Negative photosensitive resin composition, cured film and method for producing same, laminate, and semiconductor element

Abstract

Disclosed is a negative photosensitive resin composition comprising at least one of a polyimide precursor and a polybenzoxazole precursor containing a (meth) acrylic group and a urea bond repeating unit. The negative photosensitive resin composition provided by the invention can realize low-temperature curing of a cured film with the thickness of 11-25 + micron at 180-250 DEG C, and excessive cyclization reaction and shrinkage stress are avoided, so that high adhesion and uniformity of a material are kept; a cured film which is good in in-plane uniformity, excellent in mechanical property, stable in storage and good in chemical resistance and adhesion can be obtained, the problem that high-temperature cured photoresist and many heat-sensitive materials (such as flexible substrates and organic light-emitting layers) cannot be used together is solved, and the high-temperature cured photoresist is suitable for high-resolution photoetching.

Description

Technical Field

[0001] This invention belongs to the field of thermosetting materials technology, specifically relating to a negative photosensitive resin composition, a cured film and its manufacturing method, a laminate, and a semiconductor element. Background Technology

[0002] Due to its excellent heat resistance and insulation properties, polyimide is suitable for the manufacture of cured films, laminates, cured film manufacturing methods, and semiconductor devices. For example, it can be used as an insulating film or sealing material or a protective film in semiconductor devices, and it can also be used as a base film or coverlay film for flexible substrates.

[0003] In the aforementioned applications, polyimide is used either as a resin composition comprising polyimide itself or as a resin composition comprising a polyimide precursor. Such a resin composition is applied to a substrate, for example, by coating, and then subjected to exposure, development, heating, etc., as needed, thereby forming a cured resin on the substrate. Since the resin composition can be applied using known coating methods, it offers excellent manufacturing adaptability, such as a high degree of design freedom regarding the shape, size, and application location of the applicable resin composition. In addition to the high performance of polyimide, the development of industrial applications for resin compositions comprising polyimide or polyimide precursors is increasingly anticipated due to these excellent manufacturing adaptability considerations.

[0004] However, most existing resin compositions can only be cured at high temperatures. Many materials used in modern electronic devices and display technologies (such as flexible OLEDs and organic light-emitting materials) cannot withstand high temperatures. For example, the organic light-emitting layer in an OLED panel will decompose or degrade at high temperatures.

[0005] There is an urgent need to develop a new type of negative photosensitive resin composition to solve the problem that high-temperature curing resin compositions cannot be used in conjunction with many heat-sensitive materials (such as flexible substrates, organic light-emitting layers, etc.). Summary of the Invention

[0006] To address the problems existing in the prior art, the present invention provides a negative photosensitive resin composition, wherein the resin composition comprises at least one of the following groups: a polyimide precursor containing (meth)acrylate groups and urea bond repeating units as shown in formula (1), and a polybenzoxazole precursor.

[0007] Equation (1)

[0008] In this context, R and R7 independently represent hydrogen atoms or monovalent organic groups, R1, R2, and R3 independently represent tetravalent organic groups, and R4, R5, and R6 independently represent divalent organic groups.

[0009] Furthermore, the synthesis of the polyimide precursor and the polybenzoxazole precursor includes the following monomers:

[0010] ;

[0011] Furthermore, the synthesis of the polyimide precursor and the polybenzoxazole precursor includes the following monomers:

[0012] ;

[0013] Furthermore, the resin composition also includes a photopolymerization initiator, a migration inhibitor, a free radical crosslinking agent, a metal adhesion modifier, and a solvent;

[0014] Furthermore, the photopolymerization initiator includes one or more combinations of haloalkanes, acylphosphine compounds, hexaaryl biimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azido compounds, metallocene compounds, organoboron compounds, and iron-aromatic complexes.

[0015] The migration inhibitors include one or more combinations of heterocyclic compounds, thioureas and compounds with hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acylhydrazine derivative compounds.

[0016] The heterocycle includes one or more combinations of pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, and triazine ring;

[0017] Preferably, the photopolymerization initiator is a metallocene compound, and the migration inhibitor is 5-amino-1H-tetrazole;

[0018] Furthermore, the free radical crosslinking agent includes dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate and structures thereof with (meth)acryloyl groups bonded via ethylene glycol residues or propylene glycol residues, dipentaerythritol hexa(meth)acrylate and structures thereof with (meth)acryloyl groups bonded via ethylene glycol residues or propylene glycol residues; and one or more combinations of oligomers thereof;

[0019] Furthermore, the metal adhesion modifier includes one or more combinations of silane coupling agents, aluminum-based adhesives, titanium-based adhesives, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphate derivative compounds, β-ketoester compounds, and amino compounds.

