Negative photosensitive resin, photosensitive resin composition, and preparation method and application thereof

Abstract

The application discloses a kind of negative photosensitive resin, photosensitive resin composition and its preparation method and application.The preparation method of the negative photosensitive resin of the application includes: (1) tetracarboxylic dianhydride is esterified with unsaturated double bond alcohol compound in organic solvent, and aromatic diester diacid containing unsaturated side chain is generated;(2) aromatic diamine solution is added to the above-mentioned pre-esterification product to carry out polycondensation reaction;(3) active reagent is added to the product of above-mentioned step (2), then add alcohol compound containing unsaturated double bond to carry out deep esterification.The negative photosensitive resin composition of the application can be cured at 200 DEG C, and the formed cured film has excellent heat resistance and adhesion, and also has excellent photoetching performance, can meet the use demand of wafer level packaging, and has good application prospect in the field of semiconductor manufacturing and packaging.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a negative photosensitive resin, a photosensitive resin composition, its preparation method and application. Background Technology

[0002] Photoresist, a core material in semiconductor manufacturing, enables the precise transfer of micro- and nano-scale patterns through photochemical reactions. Its performance directly affects chip yield and process precision. Photoresist mainly consists of resin, photoinitiator, solvent, and additives. The resin, as the backbone component, directly determines the photoresist's resolution, etching resistance, and development stability. Depending on the application wavelength, resin systems can be classified into phenolic resins (G / I lines), poly(p-hydroxystyrene) (KrF), and methacrylate copolymers (ArF), among others. Molecular weight distribution index (PDI), purity, and batch stability are key performance indicators. Resins synthesized by traditional free radical polymerization processes generally have a PDI > 1.6, leading to significant differences in solubility during development, resulting in increased linewidth roughness (LWR) and decreased resolution. For example, KrF photoresist uses poly(p-hydroxystyrene) resin, which requires anionic polymerization to reduce PDI (target < 1.3), but the industrial production conditions are harsh (low temperature, inert environment), and molecular weight drift is prone to occur during scale-up production. Existing technologies, such as stepwise liquid-liquid separation, require solvent separation to separate components of different molecular weights. Although the PDI can be controlled to 1.05-1.2, precise matching of the solvent-regulator ratio is required (e.g., acrylic resins require an ethyl acetate / methyl tert-butyl ether system), resulting in a narrow process window and high costs. Furthermore, resin synthesis involves multi-step polycondensation reactions, and even small fluctuations in temperature and monomer feed ratio at each stage will significantly affect the final molecular weight distribution. Summary of the Invention

[0003] The purpose of this invention is to solve the core problems of photoresist resins in the prior art, such as wide molecular weight distribution, poor process stability, and insufficient yield, and to provide a method for preparing a negative photosensitive resin with adjustable molecular weight and the corresponding negative photosensitive resin.

[0004] The first aspect of this invention provides a method for preparing a negative photosensitizing resin, comprising the following steps:

[0005] (1) Tetracarboxylic acid dianhydride reacts with unsaturated double-bonded alcohols in an organic solvent for esterification;

[0006] (2) Add an aromatic diamine solution to the above esterified product to carry out a polycondensation reaction;

[0007] (3) Add an activating agent to the product of step (2) above, and then add an alcohol compound containing an unsaturated double bond for esterification.

[0008] In step (1), the molar ratio of tetracarboxylic dianhydride to unsaturated double-bonded alcohol is 1:0.1-0.3; in step (2), the molar amount of aromatic diamine is 0.7-0.9 times that of tetracarboxylic dianhydride in step (1); in step (3), the molar amount of alcohol containing unsaturated double bonds is 2-4 times that of tetracarboxylic dianhydride in step (1).

[0009] In step (1), the molar ratio of tetracarboxylic dianhydride to unsaturated double-bonded alcohol is 1:0.16-0.21; and / or, in step (2), the molar amount of aromatic diamine is 0.75-0.85 times that of tetracarboxylic dianhydride in step (1); and / or, in step (3), the molar amount of alcohol containing unsaturated double bonds is 2-2.5 times that of tetracarboxylic dianhydride in step (1).

[0010] The unsaturated double-bonded alcohol compound is selected from at least one of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 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, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 1-methacryloyloxy-3-propanol, 2-isobutenamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0011] A second aspect of the present invention provides a negative photosensitizing resin, which is prepared by the method described above for preparing a negative photosensitizing resin.

[0012] The molecular weight distribution index of the negative photosensitive resin is ≤1.55.

[0013] A third aspect of the present invention provides a negative photosensitizing resin comprising the following components in parts by weight: 100 parts of the negative photosensitizing resin described above, 0.1 to 20 parts of photosensitizer, 1 to 30 parts of crosslinking agent, 0.1 to 30 parts of adhesive aid, 0.1 to 30 parts of polymerization inhibitor, and 100 to 1000 parts of organic solvent.

