A negative photosensitive polyimide precursor resin composition

Abstract

The application discloses a negative photosensitive polyimide precursor resin composition, comprising: 100 parts by mass of a polyamic acid ester as a polyimide precursor; 1-20 parts by mass of a first radical polymerizable monomer containing an epoxy structure; 1-20 parts by mass of a second radical polymerizable monomer; 0.5-10 parts by mass of a photoinitiator; 0.5-10 parts by mass of a silane coupling agent; 0.01-5 parts by mass of a polymerization inhibitor; 0.1-10 parts by mass of a thermal alkali generator; and 50-1500 parts by mass of an organic solvent. The resin composition can not only realize low-temperature (below 230 DEG C) curing by introducing the polymerizable monomer containing the epoxy structure into the polyimide precursor composition, but also has excellent mechanical properties, excellent bonding strength with a copper surface and excellent chemical corrosion resistance after low-temperature curing, and can meet the application requirements of high-density fan-out wafer-level packaging and other advanced packaging processes.

Description

Technical Field

[0001] This invention relates to the field of polyimide technology, and more particularly to a negative-type photosensitive polyimide precursor resin composition. Background Technology

[0002] Photosensitive polyimide photoresist (PSPI) is widely used in surface passivation of integrated circuit chips and surface redistribution processes in wafer-level packaging and panel-level packaging, making it a key material in advanced wafer-level packaging processes. Traditional PSPI materials require curing temperatures above 350°C to achieve their various superior properties. However, at such high curing temperatures, wafer warpage, stress cracking, and compatibility issues with other packaging materials can easily occur in advanced packaging processes such as high-density fan-out wafer-level packaging. Therefore, low-temperature curing of PSPI is necessary. However, low-temperature cured PSPI materials often suffer from insufficient imidization, resulting in poor mechanical properties and chemical corrosion resistance, failing to meet packaging process requirements. Furthermore, poor adhesion to other materials in the packaging process, especially electroplated copper, leads to poor device reliability. In particular, current high-end wafer-level packaging processes place higher demands on low-stress, low-warpage curing processes, making the need for ultra-low temperature cured PSPI materials (curing below 200°C) increasingly urgent, and solving the aforementioned problems is becoming increasingly pressing.

[0003] Generally, to solve the above problems, photo / thermal alkali-generating agents are introduced to lower the activation energy of imidization of polyimide precursor resins, thereby achieving excellent properties of polyimide resins in various aspects during low-temperature processes. Examples include CN112639616A, CN112513219A, CN112639615A, and CN111919172A. Alternatively, the molecular weight of the precursor resin can be controlled to ensure that the molecular chains have sufficiently high mobility during low-temperature curing, thereby increasing the imidization rate, as exemplified by CN108475020A. Furthermore, CN112334833A introduces polymeric compounds containing urethane and urea bonds, while CN110741318A and CN113168093A introduce polymeric compounds containing sulfite structures to achieve comprehensive properties such as high imidization rate during low-temperature curing, good chemical resistance, and excellent copper adhesion. In addition, various copper surface additives are generally introduced to improve the adhesion between the redistribution layer and the copper surface, such as CN102375336B and CN112799281A.

[0004] Generally, the most prominent problem with PSPI materials cured below 230°C is insufficient chemical corrosion resistance, making it difficult to meet the process requirements of wafer-level packaging. The main reason for this is that at ultra-low curing temperatures, most additives, especially photocrosslinking agents and polymeric functional groups from the polyimide precursor, remain in the cured film. The chemical corrosion resistance of these additive residues is often much worse than that of polyimide itself. To address this issue, methods typically involve introducing rigid photocrosslinking agents with aliphatic cyclic skeletons to enhance the rigidity of the molecular structure of the residues in the cured film, thereby improving their chemical corrosion resistance (e.g., CN110520795A), or introducing multifunctional crosslinking agents to increase the crosslinking density of the residues in the cured film, such as CN111936930A and CN110300767A. However, the resulting materials still fail to achieve sufficiently excellent chemical corrosion resistance to meet the stringent requirements of packaging processes. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention provides a negative-type photosensitive polyimide precursor resin composition.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] This invention provides a negative photosensitive polyimide precursor resin composition, comprising:

[0008] 100 parts by weight of polyamic acid ester as a polyimide precursor;

[0009] 1-20 parts by weight of a first radical polymerizable monomer containing an epoxy structure;

[0010] 1-20 parts by mass of the second radical polymerizable monomer;

[0011] 0.5-10 parts by weight of photoinitiator;

[0012] 0.5-10 parts by weight of silane coupling agent;

[0013] 0.01-5 parts by weight of polymerization inhibitor;

[0014] 0.1-10 parts by weight of heat-generating alkali agent;

[0015] 50-1500 parts by weight of organic solvent;

[0016] Wherein, the first radical polymerizable monomer containing an epoxy structure is selected from at least one of the compounds with the structures shown in formulas (a), (b), (c), (d), (e), and (f):

[0017]

[0018] In equation (a), R1 is selected from any one of them;

[0019] R2 is selected from any one of hydrogen atoms and alkyl groups having 1 to 3 carbon atoms, and R3 and R4 are each independently selected from any one of aliphatic hydrocarbon groups having 1 to 8 carbon atoms, with m = 0 to 7.

[0020]

[0021] In equation (b), n = 0 to 6;

[0022]

[0023] In equation (c), A1 is

[0024]

[0025] In formula (d), R5 is selected from any one of hydrogen atoms and alkyl groups having 1 to 3 carbon atoms; R6 is selected from... Any one of them; p = 0 to 1;

[0026]

[0027] In equation (e), A2 is a ring structure, selected from... Any one of them.

