WO2025213449A1 - Latent curing agent, low-temperature-curable photosensitive resin composition, method for preparing patterned cured film, and insulating film - Google Patents

Abstract

The present invention relates to the technical field of photocurable photosensitive materials. Disclosed are a latent curing agent, a low-temperature-curable photosensitive resin composition, a method for preparing a patterned cured film, and an insulating film. The latent curing agent is a quaternary ammonium salt composed of quaternary ammonium cations, and anions containing a sulfonamide structure. A low-temperature-curable thermosetting resin composition comprises the following components in parts by mass: 100 parts of a polyimide precursor, 0.1-10 parts of the latent curing agent, 1-10 parts of a photoinitiator, and 5-50 parts of a cross-linking agent. The method for preparing the patterned cured film comprises: dissolving the low-temperature-curable thermosetting resin composition in an organic solvent, and carrying out exposure, development, and curing. In addition, the insulating film is formed by means of curing. The low-temperature-curable thermosetting resin composition of the present invention comprises a latent curing agent, exhibits a significant effect on improving the development film retention rate of the low-temperature-curable thermosetting resin composition in a patterning process and the tensile strength of a cured thin film, and has a relatively long stable storage period.

Description

Latent curing agent, low-temperature curing photosensitive resin composition, method for preparing patterned cured film, and insulating film Technical Field

The present invention relates to the technical field of photocurable photosensitive materials, and in particular to a latent curing agent, a low-temperature curing photosensitive resin composition, a method for preparing a patterned cured film, and an insulating film.

Background Art

The photosensitive resin composition undergoes a photocuring reaction when irradiated with light to form a photosensitive resin film. The photosensitive resin film is subjected to a photolithography process to form a photosensitive resin film pattern. These patterns can be used as insulating film patterns or protective film patterns in the manufacturing process of electronic components and semiconductor devices.

In the past, in order to improve the processability of insulating materials for electronic components and semiconductor devices, thermosetting resins were processed in the form of precursor solutions, and then processed through a high-temperature heating and curing process to form an insulating film with excellent heat resistance, electrical properties, and mechanical properties. However, the high-temperature process has the side effect of accumulating thermal stress. Currently, in order to achieve low-temperature curing of thermosetting resins, a common measure is to add a curing catalyst or a latent curing catalyst to the precursor solution to obtain better insulating film performance after low-temperature curing and maintain longer storage stability. It is common to prepare a latent curing agent by reacting an alkaline substance with an organic acid, but the residual organic acid in the monomer preparation process will reduce the effectiveness of the latent curing agent.

Summary of the Invention

The purpose of the present invention is to provide a new latent curing agent in order to overcome the defects of the above-mentioned prior art. Another purpose of the present invention is to provide a low-temperature curing thermosetting resin composition, a method for preparing a patterned cured film, and an insulating film.

To achieve the above objectives and other related objectives, the present invention provides the following technical solutions.

In a first aspect, the present invention provides a latent curing agent, which is a quaternary ammonium salt composed of a quaternary ammonium cation and an anion containing a sulfonamide structure.

Furthermore, the quaternary ammonium cation and the anion containing sulfonamide structure are as shown in the general structural formula I-1 and the general structural formula I-2. As shown:

wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are independently selected from a hydrogen atom, a hydroxyl group, a cyano group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₂₀ aromatic group, or any two of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ form an aromatic group; R ₆ is a connecting bond or a C ₁ -C ₁₀ alkylene group; R ₇ and R ₈ are independently selected from a hydrogen atom or a C ₁ -C ₁₀ alkyl group; R ₉ , R ₁₀ and R ₁₁ are independently selected from a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₅ cycloalkyl group, a C ₆ -C ₂₀ aromatic group, or R ₉ , R ₁₀ and R ₁₁ form an imidazole ring structure, a pyridine ring structure or an isoquinoline ring structure; R ₁₂ is selected from a halogen atom, a C ₁ -C R 12 is a C ₁₀ alkyl group, a C ₁ -C ₁₀ haloalkyl group, a C ₆ -C ₂₀ aromatic group, R ₁₃ is selected from nitro, cyano, carbonyl and its derivatives, sulfonyl and its derivatives, amide, or R ₁₂ and R ₁₃ form a ring with a sulfonamide structure.

