Photosensitive polyimide resin and composition thereof

Abstract

The invention provides photosensitive polyimide resin and a composition thereof. The photosensitive polyimide resin comprises a first monomer, a second monomer and a third monomer, the first monomer is an aromatic dianhydride compound, the second monomer is a diamine compound containing a flexible group, and the third monomer is a diamine compound containing a rigid group. The photosensitive polyamic acid ester resin composition comprises 80-120 parts of a photosensitive polyamic acid ester solution, 5-15 parts of a copper surface auxiliary agent, 3-10 parts of a silane auxiliary agent, 5-15 parts of an antioxidant, 3-10 parts by mass of an inorganic filler and 3-10 parts of a low-temperature curing accelerator. The photosensitive polyimide resin has high glass transition temperature and good mechanical toughness, and the composition is introduced into a functional additive system, so that the interfacial compatibility between the material and a metal copper layer and between the material and a silicon substrate is effectively improved.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials and relates to a photosensitive polyimide resin and a composition thereof. Background Art

[0002] As integrated circuits progress toward miniaturization and multifunctional integration, advanced packaging technology has become a key enabler for extending Moore's Law. Within this system, photosensitive polyimide (PSPI), a novel packaging material with both heat resistance and photochemical reactivity, has attracted considerable attention.

[0003] From the perspective of the material composition system, PSPI is mainly composed of two functional components: (1) polyimide matrix: an aromatic polymer network is formed by condensation of amide precursors (such as pyrrolidone and aromatic diamine), giving the material intrinsic high temperature resistance and mechanical strength; (2) photosensitizer: triggers photocrosslinking or photodegradation reaction under ultraviolet light irradiation, achieving micron-level (<5μm) pattern resolution. This unique composition design allows PSPI to be used as both a high-precision photoresist and a permanent dielectric layer for advanced packaging architectures. In the field of microelectronics manufacturing, PSPI mainly undertakes three core functions: (1) high-density interconnect patterning, through the photolithography process to achieve the production of circuits; (2) multi-layer stacked dielectric layers, whose low dielectric constant and low dissipation factor characteristics can effectively reduce signal transmission delay; (3) chip-level protective barrier, the material's inherent low moisture absorption rate and high barrier properties provide reliable environmental protection for devices. Especially in the redistribution layer (RDL) technology, the heterogeneous interface system composed of PSPI, copper interconnection and silicon substrate, its interface adhesion strength, thermal expansion coefficient matching and anti-oxidation stability directly determine the reliability of the three-dimensional packaging structure.

[0004] However, the current PSPI R&D system has significant limitations. Existing technologies (such as CN117659395A and CN117986579A) focus on optimizing intrinsic material properties, including increasing the glass transition temperature, reducing the dielectric constant, or enhancing photosensitivity, but ignore the synergistic mechanism of multi-material interfaces in actual packaging systems. This research approach leads to the following typical failure modes: (1) PSPI / Cu interface microcrack propagation due to thermal stress mismatch; (2) delamination failure caused by adhesion loss at the silicon substrate / PSPI interface; and (3) contact resistance surge caused by oxidation of the copper wire surface. These interface problems have seriously restricted the reliability improvement of 2.5D / 3D packaging technology.

[0005] In essence, the existing PSPI system lacks consideration of the interaction of heterogeneous interfaces in design, especially the interface performance between PSPI and metal copper and silicon. Optimizing the adhesion performance between PSPI and metal copper and silicon can effectively improve the interconnection reliability of RDL, and provide a more reliable environmental protection layer for the chip interconnection system. SUMMARY

[0006] To solve the technical problems in the prior art, the present application provides a photosensitive polyimide resin and a composition thereof, which has high glass transition temperature and good mechanical toughness. The composition introduces a functional additive system, effectively improving the interfacial compatibility between the material and the copper layer and the silicon substrate.

[0007] To achieve the above technical effects, the present application adopts the following technical solutions:

[0008] One of the objects of the present application is to provide a photosensitive polyimide resin, which comprises a first monomer, a second monomer and a third monomer.

[0009] The first monomer is an aromatic dianhydride compound.

[0010] The second monomer is a diamine compound containing a flexible group.

[0011] The third monomer is a diamine compound containing a rigid group.