[0014] A fourth aspect of the present invention provides a cured film prepared by coating and drying the above-described photosensitive resin composition.

[0015] The fifth aspect of the present invention provides a patterned curing film, which is prepared from the photosensitive resin composition of the curing film described above through a coating, exposure, development and curing process.

[0016] The sixth aspect of the present invention provides the use of the above-described photosensitive resin composition or the above-described patterned curable film in semiconductor manufacturing and / or packaging.

[0017] This invention employs a stepwise functionalization strategy of pre-esterification-polymerization-deep esterification, which allows for precise control of resin molecular weight without the need for additional molecular weight regulators, resulting in a resin with a molecular weight distribution index ≤1.55. Simultaneously, it solves the problem of uneven distribution of photosensitive groups caused by direct polymerization. The prepared negative photosensitive resin and its corresponding photosensitive resin composition exhibit excellent comprehensive performance, with photolithography sensitivity, heat resistance cyclization rate, room temperature storage stability, and copper substrate adhesion all meeting the application requirements of high-end electronic devices. Detailed Implementation

[0018] The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0019] <Preparation Method of Negative Photosensitive Resin>

[0020] In a first aspect, the present invention provides a method for preparing a negative photosensitive resin, comprising the following steps:

[0021] (1) Tetracarboxylic acid dianhydride reacts with unsaturated double-bonded alcohols in an organic solvent for esterification;

[0022] (2) Add an aromatic diamine solution to the solution obtained in step (1) to carry out a polycondensation reaction;

[0023] (3) Add an activating reagent to the solution obtained in step (2), and then add an alcohol compound containing an unsaturated double bond to carry out an esterification reaction.

[0024] In the above preparation method, in step (1), the tetracarboxylic dianhydride is selected from 4,4'-oxophthalic anhydride, 3,4'-oxophthalic anhydride, pyromellitic tetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,3,3',4'-biphenyltetracarboxylic anhydride, 2,2',3,3'-biphenyltetracarboxylic anhydride, 4,4'-terephthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic anhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 3,3 At least one of ',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, hydrogenated pyromellitic tetracarboxylic dianhydride, 2,3,5-tricarboxylated cyclopentaneacetic dianhydride, and hydrogenated biphenyl anhydride; in a specific embodiment of the present invention, the tetracarboxylic dianhydride is 4,4'-oxybis(phthalic acid) anhydride (ODPA) or 2,3,3',4'-biphenyltetracarboxylic dianhydride, and in step (1), an aromatic diester dianhydride containing unsaturated side chains is generated by esterification reaction;

[0025] The unsaturated double-bonded alcohol compounds are selected from 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 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-cyclohexyloxypropyl acrylate. At least one of 1-methacryloyloxy-3-propanol, 2-isobutenamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate; in a specific embodiment of the present invention, the unsaturated double-bonded alcohol compound is 2-hydroxyethyl methacrylate (HEMA) or 2-acrylamide ethanol;

[0026] The molar ratio of the tetracarboxylic acid dianhydride to the unsaturated double-bonded alcohol compound is 1:0.1-0.3, preferably 1:0.16-0.21;

[0027] The organic solvent only needs to be sufficient to dissolve the monomer without causing the polymer to precipitate, and is preferably N'N-dimethylformamide, N'N-dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolium ketone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylurea, phenol, m-cresol, methyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, etc. At least one of the following: diacetone alcohol, methyl isobutyl ketone, ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate;

[0028] The esterification reaction is carried out in the presence of an alkaline catalyst at a temperature of 20-60°C, specifically at room temperature; the reaction time is 1-10 hours, specifically 6 hours.

[0029] The alkaline catalyst is pyridine, triethylenediamine, or triethylamine.

[0030] In the above preparation method, in step (2), the aromatic diamine is selected from p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-Diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 1,4-bis(4'-aminophenoxy)benzene, 1,3-bis(4'-aminophenoxy)benzene, 1,3-bis(3'-aminophenoxy)benzene, 1,5-naphthyldiamine, 2,6-naphthyldiamine, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,3-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene Methyl-4-aminophenoxy)benzene (6FAPB), 4,4'-bis(2-trifluoromethyl-4-aminophenoxy)biphenyl (6FBAB), 2,2'-bis(trifluoromethyl-4,4'-diaminobiphenyl) (TFDB), 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]propane, 2,2'-bis(trifluoromethoxy-4,4'-diaminobiphenyl) (TFDOB), 3-trifluoromethyl-4,4'-diaminodiphenyl ether (3FODA), 3,3'-bis(trifluoromethyl-4,4'-diaminodiphenyl ether (6FODA), 2,2'-bis(trifluoromethoxy-5,5'-diphenyl) The aromatic diamine is at least one of the following: aminobiphenyl, 3,3'-bis(trifluoromethyl)-5,5'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-5,5'-diaminobiphenyl ether, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenoxybenzene)hexafluoropropane, 3-trifluoromethylm-phenylenediamine, tetrafluoro-p-phenylenediamine, tetrafluoro-m-phenylenediamine, 4,4'-diaminooctafluorobiphenyl, 4,4'-diaminooctafluorobiphenyl ether, and 4,4'-diaminooctafluorobiphenyl sulfide; in a specific embodiment of the present invention, the aromatic diamine is 2,2'-dimethyl-4,4'-diaminobiphenyl or 3,4'-diaminodiphenyl ether.

