Alkali-soluble resin, photosensitive resin composition, photosensitive cured film and application thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to alkali-soluble resin, a photosensitive resin composition, a photosensitive cured film and application thereof. The alkali-soluble resin provided by the invention has good alkali solubility, and by introducing a diamine residue structure as shown in formula (II), the alkali-soluble resin has excellent dielectric property, adhesion property and heat resistance after being applied to a photosensitive resin composition and forming a cured film; the compound is suitable for surface protective films and interlayer insulating films of semiconductor elements, insulating layers of organic electroluminescent elements, insulating layers of thin film transistors, and the like.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to an alkali-soluble resin, a photosensitive resin composition, a photosensitive curable film, and their applications. Background Technology

[0002] Polyimide (PI), due to its unique aromatic ring conjugation and imide structure, possesses excellent heat resistance, mechanical properties, high insulation, and chemical stability. It is widely used in aerospace, semiconductor, optoelectronics, and microelectronics fields, and is one of the most important electronic chemical materials. It is widely used as an interlayer insulator, surface passivator, stress buffer, and radiation shield. Compared to ordinary polyimide, photosensitive polyimide (PSPI) can form patterns without the need for other photoresists, saving material costs and significantly shortening the process circuitry, thus improving yield. It is an ideal insulating material for the electronics and microelectronics fields.

[0003] With the miniaturization, precision, and multifunctionality of microelectronic products, higher requirements are being placed on the properties of materials, such as dielectric, optical, and thermal properties. However, due to the unique aromatic ring conjugated structure and imide structure in its structure, polyimide has high water absorption and poor dielectric properties. It also suffers from poor adhesion to substrates and poor transparency, which greatly limits the application of photosensitive polyimide materials in the semiconductor and display fields.

[0004] Therefore, providing a new resin material is of great significance. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides an alkali-soluble resin, a photosensitive resin composition, a photosensitive curing film, and their applications. The alkali-soluble resin provided by this invention has good alkali solubility, and the cured film formed by applying it to the photosensitive resin composition exhibits excellent dielectric properties, adhesion properties, and heat resistance properties.

[0006] In a first aspect, the present invention provides an alkali-soluble resin having a structure as shown in formula (I):

[0007]

[0008] Wherein, Ar1 is a dianhydride residue, R1 is an alkyl or alkenyl group with 1 to 20 H or C atoms, r is an integer from 0 to 2, such as 0, 1, 2; n is an integer from 5 to 10000, such as 5, 10, 50, 100, 1000, 5000, 10000, etc.

[0009] Ar2 is a diamine residue, which includes at least two structural units, one of which has a structure as shown in formula (II):

[0010]

[0011] Wherein, X1 is selected from any one of the -O-, -(C=O)-, -S(=O)2- or -C(CH3)2- groups; X2 is selected from the -(C=O)O- or -O(C=O)- groups; R2, R3, R4 and R5 may be the same or different, and each is independently selected from H, OH or alkyl or haloalkyl with 1 to 5 C atoms, and at least one of R2, R3, R4 and R5 is OH.

[0012] The alkali-soluble resin provided by this invention has good alkali solubility, and the cured film formed by applying it to the photosensitive resin composition exhibits excellent dielectric properties, adhesion properties, and heat resistance properties. Specifically:

[0013] The present invention introduces the diamine residue structure shown in formula (II) into the alkali-soluble resin. On the one hand, the alkali solubility and alkali dissolution rate of the resin can be controlled by the number and ratio of phenolic hydroxyl groups. On the other hand, the dielectric properties and adhesion of the cured film prepared based on the resin are improved by the ester and ether group structures. Thus, the prepared resin has good alkali solubility, and while ensuring heat resistance, it achieves good adhesion between the cured film and the substrate, and endows it with good dielectric properties. This solves the problems of poor dielectric properties and poor adhesion to the substrate in the prior art of polyimide resin system.

[0014] As a preferred embodiment of the present invention, with the amount of the diamine residue as 100%, the amount of the structural unit shown in formula (II) is 20% to 80%, for example, 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.

