WO2024198017A1 - Negative photosensitive polyimide precursor resin composition - Google Patents

Abstract

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 free radical polymerizable monomer containing an epoxy structure; 1-20 parts by mass of a second free 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 base generator; and 50-1,500 parts by mass of an organic solvent. In a resin composition, the polymerizable monomer containing the epoxy structure is introduced into the polyimide precursor composition, so that low-temperature curing can be realized, and a cured film obtained after the low-temperature curing has excellent mechanical properties, has excellent strength of bonding with a copper surface, has excellent chemical corrosion resistance, and can meet the application requirements of advanced packaging processes such as high-density fan-out wafer-level packaging.

Description

Negative photosensitive polyimide precursor resin composition Technical Field

The invention relates to the technical field of polyimide, in particular to a negative photosensitive polyimide precursor resin composition.

Background Art

Photosensitive polyimide photoresist (PSPI) materials are widely used in surface passivation of integrated circuit chips and surface rewiring processes of wafer-level packaging and panel-level packaging. They are key materials in wafer-level advanced packaging processes. Traditional PSPI materials require a curing temperature of more than 350°C to obtain the various excellent properties of polyimide materials. At such a high curing temperature, wafer warping, stress cracking, and other packaging material compatibility problems are prone to occur in advanced packaging processes such as high-density fan-out wafer-level packaging. Therefore, PSPI needs to be cured at low temperatures. However, low-temperature cured PSPI materials often encounter problems such as insufficient imidization, poor mechanical properties, poor chemical corrosion resistance, etc., which cannot meet the requirements of the packaging process, and poor bonding with other materials in the packaging process, especially electroplated copper, resulting in poor reliability of the final device. In particular, the current high-end wafer-level packaging process has higher requirements for low-stress and low-warpage curing processes, and the demand for ultra-low-temperature cured PSPI materials that cure below 200°C is becoming increasingly urgent, and the solution to the above problems is becoming more and more urgent.

Generally speaking, in order to solve the above problems, people will introduce light/heat base generating agents to reduce the activation energy of imidization of polyimide precursor resins and thus achieve excellent performance of polyimide resins in various aspects under low-temperature processes, such as CN112639616A, CN112513219A, CN112639615A and CN111919172A, or control the molecular weight of the precursor resin so that the molecular chain can obtain sufficiently high mobility during low-temperature curing to increase the imidization rate, such as CN108475020A. For example, CN112334833A introduces polymeric compounds containing carbamate and urea bond structures, and CN110741318A and CN113168093A introduce polymeric compounds containing sulfite structures to obtain comprehensive properties of low-temperature curing, high imidization rate, good chemical resistance, and excellent copper surface bonding. In addition, in order to improve the bonding strength between the redistribution layer and the copper surface, various copper surface additives are generally introduced, such as CN102375336B and CN112799281A.

Generally speaking, the most prominent problem faced by PSPI materials cured below 230°C is the insufficient chemical corrosion resistance, which makes it difficult to meet the process requirements of wafer-level packaging processes. The main reason for this problem is that at ultra-low curing temperatures, most of the additives, especially the photocrosslinking additives and the polymerizable functional groups contained in the polyimide precursor, still remain in the cured film, and the chemical corrosion resistance of these additive residues is often much worse than that of polyimide. To improve this problem, generally, a rigid photocrosslinking agent with an aliphatic cyclic skeleton is introduced to enhance the rigidity of the molecular structure of the residue in the cured film to improve its chemical corrosion resistance, such as CN110520795A, or a multifunctional crosslinking additive is introduced to enhance the crosslinking density of the residue in the cured film to improve its chemical corrosion resistance, such as CN111936930A, CN110300767A, however, the material produced therefrom still fails to achieve sufficiently excellent chemical corrosion resistance to meet the stringent requirements of the packaging process.

Summary of the invention

In view of the above technical problems, the present invention provides a negative photosensitive polyimide precursor resin composition.

To achieve the above object, the technical solution adopted by the present invention is:

The present invention provides a negative photosensitive polyimide precursor resin composition, comprising:

100 parts by mass of polyamic acid ester as a polyimide precursor;

1-20 parts by mass of a first free radical polymerizable monomer containing an epoxy structure;

1-20 parts by mass of a second free 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 weight of a thermal alkali generating agent;

50-1500 parts by mass of an organic solvent;

The first free radical polymerizable monomer containing an epoxy structure is selected from at least one of the compounds represented by formula (a), formula (b), formula (c), formula (d), formula (e) and formula (f):

In formula (a), R ₁ is selected from Any of;

Wherein, R ₂ is selected from any one of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, R ₃ and R ₄ are each independently selected from any one of a hydrogen atom and an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and m=0 to 7;

In formula (b), n=0 to 6;

In formula (c), A ₁ is

In formula (d), R ₅ is selected from any one of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms; R ₆ is selected from Any one of; p = 0 ~ 1;

In formula (e), _A2 is a cyclic structure selected from Any of .

