A positive photosensitive polyimide resin glue with high lithography resolution and a preparation method and use thereof

Abstract

The application relates to the technical field of high polymer materials, and particularly discloses a positive photosensitive polyimide resin glue liquid with high photoetching resolution and a preparation method and application thereof. The positive photosensitive polyimide resin glue liquid is composed of a phenolic hydroxyl polyamic acid ester mixed resin, a photo-induced acid generator, a thermal-induced crosslinking agent, a solvent and the like. The phenolic hydroxyl polyamic acid ester mixed resin comprises a phenolic hydroxyl polyamic acid ester-1 and a phenolic hydroxyl polyamic acid ester-2. The positive photosensitive polyimide resin glue liquid prepared by the application is combined with optimized components such as the photo-induced acid generator and the thermal crosslinking agent, so that the photoetching resolution of the resin glue liquid can reach 3.0-3.5 mu m under the condition of a 5-6 mu m solidified film thickness, the pattern steepness is good, and the development is clean, which is significantly superior to the prior art. The resin film formed after heat curing has the characteristics of high moisture resistance, high chemical immersion resistance, high copper surface adhesion and the like, and is suitable for multilayer metal interconnection wiring of high-density integrated circuit advanced packaging.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a positive photosensitive polyimide resin liquid with high photolithographic resolution, its preparation method, and its uses. Background Technology

[0002] Photosensitive polyimide (PSPI) is currently the most important photosensitive interlayer dielectric material, widely used in the manufacturing and packaging of high-density integrated circuits, including chip surface passivation layers, alpha-particle shielding layers, and interlayer dielectric films in multilayer metal interconnect structures (RDL). For example, in the fabrication of multilayer RDLs, PSPI resin is first applied to the wafer surface to form a liquid film. After pre-baking, exposure, development, and curing, a polyimide insulating layer is formed. Then, a conductive copper layer is formed on the surface of the insulating layer by electroplating. Photoresist is then applied to the copper layer surface, and conductive lines are formed through photolithography, development, and photoresist layer stripping.

[0003] In recent years, with the rapid development of high-density integrated circuit (IC) wafer-level packaging (WLP) and panel-level packaging (PLP) technologies, higher requirements have been placed on the comprehensive performance of photosensitive interlayer dielectric materials, including photosensitive polyimide resin (PSPI), photosensitive polybenzoxazole resin (PSPBO), and photosensitive polybenzocyclobutene resin (PSBCB). These requirements include better photolithographic processability, lower curing temperature, higher heat resistance, mechanical properties, and chemical corrosion resistance. With the rapid development of advanced packaging technologies, higher requirements have been placed on the photolithographic resolution of photosensitive interlayer dielectric materials. Currently, the photolithographic pattern resolution (7.0-8.0 μm film thickness) of positively aqueous developable PSPI or PSPBO resin is greater than 5.0 μm, and improving it to 3.0-3.5 μm has become a matter of great concern.

[0004] Hitachi Chemical DuPont Microsystems of Japan disclosed a photosensitive resin composition in US 6,232,032 B1, comprising an alkali-soluble water-soluble polyimide precursor resin, a photoacid-generating agent, and a dissolution inhibitor. This composition exhibits high photosensitivity and photolithography processability, making it suitable for fabricating protective passivation films on chip surfaces and interlayer dielectric films in multilayer metal interconnect structures. The polyimide precursor resin is generated by a polycondensation reaction between an aromatic diester diacyl chloride and a phenolic hydroxyl-containing aromatic diamine.

[0005] The company discloses a positive photosensitive polyimide resin composition in US 8,426,985 B2, comprising a phenolic hydroxyl-containing alkaline water-soluble resin, a modified phenolic resin containing unsaturated crosslinkable groups, a photoacid-generating agent, a thermotropic crosslinking agent, and a solvent. This composition can be developed in alkaline aqueous solutions and exhibits excellent photosensitivity and resolution. The stereolithographic pattern on the cured resin film demonstrates excellent adhesion and thermal shock resistance. However, its pore resolution at a film thickness of 11-13 μm is still greater than 5.0 μm.

[0006] The company further discloses a positive photosensitive polyimide resin composition in US 9,395,626 B2, comprising an alkali-soluble water-soluble resin, a photoacid-generating agent, a thermotropic crosslinking agent, a nitrogen heterocyclic compound, and an organic solvent. Its pore resolution remains greater than 7 μm at a film thickness of 8-9 μm.

[0007] It is evident that the photolithographic resolution of existing positive photosensitive polyimide resin compositions cannot yet meet the requirements of advanced packaging for higher integration, especially in high-density interconnect applications with linewidths / pitches of 3.0-3.5 μm. The overall performance of existing materials (including resolution, heat resistance, chemical corrosion resistance, adhesion to copper, and resistance to damp heat) still needs further improvement. Summary of the Invention

[0008] The purpose of this invention is to provide a positive photosensitive polyimide resin liquid with high photolithographic resolution, its preparation method, and its uses, in order to solve the problems mentioned in the background art, such as the low photolithographic resolution (usually greater than 5.0 μm) of existing positive photosensitive polyimide resin compositions under thick film conditions, which makes it difficult to meet the high resolution requirements of 3.0-3.5 μm for advanced packaging of high-density integrated circuits, and the insufficient comprehensive performance of the cured film, such as resistance to damp heat, chemical corrosion, and adhesion to copper.

[0009] To achieve the above objectives, the present invention provides the following technical solution:

[0010] This invention discloses a positive photosensitive polyimide resin composition liquid with high photolithographic resolution, its preparation method, and its application. The positive photosensitive polyimide resin composition liquid has high photolithographic resolution and excellent photolithographic processability. The liquid film formed by 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 has the characteristics of high photolithographic resolution, high resistance to damp heat, and high resistance to chemical immersion, and is suitable for multilayer metal interconnect wiring in advanced packaging of high-density integrated circuits.

[0011] This invention discloses a positive photosensitive polyimide resin composition adhesive with high photolithographic resolution. The positive photosensitive polyimide resin composition adhesive is composed of the following chemical components, including: (A) a mixture of phenolic hydroxyl polyaminate resin-1 and phenolic hydroxyl polyaminate resin-2; (B) a photoacid generator; (C) a thermal crosslinking agent; (D) a thermal acid generator; (E) a sensitizer; (F) an organic solvent; (G) an adhesive promoter and other components.

[0012] This invention discloses a positive photosensitive polyimide resin composition with high photolithographic resolution. The preparation method of the hydroxyl-containing polyamide ester resin involves mixing hydroxyl-containing aromatic tetracarboxylic dianhydride-1 and aromatic tetracarboxylic dianhydride-2 to form a mixed aromatic tetracarboxylic dianhydride; then, reacting it with a fatty alcohol under heating conditions via esterification to generate a mixed aromatic diacid diester; reacting the generated mixed aromatic diacid diester with thionyl chloride to generate a mixed aromatic diester diacyl chloride; finally, reacting the mixed aromatic diester diacyl chloride with an imidazole-based nitrogen-containing organic base to generate a mixed aromatic diester diimidazolium salt compound. The mixed aromatic diester diimidazolium salt compound is then reacted with a phenolic hydroxyl-containing aromatic diamine in an organic solvent via a condensation reaction in the presence of a reactive end-capping agent to generate a phenolic hydroxyl-containing polyamide ester copolymer resin solution; the copolymer resin is precipitated in a poor solvent, separated, and thoroughly washed to obtain a solid resin. After heating and vacuum drying, a phenolic hydroxyl polyamide ester copolymer resin was obtained, with a GPC molecular weight of 1.0x104 to 3.0x104.

[0013] This invention discloses a positive photosensitive polyimide resin composition with high photolithographic resolution. The hydroxyl-containing aromatic tetracarboxylic dianhydride-1 mentioned in the preparation method of the phenolic hydroxyl polyaminate copolymer resin includes 3,3,4',4'-benzyl alcohol tetracarboxylic dianhydride (44BHTA, mp. 180-181 ℃, Mw=324.19), 2,2-dihydroxybenzophenone-3,3',4,4'-tetracarboxylic dianhydride (44DBTA, mp. 257-258 ℃, Mw=354.19), and mixtures thereof in any proportion.

