Negative photosensitive polyimide precursor resin composition

Abstract

Disclosed in the present invention is a negative photosensitive polyimide precursor resin composition, which comprises: 100 parts by mass of a polyamic acid ester; 5-20 parts by mass of a photo-crosslinking agent containing an amic acid structure; 0.5-5 parts by mass of a photopolymerization initiator; 0.5-5 parts by mass of a silane coupling agent; 0.01-1 part by mass of a polymerization inhibitor; 0.5-4 parts by mass of a thermal base generator; 1-5 parts by mass of a bridging agent; 0.5-3 parts by mass of an antioxidant; and 0.1-2 parts by mass of a bonding aid; the structural general formula of the photo-crosslinking agent is represented by Formula (1): , wherein X is a tetravalent organic group containing a cyclic structure, Y is a divalent organic group, and R1, R2, R3, R1', R2' and R3' are each independently selected from a hydrogen atom and an alkyl group having 1-3 carbon atoms. The composition provided by the present invention can enable the polyimide material after low-temperature curing to have good thermal / mechanical properties, chemical corrosion resistance and photolithographic performance.

Description

A negative photosensitive polyimide precursor resin composition TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic packaging, in particular to a negative photosensitive polyimide precursor resin composition. BACKGROUND

[0002] Photosensitive polyimide (PSPI) materials are widely used in integrated circuit chip surface passivation and surface re-routing processes of wafer-level packaging and panel-level packaging, and are indispensable key materials in wafer-level advanced packaging processes. Traditional PSPI materials require a curing temperature of 350℃ or higher to obtain excellent performance. Low-temperature curing PSPI materials often have poor mechanical properties and poor chemical corrosion resistance due to insufficient imidization, and cannot meet the requirements of packaging processes. In addition, they also have poor device reliability due to poor adhesion to other materials in the packaging process, especially electroplated copper. However, high-density fan-out wafer-level packaging and other advanced packaging processes are prone to wafer warping, stress cracking, and poor compatibility with other packaging materials at high temperatures. Therefore, in order to meet the needs of wafer-level low stress and low warping in advanced packaging processes, it is urgent to develop low-temperature curing PSPI, especially ultra-low temperature curing PSPI with a curing temperature below 200℃.

[0003] In the prior art, the introduction of photo / thermal alkali generators can reduce the activation energy of polyimide precursor resin imidization and thus realize low-temperature process to obtain polyimide resin with excellent performance, such as CN112639616A, CN112513219A, CN112639615A, CN111919172A; or control the molecular weight of the precursor resin, so that the molecular chain of the polymer can have high enough movement ability to improve the imidization rate, such as CN108475020A. For example, CN112334833A introduces a polymeric compound containing urethane and urea bond structures, CN110741318A and CN113168093A introduce a polymeric compound containing sulfite structures to obtain a low-temperature curing polyimide with high imidization rate, good chemical resistance, and excellent copper surface adhesion. In addition, in order to improve the adhesion of the re-routing layer to the copper surface, copper surface aids will be introduced into the polyimide, such as CN102375336B / CN112799281A.

[0004] In addition, the most prominent problem of low-temperature cured PSPI materials is that the chemical corrosion resistance cannot meet the process requirements of wafer-level packaging process, mainly because most of the additives, especially the photo-crosslinking additives and the polymerizable functional groups contained in the polyimide precursor, still remain in the cured film at ultra-low curing temperature. These additive residues result in much poorer chemical corrosion resistance compared to intrinsic polyimide. To improve this problem, rigid photo-crosslinking agents with aliphatic cyclic skeletons are generally introduced to enhance the rigidity of the molecular structure of the residues in the cured film to improve its chemical corrosion resistance, such as CN110520795A, or multifunctional crosslinking agents are introduced to enhance the crosslinking density of the residues in the cured film to improve its chemical corrosion resistance, such as CN111936930A and CN110300767A. However, the above methods cannot simultaneously improve or enhance the comprehensive performance of the polyimide cured film, limiting the further application of the polyimide cured film.

[0005] SUMMARY

[0006] In order to improve the chemical corrosion resistance of low-temperature cured PSPI and the device reliability in semiconductor packaging, the present application provides a negative photosensitive polyimide precursor resin composition. The negative photosensitive polyimide precursor resin composition provided by the present application adds a photo-crosslinking agent containing an amic acid structure, which can form an imide structure with good chemical stability and thermal stability in the low-temperature curing process after exposure. At the same time, it has a similar chemical structure to the polyimide main resin, and the strong intermolecular interaction between the imide rings makes the cured film have excellent thermodynamic properties and chemical stability.

