Photosensitive polyimide resin composition and photosensitive polyimide film containing the same and application thereof

Abstract

The present invention discloses a photosensitive polyimide resin composition and a photosensitive polyimide film containing the same and application thereof, belonging to the field of semiconductor technology. The present invention not only reduces the content of small molecular volatiles by introducing a thermal cross-linking compound into the photosensitive polyimide resin composition, but also avoids the high temperature decomposition of the cross-linking compound due to its own structure. At the same time, the photosensitive polyimide film prepared by the present invention has excellent chemical resistance and thermodynamic stability.

Description

Technical Field

[0001] The invention relates to the technical field of semiconductors, in particular to a photosensitive polyimide resin composition and a photosensitive polyimide film containing the same. Background Art

[0002] At present, with the continuous improvement of the requirements of the semiconductor industry, the requirements for patterned fine processing of passivation films, surface protection films, interlayer insulating films on semiconductor component circuits, etc. used in semiconductors are also constantly increasing. Therefore, for the prepared photosensitive polyimide resin composition, defects should be avoided as much as possible in the processes of slit coating, spin coating, spray coating or printing coating. Therefore, it is required that the viscosity of the prepared photosensitive polyimide resin composition should not be too high. If it is too high, it is easy to cause uneven coating during the film laying process, causing defects. At the same time, the viscosity of the prepared photosensitive polyimide resin composition should not be too low. If it is too low, the heat resistance, chemical resistance and mechanical properties of the prepared photosensitive resin film are poor.

[0003] Patent CN101017327A proposes a positive photosensitive resin precursor composition, which uses a cross-linking agent containing polyalkoxymethyl or hydroxymethyl and a cross-linking agent containing urea-type organic groups. The exposed part of the photosensitive resin prepared in this way is more soluble in alkaline developer, and the difference between the exposed area and the non-exposed area is clear, the sensitivity is high, and the heat resistance of the resin is improved; Patent CN111812943A reports a photosensitive resin composition, which uses a long-chain thermal cross-linking compound with multiple epoxy groups. This thermal cross-linking compound can provide low stress characteristics of the resin film and also improve the sensitivity of the cured film; However, after a lot of research, it was found that during the high-temperature curing process of the prepared photosensitive resin composition, the additionally added thermal cross-linking compound is difficult to fully participate in the reaction, and a small amount of small molecules will remain. These small molecules will slowly volatilize (referred to as outgas) during the application of the device, thereby adversely affecting the service life of the organic light-emitting device. Patent CN111848954A discloses a modified polyimide precursor composition, which introduces an alkoxymethyl compound with cross-linking properties into the diamine structural unit of the main chain, greatly reducing the outgas problem caused by the residual cross-linking compound molecules. However, the selected cross-linking compound is prone to high-temperature decomposition, which poses a considerable hidden danger to the heat stability of the organic light-emitting device. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a photosensitive polyimide resin composition. The thermal cross-linking compound introduced into the photosensitive polyimide resin composition can not only reduce the content of small molecular volatiles, but also avoid the high temperature decomposition of the cross-linking compound due to its own structure. At the same time, the photosensitive polyimide film prepared by the present invention has excellent chemical resistance and thermodynamic stability.

[0005] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions:

[0006] A photosensitive polyimide resin composition, i.e. a positive photosensitive resin composition, comprising 100 parts by weight of polyamic acid / polyamide ester (A) having a structural unit represented by general formula (1) and a structural unit represented by general formula (2), 1-50 parts by weight of a phenolic hydroxyl compound (B), 1-50 parts by weight of a photosensitizer (C) and 300-2000 parts by weight of an organic solvent (D);

[0007]

[0008] In the general formula (1), Ar1 represents a tetracarboxylic dianhydride residue having 1 to 6 aromatic rings, Ar2 represents a diamine residue having 1 to 6 aromatic rings and containing an unsaturated bond, and n represents an integer from 10 to 100,000, preferably an integer from 5,000 to 30,000;

[0009] Furthermore, the diamine residue containing an unsaturated bond represented by Ar2 is specifically selected from one or more structures represented by the following general formula (3) and / or general formula (4);

[0010]

[0011] In the formula, R1 and R2 are independently selected from organic groups having diamine residues and containing at least 2 to 30 carbon atoms; p and q are independently selected from integers of 1 to 10;

[0012] In the general formula (2), Ar1 represents a tetracarboxylic dianhydride residue having 1 to 6 aromatic rings, Ar3 represents a diamine residue having 1 to 10 aromatic rings, and n1 represents an integer from 10 to 100,000, preferably an integer from 5,000 to 50,000;

[0013] Furthermore, the diamine residue of the aromatic ring of Ar3 is specifically selected from the following general formula (7):

[0014]

[0015] In the formula, R6 and R7 represent a divalent to tetravalent organic group having a hydroxyl group and having 2 to 30 carbon atoms; R5 represents a trivalent to hexavalent organic group having a hydroxyl group or a fluorine atom and having 2 to 40 carbon atoms; n2 represents an integer from 100 to 3000, preferably an integer from 300 to 1000; k and s represent integers from 0 to 2, and i and j represent integers from 0 to 4;

[0016] Furthermore, the arrangement of the structural units represented by the general formula (1) and the structural units represented by the general formula (2) in (A) is block or random, and the ratio of the structural units represented by the general formula (1) to the structural units represented by the general formula (2) is 10:90 to 90:10. Considering that too many cross-linkable groups may result in some small molecules remaining, and too low a ratio may result in insufficient cross-linking density, the more preferred ratio is 20:80 to 60:40.

[0017] Preferably, the structure represented by the general formula (3) and / or the general formula (4) is a structure containing an acrylate group and / or a propiolate group, and is selected from one or more structures represented by the following formula (5) and / or formula (6);

[0018]

[0019] In the formula, R3 and R4 are independently selected from an organic group having a diamine residue and at least 2-25 carbon atoms, and y and z are independently selected from integers of 1-10.

[0020] Preferably, the structure represented by general formula (5) and / or general formula (6) is specifically selected from one or more of the following compounds:

[0021]

[0022]

[0023]

[0024] In Formula I-1 to Formula I-24, represents the diamine residue attachment site.

[0025] Preferably, the structure represented by general formula (7) is specifically selected from one or more of the following compounds:

[0026]

[0027]

[0028] In Formula II-1 to Formula II-10, represents the diamine residue attachment site.

[0029] In certain embodiments and comparative examples of 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.

[0030] Preferably, the tetracarboxylic dianhydride residue of the aromatic ring representing Ar1 in the general formula (1) and the general formula (2) is specifically selected from the following general formula (8):

[0031]

[0032] In the formula, R9, R 10 represents a trivalent or tetravalent organic group having 2 to 30 carbon atoms; R8 represents a trivalent to hexavalent organic group having 3 to 40 carbon atoms and having a hydroxyl group or a fluorine atom; R 11 , R 12 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; n3 represents an integer from 100 to 5000, preferably an integer from 500 to 1000; u and v represent an integer of 1 or 2, and g and h represent an integer of 0 to 4.

[0033] Furthermore, the structure represented by general formula (8) is specifically selected from one or more of the following compounds:

[0034]

[0035]

[0036] In Formula III-1 to Formula III-12, represents the tetracarboxylic dianhydride residue attachment site.