[0014] This invention discloses a positive photosensitive polyimide resin composition with high photolithographic resolution. The aromatic tetracarboxylic dianhydride-2 mentioned in the preparation method of the phenolic hydroxyl polyamide ester copolymer resin includes 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (3,3',4,4'-Oxydiphthalic dianhydride, 44ODPA, mp. 225-226 ℃, Mw=240.18); 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride (3,3',4,4'-Oxydiphthalic dianhydride, 34ODPA, mp. 177-178 ℃, Mw=240.18); and 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride (2,2',3,3'-Oxydiphthalic dianhydride, 33ODPA, mp. 243-244 ℃). Mw=240.18), 2,3',2,3'-benzophenone tetracarboxylic dianhydride (33BTDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (44BPDA), 2,3',3,4'-biphenyltetracarboxylic dianhydride (34BPDA), 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (44ODDA)|, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride (34ODDA), 2,3',2,3 '-Diphenyl ether tetracarboxylic dianhydride (33ODDA), 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride (44DSDA), 2,3',2,3'-diphenyl sulfone tetracarboxylic dianhydride (33DSDA), 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride (44TDPA), 2,3',2,3'-diphenyl sulfide tetracarboxylic dianhydride (TDPA), 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA), pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (44BTDA), 2,3',3,4'-benzophenone tetracarboxylic dianhydride (34BTDA), and mixtures thereof in any proportion.

[0015] This invention discloses a method for preparing a phenolic hydroxyl-containing polyamic acid ester resin. The phenolic hydroxyl-containing aromatic diamine-1 includes 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17), 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane (abbreviated as: 4HFAP, Mw=366.17), 2,2'-bis[N-(3-aminobenzoamide)-3-amino-4-hydroxyphenyl]hexafluoropropane (abbreviated as: 3HFHA, Mw=604.32), 2,2'-bis[N-(4-aminobenzoamide)-3-amino-4-hydroxyphenyl]hexafluoropropane (abbreviated as: 4HFHA, Mw=604.32), and 2,2-bis(3-amino-4-hydroxyphenyl)propane (abbreviated as: 3-HHAP, ...). Mw=258.17), bis(4-amino-3-hydroxyphenyl)methane (abbreviated as: 4HHAP, Mw=258.17), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (4MSiNA), 1,3-bis(3-aminopropyl)tetraphenyldisiloxane (4BSiNA), 1,3-bis(3-aminophenoxy)tetramethyldisiloxane (3M2SiA) and 1,3-bis(4-aminophenoxy)tetramethyldisiloxane (4MSiA), and mixtures thereof in any proportion.

[0016] This invention discloses a method for preparing a hydroxyl-containing polyamic acid ester resin. The organic solvents used in the preparation method include N'N dimethylformamide, N'N dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolium ketone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylurea, phenol, m-cresol, ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc., and mixtures thereof in any proportion.

[0017] This invention discloses a method for preparing a hydroxyl-containing polyamic acid ester resin. The reactive end-capping agent in the preparation method 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.

[0018] This invention discloses a method for preparing hydroxyl-containing polyamide ester resin. The unsuitable solvents in the preparation method include deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, and mixtures thereof in any proportion.

[0019] This invention discloses a positive photosensitive polyimide resin composition with high photolithographic resolution. The preparation method of hydroxyl-containing polyaminate resin-2 involves reacting aromatic tetracarboxylic dianhydride-2 with a fatty alcohol under heating conditions via esterification to generate an aromatic diacid diester; then, the generated aromatic diacid diester reacts with thionyl chloride to generate an aromatic diester diacyl chloride; finally, the aromatic diester diacyl chloride reacts with an imidazole-based nitrogen-containing organic base to generate an aromatic diester diimidazolium salt compound. The aromatic diester diimidazolium salt compound and phenolic hydroxyl-containing aromatic diamine-2 undergo a condensation reaction in an organic solvent in the presence of a reactive end-capping agent to generate a phenolic hydroxyl-containing polyaminate resin solution; the resin is precipitated in a poor solvent, separated, and thoroughly washed to obtain a solid resin. After heating and vacuum drying, a phenolic hydroxyl-containing polyaminate resin (PAE-2) is obtained, with a GPC molecular weight of 1.0 x 10⁴ to 3.0 x 10⁴.

[0020] This invention discloses a method for preparing hydroxyl-containing polyamic acid ester resin-2. The aromatic tetracarboxylic dianhydrides used in the preparation method include 2,3,2',3'-diphenyl ether tetracarboxylic dianhydride (abbreviated as: 23ODPA), 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride (abbreviated as: 34ODPA), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (abbreviated as: 44ODPA), and pyromellitic dianhydride (abbreviated as: PMDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (44BTDA), 2,3',3,4'-benzophenone tetracarboxylic dianhydride (34BTDA), 2,3',2,3'-benzophenone tetracarboxylic dianhydride (33BTDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (44BPDA), 2,3',3,4'-biphenyltetracarboxylic dianhydride (34BPDA), 2,3',2,3'-biphenyltetracarboxylic dianhydride (33BPDA), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (44ODDA)|、2,3' 3,4'-Diphenyl ether tetracarboxylic dianhydride (34ODDA), 2,3',2,3'-Diphenyl ether tetracarboxylic dianhydride (33ODDA), 3,3',4,4'-Diphenyl sulfone tetracarboxylic dianhydride (44DSDA), 2,3',2,3'-Diphenyl sulfone tetracarboxylic dianhydride (33DSDA), 3,3',4,4'-Diphenyl sulfide tetracarboxylic dianhydride (44TDPA), 2,3',2,3'-Diphenyl sulfide tetracarboxylic dianhydride (TDPA), 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA) and mixtures thereof in any proportion.

[0021] This invention discloses a method for preparing hydroxyl-containing polyamic acid ester resin-2. The phenolic hydroxyl aromatic diamine-2 in the preparation method includes 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17), 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane (abbreviated as: 4-HFAP, Mw=366.17), 2,2-bis(3-amino-4-hydroxyphenyl)propane (abbreviated as: 3-BAPP, Mw=258.17), bis(4-amino-3-hydroxyphenyl)methane (abbreviated as: 4BAPP, Mw=258.17), and 2,2'-bis[N-(3-aminobenzoamide)-3-amino-4-hydroxyphenyl]hexafluoropropane (abbreviated as: 3HFHA, ... Mw=604.32), 2,2'-bis[N-(4-aminobenzoylamino)-3-amino-4-hydroxyphenyl]hexafluoropropane (abbreviation: 4HFHA, Mw=604.32), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (4MSiNA), 1,3-bis(3-aminopropyl)tetraphenyldisiloxane (4BSiNA), 1,3-bis(3-aminophenoxy)tetramethyldisiloxane (3M2SiA) and 1,3-bis(4-aminophenoxy)tetramethyldisiloxane (4MSiA) and mixtures thereof in any proportion.

[0022] This invention discloses a method for preparing hydroxyl-containing polyamic acid ester resin-2. The organic solvents used in the preparation method include N'N dimethylformamide, N'N dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolium ketone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylurea, phenol, m-cresol, ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc., and mixtures thereof in any proportion.

[0023] This invention discloses a method for preparing hydroxyl-containing polyamic acid ester resin-2. The reactive end-capping agent in the preparation method 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.

[0024] This invention discloses a method for preparing hydroxyl-containing polyamic acid ester resin-2. The unsuitable solvents mentioned in the preparation method include deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, and mixtures thereof in any proportion.

[0025] This invention discloses a positive photosensitive polyimide resin composition liquid with high photolithographic resolution. The photoacid generator (B) in the resin composition includes ① diazonoquinone compounds, ② iodonium salt compounds, and ③ sulfonium salt compounds, etc.