[0007] To achieve the above object, the technical scheme adopted by the present application is:

[0008] In one aspect, the present application provides a negative photosensitive polyimide precursor resin composition, comprising:

[0009] 100 parts by mass of a polyamic acid resin as a polyimide precursor;

[0010] 5-20 parts by mass of a photo-crosslinking agent containing an amic acid structure;

[0011] 0.5-5 parts by mass of a photopolymerization initiator;

[0012] 0.5-5 parts by mass of a silane coupling agent;

[0013] 0.01-1 parts by mass of a polymerization inhibitor;

[0014] 0.5-4 parts by mass of a thermal base generator;

[0015] 1-5 parts by mass of a bridging agent;

[0016] 0.5 to 3 parts by mass of an antioxidant;

[0017] 0.1 to 2 parts by mass of an adhesion aid;

[0018] wherein the photo-crosslinking agent has a general structure as shown in formula (1):

[0019] In formula (1), X is a 4-valent organic group containing a cyclic structure, Y is a 2-valent organic group, and R1, R2, R3, R1', R2', and R3' are each independently selected from any one of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms.

[0020] In the technical solution of the present application, the cyclic structure is selected from one or more of an aromatic group or a saturated / unsaturated cyclic hydrocarbon structure.

[0021] In the technical solution of the present application, the 2-valent organic group is an organic group containing an aromatic group and / or a fatty chain having 2 to 8 carbon atoms.

[0022] As a preferred embodiment, R1 = R1'; R2 = R2'; and R3 = R3'.

[0023] In some specific embodiments, X can be exemplified by:

[0024] In some specific embodiments, Y can be exemplified by:

[0025] In some specific embodiments, the photo-crosslinking agent can be exemplified by:

[0026] As a preferred embodiment, the method for preparing the photo-crosslinking agent comprises the following steps:

[0027] Step (1) reacting a diamine containing a Y group, a group donor, and / or a group donor to obtain an amide product of a single-end amine group reaction;

[0028] Step (2) reacting the product obtained in Step (1) with a dianhydride containing an X group to obtain the photo-crosslinking agent.

[0029] In some specific embodiments, the reactions in Steps (1) and (2) are carried out under the catalysis of an organic base.

[0030] In some specific embodiments, the reactions in Steps (1) and (2) are carried out in an organic solvent; the organic solvent is preferably an organic solvent that can completely dissolve the reaction raw materials and / or products and does not contain a hydroxyl group or an amino group;

[0031] The theoretical value of the molar ratio of the tetracarboxylic dianhydride containing X group and the diamine containing Y group is 1:2;

[0032] In the technical solution of the present application, the group donor and The theoretical value of the ratio of the total amount of substance of the group donor and the group donor to the amount of substance of the diamine containing Y group is 1:1;

[0033] In the preferred embodiment, the group donor and The group donor and the group donor are their corresponding acyl chloride compounds;

[0034] In the technical solution of the present application, the reaction temperature in step (1) is preferably -10℃ to 10℃, and the reaction time in step (1) is preferably 2 to 6h;

[0035] In some specific embodiments, step (1) further comprises a purification post-treatment;

[0036] In the technical solution of the present application, the reaction temperature in step (2) is preferably 15 to 50℃, and the reaction time in step (2) is preferably 2 to 12h;

[0037] In some specific embodiments, step (2) further comprises a purification post-treatment; the purification post-treatment is to precipitate the photocrosslinking agent with a poor solvent;

[0038] In the technical solution of the present application, the tetracarboxylic dianhydride containing X group is not particularly limited, and can be specifically listed as pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenyl methane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, more preferably pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, etc., which can be used alone or in any mixture.

[0039] In the technical solution of the present application, the diamine containing Y group is not particularly limited, and can specifically include p-phenylenediamine, m-phenylenediamine, 4,4'-diamino diphenyl ether, 3,4'-diamino diphenyl ether, 3,3'-diamino diphenyl ether, 4,4'-diamino diphenyl sulfide, 3,4'-diamino diphenyl sulfide, 3,3'-diamino diphenyl sulfide, 4,4'-diamino diphenyl sulfone, 3,4'-diamino diphenyl sulfone, 3,3'-diamino diphenyl sulfone, 4,4'-diamino diphenyl, 3,4'-diamino diphenyl, 3,3'-diamino diphenyl, 4,4'-diamino benzophenone, 3,4'-diamino benzophenone, 3,3'-diamino benzophenone, 4,4'-diamino diphenyl methane, 3,4'-diamino diphenyl methane, 3,3'-diamino diphenyl methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyl dimethylsilyl)benzene, 3,3'-dimethyl-4,4'-diamino diphenyl sulfone, 9,9-bis(4-aminophenyl)fluorene, and the like, which can be used alone or in any mixture.

[0040] As a preferred embodiment, the polyamic acid ester includes a repeating unit represented by formula (2):

[0041] In formula (2), Z1 is a 4-valent organic group containing an aromatic group, Z2 is a 2-valent organic group containing an aromatic group, R4 and R5 are each independently selected from a 1-valent organic group having a structure represented by formula (3), and m is 2 to 150.

[0042] In formula (3), R6, R7, and R8 are each independently selected from a hydrogen atom, an alkyl group having a carbon atom number of 1 to 3; and n is 2 to 10.

