Photosensitive resin composition, method for manufacturing patterned cured product, cured product, and use thereof

Abstract

This invention relates to a photosensitive resin composition, a method for manufacturing a patterned cured product, the cured product, and its applications. The photosensitive resin composition comprises: (A) a hydroxyl-containing polyimide precursor resin, (B) a macromolecular crosslinking agent, (C) a diazonaphthoquinone compound, and (D) a solvent; wherein component (B) has the structure shown in Formula 1: In Formula (1), R5 represents a divalent organic group with 1-20 carbon atoms that may contain alicyclic and / or aromatic rings, or other heteroatoms; R6 represents a divalent organic group with 0-30 carbon atoms that may contain alicyclic and / or aromatic rings, or other heteroatoms; R7 and R8 represent -OH, -COOH, or ester groups with 2-4 carbon atoms; R9 represents hydrogen, an alkyl group with 1-3 carbon atoms, or an acylalkyl group; x+y≥1, z≥2, and s and t are positive integers. This photosensitive resin composition exhibits high sensitivity, and the resulting cured film has low stress, high adhesion, high elongation, and excellent adhesion to the substrate material.

Description

Technical Field

[0001] This invention relates to the field of photosensitive resin materials technology, and more specifically, to a photosensitive resin composition, a method for manufacturing a patterned curing film, the curing film, and its applications. Background Technology

[0002] With the continuous development of display light-emitting elements and semiconductor components, there has been a growing demand for micrometer-level or even lower resolution and high sensitivity in semiconductor surface protective films, interlayer insulating films, TFT substrate planarization films, and pixel definition layers. Photosensitive polyimide, polybenzoxazole, phenolic resin, and other resin compositions, which possess excellent heat resistance and electrical insulation properties, have received widespread attention and application in this field.

[0003] Current reports have proposed using compounds with two or more alkoxymethyl or hydroxymethyl groups to improve the heat resistance of photosensitive resin compositions. However, in recent years, with the increasing integration, miniaturization, and substrate size of semiconductors and display devices, there is a need to reduce the thermal stress applied to semiconductors and display devices during manufacturing, as well as to reduce substrate warpage caused by the thickening of insulating materials. For these materials, the high film shrinkage rate during high-temperature curing results in high stress on the substrate, thus leading to problems such as increased substrate warpage, which have not yet been well resolved.

[0004] To address this, existing technologies report methods for introducing flexible groups into the polyimide backbone to suppress stress generated during the fabrication of the cured film, thereby achieving low warpage. However, this leads to a reduction in the thermal and mechanical properties of the cured film. Since these films are retained as permanent films within semiconductor and display devices, their thermal and mechanical properties are crucial. Furthermore, to ensure the reliability of the device package, the adhesion between the cured film and the substrate is critical, especially in applications such as insulating films between wiring layers in wafer-level packaging. Because heat-resistant materials typically have a rigid backbone structure, and the photosensitizers, solubilizers, and acid-generating agents in their photosensitive compositions remain after curing, the adhesion between the resulting cured film and the substrate is often unsatisfactory. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a photosensitive resin composition whose cured film exhibits low stress, high adhesion, good sealing properties, and high sensitivity.

[0006] To achieve the above objectives, a first aspect of the present invention provides a photosensitive resin composition comprising:

[0007] (A) Hydroxyl-containing polyimide precursor resin;

[0008] (B) Macromolecular crosslinking agent, with a molecular weight of 600<Mw<4000, and a solubility of 1-10g / 100g in 2.38wt% TMAH;

[0009] (C) Diazonaphthoquinone compound;

[0010] (D) Solvent;

[0011] The component of the (B) macromolecular crosslinking agent is the compound represented by Structural Formula (1):

[0012]

[0013] In Formula (1), R5 represents a divalent organic group having 1 to 20 carbon atoms, which may contain an alicyclic ring and / or an aromatic ring and other heteroatoms; R6 represents a divalent organic group having 0 to 30 carbon atoms, which may contain an alicyclic ring and / or an aromatic ring and other heteroatoms; R7 and R8 represent -OH, -COOH or an ester group having 2 to 4 carbon atoms; R9 represents hydrogen, an alkyl group having 1 to 3 carbon atoms or an acylalkyl group; x+y≥1, z≥2, s and t are positive integers;

[0014] The (A) hydroxyl-containing polyimide precursor resin has a structural unit represented by the following Structural Formula (2):

[0015]

[0016] In Formula (2), Q represents a tetravalent organic group having 2 to 30 carbon atoms, D represents a divalent organic group having 2 to 60 carbon atoms, and R1 represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.

[0017] Further, D in the Structural Formula (2) represents one or a combination of two or more diamine residues represented by the following Structural Formula (3):

[0018]

[0019] In Formula (3), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R2 represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group, and a fluorine, chlorine or bromine substituent; R3 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and a fluorine, chlorine or bromine substituent; S represents a linking group, which is a tetravalent linking group having 0 to 30 carbon atoms, which may contain an alicyclic ring and / or an aromatic ring and other heteroatoms; R represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, other divalent organic groups having 1 to 10 carbon atoms, or a divalent organic group formed by bonding two or more thereof; p represents an integer of 0 to 2, and q represents an integer of 0 to 1.

[0020] Preferably, D in the structural formula (2) represents one or more combinations of diamine residues as shown in the structural formula (4):

[0021]

[0022] In formula (4), R1 represents hydrogen atoms and alkyl groups with 1 to 3 carbon atoms; R2 represents alkyl or alkoxy groups with 1 to 3 carbon atoms, hydroxyl groups, carboxyl groups, and fluorine, chlorine, or bromine substituents; R3 represents hydrogen atoms and alkyl or alkoxy groups with 1 to 3 carbon atoms, and fluorine, chlorine, or bromine substituents; p represents an integer from 0 to 2.