Among them, the above-mentioned anions and cations can improve the storage stability, film retention rate and other properties of the product. This is because the quaternary ammonium cation reduces the nucleophilicity of the nitrogen atom due to steric hindrance, and at the same time forms an ionic bond with the anion, which can enhance the gel strength due to the polyelectrolyte effect in the cross-linked network formed after exposure, thereby inhibiting swelling and precipitation during development, and thus improving the development film retention rate while ensuring storage stability.

Furthermore, it includes at least one of the following technical features:

a1) R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from hydrogen, hydroxy, cyano, methyl, ethyl, propyl, methoxy, ethoxy, phenyl, benzyl, phenylhexyl, or R ₂ and R ₃ form a phenyl group;

a2) R ₆ is a connecting bond, methylene or ethylene;

a3) R ₇ and R ₈ are each independently selected from a hydrogen atom, a methyl group or an ethyl group;

a4) R ₉ , R ₁₀ and R ₁₁ are each independently selected from methyl, ethyl, propyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylhexyl, or R ₉ , R ₁₀ and R ₁₁ form an imidazole ring, a methylimidazole ring, a pyridine ring or an isoquinoline ring;

a5) R ₁₂ is selected from a fluorine atom, a methyl group, an ethyl group, a propyl group, a phenyl group, a benzyl group, a phenethyl group, a trifluoromethyl group, and a pentafluoroethyl group;

a6) R ₁₃ is selected from one of the following structures:

a7) R ₁₂ and R ₁₃ form a ring with the sulfonamide structure selected from the following structures:

Furthermore, the quaternary ammonium cation is selected from at least one of the following structures:

wherein R ₂ and R ₃ are each independently selected from a hydrogen atom, a hydroxyl group, a cyano group, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a phenyl group, a benzyl group, a phenylhexyl group, or R ₂ and R ₃ form a phenyl group;

Preferably, the quaternary ammonium cation specifically includes the following structure:

Furthermore, the anion containing a sulfonamide structure is selected from at least one of the following structures:

In a second aspect, the present invention provides a low-temperature curing thermosetting resin composition comprising the following components in parts by weight:

Furthermore, the low-temperature curing thermosetting resin composition includes at least one of the following technical features:

c1) the molecular weight of the polyimide precursor is 3000-80000; preferably, the molecular weight is 5000-50000, and more preferably, the molecular weight is 35000-45000, such as 35400, 38900, 41400, 35600, 40100, 39700, 38900;

c2) The polyimide precursor comprises the following structural formula II:

Wherein, X is selected from a tetravalent organic group having a C ₆ -C ₃₀ aromatic structure; Y is selected from a divalent organic group having a C ₆ -C ₃₀ aromatic structure or a C ₁ -C ₂₀ alicyclic structure; R ₂₁ and R ₂₂ are each independently selected from hydrogen atoms or an organic group having a C ₃ -C ₃₀ ethylenically unsaturated bond, a urea group, or a thiourea group.

Preferably, X is selected from at least one of the following structures:

Preferably, Y is selected from at least one of the following structures:

Preferably, R ₂₁ and R ₂₂ are each independently selected from at least one of the following structures:

_R23 is an alkane structure having 1 to 8 carbon atoms, and n is a positive integer of 1-8.

Preferably, when the end group of the polyimide precursor is an amino group, the end-capping agent is an acid anhydride-containing monomer, selected from at least one of (meth)acrylic anhydride, (meth)norbornene anhydride, maleic anhydride, 4-methacryloyloxy trimellitic anhydride, phenylacetylene tricarboxylic anhydride, and 4-phenylethynylphthalic anhydride.

Preferably, when the terminal group of the polyimide precursor is a carboxyl group, the end-capping agent is an amino-containing monomer selected from at least one of 3-aminophenol, 4-aminophenol, 3-aminoanisole, and 4-aminoanisole.

c3) The photoinitiator is at least one selected from oxime ester photoinitiators, titanocene photoinitiators, acylphosphine oxide photoinitiators, benzil photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators, and quinone photoinitiators.

