A photosensitive polyimide precursor resin, preparation thereof, and a positive photosensitive photoetching composition comprising the same

Abstract

The present application relates to the technical field of electronic-grade photosensitive polymer materials. More particularly, it relates to a photosensitive polyimide precursor resin, its preparation and a positive photosensitive photoetching composition containing the same. The photosensitive polyimide precursor resin is polymerized from diamine monomer A, diamine monomer B and dianhydride monomer; wherein the diamine monomer A is a photosensitive functional monomer containing a hydroxyl group; the diamine monomer B is a flexible rotatable bridging type diamine containing an aryl ether bond, a sulfone group and / or a carbonyl group as a flexible linking group, or a large steric hindrance-non-coplanar torsion type diamine containing a fluorene, a spiro ring, an alicyclic ring and / or a polyalkyl-substituted biphenyl skeleton; and the molar ratio of total diamine monomers and dianhydride monomers is 0.8-1.05. The photosensitive polyimide precursor resin simultaneously improves the solvent solubility of the resin, the light transmittance of the cured film, the photosensitivity and the developed residual film rate under the premise of containing no trifluoromethyl group and meeting the environmental protection compliance requirements, and meets the application requirements of high-end electronic processes.

Description

Technical Field

[0001] This invention relates to the field of electronic-grade photosensitive polymer materials technology. More specifically, it relates to a photosensitive polyimide precursor resin, its preparation, and a positive-type photolithography composition comprising the same. Background Technology

[0002] Photosensitive polyimide (PSPI) combines the excellent heat resistance, mechanical strength, insulation properties and chemical stability of polyimide itself, while also having the ability to directly pattern with ultraviolet lithography. It can complete high-precision pattern processing without the need for additional photoresist, which can greatly simplify the process and improve the yield. It is an indispensable core material in the fields of high-end display and advanced packaging.

[0003] For a long time, commercial high-performance PSPI resins have generally been prepared by introducing dianhydride / diamine monomers containing trifluoromethyl groups. The strong electronegativity and large steric hindrance of trifluoromethyl groups can effectively disrupt the regularity of molecular chains, weaken intermolecular hydrogen bonds and π-π stacking effects, and at the same time endow the resin with excellent organic solvent solubility, high light transmittance and low dielectric constant. It is a classic technical solution to balance the processing performance of PSPI and the overall performance of the finished product.

[0004] However, with the continuous upgrading of global environmental compliance requirements, per- and polyfluorinated substances (PFAS) containing trifluoromethyl have been included in strict control systems such as the EU PFAS Restriction Act and China's "List of Key New Pollutants" due to their environmental persistence, bioaccumulation and potential ecotoxicity. The compliance risks and market access barriers of fluorinated PSPIs continue to intensify, and the replacement of fluorinated PSPIs has become an inevitable development trend in the industry.

[0005] To improve the solvent solubility of precursor resins, the transmittance of cured films, and the photolithographic sensitivity, traditional commercial photosensitive polyimide (PSPI) resin formulations typically incorporate fluorinated dianhydrides and fluorinated diamine monomers for skeletal modification. Fluorine atoms possess the advantage of low polarizability and the ability to weaken π-π stacking between polymer chains, enabling the easy preparation of photosensitive substrates with high solubility and high transparency.

[0006] However, throughout the entire lifecycle of fluorinated monomers—from chemical synthesis, high-purity monomer purification, photoresist formulation, substrate spin coating, high-temperature thermal curing, to the disposal of photolithography waste liquid, cleaning wastewater, and solid waste of cured film materials—various fluorinated pollutants may leach out or degrade. Fluorinated waste easily seeps into water bodies, causing excessive fluoride levels. Fluorinated exhaust gases released during processing and baking also increase the burden of tail gas treatment. Furthermore, fluorides are difficult to degrade naturally and have strong bioaccumulation, posing long-term ecological risks.