As a preferred embodiment, the polyamic acid ester has a structure as shown in formula (f):

In formula (f), X is a tetravalent organic group containing an aromatic group, Y is a divalent organic group containing an aromatic group, and R ₇ and R ₈ is independently selected from a monovalent organic group having a structure as shown in formula (g), and q is 2 to 150;

In formula (g), R ₉ , R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom and an alkyl group having 1 to 3 carbon atoms; and r is 2 to 10.

As a preferred embodiment, the second free 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;

Specifically, the second free radical polymerizable monomer is selected from tetraethylene glycol dimethacrylate, 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. Any one or more of 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-acryloxy-2-hydroxypropane, 1,3-methacryloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, and N-hydroxymethylacrylamide; preferably tetraethylene glycol dimethacrylate.

As a preferred embodiment, the preparation method of the polyamic acid ester comprises the following steps:

The tetracarboxylic acid dianhydride containing the X group, alcohols having free radical polymerizability and unsaturated double bonds and/or saturated aliphatic alcohols having 1 to 4 carbon atoms are reacted to prepare a partially esterified tetracarboxylic acid; and then the tetracarboxylic acid is subjected to amide polycondensation with a diamine containing the Y group.

The tetracarboxylic dianhydride containing the X group is not particularly limited, and specific examples thereof include pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3 ,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, more preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, etc., the above can be used alone or mixed arbitrarily. Suitable for use.

The diamine containing the Y group is not particularly limited, and specific examples thereof 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, -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., which can be used alone or in any combination.

As 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, alkyl benzoin and benzil dimethyl ketal, and is further preferably an oxime ester compound.

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

Preferably, the ester is 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 alkoxyacetates, alkyl 3-alkoxypropionates, alkyl 2-alkoxypropionates, 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;

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

Preferably, the ketone is selected from any one or more of methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone and 3-heptanone;

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

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

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

Specifically, the silane coupling agent is selected from ureapropyl triethoxysilane, γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-mercaptopropyl methyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethyl silane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropyl silane, diethoxy-3-glycidoxypropyl methyl silane, N-(3-diethyl)- Any one or more of triethoxysilylpropyl) succinimide, N-[3-(triethoxysilyl)propyl] phthalamic 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.

In the technical solution of the present invention, the polymerization inhibitor is not particularly limited, and is preferably any one or more of the phenolic free radical polymerization inhibitors;

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-phenylhydroxylamine ammonium salt and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, preferably 2-nitroso-1-naphthol.

As a preferred embodiment, the thermal base generator is a tert-butoxycarbonyl protected amine compound, and the amine compound in the tert-butoxycarbonyl protected 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, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, demethylephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N- Methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybisethylamine, 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, Any one or more of diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane and diethylene glycol bis(3-aminopropyl) ether;

Preferably, the thermal base generator is N-tert-butyloxycarbonyl-4-piperidinol.

In another aspect, the present invention provides a negative photosensitive polyimide resin composition obtained by thermal imidization of the negative photosensitive polyimide precursor resin composition;

Preferably, the temperature of the thermal imidization is 150-400°C.

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

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

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a schematic diagram of the chemical structures of EP-1 to EP-8 used in the examples and comparative examples of the present invention.

DETAILED DESCRIPTION

The following embodiments are only some embodiments of the present invention, rather than all embodiments. Therefore, the detailed description in the embodiments of the present invention provided below is not intended to limit the scope of the present invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative work belong to the protection scope of the present invention.

In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

The inventors have found that the methods in the prior art for improving the chemical corrosion resistance of ultra-low temperature cured PSPI materials are often simply to increase the cross-linking density and molecular structure strength of the PSPI materials during the exposure process. However, similar experimental verifications have found that this is not sufficient to obtain sufficiently excellent chemical corrosion resistance to meet the stringent requirements of the packaging process.

Therefore, the present invention introduces a polymerizable monomer containing an epoxy structure into the polyimide precursor composition. During the exposure process, the double bonds can be cross-linked into the main structure of the polyimide precursor. At the same time, in the subsequent thermal curing process, the epoxy group and the hydroxyl group generated after the imidization of the PSPI precursor undergo a thermal cross-linking reaction, further enhancing the cross-linking density and strength of the auxiliary agent residue in the cured film, thereby obtaining excellent chemical corrosion resistance.

