.) 4,4'-diphenyl ether dicarboxylic acid (44OPA, Mw-258.15), while keeping all other parameters the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE1-2-4: 33OPA / 44OPA(1 / 1)-3HFAP).

[0066] Resin Synthesis Example 16

[0067] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 4,4'-diphenyl ether dicarboxylic acid (44OPA, Mw-258.15) was replaced with 15.53 g (0.05 mol.) 3,4'-diphenyl ether dicarboxylic acid (34OPA, Mw-258.15) and 15.53 g (0.05 mol.) 4,4'-diphenyl ether dicarboxylic acid (44OPA, Mw-258.15), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE1-2-5: 34OPA / 44OPA(1 / 1)-3HFAP).

[0068] Resin Synthesis Example 17

[0069] In Resin Synthesis Example 12, 31.02 g (0.10 mol.) 4,4'-diphenyl ether dicarboxylic acid (44OPA, Mw-258.15) was replaced with 15.53 g (0.05 mol.) 3,3'-diphenyl ether dicarboxylic acid (33OPA, Mw-258.15) and 15.53 g (0.05 mol.) 3,4'-diphenyl ether dicarboxylic acid (34OPA, Mw-258.15), while keeping all other parameters the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE1-2-6: 33OPA / 34OPA(1 / 1)-3HFAP).

[0070] 3. Positive photosensitive resin liquid

[0071] Examples 1-6 and Comparative Examples 1-2

[0072] Example 1

[0073] 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.

[0074] 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.

[0075] The prepared positive photosensitive resin solution was evaluated for performance using the above evaluation method. The evaluation results are as follows: ① Resistance to damp heat: no microcracks or defects were observed, rated as "excellent"; ② Photolithography processability: film thickness uniformity was 0.44%, and photolithography resolution was 4.7 μm, rated as "excellent"; ③ Comprehensive mechanical properties: tensile strength was 115 MPa, and elongation at break was 46%, rated as "excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.82%, and 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".

[0076] Example 2

[0077] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, and photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 117 MPa, and elongation at break was 47%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: the cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0078] Example 3

[0079] 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 was evaluated using the above evaluation method, and the results were as follows: ① Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.73%, and photolithography resolution was 7.5 μm, rated as "Good"; ③ Comprehensive mechanical properties: tensile strength was 119 MPa, and elongation at break was 46%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.76%, and 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: one indicator was good, rated as "Good".

[0080] Example 4

[0081] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.45%, and photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 117 MPa, and elongation at break was 44%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.72%, and 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".

[0082] Example 5

[0083] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, and photolithography resolution was 4.5 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 132 MPa, and elongation at break was 45%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, and 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".

[0084] Example 6

[0085] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.46%, and photolithography resolution was 4.4 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 133 MPa, and elongation at break was 44%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.76%, and 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".

[0086] Comparative Example 1

[0087] PAE-2-1 was removed from Example 1, while all 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.45%, and photolithography resolution was 4.7 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 116 MPa, and elongation at break was 36%, rated as "Good"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, and 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 Comprehensive performance evaluation: two indicators were good, rated as "Good".

[0088] Comparative Example 2

[0089] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 1.1%, and photolithography resolution was 8.2 μm, rated as "Poor"; ③ Comprehensive mechanical properties: tensile strength was 115 MPa, and elongation at break was 36%, rated as "Good"; ④ Resistance to chemical etching: film thickness variation rate was 0.77%, and 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 Comprehensive performance evaluation: one indicator was poor, rated as "Poor".

[0090] Table 1 compares the effects of changes in the molecular structure of the aromatic dianhydride monomers 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-1-1, PAE-1-2, PAE-1-4, and PAE-5) to PAE-2-1 is 1:1. The results show that the mixed resin formed by combining the PAE-1 series resins (PAE-1-1, PAE-1-2, PAE-1-4, and PAE-5) with PAE-2-1 at a 1:1 weight ratio, and the resulting positive photosensitive resin solution, thoroughly mixed with photoacidifiers, thermal crosslinking agents, thermal acidifiers, and tackifiers, exhibits excellent overall performance, and its overall performance is rated as "excellent". The positive photosensitive resin solution prepared by combining PAE-1-3 and PAE-2-1 in a 1:1 weight ratio was rated as "good" in terms of overall performance. In contrast, the positive photosensitive resin solution prepared by using only one component of phenolic hydroxyl polyamide ester resin (PAE-1-1) or phenolic hydroxyl polyamide resin (PAE-2-1) was rated as "good or poor" in terms of overall performance.