[0031] The organic solvent selected for the aromatic diamine solution should be sufficient to fully dissolve the monomer without causing the polymer to precipitate. Preferred solvents include N'N-dimethylformamide, N'N-dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolium ketone, dimethyl sulfoxide, dimethyl sulfone, tetramethyl sulfone, tetramethylurea, phenol, m-cresol, methyl lactate, propyl lactate, butyl lactate, toluene, and xylene. At least one of the following: mesitylene, diacetone alcohol, methyl isobutyl ketone, ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate;

[0032] The mass ratio of aromatic diamine to organic solvent in the aromatic diamine solution is 1:5-8;

[0033] The molar amount of the aromatic diamine is 0.7-0.9 times the total amount of tetracarboxylic acid dianhydride in step (1) above, preferably 0.75-0.85 times;

[0034] The reaction temperature of the polycondensation reaction is controlled at 40-60℃, more preferably 40-45℃; the polymerization reaction time is 1-5h, more preferably 2-3h.

[0035] In the above preparation method, in step (3), the activating agent is selected from acetic anhydride, trifluoromethanesulfonic anhydride or trifluoroacetic anhydride, more preferably trifluoroacetic anhydride; the reaction temperature during activation is controlled at 0-30℃, more preferably 15-25℃; the activation reaction time is 10-60min, more preferably 20-30min.

[0036] The alcohols containing unsaturated double bonds are selected from 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 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-cyclohexyloxypropyl acrylate. At least one of 1-methacryloyloxy-3-propanol, 2-isobutenamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate; in a specific embodiment of the present invention, the unsaturated double-bonded alcohol compound is 2-hydroxyethyl methacrylate (HEMA) or 2-acryloyloxyethanol;

[0037] The molar amount of the alcohol compound containing unsaturated double bonds is 2-4 times, preferably 2-2.5 times, the total amount of tetracarboxylic acid dianhydride in step (1) above; the reaction temperature during esterification is controlled at 40-60℃, more preferably 40-50℃, and the reaction time for esterification is 12-24h.

[0038] This invention eliminates the need for additional molecular weight regulators. By employing a stepwise functionalization strategy of "pre-esterification-polymerization-deep esterification," precise control of molecular weight can be achieved, resulting in a negative photosensitive resin with a molecular weight distribution index ≤1.55. Furthermore, it avoids the problem of uneven distribution of photosensitive groups caused by direct polymerization, thereby preparing a high-performance photosensitive resin composition.

[0039] It is understood that the method of the present invention further includes, after the reaction described in step (3): precipitating the negative photosensitive resin solution obtained after the deep esterification reaction in a poor solvent, washing and drying it to obtain the negative photosensitive resin.

[0040] The preferred unsuitable solvent is deionized water, methanol, ethanol, or isopropanol. The amount of unsuitable solvent used is preferably 3 to 20 times the mass of the polymer solution. The cleaning process uses the aforementioned unsuitable solvent, and the amount of solvent used is preferably 1 to 6 times the mass of the polymer. The more times the polymer is cleaned, the lower the impurity content; however, too many cleaning cycles will affect the economic benefits and production efficiency of the product. Considering factors such as product quality, economic benefits, and production efficiency, the preferred number of cleaning cycles is 3 to 6. After cleaning, the polymer is preferably dried under vacuum at 20 to 50°C for at least 10 hours to obtain the negative photosensitive resin. The weight-average molecular weight of GPC is 5000 to 100000, preferably 10000 to 50000.

[0041] Secondly, the present invention provides a negative photosensitizing resin prepared by any of the above-described preparation methods.

[0042] Thirdly, the present invention provides a photosensitive resin composition comprising the following components in parts by weight:

[0043] The composition includes 100 parts of negative photosensitive resin, 0.1-20 parts of photosensitizer, 1-30 parts of crosslinking agent, 0.1-30 parts of adhesive additive, 0.1-30 parts of polymerization inhibitor, and 100-1000 parts of organic solvent.

[0044] In the above-described photosensitive resin composition, the negative photosensitive resin is prepared by the method described above.