[0023] Furthermore, Q in the structural formula (2) represents one or more combinations of dianhydride residues corresponding to the following tetracarboxylic dianhydrides: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-tetracarboxylic diphenyl ether dianhydride, 3,3',4,4'-tetracarboxylic dibenzophenone dianhydride, 3,3',4,4'-tetracarboxylic diphenylsulfonyl dianhydride, 4,4'-hexafluoroisopropylphthalic anhydride (6FDA), 4,4'-isopropylphthalic anhydride, 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclobutanetetracarboxylic dianhydride (CBDA), and cyclohexanetetracarboxylic dianhydride.

[0024] Preferably, in the macromolecular crosslinking agent with the structure shown in formula (1) above, R5 is one or more of the following structural formulas (5):

[0025]

[0026] Furthermore, the amount of macromolecular crosslinking agent used is preferably 0.1-20 parts by weight relative to 100 parts by weight of (A) of hydroxyl-containing polyimide precursor resin.

[0027] A second aspect of the present invention provides a method for manufacturing a patterned cured material, comprising the steps of forming a pattern having a resin coating using the above-described photosensitive resin composition, including the following steps:

[0028] Step 1: Coat the photosensitive resin composition onto the substrate to form a photosensitive resin coating, and then pre-bake it on a hot plate at 80℃-120℃ for 2-60 minutes to form a photosensitive film.

[0029] Step 2: Expose the above-mentioned photosensitive film using an exposure mask;

[0030] Step 3: Use an alkaline developing solution to remove the exposed portions of the above-mentioned photosensitive film and then develop it.

[0031] Step 4: Cure the developed film at a temperature of 100℃-300℃ to obtain the cured film.

[0032] A third aspect of the present invention provides a cured product prepared from the above-described photosensitive resin composition, which is a patterned cured product.

[0033] A fourth aspect of the present invention provides an application of a cured material, wherein the cured material is applied to an insulating layer, a pixel definition layer, a planarization layer of an organic electroluminescent element, or / and a surface protective layer or an insulating layer of a semiconductor device.

[0034] Compared with the prior art, the present invention has the following beneficial effects: The high-sensitivity photosensitive resin composition provided by the present invention uses the structure shown in formula (1) as a macromolecular crosslinking agent, combined with a hydroxyl-containing polyimide precursor resin and a photosensitizer, which can improve the sensitivity while endowing the cured film with excellent properties such as chemical resistance and low stress. The macromolecular crosslinking agent contains ether bonds, and after undergoing a thermal crosslinking reaction with the resin, a dense and stable crosslinked network structure is obtained, which can greatly improve the adhesion, thermal stability, mechanical strength and other properties of the cured film, while improving the adhesion between the film layer and the substrate. Detailed Implementation

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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.

[0036] <Photosensitive Resin Composition>

[0037] The photosensitive resin composition of the present invention comprises (A) a hydroxyl-containing polyimide precursor resin, (B) a macromolecular crosslinking agent, (C) a diazonaphthoquinone compound, and (D) a solvent. The specific components constituting the photosensitive resin composition are described below.

[0038] (A) Hydroxyl-containing polyimide precursor resin

[0039] In this invention, (A) the hydroxyl-containing polyimide resin precursor is an alkali-soluble resin. The alkali solubility in this invention refers to: coating a silicon wafer or glass sheet with a resin dissolved in a solvent or mixed solvent, baking at 120°C for 3 minutes to form a pre-baked film with a film thickness of 10 μm ± 0.5 μm; developing the pre-baked film in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, followed by water washing for 30 seconds, and drying the surface water stains. The alkali solubility of the pre-baked film can be obtained based on the amount of film reduction at this time.

[0040] In this invention, (A) the hydroxyl-containing polyimide precursor resin only needs to have a polyimide ring in the polyimide, without any particular limitation. In addition, the polyimide precursor only needs to have a polyimide structure with an imide ring formed by dehydration and ring closure, without any particular limitation. The hydroxyl-containing polyimide precursor resin of this invention has the structural unit represented by the following structural formula (2):

[0041]

[0042] In formula (2), Q represents a tetravalent organic group with 2 to 30 carbon atoms, D represents a divalent organic group with 2 to 60 carbon atoms, and R1 represents a hydrogen atom or a monovalent organic group with 1 to 8 carbon atoms.

[0043] In this invention, (A) the hydroxyl-containing polyimide resin precursor is obtained by reacting a diamine compound with a tetracarboxylic acid dianhydride under certain conditions.

[0044] In this invention, at least one diamine compound contains a hydroxyl group in its molecular structure; furthermore, D in structural formula (2) represents one or more combinations of diamine residues as shown in structural formula (3):

[0045]

[0046] In formula (3), R1 represents a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, R2 represents an alkyl group with 1 to 3 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group, and a fluorine, chlorine, or bromine substituent; R3 represents a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, an alkoxy group, and a fluorine, chlorine, or bromine substituent; S represents a linking group, which is a tetravalent linking group with 0 to 30 carbon atoms that may contain an alicyclic ring and / or an aromatic ring and other heteroatoms; R is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, and other divalent organic groups with 1 to 10 carbon atoms, or a divalent organic group formed by the bonding of two or more of them; p represents an integer from 0 to 2, and q represents an integer from 0 to 1.

[0047] The hydroxyl-containing diamine compound in this invention enhances the solubility of the photosensitive resin in alkaline aqueous developers, ensuring that the resin in the exposed area can be thoroughly and cleanly washed away after exposure when using alkaline aqueous developers such as TMAH aq, NaOH aq, Na2CO3 aq, etc., reducing the impact of residue and improving exposure sensitivity. The inventors have found that when the macromolecular crosslinking agent of this invention is combined with the hydroxyl-containing polyimide resin precursor composed of the diamine of formula (3), the photosensitive resin exhibits high sensitivity, high elongation and low stress after film formation, as well as excellent heat resistance and chemical resistance.