[0037] In certain embodiments and comparative examples of 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)propane dianhydride, ) ethane dianhydride, 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 other aromatic tetracarboxylic dianhydrides and 1,2,3,4-cyclopentanetetracarboxylic dianhydride and other aliphatic tetracarboxylic dianhydrides and the like.

[0038] In certain embodiments and comparative examples of the present invention, Ar1 and Ar3 in the structure of the polyimide resin (A) preferably contain F atom groups. This is because the F atom has a strong electronegativity, which can increase the light transmittance and hydrophobicity of the photosensitive polyimide resin cured film, and also can reduce the dielectric constant of the system.

[0039] In certain embodiments and comparative examples of the present invention, the polyimide resin (A) often contains a diphenyl ether structure. This is because the introduction of the diphenyl ether structure can improve the metal adhesion and heat resistance of the photosensitive polyimide resin cured film.

[0040] In certain embodiments and comparative examples of the present invention, in order to improve the adhesion between the photosensitive polyimide 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 film. The disiloxane compound is selected from 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.

[0041] In certain embodiments and comparative examples of the present invention, the polyimide resin (A) needs to use a capping agent to control the molecular weight of the polymer main chain. The capping agent used is preferably a monoamine compound, such as aniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-hydroxy-4-aminophenol, 3-hydroxy-5-aminophenol, 2-amino-4-hydroxyphenol, 3-amino-4-hydroxyphenol, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, etc.

[0042] In certain embodiments and comparative examples of 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. By reducing the proportion of carboxyl groups in the polymer, adding an alkylating agent, and alkylating the carboxyl groups to ester groups, the dissolution rate of the 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 film. Similarly, the content of ester groups should not be too large, which is not conducive to dissolution in alkaline aqueous solution. In the present invention, the amount of alkylating agent added is selected from 0.5 to 3.5 times the molar number of the polymerized monomer (tetracarboxylic dianhydride monomer Ar1), and more preferably 1.5 to 2.5 times. At this time, the imidization rate of the polyamide ester is within the range of 15% to 25%, and the photosensitive polyimide resin film has excellent sensitivity. The alkylating agent used in the present invention is preferably N,N-dimethylformamide dimethyl acetal (DMFDMA, hereinafter referred to as DFA), N,N-dimethylformamide diethyl acetal, 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.

[0043] In certain embodiments and comparative examples of the present invention, the solvent used for synthesizing the polyimide resin (A) is selected as a high-boiling point polar aprotic organic solvent, preferably N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, N-methylcaprolactam, dimethyl sulfoxide, etc.

[0044] The photosensitive polyimide resin composition of the present invention contains a phenolic hydroxyl compound (B). The photosensitive polyimide resin composition prepared by adding the phenolic hydroxyl compound has a non-exposed portion that is almost insoluble in an alkaline developer, and an exposed portion that is very easily soluble in an alkaline developer. The dissolution rates of the exposed area and the non-exposed area are significantly different, so that the development process can be accurately controlled and the sensitivity is improved.

[0045] For the phenolic hydroxyl compound (B) used in the present invention, the weight average molecular weight is preferably in the range of 300-800, and the addition ratio is preferably 1%-50% by weight, more preferably 3%-40% 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.

[0046] The photosensitive polyimide resin composition of the present invention contains (C) a photosensitizer. As the photosensitizer used in the present invention, a naphthoquinone diazide compound is usually selected. This type of naphthoquinone diazide compound is an ester compound formed by bonding a phenolic hydroxyl compound and a sulfonic acid compound of naphthoquinone diazide. Here, the phenolic hydroxyl compound used can be the same as or different from the compound containing a phenolic hydroxyl group (B).

[0047] The weight average molecular weight of the naphthoquinone diazide compound used in the present invention is preferably in the range of 300-1000, more preferably in the range of 350-800, and the addition ratio of the naphthoquinone diazide compound used is preferably 1%-50% by weight relative to 100 parts by weight of the polyimide resin (A).

[0048] The phenolic hydroxyl compound used in the (B) phenolic hydroxyl compound and the (C) photosensitizer in the photosensitive polyimide resin composition of the present invention preferably has the following structure:

[0049]

[0050]

[0051] In the photosensitive polyimide resin composition of the present invention, in order to improve the coating properties of the photosensitive polyimide film and the base substrate, the photosensitive resin composition also includes an organic solvent (D), 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, diisocyanate ... The invention relates to at least one of butyl 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, 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, and the solvent is preferably γ-butyrolactone.

[0052] In the photosensitive polyimide resin composition of the present invention, in order to improve the wettability of the photosensitive polyimide film and the base substrate, the photosensitive resin composition also includes a surfactant, such as ethanol, isopropanol, isobutyl alcohol, acetone, cyclohexanone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, ethyl lactate, propylene glycol methyl ether acetate, etc., one of which or several of which are mixed for use.

[0053] In the photosensitive polyimide resin composition of the present invention, in order to improve the adhesion between the photosensitive polyimide film and the base substrate, the photosensitive resin composition also includes a silane coupling agent, such as 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, N-(4-(triethoxysilyl)phenyl)acetamide and other aminosilane compounds and vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane and other vinylsilane compounds, one of which or several of which are selected and used in combination.

[0054] In order to improve the tensile properties and toughness of the photosensitive polyimide film, the photosensitive polyimide resin composition of the present invention further comprises at least one of inorganic particles and polyimide powder; the inorganic particles are selected from at least one of silicon dioxide and titanium dioxide.

[0055] Furthermore, the photosensitive polyimide resin composition used in the present invention and the method for producing the photosensitive polyimide film produced therefrom are described.

[0056] 1. Preparation method of photosensitive polyimide resin composition:

[0057] Under nitrogen protection, a reaction solvent, a diamine compound (Ar2), a diamine compound (Ar3) 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, a tetracarboxylic dianhydride compound (Ar1) is 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 the 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 vacuum filtration, washed with pure water 2-3 times, and then dried in a vacuum drying oven at 80°C for 48-72h to obtain a polyimide resin (A) solid. Then, component A, component B, component C and organic solvent D are mixed in a certain proportion to obtain a photosensitive polyimide resin composition slurry.

[0058] In certain embodiments and comparative examples of the present invention, in order to remove metal ions and impurities in the photosensitive polyimide resin composition slurry, the mixed composition slurry is filtered;

[0059] Among them, the pore size of the filter is preferably 0.01-5μm, more preferably 0.5μm, 0.2μm, 0.1μm, 0.05μm or 0.01μm, 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.

[0060] 2. Preparation method of photosensitive polyimide film:

[0061] 1) Preparing a pre-baked film: coating the filtered photosensitive polyimide resin composition slurry onto a base substrate, and then drying the pre-baked 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, ceramic, glass, quartz or ITO, etc.; the drying temperature is preferably in the range of 50°C to 150°C, more preferably in the range of 80°C to 130°C, and the drying time is preferably 1min to 60min; using a film thickness meter to test the thickness of the pre-baked film, at which time the thickness of the pre-baked film varies depending on the solid content and viscosity of the photosensitive polyimide resin composition slurry, and the thickness after drying is preferably in the range of 0.1 to 15μm, more preferably in the range of 5 to 10μm.

[0062] 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.

[0063] 3) Heat 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 with high heat resistance; Regarding the heat treatment method: the present invention selects a staged temperature increase at a heating rate of 2.5°C / min, the maximum curing temperature is preferably between 200°C and 300°C, and the curing time is preferably 30min to 90min.