[0020] Furthermore, the solvent includes one or more combinations of γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 3-butoxy-N,N-dimethylpropionamide, cyclopentanone, propylene glycol monomethyl ether acetate, and ethyl lactate.

[0021] A second aspect of the present invention provides a cured film formed from the negative photosensitive resin composition described in the first aspect of the present invention.

[0022] A third aspect of the present invention provides a method for manufacturing a cured film, comprising the following steps:

[0023] S1, the negative photosensitive resin composition described in the first aspect of the present invention is suitable for the process of forming a film on a substrate;

[0024] S2, the process of exposing the film;

[0025] S3 is the process of developing the exposed film.

[0026] S4 is a process of heating and curing the film in an atmosphere with a temperature of 180~250℃ and an oxygen partial pressure of 6~150Pa.

[0027] A fourth aspect of the present invention provides a laminate, the method for manufacturing the laminate comprising the step of forming a cured film using the method for manufacturing a cured film as described in the third aspect of the present invention, and the step of forming a metal layer on the surface of the cured film.

[0028] The fifth aspect of the present invention provides a semiconductor element, wherein the method for manufacturing the semiconductor element includes the method for manufacturing a cured film as described in the third aspect of the present invention or the method for manufacturing a laminate as described in the fourth aspect of the present invention.

[0029] Beneficial effects:

[0030] This invention proposes a negative photosensitive resin composition comprising at least one of a polyimide precursor containing (meth)acrylic acid groups and urea bond repeating units, and a polybenzoxazole precursor. This composition enables low-temperature curing of the curing film at 180–250°C, avoiding excessive cyclization and shrinkage stress. Furthermore, a specific photopolymerization initiator can improve the cyclization rate, making it particularly suitable for curing films 11–25+ micrometers thick. Specific migration inhibitors effectively suppress migration, improving storage stability and maintaining high adhesion and uniformity of the material. This results in a cured film with excellent in-plane uniformity, superior mechanical properties, stable storage, good chemical resistance, and good adhesion. It solves the problem of incompatibility between high-temperature curing photoresists and many heat-sensitive materials (such as flexible substrates and organic light-emitting layers), making it suitable for high-resolution lithography and expanding its applications in flexible electronics, OLED displays, and other fields. It is widely used in the manufacture of high-performance insulating layers, buffer layers, and structural layers, especially excelling in applications requiring high mechanical properties, chemical resistance, and good adhesion. Detailed Implementation

[0031] 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.

[0032] <Negative Photosensitive Resin Composition>

[0033] The first aspect of the present invention provides a negative photosensitive resin composition comprising at least one of a polyimide precursor and a polybenzoxazole precursor, a photopolymerization initiator, a migration inhibitor, a free radical crosslinking agent, a metal adhesion modifier, and a solvent.

[0034] Polyimide precursor and polybenzoxazole precursor

[0035] The resin composition of the present invention comprises at least one of the following groups: a polyimide precursor containing (meth)acrylic acid groups and urea bond repeating units as shown in formula (1), and a polybenzoxazole precursor.

[0036] Equation (1)

[0037] In this context, R and R7 independently represent hydrogen atoms or monovalent organic groups, R1, R2, and R3 independently represent tetravalent organic groups, and R4, R5, and R6 independently represent divalent organic groups.

[0038] Conventional negative photosensitive resin compositions formulated with polyimide and polybenzoxazole precursors, when cured at low temperatures below 250°C, tend to exhibit incomplete conversion of the polyimide precursor to polyimide and the polybenzoxazole precursor to polybenzoxazole. However, the modified polyimide and polybenzoxazole precursors in this invention contain urea (-NH-CO-NH-) groups, which readily undergo thermal decomposition during heating, generating amine compounds (such as primary or secondary amines). These amine compounds possess high reactivity. The generated amines can act as catalysts or reaction intermediates, promoting the dehydration and cyclization reactions of polyimide precursors (such as polyamic acid or polyamic ester) and polybenzoxazole precursors, thereby accelerating the formation of polyimide and polybenzoxazole. The modified polyimide precursor and polybenzoxazole precursor contain (meth)acryloyl groups, which can undergo free radical polymerization under light irradiation to form cross-linked structures with the side chain portions of the polyimide precursor and polybenzoxazole precursor. This cross-linking effect makes it easier for amine compounds to exist near the polyimide precursor and polybenzoxazole precursor, thereby significantly improving the conversion efficiency of polyimide precursor to polyimide and polybenzoxazole precursor to polybenzoxazole. Since the conversion of polyimide and polybenzoxazole can be completed at low temperature, excessive cyclization reaction and shrinkage stress are avoided, thus maintaining the high adhesion and uniformity of the material. In the multilayer structure, when the first layer film is coated with the second layer of photosensitive resin composition and pre-baked, it can exhibit good in-plane uniformity due to the sufficient solvent resistance of the first layer.