[0048] In this invention, at least one diamine compound contains a hydroxyl group in its molecular structure. Preferably, D in structural formula (2) represents one or more combinations of diamine residues as shown in structural formula (4):

[0049]

[0050] In formula (4), R1 represents hydrogen atoms and alkyl groups with 1 to 3 carbon atoms; R2 represents alkyl or alkoxy groups with 1 to 3 carbon atoms, hydroxyl groups, carboxyl groups, and fluorine, chlorine, or bromine substituents; R3 represents hydrogen atoms and alkyl or alkoxy groups with 1 to 3 carbon atoms, and fluorine, chlorine, or bromine substituents; p represents an integer from 0 to 2.

[0051] Diamine compounds containing alicyclic and / or aromatic rings are beneficial for improving the mechanical properties of photosensitive resins; diamine compounds containing functional groups such as sulfone, sulfoxide, siloxane bonds, and hexafluoropropyl are beneficial for improving the light transmittance of photosensitive resins; and diamine compounds containing thioether groups and siloxane bonds are beneficial for improving the adhesion of photosensitive resins.

[0052] The diamine compound in this invention also includes conventional diamine compounds in the art. These conventional diamine compounds refer to those that can be directly purchased commercially or obtained through other means. Specifically, in the above structural formula (2), D represents one or more combinations of the diamine residues corresponding to the following diamine compounds: p-phenylenediamine, m-phenylenediamine, 3-carboxy-m-phenylenediamine, 3-hydroxy-m-phenylenediamine benzidine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfide ... Products obtained from diphenyl sulfide, 1,4-di(4-aminophenoxy)benzene, di(4-aminophenoxyphenyl)sulfone, di(3-aminophenoxyphenyl)sulfone, 1,4-di(4-aminophenoxy)benzene, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2,3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3′,4,4′-tetramethyl-4,4′-diaminobiphenyl, and cycloalkyl or halogen-substituted aromatic compounds.

[0053] Preferably, the conventional diamine compound in this invention contains 4,4′-diaminodiphenyl ether, that is, D in the above structural formula (2) represents the diamine residue corresponding to 4,4′-diaminodiphenyl ether.

[0054] It should be noted that although the reactants for synthesizing (A) hydroxyl-containing polyimide precursor resin in this invention contain the above-mentioned conventional diamine compounds, the functional compounds in the reactants for synthesizing hydroxyl-containing polyimide precursor resin in this invention are mainly the diamine compounds corresponding to the diamine residues shown in structural formula (3), and their content is above 10 mol%, preferably above 50 mol%. The introduction of this structural compound is beneficial to improving the exposure and development effect, heat resistance and mechanical properties of the resin.

[0055] The tetracarboxylic dianhydride used in this invention is selected from conventional tetracarboxylic dianhydrides in the art, and its structure is not limited in this invention.

[0056] To obtain a polyimide resin precursor with excellent heat resistance, it is preferable to have an organic group containing an aromatic ring or aromatic heterocycle, i.e., Q in the above structural formula (2) represents one or more combinations of dianhydride residues corresponding to the following tetracarboxylic dianhydrides: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3' One or more combinations of the following: 4,4'-tetracarboxylic acid diphenyl ether dianhydride, 3,3',4,4'-tetracarboxylic acid dibenzophenone dianhydride, 3,3',4,4'-tetracarboxylic acid diphenyl sulfonyl dianhydride, 4,4'-hexafluoroisopropylphthalic anhydride (6FDA), 4,4'-isopropylphthalic anhydride, 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclobutanetetracarboxylic dianhydride (CBDA), and cyclohexanetetracarboxylic dianhydride.

[0057] In this invention, to ensure that the polyimide precursor resin has appropriate solubility in alkaline developer and good heat resistance and elongation after heat treatment, the number of repeating structural units is preferably in the range of 10 to 1000, more preferably 20 to 500, and particularly preferably 50 to 200. The proportion of repeating units containing hydroxyl groups relative to all repeating units is preferably between 5% and 100%, more preferably between 40% and 80%. By adjusting the ratio of hydrophilic hydroxyl groups to the hydrophobic aromatic and alkane groups in the resin structure, the dissolution rate of the resin in alkaline developer is controlled. Combined with a photosensitizer, the dissolution rate of the unexposed film in alkaline developer can be 10 nm / min to 3000 nm / min, and the dissolution rate of the exposed film in alkaline developer can be 200 nm / min to 50000 nm / min.

[0058] In this invention, the weight-average molecular weight Mw and number-average molecular weight Mn of the hydroxyl-containing polyimide precursor resin (A) were determined in the form of polystyrene equivalent values ​​using gel permeation chromatography (GPC), light scattering, small-angle X-ray scattering, etc.

[0059] Furthermore, in order to better adjust the molecular weight of the hydroxyl-containing polyimide precursor resin of the present invention, a certain amount of end-capping agent can be added during polymerization. Specific examples include, but are not limited to, one or more combinations of the following example compounds:

[0060] Monofunctional aromatic amines: 3-aminophenol, 2-aminophenol, 4-aminophenol, 3-aminobenzoic acid, 3-amino-o-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 1-amino-8-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-amino-6-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 3-amino-4,6-dihydroxypyrimidine, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline.

[0061] Monofunctional aromatic anhydrides: maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, cyclohexanepentanedicarboxylic anhydride, etc.

[0062] Monofunctional aromatic acids: benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxybenzylthiophenol, 3-carboxybenzylthiophenol, 4-carboxybenzylthiophenol, carboxynaphthalene, 2-hydroxy-naphthoic acid, 3-hydroxy-naphthoic acid, 4-hydroxy-naphthoic acid, 5-hydroxy-naphthoic acid, 6-hydroxy-naphthoic acid, 7-hydroxy-naphthoic acid, 8-hydroxy-naphthoic acid, 9-hydroxy-naphthoic acid.

[0063] The aforementioned capping agent is added in a proportion of 0.005 to 0.5, more specifically 0.01 to 0.4, of the total molar amount of all the diamine compound and tetracarboxylic dianhydride added; thereby, within the above range, a resin composition having a suitable solution viscosity and excellent film properties can be obtained.