[0045] In the above-mentioned photosensitive resin composition, the photosensitizer is selected from at least one of benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzoin derivatives, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, and 1,3-diphenyltriketone-2-(o-ethoxycarbonyl)oxime; the benzophenone derivatives include, but are not limited to, benzophenone, 4,4'-bis(dimethylamino)benzophenone, tetraethylmichalcosone, dibenzyl ketone, fluorenone, etc.; the acetophenone derivatives include... However, it is not limited to 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylacetophenone, 1-hydroxycyclohexylphenyl ketone, etc.; the thioxanone derivatives include, but are not limited to, thioxanone, 2-methylthioxanone, 2-isopropylthioxanone, diethylthioxanone, etc.; the benzoyl derivatives include, but are not limited to, benzoyl, benzoyl dimethyl ketal, benzoyl-β-methoxyethyl acetate, etc.; the benzoin derivatives include, but are not limited to, benzoin, benzoin methyl ether, etc.; in a specific embodiment of the present invention, the photosensitizer is 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime;

[0046] The crosslinking agent is selected from 2-hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, glycidyl methacrylate, ethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol diacrylate. Methacrylates, 1,4-Butanediol diacrylate, 1,4-Butanediol dimethacrylate, 1,5-Pentanediol diacrylate, 1,5-Pentanediol dimethacrylate, 1,6-Hexanediol diacrylate, 1,6-Hexanediol dimethacrylate, 1,7-Heptanediol diacrylate, 1,7-Heptanediol dimethacrylate, 1,8-Octanyldiacrylate, 1,8-Octanyldiol dimethacrylate, 1,9-Nonanediol diacrylate, 1,9-Nonanediol dimethacrylate 1,10-Decanediol diacrylate, 1,10-Decanediol dimethacrylate, polyethylene glycol diacrylate with a degree of polymerization of 2-10, polyethylene glycol dimethacrylate with a degree of polymerization of 2-10, polypropylene glycol diacrylate with a degree of polymerization of 2-10, polypropylene glycol dimethacrylate with a degree of polymerization of 2-10, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, At least one of pentaerythritol tetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol pentamethacrylate, polydipentaerythritol hexaacrylate, polydipentaerythritol hexamethacrylate, and tris(2-hydroxyethyl)isocyanurate triacrylate; in a specific embodiment of the present invention, the crosslinking agent is tetraethylene glycol dimethacrylate or 1,6-hexanediol diacrylate;

[0047] The bonding agent is selected from γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2- Cyanoethyltriethoxysilane, propionic acid-propyltriethoxysilane, 3-isocyanate-trimethoxysilane, 3-isocyanate-triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyldimethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane At least one of vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 3-(m-aminophenoxy)trimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane, and 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane; in a specific embodiment of the present invention, the adhesive aid is γ-aminopropyltriethoxysilane or 3-(methacryloyloxy)propyltrimethoxysilane;

[0048] The polymerization inhibitor is selected from at least one of hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and 2-nitroso-5-(N-ethyl-sulfopropylamino)phenol; in a specific embodiment of the present invention, the polymerization inhibitor is N-nitrosodiphenylamine;

[0049] The organic solvent is selected from N'N dimethylformamide, N'N dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolium ketone, dimethyl sulfoxide, dimethyl sulfone, tetramethyl sulfone, tetramethylurea, phenol, m-cresol, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, ethyl acetate, and butyl acetate. At least one of the following: sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate, such as N-methylpyrrolidone and ethyl lactate in a mass ratio of 5:1.

[0050] Fourthly, the present invention provides a cured film prepared by coating and drying the above-described photosensitive resin composition.

[0051] Fifthly, the present invention provides a patterned curable film, which can be formed by coating, exposing, developing and curing the above-mentioned photosensitive resin composition.

[0052] The present invention provides a method for preparing the patterned cured film, comprising the following steps:

[0053] 1) The photosensitive resin composition is spin-coated onto a wafer substrate to obtain a liquid adhesive film;

[0054] 2) Bake at 80~130℃ for 1~30 min to obtain a solid film;

[0055] 3) Cover the mask and expose it under ultraviolet i line, or under both i and g lines;

[0056] 4) Use a developer to develop and dissolve the unexposed areas;

[0057] 5) Clean with rinsing solution to obtain an uncured patterned resin film;

[0058] 6) The uncured patterned resin film is heated and cured to transform it into a patterned cured film.

[0059] The developing solution and rinsing solution used in the above preparation method are all conventional additives in the prior art. The developing solution is preferably a good solvent for the photosensitive resin composition, or a combination of a good solvent and a poor solvent. The good solvent is preferably cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, and γ-butyrolactone; the poor solvent is preferably ethyl lactate, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, tetrahydrofuran, dioxane, propylene glycol methyl ether, and propylene glycol methyl ether acetate. The rinsing solution is preferably ethyl acetate, butyl acetate, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclopentanone, and cyclohexanone.