[0039] Using at least one of the following groups of polyimide precursors containing (meth)acrylic acid groups and urea bond repeating units and polybenzoxazole precursors as components of the resin composition, low-temperature curing of 11-25+ micrometer thick curable films can be achieved at 180-250°C. This results in curable films with good in-plane uniformity, excellent mechanical properties, stable storage, good chemical resistance, and good adhesion. It solves the problem that high-temperature curable photoresists cannot be used in conjunction with many heat-sensitive materials (such as flexible substrates and organic light-emitting layers). It is suitable for high-resolution photolithography and expands its application in flexible electronics, OLED displays, and other fields. It is widely used to manufacture high-performance insulating layers, buffer layers, and structural layers, and performs particularly well in applications requiring high mechanical properties, chemical resistance, and good adhesion.

[0040] The preferred monomers for synthesizing the above-mentioned polyimide precursor and polybenzoxazole precursor include:

[0041] .

[0042] More preferably, the synthesis of the above-mentioned polyimide precursor and polybenzoxazole precursor includes the following monomers:

[0043] .

[0044] The above monomers react with dianhydride monomers and diamine monomers to obtain the polyimide precursor or polybenzoxazole precursor shown in formula (1). There are no particular limitations on the dianhydride monomers and diamine monomers. The dianhydride monomers include one or more of aromatic acid dianhydrides, dianhydrides containing a siloxane skeleton, aliphatic acid dianhydrides, and alicyclic acid dianhydrides. Examples of dianhydride monomers include 4,4'-oxophthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, etc., with 4,4'-oxophthalic acid dianhydride being a preferred dianhydride monomer. Diamine monomers include one or more of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis(3-aminophenyl) sulfide, (3-aminophenyl)(4-aminophenyl) sulfide, bis(4-aminophenyl) sulfide, bis(3-aminophenyl) sulfoxide, (3-aminophenyl)(4-aminophenyl) sulfoxide, bis(4-aminophenyl) sulfoxide, bis(3-aminophenyl) sulfone, (3-aminophenyl)(4-aminophenyl) sulfone, bis(4-aminophenyl) sulfone, and 4,4'-oxodiphenylamine, with 4,4'-oxodiphenylamine being a preferred diamine monomer.

[0045] Photopolymerization initiator

[0046] Photopolymerization initiators are a key component of this resin composition. Under specific light conditions, such as ultraviolet or visible light irradiation, they absorb light energy and generate active species such as free radicals or cations. These active species can initiate polymerization reactions in polymerizable groups in the polymer precursor, thereby transforming the resin from a liquid or semi-liquid state into a solid polymer with a three-dimensional network structure. This process not only determines the curing speed of the resin but also affects the molecular weight distribution and crosslinking density of the cured polymer. A suitable photopolymerization initiator ensures rapid and uniform curing of the resin under light irradiation while avoiding adverse effects on polymer properties from byproducts generated by initiator decomposition. For example, in some high-precision photolithography applications, the efficiency and selectivity of the photopolymerization initiator are crucial for forming fine patterns.

[0047] The photopolymerization initiator includes one or more combinations of halogenated hydrocarbon derivatives, acylphosphine compounds, hexaaryl biimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azido compounds, metallocene compounds, organoboron compounds, and iron-aromatic complexes. The content of the photopolymerization initiator is preferably 0.1% to 10% by mass relative to the total solids content of the resin composition.

[0048] The preferred photopolymerization initiator is a metallocene compound. Metallocene compounds can absorb light energy over a wide wavelength range, exhibiting particularly good activity in the visible light region. This makes them more flexible in terms of light source requirements during photocuring, applicable to various types of light sources, including LED light sources, and highly suitable for thick coatings, especially curable films 11 to 25+ micrometers thick. The active intermediates formed after the decomposition of the metallocene initiator have high reactivity, enabling rapid initiation of polymerization reactions and increasing the cyclization rate. Furthermore, their initiation efficiency is less affected by environmental humidity and temperature, making them suitable for use under various environmental conditions. An example metallocene compound is IRGACURE 784.

[0049] migration inhibitors

[0050] Migration inhibitors in resin compositions primarily prevent the migration of certain components during or after curing, thus affecting the material's performance and stability. During resin curing, due to increased temperature and chemical reactions, some molecules may migrate to the material surface, leading to altered surface properties or the formation of uneven layers. Migration inhibitors reduce the mobility of these potentially migrating components within the material by forming stable chemical bonds or physical adsorption, thereby suppressing migration. Furthermore, migration inhibitors can improve the thermal and chemical stability of the resin, preventing component loss in high-temperature or chemical environments. The use of migration inhibitors can also prevent components such as metal ions from migrating to the surface of electronic components, avoiding short circuits or corrosion, thereby improving the reliability and lifespan of encapsulation materials.

