Photosensitive polyimide resin composition, cured film and preparation method and application thereof

Abstract

The invention provides a photosensitive polyimide resin composition, a cured film as well as a preparation method and application of the cured film. The composition comprises (A) 100 parts by weight of polyimide resin with a protecting group and a structural unit shown in a general formula (1), (B) 1-50 parts by weight of a photosensitizer and (C) 1-200 parts by weight of a thermal crosslinking agent, the photosensitive polyimide resin composition disclosed by the invention has the advantages that the light sensitivity, the mechanical property, the chemical resistance and the heat resistance of a polyimide resin film can be improved, and the photosensitive polyimide resin composition can be widely applied to organic electroluminescent display devices.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescence, and specifically relates to a photosensitive polyimide resin composition, a cured film, and a preparation method and application thereof. Background Art

[0002] In recent years, with the high integration of semiconductors, the development of multilayer and thick film of insulating materials, in order to reduce the heat load transmitted to semiconductor devices in the production process and reduce the stress on the base wafer, a cured film with high heat resistance and mechanical properties after low temperature curing at about 200°C is required. On the other hand, in semiconductor components, the focus is on the micronization process of the chip or wafer material, and the commonly used method is to use a photosensitive polyimide resin composition as a development process to achieve the required fine circuit pattern requirements.

[0003] Generally, by introducing dicarboxylic acid compounds into photosensitive polyimide resins, the proportion of carboxylic acid dianhydride compounds used can be reduced to reduce the closed loop rate of photosensitive polyimide resin compositions during heat treatment, thereby reducing the curing temperature of the cured film, which can be easily achieved. However, the pattern processing of the photosensitive polyimide resin composition development process is extremely complicated, the dissolution rate of the polyamic acid precursor in the photosensitive polyimide resin composition in the alkaline developer is extremely fast, and the difference in dissolution rate between the exposed area and the non-exposed area is small, resulting in low residual film rate and contrast, and the development process is difficult to accurately control. Therefore, the positive photosensitive resin composition traditionally using the ester compound of the photosensitizer naphthoquinone diazide and the alkali-soluble resin combination can reduce the dissolution rate of the non-exposed area, but increasing the proportion of the ester compound of the photosensitizer naphthoquinone diazide will cause the exposure area to reduce the transmittance at the same photosensitive wavelength, resulting in a long development time, a decrease in dissolution contrast, and a significant reduction in sensitivity. In addition, in order to increase the solubility of the exposed area and make the polyimide resin to which the photosensitizer naphthoquinone diazide ester compound is added have good solubility, alkali-soluble groups such as phenolic hydroxyl, carboxyl and sulfonic acid groups that promote alkali solubility are introduced into the polyimide main chain structure, such as application No. 200710084697.5. However, the introduction of these groups inevitably leads to the disadvantages of reduced heat resistance and development residual film rate of the photosensitive polyimide resin film used in the device, as well as increased hygroscopicity.

[0004] CN111936552A discloses a photosensitive resin composition, in which a soft long-chain aliphatic dicarboxylic acid group and a diphenyl ether aromatic structure are introduced into a polyimide resin, and the obtained photosensitive polyimide resin film has a lower curing temperature and higher heat resistance, but the content of the carboxyl group in the polyimide resin is precisely controlled to obtain a film with excellent resolution and fine processing patterns, which cannot be accurately controlled in the actual production process, and high tensile properties cannot be obtained. CN115594848A proposes a novel photosensitive resin composition, in which a specific protective group is introduced into a polybenzoxazole precursor to protect alkali-soluble groups such as phenolic hydroxyl, carboxyl and sulfonic acid groups in the exposure area, thereby improving the dissolution contrast and development residual film rate of the photosensitive polyimide resin film, but because the photosensitive resin composition does not contain a polyimide precursor structure, the heat resistance of the formed photosensitive resin film becomes insufficient.

[0005] Therefore, how to provide a photosensitive polyimide resin film with a high development residual film rate, high heat resistance and chemical resistance after low-temperature curing, and excellent resolution and fine processing pattern characteristics has become a major problem that technicians in this field urgently need to solve. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide a photosensitive polyimide resin composition, a cured film, and a preparation method and application thereof.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In one aspect, the present invention provides a photosensitive polyimide resin composition, comprising (A) 100 parts by weight of a polyimide resin having a structural unit represented by general formula (1) and having a protective group, (B) 1-50 parts by weight of a photosensitizer, (C) 1-200 parts by weight of a thermal crosslinking agent, (D) 0.001-10 parts by weight of other additives, and (E) 300-2000 parts by weight of an organic solvent.

[0009]

[0010] In the general formula (1), R1 represents a tetravalent residue of a tetracarboxylic dianhydride compound containing at least 2 carbon atoms; R2 represents a divalent residue of a dicarboxylic acid compound containing at least 2 carbon atoms; R3 represents a divalent to hexavalent residue of a diamine compound containing at least 2 carbon atoms; R4 represents a hydrogen atom or an alkyl residue having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. In addition, when R4 represents a hydrogen atom, , the carboxyl group in the structure will also become a protecting group; n and n1 represent integers from 10 to 100000 (for example, 10, 15, 20, 30, 50, 80, 100, 300, 500, 800, 1000, 3000, 5000, 8000, 10000, 30000, 50000, 80000, 100000, etc.), preferably an integer from 10 to 50000, preferably n / n1=2-20. Considering that if the ratio of n / n1 is too large, the closed-loop rate of the polyimide resin structure during heat treatment will increase at the same time, the film shrinkage will be easy to become larger, and low-temperature curing cannot be guaranteed; if the ratio of n / n1 is too low, the heat-resistant structure (polyimide structure) is lacking, and the heat resistance of the resin film decreases; therefore, the ratio of n / n1 is more preferably 5 to 10; m is an integer from 1 to 2; p and q are integers from 0 to 4 (for example, 0, 1, 2, 3 or 4), and p+q>0;

[0011] In the general formula (1), R5 represents a hydrogen atom or a group represented by the general formula (2). From the viewpoint of obtaining a high residual film development rate, the amount of the group represented by the general formula (2) in R5 is 10 mol% or more, more preferably 30 mol% or more. From the viewpoint of further improving the thermodynamic properties and chemical resistance of the photosensitive polyimide resin film, the structure represented by the general formula (2) in R5 also contains a cross-linkable epoxy group.

[0012]

[0013] Wherein, R6 represents a methylene group; R7 and R8 each independently represent a hydrogen atom, a C1-C 20 Alkyl, C1-C 20 Cycloalkyl, C1-C 20 Silane, C1-C 20 Alkoxy, C1-C 24 Aromatic, C1-C 24 Heteroaromatic, C1-C 30 Aryl alkyl, C1-C 30 Heteroaromatic alkyl, C1-C 30 Alicyclic or C1-C 30 heteroalicyclic group; t is an integer from 1 to 6 (eg, 1, 2, 3, 4, 5 or 6), Indicates the connection site.

[0014] Preferably, the structure represented by general formula (2) can be specifically selected from one or a combination of at least two of the following structures:

[0015]

[0016]

[0017] In Formula I-1 to Formula I-8, Indicates the connection site.

[0018] In the general formula (1), the structure represented by R1(COOR4)m(OR5)p can be specifically represented by the following general formula (3):

[0019]

[0020] In the formula, R 10 , R 11 represents a trivalent or tetravalent organic group having 2 to 30 carbon atoms (e.g., 2, 3, 5, 8, 10, 15, 18, 20, 25, 28, or 30); R9 represents a trivalent to hexavalent organic group having 3 to 40 carbon atoms (e.g., 3, 5, 8, 9, 10, 13, 15, 18, 20, 25, 28, 30, 35, or 40) and having a hydroxyl group or a fluorine atom; R 12 , R 13 represents a hydrogen atom or an alkyl group having 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms; u and v represent an integer of 1 or 2, and g and h represent an integer of 0 to 4 (e.g., 0, 1, 2, 3 or 4). Indicates the connection site.

[0021] Preferably, the structure represented by general formula (3) can be specifically selected from one or more of the following structures:

[0022]

[0023] In Formula II-1 to Formula II-6, Indicates the connection site.

[0024] In the present invention, the tetracarboxylic dianhydride compound can also be selected from pyromellitic dianhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, 2,3,3,4-biphenyltetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic dianhydride, 3,3,4,4-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride , aromatic tetracarboxylic dianhydrides such as 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and the like.

[0025] In addition, in the general formula (1), the dicarboxylic acid compound defined in R2 can be selected from aliphatic dicarboxylic acid compounds or aromatic dicarboxylic acid compounds. The aliphatic dicarboxylic acid compound includes, but is not limited to, malonic acid, dimethylmalonic acid, maleic acid, dimethylmaleic acid, succinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2,3-diethylsuccinic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, etc. The aromatic dicarboxylic acid compound includes, but is not limited to, terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, benzophenone-4,4-dicarboxylic acid, diphenyl sulfone-4,4-dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, etc.