[0091] Table 1 Comparison of results between Examples 1-6 and Comparative Examples 1-2

[0092] 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-2-144OPA-3HFAP PAE-2-144OPA-3HFAP PAE-2-144OPA-3HFAP PAE-2-144OPA-3HFAP PAE-2-144OPA-3HFAP PAE-2-144OPA-3HFAP -- PAE-2-144OPA-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 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

[0093] Example 7

[0094] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, and photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 127 MPa, and elongation at break was 45%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.85%, and 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".

[0095] Example 8

[0096] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.45%, and photolithography resolution was 4.5 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 125 MPa, and elongation at break was 47%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.73%, and 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".

[0097] Example 9

[0098] 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, and the results were as follows: ① Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.47%, and photolithography resolution was 4.4 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 118 MPa, and elongation at break was 45%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.73%, and 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".

[0099] Example 10

[0100] 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 Resistance to damp heat: A small number of microcracks or defects were observed, rated as "Good"; ② Photolithography processability: Film thickness uniformity was 0.46%, and photolithography resolution was 4.8 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: Tensile strength was 110 MPa, and elongation at break was 43%, rated as "Excellent"; ④ Resistance to chemical etching: Film thickness variation rate was 0.73%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: The cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: One indicator was good, rated as "Good".

[0101] Example 11

[0102] In Example 1, PAE-1-1 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 Resistance to damp heat: A small number of microcracks or defects were observed, rated as "Good"; ② Photolithography processability: Film thickness uniformity was 0.43%, and photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: Tensile strength was 130 MPa, and elongation at break was 48%, rated as "Excellent"; ④ Resistance to chemical etching: Film thickness variation rate was 0.77%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: The cross-cut adhesion test result was 12 / 100, rated as "Poor"; ⑥ Comprehensive performance evaluation: One indicator was poor, rated as "Poor".

[0103] Comparative Example 3

[0104] PAE-2-1 was removed from Example 8, while all 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.46%, and photolithography resolution was 8.6 μm, rated as "Good"; ③ Comprehensive mechanical properties: tensile strength was 130 MPa, and elongation at break was 48%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 11 / 100, rated as "Good"; ⑥ Comprehensive performance evaluation: both indicators were good, rated as "Good".

[0105] Comparative Example 4

[0106] PAE-2-1 was removed from Example 9, while all 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 Resistance to damp heat: A small number of microcracks or defects were observed, rated as "Good"; ② Photolithography processability: Film thickness uniformity was 0.83%, and photolithography resolution was 12.6 μm, rated as "Poor"; ③ Comprehensive mechanical properties: Tensile strength was 110 MPa, and elongation at break was 38%, rated as "Good"; ④ Resistance to chemical etching: Film thickness variation rate was 0.77%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: The cross-cut adhesion test result was 8 / 100, rated as "Good"; ⑥ Comprehensive performance evaluation: One indicator was poor, rated as "Poor".

[0107] Table 2 Comparison of results from Examples 7-11

[0108] 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-2-144OPA-3HFAP PAE-2-144OPA-3HFAP PAE-2-144OPA-3HFAP PAE-2-144OPA-3HFAP PAE-2-144OPA-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

[0109] Table 2 compares the effects of changes in the molecular structure of the phenolic hydroxyl-containing polyamide ester resin-1 series (PAE-1) and phenolic hydroxyl-containing polyamide resin-2 (PAE-2) used in the preparation of the PAE-1 series resins (PAE-1-7, 1-8, 1-9) on the overall performance of the prepared positive photosensitive resins when the weight ratio of PAE-1 to PAE-2 is 1:1. The results show that the mixed resin formed by PAE-1-7 or PAE-1-8, PAE-1-9 and PAE-2-1 in a 1:1 weight ratio, when thoroughly mixed with other components such as photoacid generators, thermal crosslinking agents, thermal acid generators, and tackifiers, exhibits excellent overall performance, and its overall performance is rated as "excellent". The positive photosensitive resin solution prepared by combining PAE-1-10 or PAE-1-11 with PAE-2-1 in a 1:1 weight ratio was rated as "good or poor" in terms of overall performance. In contrast, the positive photosensitive resin solution prepared by using a single-component phenolic hydroxyl polyaminate resin (PAE-1-8 or PAE-1-9), rather than the mixed resin formed with PAE-2-1, was rated as "good or poor" in terms of overall performance.