Preferably, the photoinitiator is an oxime ester photoinitiator.

Further preferably, the oxime ester photoinitiator is selected from at least one of Irgacure OXE 01, Irgacure OXE 02, Irgacure OXE 03, Irgacure OXE 04, Irgacure OXE 05, TR-PBG-304, TR-PBG-305, TR-PBG-314, TR-PBG-3057, TR-PBG-A, TR-PBG-B, ADEKAARKLS N-1919T, ADEKAARKLS NCI-831E, ADEKAARKLS NCI-930, ADEKAARKLS NCI-730, and SpeedCure PDO;

c4) The crosslinking agent is selected from triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol or polyethylene glycol di(meth)acrylate; propylene glycol or polypropylene glycol di(meth)acrylate; glycerol di- or tri(meth)acrylate; cyclohexane di(meth)acrylate; 1,4-butanediol dimethacrylate; At least one of glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, and tricyclo[5.2.1.0,2,6]decanedimethanol di(meth)acrylate.

Preferably, the cross-linking agent is at least one selected from tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, tricyclo[5.2.1.0,2,6]decanedimethanol dimethacrylate and pentaerythritol tetramethacrylate.

Furthermore, the low-temperature curing thermosetting resin composition further comprises:

Coupling agent 0.1-10 parts;

Inhibitor               0.1-10 parts.

Furthermore, the coupling agent is selected from silane coupling agent, titanium coupling agent, aluminum coupling agent, zirconium coupling agent, and boron coupling agent.

Preferably, the coupling agent is a silane coupling agent.

Further preferably, the silane coupling agent is selected from at least one of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane.

Furthermore, the polymerization inhibitor is selected from at least one of hydroquinone, 4-methoxyphenol, tert-butylhydroquinone, 1,4-benzoquinone, phenothiazine, N-nitrosodiphenylamine, 2,6-di-tert-butyl-4-methylphenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2,2,6,6-tetramethylpiperidinol, 4-hydroxy-2,2,6,6-tetramethylpiperidinol, and N-tert-butyl-a-phenylnitrone.

In a third aspect, the present invention provides a method for preparing pattern curing, wherein the low-temperature curing photosensitive resin composition as claimed in claim 1 is dissolved in an organic solvent, and the mixture is exposed, developed and cured.

Furthermore, it includes at least one of the following technical features:

d1) the organic solvent is selected from N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, propylene glycol monomethyl ether acetate, ethyl lactate, and 2-heptanone; the organic solvent is a polar aprotic solvent;

Furthermore, the organic solvent is preferably a mixed solution of γ-butyrolactone and ethyl lactate, and further preferably, the mass ratio of γ-butyrolactone to ethyl lactate is 10:1 to 1:1;

d2) The exposure light source is a 100-3000W ultraviolet mercury lamp or an LED exposure machine;

d3) the developer is selected from at least one of cyclopentanone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and isopropyl alcohol;

d4) the curing temperature is 150 to 280° C.;

d5) The curing time is 1 to 3 hours.

In a fourth aspect, the present invention provides an insulating film formed by curing any one of the above-mentioned low-temperature curing thermosetting resin compositions.

Compared with the prior art, the present invention has the following beneficial effects:

The low-temperature curing thermosetting resin composition of the present invention includes a latent curing agent of a quaternary ammonium salt composed of a quaternary ammonium cation and an anion containing a sulfonamide structure. It has a significant effect on improving the development film retention rate of the low-temperature curing thermosetting resin composition during the patterning process and the tensile strength of the cured film, and has a long storage stability period.

DETAILED DESCRIPTION

Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages in this application are based on weight, and the test and characterization methods used are current as of the filing date of this application. Where applicable, the contents of any patents, patent applications, or publications referred to in this application are incorporated herein by reference in their entirety, and their equivalent patent families are also incorporated by reference, especially with respect to definitions of synthetic techniques, product and processing designs, polymers, comonomers, initiators, or catalysts disclosed in these documents in the art. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in this application, the definition of the term provided in this application shall prevail.