[0026] In the general formula (1), the structure represented by R3 can be specifically represented by the following general formula (4):

[0027]

[0028] In the formula, R 15 , R 16 represents a divalent to tetravalent organic group having a hydroxyl group and having 2 to 30 carbon atoms (e.g., 2, 3, 5, 8, 10, 15, 18, 20, 25, 28 or 30); R 14 It represents a trivalent to hexavalent organic group having a hydroxyl group or a fluorine atom and having 2 to 40 carbon atoms (e.g., 2, 3, 5, 8, 9, 10, 13, 15, 18, 20, 25, 28, 30, 35 or 40); k and s represent integers from 0 to 2, and i and j represent integers from 0 to 4 (0, 1, 2, 3 or 4). Indicates the connection site.

[0029] Preferably, the structure represented by general formula (4) can be specifically selected from one or more of the following structures:

[0030]

[0031] In Formula III-1 to Formula III-10, Indicates the connection site.

[0032] In the present invention, the diamine compound can also be selected from p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 2,2'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, alicyclic 1,4-diaminocyclohexane or 4,4'-methylenebis(cyclohexylamine), etc.

[0033] In the present invention, the structures represented by the above general formula (3) and general formula (4) preferably contain groups with F atoms. It should be noted that F atoms have strong electronegativity and large steric hindrance, which can increase the permeability of the photosensitive polyimide resin film.

[0034] In the present invention, the raw materials for preparing the polyimide resin having a protecting group include a tetracarboxylic dianhydride compound, a dicarboxylic acid compound and a diamine compound.

[0035] In the present invention, in order to improve the adhesion between the photosensitive polyimide resin film and the base substrate, a small amount of disiloxane compound is copolymerized in the main chain of the polyimide resin (A) without reducing the heat resistance of the photosensitive polyimide resin film, that is, preferably, the raw materials for preparing the polyimide resin include disiloxane compounds, and the disiloxane compounds can be selected from the following structures: 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA), 1,3-bis(4-anilino)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, 1,3-bis(4-aminopropyl)tetramethyldisiloxane, etc. The addition ratio is preferably 1%-15% (e.g. 1%, 3%, 5%, 8%, 10%, 12%, 14% or 15%) by weight (i.e. 1-15 parts by weight) relative to 100 parts by weight of the polyimide resin (A), and more preferably 1%-10% by weight.

[0036] In the present invention, in order to control the molecular weight of the resin polymer, an end-capping group is added to the polyimide resin (A), and the two ends of the resin polymer molecular chain are treated by the end-capping group, thereby controlling the molecular weight of the resin polymer, improving the stability of the resin polymer molecular chain, and increasing the storage stability of the photosensitive polyimide resin composition. In the preparation of the polyimide resin, its preparation raw materials include an end-capping agent, and the end-capping agent used is preferably a monoamine compound, which can be selected from the following structures: 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-amino-4,6-dihydroxypyrimidine, 1-hydroxy-2-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 2-hydroxy-3-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-carboxy-3-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 4-amino-8-hydroxyquinoline, 5-amino-8-hydroxyquinoline and the like. The addition ratio is preferably 0.5%-20% (e.g. 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 14% or 15%) by weight (i.e. 0.5-20 parts by weight) relative to 100 parts by weight of the polyimide resin (A), and more preferably 1%-10% by weight.

[0037] In the present invention, the polyimide resin (A) is formed by alkylation of the corresponding polyamic acid, which is very easy to dissolve in alkaline aqueous solution, difficult to control, and has poor stability and is not easy to store. The proportion of carboxyl groups in the polymer is reduced, and an alkylating agent is added in the preparation of the polyimide resin (A) of the present invention to alkylate the carboxyl groups into ester groups, so that the dissolution rate of the resin polymer in alkaline aqueous solution can be adjusted. Moreover, the introduction of ester groups in polyamic acid will also reduce the ratio of polyimide structures in the polyimide resin film and reduce the water absorption rate of the resin film. The content of ester groups should not be too large, otherwise it will be unfavorable for the alkaline aqueous solution to dissolve the photosensitive resin film. The alkylating agent used in the present invention can be selected from the following structures: N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal (DMFDEA, hereinafter referred to as DEA), N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dibutyl acetal, N,N-dimethylacetamide dimethyl acetal, N,N-dimethylacetamide diethyl acetal, N,N-dimethylformamide dibenzyl acetal, 1,1-dimethoxy-2-methylpropane, 1,1-diethoxy-2-methylpropane, etc. In addition, in order to achieve the best dissolution rate of the photosensitive polyimide resin film in alkaline aqueous solution, preferably, the amount of the alkylating agent added is 0.5 to 3.5 times (for example, 0.5 times, 0.8 times, 1 times, 1.5 times, 2 times, 2.5 times, 3 times or 3.5 times) the total molar amount of the tetracarboxylic dianhydride monomer used to synthesize the polyimide resin (A), and more preferably 1.5 to 2.5 times.

[0038] In the present invention, the solvent used for synthesizing the polyimide resin (A) is selected as a high boiling point polar aprotic organic solvent, which can be selected from the following solvents: at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, γ-butyrolactone, γ-valerolactone and α-methyl-γ-butyrolactone, and the solvent is preferably N-methylpyrrolidone.

[0039] The photosensitive polyimide resin composition of the present invention contains a photosensitizer (B), and the content of the photosensitizer is 1-50 parts by weight relative to 100 parts by weight of the polyimide resin having a protective group, for example, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight. As the photosensitizer used in the present invention, an ester compound formed by bonding a phenolic hydroxyl compound with a sulfonic acid of a diazide quinone is usually selected, among which diazide naphthoquinone-4-sulfonyl ester compounds and diazide naphthoquinone-5-sulfonyl ester compounds are preferably used. From the aspect of improving sensitivity, it is preferred to contain diazide naphthoquinone-4-sulfonyl ester compounds; from the aspect of compound stability and long-term reliability of the cured film, it is preferred to contain diazide naphthoquinone-5-sulfonyl ester compounds. The phenolic hydroxy compound bonded to the sulfonic acid of the diazidequinone used in the present invention can be selected from one or a combination of at least two of the following structures:

[0040]

[0041] In the present invention, the photosensitizer (B) used can be selected from the following structures:

[0042]

[0043] Wherein, Q is independently selected from or H, Indicates the connection site.

[0044] The weight average molecular weight of the naphthoquinone diazide compound used in the present invention is preferably in the range of 100-2000 (for example, 100, 130, 150, 180, 200, 300, 500, 800, 1000, 1500, 1800 or 2000), and more preferably in the range of 500-1000. The addition ratio of the naphthoquinone diazide compound used is preferably 1%-50% (for example, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 30%, 40% or 50%) by weight relative to 100 parts by weight of the polyimide resin (A), and more preferably 1%-40% by weight. They can be used alone or in combination of two or more.

[0045] The photosensitive polyimide resin composition of the present invention comprises a thermal crosslinking agent (C), and its function is that during the high-temperature curing process of the pre-baked film of the photosensitive polyimide resin, the added thermal crosslinking agent crosslinks with each other in the resin polymer to form a network structure, thereby reducing the thermal shrinkage of the photosensitive polyimide resin film during the heat treatment process. The thermal crosslinking agent of the present invention is selected from compounds containing crosslinkable hydroxyl and alkoxy groups in the structure. Relative to 100 parts by weight of the polyimide resin with a protective group, the addition amount of the thermal crosslinking agent is 1-200 parts by weight, for example 3 parts by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 150 parts by weight, 180 parts by weight or 200 parts by weight.

[0046] The thermal crosslinking agent (C) of the present invention is specifically selected from at least one of the following structures:

[0047]

[0048] For the heat crosslinking agent (C) used in the present invention, the weight average molecular weight is preferably in the range of 100-800 (e.g., 100, 200, 300, 400, 500, 600, 700 or 800). In addition, in the present invention, since crosslinkable epoxy groups are introduced into the molecular chain of the photosensitive polyimide resin, only a small amount of heat crosslinking agent (C) needs to be added. The addition ratio is preferably 1%-200% by weight, more preferably 1%-50% by weight, relative to 100 parts by weight of the polyimide resin (A). They can be used alone or in combination of two or more.

[0049] In addition, in order to improve the wettability of the photosensitive polyimide resin film and the base substrate, the photosensitive polyimide resin composition of the present invention may be added with other auxiliary agents (D). Relative to 100 parts by weight of the polyimide resin (A), the amount of the other auxiliary agent (D) added is 0.001-10 parts by weight, such as 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight or 10 parts by weight.

[0050] The other auxiliary agent (D) includes a surfactant, and specifically, the following surfactants can be selected: at least one of ethanol, isopropanol, isobutyl alcohol, acetone, cyclohexanone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate. The surfactant is preferably added in an amount of 0.001% to 2% by weight (i.e., 0.001 to 2 parts by weight) relative to 100 parts by weight of the polyimide resin (A), and more preferably in an amount of 0.01% to 1.5% by weight. They can be used alone or in combination of two or more.

[0051] In addition, in order to improve the adhesion between the photosensitive polyimide resin film and the base substrate, the other auxiliary agent (D) added to the photosensitive polyimide resin composition of the present invention further comprises a silane coupling agent, and the following silane coupling agents can be selected: 3-(trimethoxysilyl)aniline, 3-(triethoxysilyl)aniline, N-(3-(trimethoxysilyl)phenyl)acetamide, N-(3-(triethoxysilyl)phenyl)acetamide, 4-(trimethoxysilyl)aniline, 4-(triethoxysilyl)aniline, N-(4-(trimethoxysilyl)phenyl)acetamide, Aminosilane compounds such as (4-(((((methoxysilyl)phenyl)acetamide, N-(4-(triethoxysilyl)phenyl)acetamide) and vinylsilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, etc., wherein the silane coupling agent is added in an amount of preferably 0.1% to 10% by weight, more preferably 0.1% to 5% by weight, relative to 100 parts by weight of the polyimide resin (A). They may be used alone or in combination of two or more.