[0064] The present invention also claims protection for a photosensitive polyimide film, wherein the photosensitive polyimide film comprises the photosensitive polyimide resin composition as described above.

[0065] Furthermore, the present invention also protects the application of a photosensitive polyimide film in the semiconductor field.

[0066] Specifically, it also includes: the use of the photosensitive polyimide in the passivation film, surface protection film of semiconductor devices and the interlayer insulation film on the semiconductor element circuit.

[0067] Compared with the prior art, the embodiments of the present invention have the following beneficial effects:

[0068] 1) A cross-linkable unsaturated hydrocarbon group is introduced into the main chain of the polyimide resin of the present invention. During the high-temperature imidization ring closure process, the olefin and / or alkyne unsaturated bonds begin to break, and a thermal cross-linking reaction occurs between and / or within the polymer molecules to obtain a dense and stable network structure, which can improve the chemical resistance and thermodynamic stability of the photosensitive polyimide film;

[0069] 2) The polyimide resin main chain of the present invention introduces a cross-linkable unsaturated hydrocarbon group, which does not require an external cross-linking agent, thereby reducing the problem of high-temperature decomposition and volatilization caused by small molecular residues of the cross-linking compound and increasing the service life of the semiconductor device;

[0070] 3) The sources of the raw materials used in the present invention are not particularly limited, and are generally commercially available; the synthesized photosensitive polyimide resin composition and its film route are not particularly limited;

[0071] 4) The photosensitive polyimide film prepared by the present invention can be applied to the passivation film, surface protection film, and interlayer insulating film on the semiconductor element circuit of the semiconductor device, especially, it can be applied to the insulating layer in the organic electroluminescent display device and the planarization layer between the thin film transistors (TFT). DETAILED DESCRIPTION

[0072] The technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0073] The evaluation methods of the embodiments and comparative examples are as follows:

[0074] (1) Determination of film thickness

[0075] The thickness of the pre-baked film and the cured film after the heat treatment of the photosensitive polyimide resin film were measured using a film thickness meter (field emission scanning electron microscope EX-30).

[0076] (2) Mechanical properties test

[0077] Several samples of photosensitive polyimide resin cured film were prepared and made into rectangular films with a size of 100 mm*10 mm. The film samples were stretched using a tensile testing machine (RTH-20-RACK1310, Japan) with a clamp spacing of 50 mm. The stress-strain curve was obtained by starting to stretch and the mechanical properties of the film, including tensile strength (MPa), elastic modulus (GPa) and elongation at break (%), were obtained.

[0078] (3) Evaluation of thermal stability and degree of thermal crosslinking

[0079] Several samples of photosensitive polyimide resin cured film were prepared and made into 13 mm × 4 mm rectangles. Thermomechanical expansion analyzer (TMA4000, Perkin Elmer) was used for testing. The fixture spacing was 10 mm. In the first stage, the temperature was increased to 150 °C at a heating rate of 10 °C / min and maintained for 30 min. In the second stage, the temperature was reduced to 25 °C at a rate of 5 °C / min. In the third stage, the sample was heated from 25 °C to 350 °C at a heating rate of 5 °C / min, and then naturally cooled to room temperature. The displacement versus temperature curve was obtained, and the thermal expansion coefficient (CTE) and glass transition temperature (T g ). The measured linear thermal expansion coefficient value above 45ppm / ℃ is considered to have poor thermal stability, the value within the range of 35-45ppm / ℃ is considered to have good thermal stability, and the value below 35ppm / ℃ is considered to have better thermal stability. Glass transition temperature T g Represents the motion performance of molecular chain segments, T g The larger the value, the smaller the molecular chain movement, indicating that the cross-linking degree is better, and vice versa, the cross-linking degree is poor. g ) values ​​below 250°C are considered to have a poor degree of thermal crosslinking, values ​​within the range of 250°C to 280°C are considered to have a good degree of thermal crosslinking, and values ​​above 280°C are considered to have a better degree of thermal crosslinking.

[0080] (4) Gas overflow test (outgas test)

[0081] Several samples of photosensitive polyimide resin cured film were prepared. The film samples were heated at 300°C for 60 minutes under helium purge. The residual small molecules overflowing from the film were adsorbed by gas adsorbent. The gas adsorbent was taken out and desorbed at 250°C for 10 minutes. At the same time, gas chromatography-mass spectrometry (GC-Ms) was used for test and analysis to calculate the content of residual small molecules overflowing from the film samples.

[0082] (5) Determination of sensitivity

[0083] The obtained pre-baked film of the photosensitive polyimide resin was exposed to the i line (365nm) using an exposure machine (SMA-150GA-TR). After exposure, it was developed in a developing device (AD-1200MIKASA) using a tetramethylammonium hydroxide aqueous solution with a mass concentration of 2.38% as a developing solution. This was repeated twice, and then washed with pure water and blown dry. The minimum exposure amount when the exposed part was completely dissolved was taken as the sensitivity.

[0084] (6) Chemical resistance test evaluation

[0085] Five samples of 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 min. 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 min. The film thickness of the film samples after etching was tested using a film thickness meter, and the difference in film thickness before and after etching was used as an evaluation of the film chemical resistance test.

[0086] The following will describe the embodiments / synthesis examples in conjunction with the technical solution, and the specific contents are as follows:

[0087] Synthesis Example 1 Synthesis of Hydroxyl Anhydride Compound (III-10)

[0088] At room temperature, 2,2-bis(3-amino-4-hydroxyphenyl)propane (0.05 mol) (CAS: 1220-78-6) and allyl glycidyl ether (0.3 mol) (CAS: 106-92-3) were added to a 1L three-necked reaction bottle and dissolved in 100g of γ-butyrolactone (GBL), and the reaction system was cooled to -15°C. Then, trimellitic anhydride chloride (0.11 mol) (CAS: 1204-28-0) dissolved in 50g 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 at below 0°C for 5h, and then naturally warmed to room temperature. The obtained reaction was concentrated by a rotary evaporator, and then injected into 1L of toluene for precipitation. After filtering, the solid was placed in a vacuum oven at 60°C and dried for 24h to obtain 23.96g (yield 79%) of hydroxyl anhydride compound (III-10).

[0089]

[0090] Synthesis Example 2 Synthesis of Hydroxyl-containing Diamine Compound (II-4)

[0091] At room temperature, add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.06 mol) (CAS: 83558-87-6), propylene oxide (0.36 mol) (CAS: 75-56-9) and 120 ml of 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 120 ml solution of m-nitrobenzoyl chloride (0.132 mol) (CAS: 121-90-4) in acetone. After the addition is complete, continue the reaction at -15°C for 5 hours, 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 20 hours to obtain 27.91 g of the intermediate (yield 70%).

[0092]

[0093] 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 hydrogen was replaced, and the pressure in the autoclave was pressurized with hydrogen to reach 10 kgf / cm2, and the temperature was raised to 35°C and stirred for 2 hours. After the reaction was completed, the pressure was slowly released, and the reaction solution was filtered under reduced pressure to obtain a transparent solution. Ethanol and petroleum ether were added to the solution, and the solid was precipitated by stirring for 12 hours, and the solid was filtered under reduced pressure to obtain a white solid. The solid was placed in a vacuum oven and dried at 50°C for 20 hours to obtain 9.97 g (yield 55%) of a hydroxyl-containing diamine compound (II-4).