[0026] Considering the effects of inhibiting the solubility of the resin film in the unexposed area and the high solubility of the resin film in the exposed area, diazonaquinone compounds are preferred, including compounds (B1) generated by esterification of diazonaquinone sulfonic acid and polyhydroxy compounds; compounds (B2) generated by sulfonation of diazonaquinone sulfonic acid and polyamine compounds; and compounds (B3) generated by esterification and / or sulfonation of diazonaquinone sulfonic acid and polyhydroxy polyamine compounds. The proportion of diazonaquinone sulfonic acid substituted in the polyhydroxy polyamine compounds is 30% to 90%, preferably 50% to 90%. The diazonaquinone compounds include 1,2-diazonaphthoquinone-5-sulfonyl compounds and 1,2-diazonaphthoquinone-4-sulfonyl compounds, such as 2,3,4-trihydroxybenzophenone-1,2-diazonaphthoquinone-5-sulfonate. The polyhydroxy compounds mentioned include Bis-Z, BisP-EZ, BisP-AP, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, Tris℃R-PA, Bis℃HP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, Bis℃P-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-℃HP, Methylenetris-FR-CR, BisRS-26X, DML- MBPC, DML-MB℃, DML-℃HP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-Bis℃-P, DML-PFP, DML -PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-PP-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (The above are trade names, available from Honshu Chemical Industry Co., Ltd.) BIR-℃, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BI℃-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DM℃, 46DMOEP, TM-BIP-A (the above are trade names, products of Asahi Organic Materials Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, pyrogallol acetone resin, m-cresol resin, phenolic resin, etc.

[0027] The iodonium salts include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, 4-isopropyl-4'-methyldiphenyliodonium tetra(pentafluorophenyl)borate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nitrate, [4-(trifluoromethyl)phenyl](2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, and [3-(trifluoromethyl)phenyl](2,4,6-trimethyl)phenyl (4-trifluoromethyl)phenyl iodonium trifluoromethanesulfonate, [(4-trifluoromethyl)phenyl](2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, phenyl(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, phenyl[3-(trifluoromethyl)phenyl]iodonium trifluoromethanesulfonate, (4-nitrophenyl)(phenyl)iodonium trifluoromethanesulfonate, (4-tolyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, (3-tolyl) (2,4,6-Trimethylphenyl)iodonium trifluoromethanesulfonate, (2-Tolyl)(2,4,6-Trimethylphenyl)iodonium trifluoromethanesulfonate, 4-Isopropyl-4'-Methyldiphenyliodonium tetra(pentafluorophenyl)borate, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliohexafluoroantimonate, (5-Fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, diphenyliodonium hexafluorophosphate, Diphenyliodonium hexafluoroarsenate, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, (3-bromophenyl)(trimethylmethyl)iodonium trifluoromethanesulfonate, [4-(bromomethyl)phenyl](2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, bis(2,4,6-trimethylpyridine)iodonium hexafluorophosphate, 4,4'-xylyliodonium hexafluorophosphate, and mixtures thereof in any proportion.

[0028] Sulfonium salts include 1,3-benzodithiopyrrole tetrafluoroborate, cyclopropyl diphenylsulfonium tetrafluoroborate, dimethyl(methylthio)sulfonium tetrafluoroborate, diphenyl(methyl)sulfonium tetrafluoroborate, (difluoromethyl)bis(2,5-dimethylphenyl)sulfonium tetrafluoroborate, 2-[4-(3-ethoxy-2-hydroxypropoxy)phenylcarbamoyl]ethyldimethylthio-p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium methanesulfonate, triphenylsulfonium tetrafluoroborate, tri(4-tolyl)sulfonium hexafluorophosphate, tri(4-tolyl)sulfonium trifluoromethanesulfonate, triethylsulfonium bis(trifluoromethylsulfonyl)imide, and mixtures thereof in any proportion.

[0029] This invention discloses a positive photosensitive polyimide resin composition liquid with high photolithographic resolution. The thermal crosslinking agent (C) in the resin composition refers to a compound that can undergo a crosslinking reaction under heating conditions or under the action of Lewis acid, including compounds containing epoxy groups, compounds containing hydroxymethyl or alkoxymethyl groups, etc.

[0030] The compounds containing epoxy groups include any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl), and epoxy-containing organosilicon, more preferably 3,3'-[oxybismethylene]bis[3-ethyl]oxetane, 1,4-butanediol diglycidyl ether, 2,2-bis(4-epoxypropoxyphenyl)propane, 9,9-bis(4-epoxypropyloxy-3-tolyl)fluorene, 9,9-bis(4-epoxypropoxyphenyl)fluorene, and 1,3-bis[2-(7-oxabicyclo[4.1]].[0]Hept-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 1,2,7,8-diepoxyoctane, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, triglycidyl isocyanurate, 4,4'-methylenebis(N,N-dicyclopropoxyaniline), neopentyl glycol diglycidyl ether, 2,2'-(2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl)bis(ethylene oxide), pentaerythritol diglycidyl ether, vinylcyclohexene diglycidyl ether, polyethylene glycol diglycidyl ether ( Polymerization degree 1-15), polypropylene glycol diglycidyl ether (polymerization degree 1-15), polydimethylsiloxane diglycidyl ether (polymerization degree 1-15), butanediol diglycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, 5,5-dimethyl-1,3-di(epoxyethylenemethyl)imidazolidine-2,4-dione, 2,2',2''-[methimide-tris(phenoxymethylene)]tris(epoxyethylene), 1,1,1-tris(4-hydroxyphenyl)ethyl triglycidyl ether, bis(2,3-epoxycyclopentyl) ether, 3 4-Epoxy-6-methylcyclohexylcarboxylic acid-3',4'-epoxy-6'-methylcyclohexyl methyl ester, vinylcyclohexene epoxy compound, 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl methyl ester, diisoprene diester, tetraphenylglycidyl ether ethane, triphenylglycidyl ether methane, triglycidyl-p-aminophenol, triglycidyl triisocyanate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl dimethylbenzene diamine, or tetraglycidyl-1,3-diaminomethylcyclohexane; products with trade names can be listed as H P-850, HP-4032, HP-7200, HP-820, HP-4700, EXA-4710, HP-4770, EXA-859CRP, EXA-1514, EXA-4880, EXA-4850-150, EXA-4850-1000, EXA-4816, EXA-4822, BEO-60E, BPO-20E, HBE-100, DME-100, NC-3000, NC-6000 (Nippon Kayaku Co., Ltd.), and mixtures thereof in any proportion.

[0031] The compounds containing hydroxymethyl or alkoxymethyl groups include 46DM℃, 46DMOEP (trade names, manufactured by Asahi Organic Materials Co., Ltd.), DML-PC, DML-PEP, DML-℃, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-℃HP, DML-PFP, DML-PSBP, DML-POP, DML-MB℃, DMLMBPC, DML-MTrisPC, DML-Bis℃-Z, DML-Bis℃HP-Z, DML-BPC, DMLBis℃-P, DMOM-PC, DMOMPTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp- BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, available from Honshu Chemical Industry Co., Ltd.), "NIKALAC" MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (Sanwa Chemical Co., Ltd.), and mixtures thereof in any proportion.

[0032] This invention discloses a positive photosensitive polyimide resin composition liquid with high photolithographic resolution. The thermogenic acid-producing agent (D) in the resin composition refers to a compound that can produce a strong acid upon heating, with a thermal decomposition initiation temperature of 150℃-250℃, such as alkyl sulfonic acid, perfluoroalkyl sulfonic acid or pyridinium salt of alkyl sulfonic acid, alkylpyridinium salt, diaryliodomonosulfonium salt, di(alkylaryl)iodomonosulfonium salt, trialkylsulfonium salt, dialkylmonoaryl sulfonium salt or diarylmonoalkyliodomonosulfonium salt or ester compounds, including p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid di(tert-butylphenyl)iodomonosulfonium salt, trimethylsulfonium salt of trifluorobenzenesulfonic acid, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, p-toluenesulfonic acid-2-methoxyethyl ester, and mixtures thereof in any proportion.