[0043] As a preferred embodiment, the method for preparing the polyamic acid ester includes the following steps:

[0044] The tetracarboxylic dianhydride containing the Z1 group, the alcohol containing R4, and the alcohol containing R5 are reacted to produce a partially esterified tetracarboxylic acid, or the tetracarboxylic dianhydride containing the Z1 group, the alcohol containing R4, the alcohol containing R5, and a saturated aliphatic alcohol having 1 to 4 carbon atoms are reacted to produce a partially esterified tetracarboxylic acid, and then the partially esterified tetracarboxylic acid is subjected to amide polycondensation with the diamine containing the Z2 group.

[0045] The tetracarboxylic dianhydride containing the Z1 group is not particularly limited, and specifically, phtalic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenyl methane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and the like can be exemplified, and phtalic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride are preferable, and phtalic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride are more preferable, and the above can be used alone or in any mixture.

[0046] The alcohol containing R4 or the alcohol containing R5 is not particularly limited, and specifically, 2-propenoyloxy ethanol, 1-propenoyloxy-3-propanol, 2-propenoylamido ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxy ethanol, 1-methacryloyloxy-3-propanol, 2-methacryloylamido ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, and the like can be exemplified, and the above can be used alone or in any mixture.

[0047] The saturated aliphatic alcohol having 1 to 4 carbon atoms is not particularly limited, and specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and the like can be exemplified, and the above can be used alone or in any mixture.

[0048] The above-described tetracarboxylic dianhydride and the above-described alcohol are preferably stirred at 20 to 50°C in a suitable reaction solvent in the presence of a basic catalyst such as pyridine for 4 to 10 hours to obtain a partially esterified tetracarboxylic acid.

[0049] As the solvent in the above-described reaction, a solvent capable of completely dissolving the raw materials and / or the product is preferred, and a solvent capable of completely dissolving the polyimide precursor is more preferred. As such a solvent, specifically, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethyl urea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and the like can be exemplified, and these can be used alone or in any mixture.

[0050] The solution containing the partially esterified tetracarboxylic acid obtained in the above-described reaction is preferably added to a dehydration condensing agent under ice-cooling to obtain a polyacid anhydride, and then a diamine containing a Y group or a solution thereof is added to obtain the target polyamide acid ester by amide polycondensation.

[0051] As the dehydration condensing agent in the above-described reaction, there is no particular limitation, and specifically, dicyclohexyl carbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and the like can be exemplified, and these can be used alone or in any mixture.

[0052] As the diamine containing the Z2group, there is no particular limitation, and specific examples include p-phenylenediamine, m-phenylenediamine, 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, 4,4'-thiodianiline, 3,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-sulfonophenylamine, 3,4'-sulfonophenylamine, 3,3'-sulfonophenylamine, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)diphenyl, 4,4-bis(3-aminophenoxy)diphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyl dimethylsilyl)benzene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 9,9-bis(4-aminophenyl)fluorene, and the like, and these can be used alone or in any mixture.

[0053] As a preferred embodiment, the photopolymerization initiator is selected from any one or more of oxime ester compounds, benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, alkylanthraquinone, benzoin alkyl ether, benzoin, alkylbenzoin, and benzil dimethyl ketal, and is further preferably an oxime ester compound.

[0054] In the technical solution of the present application, the silane coupling agent is not particularly limited, and is preferably any one or more of silane coupling agents containing a urea bond (-NH-CO-NH-);

[0055] In particular, the silane coupling agent is selected from any one or more of ureidopropyltriethoxysilane, gamma-aminopropyl dimethoxysilane, N-(beta-aminoethyl)-gamma- aminopropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma- mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3- methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy- 3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3- (triethoxysilyl)propyl]phthalamidic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)- 2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, and N-phenylaminopropyl trimethoxysilane, preferably ureidopropyltriethoxysilane.

[0056] In the technical solution of the present application, the polymerization inhibitor is not particularly limited, and is preferably any one or more of a phenolic radical polymerization inhibitor;

[0057] In particular, the polymerization inhibitor is selected from any one or more of hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, preferably 2-nitroso-1-naphthol.

[0058] As a preferred embodiment, the heat-generating base-generating agent is a tert-butyloxycarbonyl-protected amine compound, the amine compound in the tert-butyloxycarbonyl-protected amine compound being selected from any one or more of ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanediol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybisethanolamine, 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, and diethylene glycol bis(3-aminopropyl) ether.

[0059] Preferably, the heat-generating base-generating agent is N-tert-butyloxycarbonyl-4-piperidinemethanol.

[0060] As a preferred embodiment, the bridging agent is an amino resin;

[0061] Preferably, the bridging agent is selected from any one or more of a glycol urea resin, a hydroxy ethylene urea resin, and a melamine resin, particularly preferably an alkoxymethylated melamine compound, such as hexamethoxymethyl melamine.

[0062] As a preferable embodiment, the antioxidant is a hindered phenol antioxidant, preferably a compound having a hindered structure at the ortho carbon atom of the phenolic hydroxyl group, and specifically, one or more of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)hydrazine, 2,2-oxamidyl-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 2,2'-thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] and the like, and particularly preferably one or more of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate and the like, and the above-listed compounds can be used alone or in any mixture.