[0007] Currently, environmental regulations in the microelectronics materials industry are becoming increasingly stringent. The treatment processes for the three wastes (waste gas, wastewater, and solid waste) of fluorinated photoresist consumables are complex and the disposal costs are high, putting significant pressure on enterprises to control pollution. Long-term use of fluorinated raw materials does not align with the development trend of low-carbon, harmless, and green manufacturing in the semiconductor and high-end display industry chains. Therefore, the industry urgently needs to develop high-performance, non-fluorinated photosensitive polyimide materials as an alternative. Summary of the Invention

[0008] To address the aforementioned problems, the first objective of this invention is to provide a photosensitive polyimide precursor resin. This photosensitive polyimide precursor resin, while being completely free of trifluoromethyl and meeting environmental compliance requirements, simultaneously improves the resin's solvent solubility, cured film transmittance, photosensitivity, and residual film yield, thus meeting the application requirements of high-end electronic manufacturing processes.

[0009] A second objective of this invention is to provide a method for preparing the photosensitive polyimide precursor resin as described above.

[0010] A third objective of this invention is to provide a positive photolithography composition.

[0011] To achieve the first objective mentioned above, the present invention adopts the following technical solution: This invention discloses a photosensitive polyimide precursor resin, which is polymerized from diamine monomer A, diamine monomer B, and dianhydride monomer; Neither diamine monomer A nor diamine monomer B contains trifluoromethyl in their structure. Diamine monomer A is a photosensitive functional monomer containing hydroxyl groups, and diamine monomer B is a flexible rotatable bridging diamine containing aryl ether bonds, sulfone groups and / or carbonyl groups as flexible linking groups, or a sterically hindered non-coplanar twisted diamine containing fluorene, spirocyclic, alicyclic and / or polyalkyl substituted biphenyl skeletons. The molar ratio of total diamine monomer to dianhydride monomer is 0.8–1.05.

[0012] Furthermore, the diamine monomer A is selected from 1,1-bis[3-(3-aminobenzoamide)-4-hydroxyphenyl]cyclohexane, 4,4'-(4-methylpentan-2,2-diyl)bis(2-aminophenol), 5,5'-diamino-3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirodi[indene]-6,6'-diol, and 3,3'-bis[3-(3-aminobenzoylamino)-4-hydroxyphenyl]cyclohexane. The following are any one or more of the following: [1-methyl]diphenyl sulfone, N,N′-[(1-methylene)bis(6-hydroxy-3,1-phenyl)]bis[3-amino-]benzoyl, 2,2'-diamino-4,4'-(cyclohexyl-1,1-dimethyl)diol, bis(3-amino-4-hydroxyphenyl)sulfone, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis(4-hydroxy-3-aminophenyl)propane, and 3,3'-dihydroxybenzidine.

[0013] Furthermore, the flexible rotatable bridging diamine is selected from any one or more of 4,4'-bis(3-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)benzophenone, 3,3'-diaminodiphenyl sulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diaminophenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 3,4'-diaminodiphenyl ether, 4,4'-bis(3-aminophenoxy)biphenyl, and [4-(4-aminobenzoyl)oxyphenyl]4-aminobenzoate.

[0014] Furthermore, the sterically hindered, non-coplanar twisted diamine is selected from any one or more of N,N'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis(4-amino-benzamide), 4,4'-(4-pentylcyclohexane-1,1-diyl)diphenylamine, 5(6)-1-(4-aminophenyl)-1,3,3-trimethylindene, 4,4'-diamino-2,2'-dimethylbiphenyl, 1,1-bis(4-aminophenyl)cyclohexane, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene, 9,9-dimethylfluorene-2,7-diamine, and 3,3',5,5'-tetramethylbenzidine.

[0015] Furthermore, the dianhydride monomer is selected from one or more of the following: ether-bonded dianhydrides, biphenyl-bonded dianhydrides, fluorenyl dianhydrides, sulfone-bonded dianhydrides, ketone-bonded dianhydrides, ester-bonded dianhydrides, fused-ring heterocyclic dianhydrides, bridged-ring olefin dianhydrides, cyclobutane dianhydrides, saturated hydrogenated aromatic ring dianhydrides, and straight-chain aliphatic dianhydrides.