[0064] (B) Macromolecular crosslinking agents

[0065] The macromolecular crosslinking agent is one of the key features of this invention. The macromolecular crosslinking agent contains ether bonds. When the photosensitive resin is heat-treated, the macromolecular crosslinking agent can form a crosslinking structure between the resins. This can not only reduce the shrinkage rate during film curing, but also significantly improve the adhesion, thermal stability, mechanical strength, chemical resistance and other properties of the cured film, as well as the reliability and tightness of the adhesion between the film layer and the substrate.

[0066] The macromolecular crosslinking agent used in the present invention is a compound containing a hydroxyl group, a carboxyl group or an ester group in the molecule as shown in structural formula (1); with a molecular weight 600<Mw<4000, and a solubility of 1-10g / 100g in 2.38wt% TMAH;

[0067]

[0068] In formula (1), R5 represents a divalent organic group having 1 to 20 carbon atoms, which may contain an alicyclic ring and / or an aromatic ring and other heteroatoms; R6 represents a divalent organic group having 0 to 30 carbon atoms, which may contain an alicyclic ring and / or an aromatic ring and other heteroatoms; R7 and R8 represent -OH, -COOH or an ester group having 2 to 4 carbon atoms; R9 represents hydrogen, an alkyl group having 1 to 3 carbon atoms or an acylalkyl group; x+y≥1, z≥2, s and t are positive integers;

[0069] The macromolecular crosslinking agent of the present invention contains a hydroxyl group, a carboxyl group or an ester group, which can enhance the solubility of the resin in an alkaline aqueous developer and improve the exposure sensitivity. The solubility of the macromolecular crosslinking agent in 2.38wt% TMAH is 1-10g / 100g. When the solubility is less than 1g / 100g, a large amount of exposure is required to form a cured film; when the solubility is greater than 10g / 100g, the residual film rate of the composition film after heat treatment is poor.

[0070] The macromolecular crosslinking agent of the present invention is first subjected to a nucleophilic substitution reaction through a compound containing both dihydroxyl and coumarin, 2,6-dimethyl-1,4-benzenediol, and a compound containing difluoro, dibromo or dichloro, to obtain a randomly copolymerized polyphenylene ether solid; then the polyphenylene ether solid is dissolved in a solvent, AIBN and NBS are added for stirring reaction, the organic phase is separated, washed, filtered, and dried to obtain benzyl brominated polyphenylene ether; finally, the benzyl brominated polyphenylene ether solid is dissolved in a solvent, sodium methoxide or NaOH is added for stirring reaction, the pH is adjusted to about 5-6, followed by filtration, water washing, and drying to obtain the final macromolecular crosslinking agent.

[0071] Further, in the macromolecular crosslinking agent having the structure represented by the above formula (1), R5 is one or more of the following structural formula (5):

[0072]

[0073] The macromolecular crosslinking agent may be used alone, or two or more thereof may be used in combination. The inventors have found through extensive research that the alkyl flexible chain in formula (5) not only provides low-stress properties to the cured film, but also improves the adhesion reliability and conformability of the film, and the compound with a fused ring structure containing an alicyclic ring and / or an aromatic ring is beneficial to improving the mechanical properties and heat resistance of the cured film.

[0074] For the macromolecular crosslinking agent of the present invention, in order to provide the membrane with better low stress, mechanical properties and chemical resistance, the molecular weight of the macromolecular crosslinking agent should be greater than 600, and in order to maintain the exposure sensitivity of the membrane, the molecular weight of the crosslinking agent needs to be less than 4000. Furthermore, in order to improve mechanical properties and heat resistance, the content of the macromolecular crosslinking agent is preferably 0.1 parts or more per 100 parts of resin content. In order to maintain low stress of the membrane, reliable adhesion between the membrane layer and the substrate, and good sealing, the content of the macromolecular crosslinking agent is preferably 20 parts or less. The preferred amount of the macromolecular crosslinking agent used in the present invention is 0.1-20 parts by weight.

[0075] (C) Diazonaphthoquinone compounds

[0076] The photosensitive resin composition of the present invention contains an esterified diazonaquinone compound. By adding the esterified diazonaquinone compound, a positive pattern can be formed in which the exposed portion is removed by the alkaline developer.

[0077] Esterified diazonaquinone compounds specifically refer to photosensitizers formed by linking polyhydroxyphenolic compounds with diazonaquinone groups at the 4- or 5-position via ester bonds. When ultraviolet light irradiates this compound, the diazonaquinone groups undergo degradation and rearrangement to generate an enone structure, which then reacts with water to form indanic acid, thereby achieving a change in the dissolution rate, as shown in the reaction formula below. The functional groups of these polyhydroxy compounds do not necessarily need to be completely replaced by diazonaquinone, but from the perspective of contrast between the exposed and unexposed areas, it is preferable that at least 60% (mol) of all functional groups are replaced by diazonaquinone. By using the above-mentioned diazonaquinone compounds, positively photosensitive resin compositions that are sensitive to the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a conventional ultraviolet mercury lamp can be obtained.

[0078]

[0079] The polyhydroxyphenolic compounds used in the preparation of the photosensitizer include, but are not limited to, bisphenol A, bisphenol AF, bisphenol AP, naphthol, trihydroxybenzophenone, fluorene-containing phenols, triphenylmethanephenol, triphenylethylphenol, and phenolic resin oligomers. These can be used alone or in combination. The amount of the diazonaphthoquinone compound added relative to the mass of the hydroxyl-containing polyimide precursor resin is 0.01 to 0.70, more preferably 0.05 to 0.50.

[0080] (D) Solvent

[0081] The solvent used in the photosensitive resin composition of the present invention is a solvent with a boiling point below 230°C, including but not limited to one or more combinations of N,N-dimethylacetamide, N,N-dimethylformamide, γ-butyrolactone, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol, n-butanol, cyclohexanone, ethyl lactate, and butyl lactate; the amount of solvent added is 3 to 50 times, more preferably 3 to 20 times, relative to the mass of the hydroxyl-containing polyimide precursor resin used.