[0015] The structural unit shown in formula (II) of this invention accounts for 20-80% of the total amount of diamine residues, ensuring that the proportions of phenolic hydroxyl, ester, and ether groups in the alkali-soluble resin are within a suitable range. This effectively regulates the alkali solubility of the resin, while maintaining heat resistance and achieving good adhesion to the substrate, and imparting good dielectric properties to the cured film. When the proportion of the structural unit shown in formula (II) is less than 20%, it easily leads to problems such as a high dielectric constant and insufficient adhesion of the resin, and is not conducive to regulating the alkali solubility of the resin. When the proportion of the structural unit shown in formula (II) is greater than 80%, the dielectric constant and adhesion are improved, but the heat resistance of the cured film decreases.

[0016] As a preferred embodiment of the present invention, the structural unit shown in formula (II) is selected from any one or more of the following structures:

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025] In a preferred embodiment of the present invention, the dianhydride residue is a residue obtained by removing two anhydride groups from a dianhydride. Preferably, the dianhydride residue includes, but is not limited to, residues of the following dianhydrides: pyromellitic dianhydride (PMDA), 3,3,3',4'-biphenyltetracarboxylic acid dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic acid dianhydride (α-BPDA), 4,4'-oxophthalic anhydride (ODPA), 4,4'-(hexafluoroisopropene)phthalic anhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic anhydride (BTDA), p-phenylene bis(phenyltrilate) dianhydride (TAHQ), and 3,3',4,4'-diphenylmethane sulfone tetracarboxylic anhydride (DSDA). The residues of cyclobutanetetracarboxylic dianhydride (CBDA), cyclohexanetetracarboxylic dianhydride (HPMDA), N,N'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis(1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxamide) (6FAP-ATA) or N-[5-[3-[(1,3-dioxy-2-benzofuran-5-carbonyl)amino]-4-hydroxyphenyl]sulfonyl-2-hydroxyphenyl]-1,3-dioxy-2-benzofuran-5-carboxamide (6FAP-ASA).

[0026] As a preferred embodiment of the present invention, the other one or more structural units in the diamine residues include, but are not limited to, the following diamine residues: 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[3-(4-aminobenzoamide)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzoamide)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-aminobenzoamide)-4-hydroxyphenyl]ether, 2,2-bis[3-(4-aminobenzoamide)-4-hydroxyphenyl]hexafluoropropane, N-(2-hydroxy-5-amino)phenyl-3-aminobenzoamide, N... -(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-propane-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-sulfonyl-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-ether-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-hexafluoropropane-2-yl]benzamide, 1,4-p-phenylene Diamine (PDA), m-phenylenediamine (m-PDA), o-phenylenediamine (o-PDA), 4,4'-diaminodiphenyl ether (ODA), 4,4'-diamino-p-terphenyl (DATP), 4,4'-diaminodiphenylmethane (MDA), 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl (m-TB), 2,2-bis(4-hydroxy-3-aminophenyl)propane (BAP), 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone (BAHS), 4,4'-bis(3-aminophenoxy)diphenyl sulfone (M-BAPS), p-aminobenzoic acid p-aminophenyl ester (APAB), 1 The residues selected from 1,4,4-APB, 1,3-APB, 3,3-APB, 2,2-bis(4-(4-aminophenoxy)phenyl)propane (BAPP), 6-FODA, TFMB, or 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP).

[0027] Accordingly, the present invention provides a method for preparing the alkali-soluble resin, the method comprising the following steps:

[0028] (1) The diamine shown in formula (II), at least one other diamine, dianhydride and other raw materials are dissolved in an organic solvent in sequence to obtain a polyimide acid solution; an esterification agent is added to the polyimide acid solution to carry out an esterification reaction to obtain a polyamic acid precursor solution;

[0029] (2) The polyamic acid precursor solution is precipitated using a precipitant, and the alkali-soluble resin is obtained after filtration, washing and drying.

[0030] As a preferred embodiment of the present invention, the solid content of the polyimide solution is 10-50%.

[0031] As a preferred embodiment of the present invention, the esterifying agent includes N,N'-dimethylformamide diethyl acetal (DMFDEA), N,N'-dimethylformamide dimethyl acetal (DMFDFA), N,N-dimethylformamide diisopropyl acetal (DMFDIPA), etc.