[0094]

[0095] Synthesis Example 3 Synthesis of Hydroxyl-containing Diamine Compound (II-3)

[0096] At room temperature, add 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone (0.06 mol) (CAS: 7545-50-8), propylene oxide (0.36 mol) and 120 ml 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 120 ml acetone solution of m-nitrobenzoyl chloride (0.132 mol) thereinto. After the dropwise addition is complete, continue the reaction at -15°C for 5 hours, and then naturally warm to room temperature. The obtained reaction solution is filtered under reduced pressure to obtain a white solid, which is placed in a vacuum oven at 60°C and dried for 20 hours to obtain 26.03 g of the intermediate (yield 75%).

[0097]

[0098] 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 high-pressure reactor, and hydrogen was replaced, and the pressure in the reactor was pressurized with hydrogen to reach 10 kgf / cm2, and the temperature was raised to 35°C and stirred for 2 hours. After the reaction was completed, the pressure was slowly released, and the reaction solution was filtered under reduced pressure to obtain a transparent solution. Ethanol and petroleum ether were added to the solution, and the solution was stirred for 12 hours to precipitate solids, and the solids were filtered under reduced pressure to obtain white solids. The solids were placed in a vacuum oven and dried at 50°C for 20 hours to obtain 9.80 g (yield 63%) of hydroxyl-containing diamine compound (II-3).

[0099]

[0100] Synthesis Example 4 Synthesis of unsaturated bond-containing diamine compound (I-1)

[0101] Under nitrogen protection, 2,5-diaminophenol (0.08 mol) (CAS: 636-25-9) and ethyl 2,2,2-trifluoroacetate (0.18 mol) (CAS: 406-95-1) were added into a 1L three-necked reaction bottle in sequence and dissolved in 150 ml of a mixed solvent of triethylamine and methanol (volume ratio, 1:3). The mixture was stirred at 25°C until completely dissolved and reacted for 24 h. After the reaction was completed as monitored by TLC, the reaction solution was filtered under reduced pressure to obtain a transparent solution. Ethanol and petroleum ether were added to the solution, and the solution was stirred for 12 h to precipitate a solid. The solid was filtered under reduced pressure to obtain an off-white solid. The solid was placed in a vacuum oven and dried at 50°C for 24 h to obtain intermediate 1 (23.27 g, yield 92%).

[0102]

[0103] The intermediate 1 (0.06 mol) and triethylamine (0.18 mol) obtained above were added to 120 ml of acetone, stirred at room temperature until completely dissolved, the reaction system was cooled to -15°C, and then a 120 ml acetone solution of acryloyl chloride (0.066 mol) (CAS: 814-68-6) was slowly added dropwise thereto. After the addition was completed, the reaction was continued at -15°C for 3 h, then naturally warmed to room temperature and continued to react for 5 h. After the reaction was completed, the obtained reaction solution was filtered under reduced pressure to obtain a light yellow solid. The solid was placed in a vacuum oven at 50°C and dried for 24 h to obtain intermediate 2 (23.27 g, yield 92%).

[0104]

[0105] The intermediate 2 (0.05 mol) obtained above was added to 180 ml of alkaline ammonia solution and stirred at 25 ° C for 3 h. After the reaction was completed, 360 ml of a mixed solvent of ethanol and petroleum ether (volume ratio, 1:2) was added to the solution, and stirred for 12 h to precipitate a solid. After vacuum filtration, a white solid was obtained. The solid was placed in a vacuum oven at 50 ° C and dried for 24 h to obtain an unsaturated bond-containing diamine compound (I-1) (7.66 g, yield 86%).

[0106]

[0107] Synthesis Example 5 Synthesis of unsaturated bond-containing diamine compound (I-2)

[0108] The difference from Synthesis Example 4 is that 2,5-diaminophenol (0.08 mol) (CAS: 636-25-9) is replaced by 2,5-diaminobenzene-1,4-diol (0.08 mol) (CAS: 10325-89-0), and the other components and synthesis conditions remain unchanged, and an unsaturated bond-containing diamine compound (I-2) (7.22 g, yield 82%) is obtained.

[0109] Synthesis Example 6 Synthesis of unsaturated bond-containing diamine compound (I-3)

[0110] The difference from Synthesis Example 4 is that 2,5-diaminophenol (0.08 mol) (CAS: 636-25-9) is replaced by 3,3'-dihydroxybenzidine (0.08 mol) (CAS: 2373-98-0), and the other components and synthesis conditions remain unchanged, to obtain an unsaturated bond-containing diamine compound (I-3) (13.78 g, yield 85%).

[0111] Synthesis Example 7 Synthesis of unsaturated bond-containing diamine compound (I-5)

[0112] The difference from Synthesis Example 4 is that 2,5-diaminophenol (0.08 mol) (CAS: 636-25-9) is replaced by 5,5'-oxybis(2-aminophenol) (0.08 mol) (CAS: 20817-05-4), and the other components and synthesis conditions remain unchanged, to obtain an unsaturated bond-containing diamine compound (I-5) (14.63 g, yield 86%).

[0113] Synthesis Example 8 Synthesis of unsaturated bond-containing diamine compound (I-9)

[0114] The difference from Synthesis Example 4 is that 2,5-diaminophenol (0.08 mol) (CAS: 636-25-9) is replaced by 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.08 mol) (CAS: 83558-87-6), and acryloyl chloride (0.066 mol) (CAS: 814-68-6) is replaced by propioyl chloride (0.066 mol) (CAS: 50277-65-1), and other components and synthesis conditions remain unchanged, to obtain an unsaturated bond-containing diamine compound (I-9) (17.17 g, yield 73%).

[0115] Synthesis Example 9 Synthesis of Photosensitizer Naphthoquinone Diazide Compound (D-1)

[0116] At room temperature, 1,1,1-tri(4-hydroxyphenyl)ethane (IV-3) (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 the 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 (D-1) shown below.

[0117]

[0118] Synthesis Example 10 Synthesis of thermally crosslinked compound (V-1)

[0119] 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-3) (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 / 2s, after the drop is complete, stir at 25°C for 22 hours. The next day, slowly drop 15% dilute sulfuric acid aqueous solution (162 g) at room temperature, keep stirring for 36 hours 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 hours.

[0120] 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 dripped in, and stirring was maintained for 24 hours. After that, 5 g of anion exchange resin was added to the solution, stirred for 2 hours, 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 evenly. The solution was stirred at room temperature for 36 hours, white crystals precipitated, and solids were obtained by filtration. The solids were dried in a vacuum drying oven at 50°C for 24 hours to obtain a thermally cross-linked compound (V-1), which was retained for later use.

[0121]

[0122] Synthesis Example 11 Synthesis of thermally crosslinked compound (V-2)

[0123] Under nitrogen protection, 10 g of glycidyl methacrylate (CAS: 106-91-2) was dissolved in 100 ml of a mixed solution of water and tetrahydrofuran (volume ratio of 1:1), 1 g of sodium dithionite (CAS: 7775-14-6) and 0.2 g of sodium bicarbonate were added, and the mixture was stirred at 40 ° C for 8 h. After the reaction was completed, 200 ml of n-hexane was added to the reaction solution, and the mixture was stirred for 6 h to precipitate a solid. After reduced pressure filtration, a white solid was obtained. The solid was placed in a vacuum oven and dried at 50 ° C for 24 h to obtain 9.6 g of polyglycidyl methacrylate, i.e., a thermally cross-linked compound (V-2), which was retained for later use.