[0082] (E) Other additives

[0083] From the perspective of film properties such as flexural strength, the photosensitive composition of the present invention may further contain epoxy resin, wherein the epoxy resin is preferably bisphenol A epoxy resin or bisphenol F epoxy resin, and the amount of epoxy resin added is preferably 0 to 0.2% of the mass of the hydroxyl-containing polyimide precursor resin.

[0084] To improve the adhesion and film-forming properties of the resin film to the substrate, the photosensitive resin composition provided in this embodiment of the invention further includes an adhesion promoter and a surfactant; wherein the adhesion promoter is preferably a silane coupling agent to improve the adhesion between the film and the substrate during development and inhibit the shedding of the pattern during development, preferably including one or more combinations of methacryloyloxydimethoxymethylsilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacryloyloxysilane, N-phenylaminoethyltrimethoxysilane, etc.; the amount of adhesion promoter added is preferably 0.001 to 0.2% of the mass of the hydroxyl-containing polyimide precursor resin;

[0085] The surfactants selected in this invention are fluorinated surfactants, silicone surfactants, and acrylate surfactants; the amount of surfactant added is 0.0003 to 0.05 of the mass of the hydroxyl-containing polyimide precursor resin.

[0086] <Preparation method of patterned cured material using photosensitive resin composition>

[0087] A second aspect of the present invention provides a method for preparing a patterned cured material, comprising the following steps:

[0088] Step 1: Coat the photosensitive resin composition onto the substrate to form a photosensitive resin coating, and then pre-bake it on a hot plate at 80-120℃ for 2-60 minutes to form a photosensitive film.

[0089] Step 2: Expose the above-mentioned photosensitive film using an exposure mask;

[0090] Step 3: Use an alkaline developing solution to remove the exposed portions of the above-mentioned photosensitive film and then develop it.

[0091] Step 4: Cure the developed film at a temperature of 100℃-300℃ to obtain the cured film.

[0092] First, in step one, a photosensitive resin is coated onto a substrate to ensure a uniform thickness. Examples of substrates include substrates, silicon wafers, and substrates with a metallic coating on their surface obtained by ion sputtering or electroplating. The coating method can be dip coating, spin coating, roll coating, slot coating, spray coating, etc., and these methods can be combined. To make the coating thickness more uniform, a spin coater can be used to control the uniform film thickness, but this invention is not limited to this. Preferably, the film is formed by pre-baking, with pre-baking conditions of 80-120°C on a hot plate for 2-60 minutes.

[0093] Steps two and three are the exposure and development steps, wherein the exposure radiation is preferably at a wavelength of 190nm to 500nm, and the exposure dose is 10-5000mJ / cm. 2 .

[0094] Step four involves curing the patterned resin film. The curing process, especially temperature changes under high-temperature conditions, significantly affects the degree of cross-linking of the resin film and directly influences its properties, such as heat resistance and mechanical strength. In this invention, the developed film is cured at a temperature of 100-300℃ to obtain the cured film.

[0095] The most preferred embodiment is as follows: the developed film is placed under a nitrogen flow at 100°C and heated to 270-300°C at a heating rate of 1-10°C / min, and cured at 270-300°C for 60-100 min. After natural cooling to room temperature of 25°C, the film is separated from the substrate to obtain the cured film.

[0096] <Cured product>

[0097] A third aspect of the present invention provides a cured product formed from the above-described photosensitive resin composition, which is a patterned cured product.

[0098] <Applications of Solidified Materials>

[0099] The photosensitive resin film of the present invention exhibits excellent heat resistance, chemical resistance, low stress and low coefficient of thermal expansion, and can therefore be applied to surface protective films of semiconductor devices, interlayer insulating films, insulating films of organic electroluminescent devices, etc.

[0100] 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.

[0101] Example

[0102] The following embodiments illustrate the present invention, but the present invention is not limited to the following embodiments.

[0103] The relevant abbreviations and chemical components in the examples are as follows:

[0104] 6FDA: 4,4'-Hexafluoroisopropylphthalic anhydride;

[0105] CBDA: Cyclobutanetetracarboxylic dianhydride;

[0106] ODA: 4,4′-Diaminodiphenyl ether;

[0107] B7: Tetramethoxymethylglycosan

[0108] B8: 2,4,6-Tris[bis(methoxymethyl)amino]-1,3,5-triazine

[0109] All of the above compounds were obtained through commercial means.

[0110] <Preparation of Diamine Monomers>

[0111] Synthesis example 1

[0112] Synthesis of coumarin-like structure-derived amine diamine compounds (M1)

[0113]

[0114] 3.9 g (20 mmol) of 7-aminocoumarin hydrochloride was suspended in 30 mL of n-hexane and irradiated with a 250-450 nm high-pressure mercury lamp for 48 h. After filtration, the [2+2] cyclized product of 7-aminocoumarin hydrochloride was obtained. The pH of this product was adjusted to neutral with a saturated aqueous solution of sodium bicarbonate to obtain the [2+2] cyclized diamine compound M1 of 7-aminocoumarin.

[0115] Synthesis example 2

[0116] Synthesis of coumarin-like structure-derived amine diamine compounds (M2)

[0117]

[0118] Under nitrogen protection, the [2+2] cyclization product of 7-aminocoumarin (10.0 g, 31 mmol) was dissolved in 100 mL of ethanol, and 10 mL of 0.01 mol / mL NaOH aqueous solution was added dropwise. The temperature was raised to 60 °C and the reaction was carried out for 6 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain the diamine compound M2.

[0119] Synthesis example 3

[0120] Synthesis of diamine compounds (M3) derived from the hydrolysis of coumarin-like structure-derived amines

[0121]

[0122] Under nitrogen protection, the [2+2] cyclization product of 7-aminocoumarin (10.0 g, 31 mmol) was dissolved in 100 mL of ethanol, sodium methoxide (5.4 g, 100 mmol) was added, the temperature was raised to 60 °C, and the reaction was carried out for 8 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain diamine compound M3.