[0052] In addition, in order to improve the coating properties of the photosensitive polyimide resin film and the base substrate, the photosensitive polyimide resin composition of the present invention also includes an organic solvent (E), and the following organic solvents can be selected: such as γ-butyrolactone, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol Ethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, ethylene glycol methyl ether ethyl acetate, ethylene glycol ethyl ether ethyl acetate, diethylene glycol methyl ether ethyl acetate, propylene glycol methyl At least one of ethyl ether acetate, propylene glycol ethyl ether acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate and xylene, wherein the solvent is preferably The organic solvent is γ-butyrolactone, and its addition ratio is preferably 300%-2000% by weight, i.e. 300-2000 parts by weight, for example 300 parts by weight, 500 parts by weight, 800 parts by weight, 1000 parts by weight, 1300 parts by weight, 1500 parts by weight, 1800 parts by weight or 2000 parts by weight, more preferably 500%-1500% by weight, relative to 100 parts by weight of the polyimide resin (A).

[0053] Next, the photosensitive polyimide resin composition used in the present invention and the method for producing the photosensitive polyimide resin film produced therefrom are described.

[0054] 1. Preparation method of photosensitive polyimide resin composition having protective group:

[0055] The preparation method of the photosensitive polyimide resin having a protective group comprises the following steps:

[0056] (1) a diamine compound and a disiloxane compound are heated, and a tetracarboxylic dianhydride compound and a dicarboxylic acid compound are added to react;

[0057] (2) adding a capping agent compound to the reaction solution of step (1), reacting, and then adding an alkylating agent, continuing the reaction, to obtain a polyimide precursor resin;

[0058] (3) A polyimide precursor resin is reacted with a compound having a protective group to obtain the polyimide resin having a protective group.

[0059] Preferably, the temperature in step (1) is increased to 30-60°C (eg, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C), preferably 40-50°C.

[0060] Preferably, the reaction time of step (1) is 1.5-4 h, such as 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h or 4 h, and the preferred reaction time is 2-3 h.

[0061] Preferably, the reaction temperature of adding the capping agent compound in step (2) is 30-60°C, for example, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C, and the reaction time is 2-4h, for example, 2h, 2.5h, 3h, 3.5h or 4h.

[0062] Preferably, the time for continuing the reaction by adding the alkylating agent in step (2) is 2-3 hours, such as 2 hours, 2.5 hours or 3 hours.

[0063] Preferably, the compound having a protecting group in step (3) is selected from any one of the following compounds:

[0064]

[0065] Preferably, the reaction in step (3) is carried out in a solvent, and the solvent is selected from any one of diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, ethylene glycol dimethyl ether or propylene glycol dimethyl ether, or a combination of at least two thereof.

[0066] Preferably, the reaction in step (3) is carried out in the presence of an acid catalyst, and the acid catalyst is selected from any one of p-toluenesulfonic acid, sulfuric acid, zirconium oxide sulfate, phosphoric acid or thionyl chloride, or a combination of at least two thereof.

[0067] Preferably, the reaction in step (3) is carried out at room temperature (15-30°C, such as 15°C, 18°C, 20°C, 25°C, 28°C or 30°C), and the reaction time is 3-6h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h.

[0068] Preferably, steps (1) to (3) are carried out under nitrogen protection.

[0069] In some embodiments of the present invention, the preparation method of the photosensitive polyimide resin is as follows: under nitrogen protection, a reaction solvent, a diamine compound (R3) and a disiloxane compound are added to a dry three-necked flask in sequence, the temperature is raised to 30-60°C, preferably 40-50°C reaction system, a tetracarboxylic dianhydride compound (R1) and a dicarboxylic acid compound (R2) are added, the reaction time is 1.5-4h, preferably 2-3h, and then a capping agent compound is added, and the reaction is continued for 2-4h. After the reaction is completed, the alkylating agent is added dropwise within 20 minutes, and stirring is continued for 2-3h. Then, the reaction solution is cooled to room temperature, and the solution is slowly added to 2L of pure water to precipitate a white solid. The solid is collected by reduced pressure filtration, washed with pure water 2-3 times, and then placed in a vacuum drying oven at 80°C and dried for 48-72h to obtain a polyimide precursor resin.

[0070] Under nitrogen protection, add reaction solvent, polyimide precursor resin and compound with protective group to a dry three-necked flask in sequence, continue stirring for 10-30 minutes, put the reaction flask in an ice bath, slowly add acid-catalyzed reaction reagent, remove from the ice bath after complete addition, react at room temperature for 3-6 hours, after the reaction is completed, slowly add the reaction solution into 2L pure water, precipitate white solid, collect the solid by vacuum filtration, wash with pure water 3-5 times, and dry in a vacuum drying oven at 80°C for 48-72 hours to obtain polyimide precursor resin (A) with protective group.

[0071] The preparation method of the photosensitive polyimide resin composition of the present invention comprises the following steps:

[0072] Component A, component B, component C and optional other auxiliary agent D and organic solvent E are mixed and reacted to obtain the photosensitive polyimide resin composition. Preferably, the reaction is carried out at room temperature for 5-8 hours (eg, 5 hours, 6 hours, 7 hours or 8 hours).

[0073] In the present invention, in order to remove metal ions and impurities in the photosensitive polyimide resin composition slurry, the mixed composition slurry is filtered, and the pore size of the filter is preferably 0.01 to 5 μm, more preferably 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm or 0.01 μm, and one or more of them are selected for use in combination; the material used for the filter includes polypropylene (PP), polyethylene (PE), nylon (NY) or polytetrafluoroethylene (PTFE), preferably polypropylene or polytetrafluoroethylene.

[0074] 2. Preparation method of photosensitive polyimide film:

[0075] The photosensitive polyimide film of the present invention is obtained by coating the photosensitive polyimide resin composition slurry as described above on a substrate, and then drying to obtain a pre-baked film, and then exposing, developing, and curing the pre-baked film.

[0076] The specific preparation method comprises the following steps:

[0077] 1) Preparing a prebaked film: coating the filtered photosensitive polyimide resin composition slurry onto a base substrate, and then drying the prebaked film at elevated temperature; the coating method is preferably a slit coating method, a spin coating method, a spray coating method or a printing method; the base substrate can be a silicon wafer, a ceramic, a glass, a quartz or an ITO, etc.; the drying temperature is preferably in the range of 50°C to 150°C (for example, 50°C, 70°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C), more preferably in the range of 80°C to 130°C, and the drying time is preferably 1 min~60min (for example, 1min, 3min, 5min, 10min, 15min, 20min, 30min, 40min, 50min or 60min); use a film thickness meter to test the thickness of the pre-baked film. At this time, the thickness of the pre-baked film varies depending on the solid content and viscosity of the photosensitive polyimide resin composition slurry. It is preferred that the film thickness after drying is in the range of 0.1 to 15 μm (for example, 0.1 μm, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm or 15 μm), and more preferably in the range of 5 to 10 μm.

[0078] 2) Exposure and development: The pre-baked film of the photosensitive polyimide resin obtained above is irradiated with light rays, and the light rays are exposed to the pre-baked film through a mask having a specific pattern, and the exposed part is washed away with a developer to obtain a pre-baked film of the photosensitive polyimide resin with a desired pattern; the light rays used for exposure include ultraviolet rays, visible light, electron beams, X-rays, etc. In the present invention, the i-line (365nm), h-line (405nm) or g-line (436nm) of a mercury lamp is preferably used; the developer used to wash away the exposed part is an alkaline aqueous solution, and the mass concentration of the developer is 2.375%-2.385%, including alkaline aqueous solutions such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. The advantage of the developer is that it is environmentally friendly and suitable for industrial applications.

[0079] 3) Thermal curing treatment: The obtained pre-baked film of the photosensitive polyimide resin with a specific pattern is treated at a certain temperature for a period of time to obtain a cured film of the photosensitive polyimide resin; Regarding the method of thermal treatment: the present invention selects a staged temperature increase at a heating rate of 2.5°C / min, and the maximum curing temperature is preferably between 200°C and 300°C (for example, 200°C, 220°C, 240°C, 260°C, 280°C or 300°C), and the curing time is preferably 30min to 90min (for example, 30min, 40min, 50min, 60min, 70min, 80min or 90min).

[0080] In another aspect, the present invention provides use of the photosensitive polyimide resin composition or the photosensitive polyimide cured film as described above in the preparation of semiconductor elements.

[0081] Compared with the prior art, the present invention has the following beneficial effects:

[0082] (1) A specific hydroxyl-protecting group is introduced into the molecular chain of the polyimide resin (A) of the present invention. The hydroxyl-protecting group will be detached after reacting with an acid, so that the protected carboxyl and / or phenolic hydroxyl groups are reduced. In this way, the photosensitive polyimide resin in the exposed area can be dissolved in an alkaline aqueous solution, while the resin film in the non-exposed area is almost insoluble because the carboxyl and / or phenolic hydroxyl groups in the polyimide resin are protected. Therefore, the residual film rate of the photosensitive polyimide resin film is improved, reaching up to 99%; at the same time, the introduction of the hydroxyl-protecting group can also improve the sensitivity of the polyimide resin film.