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

Component (1): Polyamic acid ester

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

(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 a structure as shown in formula (g), and q is 2 to 150);

(In formula (g), R ₉ , R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom and an alkyl group having 1 to 3 carbon atoms; r is 2 to 10).

Preparation of polyamic acid ester

In the technical solution of the present invention, the following method can be used to prepare the polyamic acid ester having the structure shown above:

The tetracarboxylic acid dianhydride containing the X group, alcohols having free radical polymerizability and unsaturated double bonds and/or saturated aliphatic alcohols having 1 to 4 carbon atoms are reacted to prepare a partially esterified tetracarboxylic acid; and then the tetracarboxylic acid is subjected to amide polycondensation with a diamine containing the Y group.

The tetracarboxylic dianhydride containing the X group is not particularly limited, and specific examples thereof include pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4 -phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, more preferably pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, etc., the above can be used alone or in any combination.

The alcohol having a radical polymerizable unsaturated double bond is not particularly limited, and specific examples thereof include 2-acryloyloxy 2-Hydroxy-3-propanol, 1-acryloxy-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, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloxyethanol, 1-methacryloxy-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, and the like. These may be used alone or in any combination.

The saturated aliphatic alcohols having 1 to 4 carbon atoms are not particularly limited, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. These may be used alone or in any combination.

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

As the solvent in the above reaction, it is preferred that the solvent can completely dissolve the reaction raw materials and/or products, and it is more preferred that the solvent can completely dissolve the photosensitive polyimide precursor. As such solvent, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can be specifically listed, and the above solvents can be used alone or in any combination.

The solution containing partially esterified tetracarboxylic acid obtained in the above reaction is preferably subjected to ice-cold conditions, after which a dehydration condensation agent is added to obtain a polyanhydride, and then a diamine containing a Y group or a solution thereof is added to obtain the target polyamic acid ester through amide polycondensation.

The dehydration condensation agent is not particularly limited, and specific examples thereof include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. These may be used alone or in any combination.

The diamine containing the Y group is not particularly limited, and specific examples thereof 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'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminodiphenyl sulfone, 4,4'-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 combination.

Component (2): First free radical polymerizable monomer containing epoxy structure

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 represented by the structures of formula (a), formula (b), formula (c), formula (d), formula (e) and formula (f):

In formula (a), R ₁ is selected from Any of;

Wherein, R ₂ is selected from any one of hydrogen atom and alkyl group with 1 to 3 carbon atoms, R ₃ and R ₄ are each independently selected from any one of H and aliphatic hydrocarbon group with 1 to 8 carbon atoms, and m=0 to 7;

Specific examples of the radical polymerizable monomer containing an epoxy structure represented by formula (a) include:

In formula (b), n=0 to 6;

Specific examples of the radical polymerizable monomer containing an epoxy structure represented by the formula (b) include:

In formula (c), A ₁ is

Specific examples of the radical polymerizable monomer containing an epoxy structure represented by the formula (c) include:

In formula (d), R ₅ is selected from any one of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms; R ₆ is selected from Any one of; p = 0 ~ 1;

Specific examples of the radical polymerizable monomer containing an epoxy structure represented by the formula (d) include:

In formula (e), _A2 is a cyclic structure selected from Any of;

Specific examples of the radical polymerizable monomer containing an epoxy structure represented by the formula (e) include:

In the technical solution of the present invention, the amount of the first radical polymerizable monomer containing an epoxy structure having the above structure added is 1-20 parts by mass based on 100 parts of polyamic acid ester from the perspective of balancing photolithography performance and chemical corrosion resistance.

Component (3): Second free radical polymerizable monomer

The present invention further compounded a second free radical polymerizable monomer containing an unsaturated bond into the negative photosensitive polyimide precursor resin composition, and the second free radical polymerizable monomer can undergo free radical polymerization reaction with the free radical polymerizable substituent on the side chain of the polyamic acid ester.

As the above-mentioned second free radical polymerizable monomer, it is preferably any one or more of the (meth)acrylate compounds that can undergo free radical polymerization reaction 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)acrylate or di(meth)acrylate of ethylene glycol or polyethylene glycol headed by diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; mono(meth)acrylate or di(meth)acrylate of propylene glycol or polypropylene glycol; mono(meth)acrylate, di(meth)acrylate or tri(meth)acrylate of glycerol; cyclohexane di(meth)acrylate; diacrylate of 1,4-butanediol; Ester and dimethacrylate, di(meth)acrylate of 1,6-hexanediol; di(meth)acrylate of neopentyl glycol; mono(meth)acrylate or di(meth)acrylate of bisphenol A; phenyl trimethacrylate; isobornyl(meth)acrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane tri(meth)acrylate; di(meth)acrylate or tri(meth)acrylate of glycerol; di(meth)acrylate, tri(meth)acrylate, or tetra(meth)acrylate of pentaerythritol; and compounds such as ethylene oxide or propylene oxide adducts of these compounds, and further preferably any one or more of difunctional (meth)acrylate compounds and trifunctional (meth)acrylate compounds.