[0012] As a preferred technical solution of the present application, the aromatic dianhydride compound includes any one or a combination of at least two of substituted or unsubstituted phthalic anhydride, substituted or unsubstituted diphenyl anhydride, substituted or unsubstituted diphenyl ether dianhydride or substituted or unsubstituted naphthalene dianhydride.

[0013] Preferably, the flexible group in the diamine compound containing a flexible group includes any one of ether group, imino group or alkylene group.

[0014] Preferably, the rigid group includes any one of phenyl group, naphthyl group, anthracene group, phenanthryl group, benzimidazole group or benzoxazole group.

[0015] As a preferred technical solution of the present application, the first monomer includes 4,4'-diphenyl ether dianhydride.

[0016] The second monomer includes 4,4'-diamino diphenyl ether (ODA) or 4,4'-bis(4-aminophenoxy)diphenyl;

[0017] The third monomer includes any one of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane, or 1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane, or a combination of at least two thereof.

[0018] A second object of the present invention is to provide a photosensitive polyamic acid ester resin composition, which comprises, in parts by mass:

[0019] 80-120 parts of photosensitive polyamic acid resin solution, 5-15 parts of copper surface additive, 3-10 parts of silane additive, 5-15 parts of antioxidant, 3-10 parts by mass of inorganic filler and 3-10 parts of low-temperature curing accelerator;

[0020] The photosensitive polyamic acid resin solution contains the photosensitive polyimide resin provided in one of the purposes.

[0021] As a preferred technical solution of the present invention, the photosensitive polyamic acid resin solution includes a photosensitive polyimide resin, a photoinitiator, a cross-linking agent and an organic solvent.

[0022] As a preferred technical solution of the present invention, the photoinitiator includes any one of 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-propanone, or a combination of at least two thereof.

[0023] Preferably, the crosslinking agent includes any one or a combination of at least two of tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, pentaerythritol triacrylate, 4-vinyltoluene, 4-vinylpyridine or divinylbenzene.

[0024] As a preferred technical solution of the present invention, the copper surface additive includes any one or a combination of at least two of 1,2,4-triazole, tetrazole, 5-aminotetrazole, 5-phenyltetrazole or 5-propyl-2H-tetrazole.

[0025] Preferably, the silane auxiliary agent includes any one or a combination of at least two of triethoxysilylpropylmaleic acid, N-(hydroxymethyl)-N-methylaminopropyltrimethoxysilane, hydroxymethyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane or vinyltriethoxysilane.

[0026] As a preferred technical solution of the present application, the antioxidant includes any one of 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, pentaerythritol tetra(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), or tris(2,4-di-tert-butylphenyl) phosphite or a combination of at least two thereof.

[0027] Preferably, the low-temperature curing accelerator includes any one of 5-methylbenzimidazole, 2-hydroxypiperidine, 2,6-dimethylpiperidine, quinoline, isoquinoline, 2,3,5-trimethylpyrazine, or p-hydroxybenzoic acid or a combination of at least two thereof.

[0028] As a preferred technical solution of the present application, the photosensitive polyamic acid ester resin composition is mixed with an imidization catalyst for imidization treatment.

[0029] A third object of the present application is to provide an application of the photosensitive polyamic acid ester resin composition provided in the second object, which is used for preparing a photoresist film.

[0030] Compared with the prior art, the present application has at least the following beneficial effects:

[0031] (1) The present application provides a photosensitive polyimide resin, which, by using a diamine compound containing a flexible group and a diamine compound containing a rigid group, ensures its inherent photosensitive sensitivity and excellent thermal stability, and improves its tensile strength and flexibility.

[0032] (2) The present application provides a photosensitive polyimide resin composition, which exhibits excellent properties in a hetero-interface of metal copper and silicon, wherein the adhesion strength of the photosensitive polyimide to the metal copper and the silicon substrate is greatly increased, and the elongation at break of the interface between the photosensitive polyimide and the metal copper is improved.

[0033] (3) The present application provides a photosensitive polyimide resin composition, which has enhanced oxidation inhibition effect on metal copper, and effectively solves the device reliability problem caused by interface failure in high-density packaging. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 A comparison chart of the mechanical properties of the photosensitive polyimide-metal copper-silicon samples prepared from the photosensitive polyimide resin compositions provided in Examples 1 and 2 and Comparative Examples 1 and 2.