[0028] In a preferred embodiment, the polyamic acid ester has a structure as shown in formula (f):

[0029]

[0030] In formula (f), X is a tetravalent organic group containing an aromatic group, Y is a divalent organic group containing an aromatic group, R7 and R8 are independently selected from monovalent organic groups having the structure shown in formula (g), and q is 2 to 150.

[0031]

[0032] In formula (g), R9 and R 10 and R 11 Each is independently selected from hydrogen atoms and alkyl groups having 1 to 3 carbon atoms; r is 2 to 10.

[0033] In a preferred embodiment, the second radical polymerizable monomer is selected from any one or more of (meth)acrylate compounds, preferably any one or more of difunctional (meth)acrylate compounds and trifunctional (meth)acrylate compounds; in the technical solution of the present invention, the (meth)acrylate compounds include acrylate compounds and / or methacrylate compounds;

[0034] Specifically, the second radical polymerizable monomer is selected from tetraethylene glycol trimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and 1,6-hexanediol dimethacrylate. The following are all of the following: acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, and N-hydroxymethylacrylamide; preferably, tetraethylene glycol trimethacrylate.

[0035] In a preferred embodiment, the method for preparing the polyamide ester includes the following steps:

[0036] A partially esterified tetracarboxylic acid is prepared by reacting a tetracarboxylic acid dianhydride containing an X group, an alcohol with an unsaturated double bond that has free radical polymerization ability, and / or a saturated aliphatic alcohol with 1 to 4 carbon atoms; then, it is subjected to amide polycondensation with a diamine containing a Y group.

[0037] There are no particular limitations on tetracarboxylic dianhydrides containing the X group, and specific examples include 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, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)propane. Phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic anhydride, benzophenone-3,3',4,4'-tetracarboxylic anhydride, biphenyl-3,3',4,4'-tetracarboxylic anhydride, more preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic anhydride, biphenyl-3,3',4,4'-tetracarboxylic anhydride, etc., the above can be used alone or in any mixture.

[0038] There are no particular limitations on the diamine containing the Y group, and specific examples include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3 ...3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'- -Diaminobiphenyl, 3,4'-Diaminobiphenyl, 3,3'-Diaminobiphenyl, 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)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-aminopropyldimethylsilyl)benzene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 9,9-bis(4-aminophenyl)fluorene, etc., can be used alone or in any mixture.

[0039] In a preferred embodiment, the photoinitiator 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-morpholino-1-propanone, alkyl anthraquinone, benzoin alkyl ether, benzoin, alkylbenzoin and benzoin dimethyl ketal, and is more preferably an oxime ester compound.

[0040] In a preferred embodiment, the organic solvent is selected from any one or more of esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides;

[0041] Preferably, the esters are selected from any one or more of ethyl acetate, n-butyl acetate, isobutyl acetate, amyl 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.

[0042] Preferably, the ether is 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.

[0043] Preferably, the ketones are selected from any one or more of methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone;

[0044] Preferably, the aromatic hydrocarbons are selected from any one or more of toluene, xylene, anisole, and limonene;

[0045] Preferably, the amide is selected from any one or more of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide.

[0046] In the technical solution of the present invention, the silane coupling agent is not particularly limited, but is preferably any one or more of the silane coupling agents containing urea bonds (-NH-CO-NH-).

[0047] Specifically, the silane coupling agent is selected from ureapropyltriethoxysilane, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-epoxypropoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane, N-(3-diethyl)-dimethoxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane, N-(β-aminoethyl)-dimethoxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane, N-(β-aminoethyl)-dimethoxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane, N-(β-aminoethyl)-dimethoxypropyltrimethoxysilane, dimethoxypropyltrimethoxysilane, dimethoxypropyltrimethoxysilane, dieth ... The preferred formulation is ureapropyltriethoxysilane, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, phenyl-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, and N-phenylaminopropyltrimethoxysilane.

[0048] In the technical solution of the present invention, the polymerization inhibitor is not particularly limited, but is preferably any one or more of phenolic radical polymerization inhibitors;

[0049] Specifically, 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, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxyamine ammonium salt, preferably 2-nitroso-1-naphthol.

[0050] In a preferred embodiment, the heat-generating alkali agent is a tert-butoxycarbonyl-protected amine compound, wherein the amine compound is selected from 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, valine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, demethylephedrine, 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)propanediol, etc. Alcohols, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidine alcohol, 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-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1 4-Butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxydiethylamine, 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, any one or more of these;

[0051] Preferably, the thermal alkali-generating agent is N-tert-butoxycarbonyl-4-piperidinemethanol.

[0052] In another aspect, the present invention provides a negative photosensitive polyimide resin composition, which is obtained by thermal imidization of the above-mentioned negative photosensitive polyimide precursor resin composition;

[0053] Preferably, the temperature of the thermal imidization is 150–400°C.

[0054] The above technical solution has the following advantages or beneficial effects:

[0055] The present invention aims to provide a negative photosensitive polyimide precursor resin composition. By introducing a polymerizable monomer containing an epoxy structure into the polyimide precursor composition, the resin composition can not only achieve low-temperature (below 230°C) curing, but also the cured film obtained after low-temperature curing has excellent mechanical properties, excellent bonding strength with copper surfaces, and excellent chemical corrosion resistance, which can meet the application requirements of advanced packaging processes such as high-density fan-out wafer-level packaging. Attached Figure Description

[0056] Figure 1 This is a schematic diagram of the chemical structure of EP-1 to EP-8 used in the embodiments and comparative examples of the present invention. Detailed Implementation

[0057] The following embodiments are merely some, not all, of the embodiments of the present invention. Therefore, the detailed descriptions of the embodiments provided below are not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0058] In this invention, unless otherwise specified, all equipment and raw materials are commercially available or commonly used in the industry. The methods described in the following embodiments are conventional methods in the art, unless otherwise specified.