[0060] Preferably, the heat curing is performed at low temperature in an oxygen-free environment at 200°C with an oxygen content of less than 100 ppm.

[0061] The patterned curable film of this invention has excellent heat resistance and adhesion properties, as well as excellent photolithography performance. It can be used for chip surface passivation in semiconductor manufacturing processes, interlayer insulation of multilayer metal interconnect structures, multilayer wiring and bump / micro solder ball fabrication processes of advanced electronic packaging (BGA, CSP, SiP, etc.) substrates, and stress buffer film for plastic-encapsulated circuits, etc.

[0062] In a sixth aspect, the present invention provides the use of the photosensitive resin composition or the patterned cured film described in any of the above claims in semiconductor manufacturing and / or packaging.

[0063] Example

[0064] The following embodiments illustrate the present invention, but the present invention is not limited to the following embodiments.

[0065] Synthesis example 1

[0066] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 1.95 g (15.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A1.

[0067] (2) Under nitrogen atmosphere, 27.07 g (127.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B1. Diamine solution B1 was added dropwise to solution A1, and the mixture was stirred at 45°C for 2 hours and then cooled to 25°C to obtain solution C1.

[0068] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C1, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D1. Add solution D1 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P1.

[0069] Synthesis example 2

[0070] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.12 g (24.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A2.

[0071] (2) Under nitrogen atmosphere, 27.07 g (127.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B2. Diamine solution B2 was added dropwise to solution A2, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C2.

[0072] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C2, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D2. Add solution D2 to pure water to settle, filter, wash and dry to obtain negative photosensitizing resin P2.

[0073] Synthesis example 3

[0074] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 4.10 g (31.5 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A3.

[0075] (2) Under nitrogen atmosphere, 27.07 g (127.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B3. Diamine solution B3 was added dropwise to solution A3, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C3.

[0076] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C3, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D3. Add solution D3 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P3.

[0077] Synthesis example 4

[0078] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 4.88 g (37.5 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A4.

[0079] (2) Under nitrogen atmosphere, 27.07 g (127.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B4. Diamine solution B4 was added dropwise to solution A4, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C4.

[0080] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C4, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D4. Add solution D4 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P4.

[0081] Synthesis example 5

[0082] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 5.86 g (45.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45°C for 1 hour to obtain solution A5.

[0083] (2) Under nitrogen atmosphere, 27.07 g (127.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B5. Diamine solution B5 was added dropwise to solution A5, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C5.

[0084] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C5, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D5. Add solution D5 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P5.

[0085] Synthesis example 6

[0086] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.12 g (24.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A6.

[0087] (2) Under nitrogen atmosphere, 22.29 g (105.0 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B6. Diamine solution B6 was added dropwise to solution A6, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C6.

[0088] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C6, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D6. Add solution D6 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P6.

[0089] Synthesis Example 7

[0090] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.12 g (24.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A7.

[0091] (2) Under nitrogen atmosphere, 23.88 g (112.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B7. Diamine solution B7 was added dropwise to solution A7, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C7.

[0092] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C7, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D7. Add solution D7 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P7.

[0093] Synthesis example 8

[0094] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.12 g (24.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A8.

[0095] (2) Under nitrogen atmosphere, 28.02 g (132.0 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B8. Diamine solution B8 was added dropwise to solution A8, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C8.

[0096] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C8, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D8. Add solution D8 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P8.

[0097] Synthesis example 9

[0098] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.12 g (24.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A9.

[0099] (2) Under nitrogen atmosphere, 28.66 g (135.0 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B9. Diamine solution B9 was added dropwise to solution A9, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C9.

[0100] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C9, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D9. Add solution D9 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P9.

[0101] Synthesis example 10

[0102] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.12 g (24.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A10.

[0103] (2) Under nitrogen atmosphere, 23.88 g (112.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B10. Diamine solution B10 was added dropwise to solution A10, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C10.

[0104] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C10, stir at 20 °C for 30 minutes, then add 39.04 g (300.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D10. Add solution D10 to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P10.

[0105] Synthesis example 11

[0106] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.12 g (24.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A11.

[0107] (2) Under nitrogen atmosphere, 23.88 g (112.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B11. Diamine solution B11 was added dropwise to solution A11, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C11.

[0108] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C11, stir at 20 °C for 30 minutes, then add 58.56 g (450.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D11. Add solution D11 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P11.

[0109] Synthesis example 12

[0110] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.12 g (24.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A12.