[0035] Figure 2 A comparison chart of the adhesion of the photosensitive polyimide-metal copper-silicon samples prepared from the photosensitive polyimide resin compositions provided in Examples 1 and 2 and Comparative Examples 1 and 2.

[0036] The present invention is further described in detail below. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. DETAILED DESCRIPTION

[0037] The technical solution of this application is further explained below through specific implementation methods.

[0038] The present invention provides a photosensitive polyimide resin, which includes a first monomer, a second monomer and a third monomer;

[0039] The first monomer is an aromatic dianhydride compound;

[0040] The second monomer is a diamine compound containing a flexible group;

[0041] The third monomer is a diamine compound containing a rigid group.

[0042] In the present invention, the use of a diamine monomer containing a flexible group imparts a certain degree of flexibility to the photosensitive polyimide resin, while the use of a diamine monomer containing a rigid group enhances the material's molecular chain stability. As a result, the photosensitive polyimide and its composition, while maintaining inherent photosensitivity and excellent thermal stability, also improve their tensile strength and flexibility. They exhibit excellent properties at heterojunctions with copper and silicon. The adhesion strength of the photosensitive polyimide to both copper and the silicon substrate is significantly enhanced, and the elongation at break at the interface between the photosensitive polyimide and copper is improved. Furthermore, the photosensitive polyimide enhances its ability to inhibit copper oxidation, effectively addressing device reliability issues caused by interface failure in high-density packaging.

[0043] In one embodiment of the present invention, the aromatic dianhydride compound includes any one or a combination of at least two of substituted or unsubstituted phthalic anhydride, substituted or unsubstituted biphenyl dianhydride, substituted or unsubstituted diphenyl ether dianhydride or naphthalene dianhydride.

[0044] In one embodiment of the present invention, the substituted or unsubstituted phthalic anhydride can be pyromellitic dianhydride or chloropyromellitic dianhydride.

[0045] In a specific embodiment of the present invention, the substituted or unsubstituted biphenyl dianhydride can be 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis(trifluoromethyl)-4,4′,5,5′-biphenyltetracarboxylic dianhydride, 3,3′-dichloro-4,4′-biphenyltetracarboxylic dianhydride or 3,3′-dimethyl-4,4′-biphenyltetracarboxylic dianhydride, etc.

[0046] In a specific embodiment of the present invention, the substituted or unsubstituted diphenyl ether dianhydride can be 4,4′-oxydiphthalic anhydride, 3,3′-difluoro-4,4′-oxydiphthalic anhydride or 2,3,5,6-tetramethyl-4,4′-oxydiphthalic anhydride.

[0047] In a specific embodiment of the present invention, the substituted or unsubstituted naphthalene dianhydride can be 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-tetrafluoro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dibromo-1,4,5,8-naphthalenetetracarboxylic dianhydride or 2,6-dimethyl-1,4,5,8-naphthalenetetracarboxylic dianhydride, etc.

[0048] In one embodiment of the present invention, the first monomer is preferably 4,4′-biphenyl ether dianhydride.

[0049] In one embodiment of the present invention, the flexible group can be any one of an ether group, an imino group, or an alkylene group, wherein the alkylene group can be a C1-C6 alkylene group, such as a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, or a 1,6-hexylene group.

[0050] In a specific embodiment of the present invention, the second monomer may be an aromatic anhydride connected by a flexible group, such as substituted or unsubstituted phthalic anhydride or naphthalic anhydride.

[0051] In one embodiment of the present invention, the second monomer is preferably 4,4'-diaminodiphenyl ether (ODA) or 4,4'-bis(4-aminophenoxy)biphenyl.

[0052] In one embodiment of the present invention, the rigid group may be any one of phenyl, naphthyl, anthracenyl, phenanthrenyl, benzimidazolyl or benzoxazolyl.

[0053] In a specific embodiment of the present invention, the third monomer is preferably any one of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane or 1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane, or a combination of at least two thereof.

[0054] In one embodiment of the present invention, the molar ratio of the first monomer, the second monomer, and the third monomer in the photosensitive polyimide resin conforms to the stoichiometric ratio of the reaction of the anhydride group and the amino group in a ratio of 1:1. Preferably, the molar ratio of the first monomer, the second monomer, and the third monomer is 2:1:1.