[0123] Synthesis example 4

[0124] Synthesis of benzocyclobutene cycloaddition derivative diamine compound (M4) with coumarin

[0125]

[0126] In a high-pressure sealed container, 1,3-bis(3-benzocyclobutene)-1,1,3,3-tetramethyldisiloxanebenzene (3.38 g, 10 mmol), 7-nitrocoumarin (3.82 g, 20 mmol), and 30 mL of N,N'-dimethylformamide were added. The mixture was heated to 200 °C and reacted for 36 h. The solution was poured into water, extracted with ethyl acetate, and concentrated to obtain a dinitro compound. This compound was then dissolved in 50 mL of ethanol, and 0.1 g of 10 wt% Pd / C was added. Hydrogen gas was bubbled through the solution, and the mixture was reacted at 50 °C for 12 h. After filtering off the Pd / C, the solution was concentrated and recrystallized to obtain the diamine compound M4.

[0127] Synthesis example 5

[0128] Synthesis of benzocyclobutene and coumarin cycloaddition derivative diamine compound (M5)

[0129]

[0130] Under nitrogen protection, diamine compound M4 (19.80 g, 30 mmol) was dissolved in 100 mL of methanol, sodium methoxide (5.4 g, 100 mmol) was added, the temperature was raised to 60 °C, and the reaction was carried out for 8 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain diamine compound M5.

[0131] Synthesis example 6

[0132] Synthesis of hydroxyl-containing diamine compounds (M6)

[0133]

[0134] BAHF (14.64 g, 40 mmol) was dissolved in 100 mL of acetone and propylene oxide (13.9 g, 239 mmol), and the solution was cooled to -15 °C. A solution of 4-nitrobenzoyl chloride (14.84 g, 80 mmol) dissolved in 100 mL of acetone was added dropwise. After the addition was complete, the reaction was carried out at -15 °C for 4 hours, and then allowed to return to room temperature. The precipitated white solid was filtered and dried under vacuum at 50 °C.

[0135] 20g of the obtained solid was placed in a 300mL stainless steel autoclave and dispersed in 200mL of propylene glycol methyl ether. 1g of 5% palladium on carbon was added. Hydrogen gas was introduced and the mixture was stirred vigorously. After about 5 hours, the reaction was stopped, the palladium compound was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain the diamine compound M6.

[0136] Synthesis of Macromolecular Crosslinking Agents

[0137] Synthesis Example 7

[0138] Synthesis of macromolecular crosslinking agent B1

[0139]

[0140] 3,8-Dihydroxy-6H-dibenzo[B,D]pyran-6-one (11.4 g, 50 mmol), 1,4-difluorobenzene (12.5 g, 110 mmol), and 2,6-dimethyl-1,4-benzenediol (6.9 g, 50 mmol) were dissolved in 80 mL of DMAc, nitrogen gas was introduced, potassium carbonate (41.5 g, 300 mmol) was added, the temperature was raised to 90 °C, and the reaction was stirred for 24 h. The mixture was poured into water, the solid was filtered out, washed three times with water, and dried at 80 °C to obtain polyphenylene ether solid.

[0141] 10 g of the above-mentioned solid polyphenylene ether was dissolved in 100 mL of carbon tetrabromide, and AIBN (0.12 g, 0.74 mmol) and NBS (17.8 g, 100 mmol) were added. The mixture was heated to 60 °C and stirred for 8 h. The mixture was then poured into water to separate the organic phase and washed three times with water. The carbon tetrabromide solution was then added dropwise to methanol. The precipitated solid was collected by filtration and dried at 80 °C to obtain benzyl brominated polyphenylene ether.

[0142] 10g of the above benzyl brominated polyphenylene ether was dissolved in 100mL of DMAc, and sodium methoxide (8.1g, 150mmol) was added. The mixture was heated to 80℃ and stirred for 20h. The solution was then poured into water, and the pH was adjusted to about 5 with acetic acid. After stirring, the solid was filtered out, washed three times with water, and dried at 80℃ to obtain the final macromolecular crosslinking agent B1.

[0143] Synthesis example 8

[0144] Synthesis of macromolecular crosslinking agent B2

[0145] The 1,4-difluorobenzene was replaced with 1,2-dibromoethane, and the synthesis was carried out according to the synthesis steps of macromolecular crosslinking agent B1.

[0146] Synthesis example 9

[0147] Synthesis of macromolecular crosslinking agent B3

[0148]

[0149] 3,8-Dihydroxy-6H-dibenzo[B,D]pyran-6-one (11.4 g, 50 mmol), 2,2'-dibromodiethyl ether (20.79 g, 90 mmol), and 2,6-dimethyl-1,4-benzenediol (6.9 g, 50 mmol) were dissolved in 80 mL of DMAc. Nitrogen gas was introduced, and potassium carbonate (41.5 g, 300 mmol) was added. The mixture was heated to 90 °C and stirred for 24 h. The solution was poured into water, the solid was filtered off, washed three times with water, and dried at 80 °C to obtain polyphenylene ether solid.

[0150] 10 g of the above-mentioned solid polyphenylene ether was dissolved in 100 mL of carbon tetrabromide, and AIBN (0.12 g, 0.74 mmol) and NBS (17.8 g, 100 mmol) were added. The mixture was heated to 60 °C and stirred for 8 h. The mixture was then poured into water to separate the organic phase and washed three times with water. The carbon tetrabromide solution was then added dropwise to methanol. The precipitated solid was collected by filtration and dried at 80 °C to obtain benzyl brominated polyphenylene ether.

[0151] 10g of the above benzyl brominated polyphenylene ether was dissolved in 100mL of ethanol, and 10mL of 0.01mol / mL NaOH aqueous solution was added dropwise. The temperature was raised to 50℃ and the reaction was carried out for 8h. The pH was adjusted to 6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain the final macromolecular crosslinking agent B3.

[0152] Synthesis example 10

[0153] Synthesis of macromolecular crosslinking agent B4

[0154] Replace 1,4-difluorobenzene with brominated-tetraethylene glycol-brominated and synthesize according to the synthesis steps of macromolecular crosslinking agent B1.