[0083] (2) A cross-linkable epoxy group is introduced into the molecular chain of the polyimide resin (A) of the present invention, and a small amount of a cross-linking agent (C) is added at the same time. During the heating and curing process, the cross-linking occurs through ring-opening to form a network structure, thereby further improving the mechanical properties and chemical resistance of the photosensitive polyimide resin film.

[0084] (3) The polyimide resin (A) of the present invention comprises a polyimide precursor and a dicarboxylic acid group. The obtained photosensitive polyimide resin film can be completely cured at 200°C and has high heat resistance. The thermal decomposition temperature (T1%) can reach above 378°C at the highest.

[0085] (4) The raw materials used in the present invention are generally commercially available; the synthesis routes of the photosensitive polyimide resin composition and the cured film are not particularly limited.

[0086] (5) The photosensitive polyimide resin film prepared by the present invention can be applied to the passivation film, surface protection film, and interlayer insulation film on the semiconductor element circuit of the semiconductor device, and in particular, can be applied to the insulating layer in the organic electroluminescent display device and the planarization layer between the thin film transistors (TFT). BRIEF DESCRIPTION OF THE DRAWINGS

[0087] Figure 1 It is the hydrogen nuclear magnetic spectrum of the precursor of compound I-7 with a protecting group synthesized in Synthesis Example 1 of the present invention.

[0088] Figure 2 1 and 2 are infrared spectra of the photosensitive polyimide resin films of Example 8 of the present invention and Comparative Example 5 before and after curing.

[0089] Figure 3 It is the infrared spectra of the photosensitive polyimide resin films of Example 8 and Comparative Example 8 of the present invention after curing. DETAILED DESCRIPTION

[0090] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0091] The technical solutions of the contents of the synthesis examples, embodiments and comparative examples of the present invention will be described clearly and completely below. Obviously, the described synthesis examples, embodiments and comparative examples are only a part of the present invention, rather than all the synthesis examples, embodiments and comparative examples.

[0092] Among them, the testing and evaluation methods of the synthesis examples, embodiments and comparative examples are as follows:

[0093] (1) Film thickness test

[0094] The pre-baked film thickness, the film thickness after development and the film thickness after curing of the photosensitive polyimide resin were measured using a film thickness meter (EX-30, field emission scanning electron microscope).

[0095] (2) Determination of residual film rate after development

[0096] The residual film rate of development is calculated according to the following formula:

[0097] Residual film rate after development (%) = film thickness after development / film thickness of pre-baked film * 100%

[0098] (3) Sensitivity test

[0099] A photosensitive polyimide resin pre-baked film with a thickness of 2 μm was formed on a silicon wafer, and the pre-baked film was exposed using an exposure machine (SMA-150GA-TR) i-line (365 nm). After exposure, a developing device (AD-1200, MIKASA) was used to develop the film using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer. The process was repeated twice, and the film was then washed with pure water and dried. After the exposed part was completely dissolved, the minimum exposure amount when the development formed a pattern was used as the sensitivity.

[0100] (4) Mechanical properties test

[0101] A photosensitive polyimide resin cured film with a thickness of 10 μm was formed on a silicon wafer, and the cured film was immersed in 45% by mass hydrofluoric acid for 5 minutes, and then peeled off from the silicon wafer. The film was made into a rectangular film with a size of 100 mm*10 mm, and the film sample was stretched using a tensile testing machine (RTH-20-RACK1310, Japan) with a clamp spacing of 50 mm. Stretching was started to obtain a stress-strain curve, thereby obtaining the mechanical performance indicators of the film, including tensile strength (MPa), elastic modulus (GPa) and elongation at break (%).

[0102] (5) Determination of thermal decomposition temperature (T 1％ )

[0103] A photosensitive polyimide resin cured film with a film thickness of 10 μm was formed on a silicon wafer, and the cured film was immersed in 45% mass fraction hydrofluoric acid for 5 minutes, and then peeled off from the silicon wafer to prepare a 10 mg photosensitive polyimide resin film sample. The sample was tested using a thermogravimetric analyzer (NETZSCH TG209F1, Germany) under nitrogen flow. The test method was as follows: in the first stage, the temperature was raised to 150° C. at a heating rate of 10° C. / min and maintained for 30 minutes, in the second stage, the temperature was lowered to 50° C., and in the third stage, the temperature was heated from 50° C. to 800° C. at a heating rate of 10° C. / min. The temperature corresponding to 1% weight loss was determined from the measured weight-temperature curve as the corresponding thermal decomposition temperature.

[0104] (6) Chemical resistance evaluation

[0105] A photosensitive polyimide resin cured film with a thickness of 10 μm was formed on a silicon wafer, and the cured film was immersed in 45% by mass hydrofluoric acid for 5 minutes, and then peeled off from the silicon wafer. Five samples of the photosensitive polyimide resin cured film were prepared and immersed in γ-butyrolactone (GBL), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), ethyl lactate (EL) and propylene glycol ethyl ether (PGEE) at room temperature for 120 minutes, respectively. Then, the etched film samples were taken out, washed twice with pure water, placed in a high-temperature clean furnace (CLH-21CDV-S, Japan), and dried at 210°C for 60 minutes. The film thickness of the film sample after etching was tested using a film thickness meter, and the film thickness deviation rate of the film sample before and after etching was used as an evaluation of the chemical resistance of the film.

[0106] The deviation rate is calculated using the following formula:

[0107] Deviation rate (%) = [(film thickness before etching - film thickness after etching) / film thickness before etching] * 100%

[0108] The following will describe the contents of the synthesis examples, embodiments and comparative examples in conjunction with the technical scheme, and the specific contents are as follows:

[0109] Synthesis Example 1 Synthesis of Precursor of Compound (I-7) Having Protective Group

[0110] Under nitrogen protection, vinyl alcohol (0.05 mol, CAS: 557-75-5), 4-bromo-1,2-butylene oxide (0.11 mol, CAS: 13287-42-8) and CsOH·H2O (0.30 mol, CAS: 35103-79-8) were added into a 500 ml three-necked reaction bottle in sequence and dissolved in 150 ml of DMSO solvent. The reaction was carried out in an oil bath at 150°C for 48 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature and poured into water. The product was extracted with ethyl acetate, and the organic phase was concentrated. Then, the precursor of compound (I-7) with a protective group (4.91 g, yield 86%) was purified by column chromatography.

[0111]

[0112] Synthesis Example 2 Synthesis of Precursor of Compound (I-8) Having Protective Group

[0113] The difference from Synthesis Example 1 is that 4-bromo-1,2-butylene oxide (0.11 mol, CAS: 13287-42-8) is replaced by 2-(-3-bromopropyl)ethylene oxide (0.11 mol, CAS: 21746-87-2), and the other components and synthesis conditions remain unchanged, and a precursor of compound (I-8) with a protective group is obtained (5.77 g, yield 90%).

[0114]

[0115] Synthesis Example 3 Synthesis of Tetracarboxylic Dianhydride Compound (II-4)

[0116] At room temperature, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF, 0.05 mol, CAS: 83558-87-6) and allyl glycidyl ether (0.3 mol, CAS: 106-92-3) were added to a 1L three-necked reaction bottle and dissolved in γ-butyrolactone (GBL) (100 g), and the reaction system was cooled to -15°C. Then, trimellitic anhydride chloride (0.11 mol, CAS: 1204-28-0) dissolved in 50 g of γ-butyrolactone (GBL) was slowly added dropwise thereto, and the temperature of the reaction liquid was ensured not to exceed 0°C during the addition process. After the addition was completed, the reaction was continued for 5 hours below 0°C, and then naturally warmed to room temperature. The obtained reaction mixture was concentrated by a rotary evaporator and injected into 1 L of toluene for precipitation. After filtering, the solid was placed in a vacuum oven and dried at 60° C. for 24 h to obtain 27.15 g (yield 76%) of tetracarboxylic dianhydride compound (II-4).

[0117]

[0118] By using the above method, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF, 0.05 mol, CAS: 83558-87-6) was replaced with 2,2-bis(3-aminophenyl)hexafluoropropane (0.05 mol, CAS: 47250-53-3), and the other components and synthesis conditions remained unchanged to obtain 24.57 g (yield 72%) of a tetracarboxylic dianhydride compound (M-1) not containing a phenolic hydroxyl group.

[0119]

[0120] Synthesis Example 4 Synthesis of long-chain dicarboxylic acid derivative (M-2)

[0121] According to the method described in the document (CN 111936552A), imidazole (0.4 mol) was added to a 250 ml three-necked flask under nitrogen protection, and dissolved in 100 g NMP by stirring at room temperature. The mixture was cooled to below -5°C, and then the temperature of the reaction solution did not exceed 0°C. Dodecanedioic acid dichloride (0.1 mol) was dissolved in 100 g NMP over 1 hour to obtain a liquid. After the addition, the reaction solution was further stirred at room temperature for 3 hours, and was poured into 1 L of pure water. The precipitate was filtered out, and the filtered precipitate was washed several times with pure water, and dried in a vacuum oven at 50°C for 100 hours to obtain a long-chain dicarboxylic acid derivative (M-2) of the following formula.