Specific examples of the above-mentioned free radical polymerization monomers include triethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylic acid, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 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., which can be used alone or in any combination, and are preferably tri-tetraethylene glycol dimethacrylate.

In the technical solution of the present invention, the amount of free radical polymerization monomer added is 1-20 parts by mass based on 100 parts of polyamic acid ester from the perspective of improving lithography resolution. If the amount is too low, it is not conducive to obtaining high lithography resolution, and if it is too high, it will reduce the chemical corrosion resistance of the cured film.

Component (4): Photoinitiator

There are no particular restrictions on the photoinitiators applicable to the present invention, and 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 anthraquinone, benzoin alkyl ether, benzoin, alkyl benzoin and benzyl dimethyl ketal. The above can be used alone or in any combination, and oxime ester compounds are more preferred.

In the technical solution of the present invention, the amount of photoinitiator added is 0.5-10 parts by mass based on 100 parts of polyamic acid ester from the perspective of improving lithography resolution and widening the lithography window. Too low a number will greatly reduce the residual film rate after development, while too high a number will easily lead to overexposure of the lithography and thus make the lithography window significantly smaller.

Other components:

The negative photosensitive polyimide precursor resin composition of the present invention may further include other components in addition to the above components.

The negative photosensitive polyimide precursor resin composition of the present invention can be prepared by dissolving the above components and any components added as needed in a solvent to form a liquid resin composition. Therefore, as other components, a solvent can be listed. As other components, resins other than the above components, silane coupling agents, polymerization inhibitors, and thermal base generating agents can also be listed.

Component (5): Organic solvent

In the technical solution of the present invention, there is no particular limitation on the applicable solvent, and specific examples thereof include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of the 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 alkoxyacetates, alkyl 3-alkoxypropionates, alkyl 2-alkoxypropionates, methyl 2-alkoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetyl Methyl acetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

Among them, examples of alkyl alkoxyacetates include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. Examples of alkyl 3-alkoxypropionates include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc. Examples of alkyl 2-alkoxypropionates include methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc. Examples of methyl 2-alkoxy-2-methylpropionate include methyl 2-methoxy-2-methylpropionate, etc. Examples of ethyl 2-alkoxy-2-methylpropionate include ethyl 2-ethoxy-2-methylpropionate, etc.

Examples of the 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.

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

Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

Examples of the sulfoxides include dimethyl sulfoxide and the like.

Examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

The solvents listed above may be used alone or in any combination.

Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and N,N-dimethylacetamide are preferably used in view of the solubility of each component and the coating property of the resin film.

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

Component (6): Silane coupling agent

In the technical solution of the present invention, a silane coupling agent is added to the negative photosensitive polyimide precursor resin composition to increase the bonding strength between the negative photosensitive polyimide precursor resin composition and the substrate.

The silane coupling agent used in the present invention is not particularly limited, and specific examples thereof include ureapropyl triethoxysilane, γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-mercaptopropyl methyl dimethoxysilane, 3-methacryloxypropyl dimethoxymethyl silane, 3-methacryloxypropyl trimethoxysilane, dimethoxymethyl-3-piperidinylpropyl ... Ethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic 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.

Preferably, the silane coupling agent is selected from any one or more silane coupling agents containing a urea bond (-NH-CO-NH-).

In the technical solution of the present invention, the amount of silane coupling agent added is 0.5-10 parts by mass based on 100 parts of polyamic acid ester from the perspective of improving the adhesion of the silicon surface and the coating uniformity. 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.

Component (7): Polymerization inhibitor

In the technical solution of the present invention, the negative photosensitive polyimide precursor resin composition, especially when containing a solvent, can be mixed with any polymerization inhibitor to improve its viscosity and stability during storage. The polymerization inhibitor is not particularly limited, and is preferably any one or more of phenolic free radical polymerization inhibitors. Specific examples of polymerization inhibitors applicable to the present invention include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, 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-phenylhydroxylamine ammonium salt and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. The above-mentioned inhibitors can be used alone or in any combination. 2-nitroso-1-naphthol is preferred.

In the technical solution of the present invention, the amount of polymerization inhibitor added is 0.01-5 parts by mass based on 100 parts of polyamic acid ester from the perspective of improving the storage stability of the glue solution. Too low a number will destroy the storage stability of the glue solution, while too high a number will destroy the lithography performance of the glue solution.