[0111] (2) Under nitrogen atmosphere, 23.88 g (112.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B12. Diamine solution B12 was added dropwise to solution A12, stirred at 45°C for 2 hours, and then cooled to 25°C to obtain solution C12.

[0112] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C12, stir at 20 °C for 30 minutes, then add 78.08 g (600.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D12. Add solution D12 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P12.

[0113] Synthesis example 13

[0114] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 44.43 g (150.0 mmol) of 2,3,3',4'-biphenyltetracarboxylic dianhydride, 4.10 g (31.5 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution A13.

[0115] (2) Under nitrogen atmosphere, 23.88 g (112.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B13. Diamine solution B13 was added dropwise to solution A13, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C13.

[0116] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C13, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D13. Add solution D13 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin P13.

[0117] Synthesis example 14

[0118] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.63 g (31.5 mmol) of 2-acrylamide ethanol and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45°C for 1 hour to obtain solution A14.

[0119] (2) Under nitrogen atmosphere, 23.88 g (112.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B14. Diamine solution B14 was added dropwise to solution A14, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C14.

[0120] (3) After adding 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C14, the mixture was stirred at 20 °C for 30 minutes. Then, 48.80 g (375.0 mmol) of hydroxyethyl methacrylate was added, and the mixture was stirred at 45 °C for 20 hours to obtain solution D14. Solution D14 was added dropwise to pure water to settle, and after filtration, washing, and drying, negative photosensitizing resin P14 was obtained.

[0121] Synthesis Example 15

[0122] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 3.63 g (31.5 mmol) of 2-acrylamide ethanol and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45°C for 1 hour to obtain solution A15.

[0123] (2) Under nitrogen atmosphere, 22.50 g (112.5 mmol) of 3,4'-diaminodiphenyl ether was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution B15. Diamine solution B15 was added dropwise to solution A15, and the mixture was stirred at 45 °C for 2 hours and then cooled to 25 °C to obtain solution C15.

[0124] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution C15, stir at 20 °C for 30 minutes, then add 48.80 g (375.0 mmol) of hydroxyethyl methacrylate, stir at 45 °C for 20 hours to obtain solution D15. Add solution D15 dropwise to pure water to settle, filter, wash, and dry to obtain negative photosensitive resin P15.

[0125] Comparative Synthesis Example 1

[0126] (1) In a 1.0 L flask equipped with a stirrer and a thermometer, under nitrogen atmosphere, 70.73 g (228.0 mmol) of 4,4'-oxophthalic dianhydride and 41.19 g (194.0 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl were dissolved in 300 g of N-methylpyrrolidone. The mixture was first stirred at 30 °C for 4 hours, and then stirred for another 12 hours at room temperature. After the reaction was completed, a polyamic acid solution was obtained.

[0127] The reaction flask was placed in a water-cooled jacket, and circulating cooling water was introduced to maintain the system temperature at 10–15°C. Under these conditions, 94.51 g (450.0 mmol) of trifluoroacetic anhydride was slowly added dropwise to the polyamic acid solution. After the addition was complete, the temperature was raised to 45°C and stirred for 3 hours. Then, 70.80 g (544.0 mmol) of hydroxyethyl methacrylate was added, and the reaction was continued at 45°C until the system stabilized.

[0128] The reaction solution was slowly added dropwise to excess pure water to allow sedimentation. After the solid precipitated, it was filtered, washed with pure water until the filtrate was neutral, and finally dried under vacuum to obtain the negative photosensitive resin DP1.

[0129] Comparative Synthesis Example 2

[0130] (1) In a 1.0-liter flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 1.95 g (15.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45°C for 1 hour to obtain solution DA2.

[0131] (2) Under nitrogen atmosphere, 27.07 g (127.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain a diamine solution DB2. The diamine solution DB2 was added dropwise to solution DA2, and after stirring at 45°C for 2 hours, it was cooled to 25°C to obtain solution DC2. Solution DC2 was added dropwise to pure water to settle, and after filtration, washing, and drying, the negative photosensitizing resin DP2 was obtained.

[0132] Comparative Synthesis Example 3

[0133] (1) In a 1.0 L flask equipped with a stirrer and a thermometer, under a nitrogen atmosphere, 46.53 g (150.0 mmol) of 4,4'-oxophthalic dianhydride, 1.95 g (15.0 mmol) of hydroxyethyl methacrylate and 1.68 g (15 mmol) of triethylenediamine were dissolved in N-methylpyrrolidone (306.97 g), and the solution was stirred at 45 °C for 1 hour to obtain solution DA3.

[0134] (2) Under nitrogen atmosphere, 27.07 g (127.5 mmol) of 2,2'-dimethyl-4,4'-diaminobiphenyl was dissolved in 191.20 g of N-methylpyrrolidone to obtain diamine solution DB3. Diamine solution DB3 was added dropwise to solution DA3, stirred at 45 °C for 2 hours, and then cooled to 25 °C to obtain solution DC3.