[0016] Further, the dianhydride monomer is selected from biphenyl diether dianhydride, 11,11-dimethyl-1H-difurano[3,4-b:3',4'-i]oxaanthra-1,3,7,9(11H)-tetraone, 5,5'-(propane-2,2-diyl)bis(isobenzofuran-1,3-dianhydride), 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-triphenyl diether tetracarboxylic dianhydride, 4,4'-biphenyl dianhydride, bisphenol A type diether dianhydride, 4 One or more of the following: 4'-terephthalodioxydiphthalic anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, bis[(3,4-dianhydride)phenyl]terephthalate, 3,3,4,4-diphenyl sulfone tetracarboxylic anhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic anhydride, 1,3-dimethyl-cyclobutanetetracarboxylic anhydride, hydrogenated pyromellitic dianhydride, cyclobutanetetracarboxylic anhydride, and 1,2,3,4-butanetetracarboxylic anhydride.

[0017] Furthermore, the weight-average molecular weight of the photosensitive polyimide precursor resin is 8000-80000.

[0018] Furthermore, the molar ratio of diamine monomer A to diamine monomer B is 0.2-5; for example, the molar ratio of diamine monomer A to diamine monomer B can be 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc.

[0019] To achieve the second objective mentioned above, the present invention adopts the following technical solution: This invention discloses a method for preparing the photosensitive polyimide precursor resin as described above, comprising the following steps: Under a nitrogen protective atmosphere, diamine monomer A and diamine monomer B are added to the reaction vessel, solvent is added and stirred until completely dissolved, and the system temperature is controlled at 15-25℃. Add dianhydride monomer in proportion, add solvent to adjust the solid content of the reaction system to 15-30%, stir the reaction at constant temperature for 2-4 hours to obtain polyamic acid solution; Add a capping agent to adjust the molecular weight, continue stirring for 0.5 h, and then add an esterifying agent to carry out the esterification reaction; After the reaction is complete, the reaction solution is poured into deionized water to precipitate, washed with water, and dried to obtain the photosensitive polyimide precursor resin.

[0020] Furthermore, the esterification reaction is carried out at a temperature of 35-50°C for 4-8 hours.

[0021] To achieve the third objective mentioned above, the present invention adopts the following technical solution: This invention discloses a positive photolithography composition comprising the photosensitive polyimide precursor resin as described above. The positive photolithography composition comprises the following components in parts by weight: 20-200 parts of photosensitive polyimide precursor resin; 10-35 parts of photoacid-producing agent; 15-25 parts of thermal crosslinking agent; Leveling agent 0.5-5 parts; 0.1-2 parts of adhesive additive; 150-600 parts of compound solvent.

[0022] Furthermore, the photoacid-generating agent is a naphthoquinone diazidesulfonate photosensitizer.

[0023] Furthermore, the thermal crosslinking agent is selected from any one or more of benzoxazine compounds, epoxy resin compounds, and alkoxymethyl compounds.

[0024] Furthermore, the leveling agent is selected from any one or more of polydimethylsiloxane-modified polyether, polyester-modified silicone, silicone acrylate copolymer, polyacrylate leveling agent, and polyether polyester copolymer.

[0025] Furthermore, the adhesive aid is selected from any one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, vinylsilane, and methacryloyloxysilane.

[0026] Furthermore, the compound solvent is composed of a main solvent and a diluent solvent, wherein the main solvent is selected from any one or more of N-methylpyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, and ethyl lactate, and the diluent solvent is selected from any one or more of propylene glycol monomethyl ether acetate and butyl acetate, and the mass ratio of the main solvent to the diluent solvent is 0.2-5; exemplaryly, the mass ratio of the main solvent to the diluent solvent can be 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc.

[0027] The beneficial effects of this invention are as follows: Compared with existing trifluoromethyl-free PSPI technology, it has the following significant advantages: 1. Significantly improved solvent solubility: The photosensitive polyimide precursor resin of the present invention utilizes its large steric hindrance effect to disrupt the regularity of the molecular chain and weaken the intermolecular forces, so that the resin has good solubility in both polar and weakly polar solvents, making it suitable for multi-component compound solvent systems and significantly enhancing process adaptability.

[0028] 2. Significantly improved visible light transmittance: It inhibits the formation of intermolecular charge transfer complexes and reduces the degree of molecular chain conjugation, so that the prepared cured film can achieve a transmittance of more than 90% at a wavelength of 400nm, which is close to the level of traditional trifluoromethyl PSPI, meeting the optical requirements of high-end displays.

[0029] 3. Simultaneous optimization of photosensitivity and residual film rate: While ensuring development resolution, the minimum exposure amount is reduced to 60mJ / cm. 2 The residual film rate after development is increased to about 70%, and the photolithography process window is greatly widened.