Component (8): thermal alkali generator

In the technical solution of the present invention, the negative photosensitive polyimide precursor resin composition may further include a thermal base generator, which may generate a base by heating to promote the imidization of polyamic acid ester.

The thermal base generator applicable to the present invention is not particularly limited, and is preferably an amine compound protected by a tert-butoxycarbonyl group;

The amine compound protected by the tert-butoxycarbonyl group is not particularly limited, and specific examples thereof 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, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohex ... Aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidinyl)-2-propanol alcohol, 1,4-butanol bis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybisethylamine, 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, diethylene glycol bis(3-aminopropyl) ether, and compounds in which the amino groups of amino acids and their derivatives are protected by tert-butoxycarbonyl, etc., which can be used alone or in any combination.

The thermal base generator in the present invention is more preferably N-tert-butyloxycarbonyl-4-piperidiniummethanol.

In the technical solution of the present invention, the amount of the thermal alkali generator added is 0.1-10 parts by mass based on 100 parts of polyamic acid ester from the perspective of increasing the degree of thermal imidization of the polyimide precursor resin. A too low amount is not conducive to increasing the degree of thermal imidization of the polyimide precursor resin, while a too high amount will significantly shorten the storage stability of the adhesive.

In the technical solution of the present invention, the negative photosensitive polyimide precursor resin composition can be thermally imidized to obtain a cured polyimide composition, and a patterned cured polyimide composition can also be prepared by using a mask with a specific pattern.

The method for preparing a patterned cured polyimide composition comprises the following steps:

(1) coating the negative photosensitive polyimide precursor resin composition on a substrate to form a negative photosensitive polyimide precursor resin layer on the substrate;

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

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

(4) The pattern is subjected to a heat treatment to form a cured pattern.

In step (1), there is no specific limitation on the coating method, and spin coating, scraper coating, screen printing, spray coating, etc. may be used, and then the layer of negative photosensitive polyimide precursor resin may be dried as required to form the layer. The drying method may be heating drying in an oven or on a hot plate, vacuum drying, etc. The substrate may be a metal substrate such as Cu, a glass substrate, a semiconductor substrate, a metal oxide insulator ( _TiO2 , _SiO2 , etc.), a silicon nitride substrate, etc.

Preferably, the drying is performed under the condition that the polyamic acid ester in the negative photosensitive polyimide precursor resin composition does not undergo imidization; specifically, the drying is performed at 70-130° C. for 1-10 minutes.

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 stepper exposure machine, a scanning exposure machine, etc.; the light source used can be ultraviolet light, visible light or radiation, etc.

In step (3), a developer is used to remove the unexposed portion of the negative photosensitive polyimide precursor resin layer after exposure to form a pattern; the developer used is a good solvent for the negative photosensitive polyimide precursor resin layer or a mixed solvent of a good solvent and a poor solvent;

Examples of the good solvent include 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. The above-mentioned can be used alone or in any combination.

Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water. These poor solvents may be used alone or in any combination.

When a mixed solvent of a good solvent and a poor solvent for the negative photosensitive polyimide precursor resin layer is selected as the developer, the ratio of the good solvent to the poor solvent is determined according to the solubility of the polymer in the resin layer.

The method of treating with the developer is not particularly limited, and any conventionally known developing method can be used, for example, a rotary spray method, a stirring method, a dipping method, and the like.

After the developer treatment, further rinsing may be performed, and the rinsing solution is preferably a solvent different from the developer used.

In step (4), the pattern obtained by the development is heated to imidize the polyamic acid ester to obtain the corresponding cured polyimide.

The temperature of the heat treatment is 150 to 400° C. Within this reaction temperature, the cross-linking reaction or the dehydration ring-closure reaction can be fully carried out.

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 the like.

Production example: Polyamic acid ester

Polyamic Acid

Disperse 103g 4,4'-oxydiphthalic anhydride (ODPA) in the solvent γ-butyrolactone (GBL), add 87g hydroxyethyl methacrylate (HEMA) to the reaction system at one time, then drop 3g pyridine, and react at room temperature for 16h. Dissolve 137g dicyclohexylcarbodiimide (DCC) in GBL, slowly drop it into the reaction system and stir for 2h. Dissolve 67g 4,4'-diaminodiphenyl ether (ODA) in GBL in a nitrogen atmosphere, slowly drop it into the reaction system, and stir for 9h after the drop is complete (if stirring is difficult during the reaction, add appropriate solvent to dilute the reaction system). After the reaction is completed, add 2g ethanol and react for 2h.