Numerical ranges in this application are approximate values, so unless otherwise indicated, they may include numerical values outside the scope. Numerical ranges include all numerical values from the lower limit to the upper limit increased by 1 unit, provided that there is an interval of at least 2 units between any lower value and any higher value. For example, if the description component, physical or other properties (such as molecular weight, melt index, etc.) is 100 to 1000, it means that all individual numerical values are clearly enumerated, such as 100, 101, 102, and all subranges, such as 100 to 166, 155 to 170, 198 to 200, etc. For a numerical value less than 1 or a scope comprising a fraction greater than 1 (such as 1.1, 1.5, etc.), 1 unit is appropriately considered to be 0.0001, 0.001, 0.01 or 0.1. For ranges containing single-digit numbers less than 10 (e.g., 1 to 5), one unit is generally considered to be 0.1. These are merely specific examples of what is intended, and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered expressly stated in this application. The numerical ranges within this application provide, among other things, calcium-containing filler content, stirring temperature, and various characteristics and properties of these components.

When used with respect to chemical compounds, unless expressly stated otherwise, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). In addition, nouns using "a," "an," or "the" also include their plural forms unless expressly stated otherwise.

The terms "comprising", "including", "having" and their derivatives do not exclude the presence of any other components, steps or processes and are irrelevant to whether these other components, steps or processes are disclosed in this application. To eliminate any doubt, all compositions using the terms "comprising", "including", or "having" in this application may include any additional additives, excipients or compounds unless expressly stated otherwise. In contrast, the term "essentially consisting of" excludes any other components, steps or processes from the scope of any description of the term below, except those necessary for operational performance. The term "consisting of" does not include any components, steps or processes that are not specifically described or listed. Unless expressly stated otherwise, the term "or" refers to the listed members alone or in any combination thereof.

Example

The embodiments of the present invention will be described in detail below. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

It should be noted that the measurement methods in the examples and comparative examples are as follows:

1. Synthesis of polyimide precursor A

Synthesis of polyimide precursor A1

At room temperature, 58.84g (0.2mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 52.04g (0.4mol) of hydroxyethyl methacrylate, and 31.64g (0.4mol) of pyridine were added to a four-necked flask under nitrogen protection. 120g of γ-butyrolactone was used to dissolve the mixture and the mixture was stirred for 4 hours. The reaction vessel was transferred to an ice-water bath (0-10°C), and 51.35g of 1-hydroxybenzotriazole and 82.53g of N,N'-dicyclohexylcarbodiimide were dissolved in 80g of γ-butyrolactone and added dropwise to the reaction flask over half an hour. After the reaction exotherm ended, 38.05g (0.19mol) of 4,4'-diaminodiphenyl ether was dispersed in 150g of γ-butyrolactone, added to the reaction, and the stirring reaction continued for 2 hours. The filtrate obtained after filtering the reaction solution was diluted with 2-methyltetrahydrofuran, precipitated in deionized water, filtered, and dried in a vacuum oven at 50°C for 72 hours to obtain a light yellow solid powder A1 with a weight-average molecular weight of 35,400.

Synthesis of polyimide precursor A2

Except for changing 58.84 g (0.2 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride in the synthesis of polyimide precursor A1 to 62.04 g (0.2 mol) of 4,4'-biphenyl ether dianhydride, the rest of the reaction and treatment were carried out according to the method of polyimide precursor A1 to obtain light yellow solid powder A2 with a weight average molecular weight of 38900.

Synthesis of polyimide precursor A3

Except for changing 58.84 g (0.2 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride in the synthesis of polyimide precursor A1 to 88.85 g (0.2 mol) of 4,4-hexafluoroisopropylphthalic anhydride, the rest of the reaction and treatment were carried out according to the method of polyimide precursor A1 to obtain a light yellow solid powder A3 with a weight average molecular weight of 41400.