[0032] In a second aspect, the present invention provides a photosensitive resin composition comprising the alkali-soluble resin described in the first aspect, as well as a photosensitizer, a crosslinking agent, a binder, and a solvent.

[0033] As a preferred embodiment of the present invention, the photosensitizer is selected from azidonaphthoquinone type photosensitizers, which are esterification products of phenolic hydroxyl compounds and azidonaphthoquinone sulfonyl chloride.

[0034] The phenolic hydroxyl compound is selected from one or more of Bis-Z, BisP-EZ, BisOPP-Z, BisP-CP, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Tris-PHBA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

[0035] The crosslinking agent described in this invention has no special requirements; it can be any thermally crosslinking compound capable of undergoing a crosslinking reaction with the alkali-soluble resin. Preferably, the crosslinking agent includes any one or more of epoxy compounds, alkoxyhydroxymethyl compounds, or alkoxyhydroxymethyl triazine ring compounds, and the functionality of the crosslinking agent is ≥2.

[0036] As a preferred embodiment of the present invention, the epoxy compound is selected from any one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and propylene glycol diglycidyl ether.

[0037] As a preferred embodiment of the present invention, the alkoxyhydroxymethyl compound is selected from polyalkoxyhydroxymethylated phenolic hydroxy compounds, wherein the phenolic hydroxy compound is selected from one or more of Bis-Z, BisP-EZ, BisOPP-Z, BisP-CP, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Tris-PHBA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP-PZ (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

[0038] As a preferred embodiment of the present invention, the alkoxyhydroxymethyltriazine ring compound is selected from one or more compounds of formula (III);

[0039]

[0040] Among them, R6 and R7 are each independently selected from H, CH2OCH3 or CH2OCH2CH3, and not all of R6 and R7 are H.

[0041] As a preferred embodiment of the present invention, the adhesive comprises any one or more of γ-glycidoxypropyltrimethoxysilane (KH560), γ-aminopropyltriethoxysilane (KH550), γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-aminophenyltrimethoxysilane, 3-(m-aminophenoxy)trimethoxysilane, 3-mercaptomethyltrimethoxysilane, or 3-mercaptopropyltriethoxysilane.

[0042] As a preferred embodiment of the present invention, the solvent is selected from any one or more of ketone solvents, ester solvents, ether solvents, aromatic hydrocarbon solvents, or other solvents, and the other solvents are selected from any one or more of N-methylpyrrolidone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

[0043] By way of example but not limitation, the ketone solvent is selected from any one or more of acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclopentanone or cyclohexanone.

[0044] By way of example but not limitation, the ester solvent is selected from any one or more of ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, propylene glycol methyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, or 1,4'-butyrolactone.

[0045] By way of example, but not limitation, the ether solvent is selected from any one or more of propylene glycol methyl ether, propylene glycol monoethyl ether, or ethylene glycol monomethyl ether.

[0046] By way of example, but not limitation, the aromatic hydrocarbon solvent is selected from toluene and / or xylene.

[0047] As a preferred embodiment of the present invention, the content of each component in the photosensitive resin composition is as follows:

[0048]

[0049] The alkali-soluble resin may be 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, etc.

[0050] The photosensitizer can be 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, etc.

[0051] The crosslinking agent can be 1 part by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, etc.

[0052] The adhesive can be 0.1 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, etc.

[0053] The solvent can be 200 parts by weight, 500 parts by weight, 1000 parts by weight, 1500 parts by weight, 1700 parts by weight, etc.

[0054] As a preferred embodiment of the present invention, the content of each component in the photosensitive resin composition is as follows:

[0055]

[0056] As a preferred embodiment of the present invention, the content of each component in the photosensitive resin composition is as follows:

[0057]

[0058] Thirdly, the present invention provides a photocurable film, which is formed by curing the photosensitive resin composition described in the second aspect.