The quenched reaction liquid was filtered, and the filtrate was immediately added into methanol to precipitate blocky solids, which were refrigerated for 12 hours and then dissolved and added dropwise into water, and filtered and dried to obtain the corresponding polyamic acid ester A.

The molecular weight of the polymer was obtained by testing with an ultra-high performance polymer chromatography (APC) instrument (see below for the specific testing method): M _w is 24,000, and PDI is 1.85.

Polyamic acid ester B

Polyamic acid ester B was obtained by replacing 103 g ODPA in the preparation example of polyamic acid ester A with 82.4 g ODPA and 14.5 g PMDA, while keeping the rest the same as in preparation example 1.

The molecular weight of the polymer was measured by APC and was as follows: M _w was 23500 and PDI was 1.91.

Polyamic Acid C

Polyamic acid ester C was obtained by replacing 103 g ODPA in the manufacturing example of polyamic acid ester A with 62 g ODPA and 29 g PMDA, while keeping the rest the same as the manufacturing example.

The molecular weight of the polymer was measured by APC and was as follows: M _w was 24200 and PDI was 1.89.

Polyamic Acid D

Polyamic acid ester D was obtained by replacing 103 g ODPA in the preparation example of polyamic acid ester A with 41.3 g ODPA and 43.6 g PMDA, while keeping the rest the same as the preparation example.

The molecular weight of the polymer was measured by APC and was as follows: M _w was 23800 and PDI was 1.95.

Polyamic Acid E

Polyamic acid ester E was obtained by replacing 103 g ODPA in the manufacturing example of polyamic acid ester A with 72.7 g PMDA and keeping the rest the same as the manufacturing example.

The molecular weight of the polymer was measured by APC and was as follows: M _w was 24500 and PDI was 1.85.

Polyamic Acid F

Polyamic acid ester F was obtained by replacing 67 g of ODA in the manufacturing example of polyamic acid ester A with 36 g of p-phenylenediamine (PPDA) and keeping the rest the same as the manufacturing example.

The molecular weight of the polymer was measured by APC and was as follows: M _w was 23,000 and PDI was 1.88.

Example:

Embodiment 1:

Under a constant temperature and humidity environment (24°C, 50% RH), 20g of polyamic acid ester A, 30g of N-methylpyrrolidone (NMP) solvent, 2.0g of triethylene glycol dimethacrylate (the second free radical polymerizable monomer, hereinafter referred to as the second monomer), 0.8g of EP-3 (the structure is shown in FIG2 , the first free radical polymerizable monomer containing an epoxy structure, hereinafter referred to as the first monomer), 0.8g of photopolymerization initiator BASF IRGACURE OXE-01, 0.8g of thermal base generator N-tert-butyloxycarbonyl-4-piperidinemethanol, 0.4g of silane coupling reagent ureapropyltriethoxysilane and 0.04g of polymerization inhibitor 2-nitroso-1-naphthol were added into a 100mL brown plastic bottle in sequence, and the mixture was shaken and dissolved on a shaker for 24 hours, and then NMP was added to adjust the viscosity of the resulting solution to about 30 poises, and secondary filtration was performed to obtain a negative photosensitive polyimide precursor resin composition.

Preparation of photolithographic patterns: Spin-coat the negative photosensitive polyimide precursor resin composition prepared above on an 8-inch silicon wafer using a coating machine (WS-650Mz-8NPPB, MYCRO), and pre-bake it on a hot plate at 100°C for 240 seconds to form a coating film about 10 μm thick. On the coating film, use a mask with a test pattern and irradiate 400 mJ/ ^cm2 of energy using an i-line stepper (Shanghai Microelectronics). Next, for the coating film, use cyclopentanone as the developer, use a developer (MST-EF1-DV, Shenzhen Kaierdi) for spray development, and rinse with propylene glycol methyl ether acetate to obtain a photolithographic pattern. Use a temperature ramp A sequential curing furnace (HCM-500D, Shanghai Siwang Electronics) was used to perform a heat treatment (200°C/2h) under a nitrogen atmosphere at a curing temperature listed in Table 1 below to obtain a cured photolithography pattern formed of resin with a thickness of about 10 μm.

Example 2

20 g of polyamic acid ester A in Example 1 was replaced by 20 g of polyamic acid ester B, and the remaining components and operation procedures were consistent with Example 1.

Example 3

20 g of polyamic acid ester A in Example 1 was replaced by 20 g of polyamic acid ester C, and the other components and operation procedures were consistent with Example 1.

Example 4

The 20 g of polyamic acid ester in Example 1 was replaced by 20 g of polyamic acid ester D, and the other components and operation procedures were consistent with Example 1.

Example 5

20 g of polyamic acid ester A in Example 1 was replaced by 20 g of polyamic acid ester E, and the remaining components and operation procedures were consistent with Example 1.