[0030] 4. Completely free of PFAS-restricted components, environmentally compliant: The entire resin system does not introduce any trifluoromethyl monomers or trifluoromethyl additives, completely avoiding PFAS-related compliance risks and conforming to the global trend of green manufacturing development. Attached Figure Description

[0031] Figure 1 The image shows the template imaging performance with an aperture of 3 μm achieved by the positive photolithography composition prepared in Example 1.

[0032] Figure 2 The image shows the template imaging performance of the positive photolithography composition prepared in Comparative Example 1 with an imaging aperture of 3 μm. Detailed Implementation

[0033] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0034] Example 1 1. Resin Preparation Diamine monomer A: 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol; Diamine monomer B: 2,2'-bis[4-(4-aminophenoxy)phenyl]propane; Dianone monomers: Bisphenol A type diether dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride; Under a nitrogen protective atmosphere, 0.008 mol of 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol and 0.028 mol of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane were added to a reaction vessel, followed by the addition of 60 ml of N-methylpyrrolidone and stirring until completely dissolved. The system temperature was controlled at 15-25 °C. Bisphenol A type diether dianhydride (0.032 mol) and 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (0.008 mol) were added at an anhydride-amine molar ratio of 0.95:1. The solid content of the reaction system was adjusted to 27% by adding solvent, and the reaction was stirred at a constant temperature for 2-4 hours to obtain a polyamic acid solution. Add the capping agent 3-aminophenol (MAP, containing 20% ​​of the molar mass of hydroxydiamine monomer) to adjust the molecular weight, and continue stirring for 0.5 h; then add the esterifying agent N,N-dimethylformamide dimethyl acetal (DMFDMA, 165% of the molar mass of dianhydride), raise the temperature to 46℃, and keep the reaction at this temperature for 6 h to complete the partial esterification. The reaction solution was poured into deionized water to precipitate the precipitate. After repeated washing and purification, it was dried in a vacuum drying oven at 50°C for 48 hours to obtain photosensitive polyimide precursor resin S1 with a molecular weight of 45,000.

[0035] 2. Preparation of positive-type photolithography composition Photoacid generator: 1,2-naphthoquinone-2-diazo-4-sulfonate; Thermal crosslinking agent: Hexamethoxymethyl melamine (HMMM); Leveling agent: Polydimethylsiloxane (PDMS) modified polyether; Adhesion aid: 3-aminopropyltriethoxysilane; Compound solvent: PGME: ethyl lactate: γ-butyrolactone = 7:2:1 (mass ratio); Weigh out the above-mentioned photosensitive polyimide precursor resin S1, photoacid generator, thermal crosslinking agent, leveling agent, and adhesive additive according to the following ratio (100 parts of photosensitive polyimide precursor resin, 20 parts of photoacid generator, 15 parts of thermal crosslinking agent, 1 part of leveling agent, 0.2 parts of adhesive additive, and 500 parts of compound solvent). Add the above-mentioned photosensitive polyimide precursor resin S1, photoacid generator, thermal crosslinking agent, leveling agent, and adhesive additive to the compound solvent system. Stir under light-protected conditions until completely dissolved. Filter through a 0.22μm organic filter membrane to obtain a positive photosensitive lithography composition.

[0036] Example 2 The resin synthesis method is the same as in Example 1, except that 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol is replaced with 5,5'-diamino-3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirodi[indene]-6,6'-diol to obtain photosensitive polyimide precursor resin S2.

[0037] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S2.

[0038] Example 3 The resin synthesis method is the same as in Example 1, except that 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diphenol is replaced with 4,4'-(4-methylpentan-2,2-diyl)bis(2-aminophenol) to obtain photosensitive polyimide precursor resin S3.

[0039] The synthesis method of the positive photosensitive lithography composition is the same as in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S3.

[0040] Example 4 The resin synthesis method is the same as in Example 1, except that 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol is replaced with 9,9-bis(3-amino-4-hydroxyphenyl)fluorene to obtain photosensitive polyimide precursor resin S4.

[0041] The synthesis method of the positive photosensitive lithography composition is the same as in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S4.