[0059] It is understood that the curing of the photosensitive resin composition to form a cured film typically includes some pretreatment, such as coating, hot plate drying, exposure, development, and then curing. Each step employs conventional methods in the art. For example, coating may be performed using a rotational viscometer, drying may be done using a hot plate, and curing may be performed under nitrogen atmosphere.

[0060] The photosensitive curable film of the present invention has good adhesion and dielectric properties, while retaining good heat resistance; in the adhesion test (100-cross test method), the peeling area of ​​the photosensitive curable film is <5% (denoted as A), the dielectric constant DK≤3.50, the dielectric loss Df≤0.0100, and the 5% thermal weight loss temperature T5%≥320℃.

[0061] Fourthly, the present invention provides the application of the photocurable film described in the third aspect as a protective film or insulating layer in semiconductor devices, organic electroluminescent devices, and thin-film transistors.

[0062] The technical solution provided by the embodiments of the present invention has the following advantages compared with the prior art:

[0063] The alkali-soluble resin provided by this invention has good alkali solubility. By introducing the diamine residue structure shown in formula (II), it has excellent dielectric properties, adhesion properties and heat resistance when applied to a photosensitive resin composition and forming a cured film. It is suitable for surface protective films and interlayer insulating films of semiconductor devices, insulating layers of organic electroluminescent devices and insulating layers of thin film transistors, etc. Detailed Implementation

[0064] To better understand the above-mentioned objectives, features, and advantages of the present invention, the solutions of the present invention will be further described below. It should be noted that, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.

[0065] Many specific details are set forth in the following description in order to provide a full understanding of the invention, but the invention may also be practiced in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of the invention, and not all embodiments.

[0066] Some of the raw materials involved in the embodiments of the present invention are as follows:

[0067] Photosensitive agent: where Q represents the degree of esterification;

[0068]

[0069] Crosslinking agent:

[0070]

[0071]

[0072] Dihydride: 4,4'-O-diphthalic anhydride (ODPA);

[0073] Diamine: p-phenylenediamine (PDA), 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl (m-TB);

[0074] Esterifying agent: N,N'-dimethylformamide diethyl acetal (DMFDEA).

[0075] Synthesis example 1

[0076] This synthesis example provides a method for preparing structural unit II-10, and the preparation route is as follows:

[0077]

[0078] The specific preparation method includes the following steps:

[0079] (1) Synthesis of intermediate II-10-1

[0080] In a 5L glass reaction flask, add 1780.00g of thionyl chloride, start stirring, add 500.00g of p-nitrobenzoic acid, add 10mL of DMF, and after the addition is complete, start heating to 50℃, keep warm and stir for 2 hours, then continue heating to 65℃, keep warm and stir for 1 hour. The tail gas is absorbed by alkaline solution.

[0081] Post-processing: Remove heating, cool to 30℃, remove thionyl chloride under reduced pressure, wait until no distillate flows out, cool to room temperature, depressurize, add 1000 mL of n-heptane, under N2 protection, cool to 0–10℃, stir to induce crystallization for 2 h, filter under reduced pressure, wash the filter cake with 100 mL of n-heptane, and dry the filter cake under vacuum at 60℃ to obtain 532.00 g of yellow crystals, yield 95.83%. GC-MS analysis of the obtained yellow crystalline compound showed that the m / z of the product was 185.99 (M+).

[0082] (2) Synthesis of intermediate II-10-3

[0083] In a 3L glass reaction flask under N2 atmosphere, add 58.51g II-10-2, 1800mL toluene, 371.12g p-nitrobenzoyl chloride (II-10-1), and 226.00g pyridine. After the addition is complete, start stirring and heating. Heat to 105℃ and maintain the temperature with stirring for 5 hours. Take a sample for LC analysis.

[0084] Post-processing: Cool to 25℃, add 1L of water and stir for 30min, filter under reduced pressure, wash the filter cake with 500mL of water and 200mL of methanol in sequence, add the filter cake to a 2L reaction flask, add 1500mL of methanol, 800mL of dichloromethane and 700mL of THF, after the addition is complete, start stirring, heat to reflux, keep warm and stir for 2h, cool naturally to 25℃, stir for 1h, filter, wash the filter cake with 100mL of tetrahydrofuran, air dry naturally to obtain 130.00g of yellow solid.