[0055] In one embodiment of the present application, the number average molecular weight of the photosensitive polyimide resin can be adjusted according to actual production needs, and is not specifically limited herein. As an example, the number average molecular weight of the photosensitive polyimide resin can be 10,000 to 100,000 g / mol.

[0056] In one embodiment of the present application, the structure of the photosensitive polyimide resin can be as shown in Formula 1, where n can be 100-300.

[0057]

[0058] In one embodiment of the present application, a photosensitive polyimide resin composition is provided, which includes, in terms of mass parts:

[0059] The photosensitive polyimide resin composition includes a photosensitive polyimide acid ester solution 80-120 parts by mass, a copper surface aid 5-15 parts by mass, a silane aid 3-10 parts by mass, an antioxidant 5-15 parts by mass, an inorganic filler 3-10 parts by mass, and a low-temperature curing accelerator 3-10 parts by mass.

[0060] The photosensitive polyimide acid ester solution contains the photosensitive polyimide resin provided in one embodiment.

[0061] The photosensitive polyimide acid ester solution can be 80 parts by mass, 85 parts by mass, 90 parts by mass, 95 parts by mass, 100 parts by mass, 105 parts by mass, 110 parts by mass, 115 parts by mass, or 120 parts by mass, etc., the copper surface aid can be 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, 13 parts by mass, 14 parts by mass, or 15 parts by mass, etc., the silane aid can be 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, or 10 parts by mass, etc., the antioxidant can be 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, 13 parts by mass, 14 parts by mass, or 15 parts by mass, etc., the inorganic filler can be 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, or 10 parts by mass, etc., and the low-temperature curing accelerator can be 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, or 10 parts by mass, etc., but is not limited to the listed values, and other values not listed within the above ranges are also applicable.

[0062] In the present application, the photosensitive polyimide acid ester resin composition effectively improves the interfacial compatibility between the photosensitive polyimide acid ester resin and the metal copper layer and the silicon substrate by introducing a functional additive system (including a copper surface aid, a silane aid, an antioxidant, an inorganic filler, and a low-temperature curing accelerator), greatly increases the adhesion strength between the photosensitive polyimide and the metal copper and the silicon substrate, and improves the elongation at break of the interface between the photosensitive polyimide and the metal copper.

[0063] In one embodiment of the present invention, the photosensitive polyamic acid resin solution includes a photosensitive polyimide resin, a photoinitiator, a cross-linking agent and an organic solvent.

[0064] In a specific embodiment of the present invention, the photoinitiator includes any one of 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-propanone, or a combination of at least two thereof.

[0065] In one embodiment of the present invention, the crosslinking agent includes any one or a combination of at least two of tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, pentaerythritol triacrylate, 4-vinyltoluene, 4-vinylpyridine or divinylbenzene.

[0066] In one embodiment of the present invention, the organic solvent can be selected based on the solubility of the photosensitive polyimide resin, photoinitiator, and crosslinker, with the selection being based on the ability to completely dissolve the photosensitive polyimide resin, photoinitiator, and crosslinker. Further limitations are not provided herein. For example, the organic solvent can be N-methylpyrrolidone.

[0067] In one embodiment of the present invention, the mass fractions of the photosensitive polyimide resin, photoinitiator, and crosslinker in the photosensitive polyamic acid resin solution can be adjusted according to production needs and are not specifically limited herein. For example, the mass fraction of the photosensitive polyimide resin can be 60% to 90%, the mass fraction of the photoinitiator can be 1% to 10%, and the mass fraction of the crosslinker can be 3% to 10%.

[0068] In one embodiment of the present invention, the copper surface additive is a reagent containing a nitrogen azole basic unit, preferably any one or a combination of at least two of 1,2,4-triazole, tetrazole, 5-aminotetrazole, 5-phenyltetrazole or 5-propyl-2H-tetrazole.

[0069] In a specific embodiment of the present invention, the silane auxiliary agent includes any one or a combination of at least two of triethoxysilylpropylmaleic acid, N-(hydroxymethyl)-N-methylaminopropyltrimethoxysilane, hydroxymethyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane or vinyltriethoxysilane.