Example 6

20 g of polyamic acid ester A in Example 1 was replaced by 10 g of polyamic acid ester E and 10 g of polyamic acid ester F, and the remaining components and operation procedures were consistent with Example 1.

Example 7

Replace 0.8 g EP-3 in Example 6 with 0.4 g EP-3, and keep the other components and operating procedures the same as in Example 6.

Example 8

Replace 0.8 g EP-3 in Example 6 with 0.2 g EP-3, and keep the other components and operating procedures the same as in Example 6.

Embodiment 9

0.8 g of EP-3 in Example 6 was replaced by 0.8 g of EP-1, and the other components and operation procedures were consistent with Example 6.

Example 10

0.8 g of EP-3 in Example 6 was replaced by 0.8 g of EP-2, and the other components and operation procedures were consistent with Example 6.

Embodiment 11

0.8 g of EP-3 in Example 6 was replaced by 0.8 g of EP-4, and the other components and operation procedures were consistent with Example 6.

Example 12

0.8 g of EP-3 in Example 6 was replaced by 0.8 g of EP-5, and the other components and operation procedures were consistent with Example 6.

Example 13

0.8 g of EP-3 in Example 6 was replaced by 0.8 g of EP-6, and the other components and operation procedures were consistent with Example 6.

Embodiment 14

The curing process in Example 6 was changed to 175° C./2 h, and the other components and operation procedures remained the same as in Example 6.

Embodiment 15

The curing process in Example 11 was changed to 175°C/2h, and the other components and operation procedures were consistent with Example 6.

Comparative Example 1

0.8 g of EP-3 in Example 6 was replaced by 0.8 g of EP-7, and the other components and operation procedures were consistent with Example 6.

Comparative Example 2

0.8 g of EP-3 in Example 6 was replaced by 0.8 g of EP-8, and the other components and operation procedures were consistent with Example 6.

Comparative Example 3

0.8 g of EP-3 in Example 6 was removed, and the remaining components and operation procedures were consistent with Example 6.

Effect implementation:

1. Weight average molecular weight test:

The polymer weight average molecular weight _Mw and polymer dispersity index (PDI) involved in the present invention are obtained by testing an ultra-high performance polymer chromatography analyzer (ACQUITYAPC), and the relevant test conditions are as follows: the chromatographic column model is ACQUITY APC XT45 1.7μm/ACQUITY APC XT200 2.5μm/ACQUITY APC XT450 2.5μm, the column oven and the detector temperature are both 40°C, the mobile phase is tetrahydrofuran (THF), and the flow rate is 0.5mL/min.

2. Preparation and evaluation methods of photolithography patterns:

The photosensitive polyamic acid ester composition prepared in the above embodiment was spin-coated on an 8-inch silicon wafer by a coating machine (WS-650Mz-8NPPB, MYCRO), and pre-baked on a hot plate for 240 seconds at 100°C to form a coating film about 10 μm thick. On the coating film, a mask with a test pattern was used, and an i-line stepper (Shanghai Microelectronics) was used to irradiate 400mJ/ ^cm2 of energy. Then, for the coating film, cyclopentanone was used as a developer, and a developer (MST-EF1-DV, Shenzhen Kaierdi) was used for spray development, and propylene glycol methyl ether acetate was used for rinsing to obtain a photolithographic pattern. A temperature-increasing program curing furnace was used The resulting mixture was heated at a curing temperature listed in Table 1 under a nitrogen atmosphere (HCM-500D, Shanghai Siwang Electronics) for 2 hours to obtain a cured photolithography pattern of about 10 μm thick formed by the composition.

The cured photolithography pattern obtained above was sliced and analyzed using a focused ion beam electron microscope (FIB, Helios G4, Thermo Fisher), and the photolithography accuracy and cross-sectional morphology profile were evaluated. Then, the photolithography performance of the negative photosensitive resin composition was evaluated: the photolithography line accuracy less than 10 μm was rated as “excellent”, the photolithography line accuracy between 10 and 20 μm was rated as “good”, the photolithography line accuracy between 20 and 50 μm was rated as “acceptable”, and the photolithography line accuracy greater than 50 μm was rated as “poor”.

3. Mechanical properties test of cured film:

The cured exposure film prepared by the above method with a mask plate of a specific pattern and a curing method was soaked in a 1% hydrofluoric acid aqueous solution for 10 minutes and then peeled off from the silicon wafer to obtain a 5mm×10cm film strip. After drying the moisture in an oven at 150°C, the film strip was subjected to a mechanical tensile test using a universal stretching machine (Shenzhen Sansi Zongheng Technology Co., Ltd.), and its mechanical properties were evaluated based on its elongation at break: an elongation at break greater than 50% was rated as "excellent", an elongation at break between 40% and 50% was rated as "good", an elongation at break between 20% and 40% was rated as "acceptable", and an elongation at break less than 20% was rated as "poor".