[0063] As a preferable embodiment, the adhesion aid is an azole compound;

[0064] Preferably, the adhesion aid is one or more of any of 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, phenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole and 1-methyl-1H-tetrazole, and particularly preferably one or more of 1H-benzotriazole, 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole; in the technical solution of the present application, the adhesion aid can improve the adhesion strength at the interface with the metal substrate.

[0065] As a preferable embodiment, an organic solvent is further included;

[0066] Preferably, the organic solvent is selected from any one or more of esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides;

[0067] Preferably, the esters are selected from any one or more of ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate, alkyl 3-alkoxypropionate, alkyl 2-alkoxypropionate, methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate and ethyl 2-oxobutyrate;

[0068] Preferably, the ethers are selected from any one or more of diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate;

[0069] Preferably, the ketones are selected from any one or more of methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone and 3-heptanone;

[0070] Preferably, the aromatic hydrocarbons are selected from any one or more of toluene, xylene, anisole and limonene;

[0071] Preferably, the amides are selected from any one or more of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide.

[0072] Preferably, the organic solvent is selected from any one or more of N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide and N,N-dimethylacetamide, in consideration of solubility of each component and resin film coatability;

[0073] In the technical solution of the present application, the amount of the organic solvent is determined so that the negative photosensitive polyimide precursor resin composition can obtain a uniform glue solution; in some specific embodiments, in order to meet the requirement of glue coating thickness, the amount of the organic solvent is determined so that the viscosity of the negative photosensitive polyimide precursor resin composition is 20-80 poise.

[0074] In another aspect, the present application provides a negative photosensitive polyimide resin composition obtained by thermal imidization of the above-mentioned negative photosensitive polyimide precursor resin composition, wherein the thermal imidization is preferably performed at a temperature of 150 to 400°C.

[0075] In the technical solution of the present application, the above-mentioned negative photosensitive polyimide precursor resin composition can be cured by thermal imidization to obtain a cured negative photosensitive polyimide resin composition, and can also be prepared into a patterned negative photosensitive polyimide resin composition by using a mask with a specific pattern.

[0076] The method for preparing the patterned negative photosensitive polyimide resin composition comprises the following steps:

[0077] (1) coating the above-mentioned negative photosensitive polyimide precursor resin composition on a substrate to form a negative photosensitive polyimide precursor resin layer on the substrate;

[0078] (2) exposing the negative photosensitive polyimide precursor resin layer on the substrate;

[0079] (3) developing the exposed negative photosensitive polyimide precursor resin layer to form a pattern;

[0080] (4) heating the pattern to form a cured pattern.

[0081] In step (1), the coating method is not particularly limited, and methods such as spin coating, blade coating, screen printing, spray coating, etc. can be used, and then the negative photosensitive polyimide precursor resin layer is formed by drying as needed; the drying method can be heating drying using an oven or a hot plate, vacuum drying, etc.; and the substrate can be a metal substrate such as Cu, a glass substrate, a semiconductor substrate, a metal oxide insulator (TiO2, SiO2, etc.), a silicon nitride substrate, etc.

[0082] Preferably, the drying is performed under conditions in which the polyamic acid ester in the negative photosensitive polyimide precursor resin composition does not undergo imidization; specifically, the drying is performed at 70 to 130°C for 1 to 10 minutes.

[0083] In step (2), the negative photosensitive polyimide precursor resin layer is exposed through a mask with a specific pattern; the exposure device used can be a parallel exposure machine, a projection exposure machine, a step exposure machine, a scanning exposure machine, etc.; and the light source used can be ultraviolet light, visible light, or radioactive rays, etc.

[0084] In step (3), the unexposed part of the negative photosensitive polyimide precursor resin layer after exposure is removed using a developing solution to form a pattern; the developing agent used is a good solvent for the negative photosensitive polyimide precursor resin layer or a mixed solvent of a good solvent and a poor solvent.

[0085] As the good solvent, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, cyclohexanone, and the like can be exemplified, and the above exemplifications can be used singly or arbitrarily mixed;

[0086] As the poor solvent, toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water, and the like can be exemplified, and the above exemplifications can be used singly or arbitrarily mixed;

[0087] When the mixed solvent of the good solvent and the poor solvent of the negative photosensitive polyimide precursor resin layer is selected as the developing solution, the ratio of the good solvent and the poor solvent is determined according to the solubility of the polymer in the resin layer.

[0088] As the method of the developing solution treatment, there is no particular limitation, and the known developing methods, such as a rotary spray method, an agitation method, an immersion method, and the like, can be used.

[0089] After the developing solution treatment, further rinsing can be performed, and the rinsing solution is preferably a solvent different from the developing solution used.

[0090] In the step (4), the polyamic acid ester is imidized by heating the pattern obtained by the above developing to obtain the corresponding cured polyimide.

[0091] The temperature of the heating treatment is 150 to 400°C, and within the reaction temperature, the crosslinking reaction or the dehydration ring-closing reaction can be sufficiently performed.