[0155] Synthesis example 11

[0156] Synthesis of macromolecular crosslinking agent B5

[0157] The 3,8-dihydroxy-6H-dibenzo[B,D]pyran-6-one was replaced with the cycloaddition product of benzocyclobutene and coumarin, and synthesized according to the synthesis steps of macromolecular crosslinking agent B1.

[0158] The preparation of the cycloaddition product of benzocyclobutene and coumarin is as follows:

[0159]

[0160] In a high-pressure sealed container, 10 mmol of tricyclo[6.2.0.03,6]dec-1,3(6),7-triene, 20 mmol of 6-hydroxycoumarin, and 10 mL of N,N-dimethylformamide were added. After reacting at 220 °C for 36 h, the mixture was poured into water, extracted with ethyl acetate, and concentrated to obtain the cycloaddition product of benzocyclobutene and coumarin.

[0161] Synthesis example 12

[0162] Synthesis of macromolecular crosslinking agent B6

[0163] The 3,8-dihydroxy-6H-dibenzo[B,D]pyran-6-one was replaced with a cycloaddition product containing a siloxane bis(enophile compound) and coumarin, and synthesized according to the synthesis steps of macromolecular crosslinking agent B1.

[0164] The preparation of cycloaddition products containing siloxane bis(enophilic compound) and coumarin is as follows:

[0165]

[0166] Under nitrogen protection, 10 mmol of a siloxane bis(enophile compound), 20 mmol of 6-hydroxycoumarin, and 10 mL of N,N'-dimethylformamide were added. After reacting at 30 °C for 36 h, the mixture was poured into water, extracted with ethyl acetate, and concentrated to obtain the cycloaddition product containing the siloxane bis(enophile compound) and coumarin.

[0167] Synthesis of Diazonaphthoquinone Compounds

[0168] Synthesis example 13

[0169] Synthesis of diazonoquinone compounds (C1)

[0170]

[0171] Under the protection of a dry nitrogen stream, phenol (57.6 g, 100 mmol) and 5-diazonaphthoquinone sulfonyl chloride (93.9 g, 350 mmol) were dissolved in 500 mL of dioxane. While the system temperature did not exceed 30 °C, a reagent mixture of 50 mL dioxane / 30 mL triethylamine was added dropwise. The reaction was carried out for 3 h. The triethylamine salt was filtered out, and the filtrate was added dropwise to water. The precipitate was filtered and dried to obtain diazinonaquinone compound C1.

[0172] Synthesis example 14

[0173] Synthesis of diazonoquinone compounds (C2)

[0174] D is or H

[0175] Under a dry nitrogen atmosphere, bisphenol AF (33.6 g, 100 mmol) and 2,1,5-diazonaphthoquinone sulfonyl chloride (51.1 g, 190 mmol) were dissolved in 400 mL of dioxane. While maintaining a system temperature not exceeding 30 °C, 15 g of triethylamine in 100 mL of THF was added dropwise. After complete addition, the mixture was stirred for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then filtered, collected, and dried to obtain 55 g of didiazonaphthoquinone compound C2.

[0176] Synthesis of Hydroxyl-Containing Polyimide Precursor Resins

[0177] Synthesis Example 15

[0178] Synthesis of hydroxyl-containing polyimide precursor resin A1

[0179] Under a dry nitrogen atmosphere, diamine compound M1 (3.222 g, 10 mmol), diamine compound M2 (28.650 g, 80 mmol), end-capping agent m-aminophenol (2.181 g, 20 mmol), and ODA (0 g, 0 mmol) were dissolved in 200 g of N-methylpyrrolidone (NMP). The mixture was stirred at room temperature for 0.2 h, then 6FDA (35.36 g, 80 mmol) and CBDA (3.92 g, 20 mmol) were added, and the mixture was stirred at room temperature for 8 h. The temperature was then raised to 90 °C and reacted for 6 h. The solution was then poured into 2 L of ethanol, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum drying oven at 60 °C for 24 h to obtain resin precursor A1.

[0180] Synthesis Examples 16-24 Resin Precursor A2-10

[0181] The synthesis method of resin precursor A2-10 is the same as that of resin precursor A1, the difference lies in the diamine compound and the imidization method, as detailed in Table 1.

[0182] Table 1

[0183]

[0184] Example 1

[0185] Resin precursor A1 (2.0 g), macromolecular crosslinking agent B1 (0.3 g), diazonoquinone compound C1 (0.5 g), C2 (0.1 g), bisphenol F epoxy resin (0.1 g), silane coupling agent 3-aminopropyltrimethoxysilane (0.02 g), and surfactant TEGO GLIDE 300 (0.01 g) were dissolved in 5.39 g of γ-butyrolactone and 2.31 g of ethyl lactate. After stirring at room temperature for 3 h, the mixture was filtered through an organic filter membrane with a pore size of 0.45 μm to obtain the photosensitive resin composition slurry.

[0186] The photosensitive resin composition slurry is coated onto a silicon wafer or glass substrate, baked at 120°C for 3 minutes, exposed, developed in a 2.38wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then washed with water for 30 seconds to obtain a patterned film. After heat treatment at 300°C for 1 hour, the final film used for performance evaluation is obtained.

[0187] Examples 2-16, Comparative Examples 1-6

[0188] The synthesis methods of Examples 2-16 and Comparative Examples 1-6 are the same as those of Example 1, except that the selection and proportion of raw materials are different. The specific formulations are shown in Table 2. The photosensitive resin compositions prepared in Examples 1-16 and Comparative Examples 1-6 were evaluated for their imaging ability, stress, adhesion, sealing, elongation at break, heat resistance, and chemical resistance. The results are shown in Table 2.

[0189] <Evaluation Methods>

[0190] (1) Imaging capability

[0191] The developed film was inspected using SEM (JEOL JSM-6510) to check the etched lines. Excellent results were achieved when lines less than 5 μm in width could be clearly etched without bending or defects, and the linewidth ratio was consistent with the mask design. Good results were achieved when lines between 5 and 10 μm in width could be clearly etched without bending or defects, and the linewidth ratio was consistent with the mask design. Poor results were achieved when only lines wider than 10 μm could be clearly etched without bending or defects, and the linewidth ratio was consistent with the mask design.