Synthesis of polyimide precursor A4

Except for changing 58.84 g (0.2 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride in the synthesis of polyimide precursor A1 to 29.42 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 21.81 g (0.1 mol) of pyromellitic anhydride, the rest of the reaction and treatment were carried out according to the method of polyimide precursor A1 to obtain a light yellow solid powder A4 with a weight average molecular weight of 35600.

Synthesis of polyimide precursor A5

Except for changing 38.05 g (0.19 mol) of 4,4'-diaminodiphenyl ether in the synthesis of polyimide precursor A1 to 60.84 g (0.19 mol) of 2,2'-bis(trifluoromethyl)diaminobiphenyl, the rest of the reaction and treatment were carried out according to the method of polyimide precursor A1 to obtain light yellow solid powder A5 with a weight average molecular weight of 40100.

Synthesis of polyimide precursor A6

Except for changing 38.05 g (0.19 mol) of 4,4'-diaminodiphenyl ether in the synthesis of polyimide precursor A1 to 70.0 g (0.19 mol) of 4,4'-bis(4-aminophenoxy)biphenyl, the rest of the reaction and treatment were carried out according to the method of polyimide precursor A1 to obtain light yellow solid powder A6 with a weight average molecular weight of 39700.

2. Composition of the Low-Temperature Curing Photosensitive Resin Composition

1. Polyimide precursor A, 100 parts

Polyimide precursors A1 to A6;

2. Latent curing agent B, 3 parts

Other latent curing agents

Non-latent curing agent

3. Initiator C, 4 parts

C1：Irgacure OXE 02

C2:TR-PBG-305

C3: SpeedCure PDO

4. Cross-linking agent D, 20 parts

D1: Tetraethylene glycol dimethacrylate

D2: Trimethylolpropane trimethacrylate

D3: Tricyclo[5.2.1.0,2,6]decanedimethanol dimethacrylate

D4: Pentaerythritol tetramethacrylate

5. Coupling agent E, 2 parts

E1: γ-glycidyloxypropyltrimethoxysilane

6. Inhibitor F, 0.1 part

F1: 2,6-di-tert-butyl-4-methylphenol

In addition to the above ingredients, the low-temperature curing photosensitive resin composition also contains the following substances (based on 100 parts of the total amount of polyimide precursor A):

200 parts of a mixed solvent with a mass ratio of γ-butyrolactone/ethyl lactate = 4/1

Example 1

A low-temperature curing photosensitive resin composition comprising the following components in parts by weight:

The low-temperature curable photosensitive resin composition and 200 parts of a mixed solvent of γ-butyrolactone/ethyl lactate = 4/1 were fully dissolved to form a low-temperature curable photosensitive resin composition solution.

Method for preparing patterned cured film

The above solution was spin-coated onto a silicon wafer and baked on a contact hotplate at 100°C for 4 minutes to form a 10µm thin film. A 200W UV mercury lamp was used for pattern exposure, followed by development in a developer. The developed patterned film was cured in a nitrogen oven at a heating rate of 5°C/minute from room temperature to 150°C for 0.5 hours and 230°C for 3 hours. The film was then cooled to room temperature at a rate of 2°C/minute to obtain a patterned cured film. Specific storage stability, sensitivity, and elongation at break are shown in Table 1.

It should be noted that the testing methods for film retention rate, tensile strength and storage stability in the examples and comparative examples are as follows:

Film retention rate

The low-temperature curing photosensitive resin composition solution was spin-coated and baked onto a silicon wafer to form a 10 μm thin film. The film was then exposed using a 200W UV mercury lamp exposure machine at an exposure energy of 150 mJ. The film was then developed in a developer. The film retention ratio was calculated as the residual film thickness after development (T1) divided by the original film thickness before development (T0). A film retention ratio of 90% or greater was considered excellent; a film retention ratio of less than 90% but greater than 85% was considered fair; and a film retention ratio of less than 85% was considered poor.

tensile strength

Tensile strength of tensile strips was measured using a universal tensile testing machine after being conditioned at 23°C and 50% relative humidity for at least 12 hours. A tensile strength of 150 MPa or greater was considered excellent; a tensile strength of less than 150 MPa but greater than 130 MPa was considered fair; and a tensile strength of less than 130 MPa was considered poor.