[0085] The mixture was further separated by column chromatography using a mobile phase of n-heptane:ethyl acetate = 1:1. The eluent was collected after washing, and its structure was determined by NMR and LC-MS. The product was then distilled under reduced pressure to give 16.45 g of a pale white solid, yield: 12.0%. GC-MS analysis of the obtained pale white compound showed an m / z of 533.08 (M+).

[0086] (3) Synthesis of compound II-10

[0087] In a 2L autoclave, add 15.00g II-10-3, 300mL anhydrous ethanol, 3.00g Pd / C (5%), and 10.00g pyridine. Start stirring, seal the autoclave lid, check for air tightness, purge air three times, introduce hydrogen gas, start heating, heat to 60℃, and maintain this temperature with stirring for 6 hours. Perform TLC analysis (reference requirements: developing solvent n-heptane: ethyl acetate = 1:1, no II-10-3).

[0088] Post-processing: Cool to 25℃, depressurize, transfer the reaction solution, filter, add the filter cake to 250mL THF, stir, filter, repeat the above operation once, concentrate the filtrate under reduced pressure, add the residue to a 1000mL reaction flask, add 75mL tetrahydrofuran and 150mL ethyl acetate, after the addition is complete, start stirring, heat to 50℃, stir for 2h, filter, wash the filter cake with 50mL tetrahydrofuran (air dry to obtain 11.65g of off-white solid). Sample and LC analysis. Yield: 87.62%. GC-MS analysis of the obtained white compound showed that the m / z of the product was 473.13 (M+), which is compound II-10.

[0089] Synthesis example 2

[0090] This synthesis example provides a method for preparing structural unit II-6, and the preparation route is as follows:

[0091]

[0092] The specific preparation method includes the following steps:

[0093] (1) Synthesis of intermediate II-6-3

[0094] In a 3L glass reaction flask under N2 atmosphere, add 50.55g of 4,4'-dihydroxydiphenyl ether (Ⅱ-6-2), 1800mL of toluene, 403.12g of 2-hydroxy-4-nitrobenzoyl chloride (Ⅱ-6-1), and 226.00g of pyridine. After the addition is complete, start stirring and heating. Heat to 105℃ and maintain the temperature with stirring for 5 hours. Take a sample for LC analysis.

[0095] Post-processing: Cool to 25℃, add 1L of water and stir for 30min, filter under reduced pressure, wash the filter cake with 500mL of water and 200mL of methanol in sequence, add the filter cake to a 2L reaction flask, add 1500mL of methanol, 800mL of dichloromethane and 700mL of THF, after the addition is complete, start stirring, heat to reflux, keep warm and stir for 2h, cool naturally to 25℃, stir for 1h, filter, wash the filter cake with 100mL of tetrahydrofuran, air dry naturally to obtain 138.00g of yellow solid.

[0096] The mixture was further separated by column chromatography using a mobile phase of n-heptane:ethyl acetate = 1:1. The eluent was collected after washing, and its structure was determined by NMR and LC-MS. The product was then distilled under reduced pressure to give 20.63 g of a pale white solid, yield: 15.5%. GC-MS analysis of the obtained pale white compound showed an m / z of 533.08 (M+).

[0097] (2) Synthesis of compound II-6

[0098] In a 2L autoclave, add 15.00g of II-6-3, 300mL of anhydrous ethanol, 3.00g of Pd / C (5%), and 10.00g of pyridine. Start stirring, seal the autoclave lid, check for air tightness, purge air three times, introduce hydrogen gas, start heating, heat to 60℃, and maintain the temperature with stirring for 6 hours. Perform TLC analysis (reference requirements: developing solvent n-heptane: ethyl acetate = 1:1, no II-6-3).

[0099] Post-processing: Cool to 25℃, depressurize, transfer the reaction solution, filter, add the filter cake to 250mL THF, stir, filter, repeat the above operation once, concentrate the filtrate under reduced pressure, add the residue to a 1000mL reaction flask, add 75mL tetrahydrofuran and 150mL ethyl acetate, after the addition is complete, start stirring, heat to 50℃, stir for 2h, filter, wash the filter cake with 50mL tetrahydrofuran (air dry to obtain 11.66g of off-white solid). Sample and LC analysis. Yield: 87.62%. GC-MS analysis of the obtained white compound showed that the m / z of the product was 473.13 (M+), which is compound II-6.