[0122]

[0123] Synthesis Example 5 Synthesis of diamine compound (III-5)

[0124] At room temperature, add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.06mol, CAS: 83558-87-6), propylene oxide (0.36mol, CAS: 75-56-9) and 120ml acetone to a 1L three-necked reaction bottle, stir at room temperature until completely dissolved, and cool the reaction system to -15°C. Then, slowly drop a 120ml acetone solution of m-nitrobenzoyl chloride (0.132mol, CAS: 121-90-4) thereinto. After the addition is complete, continue the reaction at -15°C for 5h, and then naturally warm to room temperature. The obtained reaction solution is filtered under reduced pressure to obtain an off-white solid, which is placed in a vacuum oven at 60°C and dried for 20h to obtain an intermediate (27.91g, yield 70%).

[0125]

[0126] The intermediate obtained above (0.03 mol), 5% palladium carbon (0.024 mol) and 170 ml of ethylene glycol methyl ether were added to a 500 ml autoclave, and the hydrogen was replaced and pressurized with hydrogen to a pressure of 10 kgf / cm 2 , raise the temperature to 35°C and stir for 2h. After the reaction is completed, slowly release the pressure, filter the reaction solution under reduced pressure to obtain a transparent solution. Add ethanol and petroleum ether to the solution, stir for 12h to precipitate solid, filter under reduced pressure to obtain a white solid, put the solid into a vacuum oven at 50°C and dry for 20h to obtain diamine compound (III-5) (9.97g, yield 55%).

[0127]

[0128] By using the above method, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF) (0.05 mol, CAS: 83558-87-6) was replaced with 2,2-bis(3-aminophenyl)hexafluoropropane (0.05 mol, CAS: 47250-53-3), and the other components and synthesis conditions remained unchanged to obtain a diamine compound (M-3) (10.82 g, yield 63%) without a phenolic hydroxyl group.

[0129]

[0130] Synthesis Example 6 Synthesis of Photosensitizer Naphthoquinone Diazide Compound (V-3)

[0131] At room temperature, 1,1,1-tri(4-hydroxyphenyl)ethane (IV-2) (0.05 mol, CAS: 27955-94-8), 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (0.125 mol, CAS: 1001756-09-7) and 1,4-dioxane (450 g) were added to a 1 L reaction bottle, stirring was started, nitrogen was replaced, and stirring was performed until completely dissolved. A mixed solution of triethylamine (0.135 mol) and 1,4-dioxane (45 g) was slowly added dropwise thereto, and the temperature was raised to 35°C after the addition was completed, and the reaction was performed for 4 hours. After completion, the mixture was filtered under reduced pressure, and the filtrate was dripped into 3 L of water, and the precipitated solid was filtered and collected. Finally, the precipitate was washed twice with 10 L of pure water, and dried in a vacuum drying oven at 50°C for 24 hours to obtain the photosensitizer naphthoquinone diazide compound (V-3) shown below.

[0132]

[0133] Synthesis Example 7 Synthesis of Thermal Crosslinking Agent (VI-6)

[0134] At room temperature (25°C), add an aqueous solution of sodium hydroxide (0.5 mol) in 200 g pure water to a 2L three-necked flask, slowly stir, then slowly add 1,1,1-tris(4-hydroxyphenyl)ethane (IV-2) (0.1 mol, CAS: 27955-94-8), stir to completely dissolve, then drop 37% formaldehyde aqueous solution (175 g) into the reaction flask, the drop rate is 1 drop / 2 s, after the drop is complete, stir at 25°C for 22 h. The next day, slowly drop 15% dilute sulfuric acid aqueous solution (162 g) at room temperature, keep stirring for 36 h after the drop is complete, precipitate a white solid, filter, and wash with 300 ml pure water to obtain a white solid, put it into a 50°C vacuum drying oven and dry it for 48 h.

[0135] At room temperature, the white solid obtained above was dissolved in 100 ml of ethanol, and 0.5 g of concentrated sulfuric acid was slowly added and stirred for 24 h. After that, 5 g of anion exchange resin was added to the solution, stirred for 2 h, and filtered to obtain a clear filtrate. The filtrate was concentrated until no liquid flowed out, and then 150 ml of ethyl lactate was added and stirred to completely dissolve it. The solution was stirred at room temperature for 36 h, white crystals precipitated, and the solid was filtered to obtain a solid, which was dried in a vacuum drying oven at 50 ° C for 24 h to obtain a thermal crosslinking agent (VI-6), which was retained for later use.

[0136]

[0137] Synthesis Example 8 Synthesis of polyimide precursor resin (A-1) having a protecting group

[0138] Under nitrogen protection, N-methylpyrrolidone (hereinafter referred to as NMP) (600 g), the diamine compound (III-5) in Synthesis Example 5 (170 mmol) and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) (10 mmol, CAS: 2469-55-8) were added to a dry three-necked flask in sequence, the temperature was raised to 50°C, and the tetracarboxylic dianhydride compound (II-4) in Synthesis Example 3 (140 mmol), 4,4-diphenyl ether dicarboxylic acid (hereinafter referred to as OB BA, CAS: 2215-89-6, 60mmol) and NMP (20g), react for 2h, add end-capping agent compound 3-aminophenol (MAP) (20mmol) (CAS: 591-27-5) and NMP (10g), continue to react for 2h, after the reaction is completed, add alkylating agent N, N-dimethylformamide diethyl acetal (DEA) (310mmol, CAS: 1188-33-6) and NMP (10g) dropwise within 20 minutes, and continue stirring at 50°C for 3h. Then, the reaction solution is cooled to room temperature, and the solution is slowly added to 2L of pure water to precipitate a white solid, which is collected by vacuum filtration, washed twice with pure water, and then placed in a vacuum drying oven at 80°C for 48h to obtain 71.88g of polyimide precursor resin.

[0139] Under nitrogen protection, diethylene glycol dimethyl ether (500 g, CAS: 111-96-6), polyimide precursor resin (50 g) and a compound having a protective group, [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol, CAS: 3678-15-7) were added in sequence to a dry three-necked flask, and stirring was continued for 30 min. The reaction flask was placed in an ice bath, and p-toluenesulfonic acid (CAS: 104-15-4, 45 mmol) was slowly added dropwise. After complete addition, the ice bath was removed, and the reaction was carried out at room temperature for 5 h. After the reaction was completed, the reaction solution was slowly added to 2 L of pure water to precipitate a white solid. The solid was collected by vacuum filtration, washed three times with pure water, and then dried in a vacuum drying oven at 80°C for 48 h to obtain 79.32 g of a polyimide precursor resin (A-1) having a protective group.

[0140] Synthesis Example 9 Synthesis of polyimide precursor resin (A-2) having a protecting group

[0141] The difference from Synthesis Example 8 is that the molar number of the tetracarboxylic dianhydride compound (II-4) (140 mmol) is adjusted to (168 mmol), the molar number of 4,4-diphenyl ether dicarboxylic acid (60 mmol) is adjusted to (32 mmol), and the other components and synthesis conditions remain unchanged, to obtain 78.59 g of a polyimide precursor resin (A-2) having a protective group.

[0142] Synthesis Example 10 Synthesis of polyimide precursor resin (A-3) having a protective group

[0143] The difference from Synthesis Example 8 is that the molar number of the tetracarboxylic dianhydride compound (II-4) (140 mmol) is adjusted to (170 mmol), the molar number of 4,4-diphenyl ether dicarboxylic acid (60 mmol) is adjusted to (30 mmol), and the other components and synthesis conditions remain unchanged, to obtain 77.67 g of a polyimide precursor resin (A-3) having a protective group.

[0144] Synthesis Example 11 Synthesis of polyimide precursor resin (A-4) having a protecting group

[0145] The difference from Synthesis Example 8 is that the molar number of the tetracarboxylic dianhydride compound (II-4) (140 mmol) is adjusted to (172 mmol), the molar number of 4,4-diphenyl ether dicarboxylic acid (60 mmol) is adjusted to (28 mmol), and the other components and synthesis conditions remain unchanged, to obtain 78.23 g of a polyimide precursor resin (A-4) having a protective group.

[0146] Synthesis Example 12 Synthesis of polyimide precursor resin (A-5) having a protecting group

[0147] The difference from Synthesis Example 8 is that the molar number of the tetracarboxylic dianhydride compound (II-4) (140 mmol) is adjusted to (174 mmol), the molar number of 4,4-diphenyl ether dicarboxylic acid (60 mmol) is adjusted to (26 mmol), and the other components and synthesis conditions remain unchanged, to obtain 80.67 g of a polyimide precursor resin (A-5) having a protective group.

[0148] Synthesis Example 13 Synthesis of polyimide precursor resin (A-6) having a protecting group

[0149] The difference from Synthesis Example 8 is that the molar number of the tetracarboxylic dianhydride compound (II-4) (140 mmol) is adjusted to (176 mmol), the molar number of 4,4-diphenyl ether dicarboxylic acid (60 mmol) is adjusted to (24 mmol), and the other components and synthesis conditions remain unchanged, to obtain 77.55 g of a polyimide precursor resin (A-6) having a protective group.