[0059] The inventors discovered that existing methods for improving the chemical corrosion resistance of ultra-low temperature curing PSPI materials often only involve increasing the crosslinking density and molecular structure strength of the PSPI material during the exposure process. However, similar experimental verifications have shown that this is insufficient to obtain sufficiently excellent chemical corrosion resistance to meet the stringent requirements of the packaging process.

[0060] Therefore, this invention introduces a polymerizable monomer containing an epoxy structure into the polyimide precursor composition. During the exposure process, the double bonds can be crosslinked into the main structure of the polyimide precursor. At the same time, in the subsequent thermosetting process, the epoxy groups undergo a thermocrosslinking reaction with the hydroxyl groups generated after imidization of the PSPI precursor, further enhancing the crosslinking density and strength of the additive residues in the cured film, thereby obtaining excellent chemical corrosion resistance.

[0061] The negative photosensitive polyimide precursor resin composition provided by the present invention comprises: (1) a polyamic acid ester as a polyimide precursor; (2) a first radical polymerizable monomer containing an epoxy structure; (3) a second radical polymerizable monomer; and (4) a photoinitiator.

[0062] Component (1): Polyamate

[0063] In the technical solution of the present invention, polyamic acid ester is converted into polyimide through thermal imidization, and as the photosensitive polyimide precursor in the present invention, it has the structure shown in formula (f):

[0064]

[0065] (In formula (f), X is a tetravalent organic group containing an aromatic group, Y is a divalent organic group containing an aromatic group, R7 and R8 are independently selected from monovalent organic groups having the structure shown in formula (g), and q is 2 to 150).

[0066]

[0067] (In formula (g), R9, R 10 and R 11 Each is independently selected from hydrogen atoms and alkyl groups having 1 to 3 carbon atoms; r is 2 to 10).

[0068] Preparation of polyamic acid esters

[0069] In the technical solution of the present invention, the polyamic acid ester having the structure shown above can be prepared by the following method:

[0070] A partially esterified tetracarboxylic acid is prepared by reacting a tetracarboxylic acid dianhydride containing an X group, an alcohol with an unsaturated double bond that has free radical polymerization ability, and / or a saturated aliphatic alcohol with 1 to 4 carbon atoms; then, it is subjected to amide polycondensation with a diamine containing a Y group.

[0071] There are no particular limitations on tetracarboxylic dianhydrides containing the X group, and specific examples include 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, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)propane. Phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic anhydride, benzophenone-3,3',4,4'-tetracarboxylic anhydride, biphenyl-3,3',4,4'-tetracarboxylic anhydride, more preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic anhydride, biphenyl-3,3',4,4'-tetracarboxylic anhydride, etc., the above can be used alone or in any mixture.

[0072] There are no particular limitations on alcohols with unsaturated double bonds that are capable of free radical polymerization. Specific examples include 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamide 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-tert-butoxypropyl acrylate, and 2-hydroxy-3-cyclohexyloxy... Propylene acrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-methacrylamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, etc., can be used alone or in any combination.

[0073] There are no particular restrictions on saturated aliphatic alcohols with 1 to 4 carbon atoms. Examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol. These can be used alone or in any mixture.

[0074] The above-mentioned tetracarboxylic acid dianhydride and the above-mentioned alcohol are preferably reacted in the presence of an alkaline catalyst such as pyridine in a suitable reaction solvent at 20-50°C for 4-10 hours by stirring, to obtain partially esterified tetracarboxylic acid.

[0075] The solvent used in the above reaction is preferably a solvent that can completely dissolve the reactants and / or products, and more preferably a solvent that can also completely dissolve the photosensitive polyimide precursor. Examples of such solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. These can be used individually or in any mixture.

[0076] The solution containing partially esterified tetracarboxylic acid obtained in the above reaction is preferably subjected to a dehydrating condensing agent under ice-cold conditions to obtain polyanhydride. Then, a diamine or its solution containing a Y group is added, and the target polyamic acid ester is obtained by amide polycondensation.

[0077] There are no particular limitations on the above-mentioned dehydrating condensing agents. Specific examples include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. These can be used alone or in any combination.

[0078] There are no particular limitations on the diamine containing the Y group, and specific examples include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3 ...3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'- -Diaminobiphenyl, 3,4'-Diaminobiphenyl, 3,3'-Diaminobiphenyl, 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)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-aminopropyldimethylsilyl)benzene, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 9,9-bis(4-aminophenyl)fluorene, etc., can be used alone or in any mixture.

[0079] Component (2): First radical polymerizable monomer containing epoxy structure

[0080] In the technical solution of the present invention, a free radical polymerizable monomer containing an epoxy structure is added to the negative photosensitive polyimide precursor resin composition, which is selected from at least one of the compounds with the structures shown in formula (a), formula (b), formula (c), formula (d), formula (e), and formula (f):

[0081]

[0082] In equation (a), R1 is selected from any one of them;

[0083] R2 is selected from any one of hydrogen atoms and alkyl groups having 1 to 3 carbon atoms, and R3 and R4 are each independently selected from any one of H and aliphatic hydrocarbon groups having 1 to 8 carbon atoms, with m = 0 to 7.