[0033] This invention discloses a positive photosensitive polyimide resin composition liquid with high photolithographic resolution. The sensitizer (E) in the resin composition includes compounds containing phenolic hydroxyl, hydroxyl or carboxyl groups, which can improve the solubility of the exposed part in the developer, improve photosensitivity and shorten the development time.

[0034] The compounds containing phenolic hydroxyl groups include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Bis℃HP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, Bis℃P-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-℃HP, methylenetris-FR-CR, BisRS-26X (these are trade names, available from Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (… The above are trade names, obtained by Asahi Organic Materials Co., Ltd., including 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 9,9-bis(4-hydroxyphenyl)fluorene, 4,4'-dihydroxydiphenylcyclohexane, 1,4-naphthodiol, 1,5-naphthodiol, 1,6-naphthodiol, 1,7-naphthodiol, 2,3-naphthodiol, 2,7-naphthodiol, 2,6-naphthodiol, bis(4-hydroxyphenyl) sulfide, spiro[fluorene-9,9'-xanthan]-3',6'-diol, and mixtures thereof in any proportion.

[0035] The organic compounds containing hydroxyl groups refer to saturated or unsaturated fatty alcohols containing 2-16 carbons, including ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, pentanol, n-hexanol, cyclopropylmethanol, cyclohexylmethanol, 4-methyl-1-cyclohexylmethanol, 3,4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-tert-butylcyclohexanol, heptanol, octanol, cyclooctanol, 1-cyclohexyl-1-pentanol, 3,5,5-trimethylcyclohexanol, norberyl. 2-methyl-2-methanol, cis-4-hepten-1-ol, cis-3-octen-1-ol, 2,7-octadienol, 2,4,4-methyl-2-pentanol, cyclohexylmethanol, cis-2-hexen-1-ol, n-hexanol, 1-hexadecyl alcohol, 2-ethyl-1-butanol, DL-2-methyl-1-butanol, isoamyl alcohol, 3-methyl-2-butanol, 4-methyl-2-pentanol, isobutanol, neopentanol, and mixtures thereof in any proportion.

[0036] The organic compounds containing carboxyl groups refer to carboxylic acid compounds containing 2 to 16 carbon atoms, including acetic acid, propionic acid, butyric acid, valeric acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-n-pentanoic acid, 4-methyln-pentanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-nonanoic acid, isononanoic acid, n-decanoic acid, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 10-undecenoic acid, p-methoxybenzoic acid, m-methylbenzoic acid, benzoic acid, mandelic acid, trans-2-hexenoic acid, 3,7-dimethyl-6-octanoic acid, sorbic acid, 3,5,5-trimethylhexanoic acid, lauric acid, myrcenoic acid, and mixtures thereof in any proportion.

[0037] This invention discloses a positive photosensitive polyimide resin composition liquid with high photolithographic resolution. The organic solvent (F) in the resin composition refers to a compound that can dissolve components (A) to (E) to form a homogeneous solution, including N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, etc., and mixtures thereof in any proportion.

[0038] This invention discloses a positive photosensitive polyimide resin composition adhesive with high photolithographic resolution. The adhesive (G) in the resin composition includes γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3-isocyanate-trimethoxysilane, 3-isocyanate-triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane. Silanes, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyldimethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 3-(m-aminophenoxy)trimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, and mixtures thereof in any proportion.

[0039] This invention discloses a method for preparing a positive photosensitive polyimide resin composition liquid with high photolithographic resolution. The method involves dissolving 100 parts by weight of a phenolic hydroxyl polyamide resin (A), 3-40 parts by weight of a photoacid-generating agent (B), 3-40 parts by weight of a thermal crosslinking agent (C), 0.1-20 parts by weight of a thermal acid-generating agent (D), 3-40 parts by weight of a sensitizer (E), and 3-40 parts by weight of a tackifier (G) in batches with stirring in an organic solvent (F) to form a homogeneous solution. After filtration and dispensing, a positive photosensitive polyimide resin liquid is obtained, with a solid content of 15-45 wt.% and a solution viscosity of 500-4000 mPa·s at room temperature.

[0040] The positive photosensitive polyimide resin composition adhesive with high photolithographic resolution described in this invention is suitable not only for fabricating dielectric insulating films of multilayer metal interconnect circuits (RDLs) on the surface of 12-inch silicon wafers, but also for fabricating such films on large-area (≥600mm long x 600mm wide) glass substrates. Its photolithographic patterning process includes:

[0041] 1) Coating: A uniform liquid film is formed by spin-coating positive photosensitive polyimide resin liquid onto the surface of a wafer or by inkjet printing onto a large-area glass substrate.

[0042] 2) Pre-baking: Pre-baking is performed at 80-150℃ to form a semi-solid film;

[0043] 3) Exposure: Ultraviolet light is used to expose the material through a photomask or photomask;

[0044] 4) Development + Rinsing: Aqueous developer (2.38% TMAH) is used for development by spraying or immersion, followed by rinsing with ultrapure water to form a three-dimensional pattern;

[0045] 5) Heat curing: The precursor resin three-dimensional pattern on the substrate surface is heat-cured and transformed into a high heat-resistant curable resin three-dimensional pattern;

[0046] 6) A continuous conductive copper layer is formed on the surface of the resin three-dimensional pattern by electroplating copper; then, the continuous conductive copper layer is etched to form conductive copper lines by photolithography patterning process, completing one RDL process (1P1M); repeat the above process to form a second RDL process (2P2M) on its surface; continue to repeat the above process to form a third RDL process (3P3M).

[0047] Compared with the prior art, the beneficial effects of the present invention are:

[0048] This invention employs a mixed resin system containing phenolic hydroxyl polyamide ester resin-1 and resin-2, along with optimized photoacid-generating agents, thermal crosslinking agents, and other components. This allows the resin solution to achieve a photolithographic resolution of 3.0-3.5 μm under a curing film thickness of 5-6 μm, exhibiting good pattern steepness and clean development, significantly superior to existing technologies. The cured polyimide film has a tensile strength ≥100 MPa and an elongation at break ≥40%, demonstrating excellent flexibility and mechanical strength, meeting the mechanical requirements of advanced packaging for interlayer dielectric films. The resin film formed after heat curing exhibits high resistance to damp heat and high resistance to chemical immersion, making it suitable for multilayer metal interconnect wiring in high-density integrated circuit advanced packaging. Detailed Implementation

[0049] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0050] Comprehensive performance evaluation method:

[0051] The performance of the positive photosensitive polyimide resin liquid was evaluated using the following evaluation method:

[0052] 1) Photolithography resolution: Positive photosensitive polyimide resin liquid is spin-coated onto the surface of a 12-inch silicon wafer to form a liquid film of uniform thickness (6-8 μm); after baking at 100-110℃ for 1-3 min, a mask is placed on its surface and exposed with ultraviolet lamps (i and g lines); aqueous developer (2.38% TMAH) is used for development by spraying or immersion, and after rinsing with ultrapure water, it is heated and cured in a nitrogen-protected forced-air oven (150℃ / 1h, 200℃ / 1h, 230℃ / 1h) to obtain a cured resin stereolithography pattern with a thickness of 5-6 μm.

[0053] The lithographic resolution is evaluated by observing the three-dimensional patterns under an optical microscope: If the uniformity of the cured resin film thickness (5-6 μm) is ≤0.5%, the resolution of each raised strip pattern and through-hole is ≤5.0µm, the patterns are cleanly developed without foreign matter residue, and the ratio of the top width to the bottom width of the pattern (steepness) is greater than 1 / 2, the lithographic resolution is rated as "excellent"; if the uniformity of the cured film thickness is ≤1.0%, the resolution of each pattern is ≤7-8 µm, the patterns are cleanly developed without foreign matter residue, and the ratio of the top width to the bottom width of the pattern (steepness) is greater than 1 / 2, the lithographic resolution is rated as "good"; if the uniformity of the cured film thickness is ≥1.1%, the resolution of the pattern is ≥12 µm, the patterns are not cleanly developed with foreign matter residue, and the ratio of the top width to the bottom width of the pattern (steepness) is ≤1 / 2, the lithographic resolution is rated as "poor".