[0150] Synthesis Example 14 Synthesis of polyimide precursor resin (A-7) having a protecting group

[0151] The difference from Synthesis Example 8 is that the molar number of the tetracarboxylic dianhydride compound (II-4) (140 mmol) is adjusted to (178 mmol), the molar number of 4,4-diphenyl ether dicarboxylic acid (60 mmol) is adjusted to (22 mmol), and the other components and synthesis conditions remain unchanged, to obtain 77.10 g of a polyimide precursor resin (A-7) having a protective group.

[0152] Synthesis Example 15 Synthesis of polyimide precursor resin (A-8) having a protective group

[0153] The difference from Synthesis Example 8 is that the molar number of the tetracarboxylic dianhydride compound (II-4) (140 mmol) is adjusted to (180 mmol), the molar number of 4,4-diphenyl ether dicarboxylic acid (60 mmol) is adjusted to (20 mmol), and the other components and synthesis conditions remain unchanged, to obtain 80.18 g of a polyimide precursor resin (A-8) having a protective group.

[0154] Synthesis Example 16 Synthesis of polyimide precursor resin (A-9) having a protecting group

[0155] The difference from Synthesis Example 8 is that the molar number of the tetracarboxylic dianhydride compound (II-4) (140 mmol) is adjusted to (190 mmol), the molar number of 4,4-diphenyl ether dicarboxylic acid (60 mmol) is adjusted to (10 mmol), and the other components and synthesis conditions remain unchanged, to obtain 78.87 g of a polyimide precursor resin (A-9) having a protective group.

[0156] Synthesis Example 17 Synthesis of polyimide precursor resin (A-10) having a protecting group

[0157] The difference from Synthesis Example 15 is that the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protecting group is replaced by the compound (I-7) (620 mmol) having a protecting group in Synthesis Example 1, and the other components and synthesis conditions remain unchanged, to obtain 79.45 g of a polyimide precursor resin (A-10) having a protecting group.

[0158] Synthesis Example 18 Synthesis of polyimide precursor resin (A-11) having a protecting group

[0159] The difference from Synthesis Example 15 is that the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protecting group is replaced by the compound (I-8) (620 mmol) having a protecting group in Synthesis Example 2, and the other components and synthesis conditions remain unchanged, to obtain 77.81 g of a polyimide precursor resin (A-11) having a protecting group.

[0160] Synthesis Example 19 Synthesis of polyimide precursor resin (A-12) having a protective group

[0161] The difference from Synthesis Example 15 is that the molar number of the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protective group is adjusted to (186 mmol), and the other components and synthesis conditions remain unchanged, thereby obtaining 82.02 g of a polyimide precursor resin (A-12) having a protective group.

[0162] Synthesis Example 20 Synthesis of polyimide precursor resin (A-13) having a protective group

[0163] The difference from Synthesis Example 15 is that the molar number of the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protective group is adjusted to (248 mmol), and the other components and synthesis conditions remain unchanged, thereby obtaining 80.01 g of a polyimide precursor resin (A-13) having a protective group.

[0164] Synthesis Example 21 Synthesis of polyimide precursor resin (A-14) having a protecting group

[0165] The difference from Synthesis Example 15 is that the molar number of the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protective group is adjusted to (310 mmol), and the other components and synthesis conditions remain unchanged, thereby obtaining 78.92 g of a polyimide precursor resin (A-14) having a protective group.

[0166] Synthesis Example 22 Synthesis of polyimide precursor resin (A-15) having a protecting group

[0167] The difference from Synthesis Example 15 is that the molar number of the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protective group is adjusted to (372 mmol), and the other components and synthesis conditions remain unchanged, thereby obtaining 79.33 g of a polyimide precursor resin (A-15) having a protective group.

[0168] Synthesis Example 23 Synthesis of polyimide precursor resin (A-16) having a protecting group

[0169] The difference from Synthesis Example 15 is that the molar number of the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protective group is adjusted to (434 mmol), and the other components and synthesis conditions remain unchanged, thereby obtaining 79.70 g of a polyimide precursor resin (A-16) having a protective group.

[0170] Synthesis Example 24 Synthesis of polyimide precursor resin (A-17) having a protecting group

[0171] The difference from Synthesis Example 15 is that the molar number of the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protective group is adjusted to (496 mmol), and the other components and synthesis conditions remain unchanged, thereby obtaining 79.70 g of a polyimide precursor resin (A-17) having a protective group.

[0172] Synthesis Example 25 Synthesis of polyimide precursor resin (A-18) having a protective group

[0173] The difference from Synthesis Example 15 is that the molar number of the compound [(vinyloxy)methyl]ethylene oxide (I-1) (620 mmol) having a protective group is adjusted to (558 mmol), and the other components and synthesis conditions remain unchanged, thereby obtaining 81.52 g of a polyimide precursor resin (A-18) having a protective group.

[0174] Synthesis Example 26 Synthesis of polyimide precursor resin (A-19)

[0175] The difference from Synthesis Example 15 is that the tetracarboxylic dianhydride compound (II-4) (180 mmol) is replaced by 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA) (180 mmol, CAS: 2420-87-3), the diamine compound (III-5) (170 mmol) is replaced by 4,4'-diaminodiphenyl ether (170 mmol, CAS: 101-80-4), and no compound with a protecting group is added. The other components and synthesis conditions remain unchanged, and 80.38 g of polyimide precursor resin (A-19) is obtained.

[0176] Synthesis Example 27 Synthesis of polyimide precursor resin (A-20) having a protecting group

[0177] The difference from Synthesis Example 15 is that 4,4-diphenyl ether dicarboxylic acid (CAS: 2215-89-6, 20 mmol) is replaced by the dicarboxylic acid derivative (M-2) (20 mmol) in Synthesis Example 4, and other components and synthesis conditions remain unchanged, to obtain 78.51 g of polyimide precursor resin (A-20).

[0178] Synthesis Example 28 Synthesis of polyimide precursor resin (A-21) having a protecting group

[0179] The difference from Synthesis Example 15 is that the molar number of 4,4-diphenyl ether dicarboxylic acid (CAS: 2215-89-6) (20 mmol) is adjusted to 200 mmol, and at the same time, the tetracarboxylic dianhydride compound (II-4, 180 mmol) is not added. The other components and synthesis conditions remain unchanged, and 79.17 g of polyimide precursor resin (A-21) is obtained.

[0180] Synthesis Example 29 Synthesis of polyimide precursor resin (A-22) having a protecting group

[0181] The difference from Synthesis Example 15 is that the molar number of the tetracarboxylic dianhydride compound (II-4, 180 mmol) is adjusted to 200 mmol, and at the same time, 4,4-diphenyl ether dicarboxylic acid (CAS: 2215-89-6, 20 mmol) is not added. The other components and synthesis conditions remain unchanged, and 79.91 g of polyimide precursor resin (A-22) is obtained.

[0182] Synthesis Example 30 Synthesis of polyimide precursor resin (A-23)

[0183] The difference from Synthesis Example 15 is that the tetracarboxylic dianhydride compound (II-4) (180 mmol) is replaced by a tetracarboxylic dianhydride compound (M-1) (180 mmol) not containing a phenolic hydroxyl group, and the diamine compound (III-5) (170 mmol) is replaced by a diamine compound (M-3) (170 mmol) not containing a phenolic hydroxyl group, and the other components and synthesis conditions remain unchanged, to obtain 82.21 g of a polyimide precursor resin (A-23).

[0184] Synthesis Example 31 Synthesis of polyimide precursor resin (A-24)

[0185] The difference from Synthesis Example 15 is that no compound having a protecting group is added, and other components and synthesis conditions remain unchanged, thereby obtaining 81.07 g of a polyimide precursor resin (A-24).

[0186] The raw material components and amounts used in the preparation of polyimide resins (A-1) to (A-24) are shown in Table 1 below.

[0187] Table 1

[0188]

[0189]

[0190] Example 1

[0191] Under nitrogen protection, 10 g of polyimide resin (A-1), 2.95 g of the photosensitizer naphthoquinone diazide compound (V-3) in Synthesis Example 6, and 22.1 g of the thermal crosslinker (VI-6) in Synthesis Example 7 were added to 800 g of γ-butyrolactone (GBL), stirred at 25°C until completely dissolved, reacted for 6 hours, 0.17 g of silane coupling agent compound vinyltrichlorosilane (CAS: 75-94-5) and 0.08 g of ethyl lactate (EL) were added, and stirring was continued for 2 hours. The reaction solution was filtered through a filter made of polytetrafluoroethylene (PTFE) with a pore size of 0.2 μm to obtain a photosensitive polyimide resin composition (S-1) with a protective group.

[0192] The filtered photosensitive polyimide resin composition (S-1) with a protective group was respectively coated onto a 6-inch silicon wafer and a 10 cm*10 cm glass substrate by spin coating, and dried at 120° C. for 3 min. The thickness of the pre-baked film under different conditions was measured using a film thickness meter. Next, the pre-baked film was exposed through a mask using an i-line (365 nm) of a mercury lamp, and the exposed part was dissolved using a tetramethylammonium hydroxide developer having a mass concentration of 2.38% to obtain a pre-baked film of a photosensitive polyimide resin with a specific pattern. After development, the pre-baked film of the photosensitive polyimide resin was placed in a high-temperature clean furnace (CLH-21CDV-S, Japan), and the temperature was increased to 150° C. and 180° C. at a heating rate of 2.5° C. / min, and each temperature was maintained for 10 min. Finally, the temperature was increased to 200° C., maintained at 200° C. for heat treatment for 1 h, and then cooled to below 50° C. to obtain a cured film (F-1) of the photosensitive polyimide resin.