[0051] Migration inhibitors include one or more combinations of heterocyclic compounds, thioureas and compounds with hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acylhydrazine derivative compounds. The heterocycles include one or more combinations of pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, pyrazole rings, isoxazole rings, isothiazole rings, tetrazolium rings, pyridine rings, pyridazine rings, pyrazine rings, piperidine rings, piperazine rings, morpholine rings, 2H-pyran rings, 6H-pyran rings, and triazine rings.

[0052] The preferred migration inhibitor is 5-amino-1H-tetrazole, which can form a stable bond with components that may migrate through chemical reaction or physical adsorption, thereby more effectively inhibiting migration, improving storage stability, and preventing components such as metal ions from migrating to the surface of electronic components, avoiding short circuits or corrosion, and improving the reliability and lifespan of packaging materials.

[0053] free radical crosslinking agent

[0054] Free radical crosslinking agents play a role in enhancing the crosslinking network during resin curing. They can react with active functional groups in polymer precursors to generate free radical intermediates, thereby initiating crosslinking reactions between polymer chains. This crosslinking effect can significantly improve the mechanical strength, thermal stability, and chemical stability of the polymer. The amount and type of free radical crosslinking agent added can be adjusted according to the desired final properties of the resin. For example, when preparing high-strength, high-temperature resistant polymer materials, increasing the amount of free radical crosslinking agent can increase the crosslinking density of the polymer, thereby enhancing its heat resistance and mechanical properties. Furthermore, free radical crosslinking agents can also synergistically work with photopolymerization initiators to further optimize the resin curing process and performance. Their content relative to the total solids content of the curable resin composition of the present invention is more preferably 5% by mass or more, and more preferably 30% by mass or less.

[0055] The free radical crosslinking agents of this invention include dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate and structures thereof with (meth)acryloyl groups bonded via ethylene glycol residues or propylene glycol residues, dipentaerythritol hexa(meth)acrylate and structures thereof with (meth)acryloyl groups bonded via ethylene glycol residues or propylene glycol residues; and one or more combinations of oligomers thereof. An example free radical crosslinking agent is tetraethylene glycol dimethacrylate.

[0056] Metal adhesion modifier

[0057] Metal adhesion modifiers are primarily used to improve the adhesion between resin materials and metal surfaces. The adhesion between resin and metal is often affected by factors such as surface energy differences and chemical inertness, leading to insufficient bond strength. Metal adhesion modifiers enhance the chemical bonding ability between the resin and the metal surface by forming a bridge. They can react chemically with the metal surface to form strong chemical bonds while maintaining good compatibility with the resin material, thus significantly improving bond strength and durability. This modifier can also improve the wettability of the resin on the metal surface, allowing the resin to cover the metal surface more evenly, further improving the adhesion effect. By using metal adhesion modifiers, the problem of poor resin-metal adhesion can be effectively solved.

[0058] The metal adhesion modifiers of this invention include one or more combinations of silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds. An example metal adhesion modifier is the silane coupling agent N[3-(triethoxysilyl)propyl]maleic acid. The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably in the range of 0.5 to 5 parts by weight.

[0059] solvent

[0060] Solvents dissolve and dilute polymer precursors and other additives, enabling the resin composition to have suitable viscosity and flowability, facilitating processing and coating. Examples of solvents include γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 3-butoxy-N,N-dimethylpropionamide, cyclopentanone, propylene glycol monomethyl ether acetate, and ethyl lactate. Solvents may contain only one type or more, preferably with a total solids concentration of 40-70% by mass in the resin composition of the present invention.

[0061] Other ingredients

[0062] If desired, various types of additives, such as polymerization inhibitors, defoamers, coupling agents, fillers, adhesive additives, leveling agents, and polymerization inhibitors, can be further added to the resin composition of the present invention. As fillers, fine inorganic fillers (e.g., silica, mica, talc, barium sulfate, wollastonite, or calcium carbonate) and fine organic polymer fillers can be incorporated. The appropriate amounts of these fillers are preferably selected.

[0063] <Curated films, laminates, semiconductor devices>

[0064] A cured film can be formed using the above-described negative photosensitive resin composition. The cured film is manufactured by the following steps:

[0065] S1, the negative photosensitive resin composition according to any one of claims 1 to 6 is applicable to the process of forming a film on a substrate;

[0066] S2, the process of exposing the film;

[0067] S3 is the process of developing the exposed film.

[0068] S4 is a process of heating and curing the film in an atmosphere with a temperature of 180~250℃ and an oxygen partial pressure of 6~150Pa.

[0069] In step S1, the substrate for which the resin composition is applied is a metal substrate or a substrate containing a metal layer.