[0084] Specific examples of free radical polymerizable monomers with epoxy-containing structures as shown in formula (a) can be listed below:

[0085]

[0086] In equation (b), n = 0 to 6;

[0087] Specific examples of free radical polymerizable monomers with epoxy-containing structures as shown in formula (b) can be listed below:

[0088]

[0089]

[0090] In equation (c), A1 is Specific examples of free radical polymerizable monomers with epoxy-containing structures as shown in formula (c) can be listed below:

[0091]

[0092] In formula (d), R5 is selected from any one of hydrogen atoms and alkyl groups having 1 to 3 carbon atoms; R6 is selected from... Any one of them; p = 0 to 1;

[0093] Specific examples of free radical polymerizable monomers with epoxy-containing structures as shown in formula (d) can be listed below:

[0094]

[0095] In equation (e), A2 is a ring structure, selected from... any one of them;

[0096] Specific examples of free radical polymerizable monomers with epoxy-containing structures as shown in formula (e) can be listed below:

[0097]

[0098] In the technical solution of the present invention, the amount of the first free radical polymerizable monomer with the epoxy structure having the above structure added is 1-20 parts by mass based on 100 parts of polyamic acid ester, considering the balance between photolithography performance and chemical corrosion resistance.

[0099] Component (3): Second radical polymerizable monomer

[0100] The present invention further incorporates a second free radical polymerizable monomer containing unsaturated bonds into the negative photosensitive polyimide precursor resin composition, which can undergo free radical polymerization reaction with the free radical polymerizable substituents on the side chains of the above-mentioned polyamic acid ester.

[0101] As the aforementioned second free radical polymerizable monomer, it is preferably any one or more of (meth)acrylate compounds that can undergo free radical polymerization under the action of a photoinitiator. In the technical solution of the present invention, the (meth)acrylate compounds include acrylate compounds and / or methacrylate compounds: including, but not limited to, mono(meth)acrylates or di(meth)acrylates of ethylene glycol or polyethylene glycol, primarily diethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate; mono(meth)acrylates or di(meth)acrylates of propylene glycol or polypropylene glycol; mono(meth)acrylates, di(meth)acrylates or tri(meth)acrylates of glycerol; cyclohexane di(meth)acrylates; and diacrylates of 1,4-butanediol. The compounds include esters and dimethacrylates, di(meth)acrylates of 1,6-hexanediol; di(meth)acrylates of neopentyl glycol; mono(meth)acrylates or di(meth)acrylates of bisphenol A; phenyl trimethacrylate; isobornyl (meth)acrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane tri(meth)acrylate; di(meth)acrylates or tri(meth)acrylates of glycerol; di(meth)acrylates, tri(meth)acrylates, or tetra(meth)acrylates of pentaerythritol; and ethylene oxide or propylene oxide adducts of these compounds, preferably any one or more of difunctional (meth)acrylate compounds and trifunctional (meth)acrylate compounds.

[0102] Specific examples of free radical polymerization monomers mentioned above include tetraethylene glycol trimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol dimethacrylate. Pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-hydroxymethylacrylamide, etc., can be used alone or in any mixture, with triethylene glycol trimethacrylate being the preferred choice.

[0103] In the technical solution of the present invention, the amount of free radical polymerizable monomer added is 1-20 parts by mass based on 100 parts of polyamic acid ester, considering the improvement of photolithography resolution. If the amount is too low, it will not be conducive to obtaining high photolithography resolution, and if it is too high, it will reduce the chemical corrosion resistance of the cured film.

[0104] Component (4): Photoinitiator

[0105] There are no particular limitations on the photoinitiator applicable to this invention. Specific examples include 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-morpholino-1-propanone, alkyl anthraquinones, benzoin alkyl ethers, benzoin, alkylbenzoin, and benzoin dimethyl ketal, etc. These can be used alone or in any combination, with oxime ester compounds being more preferred.

[0106] In the technical solution of the present invention, the amount of photoinitiator added is based on improving photolithography resolution and widening the photolithography window. It is 0.5-10 parts by weight for 100 parts of polyamic acid ester. Too low a part will significantly reduce the residual film rate of development, while too high a part will easily lead to photolithography overexposure, which will result in the photolithography window being significantly smaller.

[0107] Other components:

[0108] The negative-type photosensitive polyimide precursor resin composition of the present invention may also include other components besides those described above.

[0109] The negative-type photosensitive polyimide precursor resin composition of the present invention can be dissolved in a solvent to form a liquid resin composition by dissolving the above-mentioned components and any other components added as needed. Therefore, solvents can be listed as other components. Other components may also include resins, silane coupling agents, polymerization inhibitors, and thermal alkali-generating agents, in addition to the components mentioned above.

[0110] Component (5): Organic solvent

[0111] In the technical solution of this invention, there are no particular limitations on the applicable solvents, but specific examples include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

[0112] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters, alkyl 3-alkoxypropionate esters, alkyl 2-alkoxypropionate esters, methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate esters, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, and ethyl 2-oxobutyrate.

[0113] Alkyl alkoxyacetic acid esters include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate. Alkyl 3-alkoxypropionic acid esters include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate. Alkyl 2-alkoxypropionic acid esters include methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate. Methyl 2-alkoxy-2-methylpropionate includes methyl 2-methoxy-2-methylpropionate. Ethyl 2-alkoxy-2-methylpropionate includes ethyl 2-ethoxy-2-methylpropionate.

[0114] Examples of ethers include 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.