[0042] Example 5 The resin synthesis method is the same as in Example 1, except that 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol is replaced with bis(3-amino-4-hydroxyphenyl) sulfone to obtain photosensitive polyimide precursor resin S5.

[0043] The synthesis method of the positive photosensitive lithography composition is the same as in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S5.

[0044] Example 6 The resin synthesis method is the same as in Example 1, except that 2,2'-bis[4-(4-aminophenoxy)phenyl]propane is replaced with 9,9-bis(3-fluoro-4-aminophenyl)fluorene to obtain photosensitive polyimide precursor resin S6.

[0045] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S6.

[0046] Example 7 The resin synthesis method is the same as in Example 2, except that 2,2'-bis[4-(4-aminophenoxy)phenyl]propane is replaced with 9,9-bis(3-fluoro-4-aminophenyl)fluorene to obtain photosensitive polyimide precursor resin S6.

[0047] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S7.

[0048] Example 8 The resin synthesis method is the same as in Example 2, except that only bisphenol A type diether dianhydride is used as the dianhydride monomer to obtain photosensitive polyimide precursor resin S8.

[0049] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S8.

[0050] Example 9 The resin synthesis method is the same as in Example 2, except that only 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride is used as the dianhydride monomer to obtain photosensitive polyimide precursor resin S9.

[0051] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S9.

[0052] Comparative Example 1 The resin synthesis method is the same as in Example 1, except that 2,2'-bis[4-(4-aminophenoxy)phenyl]propane in the diamine is replaced with p-phenylenediamine to obtain photosensitive polyimide precursor resin S10.

[0053] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S10.

[0054] Comparative Example 2 The resin synthesis method is the same as in Example 1, except that 2,2'-bis[4-(4-aminophenoxy)phenyl]propane in the diamine is replaced with 9,9-bis(4-aminophenyl)fluorene to obtain photosensitive polyimide precursor resin S11.

[0055] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with photosensitive polyimide precursor resin S11.

[0056] Comparative Example 3 The resin synthesis method is the same as in Example 1, except that 2,2'-bis[4-(4-aminophenoxy)phenyl]propane in the diamine is replaced with 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, to obtain photosensitive polyimide precursor resin S12.

[0057] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with photosensitive polyimide precursor resin S12.

[0058] Comparative Example 4 The resin synthesis method is the same as in Example 2, except that only 3,3',4,4'-biphenyltetracarboxylic acid dianhydride is used as the dianhydride monomer to obtain photosensitive polyimide precursor resin S13.

[0059] The synthesis method of the positive photosensitive lithography composition is the same as that in Example 1, except that the photosensitive polyimide precursor resin S1 is replaced with the photosensitive polyimide precursor resin S13.

[0060] Performance evaluation methods 1) Imaging capability evaluation: Using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Limited), the photoresists obtained in the examples and comparative examples were coated onto glass substrates by spin coating and dried to obtain the coating. Next, the coating was exposed using an i-line stepper under the cover of a photomask, followed by development in 2.38 wt% tetramethylammonium hydroxide (TMAH) for 60 s, and then rinsed with pure water. The etched lines or trenches were inspected using a scanning electron microscope (SEM). Excellent results were achieved when lines or trenches less than 3 μm in width were clearly etched without bending or defects; good results were achieved when lines or trenches between 3 and 10 μm in width were clearly etched without bending or defects; and poor results were achieved when lines or trenches greater than 10 μm in width were clearly etched without bending or defects.

[0061] 2) Solubility evaluation The photosensitive polyimide precursor resin to be tested was mixed with compound solvent A (PGME: ethyl lactate: γ-butyrolactone = 7:2:1, mass ratio) at a mass ratio of 3:7, stirred at room temperature for 2 hours, and the dissolution state was observed. The evaluation criteria are as follows: Advantages: Completely dissolves, the solution is clear and transparent, and there is no precipitation; Good: It initially appears as a mist when dissolved, but becomes clear after stirring and standing, with virtually no precipitate. Poor: Flocculent matter or large amount of sediment appears.

[0062] The resin solution was then mixed with compound solvent B (PGME:PGMEA:butyl acetate = 7:2:1, mass ratio) at a mass ratio of 3:7, and the dissolution state was observed. The rating criteria were the same as above.