[0124]

[0125] Synthesis Example 12 Synthesis of thermally crosslinked compound (V-3)

[0126] Under nitrogen protection, bisphenol A (0.03 mol) (CAS: 80-05-7), formaldehyde (0.12 mol) and aniline (0.06 mol) were dissolved in 150 ml of a mixed solution of toluene and ethanol (volume ratio of 1:1), and reacted at room temperature for 5 h. After the reaction was completed, it was washed three times with a saturated sodium bicarbonate solution and distilled water in turn to obtain a light yellow colloidal substance, i.e., a thermally cross-linked compound (V-3), which was retained for later use.

[0127]

[0128] Synthesis Example 13 Synthesis of cross-linkable diamine compound (V-4)

[0129] Under nitrogen protection, 3,5-dimethoxy-4-methylbenzaldehyde (0.1 mol) (CAS: 1011-27-4) and 2,6-dimethoxyaniline (0.3 mol) (CAS: 2734-70-5) were added to a 100 ml three-necked flask, and the temperature was raised to 150 ° C for reaction for 3 hours. After the reaction was completed, the temperature was lowered to room temperature, 100 ml of ethanol was added, and the mixture was stirred for 2 hours to precipitate a solid. The solid was placed in a vacuum oven and dried at 50 ° C for 24 hours to obtain a cross-linkable diamine compound (V-4), which was retained for later use.

[0130]

[0131] Synthesis Example 14 Synthesis of polyimide resin (A-1)

[0132] Under dry nitrogen, the unsaturated bond-containing diamine compound (I-1) (18 mmol) in Synthesis Example 4, the hydroxyl-containing diamine compound (II-4) (27 mmol) in Synthesis Example 2 and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) (2.5 mmol) were dissolved in 150 g of N-methylpyrrolidone (NMP), added to the reaction bottle, heated to 50 ° C, and N, N'-((perfluoropropane-2,2-diacyl)bis(6-hydroxy-3,1-phenylene)bis(1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxamide) (III-7) (CAS: 223255-30 -9) (50.0mmol) and 20gNMP were added, and the reaction was continued for 2h. The end-capping agent 3-aminophenol (MAP) (2.5mmol) and 10gNMP were added, and the reaction was continued for 2h. After the reaction was completed, the alkylating agent N,N-dimethylformamide dimethyl acetal (DFA) (80mmol) and 10gNMP were added dropwise within 20 minutes, and stirring was continued at 50°C for 3h. Then, the reaction solution was cooled to room temperature, and the solution was slowly added to 2L of pure water to precipitate a white solid. The solid was collected by vacuum filtration, washed twice with pure water, and dried in a vacuum drying oven at 80°C for 48h to obtain 73.06g of polyimide resin (A-1).

[0133] Synthesis Example 15 Synthesis of polyimide resin (A-2)

[0134] The difference from Synthesis Example 14 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-2) in Synthesis Example 5 to obtain 71.88 g of polyimide resin (A-2).

[0135] Synthesis Example 16 Synthesis of polyimide resin (A-3)

[0136] The difference from Synthesis Example 14 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-3) in Synthesis Example 6 to obtain 75.31 g of polyimide resin (A-3).

[0137] Synthesis Example 17 Synthesis of polyimide resin (A-4)

[0138] The difference from Synthesis Example 14 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 to obtain 70.22 g of polyimide resin (A-4).

[0139] Synthesis Example 18 Synthesis of polyimide resin (A-5)

[0140] The difference from Synthesis Example 14 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-9) in Synthesis Example 8 to obtain 76.31 g of polyimide resin (A-5).

[0141] Synthesis Example 19 Synthesis of polyimide resin (A-6)

[0142] Under dry nitrogen, the unsaturated bond-containing diamine compound (I-1) (18 mmol) in Synthesis Example 4, the hydroxyl-containing diamine compound (II-3) (27 mmol) in Synthesis Example 3 and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) (2.5 mmol) were dissolved in 150 g of N-methylpyrrolidone (NMP), added to a reaction bottle, heated to 50°C, and the hydroxyl-containing anhydride compound (III-10) (50.0 mmol) and 20 g of NMP in Synthesis Example 1 were added, and the reaction was continued for 2 h. The end-capping agent 3-aminophenol (MAP) (2.5 mmol) and 10 g of NMP were added, and the reaction was continued for 2 h. After the reaction was completed, the alkylating agent N,N-dimethylformamide dimethyl acetal (DFA) (80 mmol) and 10 g of NMP were added dropwise within 20 minutes, and stirring was continued at 50°C for 3 h. The reaction solution was then cooled to room temperature and slowly added to 2 L of pure water to precipitate a white solid, which was collected by vacuum filtration, washed twice with pure water, and dried in a vacuum drying oven at 80°C for 48 hours to obtain 79.29 g of polyimide resin (A-6).

[0143] Synthesis Example 20 Synthesis of polyimide resin (A-7)

[0144] The difference from Synthesis Example 19 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-2) in Synthesis Example 5 to obtain 71.88 g of polyimide resin (A-7).

[0145] Synthesis Example 21 Synthesis of polyimide resin (A-8)

[0146] The difference from Synthesis Example 19 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-3) in Synthesis Example 6 to obtain 77.26 g of polyimide resin (A-8).

[0147] Synthesis Example 22 Synthesis of polyimide resin (A-9)

[0148] The difference from Synthesis Example 19 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 to obtain 76.45 g of polyimide resin (A-9).

[0149] Synthesis Example 23 Synthesis of polyimide resin (A-10)

[0150] The difference from Synthesis Example 19 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-9) in Synthesis Example 8 to obtain 75.10 g of a polyimide resin (A-10).

[0151] Synthesis Example 24 Synthesis of polyimide resin (A-11)

[0152] Under dry nitrogen, the unsaturated bond-containing diamine compound (I-1) (18 mmol), 4,4'-diaminodiphenyl ether (ODA) (27 mmol) and 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA) (2.5 mmol) in Synthesis Example 4 were dissolved in 150 g of N-methylpyrrolidone (NMP), added to a reaction bottle, heated to 50°C, 4,4'-oxydiphthalic anhydride (ODPA) (50.0 mmol) and 20 g of NMP were added, reacted for 2 h, capping agent 3-aminophenol (MAP) (2.5 mmol) and 10 g of NMP were added, and the reaction was continued for 2 h. After the reaction was completed, the alkylating agent N,N-dimethylformamide dimethyl acetal (DFA) (80 mmol) and 10 g of NMP were added dropwise within 20 minutes, and stirring was continued at 50°C for 3 h. The reaction solution was then cooled to room temperature and slowly added to 2 L of pure water to precipitate a white solid, which was collected by vacuum filtration, washed twice with pure water, and dried in a vacuum drying oven at 80°C for 48 hours to obtain 78.92 g of polyimide resin (A-11).

[0153] Synthesis Example 25 Synthesis of polyimide resin (A-12)

[0154] The difference from Synthesis Example 24 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-2) in Synthesis Example 5 to obtain 75.53 g of polyimide resin (A-7).

[0155] Synthesis Example 26 Synthesis of polyimide resin (A-13)

[0156] The difference from Synthesis Example 24 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-3) in Synthesis Example 6 to obtain 74.28 g of polyimide resin (A-13).