[0115] Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

[0116] Examples of aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

[0117] Examples of sulfoxides include dimethyl sulfoxide.

[0118] Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0119] The solvents listed above can be used alone or in any mixture.

[0120] Among them, considering the solubility of each component and the coating properties of the resin film, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and N,N-dimethylacetamide are preferred.

[0121] In the technical solution of the present invention, the amount of solvent added as used above can be determined according to the viscosity and coating thickness requirements of the negative photosensitive polyimide precursor resin composition, and is 50-1500 parts by weight based on 100 parts of polyamic acid ester.

[0122] Component (6): Silane coupling agent

[0123] In the technical solution of the present invention, adding a silane coupling agent to the above-mentioned negative photosensitive polyimide precursor resin composition can increase its adhesion strength to the substrate.

[0124] The silane coupling agent used in this invention is not particularly limited, but may include ureapropyltriethoxysilane, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-epoxypropoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane, N... -(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, and N-phenylaminopropyltrimethoxysilane; preferably ureapropyltriethoxysilane.

[0125] Preferably, the silane coupling agent is selected from any one or more silane coupling agents containing urea bonds (-NH-CO-NH-).

[0126] In the technical solution of the present invention, the amount of silane coupling agent added is based on improving the adhesion of the silicon surface and the uniformity of coating. It is 0.5-10 parts by weight per 100 parts of polyamic acid ester. If the amount is too low, the adhesion performance of the silicon surface will be poor, and if it is too high, the coating uniformity will be significantly damaged.

[0127] Component (7): Polymerization inhibitor

[0128] In the technical solution of this invention, the negative photosensitive polyimide precursor resin composition, especially when containing a solvent, can be arbitrarily mixed with polymerization inhibitors to improve its viscosity and stability during storage. There are no particular limitations on the polymerization inhibitors, but one or more of phenolic radical polymerization inhibitors are preferred. The polymerization inhibitors applicable to this invention may include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxyamine ammonium salt, etc. These can be used alone or in any combination, with 2-nitroso-1-naphthol being preferred.

[0129] In the technical solution of this invention, the amount of polymerization inhibitor added is considered from the perspective of improving the storage stability of the adhesive solution. Based on 100 parts of polyamic acid ester, it is 0.01-5 parts by mass. Too few parts will destroy the storage stability of the adhesive solution, while too many parts will destroy the photolithography performance of the adhesive solution.

[0130] Component (8): Thermal alkali-producing agent

[0131] In the technical solution of the present invention, the negative photosensitive polyimide precursor resin composition may further include a thermal alkali-generating agent, which can generate alkali by heating to promote the imidization of polyamide ester.

[0132] The heat-generating alkali agent applicable to this invention is not particularly limited, but is preferably an amine compound protected by tert-butoxycarbonyl.

[0133] As for amine compounds protected by a tert-butoxycarbonyl group, there are no particular limitations, and specific examples include 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, valine, and 3-amino-1,2-propanediol. Alcohols, 2-amino-1,3-propanediol, Tyramine, Demethylephedrine, 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, di... Isopropanolamine, 3-pyrrolidone, 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-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxygen Compounds such as diethylamine, 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; as well as compounds in which the amino group of amino acids and their derivatives is protected by a tert-butoxycarbonyl group, can be used alone or in any combination.

[0134] The thermal alkali-generating agent in this invention is further preferably N-tert-butoxycarbonyl-4-piperidinemethanol.

[0135] In the technical solution of the present invention, the amount of thermal alkali agent added is considered from the perspective of improving the degree of thermal imidization of polyimide precursor resin. Based on 100 parts of polyamic acid ester, it is 0.1-10 parts by weight. If the amount is too low, it will not be conducive to improving the degree of thermal imidization of polyimide precursor resin, and if the amount is too high, it will significantly shorten the storage stability of the adhesive.

[0136] In the technical solution of the present invention, the above-mentioned negative photosensitive polyimide precursor resin composition can be obtained by thermal imidization to obtain a cured polyimide composition, and patterned cured polyimide compositions can also be prepared by using a mask with a specific pattern.

[0137] The preparation method of the patterned cured polyimide composition includes the following steps:

[0138] (1) The above negative photosensitive polyimide precursor resin composition is coated on a substrate to form a negative photosensitive polyimide precursor resin layer on the substrate;

[0139] (2) Expose the negative photosensitive polyimide precursor resin layer on the substrate;

[0140] (3) The exposed negative photosensitive polyimide precursor resin layer is developed to form a pattern;

[0141] (4) Heat the pattern to form a solidified pattern.

[0142] In step (1), there are no specific restrictions on the coating method. Spin coating, scraping coating, screen printing, spraying, etc. can be used. Then, it is dried as needed to form a negative photosensitive polyimide precursor resin layer. As for the drying method, heating drying in an oven or heating plate, vacuum drying, etc. can be used. As for the substrate, metal substrates such as Cu, glass substrates, semiconductor substrates, metal oxide insulators (TiO2, SiO2, etc.), silicon nitride substrates, etc. can be used.

[0143] Preferably, the drying is carried out under conditions where the polyamide ester in the negative photosensitive polyimide precursor resin composition does not form imide; specifically, drying at 70-130°C for 1-10 minutes.

[0144] 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. The light source used can be ultraviolet light, visible light, or radiation, etc.

[0145] In step (3), a developer is used to remove the unexposed portion of the negative photosensitive polyimide precursor resin layer after exposure treatment to form a pattern; the applicable developer is a good solvent for the negative photosensitive polyimide precursor resin layer or a mixture of a good solvent and a bad solvent.