[0070] The film obtained by using the resin composition is cured by heating at 180-250°C in an atmosphere with an oxygen partial pressure of 6-150 Pa, which can produce a cured film with excellent mechanical properties, chemical resistance and good adhesion, thus completing the present invention.

[0071] The method for manufacturing the laminate includes the step of forming a cured film using the above-described method for manufacturing a cured film, and the step of forming a metal layer on the surface of the cured film.

[0072] The manufacturing method of a semiconductor device includes the manufacturing method of the above-mentioned cured film or the manufacturing method of the above-mentioned laminate.

[0073] The above and other advantages of the present invention can be better understood through the following embodiments, but the following embodiments are not intended to limit the scope of the present invention.

[0074] Example

[0075] The following embodiments illustrate the present invention, but the present invention is not limited to the following embodiments.

[0076] IRGACURE 784: Bis-2,6-Difluoro-3-pyrrolidinyl dicthecinene

[0077] OXE-01: 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime)

[0078] Synthesis Example 1: Synthesis of Compound A

[0079] 26.3 g (0.25 mol) of 2-(2-aminoethoxy)ethanol was placed in a 500 mL detachable flask, and 150 mL of tetrahydrofuran was added. The mixture was stirred at room temperature. Then, over 30 minutes in an ice bath, a solution of 38.8 g (0.25 mol) of 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd., product name: Karenz MOI) with 150 mL of tetrahydrofuran was added dropwise to the flask, and the mixture was stirred at room temperature for 5 hours. The tetrahydrofuran was then distilled off using a rotary evaporator, and the resulting product was purified to obtain compound A.

[0080]

[0081] Synthesis Example 2: Synthesis of Compound B

[0082] In Synthesis Example 1, 2-(2-aminoethoxy)ethanol was replaced with diethanolamine, otherwise the process was the same as in Synthesis Example 1, yielding compound B.

[0083]

[0084] Synthesis Example 3: Synthesis of Compound C

[0085] In Synthesis Example 1, 2-(2-aminoethoxy)ethanol was replaced with diethanolamine, and 38.8 g (0.25 mol) of 2-methacryloyloxyethyl isocyanate was replaced with 59.8 g (0.25 mol) of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (Showa Denko Corporation, product name: Karenz BEI). Otherwise, the process was the same as in Synthesis Example 1, yielding compound C.

[0086]

[0087] Synthesis Example 4: Synthesis of Compound D

[0088] The diethanolamine 26.3 g (0.25 mol) in Synthesis Example 3 was replaced with N,N'-bis(2-hydroxyethyl)ethylenediamine 37.1 g (0.25 mol), and the 1,1-(bisacryloyloxymethyl)ethyl isocyanate 59.8 g (0.25 mol) was replaced with 119.6 g (0.50 mol). Otherwise, the same procedure as in Synthesis Example 3 was followed to obtain compound D.

[0089]

[0090] Preparation Example 1: Synthesis of polyimide precursor (Aa-1)

[0091] 20.0 g (64.5 mmol) of 4,4'-oxophthalic dianhydride (obtained by drying 4,4'-oxophthalic acid at 140 °C for 12 h), 33.6 g (129 mmol) of compound A, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether were mixed and stirred at 60 °C for 18 h to synthesize a diester of 4,4'-oxophthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10 °C, and while maintaining the temperature at -10 ± 4 °C, 16.12 g (135.5 mmol) of SOCl2 was added over 10 minutes. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 h. Then, a solution of 11.08 g (58.7 mmol) of 4,4'-oxodiphenylamine dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at 20–23 °C. The reaction mixture was then stirred overnight at room temperature. Next, 5 L of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 L of water, and stirred again for 30 minutes, followed by filtration again. The resulting polyimide precursor was then dried under reduced pressure at 45 °C for 3 days to obtain polyimide precursor (Aa-1).

[0092] Preparation Example 2: Synthesis of Polyimide Precursor (Aa-2)

[0093] By replacing compound A in Preparation Example 1 with compound B, and otherwise remaining the same as in Preparation Example 1, polyimide precursor (Aa-2) was obtained.

[0094] Preparation Example 3: Synthesis of polyimide precursor (Aa-3)

[0095] By replacing compound A in Preparation Example 1 with compound C, and otherwise remaining the same as in Preparation Example 1, polyimide precursor (Aa-3) was obtained.

[0096] Preparation Example 4: Synthesis of polyimide precursor (Aa-4)

[0097] By replacing compound A in Preparation Example 1 with compound D, and otherwise remaining the same as in Preparation Example 1, polyimide precursor (Aa-4) was obtained.

[0098] Preparation Example 5: Synthesis of polyimide precursor q

[0099] The compound A in Preparation Example 1 was replaced with 2-hydroxyethyl methacrylate, otherwise the preparation was the same as in Preparation Example 1, to obtain polyimide precursor q.