[0193] Example 2

[0194] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-2), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-2) and a cured film (F-2) of the photosensitive polyimide resin.

[0195] Example 3

[0196] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-3), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-3) and a cured film (F-3) of the photosensitive polyimide resin.

[0197] Example 4

[0198] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-4), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-4) and a cured film (F-4) of the photosensitive polyimide resin.

[0199] Example 5

[0200] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-5), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-5) and a cured film (F-5) of the photosensitive polyimide resin.

[0201] Example 6

[0202] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-6), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-6) and a cured film (F-6) of the photosensitive polyimide resin.

[0203] Example 7

[0204] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-7), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-7) and a cured film (F-7) of the photosensitive polyimide resin.

[0205] Example 8

[0206] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-8), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-8) and a cured film (F-8) of the photosensitive polyimide resin.

[0207] Example 9

[0208] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-9), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-9) and a cured film (F-9) of the photosensitive polyimide resin.

[0209] Example 10

[0210] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-10), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-10) and a cured film (F-10) of the photosensitive polyimide resin.

[0211] Embodiment 11

[0212] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-11), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-11) and a cured film (F-11) of the photosensitive polyimide resin.

[0213] Example 12

[0214] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-12), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-12) and a cured film of the photosensitive polyimide resin (F-12).

[0215] Embodiment 13

[0216] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-13), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-13) and a cured film of the photosensitive polyimide resin (F-13).

[0217] Embodiment 14

[0218] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-14), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-14) and a cured film of the photosensitive polyimide resin (F-14).

[0219] Embodiment 15

[0220] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-15), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-15) and a cured film of the photosensitive polyimide resin (F-15).

[0221] Example 16

[0222] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-16), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-16) and a cured film of the photosensitive polyimide resin (F-16).

[0223] Embodiment 17

[0224] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-17), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-17) and a cured film of the photosensitive polyimide resin (F-17).

[0225] Embodiment 18

[0226] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-18), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-18) and a cured film of the photosensitive polyimide resin (F-18).

[0227] Comparative Example 1

[0228] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-19), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-19) and a cured film of the photosensitive polyimide resin (F-19).

[0229] Comparative Example 2

[0230] The difference from Example 8 is that the amount of the photosensitizer naphthoquinone diazide compound (V-3) added is increased to 5.90 g, and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-20) and a cured film of the photosensitive polyimide resin (F-20).

[0231] Comparative Example 3

[0232] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-20), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-21) and a cured film of the photosensitive polyimide resin (F-21).

[0233] Comparative Example 4

[0234] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-21), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-22) and a cured film of the photosensitive polyimide resin (F-22).

[0235] Comparative Example 5

[0236] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-22), and the other components and synthesis conditions remain unchanged, thereby obtaining a photosensitive polyimide resin composition (S-23) and a cured film of the photosensitive polyimide resin (F-23).

[0237] Comparative Example 6

[0238] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-23), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-24) and a cured film of the photosensitive polyimide resin (F-24).

[0239] Comparative Example 7

[0240] The difference from Example 8 is that the polyimide resin (A-8) is replaced by an equal mass of polyimide resin (A-24), and the other components and synthesis conditions remain unchanged, to obtain a photosensitive polyimide resin composition (S-25) and a cured film of the photosensitive polyimide resin (F-25).

[0241] Comparative Example 8

[0242] The difference from Comparative Example 5 is that the curing temperature of the photosensitive polyimide resin composition (S-23) is increased from 200° C. to 250° C. to obtain a cured film (F-26) of the photosensitive polyimide resin.

[0243] The residual film rate, mechanical properties, photosensitivity, heat resistance and chemical resistance of the photosensitive polyimide resin film and the cured film were tested and evaluated. The test results are shown in Tables 2 and 3 below.

[0244] Table 2: Performance test data of photosensitive polyimide resin film

[0245]

[0246]

[0247] Table 3: Performance test data of photosensitive polyimide resin film

[0248]

[0249] By comparing Examples 1 to 8, it can be seen that by controlling the molar ratio of the tetracarboxylic dianhydride compound (R1) and the dicarboxylic acid compound (R2) in the polyimide resin, when the ratio of the structural units R1 and R2 is 90%:10%, the photosensitive polyimide resin film exhibits more excellent mechanical properties, photosensitivity, heat resistance and chemical resistance, and the development residual film rate reaches 99%, and the non-exposed part is almost insoluble.

[0250] From the comparison between Example 9 and Example 8, it can be seen that further increasing the addition ratio of the tetracarboxylic dianhydride compound (R1) (the addition amount reaches 95%) causes incomplete curing of the photosensitive polyimide resin film system, thereby reducing the thermodynamic properties and chemical resistance of the photosensitive polyimide resin film.

[0251] From the comparison between Examples 10 to 11 and Example 8, it can be seen that the longer and more numerous the polyimide resin molecular chain segments are, the higher the elongation at break of the photosensitive polyimide resin film is, and the better the flexibility is.

[0252] From the comparison between Examples 12 to 18 and Example 8, it can be seen that the residual film rate of the photosensitive polyimide resin film shows a downward trend when the addition ratio of the hydroxyl protective group (R5) is reduced, which is related to the dissolution of the hydroxyl group in the polyimide resin structure in the alkaline aqueous solution, which is in line with the experimental expectation. At the same time, the sensitivity of the polyimide resin film also decreases, indicating that the presence of the hydroxyl protective group (R5) can also improve the sensitivity of the polyimide resin film.

[0253] From the comparison between Comparative Example 1 and Example 8, it can be seen that when ordinary diamine and anhydride compounds are added to the system of the present invention, they cannot be completely cured at 200°C, and the heat resistance, mechanical properties and chemical resistance of the obtained photosensitive polyimide resin film are significantly reduced. The development residual film rate of the resin film is reduced to 88%, indicating that the addition of the above two compounds is not suitable for low-temperature curing system.

[0254] From the comparison between Comparative Example 2 and Example 8, it can be seen that increasing the amount of photosensitizer used in the polyimide resin composition significantly reduces the sensitivity, heat resistance and chemical resistance of the obtained photosensitive polyimide resin film, but has little effect on the residual film rate of the resin film after development.

[0255] From the comparison between Comparative Example 3 and Example 8, it can be seen that the use of long-chain aliphatic dicarboxylic acid compounds instead of traditional short-chain dicarboxylic acid compounds can achieve the effect of low-temperature curing, but the excessively long polyimide resin molecular chain segments lead to a decrease in the tensile properties of the photosensitive polyimide resin film.

[0256] From the comparison between Comparative Example 4 and Example 8, it can be seen that without introducing tetracarboxylic dianhydride groups into the polyimide resin structure, no polyimide structure is generated during the high-temperature curing process. The same low-temperature curing effect can be achieved. However, the lack of a heat-resistant structure (polyimide) causes the heat resistance of the photosensitive polyimide resin film to decrease significantly.

[0257] From the comparison between Comparative Example 5 and Example 8, it can be seen that no dicarboxylic acid group is introduced into the polyimide resin structure, so that a complete polyimide structure is formed during high temperature curing. However, under the premise of curing at 200°C, such curing becomes very incomplete (see Appendix Figure 2 The mechanical properties, heat resistance and chemical resistance of the obtained photosensitive polyimide resin film are comprehensively reduced.

[0258] From the comparison between Comparative Example 6 and Example 8, it can be seen that the diamine and acid anhydride compounds used do not contain phenolic hydroxyl structures. Although they contain the hydroxyl protecting group (R5) of the present invention, the photosensitive polyimide resin film does not fully dissolve in the exposed area during the exposure process, the exposure time of the resin film is long, and the sensitivity is very low.

[0259] From the comparison between Comparative Example 7 and Example 8, it can be seen that without introducing the hydroxyl protecting group (R5) of the present invention into the polyimide resin structure, the developing residual film rate of the obtained photosensitive polyimide resin film is as low as 83%, and the thermal decomposition temperature (T 1％ ) decreased by 5.3%. In addition, not introducing the hydroxyl protecting group (R5) is also accompanied by a decrease in the content of crosslinkable groups, and the mechanical properties and chemical resistance of the photosensitive polyimide resin film are also reduced.

[0260] From the comparison between Comparative Example 8 and Comparative Example 5, it can be seen that the photosensitive polyimide resin film obtained in Comparative Example 5 can be completely cured by raising the curing temperature to 250°C (see Figure 5). Figure 3 The mechanical properties, heat resistance and chemical resistance of the resin film are significantly improved, but the photosensitivity is lower than that of the photosensitive polyimide resin film used in the present invention.

[0261] In summary, the photosensitive polyimide resin film prepared by using the specific hydroxyl-protected group (R5) component of the present invention has a very high residual film rate after development. At the same time, the resin film can be completely cured at 200°C, and the obtained photosensitive polyimide resin cured film has high mechanical properties, heat resistance and chemical resistance.