[0146] As good solvents, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, cyclohexanone, etc. can be used alone or in any mixture.

[0147] Examples of unsuitable solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water. These can be used individually or in any mixture.

[0148] When using a mixed solvent of good and bad solvents for the negative photosensitive polyimide precursor resin layer as the developer, the ratio of good to bad solvent is determined based on the solubility of the polymer in the resin layer.

[0149] There are no particular limitations on the method of developing the solution; any existing known developing method can be used, such as rotary spraying, agitation, immersion, etc.

[0150] After treatment with the developer, further rinsing can be performed, preferably with a solvent different from the developer used.

[0151] In step (4), the polyamide ester is imidized by heating the pattern obtained by the above development to obtain the corresponding cured polyimide.

[0152] The heat treatment temperature is 150–400°C. Within this reaction temperature range, the cross-linking reaction or the dehydration and ring-closing reaction can be fully carried out.

[0153] The negative photosensitive polyimide precursor resin composition of the present invention can be applied to semiconductor devices by the above method, and can also be used for interlayer insulation of multilayer circuits, cover coating of flexible copper clad laminates, and other applications.

[0154] Manufacturing example: polyamide ester

[0155] Polyamate A

[0156] 103 g of 4,4'-oxophthalic anhydride (ODPA) was dispersed in γ-butyrolactone (GBL). 87 g of hydroxyethyl methacrylate (HEMA) was added to the reaction system in one step, followed by the dropwise addition of 3 g of pyridine. The reaction was carried out at room temperature for 16 h. 137 g of dicyclohexylcarbodiimide (DCC) was dissolved in GBL and slowly added to the reaction system, followed by stirring for 2 h. 67 g of 4,4'-diaminodiphenyl ether (ODA) was dissolved in GBL under a nitrogen atmosphere and slowly added to the reaction system, followed by stirring for 9 h (if stirring is difficult during the reaction, the reaction system can be diluted with solvent as needed). After the reaction was complete, 2 g of ethanol was added and the reaction was carried out for 2 h.

[0157] The quenched reaction liquid was filtered, and the filtrate was immediately added to methanol to precipitate lumpy solids. After being refrigerated for 12 hours, the solids were dissolved and added dropwise to water. After filtration and drying, the corresponding polyamic acid ester A was obtained.

[0158] The molecular weight of the polymer was determined using an ultra-high performance polymer chromatography (APC) instrument (details of the test method are described below): M w It is 24000, and PDI is 1.85.

[0159] Polyamate B

[0160] Polyamate B was obtained by replacing 103g of ODPA in the manufacturing example of polyamate A with 82.4g of ODPA and 14.5g of pyromellitic dianhydride (PMDA), while keeping the rest the same as in manufacturing example 1.

[0161] The molecular weight of the polymer, obtained using APC testing, is: M w It is 23500, and PDI is 1.91.

[0162] Polyamate C

[0163] Polyamate C was obtained by replacing 103g of ODPA in the manufacturing example of polyamate A with 62g of ODPA and 29g of PMDA, while keeping the rest consistent with the manufacturing example.

[0164] The molecular weight of the polymer, obtained using APC testing, is: M w It is 24200, and PDI is 1.89.

[0165] Polyamate D

[0166] Polyamate D was obtained by replacing 103g of ODPA in the manufacturing example of polyamate A with 41.3g of ODPA and 43.6g of PMDA, while keeping the rest consistent with the manufacturing example.

[0167] The molecular weight of the polymer, obtained using APC testing, is: M w It is 23800, and PDI is 1.95.

[0168] Polyamate E

[0169] Polyamate E was obtained by replacing 103g of ODPA in the polyamate A manufacturing example with 72.7g of PMDA, while keeping the rest consistent with the manufacturing example.

[0170] The molecular weight of the polymer, obtained using APC testing, is: M w It is 24500, and PDI is 1.85.

[0171] Polyamate F

[0172] Polyamate F was obtained by replacing 67g of ODA in the polyamate A manufacturing example with 36g of p-phenylenediamine (PPDA), while keeping the rest the same as in the manufacturing example.

[0173] The molecular weight of the polymer, obtained using APC testing, is: M w It is 23000, and PDI is 1.88.

[0174] Example:

[0175] Example 1:

[0176] Under constant temperature and humidity (24℃, 50% RH), 20g of polyamic acid ester A, 30g of N-methylpyrrolidone (NMP) solvent, 2.0g of tetraethylene glycol trimethacrylate (second radical polymerizable monomer, hereinafter referred to as the second monomer), and 0.8g of EP-3 (structure as shown) were added sequentially to a 100mL brown plastic bottle. Figure 1 As shown, the following were prepared: a first free radical polymerizable monomer containing an epoxy structure (hereinafter referred to as the first monomer), 0.8 g of photopolymerization initiator BASF IRGACURE OXE-01, 0.8 g of thermal alkali-generating agent N-tert-butoxycarbonyl-4-piperidinemethanol, 0.4 g of silane coupling reagent ureapropyltriethoxysilane, and 0.04 g of polymerization inhibitor 2-nitroso-1-naphthol. After being shaken and dissolved on a shaker for 24 h, NMP was added to adjust the viscosity of the resulting solution to approximately 30 poise. After secondary filtration, the negative photosensitive polyimide precursor resin composition was obtained.