[0100] <Example 1> Preparation of negative photosensitive resin composition 1

[0101] 100 g of polyimide precursor Aa-1, 3.4 g of metallocene compound IRGACURE784 as photopolymerization initiator, 3 g of nitrogen-containing heterocyclic compound 5-amino-1H-tetrazole as migration inhibitor, 4 g of N-[3-(triethoxysilyl)propyl]maleic acid as metal adhesion modifier, 10 g of tetraethylene glycol dimethacrylate as free radical crosslinking agent, and 2.0 g of p-benzoquinone as polymerization inhibitor were dissolved in 200 g of N-methylpyrrolidone solvent. The viscosity of the resulting solution was adjusted to approximately 40 poise by further adding a small amount of this solvent, thus forming negative photosensitive resin composition 1.

[0102] <Example 2> Preparation of negative photosensitive resin composition 2

[0103] By replacing polymer Aa-1 in Example 1 with polymer Aa-2, while keeping other conditions unchanged, negative photosensitive resin composition 2 was obtained.

[0104] <Example 3> Preparation of negative photosensitive resin composition 3

[0105] By replacing polymer Aa-1 in Example 1 with polymer Aa-3, while keeping other conditions unchanged, negative photosensitive resin composition 3 was obtained.

[0106] <Example 4> Preparation of negative photosensitive resin composition 4

[0107] By replacing polymer Aa-1 in Example 1 with polymer Aa-4, while keeping other conditions unchanged, negative photosensitive resin composition 4 was obtained.

[0108] <Example 5> Preparation of negative photosensitive resin composition 5

[0109] In Example 1, polymer Aa-1 was replaced with polymer Aa-4, and photopolymerization initiator IRGACURE 784 was replaced with OXE-01, while other conditions remained unchanged, to obtain negative photosensitive resin composition 5.

[0110] <Example 6> Preparation of negative photosensitive resin composition 6

[0111] In Example 1, polymer Aa-1 was replaced with polymer Aa-4, and migration inhibitor 5-amino-1H-tetrazole was replaced with migration inhibitor 1H-tetrazole, while other conditions remained unchanged, to obtain negative photosensitive resin composition 6.

[0112] <Comparative Example 1> Preparation of Negative Photosensitive Resin Composition Q

[0113] By replacing polymer Aa-1 in Example 1 with polymer q, while keeping other conditions unchanged, a negative photosensitive resin composition Q was obtained.

[0114] The prepared negative photosensitive resin composition was evaluated as follows.

[0115] <Resolution (exposure latitude) evaluation>

[0116] The photosensitive resin compositions used in each embodiment and comparative example were filtered through a filter with a pore width of 0.8 μm and pressurized at a pressure of 0.3 MPa, and then spin-coated onto silicon wafers with a diameter of 200 mm (8 inches, 1 inch = 2.54 cm). The silicon wafers coated with the photosensitive resin compositions were dried on a hot plate at 100 °C for 5 minutes, thereby forming a 20 μm thick photosensitive film on the silicon wafer. The photosensitive film on the silicon wafer was exposed using a stepper (Nikon NSR 2005i9C). Exposure was performed using an i-line at a wavelength of 365 nm and at concentrations of 200, 300, 400, 500, 600, 700, and 800 mJ / cm². 2Resin layers were obtained by exposing the resin layers to various exposure energies from 5 μm to 25 μm using photomasks with 1 μm graduations and gaps. The resin layers were then spray-developed with cyclopentanone for 60 seconds. A smaller linewidth in the obtained resin layer (pattern) indicates a greater difference in solubility between the irradiated and non-irradiated areas relative to the developer, which is preferred. Furthermore, a small change in linewidth relative to the exposure energy indicates excellent resolution and a wide exposure latitude, which is also preferred. The measurement limit was 5 μm. The smallest size at which a pattern with a sharp-edged linewidth and no residue remaining on the substrate was obtained was used as the benchmark value. Evaluations were conducted according to the following evaluation criteria, and the evaluation results are recorded in the table. In the table, values ​​from "200" to "800" represent exposure energy (mJ / cm²). 2 The more exposures assigned to an A rating, the wider the exposure range that can be covered to obtain a good pattern, resulting in excellent exposure latitude.

[0117] [Evaluation Criteria] A: The above benchmark value is 5 μm or more and 8 μm or less. B: The above benchmark value is more than 8 μm but less than 10 μm. C: The above benchmark value is more than 10 μm but less than 15 μm. D: The above benchmark value is more than 15 μm but less than 20 μm. E: The above benchmark value is more than 20 μm. F: A pattern with a linewidth having sharp edges was not obtained.