[0063] 3) Evaluation of photosensitivity The positive-type photolithography composition was spin-coated onto a glass substrate, pre-baked at 115°C for 120 seconds to form a uniform coating, and then subjected to gradient exposure followed by development. The minimum exposure required for the exposed areas to be completely dissolved and removed was taken as the photosensitivity, measured in mJ / cm². 2 The lower the value, the higher the sensitivity.

[0064] 4) Evaluation of residual film rate The coating thickness after pre-baking was measured as d1. After exposure, development, and heat curing at 230℃ for 1 hour, the cured film thickness was measured as d2. The residual film rate was calculated according to the formula: Residual film rate (%) = (d2 / d1)×100%.

[0065] 5) Light transmittance evaluation The transmittance of the cured film in the wavelength range of 300~800nm ​​was tested using a UV-Vis spectrophotometer, and the transmittance at a wavelength of 400nm was used as an evaluation index for visible light transmittance.

[0066] The performance test results are shown in Table 1 below.

[0067] Table 1

[0068] The combination of two types of diamines precisely adjusts the overall hydroxyl density and molecular packing density, while providing photosensitive grafting sites and film alkali resistance, balancing exposure sensitivity and residual film rate; the combination of ether anhydride and ester anhydride / biphenyl anhydride adjusts the flexibility and conjugation strength of the main chain, weakens charge transfer absorption, and simultaneously optimizes crosslinking reaction activity and UV transmittance, improving the uniformity of thick film exposure and the perpendicularity of the pattern sidewalls.

[0069] Based on this, the grafting rate of photosensitive double bonds and the molecular weight of resin are precisely controlled to match the sensitivity, swelling degree and development rate; with the addition of trace amounts of adhesion promoters and solubility regulators, the shortcomings of low polarity system in adhesion and residual resin in development are compensated, and finally, under the premise of good solubility, stable high-resolution photolithography imaging is achieved.

[0070] Figure 1 The image shows the template imaging performance with an aperture of 3µm achieved using the positive photolithography composition prepared in Example 1. It can be seen that the resulting pattern lines are fine and the edges are clear. Figure 2 The resulting pattern has thick lines and defects at the edges.

[0071] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A photosensitive polyimide precursor resin, characterized in that, The photosensitive polyimide precursor resin is polymerized from diamine monomer A, diamine monomer B, and dianhydride monomer; Wherein, the diamine monomer A is a photosensitive functional monomer containing a hydroxyl group; The diamine monomer B is a flexible rotatable bridging diamine containing aryl ether bonds, sulfone groups and / or carbonyl groups as flexible linking groups, or a highly sterically hindered non-coplanar twisted diamine containing fluorene, spirocyclic, alicyclic and / or polyalkyl substituted biphenyl skeletons. The molar ratio of total diamine monomer to dianhydride monomer is 0.8–1.

05.

2. The photosensitive polyimide precursor resin according to claim 1, characterized in that, The diamine monomer A is selected from 1,1-bis[3-(3-aminobenzoamide)-4-hydroxyphenyl]cyclohexane, 4,4'-(4-methylpentan-2,2-diyl)bis(2-aminophenol), 5,5'-diamino-3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirodi[indene]-6,6'-diol, and 3,3'-bis[3-(3-aminobenzoylamino)-4-hydroxyphenyl] Diphenyl sulfone, N,N′-[(1-methylene)bis(6-hydroxy-3,1-phenyl)]bis[3-amino-]benzoyl, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol, bis(3-amino-4-hydroxyphenyl) sulfone, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis(4-hydroxy-3-aminophenyl)propane, and 3,3'-dihydroxybenzidine are any one or more of these.

3. The photosensitive polyimide precursor resin according to claim 1, characterized in that, The flexible rotatable bridging diamine is selected from any one or more of 4,4'-bis(3-aminophenoxy)benzophenone, 4,4'-bis(4-aminophenoxy)benzophenone, 3,3'-diaminodiphenyl sulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diaminophenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 3,4'-diaminodiphenyl ether, 4,4'-bis(3-aminophenoxy)biphenyl, and [4-(4-aminobenzoyl)oxyphenyl]4-aminobenzoate. The sterically hindered, non-coplanar twisted diamine is selected from any one or more of N,N'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis(4-amino-benzamide), 4,4'-(4-pentylcyclohexane-1,1-diyl)diphenylamine, 5(6)-1-(4-aminophenyl)-1,3,3-trimethylindene, 4,4'-diamino-2,2'-dimethylbiphenyl, 1,1-bis(4-aminophenyl)cyclohexane, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene, 9,9-dimethylfluorene-2,7-diamine, and 3,3',5,5'-tetramethylbenzidine.