[0070] In one embodiment of the present application, the antioxidant includes any one or a combination of at least two of 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), or tris(2,4-di-tert-butylphenyl)phosphite.

[0071] In one embodiment of the present application, the low-temperature curing promoter includes any one or a combination of at least two of 5-methylbenzimidazole, 2-hydroxypiperidine, 2,6-dimethylpiperidine, quinoline, isoquinoline, 2,3,5-trimethylpyrazine, or p-hydroxybenzoic acid.

[0072] In one embodiment of the present application, the inorganic filler can be selected according to the coating needs of the photosensitive polyimide acid ester resin composition, which is not specifically limited herein. As an enumeration, the inorganic filler can be TEOS-SiO2, nano-aluminum oxide, or the like.

[0073] In one embodiment of the present application, the photosensitive polyimide acid ester resin composition is mixed with an imidization catalyst for imidization treatment.

[0074] In one embodiment of the present application, the method for imidization treatment of the photosensitive polyimide acid ester resin composition includes mixing the photosensitive polyimide acid ester resin composition with an imidization catalyst and heating for thermal imidization reaction.

[0075] In one embodiment of the present application, the temperature for thermal imidization reaction is 200-300°C, and the time is 1-2h. Among them, the temperature for thermal imidization reaction can be 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, or 300°C, etc., but is not limited to the enumerated values, and other values not listed in this range are also applicable.

[0076] In one embodiment of the present application, the preparation method of the photosensitive polyimide acid ester resin composition can be:

[0077] The first monomer, the second monomer, and the third monomer are mixed with an organic solvent to perform imidization reaction to obtain a polyimide acid;

[0078] The polyimide acid is mixed with a photoinitiator and a crosslinking agent to perform reaction, and then a photosensitive polyimide resin solution is obtained;

[0079] The photosensitive polyimide resin solution is mixed with a copper surface aid, a silane aid, an antioxidant, an inorganic filler, and a low-temperature curing promoter to obtain a photosensitive polyimide resin composition.

[0080] In one embodiment of the present application, the imidization reaction is carried out using conventional imidization reaction conditions in the art, without further limitation on the reaction temperature and time.

[0081] In one embodiment of the present application, the reaction conditions of the polyamic acid with the photoinitiator and the crosslinking agent can be adjusted according to the crosslinking degree, without further limitation.

[0082] In one embodiment of the present application, the photosensitive polyamic acid ester resin composition is used to prepare a photoresist film.

[0083] In one embodiment of the present application, the photoresist film can be prepared by spin coating the photosensitive polyamic acid ester resin composition on copper and silicon under air and room temperature, followed by thermal imidization reaction and curing.

[0084] Example 1

[0085] The present embodiment provides a photosensitive polyamic acid ester resin composition, and a preparation method thereof, comprising:

[0086] The first monomer, the second monomer and the third monomer are pretreated. 4,4'-oxydianiline (ODA) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) are treated in a vacuum oven at 60°C for 4h; 4,4'-oxydiphthalic anhydride (ODPA) is treated in a vacuum oven at 160°C for 4h.

[0087] At room temperature, 0.1 mol of ODA and 0.1 mol of 6FAP are added to a three-necked flask, and 200g of N-methylpyrrolidone is added to fully dissolve the mixture under stirring. Then, 0.2 mol of ODPA is added under nitrogen atmosphere, and 100g of N-methylpyrrolidone is added again to dilute and fully dissolve the mixture, followed by stirring for 12h to obtain a polyamic acid solution.

[0088] 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) and tetraethylene glycol dimethacrylate are added to the obtained polyamic acid solution to obtain a photosensitive polyimide resin solution.

[0089] The photosensitive polyimide resin solution is taken as 100 parts by mass, and 10 parts by mass of 5-amino tetrazole, 5 parts by mass of triethoxysilylpropyl maleic acid, 10 parts by mass of 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 5 parts by mass of TEOS-SiO2 and 5 parts by mass of 5-methylbenzimidazole are added in batches to obtain the final photosensitive polyamic acid ester resin composition.

[0090] Example 2

[0091] This example is the same as Example 1 except that 4,4'-diaminodiphenyl ether is replaced with 4,4'-bis(4-aminophenoxy)diphenyl ether.