Storage stability:

The prepared low-temperature curing photosensitive resin composition solution was tested for initial viscosity at room temperature using a Brookfield viscometer. The solution was then sealed in a brown glass bottle and aged in a 50°C constant temperature oven. Furthermore, the viscosity of the aged composition was measured daily using a Brookfield viscometer, and the number of days the viscosity remained within 5% of the initial viscosity was calculated. If the viscosity remained within 7 days or longer, it was considered excellent; if the viscosity remained within 7 days but not less than 5 days, it was considered good; if the viscosity remained within 5 days, it was considered poor.

According to the method of Example 1, when the coupling agent (γ-glycidyloxypropyltrimethoxysilane), the polymerization inhibitor (2,6-di-tert-butyl-4-methylphenol) and the organic solvent (a mixed solvent of γ-butyrolactone/ethyl lactate = 4/1) remain unchanged, the specific components and proportions of Examples 2-30 and Comparative Examples 1-8 are shown in Table 1 below.

Table 1 Component ratios and test results of the embodiments and comparative examples

The results of Example 1 and Comparative Examples 1 and 2 show that component B has a significant effect on improving the development film retention rate and the tensile strength of the film after curing; the results of Example 2 and Comparative Example 3 show that component D has a significant effect on improving the development film retention rate and the tensile strength of the film after curing. The development film retention rate has a significant effect on the tensile strength of the film after curing; the results of Example 2 and Comparative Examples 4 to 5 show that component B that does not meet the structure of the claim is at a disadvantage in terms of the development film retention rate and the tensile strength of the film after curing; the results of Example 2 and Comparative Examples 7 and 8 show that component B of the claim structure has a significant advantage in storage stability.

An insulating film is prepared by preparing Example 5 and Example 6 according to the method for preparing the patterned cured film in Example 1, to obtain an insulating film with a thickness of 1-100 μm.

These insulating films can be used as insulating layers in semiconductors, electronic products, display panels, and photovoltaic devices.

Claims (12)