[0118] <Evaluation of preservation stability>

[0119] Each of the examples and comparative examples, consisting of 10 g of photosensitive resin compositions, was sealed in a container (material: light-proof glass, capacity: 100 mL) and left to stand for one week at 25 °C and 65% relative humidity. For each photosensitive resin composition before and after standing, viscosity was measured at 25 °C using a RE-85L (manufactured by TOKI SANGYO CO.,LTD), and the absolute value of the viscosity change rate was calculated. It can be said that the smaller the change rate, the higher the storage stability of the photosensitive resin composition.

[0120] [Evaluation Criteria] A: The absolute value of the viscosity change rate is 0% or more and less than 5%. B: The absolute value of the viscosity change rate is 5% or more and less than 8%. C: The absolute value of the viscosity change rate is 8% or more and less than 10%. D: The absolute value of the viscosity change rate is 10% or more.

[0121] <Evaluation of Mechanical Properties (Elongation at Break)>

[0122] The photosensitive resin compositions of each embodiment and comparative example were spin-coated onto silicon wafers. The silicon wafers coated with the photosensitive resin compositions were then dried on a hot plate at 100 °C for 5 minutes, thereby forming a uniform film with a thickness of 20 μm on the silicon wafers. Next, a stepper (Nikon NSR2005i9C) was used at 500 mJ / cm². 2 The film formed on the silicon wafer was exposed using the appropriate exposure energy. Under a nitrogen atmosphere and an oxygen partial pressure of 6–150 Pa, the exposed photosensitive resin composition layer (resin layer) was heated at a rate of 10 °C / min, and then heated for 2 hours after reaching the target temperature of 180 °C. The cured resin layer was then immersed in a 4.9% by mass hydrofluoric acid solution and peeled off from the silicon wafer to obtain the resin film. The elongation at break of the resin film was measured using a tensile testing machine (Tensilon) with a crosshead speed of 300 mm / min, a specimen width of 10 mm, and a specimen length of 50 mm, along the long side of the film, at 25 °C and 65% relative humidity (RH) according to JIS-K6251. For evaluation, the elongation at break along the long side was measured five times, and the average value of the elongation at break along the long side was used for evaluation according to the following evaluation criteria.

[0123] [Evaluation Criteria] A: The average elongation at break in the long direction is 65% or higher. B: The average elongation at break in the long direction is less than 65%.

[0124] <Evaluation of Chemical Resistance>

[0125] The compositions described in the examples and comparative examples were spin-coated onto a 4-inch diameter silicon wafer at 1000 rpm and heated at 100°C for 2 minutes on a hot plate to form a 20 μm film. A stepper (Nikon NSR2005i9C) was used at 500 mJ / cm². 2 The entire surface of the formed photosensitive film was exposed using the specified exposure energy. Then, the wafer, after being exposed to the entire surface, was heated to 180 °C for 2 h on a heating plate with an oxygen partial pressure of 6–150 Pa under a nitrogen gas flow and cured. After curing, the obtained wafer was immersed in N-methyl-2-pyrrolidone for 3 hours, cleaned with isopropanol, and then air-dried. The presence or absence of cracks in the cured film of the obtained wafer was visually inspected. Chemical resistance was evaluated according to the following evaluation criteria.

[0126] [Evaluation Criteria] A: No cracks were found across the entire surface of the wafer. B: Cracks were found in at least a portion of the wafer.

[0127] <Circulation Rate Test>

[0128] The compositions described in the examples and comparative examples were spin-coated onto a 4-inch diameter silicon wafer at 1000 rpm and heated at 100°C for 2 minutes on a hot plate to form a 20 μm film. A stepper (Nikon NSR2005i9C) was used at 500 mJ / cm². 2 The exposure energy was used to expose the entire surface of the formed photosensitive film. Under a nitrogen atmosphere with an oxygen partial pressure of 6–150 Pa, the exposed photosensitive resin composition layer (resin layer) was heated at a rate of 10 °C / min to cure at 180 °C. After reaching the target curing temperature, it was heated for 2 hours. The film was then soaked in 10% hydrofluoric acid and dried. The center position of the film was cut and tested on a testing instrument (FT-IR). Using a 400 °C cured film as a reference, the reading was taken at 1380 cm⁻¹. -1 and 1500 cm -1 The ratio of absorbance values, after correction (based on 400℃), yields the cyclization rate calculation formula:

[0129]

[0130] Where X: cyclization rate (%);

[0131] A 固化温度,1380 The characteristic peak intensity of the film sample after baking at the curing temperature was 1380 cm⁻¹.

[0132] A 固化温度,1500 The characteristic peak intensity of the film sample at 1500 cm⁻¹ after baking at the curing temperature;

[0133] A 400,1380 The characteristic peak intensity of the film sample after baking at 400℃ was 1380 cm⁻¹.