[0110] Example 12

[0111] 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 Resistance to damp heat: A small number of microcracks or defects were observed, rated as "Good"; ② Photolithography processability: Film thickness uniformity was 0.48%, and photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: Tensile strength was 120 MPa, and elongation at break was 46%, rated as "Excellent"; ④ Resistance to chemical etching: Film thickness variation rate was 0.82%, and a small number of microcracks or defects were observed, rated as "Good"; ⑤ Adhesion to copper surface: The cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: Both indicators were good, rated as "Good".

[0112] Example 13

[0113] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.45%, and photolithography resolution was 4.5 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 125 MPa, and elongation at break was 47%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.73%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: the cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0114] Example 14

[0115] In Example 2, PAE-2-1 was replaced with PAE-2-4, 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.48%, and photolithography resolution was 4.7 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 121 MPa, and elongation at break was 44%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.75%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: the cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0116] Example 15

[0117] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.46%, and photolithography resolution was 4.8 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 114 MPa, and elongation at break was 43%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.75%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: the cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0118] Example 16

[0119] 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.43%, and photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: tensile strength was 130 MPa, and elongation at break was 48%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.77%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: the cross-cut adhesion test result was 0 / 100, rated as "Excellent"; ⑥ Comprehensive performance evaluation: all indicators were excellent, rated as "Excellent".

[0120] Comparative Example 5

[0121] PAE-1-2 was removed from Example 13, while all 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 Resistance to damp heat: no microcracks or defects were observed, rated as "Excellent"; ② Photolithography processability: film thickness uniformity was 0.46%, and photolithography resolution was 8.6 μm, rated as "Good"; ③ Comprehensive mechanical properties: tensile strength was 130 MPa, and elongation at break was 48%, rated as "Excellent"; ④ Resistance to chemical etching: film thickness variation rate was 0.74%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: cross-cut adhesion test result was 11 / 100, rated as "Good"; ⑥ Comprehensive performance evaluation: both indicators were good, rated as "Good".

[0122] Comparative Example 6

[0123] PAE-1-2 was removed from Example 15, while all 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 Resistance to damp heat: A small number of microcracks or defects were observed, rated as "Good"; ② Photolithography processability: Film thickness uniformity was 0.43%, and photolithography resolution was 4.6 μm, rated as "Excellent"; ③ Comprehensive mechanical properties: Tensile strength was 110 MPa, and elongation at break was 38%, rated as "Good"; ④ Resistance to chemical etching: Film thickness variation rate was 0.77%, and no microcracks or defects were observed, rated as "Excellent"; ⑤ Adhesion to copper surface: The cross-cut adhesion test result was 8 / 100, rated as "Good"; ⑥ Comprehensive performance evaluation: All three indicators were good, rated as "Good".

[0124] Table 3 Comparison of results from Examples 12-16

[0125] 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-2-233OPA-3HFAP PAE-2-334OPA-3HFAP PAE-2-433OPA / 44OPA(1 / 1)-3HFAP PAE-2-534OPA / 44OPA-(1 / 1)-3HFAP PAE-2-633OPA / 34OPA-(1 / 1)-3HFAP PAE-2-334OPA-3HFAP PAE-2-534OPA / 44OPA-(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℃) 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

[0126] Table 3 compares the effects of different molecular structures of aromatic diacids (33-OPA, 34-OPA, 44-OPA, 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) in Examples 12-16 is 1:1. The results show that the positive photosensitive resin solution formed by thoroughly mixing the mixed resin of PAE-2-3 or PAE-2-4, PAE-2-5, PAE-2-6 with PAE-1-2 in a 1:1 weight ratio with components such as photoacid generators, thermal crosslinking agents, thermal acid generators, and tackifiers exhibits excellent overall performance, and its overall performance is rated as "excellent". The positive photosensitive resin solution prepared from a 1:1 weight ratio mixture of phenolic hydroxyl polyamide resin (PAE-2-2) and PAE-1-2 received a "good" rating for both damp heat resistance and chemical resistance, and a "good" overall performance rating. In contrast, the positive photosensitive resin solution prepared from a single-component phenolic hydroxyl polyamide resin (PAE-2-3 or PAE-2-5), rather than the mixture formed with PAE-1-2, received a "good" overall performance rating.