[0054] 2) Mechanical Properties of the Thin Film: A positive photosensitive polyimide resin solution was spin-coated onto the surface of a 12-inch silicon wafer to form a uniformly thick film. After baking at 120 °C for 3 min, the film was exposed to UV lamps (i and g lines) without a mask. It was then developed using an aqueous developer (2.38% TMAH) via spraying or immersion, rinsed with ultrapure water, and cured in a nitrogen-protected oven (150 °C / 1 h, 200 °C / 1 h, 230 °C / 1 h). The silicon wafer with the film was 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 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 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 ≥20%, 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".

[0055] 3) Chemical resistance: The photolithographic 3D pattern of the resin after heat curing was immersed in a caustic solution (1 wt.% potassium hydroxide + 39 wt.% 3-methoxy-3-methyl-1-butanol + 60 wt.% dimethyl sulfoxide (DMSO)) at 100 ℃ for 1 hour. After washing with water and air drying, the chemical resistance of the cured resin film was evaluated by measuring the film thickness change and observing under an optical microscope: if the thickness change of the cured resin film after immersion is within ±1% and no cracks or defects are produced, it is rated as "excellent"; if the thickness change of the cured resin film after immersion is within ±3% and no cracks or defects are produced, it is rated as "good"; if the thickness change of the cured resin film after immersion exceeds ±5% or cracks or defects are produced, it is rated as "poor".

[0056] 4) Moisture and heat resistance: A positive photosensitive polyimide resin liquid was spin-coated onto the surface of a 12-inch silicon wafer to form a liquid film. After baking at 120 °C for 3 min, the surface was exposed to ultraviolet light (i and g lines) without a mask. The substrate was developed by spraying or immersion with an aqueous developer (2.38% TMAH), rinsed with ultrapure water, and then cured in a nitrogen-protected oven (150 °C / 1 h, 200 °C / 1 h, 230 °C / 1 h) to form a cured resin film on the substrate surface. The substrate was then placed in a pressure cooker at 120 °C / 2 atm for 100 h and subjected to three thermal shock cycles from room temperature to 260 °C. The longitudinal section of the copper-tin bumps covered with the resin film was cut using FIB, and the interface morphology between the copper-tin bumps and the resin film was observed using an optical microscope. If no cracks or voids are found at the interface between the copper-tin protrusion and the cured resin, it is rated as "Excellent"; if a few cracks or voids are found at the interface between the copper-tin protrusion and the cured resin, it is rated as "Good"; if many cracks or voids are found at the interface between the copper-tin protrusion and the cured resin, it is rated as "Poor".

[0057] 5) Adhesion to Copper: A positive photosensitive polyimide resin solution was spin-coated onto the surface of a 12-inch silicon wafer to form a uniformly thick film. After baking at 100-110℃ for 1-3 minutes, the film was exposed to UV light (i and g lines) without a mask. It was then developed using an aqueous developer (2.38% TMAH) by spraying or immersion, rinsed with ultrapure water, and cured in a nitrogen-protected oven (150℃ / 1h, 200℃ / 1h, 230℃ / 1h) to obtain a cured resin film with a thickness of 10-12µm. The adhesion between the film and metallic copper was evaluated using a cross-cut test: 0 crosses peeled off per 100 crosses was considered "Excellent"; 1-10 crosses peeled off per 100 crosses was considered "Good"; and more than 11 crosses peeled off per 100 crosses was considered "Poor".

[0058] 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".

[0059] Example of synthesis of phenolic hydroxyl resin

[0060] 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.

[0061] PAE-1-1 to PAE-11

[0062] Resin Synthesis Example 1

[0063] In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, thermometer, and nitrogen protection device, 32.42 g (0.10 mol.) of 3,3,4',4'-benzyl alcohol tetracarboxylic dianhydride (44BHTA, Mw=324.19), 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 aromatic diethyl diacid ester. The product was then reacted with 23.79 g of S℃l2 at 0-10℃ for 2 h, followed by 4 h at room temperature to produce the corresponding aromatic diethyl diacyl chloride solution.

[0064] 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 aromatic diethyl dichloroisocyanurate solution prepared above was added dropwise to the 3HFAP / NMP solution over a period of 0.5 h; then, the reaction was allowed to proceed at room temperature for 10 h; finally, 1.48 g (0.10 mol.) of NMP was added. 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: PAE-1-1: 44BHTA-3HFAP).

[0065] Resin Synthesis Example 2

[0066] In Resin Synthesis Example 1, 32.42 g (0.10 mol.) of 3,3,4',4'-benzyl tetracarboxylic dianhydride (44BHTA, Mw=324.19) was replaced with 35.42 g (0.10 mol.) of 2,2'-dihydroxybenzophenone-3,3',4,4'-tetracarboxylic dianhydride (44DBTA, mp. 257-258 ℃, Mw=354.19), while maintaining the same other parameters, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-2: 44DBTA-3HFAP).

[0067] Resin Synthesis Example 3

[0068] In Resin Synthesis Example 1, 32.42 g (0.10 mol.) of 3,3,4',4'-benzyl alcohol tetracarboxylic dianhydride (44BHTA, Mw=324.19) was replaced with a mixture of 16.21 g (0.05 mol.) of 3,3,4',4'-benzyl alcohol tetracarboxylic dianhydride (44BHTA, Mw=324.19) and 12.01 g (0.05 mol.) of 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (abbreviated as: 44ODPA, Mw=240.18), otherwise the same, to obtain a high-purity phenolic hydroxyl polyaminate resin solid (abbreviated as: PAE-1-3: 44BHTA / 44ODPA(1 / 1)-3HFAP).

[0069] Resin Synthesis Example 4

[0070] In Resin Synthesis Example 3, 12.01 g (0.05 mol.) 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (abbreviated as: 44ODPA, Mw=240.18) was replaced with 32.63 g (0.10 mol.) 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (abbreviated as: 34ODPA, Mw=240.18), and all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-4: 44BHTA / 34ODPA(1 / 1)-3HFAP).

[0071] Resin Synthesis Example 5

[0072] In Resin Synthesis Example 3, 12.01 g (0.05 mol.) 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (abbreviated as: 44ODPA, Mw=240.18) was replaced with 32.63 g (0.10 mol.) 2,2,3',3'-diphenyl ether tetracarboxylic dianhydride (abbreviated as: 33ODPA, Mw=240.18), and all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-5: 44BHTA / 33ODPA(1 / 1)-3HFAP).

[0073] Resin Synthesis Example 6

[0074] In Resin Synthesis Example 3, 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: PAE1-1-5: 44BHTA / 44ODPA(1 / 1)-4HFAP).

[0075] Resin Synthesis Example 6

[0076] Replace 36.62 g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) in resin synthesis example 3 with

[0077] 36.62 g (0.10 mol.) of 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane (abbreviation: 4HFAP, Mw=366.17), with other parameters the same, yielded a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviation: PAE1-1-5: 44BHTA / 44ODPA(1 / 1)-4HFAP).

[0078] Resin Synthesis Example 7

[0079] In Resin Synthesis Example 3, 36.62 g (0.10 mol.) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) was replaced with 60.43 g (0.10 mol.) 2,2'-bis[N-(3-aminobenzoamide)-3-amino-4-hydroxyphenyl]hexafluoropropane (abbreviated as: 3HFHA, Mw=604.32), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyaminate resin solid (abbreviated as: PAE1-1-7: 44BHTA / 44ODPA(1 / 1)-3HFHA).

[0080] Resin Synthesis Example 8

[0081] In Resin Synthesis Example 3, 36.62 g (0.10 mol.) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviation: 3HFAP, Mw=366.17) was replaced with 60.43 g (0.10 mol.) 2,2'-bis[N-(3-aminobenzoamide)-4-amino-3-hydroxyphenyl]hexafluoropropane (abbreviation: 4HFHA, Mw=604.32), and all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyaminate resin solid (abbreviation: PAE1-1-8: 44BHTA / 44ODPA(1 / 1)-4HFHA).