[0157] Synthesis Example 27 Synthesis of polyimide resin (A-14)

[0158] The difference from Synthesis Example 24 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 to obtain 72.85 g of polyimide resin (A-14).

[0159] Synthesis Example 28 Synthesis of polyimide resin (A-15)

[0160] The difference from Synthesis Example 24 is that the unsaturated bond-containing diamine compound (I-1) in Synthesis Example 4 is replaced with an equal amount of the unsaturated bond-containing diamine compound (I-9) in Synthesis Example 8 to obtain 72.33 g of a polyimide resin (A-15).

[0161] Synthesis Example 29 Synthesis of polyimide resin (A-16)

[0162] The difference from Synthesis Example 17 is that the amount of the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 (18 mmol) is changed to (9 mmol), and the amount of the hydroxyl diamine compound (II-4) in Synthesis Example 2 (27 mmol) is changed to (36 mmol), and 77.62 g of polyimide resin (A-16) is obtained.

[0163] Synthesis Example 30 Synthesis of polyimide resin (A-17)

[0164] The difference from Synthesis Example 17 is that the amount of the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 (18 mmol) is changed to (13.5 mmol), and the amount of the hydroxyl diamine compound (II-4) in Synthesis Example 2 (27 mmol) is changed to (31.5 mmol), and 73.81 g of polyimide resin (A-17) is obtained.

[0165] Synthesis Example 31 Synthesis of polyimide resin (A-18)

[0166] The difference from Synthesis Example 17 is that the amount of the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 (18 mmol) is changed to (22.5 mmol), and the amount of the hydroxyl diamine compound (II-4) in Synthesis Example 2 (27 mmol) is changed to (22.5 mmol), and 76.39 g of polyimide resin (A-18) is obtained.

[0167] Synthesis Example 32 Synthesis of polyimide resin (A-19)

[0168] The difference from Synthesis Example 17 is that the amount of the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 (18 mmol) is changed to (27 mmol), and the amount of the hydroxyl diamine compound (II-4) in Synthesis Example 2 (27 mmol) is changed to (18 mmol), and 75.06 g of polyimide resin (A-19) is obtained.

[0169] Synthesis Example 33 Synthesis of polyimide resin (A-20)

[0170] The difference from Synthesis Example 17 is that the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 is replaced with an equal amount of 4,4'-diaminodiphenyl ether (ODA) to obtain 76.19 g of a polyimide resin (A-20).

[0171] Synthesis Example 34 Synthesis of polyimide resin (A-21)

[0172] The difference from Synthesis Example 17 is that the unsaturated bond-containing diamine compound (I-5) in Synthesis Example 7 is replaced with an equal amount of the crosslinkable diamine compound (V-4) in Synthesis Example 13 to obtain 71.52 g of polyimide resin (A-21).

[0173] The components and amounts of polyimide resins (A-1) to (A-21) are shown in Table 1 below.

[0174] Table 1: Components and dosage of polyimide resins (A-1 to 21)

[0175]

[0176]

[0177] Example 1

[0178] Under nitrogen protection, 10 g of polyimide resin (A-1), 3.32 g of the naphthoquinone diazide compound (D-1) in Synthesis Example 9 and 1.25 g of a phenolic hydroxyl compound (IV-3) were added to a mixed solvent of 30 g of propylene glycol ethyl ether and 50 g of γ-butyrolactone (GBL), stirred at 25°C until completely dissolved, reacted for 6 hours, and the reaction solution was filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 0.01 μm to obtain a photosensitive polyimide resin composition (S-1).

[0179] The filtered photosensitive polyimide resin composition (S-1) was applied to a 6-inch silicon wafer by spin coating and dried at 120°C for 3 minutes to obtain a pre-baked film and silicon wafer assembly of about 10 μm. The thickness of the pre-baked film was measured using a film thickness meter. Next, the pre-baked film was exposed to the i-line (365 nm) of a mercury lamp through a mask, and a tetramethylammonium hydroxide developer with a mass concentration of 2.38% was used to dissolve the exposed part 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 200°C at a heating rate of 2.5°C / min, and each temperature was maintained for 10 minutes. Finally, the temperature was increased to 250°C, maintained at 250°C for heat treatment for 1 hour, and then cooled to below 50°C to obtain a cured film (F-1) of a photosensitive polyimide resin with high heat resistance.

[0180] The mechanical properties, sensitivity and gas outflow of the cured film (F-1) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-1) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0181] Example 2

[0182] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-2), thereby obtaining a photosensitive polyimide resin composition (S-2) and a cured film (F-2) of a highly heat-resistant photosensitive polyimide resin.

[0183] The mechanical properties, sensitivity and gas outflow of the cured film (F-2) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-2) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0184] Example 3

[0185] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-3), thereby obtaining a photosensitive polyimide resin composition (S-3) and a cured film (F-3) of a highly heat-resistant photosensitive polyimide resin.

[0186] The mechanical properties, sensitivity and gas outflow of the cured film (F-3) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-3) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0187] Example 4

[0188] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-4), thereby obtaining a photosensitive polyimide resin composition (S-4) and a cured film (F-4) of a highly heat-resistant photosensitive polyimide resin.

[0189] The mechanical properties, sensitivity and gas outflow of the cured film (F-4) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-4) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0190] Example 5

[0191] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-5), thereby obtaining a photosensitive polyimide resin composition (S-5) and a cured film (F-5) of a highly heat-resistant photosensitive polyimide resin.

[0192] The mechanical properties, sensitivity and gas outflow of the cured film (F-5) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-5) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0193] Example 6

[0194] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of polyimide resin (A-6), thereby obtaining a photosensitive polyimide resin composition (S-6) and a cured film (F-6) of a highly heat-resistant photosensitive polyimide resin.

[0195] The mechanical properties, sensitivity and gas outflow of the cured film (F-6) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-6) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0196] Example 7

[0197] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-7), thereby obtaining a photosensitive polyimide resin composition (S-7) and a cured film (F-7) of a highly heat-resistant photosensitive polyimide resin.

[0198] The mechanical properties, sensitivity and gas outflow of the cured film (F-7) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-7) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0199] Example 8

[0200] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-8), thereby obtaining a photosensitive polyimide resin composition (S-8) and a cured film (F-8) of a highly heat-resistant photosensitive polyimide resin.

[0201] The mechanical properties, sensitivity and gas outflow of the cured film (F-8) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-8) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0202] Example 9

[0203] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of polyimide resin (A-9), thereby obtaining a photosensitive polyimide resin composition (S-9) and a cured film (F-9) of a highly heat-resistant photosensitive polyimide resin.

[0204] The mechanical properties, sensitivity and gas outflow of the cured film (F-9) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-9) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0205] Example 10

[0206] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-10), thereby obtaining a photosensitive polyimide resin composition (S-10) and a cured film (F-10) of a highly heat-resistant photosensitive polyimide resin.

[0207] The mechanical properties, sensitivity and gas outflow of the cured film (F-10) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-10) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0208] Embodiment 11

[0209] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-11), thereby obtaining a photosensitive polyimide resin composition (S-11) and a cured film (F-11) of a highly heat-resistant photosensitive polyimide resin.

[0210] The mechanical properties, sensitivity and gas outflow of the cured film (F-11) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-11) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0211] Example 12

[0212] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-12), thereby obtaining a photosensitive polyimide resin composition (S-12) and a cured film (F-12) of a highly heat-resistant photosensitive polyimide resin.