[0092] Example 3

[0093] This example is the same as Example 1 except that 2,2-bis(3-amino-4- hydroxyphenyl)hexafluoropropane is replaced with 1,1-bis(4-aminophenyl)-1-phenyl- 2,2,2-trifluoroethane.

[0094] Example 4

[0095] This example is the same as Example 1 except that 2,2-bis(3-amino-4- hydroxyphenyl)hexafluoropropane is replaced with 1,1-bis[4-(4-aminophenoxy)phenyl]- 1-phenyl-2,2,2-trifluoroethane.

[0096] Example 5

[0097] In this example, 5 mass parts of 5-amino tetrazole, 3 mass parts of triethoxysilylpropyl maleic acid, 5 mass parts of 1,2-bis[β-(3,5-di-tert-butyl-4- hydroxyphenyl)propionyl]hydrazine, 3 mass parts of TEOS-SiO2, and 3 mass parts of 5-methylbenzimidazole are added in batches based on 80 mass parts of the photosensitive polyimide resin solution to obtain the final photosensitive polyamic acid resin composition. The remaining conditions are the same as in Example 1.

[0098] Example 6

[0099] In this example, 15 mass parts of 5-amino tetrazole, 10 mass parts of triethoxysilylpropyl maleic acid, 15 mass parts of 1,2-bis[β-(3,5-di-tert-butyl-4- hydroxyphenyl)propionyl]hydrazine, 10 mass parts of TEOS-SiO2, and 10 mass parts of 5-methylbenzimidazole are added in batches based on 120 mass parts of the photosensitive polyimide resin solution to obtain the final photosensitive polyamic acid resin composition. The remaining conditions are the same as in Example 1.

[0100] Comparative Example 1

[0101] In this comparative example, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is replaced with 4,4'-diaminodiphenyl ether in an equimolar amount, and no copper surface aid is added, and the remaining conditions are the same as in Example 1.

[0102] Comparative Example 2

[0103] In this comparative example, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-diaminodiphenyl ether were replaced by 4,4'-bis(4-aminophenoxy)biphenyl in equal moles and no copper surface additive was added. Other conditions were the same as those in Example 1.

[0104] Comparative Example 3

[0105] In this comparative example, except that 4,4'-diaminodiphenyl ether was replaced by an equal mole of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and no copper surface additive was added, the other conditions were the same as those in Example 1.

[0106] Comparative Example 4

[0107] In this comparative example, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was replaced by an equal mole of 4,4'-diaminodiphenyl ether, and other conditions were the same as those in Example 1.

[0108] Comparative Example 5

[0109] In this comparative example, except that no copper surface additive is added, the other conditions are the same as those in Example 1.

[0110] The photosensitive polyamic acid ester resin compositions provided in Examples 1-6 and Comparative Examples 1-5 were mixed with 5-methylbenzimidazole and spin-coated on a copper sheet on a silicon substrate under room temperature conditions to obtain a photosensitive polyimide-metal copper-silicon sample. The thickness of the photosensitive polyimide was about 10 μm.

[0111] The photosensitive polyimide-metal copper-silicon sample obtained in the above implementation process was cut into a size suitable for stretching with the help of a focused ion beam microscope (FIB). The cut sample was in situ stretched under a transmission electron microscope to obtain the PSPI-Cu interface adhesion. The test results are shown in Table 1.

[0112] The elongation at break was measured by uniaxial stretching of the sample at room temperature using a dynamic mechanical analyzer (DMA).

[0113] Table 1

[0114]

[0115]

[0116] It can be seen from the test results in Table 1 that the adhesion strength of the photosensitive polyimide provided by the present application to the metal copper and the silicon substrate is greatly increased, and the elongation at break of the interface between the photosensitive polyimide and the metal copper is improved. It can be seen from the comparison of Comparative Examples 3 and 4 with Example 1 that the use of only diamine compounds containing flexible groups or the use of diamine compounds containing only rigid groups cannot effectively improve the adhesion strength of the photosensitive polyimide to the metal copper and the silicon substrate. It can be seen from the comparison of Comparative Example 5 with Example 1 that when the copper surface additive is not applied, the adhesion strength of the photosensitive polyimide to the metal copper and the silicon substrate is also low, indicating that the synergistic effect of the photosensitive polyimide and the copper surface additive can enhance the adhesion strength of the photosensitive polyimide to the metal copper and the silicon substrate.