[0082] Resin Synthesis Example 9

[0083] In Resin Synthesis Example 3, 36.62 g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) was replaced with 25.82 g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (abbreviated as: 3HHAP, Mw=258.17), while all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide ester resin solid (abbreviated as: PAE1-1-9: 44BHTA / 44ODPA(1 / 1)-3HHAP).

[0084] Resin Synthesis Example 10

[0085] In Resin Synthesis Example 3, 36.62 g (0.10 mol.) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (abbreviated as: 3HFAP, Mw=366.17) was replaced with 25.82 g (0.10 mol.) of 2,2-bis(4-amino-3-hydroxyphenyl)propane (abbreviated as: 4HHAP, 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: 44BHTA / 44ODPA(1 / 1)-4HHAP).

[0086] PAE-2-1

[0087] Resin Synthesis Example 11

[0088] 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 S℃l2 at 0-10℃ for 2 h, followed by 4 h at room temperature to produce a solution of the corresponding 44ODPA diethyl diacyl chloride.

[0089] 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 and subjected to adsorption by anionic and cationic resins to remove residual metal or non-metal ions, yielding high-purity phenolic hydroxyl-containing polyamic acid ester resin solid (abbreviated as: PAE-2-1: 44ODPA-3HFAP).

[0090] Resin Synthesis Example 12

[0091] In Resin Synthesis Example 11, 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 all other parameters remained the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE-2-2:33ODPA-3HFAP).

[0092] Resin Synthesis Example 13

[0093] In Resin Synthesis Example 11, 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).

[0094] Resin Synthesis Example 14

[0095] In Resin Synthesis Example 11, 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), otherwise the same, to obtain a high-purity phenolic hydroxyl polyamide resin solid (abbreviated as: PAE-2-4:33ODPA / 44ODPA(1 / 1)-3HFAP).

[0096] Resin Synthesis Example 15

[0097] In Resin Synthesis Example 11, 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).

[0098] Resin Synthesis Example 16

[0099] In Resin Synthesis Example 11, 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).

[0100] 3. Positive photosensitive polyimide resin liquid

[0101] Examples 1-5 and Comparative Examples 1-2

[0102] Example 1

[0103] In a cleanroom equipped with a yellow light, 50g of phenolic hydroxyl polyamide ester resin-1 (PAE-1-1-1) prepared in Resin Synthesis Example 1 and 50g of phenolic hydroxyl polyamide resin-2 (PAE-2-1) prepared in Resin Synthesis Example 11 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 with a solid content of 35%. At wt.%, the solution viscosity is 1500 mPa·s.

[0104] 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 to form a liquid film with a thickness of 5-7 μm. After baking at 100-110 °C for 1-3 min, a mask is placed on its surface and exposed using ultraviolet lamps (i and g lines). Spray development is performed using a tetramethylamine hydroxide alkaline aqueous solution (2.38% TMAH), followed by rinsing with deionized ultrapure water and then curing in a nitrogen-protected oven (150 °C / 1 h, 200 °C / 1 h, 200 °C / 1 h) to obtain a stereolithographic pattern formed by a thermosetting resin film (thickness of 5-6 μm).

[0105] The prepared positive photosensitive polyimide resin solution was evaluated using the above evaluation method. The evaluation results are as follows: ① Photolithographic resolution is "excellent"; ② Comprehensive mechanical properties are "excellent"; ③ Chemical corrosion resistance is "excellent"; ④ Damp heat resistance is "excellent"; ⑤ Copper adhesion is "excellent"; ⑥ Comprehensive performance evaluation is "excellent".

[0106] Example 2

[0107] In Example 1, PAE-1-1 was replaced with PAE-1-2, while other aspects remained the same, to obtain a positive photosensitive polyimide resin adhesive. The performance of the positive photosensitive polyimide resin adhesive was evaluated using the above evaluation method. The evaluation results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0108] Example 3

[0109] In Example 1, PAE-1-1 was replaced with PAE-1-3, while other aspects remained the same, to obtain a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical resistance: "Excellent"; ④ Moisture and heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0110] Example 4

[0111] In Example 1, PAE-1-1 was replaced with PAE-1-4, while other aspects remained the same, to obtain a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0112] Example 5

[0113] In Example 1, PAE-1-1 was replaced with PAE-1-5, while other aspects remained the same, to obtain a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Overall mechanical properties: "Good"; ③ Chemical resistance: "Excellent"; ④ Moisture and heat resistance: "Good"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Good".

[0114] Comparative Example 1

[0115] PAE-2-1 was removed from Example 1, while all other aspects remained the same, resulting in a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Overall mechanical properties: "Good"; ③ Chemical resistance: "Excellent"; ④ Moisture and heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance: "Good".

[0116] Comparative Example 2

[0117] PAE-1-1 was removed from Example 1, while all other aspects remained the same, resulting in a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Good"; ② Overall mechanical properties: "Excellent"; ③ Chemical resistance: "Excellent"; ④ Moisture and heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Good".

[0118] Table 1 Comparison of results from Examples 1-5 and Comparative Examples 1-2 - Changes in dianhydride structure ODPA

[0119] PAE-1 PAE-1-144BHTA-3HFAP PAE-1-244DBTA / 3HFAP PAE-1-344BHTA / 44ODPA(1 / 1)-3HFAP PAE-1-444BHTA / 34ODPA(1 / 1)-3HFAP PAE-1-544BHTA / 33ODPA(1 / 1)-3HFAP PAE-1-344BHTA / 44ODPA(1 / 1)-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 Solid content of adhesive (wt.%) 35 35 35 35 35 35 35 <![CDATA[Viscosity of the glue solution, mPa.s (23 ℃ )]]> 1500 1500 1500 1500 1500 1500 1500 <![CDATA[curing temperature ( ℃ )]]> 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h ① Photolithographic resolution excellent excellent excellent excellent excellent excellent good ②Comprehensive mechanical properties excellent excellent excellent excellent good good excellent ③ Resistance to chemical corrosion excellent excellent excellent excellent excellent excellent excellent ④ Resistance to damp heat excellent excellent excellent excellent good excellent excellent ⑤ Adhesion to copper excellent excellent excellent excellent excellent excellent excellent ⑥ Comprehensive performance evaluation good excellent excellent excellent good good good

[0120] Table 1 compares the effects of the different molecular structures of the hydroxyl-containing aromatic tetracarboxylic acid dianhydride monomers of the PAE-1 series resins (PAE-1-1, 1-2, 1-3, 1-4) on the overall performance of the prepared positive photosensitive polyimide resins when the weight ratio of the PAE-1 series resins (PAE-1-1, 1-2, 1-3, 1-4) in Examples 1-5 is 1:1. The results show that the mixed resin formed by combining PAE-1-1 or PAE-1-2, PAE-1-3, PAE-1-4 with PAE-2-1 in a 1:1 weight ratio, and the positive photosensitive polyimide resin solution formed by fully mixing with other components such as photoacid generators, thermal crosslinking agents, thermal acid generators, and tackifiers, has excellent overall performance, and the overall performance evaluation is "excellent". The positive photosensitive polyimide resin adhesive prepared from a mixed resin formed by combining PAE-1-5 and PAE-2-1 in a 1:1 weight ratio exhibits poor resistance to damp heat, and its overall performance is rated as "good". In contrast, when either the phenolic hydroxyl polyaminate resin (PAE-1-1) or the phenolic hydroxyl polyaminate resin (PAE-2-1) is a single component, rather than a mixture of both, the overall performance of the prepared positive photosensitive polyimide resin adhesive is rated as "good or poor".

[0121] Example 6

[0122] In Example 1, PAE-1-1 was replaced with PAE-1-6, while other aspects remained the same, to obtain a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0123] Example 7

[0124] In Example 1, PAE-1-1 was replaced with PAE-1-7, while other aspects remained the same, to obtain a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0125] Example 8

[0126] In Example 1, PAE-1-1 was replaced with PAE-1-8, while other aspects remained the same, to obtain a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0127] Example 9

[0128] In Example 1, PAE-1-1 was replaced with PAE-1-9, while other aspects remained the same, to obtain a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0129] Example 10

[0130] In Example 1, PAE-1-1 was replaced with PAE-1-10, while all other aspects remained the same, resulting in a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Good"; ② Overall mechanical properties: "Excellent"; ③ Chemical resistance: "Excellent"; ④ Moisture and heat resistance: "Excellent"; ⑤ Copper adhesion: "Poor"; ⑥ Overall performance evaluation: "Poor".