[0092] In another aspect, the present application provides the use of the above-mentioned negative photosensitive polyimide precursor resin composition or the above-mentioned negative photosensitive polyimide resin composition in electronic packaging.

[0093] The negative photosensitive polyimide precursor resin composition in the present application can be applied to the preparation of semiconductor devices by the above-mentioned method, and can also be used for the interlayer insulation of multilayer circuits, the covering coating of flexible copper-clad plates, and the like.

[0094] The above technical solution has the following advantages or beneficial effects:

[0095] In order to improve the chemical corrosion resistance of the low-temperature cured PSPI material and the reliability of the device, the light crosslinking agent containing amide acid structure is introduced into the polyamide acid ester as the polyimide precursor. The light crosslinking agent can form the imide structure with good chemical stability and thermal stability after exposure, and the chemical structure of the imide ring is similar to that of the polyimide main resin. The strong intermolecular interaction between the imide rings can make the thermodynamic performance of the cured film better and the chemical stability better. The molecular structure of the traditional commonly used light crosslinking agent is poor in stability compared with the imide structure, and cannot form the similar strong interaction with the polyimide main resin, thus inevitably damaging the thermodynamic performance and chemical stability of the cured film. The negative photosensitive polyimide precursor resin composition provided by the application can be cured at low temperature (250 DEG C and below), and the negative photosensitive polyimide composition after curing has excellent thermal / mechanical performance, excellent chemical corrosion resistance and excellent lithography performance, and can meet the application requirements of advanced packaging processes such as high-density fan-out wafer-level packaging. BRIEF DESCRIPTION OF DRAWINGS

[0096] Figure 1 is the structural formula of the light crosslinking agent in the embodiments 1-14 of the application.

[0097] Figure 2 is the structural formula of the light crosslinking agent in the comparative examples 1-3 of the application. DETAILED DESCRIPTION

[0098] The following examples are only a part of the embodiments of the application, not all the embodiments. Therefore, the detailed description of the embodiments of the application provided below is not intended to limit the scope of the claimed application, but only represents selected embodiments of the application. Based on the embodiments of the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application.

[0099] In the application, all the equipment and raw materials, etc. can be purchased from the market or commonly used in the industry, unless otherwise specified. The methods in the following examples are conventional methods in the art, unless otherwise specified.

[0100] The room temperature in the following examples is 20-30 DEG C.

[0101]

Synthesis Example

[0102] Synthesis Example 1 Polyamide acid ester P1

[0103] Disperse 103 g of 4,4'-oxydiphthalic anhydride (ODPA) in solvent gamma-butyrolactone (GBL), add 106 g of hydroxyethyl methacrylate at one time, and then drop 3 g of pyridine, and react at 50 degrees Celsius for 6 hours; after the temperature drops to room temperature, dissolve 137 g of dicyclohexyl carbodiimide (DCC) in GBL, slowly drop into the reaction system, and stir for 2 hours; dissolve 67 g of 4,4'-diaminodiphenyl ether (ODA) in GBL in a nitrogen atmosphere, slowly drop into the reaction system, and stir for 9 hours; if stirring is difficult during the entire reaction period, the reaction system can be appropriately diluted by adding solvent; after the reaction is completed, add 5 mL of ethanol and continue to react for 2 hours; press filter the quenched reaction liquid, immediately add methanol to the filtrate to precipitate blocky solids, store in a refrigerator for 12 hours, then dissolve and drop into water, filter and dry to obtain the corresponding polyamic acid ester P1. The structural formula of the polyamic acid ester P1 prepared in this synthesis example is shown below, and the molecular weight M w is 27250, and the PDI is 1.78.

[0104] Synthesis Example 2: Polyamic Acid Ester P2

[0105] Use 71 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB) instead of 67 g of 4,4'-diaminodiphenyl ether (ODA) in the synthesis example 1, and the rest of the components and operation procedures remain the same as in the synthesis example 1, to obtain the polyamic acid ester P2. The molecular weight M w of the polymer is obtained by APC test, which is 28230, and the PDI is 1.85.

[0106] Synthesis Example 3: Polyamic Acid Ester P3

[0107] Use 70.5 g of 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA) instead of 103 g of 4,4'-oxydiphthalic anhydride (ODPA) in the synthesis example 1, and the rest of the components and operation procedures remain the same as in the synthesis example 1, to obtain the polyamic acid ester P3. The molecular weight M w of the polymer is obtained by APC test, which is 27980, and the PDI is 1.91.

[0108] Synthesis Example 4: Photocrosslinking Agent PC-1

[0109] The preparation method of the photocrosslinking agent in this synthesis example includes the following steps:

[0110] (1) 134 g of 4,4'-diaminodiphenyl ether (ODA) and 3 g of pyridine were dissolved in GBL, and 69.6 g of methacryloyl chloride was slowly added dropwise to the reaction system under ice-bath conditions, and then the temperature was raised to room temperature and stirring was continued for 3 h. The intermediate product A-1 was obtained by recrystallization separation and purification to give 142 g.