4. The photosensitive polyimide precursor resin according to claim 1, characterized in that, The dianhydride monomer is selected from one or more of the following: ether-bonded dianhydrides, biphenyl-bonded dianhydrides, fluorenyl dianhydrides, sulfone-bonded dianhydrides, ketone-bonded dianhydrides, ester-bonded dianhydrides, fused-ring heterocyclic dianhydrides, bridged-ring olefin dianhydrides, cyclobutane dianhydrides, saturated hydrogenated aromatic ring dianhydrides, and straight-chain aliphatic dianhydrides. Preferably, the dianhydride monomer is selected from biphenyl diether dianhydride, 11,11-dimethyl-1H-difurano[3,4-b:3',4'-i]benzoxanthracene-1,3,7,9(11H)-tetraone, 5,5'-(propane-2,2-diyl)bis(isobenzofuran-1,3-dianhydride), 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-triphenyl diether tetracarboxylic dianhydride, 4,4'-biphenyl dianhydride, bisphenol A type diether dianhydride, 4,4'-terephthalodioxydiphthalic anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and bis[(3,4-dianhydride)phenyl] One or more of the following: terephthalate, 3,3,4,4-diphenylsulfone tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,3-dimethyl-cyclobutanetetracarboxylic dianhydride, hydrogenated pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, and 1,2,3,4-butanetetracarboxylic dianhydride.

5. The photosensitive polyimide precursor resin according to claim 1, characterized in that, The weight-average molecular weight of the photosensitive polyimide precursor resin is 8000-80000.

6. The photosensitive polyimide precursor resin according to claim 1, characterized in that, The molar ratio of diamine monomer A to diamine monomer B is 0.2–5.

7. The method for preparing the photosensitive polyimide precursor resin according to any one of claims 1-6, characterized in that, Includes the following steps: Under a nitrogen protective atmosphere, diamine monomer A and diamine monomer B are added to the reaction vessel, solvent is added and stirred until completely dissolved, and the system temperature is controlled at 15-25℃. Add dianhydride monomer in proportion, add solvent to adjust the solid content of the reaction system to 15-30%, stir the reaction at constant temperature for 2-4 hours to obtain polyamic acid solution; Add a capping agent to adjust the molecular weight, continue stirring for 0.5 h, and then add an esterifying agent to carry out the esterification reaction; After the reaction is complete, the reaction solution is poured into deionized water to precipitate, washed with water, and dried to obtain the photosensitive polyimide precursor resin.

8. The preparation method according to claim 7, characterized in that, The esterification reaction is carried out at a temperature of 35-50°C for 4-8 hours.

9. A positive-type photolithography composition, characterized in that, It contains the following components by mass: 20-200 parts of the photosensitive polyimide precursor resin according to any one of claims 1-6; 10-35 parts of photoacid-producing agent; 15-25 parts of thermal crosslinking agent; Leveling agent 0.5-5 parts; 0.1-2 parts of adhesive additive; 150-600 parts of compound solvent.

10. The positive-type photolithography composition according to claim 9, characterized in that, The photoacid-generating agent is a naphthoquinone diazidesulfonate photosensitizer; The thermal crosslinking agent is selected from any one or more of benzoxazine compounds, epoxy resin compounds, and alkoxymethyl compounds; The leveling agent is selected from any one or more of the following: polydimethylsiloxane-modified polyether, polyester-modified silicone, silicone acrylate copolymer, polyacrylate leveling agent, and polyether polyester copolymer; The adhesive aid is selected from any one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, vinylsilane, and methacryloxysilane. The compound solvent is composed of a main solvent and a diluent solvent. The main solvent is selected from one or more of N-methylpyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, and ethyl lactate. The diluent solvent is selected from one or more of propylene glycol monomethyl ether acetate and butyl acetate. The mass ratio of the main solvent to the diluent solvent is 0.2-5.

Images