[0100] The preparation methods for other structural units are similar to those for II-10 and II-6, and can be obtained by referring to the above synthesis methods. They will not be listed one by one in this invention.

[0101] Preparation Example 1

[0102] This preparation example provides a method for preparing an alkali-soluble resin, the method comprising the following steps:

[0103] The reaction vessel was purged with nitrogen beforehand. After 30 minutes, 98.23 g of N-methylpyrrolidone (NMP, dehydrated with molecular sieve 24 hours in advance) was added, followed by 4.32 g (0.04 mol) of PDA and 4.72 g (0.01 mol) of II-10. The mixture was stirred at 25 °C until completely dissolved. Then, 15.51 g (0.05 mmol) of compound ODPA was added, and the mixture was stirred at room temperature for 2 hours. 16.19 g of DMFDEA was added, the temperature was raised to 60 °C and maintained for 4 hours, and then cooled to room temperature to obtain an alkali-soluble resin solution. The resin solution was added to 3 L of deionized water, and the mixture was precipitated, filtered, and washed three times. The resin was then dried under vacuum at 80 °C for 72 hours to obtain an alkali-soluble resin, named A-1.

[0104] Preparation Example 2

[0105] This preparation example provides a method for preparing an alkali-soluble resin, which is the same as that in Preparation Example 1. The difference is that in this preparation example, the amount of PDA used is 0.01 mol and the amount of II-10 used is 0.04 mol, and an alkali-soluble resin is obtained, named A-2.

[0106] Preparation Example 3

[0107] This preparation example provides a method for preparing an alkali-soluble resin, which is the same as that in Preparation Example 1. The difference is that in this preparation example, the amount of PDA used is 0.03 mol and the amount of II-10 used is 0.02 mol, and an alkali-soluble resin is obtained, named A-3.

[0108] Preparation Example 4

[0109] This preparation example provides a method for preparing an alkali-soluble resin, which is the same as that in Preparation Example 1. The difference is that in this preparation example, PDA is replaced with m-TB, and the molar amounts of each raw material are the same as in Preparation Example 1, resulting in an alkali-soluble resin named A-4.

[0110] Preparation Example 5

[0111] This preparation example provides a method for preparing an alkali-soluble resin, which is the same as that in Preparation Example 1. The difference is that in this preparation example, II-10 is replaced with II-6 to obtain an alkali-soluble resin, named A-5.

[0112] Preparation Example 6

[0113] This preparation example provides a method for preparing an alkali-soluble resin, which is the same as that in Preparation Example 1. The difference is that in this preparation example, II-10 is replaced with II-26, and the molar amounts of each raw material are the same as in Preparation Example 1, resulting in an alkali-soluble resin named A-6.

[0114] Comparative Preparation Example 1

[0115] This comparative preparation example provides a method for preparing an alkali-soluble resin, which is the same as that in Preparation Example 1. The difference is that in this comparative preparation example, the amount of PDA used is 0.05 mol, and II-10 is not added, resulting in an alkali-soluble resin named A-7.

[0116] Comparative Preparation Example 2

[0117] This comparative preparation example provides a method for preparing an alkali-soluble resin, which is the same as that in Preparation Example 1. The difference is that in this comparative preparation example, the amount of II-10 used is 0.05 mol, and PDA is not added, resulting in an alkali-soluble resin named A-8.

[0118] Example 1

[0119] This embodiment provides a photosensitive resin composition and its preparation method, the preparation method comprising:

[0120] 10g of the alkali-soluble resin prepared in Preparation Example 1, 1g of B-1, 2g of B-2, 0.1g of γ-glycidyl etheroxypropyltrimethoxysilane, 0.8g of C-1 and 0.2g of C-2 were dissolved in 30g of 1,4-butyrolactone and mixed thoroughly to obtain a photosensitive resin composition.