[0177] Photolithography pattern preparation: The negative-type photosensitive polyimide precursor resin composition prepared above was spin-coated onto an 8-inch silicon wafer using a spin coater (WS-650Mz-8NPPB, MYCRO). Pre-baking was performed at 100°C for 240 seconds on a hot plate to form a coating film approximately 10 μm thick. On this coating film, a mask with a test pattern was used, and the film was irradiated with 400 mJ / cm² using an i-line stepper (Shanghai Microelectronics). 2 The energy was then used. Next, for this coating, cyclopentanone was used as the developer, and spray development was performed using a developer (MST-EF1-DV, Shenzhen Kairui). The coating was then rinsed with propylene glycol methyl ether acetate to obtain the photolithographic pattern. A temperature-programmed curing oven (HCM-500D, Shanghai Siwan Electronics) was used under a nitrogen atmosphere at the curing temperatures described in Table 1 below (200℃ / 2h) to obtain a cured photolithographic pattern of approximately 10 μm thickness formed from the resin.

[0178] Example 2

[0179] Replace 20g of polyamic acid ester A in Example 1 with 20g of polyamic acid ester B, while keeping the remaining components and operating procedures the same as in Example 1.

[0180] Example 3

[0181] Replace 20g of polyamic acid ester A in Example 1 with 20g of polyamic acid ester C, while keeping the remaining components and operating procedures the same as in Example 1.

[0182] Example 4

[0183] Replace 20g of polyamic acid ester in Example 1 with 20g of polyamic acid ester D, while keeping the remaining components and operating procedures the same as in Example 1.

[0184] Example 5

[0185] Replace 20g of polyamic acid ester A in Example 1 with 20g of polyamic acid ester E, while keeping the remaining components and operating procedures the same as in Example 1.

[0186] Example 6

[0187] In Example 1, 20g of polyamate A was replaced with 10g of polyamate E and 10g of polyamate F, while the remaining components and operating procedures remained the same as in Example 1.

[0188] Example 7

[0189] Replace 0.8g EP-3 in Example 6 with 0.4g EP-3, while keeping the remaining components and operating procedures the same as in Example 6.

[0190] Example 8

[0191] Replace 0.8g EP-3 in Example 6 with 0.2g EP-3, while keeping the remaining components and operating procedures the same as in Example 6.

[0192] Example 9

[0193] Replace 0.8g of EP-3 in Example 6 with 0.8g of EP-1, while keeping the remaining components and operating procedures the same as in Example 6.

[0194] Example 10

[0195] Replace 0.8g of EP-3 in Example 6 with 0.8g of EP-2, while keeping the remaining components and operating procedures the same as in Example 6.

[0196] Example 11

[0197] Replace 0.8g of EP-3 in Example 6 with 0.8g of EP-4, while keeping the remaining components and operating procedures the same as in Example 6.

[0198] Example 12

[0199] Replace 0.8g of EP-3 in Example 6 with 0.8g of EP-5, while keeping the remaining components and operating procedures the same as in Example 6.

[0200] Example 13

[0201] Replace 0.8g of EP-3 in Example 6 with 0.8g of EP-6, while keeping the remaining components and operating procedures the same as in Example 6.

[0202] Example 14

[0203] The curing process in Example 6 was changed to 175℃ / 2h, while the remaining components and operating procedures remained the same as in Example 6.

[0204] Example 15

[0205] The curing process in Example 11 was changed to 175℃ / 2h, while the remaining components and operating procedures remained the same as in Example 6.

[0206] Comparative Example 1

[0207] Replace 0.8g of EP-3 in Example 6 with 0.8g of EP-7, while keeping the remaining components and operating procedures the same as in Example 6.

[0208] Comparative Example 2

[0209] Replace 0.8g of EP-3 in Example 6 with 0.8g of EP-8, while keeping the remaining components and operating procedures the same as in Example 6.

[0210] Comparative Example 3

[0211] The 0.8g of EP-3 in Example 6 was removed, and the remaining components and operating procedures remained the same as in Example 6.

[0212] Implementation of effects:

[0213] 1. Weight-average molecular weight test:

[0214] The polymer weight-average molecular weight M involved in this invention w The polymer dispersity index (PDI) was obtained using an ultra-high performance polymer chromatography instrument (ACQUITYAPC). The relevant test conditions were as follows: the chromatographic column model was ACQUITYAPC XT45 1.7μm / ACQUITYAPC XT200 2.5μm / ACQUITYAPCXT450 2.5μm, the column oven and detector temperature were both 40℃, the mobile phase was tetrahydrofuran (THF), and the flow rate was 0.5mL / min.

[0215] 2. Methods for preparing and evaluating photolithographic patterns:

[0216] The photosensitive polyaminate composition prepared in the above examples was spin-coated onto an 8-inch silicon wafer using a spin coater (WS-650Mz-8NPPB, MYCRO). Pre-baking was performed at 100°C on a hot plate for 240 seconds to form a coating film approximately 10 μm thick. On this coating film, a mask with a test pattern was used, and the film was irradiated with 400 mJ / cm² using an i-line stepper (Shanghai Microelectronics). 2The energy was then used. Next, for this coating, cyclopentanone was used as the developer, and spray development was performed using a developer (MST-EF1-DV, Shenzhen Kairui). The coating was then rinsed with propylene glycol methyl ether acetate to obtain the photolithographic pattern. A temperature-programmed curing oven (HCM-500D, Shanghai Siwan Electronics) was used to heat-treat the coating for 2 hours under a nitrogen atmosphere at the curing temperatures listed in Table 1, resulting in a cured photolithographic pattern of approximately 10 μm thickness formed from the composition.