[0213] The mechanical properties, sensitivity and gas outflow of the cured film (F-12) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-12) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0214] Example 13

[0215] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-13), thereby obtaining a photosensitive polyimide resin composition (S-13) and a cured film (F-13) of a highly heat-resistant photosensitive polyimide resin.

[0216] The mechanical properties, sensitivity and gas outflow of the cured film (F-13) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-13) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0217] Embodiment 14

[0218] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-14), thereby obtaining a photosensitive polyimide resin composition (S-14) and a cured film (F-14) of a highly heat-resistant photosensitive polyimide resin.

[0219] The mechanical properties, sensitivity and gas outflow of the cured film (F-14) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-14) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0220] Embodiment 15

[0221] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-15), thereby obtaining a photosensitive polyimide resin composition (S-15) and a cured film (F-15) of a highly heat-resistant photosensitive polyimide resin.

[0222] The mechanical properties, sensitivity and gas outflow of the cured film (F-15) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-15) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0223] Example 16

[0224] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of polyimide resin (A-16) to obtain a photosensitive polyimide resin composition (S-16) and a cured film (F-16) of a highly heat-resistant photosensitive polyimide resin.

[0225] The mechanical properties, sensitivity and gas outflow of the cured film (F-16) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-16) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0226] Embodiment 17

[0227] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of polyimide resin (A-17), thereby obtaining a photosensitive polyimide resin composition (S-17) and a cured film (F-17) of a highly heat-resistant photosensitive polyimide resin.

[0228] The mechanical properties, sensitivity and gas outflow of the cured film (F-17) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-17) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0229] Embodiment 18

[0230] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of polyimide resin (A-18), thereby obtaining a photosensitive polyimide resin composition (S-18) and a cured film (F-18) of a highly heat-resistant photosensitive polyimide resin.

[0231] The mechanical properties, sensitivity and gas outflow of the cured film (F-18) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-18) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0232] Embodiment 19

[0233] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of polyimide resin (A-19) to obtain a photosensitive polyimide resin composition (S-19) and a cured film (F-19) of a highly heat-resistant photosensitive polyimide resin.

[0234] The mechanical properties, sensitivity and gas outflow of the cured film (F-19) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-19) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0235] Comparative Example 1

[0236] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-20), thereby obtaining a photosensitive polyimide resin composition (S-20) and a cured film (F-20) of a highly heat-resistant photosensitive polyimide resin.

[0237] The mechanical properties, sensitivity and gas outflow of the cured film (F-20) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-20) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0238] Comparative Example 2

[0239] The difference from Example 1 is that the polyimide resin (A-1) is replaced with an equal mass of the polyimide resin (A-21), thereby obtaining a photosensitive polyimide resin composition (S-21) and a cured film (F-21) of a highly heat-resistant photosensitive polyimide resin.

[0240] The mechanical properties, sensitivity and gas outflow of the cured film (F-21) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-21) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0241] Comparative Example 3

[0242] The difference from Example 1 is that 8.15 g of the heat-crosslinking compound (V-1) was additionally added to obtain a photosensitive polyimide resin composition (S-22) and a cured film (F-22) of a photosensitive polyimide resin with high heat resistance.

[0243] The mechanical properties, sensitivity and gas outflow of the cured film (F-22) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-22) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0244] Comparative Example 4

[0245] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-20), and 8.15 g of thermal cross-linking compound (V-1) are additionally added to obtain a photosensitive polyimide resin composition (S-23) and a cured film (F-23) of a highly heat-resistant photosensitive polyimide resin.

[0246] The mechanical properties, sensitivity and gas outflow of the cured film (F-23) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-23) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0247] Comparative Example 5

[0248] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-20), and 8.15 g of thermal cross-linking compound (V-2) are additionally added to obtain a photosensitive polyimide resin composition (S-24) and a cured film (F-24) of a highly heat-resistant photosensitive polyimide resin.

[0249] The mechanical properties, sensitivity and gas outflow of the cured film (F-24) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-24) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0250] Comparative Example 6

[0251] The difference from Example 1 is that the polyimide resin (A-1) is replaced by an equal mass of polyimide resin (A-20), and 8.15 g of thermal cross-linking compound (V-3) are additionally added to obtain a photosensitive polyimide resin composition (S-25) and a cured film (F-25) of a highly heat-resistant photosensitive polyimide resin.

[0252] The mechanical properties, sensitivity and gas outflow of the cured film (F-25) of the photosensitive polyimide resin were tested, and the thermal stability, degree of thermal crosslinking and chemical resistance of the cured film (F-25) of the photosensitive polyimide resin were evaluated. The results are shown in Tables 2 and 3 below.

[0253] Table 1 below shows the components and amounts of the prepared polyimide resins (A-1) to (A-21); Tables 2 and 3 show the performance test data of the photosensitive polyimide films prepared in Examples 1 to 19 and Comparative Examples 1 to 6.

[0254] Table 2: Performance test data of photosensitive polyimide film

[0255]

[0256]

[0257] Table 3: Performance test data of photosensitive polyimide film

[0258]

[0259]

[0260] From the comparison data of Examples 6 to 15 and Examples 1 to 5, it can be seen that the mechanical properties, thermal stability, degree of thermal crosslinking, outgassing evaluation and sensitivity test of the photosensitive polyimide films of Examples 1 to 5 are better than those of the photosensitive polyimide films of Examples 6 to 15. The reason is that the Ar1 monomer (carboxylic acid dianhydride) and Ar3 monomer (diamine) used in the photosensitive polyimide resin compositions of Examples 1 to 5 contain F atoms, hydroxyl groups, amide groups and the like, and the excess F atoms easily form hydrogen bonds with the hydroxyl groups and / or acyl groups in the molecular chain, so that the formed photosensitive polyimide film exhibits excellent mechanical properties and transmittance, and the hydroxyl groups and amide groups contained can promote the dissolution of the photosensitive polyimide film, while improving the heat resistance and mechanical properties of the film.

[0261] By comparing Examples 16 to 19 with Example 4, it can be seen that by controlling the ratio of the two diamine compounds (Ar2 and Ar3), when Ar3 / Ar2 is 1.5, the thermodynamic properties exhibited by the photosensitive polyimide film are more stable, and the sensitivity is also more excellent; for Examples 16 and 17 (Ar3 / Ar2 is greater than 1.5), too few cross-linkable unsaturated groups lead to insufficient degree of thermal cross-linking, and the mechanical properties of the formed photosensitive polyimide film are significantly reduced. At the same time, the chemical resistance and thermal stability are not good; for Examples 18 and 19 (Ar3 / Ar2 is less than 1.5), too many cross-linkable unsaturated groups, although the degree of thermal cross-linking is excellent, which increases the mechanical properties and chemical resistance of the photosensitive polyimide film, but too many cross-linking groups do lead to the volatilization of small molecular gases, which is not convenient for the later use of the device, and also reduces the sensitivity of the photosensitive polyimide film.

[0262] From the comparison between Comparative Example 1 and Example 1, it can be seen that when no thermal cross-linking compound is introduced into the photosensitive polyimide resin composition, the thermodynamic properties of the formed photosensitive polyimide film are not good, and the photosensitivity of the polyimide resin film is also poor.

[0263] From the comparison between Comparative Example 2 and Example 1, it can be seen that the photosensitive polyimide film formed by introducing the cross-linkable diamine compound having an alkoxy group into the photosensitive polyimide resin composition has poor mechanical properties and a high gas outflow.