[0111] (2) 52 g of 4,4'-oxydiphthalic anhydride (ODPA) and 90 g of the intermediate product A-1 were dissolved in GBL, and the reaction was stirred at room temperature for 8 h. After the reaction was completed, the reaction solution was slowly added dropwise into a mixture of methanol / pure water (1 / 1) to precipitate a white solid, which was filtered and washed repeatedly with pure water, and dried to obtain the photocrosslinking agent PC-1.

[0112] Synthesis Example 5 Photocrosslinking agent PC-2

[0113] The preparation method in this synthesis example is the same as that of Synthesis Example 4, except that in step (1), 72.4 g of p-phenylenediamine (PPDA) is used instead of 134 g of 4,4'-diaminodiphenyl ether (ODA) in Synthesis Example 4 to synthesize 90 g of the intermediate product A-2; and in step (2), 59 g of the intermediate product A-2 is reacted (as shown below) to obtain the photocrosslinking agent PC-2.

[0114] Synthesis Example 6 Photocrosslinking agent PC-3

[0115] The preparation method in this synthesis example is the same as that of Synthesis Example 4, except that in step (1), 142.2 g of 2,2'-dimethyl-4,4'-diaminobiphenyl (mTB) is used instead of 134 g of 4,4'-diaminodiphenyl ether (ODA) component in Synthesis Example 4 to synthesize 152 g of the intermediate product A-3; and in step (2), 94 g of the intermediate product A-3 is reacted (as shown below) to obtain the photocrosslinking agent PC-3.

[0116] Synthesis Example 7 Photocrosslinking agent PC-4

[0117] The preparation method in this synthesis example is the same as that of Synthesis Example 4, except that in step (1), 152.2 g of 4,4'-diaminobenzanilide (DABA) is used instead of 134 g of 4,4'-diaminodiphenyl ether (ODA) component in Synthesis Example 4 to synthesize 148 g of the intermediate product A-4; and in step (2), 99 g of the intermediate product A-4 is reacted (as shown below) to obtain the photocrosslinking agent PC-4.

[0118] Synthesis Example 8 Photocrosslinking agent PC-5

[0119] The preparation method in this synthesis example is the same as that in Synthesis Example 4, except that in step (1), 72.7 g of pyromellitic dianhydride (PMDA) is used instead of 103 g of 4,4'-oxydiphthalic anhydride (ODPA) component in Synthesis Example 4 to obtain a photo-crosslinking agent PC-5.

[0120] Synthesis Example 9 Photo-crosslinking agent PC-6

[0121] The preparation method in this synthesis example is the same as that in Synthesis Example 4, except that in step (1), 72.7 g of pyromellitic dianhydride (PMDA) is used instead of 103 g of 4,4'-oxydiphthalic anhydride (ODPA) component in Synthesis Example 4 to obtain a photo-crosslinking agent PC-5.

[0122] FIG. 1 shows the structural formula of the photo-crosslinking agents PC-1 to PC-6 prepared in Synthesis Examples 4 to 9.

[0123]

EXAMPLE

[0124] Example 1

[0125] In a constant temperature and humidity (24°C, 50% RH) environment, 20 g of polyamic acid resin P1, 30 g of N-methylpyrrolidone (NMP) solvent, 2.0 g of photo-crosslinking agent PC-1, 0.4 g of hexamethoxymethyl melamine (TC-1), 0.8 g of photopolymerization initiator BASF IRGACURE OXE-01, 0.4 g of silane coupling agent (ureidopropyl triethoxysilane), 0.04 g of polymerization inhibitor (2-nitroso-1-naphthol), 0.4 g of thermal alkali generator (N-tert-butoxycarbonyl-4-piperidinemethanol), 0.2 g of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (AO-1), and 0.04 g of benzotriazole (MA-1) were sequentially added to a 100 mL brown glue bottle, and after being dissolved uniformly on a shaker for 24 h, the viscosity of the obtained solution was adjusted to about 30 poise by adding NMP, and a negative photosensitive polyimide precursor resin composition was obtained after secondary filtration.

[0126] Preparation of a cured film with a photoetching pattern:

[0127] The negative photosensitive polyimide precursor resin composition prepared by spin coating on an 8-inch silicon wafer was pre-baked at 100°C for 240 seconds using a hot plate to form a coating film with a thickness of about 10 μm. On the coating film, a mask with a test pattern was used, and an i-line projection stepper exposure machine was used to irradiate 400 mJ / cm 2The energy of the light source was 1000 mJ / cm2. Next, the coating film was subjected to spray development using cyclopentanone as a developing solution, using a developing machine, and to rinsing with propylene glycol methyl ether acetate, thereby obtaining a lithographic pattern. The lithographic pattern was heated and treated for 2 hours under the curing conditions described in Table 1 in a nitrogen atmosphere using a temperature-programmed curing oven, thereby obtaining a cured film having a lithographic pattern and having a thickness of about 10 μm.

[0128] Example 2

[0129] Example 1 was repeated, except that 2.0 g of the photocrosslinking agent PC-1 was replaced with 2.0 g of the photocrosslinking agent PC-2, and the other components and the operation procedure were kept constant.