[0135] (3) Add 58.91 g (280.5 mmol) of trifluoroacetic anhydride to solution DC3, stir at 20 °C for 30 minutes, then add 44.69 g (375.0 mmol) of 4-vinylaniline, stir at 45 °C for 20 hours to obtain solution DD3. Add solution DD3 to pure water to settle, filter, wash, and dry to obtain negative photosensitizing resin DP3.

[0136] The weight-average molecular weight and molecular weight distribution index (PDI) of the resin were tested by GPC method. The eluent was an NMP solution of LiBr (0.03 mol / L) and H3PO4 (0.06 mol / L), the resin concentration was 1.0 mg / ml, and the standard was polystyrene. The results are shown in Table 1.

[0137] Table 1

[0138] Preparation of photosensitive resin composition

[0139] Example 1

[0140] Take 20g of the negative photosensitizing resin P1 from Synthesis Example 1, 1.0g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 4.0g of tetraethylene glycol dimethacrylate, 1.65g of 3-(methacryloyloxy)propyltrimethoxysilane, and 0.1g of N-nitrosodiphenylamine and add them sequentially to a mixed solvent of 42g of N-methylpyrrolidone and ethyl lactate (mass ratio 5 / 1). Stir and mix thoroughly to obtain the negative photosensitizing resin composition.

[0141] Examples 2-15, Comparative Examples 1-3

[0142] Examples 2-15 and Comparative Examples 1-3 were synthesized using the same methods as Example 1, except that the types of negative photosensitive resins were different, as detailed in Table 2.

[0143] The negative photosensitive resin compositions prepared in Examples 1-15 and Comparative Examples 1-3 were evaluated for properties such as sensitivity, cyclization rate, storage stability, and adhesion. The results are shown in Table 2.

[0144] Sensitivity evaluation:

[0145] Sensitivity evaluation aims to determine the minimum exposure required for effective photocuring of the photosensitive resin composition.

[0146] The specific steps are as follows: First, the photosensitive resin composition is coated onto a silicon wafer using a spin coater (e.g., Act8 from Tokyo Electron Co., Ltd.). It is then dried at 100°C for 120 seconds, followed by drying at 110°C for another 120 seconds, ultimately forming a uniform photosensitive resin film with a dry film thickness of 10–12 μm. The development time is determined by immersing the obtained photosensitive resin film in cyclopentanone, recording the time required for complete dissolution, and setting twice this time as the formal development time. Next, the resin film is patterned using an i-line stepper (e.g., FPA-3000iW from Canon Co., Ltd.) with an exposure gradient of 100 mJ / cm² within an exposure range of 100–1100 mJ / cm². After exposure, the resin film is developed using a spin-dip development method, with cyclopentanone as the developer, for a development time twice the previously determined dissolution time, followed by rinsing with propylene glycol monomethyl ether acetate (PGMEA).

[0147] Sensitivity is defined as the minimum exposure required for the remaining thickness of the patterned resin film after exposure to exceed 80% of the initial film thickness before exposure. The evaluation criteria are: Grade A for sensitivity less than 200 mJ / cm², Grade B for 200-350 mJ / cm², and Grade C for sensitivity greater than 350 mJ / cm².

[0148] Evaluation of cyclization rate:

[0149] Cycloning rate evaluation is performed by analyzing the degree of imidization of the resin film during heat treatment using infrared spectroscopy (IR), which reflects the heat resistance of the final cured product.

[0150] Measurements were performed using a Fourier transform infrared spectrometer (e.g., Shimadzu's IRAffinity-1S). Measurement conditions were transmission method, wavenumber range 400–4000 cm⁻¹. -1 A total of 16 scans were performed. Using a blank silicon wafer as a background, the patterned resin film obtained in the sensitivity evaluation was first measured to obtain the initial infrared spectrum IR1. Then, the patterned resin film was subjected to two heat treatments in a nitrogen atmosphere: one was heating at 230℃ for 2 hours (to obtain patterned cured material 1, whose spectrum is denoted as IR2), and the other was heating at 375℃ for 2 hours (to obtain patterned cured material 2, whose spectrum is denoted as IR3).

[0151] The characteristic peak of polyimide is 1368 cm⁻¹. -1 Peak area calculation, cyclization rate The values ​​A1, A2, and A3 represent the characteristic peak areas of the initial membrane, the membrane treated at 230℃, and the membrane treated at 375℃, respectively. The evaluation criteria are as follows: a calculated cyclization rate greater than 95% is rated A, 85%-95% is rated B, and less than 85% is rated C.

[0152] Evaluation of preservation stability:

[0153] Storage stability evaluation is a core evaluation indicator used to assess the performance stability of photosensitive resin compositions during storage and the reproducibility of subsequent processes.