[0131] Comparative Example 3

[0132] PAE-2-1 was removed from Example 8, while all other aspects remained the same, resulting in a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Excellent"; ② Overall mechanical properties: "Poor"; ③ Chemical resistance: "Excellent"; ④ Moisture and heat resistance: "Good"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Poor".

[0133] Table 2 Comparison of Results from Examples 7-11 - Changes in Diamine Structure

[0134] PAE-1 PAE-1-644BTHA / 44ODPA-(1 / 1)-4HFAP PAE-1-744BTHA / 44ODPA-(1 / 1)-3HFHA PAE-1-844BTHA / 44ODPA-(1 / 1)-4HFHA PAE-1-944BTHA / 44ODPA-(1 / 1)-3BAPP PAE-1-844BTHA / 44ODPA-(1 / 1)-4BAPP PAE-1-844BTHA / 44ODPA-(1 / 1)-4HFHA 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 35 35 35 35 35 <![CDATA[Viscosity of the glue solution, mPa·s (23 ℃ )]]> 1500 1500 1500 1500 1500 1500 <![CDATA[curing temperature ( ℃ )]]> 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h ① Photolithographic resolution excellent excellent excellent excellent good excellent ② With high photolithographic resolution excellent excellent excellent excellent excellent Difference ③ Resistance to chemical corrosion excellent excellent excellent excellent excellent excellent ④ Resistance to damp heat excellent excellent excellent excellent excellent good ⑤ Adhesion to copper excellent excellent excellent excellent Difference excellent ⑥ Comprehensive performance evaluation excellent excellent excellent excellent Difference Difference

[0135] Table 2 compares the effects of the different molecular structures of the hydroxyl-containing aromatic dianhydride monomers (4HFAP, 3HFHA, 4HFHA) in the PAE-1 series resins (PAE-1, PAE-1-6, PAE-1-7, PAE-1-8, PAE-1-9 and PAE-2-1) at a weight ratio of 1:1 on the overall performance of the prepared positive photosensitive polyimide resin when the weight ratio of the PAE-1 series resins (PAE-1-6 or PAE-1-7, PAE-1-8, PAE-1-9 and PAE-2-1 is 1:1. The results show that the positive photosensitive polyimide resin adhesive formed by thoroughly mixing the mixed resin of PAE-1-6 or PAE-1-7, PAE-1-8, PAE-1-9 and PAE-2-1 at a weight ratio of 1:1 with other components such as photoacid generators, thermal crosslinking agents, thermal acid generators, and tackifiers has excellent overall performance, and the overall performance evaluation is "excellent". The overall performance evaluation of the positive photosensitive polyimide resin adhesive prepared by combining PAE-1-10 and PAE-2-1 in a 1:1 weight ratio was "poor". In contrast, when the phenolic hydroxyl polyaminate resin (PAE-1-8) was only a single component and did not form a mixed resin with PAE-2-1, the overall performance evaluation of the prepared positive photosensitive polyimide resin adhesive was also "poor".

[0136] Example 11

[0137] In Example 2, PAE-2-1 was replaced with PAE-2-2, while other aspects remained the same, to obtain a positive photosensitive polyimide resin adhesive. The performance of the positive photosensitive polyimide resin adhesive was evaluated using the above evaluation method. The evaluation results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0138] Example 12

[0139] In Example 2, PAE-2-1 was replaced with PAE-2-3, while other aspects remained the same, to obtain a positive photosensitive polyimide resin adhesive. The performance of the positive photosensitive polyimide resin adhesive was evaluated using the above evaluation method. The evaluation results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0140] Example 13

[0141] In Example 2, PAE-2-1 was replaced with PAE-2-4, while other aspects remained the same, to obtain a positive photosensitive polyimide resin adhesive. The performance of the positive photosensitive polyimide resin adhesive was evaluated using the above evaluation method. The evaluation results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0142] Example 14

[0143] In Example 2, PAE-2-1 was replaced with PAE-2-5, while other aspects remained the same, to obtain a positive photosensitive polyimide resin adhesive. The performance of the positive photosensitive polyimide resin adhesive was evaluated using the above evaluation method. The evaluation results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Excellent".

[0144] Example 15

[0145] In Example 2, PAE-2-1 was replaced with PAE-2-6, while other aspects remained the same, to obtain a positive photosensitive polyimide resin adhesive. The performance of the positive photosensitive polyimide resin adhesive was evaluated using the above evaluation method. The evaluation results were as follows: ① Photolithographic resolution: "Excellent"; ② Comprehensive mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Good"; ④ Damp heat resistance: "Excellent"; ⑤ Copper adhesion: "Excellent"; ⑥ Overall performance evaluation: "Good".

[0146] Comparative Example 4

[0147] PAE-1-2 was removed from Example 13, while all other aspects remained the same, to obtain a positive photosensitive polyimide resin solution. Its performance was evaluated using the above evaluation method, and the results were as follows: ① Photolithographic resolution: "Good"; ② Overall mechanical properties: "Excellent"; ③ Chemical corrosion resistance: "Excellent"; ④ Damp heat resistance: "Poor"; ⑤ Copper adhesion: "Good"; ⑥ Overall performance evaluation: "Poor".

[0148] Table 3 Comparison of results from Examples 12-16 - Changes in diacid structure

[0149] PAE-1 PAE-1-744BTHA / 44ODPA-(1 / 1)-3HFHA PAE-1-744BTHA / 44ODPA-(1 / 1)-3HFHA PAE-1-744BTHA / 44ODPA-(1 / 1)-3HFHA PAE-1-744BTHA / 44ODPA-(1 / 1)-3HFHA PAE-1-744BTHA / 44ODPA-(1 / 1)-3HFHA -- 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 Solid content of adhesive (wt.%) 35 35 35 35 35 35 <![CDATA[Viscosity of the glue solution, mPa·s (23 ℃ )]]> 1500 1500 1500 1500 1500 1500 <![CDATA[curing temperature( ℃ )]]> 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h 220 / 1h ① Photolithographic resolution excellent excellent excellent excellent excellent good ②Comprehensive mechanical properties excellent excellent excellent excellent excellent excellent ③ Resistance to chemical corrosion excellent excellent excellent excellent good excellent ④ Resistance to damp heat excellent excellent excellent excellent excellent Difference ⑤ Adhesion to copper excellent excellent excellent excellent excellent good ⑥ Comprehensive performance evaluation excellent excellent excellent excellent good Difference

[0150] Table 3 compares the effects of the different molecular structures of the PAE-2 series resins (PAE-2-2, 2-3, 2-4, 2-5) in Examples 11-15 (PAE-2-2, 2-3, 2-4, 2-5) on the overall performance of the prepared positive photosensitive polyimide resin when the weight ratio of PAE-2-2 resin-1 (PAE-1-2) and PAE-2-5 resin-2 series resin (PAE-2-2, 2-3, 2-4, 2-5) is 1:1. The results show that the mixed resin formed by PAE-2-2, 2-3, PAE-2-4, PAE-2-5 and PAE-1-1 in a 1:1 weight ratio, when thoroughly mixed with other components such as photoacid generators, thermal crosslinking agents, and tackifiers, exhibits excellent overall performance, and the overall performance evaluation is "Excellent". The overall performance evaluation of the positive photosensitive polyimide resin adhesive prepared by combining PAE-2-6 and PAE-1-1 in a 1:1 weight ratio was "good". In contrast, when the phenolic hydroxyl polyamide resin (PAE-2-3) was only a single component, rather than a mixed resin formed with PAE-1-1, the overall performance evaluation of the prepared positive photosensitive polyimide resin adhesive was "poor".