[0130] Example 3

[0131] Example 1 was repeated, except that 2.0 g of the photocrosslinking agent PC-1 was replaced with 2.0 g of the photocrosslinking agent PC-3, and the other components and the operation procedure were kept constant.

[0132] Example 4

[0133] Example 1 was repeated, except that 2.0 g of the photocrosslinking agent PC-1 was replaced with 2.0 g of the photocrosslinking agent PC-4, and the other components and the operation procedure were kept constant.

[0134] Example 5

[0135] Example 1 was repeated, except that 2.0 g of the photocrosslinking agent PC-1 was replaced with 2.0 g of the photocrosslinking agent PC-5, and the other components and the operation procedure were kept constant.

[0136] Example 6

[0137] Example 1 was repeated, except that 2.0 g of the photocrosslinking agent PC-1 was replaced with 2.0 g of the photocrosslinking agent PC-6, and the other components and the operation procedure were kept constant.

[0138] Example 7

[0139] Example 4 was repeated, except that 20 g of the polyamic acid ester PI was replaced with 20 g of the polyamic acid ester P2, and the other components and the operation procedure were kept constant.

[0140] Example 8

[0141] Example 4 was repeated, except that 20 g of the polyamic acid ester PI was replaced with 20 g of the polyamic acid ester P3, and the other components and the operation procedure were kept constant.

[0142] Example 9

[0143] Example 4 was repeated, except that 2.0 g of the photocrosslinking agent PC-4 was replaced with 1.0 g of the photocrosslinking agent PC-4, and the other components and the operation procedure were kept constant.

[0144] Example 10

[0145] Example 4 was replaced by 1.5 g of photo-crosslinking agent PC-4, and the remaining components and operation procedures were consistent with Example 4.

[0146] Example 11

[0147] Example 4 was replaced by 2.5 g of photo-crosslinking agent PC-4, and the remaining components and operation procedures were consistent with Example 4.

[0148] Example 12

[0149] Example 4 was replaced by 3.0 g of photo-crosslinking agent PC-4, and the remaining components and operation procedures were consistent with Example 4.

[0150] Example 13

[0151] The curing process in Example 1 was changed to 230℃ / 2h, and the remaining components and operation procedures were consistent with Example 1.

[0152] Example 14

[0153] The curing process in Example 4 was changed to 230℃ / 2h, and the remaining components and operation procedures were consistent with Example 4.

[0154] Comparative Example 1

[0155] Example 1 was replaced by 2.0 g of photo-crosslinking agent PC-7, and the remaining components and operation procedures were consistent with Example 1.

[0156] Comparative Example 2

[0157] Example 1 was replaced by 2.0 g of photo-crosslinking agent PC-8, and the remaining components and operation procedures were consistent with Example 1.

[0158] Comparative Example 3

[0159] Example 1 was replaced by 2.0 g of photo-crosslinking agent PC-9, and the remaining components and operation procedures were consistent with Example 1.

[0160] Figure 2 shows the structural formula of the photo-crosslinking agent used in Comparative Examples 1-3.

[0161] Effect test

[0162] 1. Weight average molecular weight test:

[0163] The weight average molecular weight M of the polymerw and Polymer dispersity index (PDI) were obtained by ultra-high performance polymer chromatography analyzer.

[0164] 2. Evaluation method of lithography pattern:

[0165] The sliced analysis of the cured film obtained above was carried out by focused ion beam electron microscope to evaluate the lithography precision and cross-sectional profile, and then the negative photosensitive polyimide precursor resin composition was evaluated for lithography performance: the lithography line precision less than 10 μm was evaluated as 'excellent', the lithography line precision between 10-20 μm was evaluated as 'good', the lithography line precision between 20-50 μm was evaluated as 'fair', and the lithography line precision more than 50 μm was evaluated as 'poor'.

[0166] 3. Test of chemical resistance (resistance to etching) of the cured film:

[0167] The cured film prepared above was immersed in 1% hydrofluoric acid aqueous solution for 10 min, and then peeled to obtain an intact cured film. After drying the moisture in an oven at 150°C, the cured film was immersed in a dimethyl sulfoxide solution containing 2.38% tetramethylammonium hydroxide for 60 min at 50°C. The chemical resistance of the cured film was evaluated according to the weight loss before and after the etching treatment: the weight loss less than 5% was evaluated as 'excellent', the weight loss between 5%-15% was evaluated as 'good', the weight loss between 15%-25% was evaluated as 'fair', and the weight loss more than 25% was evaluated as 'poor'.

[0168] 4. Test of mechanical and thermal properties of the cured film:

[0169] The cured film prepared above was immersed in 1% hydrofluoric acid aqueous solution for 10 min, and then peeled to obtain a film sample with a size of 5 mm x 10 cm. After drying the moisture in an oven at 150°C, the mechanical tensile test of the film sample was carried out by using a universal tensile machine, and the mechanical properties were evaluated according to the elongation at break: the elongation at break more than 50% was evaluated as 'excellent', the elongation at break between 40%-50% was evaluated as 'good', the elongation at break between 20%-40% was evaluated as 'fair', and the elongation at break less than 20% was evaluated as 'poor'.