[0154] The photosensitive resin composition, prepared within 24 hours, was spin-coated onto a silicon substrate. The drying film thickness was controlled to reach 10 μm. Step drying was then performed on a hot plate: heating at 100°C for 120 seconds, followed immediately by heating at 110°C for 120 seconds, forming a photosensitive resin film. The film thickness was measured and recorded as film thickness 1 (initial film thickness). The same batch of photosensitive resin composition was stored at room temperature (25°C) for 14 days. After the storage period, the composition was re-coated under the exact same process conditions as the initial test (including rotation speed and heat treatment procedure) to form a photosensitive resin film. The film thickness was measured and recorded as film thickness 2 (aged film thickness).

[0155] The evaluation criterion for preservation stability is the film thickness change rate, calculated using the formula: (film thickness 2 - film thickness 1) / film thickness 1 × 100%. A change rate less than 5% indicates good preservation stability, rated as Grade A. A change rate of 5-10% is rated as Grade B. A change rate greater than 10% is rated as Grade C.

[0156] Evaluation of Cu adhesion properties:

[0157] The evaluation of Cu adhesion mainly examines the interfacial bonding strength between the cured resin film and the copper substrate, which is crucial for the reliability of electronic devices.

[0158] The photosensitive resin composition, prepared within 24 hours, was coated onto a copper-plated silicon substrate, and the process was controlled to form a resin film with a dry film thickness of approximately 10 μm. This resin film was then fully cured at 230°C for 2 hours under a nitrogen atmosphere, yielding a test sample with a cured film thickness of approximately 8 μm. The cross-section of the test sample was observed at high magnification using a scanning electron microscope (e.g., Hitachi Advanced Technology's IM4000), focusing on the interfacial bonding area between the cured resin and the copper layer.

[0159] The evaluation criteria are divided into three levels: Grade A is defined as the complete absence of any separation at the interface. Grade B is defined as the observation of minute separations with a width of less than 0.2 μm. Grade C is defined as the separation width being greater than or equal to 0.2 μm.

[0160] Table 2

[0161] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a negatively photosensitive resin, characterized in that, Includes the following steps: (1) Tetracarboxylic acid dianhydride reacts with unsaturated double-bonded alcohols in an organic solvent for esterification; (2) Add an aromatic diamine solution to the above esterified product to carry out a polycondensation reaction; (3) Add an activating agent to the product of step (2) above, and then add an alcohol compound containing an unsaturated double bond to carry out an esterification reaction.

2. The method for preparing the negative photosensitive resin as described in claim 1, characterized in that, In step (1), the molar ratio of tetracarboxylic dianhydride to unsaturated double-bonded alcohol is 1:0.1-0.3; in step (2), the molar amount of aromatic diamine is 0.7-0.9 times that of tetracarboxylic dianhydride in step (1); in step (3), the molar amount of alcohol containing unsaturated double bonds is 2-4 times that of tetracarboxylic dianhydride in step (1).

3. The method for preparing the negative photosensitive resin as described in claim 1, characterized in that, The unsaturated double-bonded alcohol compound is selected from at least one of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 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, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 1-methacryloyloxy-3-propanol, 2-isobutenamide ethanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

4. The method for preparing the negative photosensitive resin as described in claim 2, characterized in that, In step (1), the molar ratio of tetracarboxylic dianhydride to unsaturated double-bonded alcohol is 1:0.16-0.21; and / or, in step (2), the molar amount of aromatic diamine is 0.75-0.85 times that of tetracarboxylic dianhydride in step (1); and / or, in step (3), the molar amount of alcohol containing unsaturated double bonds is 2-2.5 times that of tetracarboxylic dianhydride in step (1).

5. A negative photosensitizing resin, characterized in that, It is prepared by the preparation method according to any one of claims 1-4.

6. The negative photosensitive resin as described in claim 5, characterized in that, The molecular weight distribution index (PDI) of the negative photosensitive resin is ≤1.

55.

7. A photosensitive resin composition, characterized in that, The composition comprises the following components in parts by weight: 100 parts of the negative photosensitive resin as described in claim 5, 0.1 to 20 parts of photosensitizer, 1 to 30 parts of crosslinking agent, 0.1 to 30 parts of adhesive aid, 0.1 to 30 parts of polymerization inhibitor, and 100 to 1000 parts of organic solvent.

8. A cured film, characterized in that, It is prepared by coating and drying the photosensitive resin composition described in claim 7.

9. A patterned cured film, characterized in that, The photosensitive resin composition of claim 7 is prepared by coating, exposure, development and curing.

10. The use of the photosensitive resin composition of any one of claims 6-7 or the patterned curable film of claim 9 in semiconductor manufacturing and / or packaging.

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