[0151] In summary, this invention discloses a positive photosensitive polyimide resin composition liquid with high photolithographic resolution, its preparation method, and its application. The positive photosensitive polyimide resin composition liquid has high photolithographic resolution and excellent photolithographic processability. The liquid film formed by 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 has the characteristics of high resistance to moisture and 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.

[0152] It should be understood that numerous specific implementation decisions can be made during the development of any practical implementation, such as in any engineering or design project. Such development efforts may be complex and time-consuming, but for those skilled in the art who benefit from this disclosure, the development effort will be a routine work of design, manufacturing, and production without requiring much experimentation.

[0153] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A positive photosensitive polyimide resin solution with high photolithographic resolution, characterized in that, The positive photosensitive polyimide resin adhesive is composed of the following chemical components, including: A, a mixture of phenolic hydroxyl polyamide ester resin-1 and phenolic hydroxyl polyamide ester resin-2; B, a photoacid-generating agent; C, a thermal crosslinking agent; D, a thermal acid-generating agent; E, a sensitizer; F, an organic solvent; and G, an adhesive aid. The preparation method of the phenolic hydroxyl-containing polyamide ester resin-1 includes the following steps: mixing hydroxyl-containing aromatic tetracarboxylic dianhydride-1 and aromatic tetracarboxylic dianhydride-2 to form a mixed aromatic tetracarboxylic dianhydride; reacting it with a fatty alcohol under heating conditions to generate a mixed aromatic diacid diester; reacting the mixed aromatic diacid diester with thionyl chloride to generate a mixed aromatic diester diacyl chloride; reacting the mixed aromatic diester diacyl chloride with an imidazole-based nitrogen-containing organic base to generate a mixed aromatic diester diimidazolium salt compound; polycondensing the mixed aromatic diester diimidazolium salt compound with a phenolic hydroxyl-containing aromatic diamine in an organic solvent in the presence of a reactive end-capping agent to generate a phenolic hydroxyl-containing polyamide ester copolymer resin solution; precipitating, separating, washing, and drying the copolymer resin in a poor solvent to obtain a solid resin with a GPC molecular weight of 1.0 × 10⁻⁶. 4 Up to 3.0×10 4 ; The hydroxyl-containing aromatic tetracarboxylic dianhydride-1 is selected from: 3,3,4',4'-dibenzyl alcohol tetracarboxylic dianhydride, 2,2-dihydroxybenzophenone tetracarboxylic dianhydride, or a mixture thereof in any proportion; The aromatic tetracarboxylic dianhydride-2 is selected from: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3',2,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,3',3,4'-biphenyl tetracarboxylic dianhydride, 2,3',2,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, 2,3', 2,3'-Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-Diphenyl sulfone tetracarboxylic dianhydride, 2,3',2,3'-Diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-Diphenyl sulfide tetracarboxylic dianhydride, 2,3',2,3'-Diphenyl sulfide tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-benzophenone tetracarboxylic dianhydride, or mixtures thereof in any proportion.

2. The positive photosensitive polyimide resin liquid according to claim 1, characterized in that: The phenolic hydroxyl-containing aromatic diamine is selected from: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2'-bis[N-(3-aminobenzoamido)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2'-bis[N-(4-aminobenzoylamino)-3-amino-4-hydroxyphenyl]hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)methane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, 1,3-bis(3-aminophenoxy)tetramethyldisiloxane, 1,3-bis(4-aminophenoxy)tetramethyldisiloxane, or mixtures thereof in any proportion. The organic solvents include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolium ketone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylurea, phenol, m-cresol, ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, and mixtures thereof in any proportion; The reactive end-capping agents include: 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 unsuitable solvents include: deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, and mixtures thereof in any proportion.

3. The positive photosensitive polyimide resin liquid according to claim 1, characterized in that: The preparation method of the phenolic hydroxyl polyamate resin-2 includes the following steps: Aromatic tetracarboxylic dianhydride-2 is esterified with a fatty alcohol under heating conditions to generate aromatic diacid diester; The aromatic diacid diester is reacted with thionyl chloride to generate aromatic diester diacyl chloride; The aromatic diester diacyl chloride is reacted with an imidazole nitrogen-containing organic base to generate an aromatic diester diimidazolium salt compound; The aromatic diester diimidazole salt compound and phenolic hydroxyl-containing aromatic diamine-2 are polycondensed in an organic solvent in the presence of a reactive end-capping agent to generate a phenolic hydroxyl-containing polyamic acid ester resin solution. The resin was precipitated in a poor solvent, separated, washed, and dried to obtain a solid resin with a GPC molecular weight of 1.0 × 10⁻⁶. 4 Up to 3.0×10 4 .

4. The positive photosensitive polyimide resin adhesive according to claim 3, characterized in that: The aromatic tetracarboxylic dianhydride-2 is selected from: 2,3,2',3'-diphenyl ether tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-benzophenone tetracarboxylic dianhydride, 2,3',2,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,3',2,3'-biphenyltetracarboxylic dianhydride. 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, 2,3',2,3'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 2,3',2,3'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 2,3',2,3'-diphenyl sulfide tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, or mixtures thereof in any proportion; The phenolic hydroxyl-containing aromatic diamine-2 is selected from: 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, or mixtures thereof in any proportion.

5. The positive photosensitive polyimide resin liquid according to claim 3, characterized in that: The organic solvents include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolium ketone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylurea, phenol, m-cresol, ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, and mixtures thereof in any proportion; the reactive end-capping agents include: 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, propyneamine, and mixtures thereof in any proportion; the unsuitable solvents include: deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, and mixtures thereof in any proportion.

6. The positive photosensitive polyimide resin liquid according to claim 1, characterized in that: The photoacid-producing agent B is a diazonoquinone compound, an iodonium salt compound, or a sulfonium salt compound; the thermal crosslinking agent C is a compound containing an epoxy group, or a compound containing hydroxymethyl or alkoxymethyl groups; and the organic solvent F is a polar solvent capable of dissolving components A to E to form a homogeneous solution, including N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, n-propyl acetate, and lactic acid. The following are included: methyl ester, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and mixtures thereof in any proportion; the adhesive G is a silane coupling agent.

7. The method according to claim 6, characterized in that: Tackifier G includes γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyl ether oxypropyltrimethoxysilane, γ-glycidyl ether oxypropyltriethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3-isocyanate-based trimethoxysilane, 3-isocyanate-based triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltri ... 3-Mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 3-(m-aminophenoxy)trimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, and mixtures thereof in any proportion.

8. A method for preparing a positive photosensitive polyimide resin adhesive according to any one of claims 1 to 7, characterized in that, Includes the following steps: In a clean environment with yellow light, 100 parts by weight of component 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 are added in batches to organic solvent F under stirring to form a homogeneous solution. After filtration and dispensing, a positive photosensitive polyimide resin liquid with a solid content of 15-45 wt.% and a room temperature viscosity of 500-4000 mPa·s is obtained.

9. The use of a positive photosensitive polyimide resin liquid according to any one of claims 1 to 7, characterized in that, The adhesive is used to fabricate a dielectric insulating layer film for multilayer metal interconnect circuits on the surface of a 12-inch silicon wafer or a glass substrate. The photolithography patterning process for the dielectric insulating layer film includes the following steps: Coating: The adhesive is spin-coated onto the surface of a wafer or inkjet-printed onto the surface of a glass substrate to form a liquid adhesive film; Pre-baking: Bake at 80~150°C to form a semi-solid film; Exposure: Ultraviolet light is used to expose the image through a photomask. Development and rinsing: The development is carried out by spraying or immersion with water-based developer, followed by rinsing with ultrapure water to form a three-dimensional pattern; Heat curing: Heat at 180~230°C to cure, forming a three-dimensional pattern of heat-resistant curable resin; Electroplating and etching: A conductive copper layer is formed by electroplating on the surface of the resin 3D pattern, and then a conductive copper circuit is formed by photolithography and etching, completing one layer of RDL process; repeat the above process to form a multi-layer RDL structure.