[0262] The applicant declares that the present invention illustrates the process method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned process steps, that is, it does not mean that the present invention must rely on the above-mentioned process steps to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A photosensitive polyimide resin composition, characterized in that: The photosensitive polyimide resin composition comprises (A) 100 parts by weight of a polyimide resin having a protective group and a structural unit represented by the general formula (1), (B) 1-50 parts by weight of a photosensitizer, (C) 1-200 parts by weight of a thermal crosslinking agent, (D) 0.001-10 parts by weight of other additives, and (E) 300-2000 parts by weight of an organic solvent. In the general formula (1), R1 represents a tetravalent residue of a tetracarboxylic dianhydride compound containing at least 2 carbon atoms; R2 represents a divalent residue of a dicarboxylic acid compound containing at least 2 carbon atoms; R3 represents a divalent to hexavalent residue of a diamine compound containing at least 2 carbon atoms; R4 represents a hydrogen atom or an alkyl residue having 1 to 20 carbon atoms, n and n1 represent integers of 10 to 100,000; m is an integer of 1 to 2; p and q are integers of 0 to 4, and p+q>0; R5 represents a hydrogen atom or a structure represented by the general formula (2), Wherein, R6 represents a methylene group; R7 and R8 each independently represent a hydrogen atom, a C1-C 20 Alkyl, C1-C 20 Cycloalkyl, C1-C 20 Silane, C1-C 20 Alkoxy, C1-C 24 Aromatic, C1-C 24 Heteroaromatic, C1-C 30 Aryl alkyl, C1-C 30 Heteroaromatic alkyl, C1-C 30 Alicyclic or C1-C 30 Heteroalicyclic group; t is an integer from 1 to 6, and "*-" indicates a connection site.

2. The photosensitive polyimide resin composition according to claim 1, characterized in that: n / n1=2 to 20, more preferably n / n1=5 to 10; Preferably, the structure represented by general formula (2) can be specifically selected from one or a combination of at least two of the following structures: In Formula I-1 to Formula I-8, "*-" represents a linking site.

3. The photosensitive polyimide resin composition according to claim 1, characterized in that: In the general formula (1), R1(COOR4) m (OR5) p The structure represented is selected from any one of the structures represented by the following general formula (3): In the formula, R 10 , R 11 represents a trivalent or tetravalent organic group having 2 to 30 carbon atoms; R9 represents a trivalent to hexavalent organic group having 3 to 40 carbon atoms and having a hydroxyl group or a fluorine atom; R 12 , R 13 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; u and v represent an integer of 1 or 2, and g and h represent an integer of 0 to 4; "*-" represents a connection site. Preferably, the structure represented by general formula (3) can be specifically selected from one or more of the following structures: In Formula II-1 to Formula II-6, "*-" represents a linking site. Preferably, the tetracarboxylic dianhydride compound is selected from pyromellitic dianhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, 2,3,3,4-biphenyltetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic dianhydride, 3,3,4,4-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1 , aromatic tetracarboxylic dianhydrides such as 1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride; Preferably, in the general formula (1), the dicarboxylic acid compound defined in R2 is selected from aliphatic dicarboxylic acid compounds or aromatic dicarboxylic acid compounds; Preferably, the aliphatic dicarboxylic acid compound is selected from malonic acid, dimethylmalonic acid, maleic acid, dimethylmaleic acid, succinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2,3-diethylsuccinic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid; Preferably, the aromatic dicarboxylic acid compound is selected from terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, benzophenone-4,4-dicarboxylic acid, diphenyl sulfone-4,4-dicarboxylic acid or 4,4-biphenyl dicarboxylic acid.

4. The photosensitive polyimide resin composition according to claim 1, characterized in that: In the general formula (1), the structure represented by R3 is selected from any one of the structures represented by the following general formula (4): In the formula, R 15 , R 16 represents a divalent to tetravalent organic group having a hydroxyl group and having 2 to 30 carbon atoms; R 14 represents a trivalent to hexavalent organic group having 2 to 40 carbon atoms and having a hydroxyl group or a fluorine atom; k and s represent integers from 0 to 2, and i and j represent integers from 0 to 4; "*-" represents a connection site. Preferably, the structure represented by general formula (4) can be specifically selected from one or more of the following structures: In Formula III-1 to Formula III-10, "*——" represents a connection site. Preferably, the diamine compound can also be selected from p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 2,2'-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, alicyclic 1,4-diaminocyclohexane or 4,4'-methylenebis(cyclohexylamine).

5. The photosensitive polyimide resin composition according to claim 1, characterized in that: The raw materials for preparing the polyimide resin having a protective group include a tetracarboxylic dianhydride compound, a dicarboxylic acid compound, a diamine compound, a disiloxane compound, a capping agent, an alkylating agent and a compound having a protective group; Preferably, the disiloxane compound may be selected from at least one of the following compounds: 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-anilino)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, 1,3-bis(4-aminopropyl)tetramethyldisiloxane; Preferably, the amount of the disiloxane compound added is 1-15 parts by weight relative to 100 parts by weight of the polyimide resin (A); Preferably, the blocking agent is a monoamine compound; Preferably, the monoamine compound is selected from 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-amino-4,6-dihydroxypyrimidine, 1-hydroxy-2-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 2-hydroxy-3-aminonaphthalene, At least one of naphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-carboxy-3-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 4-amino-8-hydroxyquinoline or 5-amino-8-hydroxyquinoline; Preferably, relative to 100 parts by weight of the polyimide resin (A), the amount of the end-capping agent added is 0.5-20 parts by weight; Preferably, the compound having a protecting group is selected from any one of the following compounds: Preferably, the method for preparing the photosensitive polyimide resin having a protecting group comprises the following steps: (1) a diamine compound and a disiloxane compound are heated, and a tetracarboxylic dianhydride compound and a dicarboxylic acid compound are added to react; (2) adding a capping agent compound to the reaction solution of step (1), reacting, and then adding an alkylating agent, continuing the reaction, to obtain a polyimide precursor resin; (3) reacting a polyimide precursor resin with a compound having a protective group to obtain the polyimide resin having a protective group; Preferably, the temperature in step (1) is increased to 30-60°C, preferably 40-50°C. Preferably, the reaction time of step (1) is 1.5-4 h, preferably 2-3 h. Preferably, the reaction temperature of adding the end-capping agent compound in step (2) is 30-60° C., and the reaction time is 2-4 hours; Preferably, the time for continuing the reaction by adding the alkylating agent in step (2) is 2-3 hours; Preferably, the reaction in step (3) is carried out in a solvent, and the solvent is selected from any one of diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, ethylene glycol dimethyl ether or propylene glycol dimethyl ether, or a combination of at least two thereof; Preferably, the reaction in step (3) is carried out in the presence of an acid catalyst, and the acid catalyst is selected from any one or a combination of at least two of p-toluenesulfonic acid, sulfuric acid, zirconium oxide sulfate, phosphoric acid or thionyl chloride; Preferably, the reaction in step (3) is carried out at room temperature for 3-6 hours; Preferably, steps (1) to (3) are carried out under nitrogen protection.

6. The photosensitive polyimide resin composition according to claim 1, characterized in that: The photosensitizer (B) is an ester compound formed by bonding a phenolic hydroxyl compound with a sulfonic acid of a diazide quinone; preferably a diazide naphthoquinone-4-sulfonyl ester compound or a diazide naphthoquinone-5-sulfonyl ester compound; Preferably, the photosensitizer (B) can be selected from the following structures: Wherein, Q is independently selected from or H, Indicates the connection site. Preferably, the thermal crosslinking agent (C) is selected from at least one of the compounds of the following structures: Preferably, other auxiliary agents (D) include surfactants and / or silane coupling agents; Preferably, the surfactant is selected from at least one of ethanol, isopropanol, isobutanol, acetone, cyclohexanone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate; Preferably, the silane coupling agent is selected from at least one of aminosilane compounds and / or vinylsilane compounds; Preferably, the aminosilane compound is selected from at least one of 3-(trimethoxysilyl)aniline, 3-(triethoxysilyl)aniline, N-(3-(trimethoxysilyl)phenyl)acetamide, N-(3-(triethoxysilyl)phenyl)acetamide, 4-(trimethoxysilyl)aniline, 4-(triethoxysilyl)aniline, N-(4-(trimethoxysilyl)phenyl)acetamide or N-(4-(triethoxysilyl)phenyl)acetamide; Preferably, the vinylsilane compound is selected from at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane or vinyltri(β-methoxyethoxy)silane; Preferably, the organic solvent (E) is selected from the group consisting of γ-butyrolactone, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, dipropylene At least one of ketone alcohol, ethylene glycol methyl ether ethyl acetate, ethylene glycol ethyl ether ethyl acetate, diethylene glycol methyl ether ethyl acetate, diethylene glycol ethyl ether ethyl acetate, propylene glycol methyl ether ethyl acetate, propylene glycol ethyl ether ethyl acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate and xylene, preferably γ-butyrolactone.

7. The method for preparing the photosensitive polyimide resin composition according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: Mixing component A, component B, component C, other auxiliary agent D and organic solvent E, and reacting to obtain the photosensitive polyimide resin composition; Preferably, the reaction is carried out at room temperature for 5-8 hours.

8. A photosensitive polyimide cured film, characterized in that: The photosensitive polyimide cured film is obtained by coating a slurry of the photosensitive polyimide resin composition according to any one of claims 1 to 6 on a substrate, and then drying to obtain a pre-baked film, and then exposing, developing, and curing the pre-baked film.

9. Use of the photosensitive polyimide resin composition according to any one of claims 1 to 6 or the photosensitive polyimide cured film according to claim 9 in the preparation of semiconductor devices.

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