[0121] Examples 2-6

[0122] This embodiment provides a photosensitive resin composition and its preparation method. The preparation method is the same as that in Example 1. The difference from Example 1 is that the alkali-soluble resin A-1 is replaced with A-2 (Example 2), A-3 (Example 3), A-4 (Example 4), A-5 (Example 5), and A-6 (Example 6), respectively.

[0123] Comparative Examples 1-2

[0124] This comparative example provides a photosensitive resin composition and its preparation method, which is the same as that in Example 1. The difference from Example 1 is that the alkali-soluble resin A-1 is replaced with A-7 (Comparative Example 1) and A-8 (Comparative Example 2) respectively.

[0125] Application examples

[0126] The photosensitive resin compositions prepared in the examples and comparative examples were used to prepare photosensitive curable films and their performance was tested.

[0127] 1. The preparation method of photosensitive curable film is as follows:

[0128] The photosensitive resin compositions prepared in the examples and comparative examples were wet-coated using a rotational viscometer (Mikasa: MS-B150+DA-60S), pre-dried on a hot plate, and then exposed and developed before being transferred to nitrogen for further curing. The curing temperature was 150-250°C for 30-180 min, and the mixture was then cooled to room temperature before being removed.

[0129] 2. Performance Testing

[0130] (1) Dielectric constant (DK) & dielectric loss (Df)

[0131] The test was conducted using a Keysight N5290A vector network analyzer (cavity resonator method) at a frequency of 1 kHz. The sample size was 6 × 6 cm. The results are shown in Table 1.

[0132] (2) Adhesion

[0133] Adhesion was evaluated using the cross-cut adhesion test, in which 10 rows and 10 columns of cross-cut adhesion were performed on the cured film surface at 1mm intervals using a cross-cut tester. The adhesion strength was 350–400 g / cm². 2 The 3M 600 adhesive tape was applied smoothly to the test grid. After 1 minute, the tape was quickly peeled off vertically (90°). The same test was performed twice at the same location. The adhesion between the cured film and the substrate was evaluated based on the adhesion state of the cured film. A small piece of cured film detached from the intersection of the scribe lines with a detachment area of ​​<5% was classified as A; a small piece of cured film detached from the intersection of the scribe lines with a detachment area of ​​5% to 15% was classified as B; and a large area of ​​cured film detached from the intersection of the scribe lines with a detachment area of ​​>15% was classified as C. The results are shown in Table 1.

[0134] (3) Thermal weight loss temperature

[0135] The thermal decomposition temperature was determined using a thermogravimetric analyzer (model TGA-55) at a heating rate of 10℃ / min and a sample size of 3–5 mg. The temperature range was RT–700℃. The results are shown in Table 1.

[0136] The test results are shown in Table 1:

[0137] Table 1

[0138]

[0139] As can be seen from Table 1, the photosensitive resin composition provided by the present invention, after being coated with a rotational viscometer, dried on a hot plate, exposed, developed, and thermally cured under nitrogen, produces a photosensitive cured film that exhibits excellent adhesion (adhesion result A) and excellent dielectric properties (DK≤3.50, Df≤0.0100), as well as good heat resistance (5% thermogravimetric temperature ≥320℃). It is suitable for surface protective films and interlayer insulating films of semiconductor devices, insulating layers of organic electroluminescent devices, and insulating layers of thin-film transistors.

[0140] A comparison of Examples 1-6 and Comparative Examples 1-2 reveals that when the structural unit shown in Formula (II) accounts for 20-80% of the total amount of diamine residues, the proportions of phenolic hydroxyl groups, ester groups, and ether groups in the alkali-soluble resin are within a suitable range. This ensures that the prepared alkali-soluble resin has good alkali solubility and, when applied to the photosensitive resin composition to form a cured film, it also possesses good dielectric properties, adhesion properties, and heat resistance. When the amount of the structural unit shown in Formula (II) is <20%, the adhesion and dielectric properties of the cured film cannot be guaranteed; when the amount of the structural unit shown in Formula (II) is >80%, the heat resistance of the cured film decreases significantly.