[0127] In summary, this invention discloses a positive photosensitive resin liquid with high resistance to damp heat and moisture, its preparation method, and its applications. The positive photosensitive resin liquid possesses excellent photolithography processability; the liquid film formed after coating can form a high-quality three-dimensional photolithographic pattern after pre-baking, exposure, development, rinsing, and heat curing (180-230 ℃). The resin film formed after heat curing exhibits high resistance to damp heat and moisture, as well as high resistance to chemical wetting and high copper surface adhesion, making it suitable for multilayer metal interconnect wiring in advanced packaging of high-density integrated circuits.

Claims

1. A positive photosensitive resin liquid with high resistance to damp heat, comprising the following components: (A) A mixed resin containing phenolic hydroxyl polyamide ester resin-1 and phenolic hydroxyl polyamide resin-2; (B) Photoacid-producing agents; (C) Thermal crosslinking agent; (D) Thermotropic acid-producing agents; (E) Sensitive agents; (F) Organic solvents; and (G) Adhesives; in, The phenolic hydroxyl polyamide ester resin-1 is formed by polycondensation reaction of biphenyl-type aromatic dianhydride, phenolic hydroxyl aromatic diamine and reactive end-capping agent; the phenolic hydroxyl polyamide resin-2 is formed by polycondensation reaction of aromatic diacyl chloride or its derivative, phenolic hydroxyl aromatic diamine and reactive end-capping agent.

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

50.

3. The positive photosensitive resin solution according to claim 1, wherein: The preparation method of the phenolic hydroxyl polyamate resin-1 includes: Aromatic dianhydrides of the biphenyl type are reacted with fatty alcohols under heating conditions via esterification to generate aromatic diacid diesters; then reacted with thionyl chloride to generate aromatic diester diacyl chlorides; further reacted with imidazole-based nitrogen-containing organic bases to generate aromatic diester diimidazolium salts; finally, reacted with phenolic hydroxyl-containing aromatic diamines in an organic solvent via polycondensation in the presence of a reactive end-capping agent to generate a resin solution. After precipitation in a poor solvent, separation, washing, and drying, the product is obtained with a number-average molecular weight of 1.0 × 10⁻⁶. 4 Up to 3.0×10 4 .

4. The positive photosensitive resin solution according to claim 1, wherein: The preparation method of the phenolic hydroxyl polyamide resin-2 includes: Aromatic diacids are reacted with thionyl chloride to form aromatic diacyl chlorides; then reacted with imidazole-based nitrogen-containing organic bases to form aromatic diimidazolium salts; subsequently, these salts are reacted with phenolic hydroxyl-containing aromatic diamines in an organic solvent via a condensation reaction in the presence of a reactive end-capping agent to form a resin solution. This solution is then precipitated in a poor solvent, separated, washed, and dried to obtain the product, which has a number-average molecular weight of 1.0 × 10⁻⁶. 4 Up to 3.0×10 4 .

5. The positive photosensitive resin solution according to claim 1, wherein: The photoacid-producing agent is a diazonoquinone compound, an iodonium salt compound, or a sulfonium salt compound; The thermal crosslinking agent is a compound containing an epoxy group or a compound containing hydroxymethyl / alkoxymethyl groups; The thermally induced acid-producing agent is a compound that can produce strong acid when heated, and its thermal decomposition initiation temperature is 150℃-250℃.

6. The positive photosensitive resin solution according to claim 1, wherein: The sensitizer is a compound containing phenolic hydroxyl, hydroxyl, or carboxyl groups; The organic solvent is selected from one or more of the following: N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, ethyl acetate, cyclopentanone, and cyclohexanone; The adhesion promoter is a silane coupling agent.

7. The positive photosensitive resin liquid according to claim 1, wherein: The biphenyl-type aromatic dianhydride is one or more of 2,3,2',3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride.

8. The positive photosensitive resin solution according to claim 1 or 3, wherein: The phenolic hydroxyl-containing aromatic diamine is selected from one or more of the following: 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, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, and 4,4'-diamino-3,3'-dihydroxydiphenyl ether.

9. A method for preparing a positive photosensitive resin liquid as described in claim 1, wherein: In a Class 1000 cleanroom equipped with a yellow light source, 100 parts by weight of component (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 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.

10. The use of the positive photosensitive resin liquid as described in claim 1 in the manufacture of multilayer metal interconnect circuit layers for advanced packaging of high-density integrated circuits, wherein: The resin solution is coated, pre-baked, exposed, developed, rinsed, and cured by heating to form a thermosetting resin film, wherein the curing temperature is 180-230℃.

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