A latent curing agent is characterized in that the latent curing agent is a quaternary ammonium salt composed of a quaternary ammonium cation and an anion containing a sulfonamide structure. The latent curing agent according to claim 1, characterized in that the quaternary ammonium cation and the anion containing a sulfonamide structure are as shown in the general structural formula I-1 and the general formula I-2:
wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are independently selected from a hydrogen atom, a hydroxyl group, a cyano group, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₂₀ aromatic group, or any two of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ form an aromatic group; R ₆ is a connecting bond or a C ₁ -C ₁₀ alkylene group; R ₇ and R ₈ are independently selected from a hydrogen atom or a C ₁ -C ₁₀ alkyl group; R ₉ , R ₁₀ and R ₁₁ are independently selected from a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₅ cycloalkyl group, a C ₆ -C ₂₀ aromatic group, or R ₉ , R ₁₀ and R ₁₁ form an imidazole ring structure, a pyridine ring structure or an isoquinoline ring structure; R ₁₂ is selected from a halogen atom, a C ₁ -C R 12 is a C ₁₀ alkyl group, a C ₁ -C ₁₀ haloalkyl group, a C ₆ -C ₂₀ aromatic group, R ₁₃ is selected from nitro, cyano, carbonyl and its derivatives, sulfonyl and its derivatives, amide, or R ₁₂ and R ₁₃ form a ring with a sulfonamide structure. The latent curing agent according to claim 2, characterized in that it includes at least one of the following technical features: a1) R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from hydrogen, hydroxy, cyano, methyl, ethyl, propyl, methoxy, ethoxy, phenyl, benzyl, phenylhexyl, or R ₂ and R ₃ form a phenyl group; a2) R ₆ is a connecting bond, methylene or ethylene; a3) R ₇ and R ₈ are each independently selected from a hydrogen atom, a methyl group or an ethyl group; a4) R ₉ , R ₁₀ and R ₁₁ are each independently selected from methyl, ethyl, propyl, cyclopentyl, cyclohexyl, phenyl, benzyl, phenylhexyl, or R ₉ , R ₁₀ and R ₁₁ form an imidazole ring, a methylimidazole ring, a pyridine ring or an isoquinoline ring; a5) R ₁₂ is selected from a fluorine atom, a methyl group, an ethyl group, a propyl group, a phenyl group, a benzyl group, a phenethyl group, a trifluoromethyl group, and a pentafluoroethyl group; a6) R ₁₃ is selected from one of the following structures:
a7) R ₁₂ and R ₁₃ form a ring with the sulfonamide structure selected from the following structures:
The latent curing agent according to claim 3, characterized in that it includes at least one of the following technical features: b1) The quaternary ammonium cation is selected from at least one of the following structures:
wherein R ₂ and R ₃ are each independently selected from a hydrogen atom, a hydroxyl group, a cyano group, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a phenyl group, a benzyl group, a phenylhexyl group, or R ₂ and R ₃ form a phenyl group; b2) the anion containing the sulfonamide structure is selected from at least one of the following structures:
A low-temperature curing thermosetting resin composition, characterized by comprising the following components in parts by mass:
The low-temperature curing thermosetting resin composition according to claim 5, characterized in that the low-temperature curing thermosetting resin composition comprises at least one of the following technical features: c1) the molecular weight of the polyimide precursor is 3000-80000; c2) The polyimide precursor comprises the following structural formula II:
wherein X is selected from a tetravalent organic group having an aromatic radical of C ₆ -C ₃₀ ; Y is selected from a divalent organic group having an aromatic radical of C ₆ -C ₃₀ or a C ₁ -C ₂₀ alicyclic radical; R ₂₁ and R ₂₂ are each independently selected from a hydrogen atom or an organic group having a C ₃ -C ₃₀ ethylenically unsaturated bond, a urea group, or a thiourea group; c3) the photoinitiator is at least one selected from the group consisting of oxime ester photoinitiators, titanocene photoinitiators, acylphosphine oxide photoinitiators, benzil photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators, and quinone photoinitiators; c4) The crosslinking agent is selected from at least one of triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol or polyethylene glycol di(meth)acrylate; propylene glycol or polypropylene glycol di(meth)acrylate; glycerol di- or tri(meth)acrylate; cyclohexane di(meth)acrylate; 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; bisphenol A di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tri- or tetra(meth)acrylate; and tricyclo[5.2.1.0,2,6]decanedimethanol di(meth)acrylate. The low-temperature curing thermosetting resin composition according to claim 5, characterized in that the low-temperature curing thermosetting resin composition further comprises:
Coupling agent 0.1-10 parts;
Inhibitor 0.1-10 parts. The low-temperature curing thermosetting resin composition according to claim 7, characterized in that the coupling agent is selected from at least one of an alkane coupling agent, a titanium coupling agent, an aluminum coupling agent, a zirconium coupling agent, and a boron coupling agent. The low-temperature curing thermosetting resin composition according to claim 7, characterized in that the polymerization inhibitor is selected from hydroquinone, 4-methoxyphenol, tert-butylhydroquinone, 1,4-benzoquinone, phenothiazine, N-nitrosodiphenylamine, 2,6-di-tert-butyl-4-methylphenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2,2,6,6-tetramethylpiperidinol, 4-hydroxy-2,2,6,6-tetramethylpiperidinol, N-tert-butyl-a-phenylnitrone. At least one. A method for preparing a patterned cured film, characterized in that the low-temperature curing thermosetting resin composition according to any one of claims 5 to 9 is dissolved in an organic solvent, and the mixture is exposed, developed and cured. The method for preparing a patterned cured film according to claim 10, characterized in that it includes at least one of the following technical features: c1) the organic solvent is at least one selected from butyrolactone and/or ethyl lactate; c2) the exposure light source is selected from a 100-3000W ultraviolet mercury lamp or an LED exposure machine; c3) the developer is selected from at least one of cyclopentanone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and isopropyl alcohol; c4) the curing temperature is 150 to 280° C.; c5) The curing time is 1 to 3 hours. An insulating film, characterized in that it is formed by curing the low-temperature curing thermosetting resin composition according to any one of claims 5 to 9.