[0170] The film sample prepared above was tested by using a dynamic mechanical thermal analyzer, and the modulus-temperature curve and glass transition temperature were obtained, so as to evaluate the thermal properties.

[0171] The weight of each component of the negative photosensitive polyimide precursor resin composition in the above examples and comparative examples, the curing conditions, and the performance test data of the cured film prepared are shown in Tables 1-2.

[0172] Table 1

[0173] Table 2

[0174] As can be seen from Tables 1-2, the polyimide precursors prepared by the present application can all obtain a higher imide rate at a curing temperature below 250°C, i.e. a cured film with better comprehensive performance. Among them, the structure and content of the photocrosslinking agent both affect the performance of the cured film: the performance of the cured film prepared by the photocrosslinking agent with a suitable content is optimal, and too high or too low will lead to a decline in the performance of photolithography.

[0175] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A negative photosensitive polyimide precursor resin composition, characterized in that comprises: 100 parts by mass of a polyamic acid salt as a polyimide precursor; 5 to 20 parts by mass of a photo-crosslinking agent containing an amic acid structure; 0.5 to 5 parts by mass of a photopolymerization initiator; 0.5 to 5 parts by mass of a silane coupling agent; 0.01 to 1 part by mass of a polymerization inhibitor; 0.5 to 4 parts by mass of a thermal base generator; 1 to 5 parts by mass of a bridging agent; 0.5 to 3 parts by mass of an antioxidant; 0.1 to 2 parts by mass of an adhesion aid; The general structural formula of the photocrosslinking agent is shown in formula (1): in formula (1), X is a 4-valent organic group containing a cyclic structure, Y is a 2-valent organic group, and R1, R2, R3, R1', R2', and R3' are each independently selected from any one of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms.

2. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized by The 2-valent organic group is an organic group containing an aromatic group and / or an aliphatic chain having 2 to 8 carbon atoms.

3. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized by The method for producing the photo-crosslinking agent includes the following steps: Step (1) a diamine comprising a Y group, group donor and / or a single-end amine group-reacted amidation product is obtained by a group donor reaction; Step (2) the product obtained in Step (1) is reacted with a dianhydride containing an X group to obtain the photo-crosslinking agent.

4. The negative photosensitive polyimide precursor resin composition according to claim 3, characterized by The reaction temperature in Step (1) is -10°C to 10°C; and / or, the reaction time in Step (1) is preferably 2 to 6 hours; and / or, the reaction temperature in Step (2) is preferably 15 to 50°C; and / or, the reaction time in Step (2) is preferably 2 to 12 hours; and / or, the The group donor is and / or, the The group donor is 5. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein The polyamic acid ester includes a repeating unit represented by Formula (2): In formula (2), Z1is a 4-valent organic group containing an aromatic group, Z2is a 2-valent organic group containing an aromatic group, R4and R5are each independently selected from a 1-valent organic group having a structure as shown in formula (3), and m is 2 to 150. in formula (3), R6, R7, and R8 are each independently selected from a hydrogen atom and an alkyl group having 1 to 3 carbon atoms; and n is 2 to 10.

6. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein The photopolymerization initiator is selected from any one or more of an oxime ester compound, a benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, an alkyl anthraquinone, a benzoin alkyl ether, benzoin, an alkylbenzoin, and a benzil dimethyl ketal.

7. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein The bridging agent is an amino resin.

8. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein The bridging agent is selected from any one or more of a diol urea resin, a hydroxy ethylene urea resin, and a melamine resin.

9. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein The antioxidant is a hindered phenol-based antioxidant.

10. The negative photosensitive polyimide precursor resin composition according to claim 9, wherein The antioxidant is a compound in which the ortho carbon atom of a phenolic hydroxyl group has a hindered structure.

11. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized in that, The adhesion aid is an azole compound.

12. The negative photosensitive polyimide precursor resin composition according to claim 11, wherein The adhesion aid is selected from any one or more of 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, phenyl triazole, 1,5-dimethyl triazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, hydroxyphenyl benzotriazole, tolyl triazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

13. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein An organic solvent is also included.

14. The negative photosensitive polyimide precursor resin composition according to claim 13, wherein The organic solvent is selected from any one or more of an ester, an ether, a ketone, an aromatic hydrocarbon, a sulfoxide, and an amide.

15. Use of the negative-working photosensitive polyimide precursor resin composition according to claim 1 in electronic packaging.

16. A negative photosensitive polyimide resin composition, characterized by comprising: The negative photosensitive polyimide precursor resin composition according to claim 1 is thermally imidized.

17. The negative photosensitive polyimide resin composition according to claim 16, wherein The temperature of the thermal imidization is 150 to 400°C.

18. Use of the negative photosensitive polyimide resin composition according to claim 17 in electronic packaging.

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