[0264] It can be seen from the comparison between Comparative Example 3 and Example 1 that the introduction of too much thermal cross-linking compound component and amount into the photosensitive polyimide resin composition will seriously increase the gas outflow of the photosensitive polyimide film.

[0265] From the comparison of Comparative Examples 4 to 6 with Example 1, it can be seen that the thermally cross-linked compounds (cross-linkable compounds having alkoxy groups, cross-linkable compounds having epoxy groups, cross-linkable compounds having benzoxazine) additionally added to the photosensitive polyimide resin composition are difficult to fully participate in the reaction. Although the mechanical properties of the photosensitive polyimide film are significantly improved, the gas overflow problem of the photosensitive polyimide film cannot be improved.

[0266] In summary, in the present invention, by adding a cross-linkable diamine compound (Ar2), a highly photosensitive polyimide film having high heat resistance and chemical resistance as well as excellent mechanical properties and low gas outflow can be obtained.

[0267] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A photosensitive polyimide resin composition, characterized in that: The photosensitive polyimide resin composition comprises 100 parts by weight of polyamic acid / polyamide ester (A) having a structural unit represented by general formula (1) and a structural unit represented by general formula (2), 1-50 parts by weight of a phenolic hydroxyl compound (B), 1-50 parts by weight of a photosensitizer (C) and 300-2000 parts by weight of an organic solvent (D); In the general formula (1) and the general formula (2), Ar1 represents a tetracarboxylic dianhydride residue having 1 to 6 aromatic rings; In the general formula (1), Ar2 represents a diamine residue having 1 to 6 aromatic rings and containing an unsaturated bond, and n represents an integer from 10 to 100,000; Furthermore, the diamine residue containing an unsaturated bond represented by Ar2 is specifically selected from a structure containing an acrylate group and / or a propiolate group, and is selected from one or more structures represented by the following formula (5) and / or formula (6); In the formula, R3 and R4 are independently selected from organic groups having diamine residues and containing at least 2 to 25 carbon atoms, and y and z are independently selected from integers of 1 to 10; The structure represented by general formula (5) and / or general formula (6) is specifically selected from one or more of the following compounds: In Formula I-1 to Formula I-24, represents the diamine residue attachment site; In the general formula (2), Ar3 represents a diamine residue having 1 to 10 aromatic rings, and n1 represents an integer from 10 to 100,000; Furthermore, the diamine residue of the aromatic ring of Ar3 is specifically selected from the following general formula (7): In the formula, R6 and R7 represent a divalent to tetravalent organic group having a hydroxyl group and having 2 to 30 carbon atoms; R5 represents a trivalent to hexavalent organic group having a hydroxyl group or a fluorine atom and having 2 to 40 carbon atoms; n2 represents an integer from 100 to 3000; k and s represent integers from 0 to 2, and i and j represent integers from 0 to 4; And, the arrangement of the structural units represented by the general formula (1) and the structural units represented by the general formula (2) in (A) is block or random, and the ratio of the structural units represented by the general formula (1) to the structural units represented by the general formula (2) is 10:90 to 90:

10.

2. The photosensitive polyimide resin composition according to claim 1, characterized in that: In the general formula (1), n ​​represents an integer from 5000 to 30000; in the general formula (2), n1 represents an integer from 5000 to 50000; in the general formula (7), n2 represents an integer from 300 to 1000; the ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) is 20:80 to 60:

40.

3. The photosensitive polyimide resin composition according to claim 1, characterized in that: The structure represented by general formula (7) is specifically selected from one or more of the following compounds: In Formula II-1 to Formula II-10, represents the diamine residue attachment site.

4. The photosensitive polyimide resin composition according to claim 1, characterized in that: The tetracarboxylic dianhydride residue of the aromatic ring representing Ar1 in the general formula (1) and the general formula (2) is specifically selected from the following general formula (8): In the formula, R9, R 10 represents a trivalent or tetravalent organic group having 2 to 30 carbon atoms; R8 represents a trivalent to hexavalent organic group having 3 to 40 carbon atoms and having a hydroxyl group or a fluorine atom; R 11 , R 12 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; n3 represents an integer from 100 to 5000; u and v represent an integer from 1 or 2; and g and h represent an integer from 0 to 4.

5. The photosensitive polyimide resin composition according to claim 4, characterized in that: In the general formula (8), n3 represents an integer of 500 to 1,000.

6. The photosensitive polyimide resin composition according to claim 5, characterized in that: The structure represented by general formula (8) is specifically selected from one or more of the following compounds: In Formula III-1 to Formula III-12, represents the tetracarboxylic dianhydride residue attachment site.

7. The photosensitive polyimide resin composition according to claim 1, characterized in that: Ar1 and Ar3 in the structure of the polyimide resin (A) contain F atomic groups, and the structure of the polyimide resin (A) contains multiple diphenyl ether structures; A disiloxane compound is copolymerized in the main chain of the polyimide resin (A), and the disiloxane compound is selected from 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA), 1,3-bis(4-anilino)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane or 1,3-bis(4-aminopropyl)tetramethyldisiloxane; The polyimide resin (A) uses a capping agent to control the molecular weight of the polymer main chain, and the capping agent is a monoamine compound, specifically aniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-hydroxy-4-aminophenol, 3-hydroxy-5-aminophenol, 2-amino-4-hydroxyphenol, 3-amino-4-hydroxyphenol, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-6-aminonaphthalene or 2-hydroxy-7-aminonaphthalene.

8. The photosensitive polyimide resin composition according to any one of claims 1 to 7, characterized in that: The weight average molecular weight of the phenolic hydroxyl compound (B) is 300-800, and the addition ratio is 3%-40% by weight relative to 100 parts by weight of the polyimide resin (A); The photosensitizer (C) is a naphthoquinone diazide compound, and the weight average molecular weight of the naphthoquinone diazide compound is 300-1000.

9. The photosensitive polyimide resin composition according to claim 8, characterized in that: The weight average molecular weight of the naphthoquinonediazide compound is 350-800.

10. The photosensitive polyimide resin composition according to any one of claims 1 to 7, characterized in that: The organic solvent (D) is at least 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 One of ketone, diacetone 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.

11. The photosensitive polyimide resin composition according to claim 1, characterized in that: The photosensitive polyimide resin composition also includes a surfactant and a silane coupling agent; Wherein, the surfactant is at least one of ethanol, isopropanol, isobutanol, acetone, cyclohexanone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, ethyl lactate, and propylene glycol methyl ether acetate; The silane coupling agent is at least one of aminosilane compounds such as 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, and N-(4-(triethoxysilyl)phenyl)acetamide, and vinylsilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and vinyltri(β-methoxyethoxy)silane.

12. The photosensitive polyimide resin composition according to claim 1, characterized in that: The photosensitive polyimide resin composition further comprises inorganic particles and polyimide powder; the inorganic particles are at least one of silicon dioxide and titanium dioxide.

13. A photosensitive polyimide film, characterized in that: The invention comprises the photosensitive polyimide resin composition as claimed in claim 1.

14. Use of the photosensitive polyimide film according to claim 13 in the semiconductor field.

15. The use according to claim 14, characterized in that: Also includes: The photosensitive polyimide is used in the passivation film, surface protection film of semiconductor devices and the interlayer insulation film on the semiconductor element circuit.

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