[0217] The cured photolithographic pattern obtained above was analyzed by cross-section analysis using a focused ion beam electron microscope (FIB, Helios G4, Thermo Fisher) to evaluate its photolithographic accuracy and cross-sectional morphology. The photolithographic performance of the negative photosensitive resin composition was then evaluated: a photolithographic line accuracy of less than 10 μm was rated as "excellent", a photolithographic line accuracy of 10–20 μm was rated as "good", a photolithographic line accuracy of 20–50 μm was rated as "fair", and a photolithographic line accuracy of more than 50 μm was rated as "poor".

[0218] 3. Mechanical property testing of the cured film:

[0219] The cured exposure film prepared by the above method with a mask of a specific pattern and curing method is immersed in 1% hydrofluoric acid aqueous solution for 10 min and then peeled off from the silicon wafer to obtain a 5 mm × 10 cm film strip. After drying the moisture in an oven at 150 °C, the film strip is subjected to mechanical tensile testing using a universal tensile tester (Shenzhen Sansi Zongheng Technology). The mechanical properties are evaluated according to the elongation at break: an elongation at break greater than 50% is rated as "excellent", an elongation at break between 40% and 50% is rated as "good", an elongation at break between 20% and 40% is rated as "fair", and an elongation at break less than 20% is rated as "poor".

[0220] 4. Chemical resistance test of the cured film:

[0221] The cured exposure film prepared by the above method with a mask of a specific pattern and curing method is immersed in a 1% hydrofluoric acid aqueous solution for 10 min and then peeled off from the silicon wafer to obtain a complete cured film. After drying the moisture in an oven at 150°C, it is immersed in a dimethyl sulfoxide solution containing 2.38% tetramethylammonium hydroxide at 50°C for 60 min. The chemical resistance is evaluated according to the weight loss of the cured film before and after the chemical resistance treatment: less than 5% weight loss is rated as "excellent", 5%-15% weight loss is rated as "good", 15%-25% weight loss is rated as "fair", and more than 25% weight loss is rated as "poor".

[0222] The components and contents of the negative photosensitive polyimide precursor resin compositions prepared in the above examples and comparative examples, as well as the curing process, are shown in Table 1, and the relevant performance test data are shown in Table 2. As can be seen from Tables 1 and 2, compared to Comparative Examples 1-3, the examples with added free radical polymerizable compounds having an epoxy structure generally exhibit good mechanical properties, photolithographic properties, and chemical corrosion resistance under different resin systems. The examples with added free radical polymerizable epoxy compounds EP-5 / 6 show good chemical corrosion resistance but poor photolithographic resolution, while Comparative Example 3, without added epoxy additives, has very poor chemical corrosion resistance.

[0223] Table 1

[0224]

[0225]

[0226] Table 2

[0227]

[0228]

[0229] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A negatively photosensitive polyimide precursor resin composition, characterized in that, comprises: 100 parts by mass of a polyamide acid ester as a polyimide precursor; 1 to 20 parts by mass of a first radically polymerizable monomer containing an epoxy structure; 1 to 20 parts by mass of a second radically polymerizable monomer; 0.5 to 10 parts by mass of a photoinitiator; 0.5 to 10 parts by mass of a silane coupling agent; 0.01 to 5 parts by mass of a polymerization inhibitor; 0.1 to 10 parts by mass of a thermal base generator; 50 to 1500 parts by mass of an organic solvent; wherein the first radically polymerizable monomer containing an epoxy structure is selected from at least one of compounds having structures represented by formula (a), formula (b), formula (c), formula (d), formula (e), and formula (f): In formula (a), R1is selected from any one of the group consisting of wherein R2 is selected from any one of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, R3 and R4 are each independently selected from any one of H and an aliphatic group having 1 to 8 carbon atoms, and m = 0 to 7; in formula (b), n = 0 to 6; In formula (c), A1is In formula (d), R5is selected from any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms; R6is selected from any one of any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms; p = 0 to 1. In formula (e), A2is a cyclic structure selected from any one of any one of the following.

2. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized by the polyamide acid ester has a structure represented by formula (f): in formula (f), X is a 4-valent organic group containing an aromatic group, Y is a 2-valent organic group containing an aromatic group, R7 and R8 are each independently selected from a 1-valent organic group having a structure represented by formula (g), and q = 2 to 150; In formula (g), R9, R 10 and R 11 are each independently selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms; and r is 2 to 10.

3. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized by the second radically polymerizable monomer is selected from any one or several of (meth)acrylate compounds.

4. The negative photosensitive polyimide precursor resin composition according to claim 3, characterized by the second radically polymerizable monomer is selected from any one or several of difunctional (meth)acrylate compounds and trifunctional (meth)acrylate compounds.

5. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein the photoinitiator is selected from any one or several 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.

6. The negative photosensitive polyimide precursor resin composition according to claim 5, wherein the photoinitiator is an oxime ester compound.

7. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein the organic solvent is selected from any one or several of esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

8. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein the silane coupling agent is selected from any one or several of silane coupling agents containing a urea bond (-NH-CO-NH-).

9. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein the polymerization inhibitor is selected from any one or several of phenolic radical polymerization inhibitors.

10. The negative photosensitive polyimide precursor resin composition according to claim 1, wherein the thermal base generator is a tert-butoxycarbonyl-protected amine compound.

11. A negative-type photosensitive polyimide resin composition, characterized in that, a negative photosensitive polyimide precursor resin composition according to any one of claims 1 to 8 is thermally imidized.

12. The negative photosensitive polyimide resin composition according to claim 11, wherein the temperature of the thermal imidization is 150 to 400°C.

Images