[0117] The applicant declares that the present invention is intended to illustrate the detailed structural features of the present invention through the above-described embodiments, but the present invention is not limited to the above-described detailed structural features. This does not mean that the present invention must rely on the above-described detailed structural features in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for selected components, additions of auxiliary components, and selection of specific embodiments, etc., fall within the scope of protection and disclosure of the present invention.

[0118] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

[0119] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0120] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A photosensitive polyimide resin, characterized in that: The photosensitive polyimide resin includes a first monomer, a second monomer and a third monomer; The first monomer is an aromatic dianhydride compound; The second monomer is a diamine compound containing a flexible group; The third monomer is a diamine compound containing a rigid group.

2. The photosensitive polyimide resin according to claim 1, wherein The aromatic dianhydride compound includes any one or a combination of at least two of substituted or unsubstituted phthalic anhydride, substituted or unsubstituted biphenyl dianhydride, substituted or unsubstituted diphenyl ether dianhydride or substituted or unsubstituted naphthalene dianhydride; Preferably, the flexible group in the diamine compound containing a flexible group includes any one of an ether group, an imino group or an alkylene group; Preferably, the rigid group includes any one of phenyl, naphthyl, anthracenyl, phenanthrenyl, benzimidazolyl or benzoxazolyl.

3. The photosensitive polyimide resin according to claim 1, wherein The first monomer includes 4,4'-biphenyl ether dianhydride; The second monomer includes 4,4'-diaminodiphenyl ether (ODA) or 4,4'-bis(4-aminophenoxy)biphenyl; The third monomer includes any one of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane, or 1,1-bis[4-(4-aminophenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane, or a combination of at least two thereof.

4. A photosensitive polyamic acid ester resin composition, characterized in that The photosensitive polyamic acid ester resin composition comprises, in parts by mass: 80-120 parts of photosensitive polyamic acid resin solution, 5-15 parts of copper surface additive, 3-10 parts of silane additive, 5-15 parts of antioxidant, 3-10 parts by mass of inorganic filler and 3-10 parts of low-temperature curing accelerator; The photosensitive polyamic acid resin solution contains the photosensitive polyimide resin according to any one of claims 1 to 3.

5. The photosensitive polyamic acid ester resin composition according to claim 4, characterized in that: The photosensitive polyamic acid resin solution comprises a photosensitive polyimide resin, a photoinitiator, a cross-linking agent and an organic solvent.

6. The photosensitive polyamic acid ester resin composition according to claim 5, characterized in that The photoinitiator includes any one or a combination of at least two of 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-propanone; Preferably, the crosslinking agent includes any one or a combination of at least two of tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, pentaerythritol triacrylate, 4-vinyltoluene, 4-vinylpyridine or divinylbenzene.

7. The photosensitive polyamic acid ester resin composition according to claim 4, characterized in that: The copper surface additive includes any one of 1,2,4-triazole, 1H-1,2,3-triazole, tetrazole or 5-aminotetrazole, 5-phenyltetrazole, 5-propyl-2H-tetrazole or a combination of at least two thereof; Preferably, the silane auxiliary agent includes any one or a combination of at least two of triethoxysilylpropylmaleic acid, N-(hydroxymethyl)-N-methylaminopropyltrimethoxysilane, hydroxymethyltriethoxysilane, (3-glycidoxypropyl)trimethoxysilane or vinyltriethoxysilane.

8. The photosensitive polyamic acid ester resin composition according to claim 4, characterized in that The antioxidant includes any one or a combination of at least two of 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) or tris(2,4-di-tert-butylphenyl)phosphite; Preferably, the low-temperature curing accelerator includes any one or a combination of at least two of 5-methylbenzimidazole, 2-hydroxypiperidine, 2,6-dimethylpiperidine, quinoline, isoquinoline, 2,3,5-trimethylpyrazine or p-hydroxybenzoic acid.

9. The photosensitive polyamic acid ester resin composition according to claim 4, characterized in that: The photosensitive polyamic acid ester resin composition is mixed with an imidization catalyst to perform imidization treatment.

10. Use of the photosensitive polyamic acid ester resin composition according to any one of claims 4 to 9, characterized in that: The photosensitive polyamic acid ester resin composition is used for preparing a photoresist film.

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