[0134] A 400,1500 The characteristic peak intensity of the film sample at 1500 cm⁻¹ after baking at 400℃.

[0135] [Evaluation Criteria] A: The average cyclization rate is 100-90%; B: The average cyclization rate is 89-70%; C: The average cyclization rate is below 70%.

[0136] The evaluation results are shown in the table below:

[0137] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Negative photosensitive resin composition 1 2 3 4 5 6 Q Curing temperature (°C) 180 180 180 180 180 180 180 Curing time (min) 120 120 120 120 120 120 120 Film thickness (μm) 20 20 20 20 20 20 20 <![CDATA[Exposure latitude (500 mJ / cm 2 ).]]> A A A A A A B <![CDATA[Exposure latitude (600 mJ / cm 2 ).]]> A A A A A A A <![CDATA[Exposure latitude (700 mJ / cm 2 ).]]> A A A A A A A <![CDATA[Exposure latitude (800 mJ / cm 2 )]]> A A A A A A B Preservation stability A A A A A B B Elongation at break B B A A A A B Chemical resistance A A A A A A B cyclization rate A A A A B A C

[0138] It should be noted that, based on the explanations and descriptions in the foregoing specification, those skilled in the art can make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and alterations to the present invention should also be within the scope of protection of the claims of the present invention. Furthermore, although some specific terms are used in this specification, these terms are only for convenience of explanation and do not constitute any limitation on the invention.

Claims

1. A negative photosensitive resin composition, characterized in that, The resin composition comprises at least one of the following groups: a polyimide precursor containing (meth)acrylic acid groups and repeating urea bonds, as shown in formula (1), and a polybenzoxazole precursor. Equation (1) In this context, R and R7 independently represent hydrogen atoms or monovalent organic groups, R1, R2, and R3 independently represent tetravalent organic groups, and R4, R5, and R6 independently represent divalent organic groups.

2. The negative photosensitive resin composition according to claim 1, characterized in that, The synthesis of the polyimide precursor and the polybenzoxazole precursor includes the following monomers: 。 3. The negative photosensitive resin composition according to claim 2, characterized in that, The synthesis of the polyimide precursor and the polybenzoxazole precursor includes the following monomers: 。 4. The negative photosensitive resin composition according to claim 1, characterized in that, The resin composition further includes a photopolymerization initiator, a migration inhibitor, a free radical crosslinking agent, a metal adhesion modifier, and a solvent; The photopolymerization initiator includes one or more combinations of halogenated hydrocarbon derivatives, acylphosphine compounds, hexaaryl biimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azido compounds, metallocene compounds, organoboron compounds, and iron-aromatic complexes. The migration inhibitors include one or more combinations of heterocyclic compounds, thioureas and compounds with hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acylhydrazine derivative compounds. The heterocycles include one or more combinations of pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, pyrazole rings, isoxazole rings, isothiazole rings, tetrazolium rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, piperidine rings, piperazine rings, morpholine rings, 2H-pyran rings, 6H-pyran rings, and triazine rings.

5. The negative photosensitive resin composition according to claim 4, characterized in that, The photopolymerization initiator is a metallocene compound; the migration inhibitor is 5-amino-1H-tetrazole.

6. The negative photosensitive resin composition according to claim 4, characterized in that, The free radical crosslinking agent includes dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate and structures thereof with (meth)acryloyl groups bonded via ethylene glycol residues or propylene glycol residues, dipentaerythritol hexa(meth)acrylate and structures thereof with (meth)acryloyl groups bonded via ethylene glycol residues or propylene glycol residues; and one or more combinations of oligomers thereof; The metal adhesion modifier includes one or more combinations of silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds with sulfonamide structures, compounds with thiourea structures, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds. The solvent includes one or more combinations of γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 3-butoxy-N,N-dimethylpropionamide, cyclopentanone, propylene glycol monomethyl ether acetate, and ethyl lactate.

7. A cured film formed from the negative photosensitive resin composition according to any one of claims 1 to 6.

8. A method for manufacturing a cured film, characterized in that, Includes the following steps: S1, the negative photosensitive resin composition according to any one of claims 1 to 6 is applicable to the process of forming a film on a substrate; S2, the process of exposing the film; S3 is the process of developing the exposed film. S4 is a process of heating and curing the film in an atmosphere with a temperature of 180~250℃ and an oxygen partial pressure of 6~150Pa.

9. A laminated body, characterized in that, The method for manufacturing the laminate includes the step of forming a cured film according to the method for manufacturing a cured film as described in claim 8, and the step of forming a metal layer on the surface of the cured film.

10. A semiconductor element, characterized in that, The method for manufacturing the semiconductor element includes the method for manufacturing the cured film as described in claim 8 or the method for manufacturing the laminate as described in claim 9.

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