4. Chemical resistance test of cured film:

The cured exposure film prepared by the above method with a mask plate having a specific pattern and a curing method was soaked in a 1% hydrofluoric acid aqueous solution for 10 minutes, then peeled off from the silicon wafer to obtain a complete cured film, dried in an oven at 150°C, and then soaked in a dimethyl sulfoxide solution containing 2.38% by mass of tetramethylammonium hydroxide at 50°C for 60 minutes. The chemical resistance of the cured film was evaluated according to the weight loss of the cured film before and after the chemical resistance treatment: a weight loss of less than 5% was rated as "excellent", a weight loss between 5% and 15% was rated as "good", a weight loss between 15% and 25% was rated as "acceptable", and a weight loss of more than 25% was rated as "poor".

The components and contents of the negative photosensitive polyimide precursor resin compositions prepared in the above-mentioned embodiments and comparative examples, and the curing process are shown in Table 1, and the relevant performance test data are shown in Table 2. From Table 1 and Table 2, it can be seen that compared with Comparative Examples 1-3, the embodiments to which a free radical polymerizable compound having an epoxy structure is added generally show that different resin systems can simultaneously have good mechanical properties, photolithographic properties and chemical corrosion resistance, the ones to which the epoxy compound EP-5/6 without free radical polymerizable is added have good chemical corrosion resistance but poor photolithographic resolution, and the chemical corrosion resistance of Comparative Example 3 without adding an epoxy additive is very poor.

Table 1

Table 2

The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims (12)

1. A negative photosensitive polyimide precursor resin composition, characterized in that it comprises:

   100 parts by mass of polyamic acid ester as a polyimide precursor;

   1-20 parts by mass of a first free radical polymerizable monomer containing an epoxy structure;

   1-20 parts by mass of a second free 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 weight of a thermal alkali generating agent;

   50-1500 parts by mass of an organic solvent;

   The first free radical polymerizable monomer containing an epoxy structure is selected from at least one of the compounds represented by formula (a), formula (b), formula (c), formula (d), formula (e) and formula (f):
   

   In formula (a), R ₁ is selected from Any of;

   Wherein, R ₂ is selected from any one of hydrogen atom and alkyl group with 1 to 3 carbon atoms, R ₃ and R ₄ are each independently selected from any one of H and aliphatic hydrocarbon group with 1 to 8 carbon atoms, and m=0 to 7;
   

   In formula (b), n=0 to 6;
   

   In formula (c), A ₁ is
   

   In formula (d), R ₅ is selected from any one of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms; R ₆ is selected from Any one of; p = 0 ~ 1;
   

   In formula (e), _A2 is a cyclic structure selected from Any of .
2. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized in that the polyamic acid ester has a structure as shown in formula (f):
   

   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 a structure as shown in formula (g), and q is 2 to 150;
   

   In formula (g), R ₉ , R ₁₀ and R ₁₁ are each independently selected from a hydrogen atom and 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 in that the second free radical polymerizable monomer is selected from any one or more of (meth)acrylate compounds.
4. The negative photosensitive polyimide precursor resin composition according to claim 3 is characterized in that the second free radical polymerizable monomer is any one or more of a difunctional (meth)acrylate compound and a trifunctional (meth)acrylate compound.
5. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized in that 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, alkyl benzoin and benzyl dimethyl ketal.
6. The negative photosensitive polyimide precursor resin composition according to claim 5, characterized in that the photoinitiator is an oxime ester compound.
7. The negative photosensitive polyimide precursor resin composition according to claim 1 is characterized in that the organic solvent is selected from any one or more of esters, ethers, ketones, aromatic hydrocarbons, sulfoxides and amides.
8. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized in that the silane coupling agent is selected from any one or more silane coupling agents containing a urea bond (-NH-CO-NH-).
9. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized in that the polymerization inhibitor is selected from any one or more of phenolic free radical polymerization inhibitors.
10. The negative photosensitive polyimide precursor resin composition according to claim 1, characterized in that the thermal base generator is a tert-butoxycarbonyl protected amine compound.
11. A negative photosensitive polyimide resin composition, characterized in that it is obtained by thermal imidization of the negative photosensitive polyimide precursor resin composition according to any one of claims 1 to 10.
12. The negative photosensitive polyimide resin composition according to claim 11, characterized in that the temperature of the thermal imidization is 150 to 400°C.