[0141] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0142] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments described herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An alkali-soluble resin, characterized in that, The alkali-soluble resin has a structure as shown in formula (I): Wherein, Ar1 is a dianhydride residue, R1 is an alkyl or alkenyl group with 1 to 20 H or C atoms, r is an integer from 0 to 2, and n is an integer from 5 to 10000; Ar2 is a diamine residue, which includes at least two structural units, one of which has a structure as shown in formula (II): Wherein, X1 is selected from any one of the -O-, -(C=O)-, -S(=O)2- or -C(CH3)2- groups; X2 is selected from the -(C=O)O- or -O(C=O)- groups; R2, R3, R4 and R5 are each independently selected from H, OH or alkyl or haloalkyl groups with 1 to 5 C atoms, and at least one of R2, R3, R4 and R5 is OH.

2. The alkali-soluble resin according to claim 1, characterized in that, Based on the amount of the diamine residue as 100%, the amount of the structural unit shown in formula (II) is 20-80%.

3. The alkali-soluble resin according to claim 1 or 2, characterized in that, The structural unit shown in equation (II) is selected from any one or more of the following structures:

4. The alkali-soluble resin according to any one of claims 1-3, characterized in that, The dianhydride residues include pyromellitic dianhydride, 3,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 4,4'-oxophthalic acid dianhydride, 4,4'-(hexafluoroisopropene)phthalic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, p-phenylene-bisphenyltriester dianhydride, 3,3',4,4'-diphenylmethanesulfonate tetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, N Any one or more residues of N'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis(1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxamide) or N-[5-[3-[(1,3-dioxy-2-benzofuran-5-carbonyl)amino]-4-hydroxyphenyl]sulfonyl-2-hydroxyphenyl]-1,3-dioxy-2-benzofuran-5-carboxamide].

5. The alkali-soluble resin according to any one of claims 1-4, characterized in that, The other one or more structural units in the diamine residue include 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[3-(4-aminobenzoamide)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzoamide)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-aminobenzoamide)-4-hydroxyphenyl]ether, 2,2-bis[3-(4-aminobenzoamide)-4-hydroxyphenyl]hexafluoropropane, N-(2-hydroxy-5-amino)phenyl- 3-Aminobenzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-propane-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-sulfonyl-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-ether-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-etheryl-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl] phenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-hexafluoropropane-2-yl]benzamide, 1,4-p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diamino-p-terphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-bis(3-amino)propane, 4,4'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-bis(3-amino)propane, 4,4'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-bis(3-amino)propane, 4,4'-diaminodiphenyl sulfone ... The residues selected from phenoxy)diphenyl sulfone, p-aminophenyl benzoate, 1,4-bis(4'-aminophenoxy)benzene, 1,3-bis(4'-aminophenoxy)benzene, 1,3-bis(3'-aminophenoxy)benzene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, or 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

6. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises the alkali-soluble resin according to any one of claims 1-5, as well as a photosensitizer, a crosslinking agent, a binder, and a solvent.

7. The photosensitive resin composition according to claim 6, characterized in that, The photosensitizer is selected from azonaphthoquinone type photosensitizers; And / or, the crosslinking agent includes any one or more of epoxy compounds, alkoxyhydroxymethyl compounds, or alkoxyhydroxymethyltriazine ring compounds, and the crosslinking agent has a functionality ≥2.

8. The photosensitive resin composition according to claim 6 or 7, characterized in that, The adhesive comprises any one or more of γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-aminophenyltrimethoxysilane, 3-(m-aminophenoxy)trimethoxysilane, 3-mercaptomethyltrimethoxysilane, or 3-mercaptopropyltriethoxysilane. And / or, the solvent is selected from any one or more of ketone solvents, ester solvents, ether solvents, aromatic hydrocarbon solvents, or other solvents, wherein the other solvent is selected from any one or more of N-methylpyrrolidone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

9. A photosensitive curable film, characterized in that, The photosensitive curable film is formed by curing the photosensitive resin composition according to any one of claims 6-8.

10. The application of the photocurable film of claim 9 as a protective film or insulating layer in semiconductor devices, organic electroluminescent devices, and thin-film transistors.

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