[0192] (2) Evaluation of stress

[0193] The photosensitive resin composition slurry was uniformly dropped onto a silicon wafer and spun evenly using a spin coater at a speed of 300 rpm. The wafer was then placed on a hot plate and pre-baked at 120°C for 3 minutes, followed by exposure and development. The temperature was then increased from 100°C to 300°C at a rate of 5°C / min, and cured at 300°C for 1 hour to obtain a film thickness of 10 μm. When the temperature dropped below 50°C, the silicon wafer was removed, and the stress of the cured film was confirmed using a stress measuring device FLX2908 (manufactured by KLATencor).

[0194] (3) Adhesion

[0195] The developed film was observed for line detachment using an optical microscope (OLS5000). Defects were defined as lines detached only when the line width was less than 2 μm, good when the line width was less than 10 μm, and bad when the line width was greater than 5 μm.

[0196] (4) Evaluation of sealing characteristics

[0197] Using a single-edged blade, 10 rows and 10 columns of checkerboard-like cuts were made at 2mm intervals on the cured film on the substrate. The cured film substrate with the cuts was placed in a pressure cooker test (PCT) apparatus (Tabai Espec Co., Ltd. HAST CHAMBEREHS-211MD) and subjected to 400 hours of PCT treatment at 121°C and 2 atmospheres. The adhesion characteristics between the metal material and the resin cured film were evaluated by counting the number of cells peeled off out of 100 cells due to the use of transparent tape. The peel test was performed as follows: less than 10 peels were classified as excellent, 10 or more but less than 20 as good, and more than 20 as poor.

[0198] (5) Heat resistance

[0199] A small sample was taken and its residual weight (R) at 400℃ was determined using a thermogravimetric analyzer (TGA, NETZSCH STA2500 Regulus). 400 ). With R 400 >80% is considered excellent, 75% is considered good. <R 400 <80% is considered good, R 400 <75% is considered poor.

[0200] (6) Chemical resistance

[0201] The heat-treated film (area greater than 5*5cm, thickness 2μm) was placed in N-methylpyrrolidone for 72h, and the film thickness change before and after immersion in N-methylpyrrolidone at 40℃ for 120s was measured. ΔTHK=(THK1-THK0) / THK0×100%, where ΔTHK represents the film thickness change rate, THK1 represents the film thickness after immersion, and THK represents the film thickness before immersion. ΔTHK<1% is considered excellent, 1%<ΔTHK<2% is considered good, and ΔTHK>2% is considered poor.

[0202] (7) Test of elongation at break

[0203] A photosensitive resin composition slurry was coated onto an 8-inch silicon wafer using spin coating and pre-baked at 120°C for 3 minutes, resulting in a pre-baked film thickness of 10 μm. Then, an inert gas oven was used with an oxygen concentration below 100 ppm, and the temperature was increased to 300°C at a rate of 3°C / min, and maintained at 300°C for 1 hour. The wafer was removed when the temperature reached below 50°C, allowed to cool slowly, and then immersed in 0.5% hydrofluoric acid for 30 minutes to peel the resin composition film from the wafer. The film was cut into strips 1 cm wide and 10 cm long, and stretched using a tensile testing machine at a temperature of 23.0°C and 45.0% RH at a tensile speed of 50 mm / min to determine the elongation at break. For each test sample, 10 strips were measured, and the average of the five highest values ​​was calculated. A value of 20% or more at the breaking point is rated as "excellent", a value of 10% or more but less than 20% is rated as "good", and a value of less than 10% is rated as "poor".

[0204] Table 2

[0205]

[0206] 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 photosensitive resin composition, characterized in that, comprising: (A) a hydroxyl-containing polyimide precursor resin; (B) a macromolecular crosslinking agent, having a molecular weight of 600<Mw<4000 and a solubility of 1-10 g / 100 g in 2.38 wt% TMAH; (C) a diazonaphthoquinone compound; (D) a solvent; The component of the (B) macromolecular crosslinking agent is a compound represented by structural formula (1): ， In formula (1), R5 represents a divalent organic group having 1 to 20 carbon atoms which may contain an alicyclic ring and / or an aromatic ring and other heteroatoms; R6 represents a divalent organic group having 0 to 14 carbon atoms which may contain an alicyclic ring and / or an aromatic ring, wherein R6 may or may not contain a siloxane group; when R6 contains a siloxane group, R6 has the following structure: ； R7 and R8 represent -OH, -COOH or an ester group having 2 to 4 carbon atoms; R9 represents hydrogen, an alkyl group having 1 to 3 carbon atoms or an acylalkyl group; x+y≥1, z≥2, and s and t are positive integers.

2. A photosensitive resin composition as described in claim 1, characterized in that, The (A) hydroxyl-containing polyimide precursor resin has a structural unit represented by the following structural formula (2): ， In formula (2), Q represents a tetravalent organic group having 2 to 30 carbon atoms, D represents a divalent organic group having 2 to 60 carbon atoms, and R1 represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.

3. A photosensitive resin composition as described in claim 2, characterized in that, D in the structural formula (2) represents one or a combination of more of the following diamine residues represented by structural formula (3): ， In formula (3), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R2 represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group, a hydroxyl group, a carboxyl group, and a fluorine, chlorine or bromine substituent; R3 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group, and a fluorine, chlorine or bromine substituent; S represents a linking group, which is a tetravalent linking group having 0 to 30 carbon atoms and may contain an alicyclic ring and / or an aromatic ring and other heteroatoms; R is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, another divalent organic group having 1 to 10 carbon atoms, or a divalent organic group formed by bonding two or more thereof; p represents an integer of 0 to 2, and q represents an integer of 0 to 1.

4. A photosensitive resin composition as described in claim 2 or 3, characterized in that, D in the structural formula (2) represents one or a combination of more of the following diamine residues represented by structural formula (4): ； In formula (4), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R2 represents an alkyl group or alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, a carboxyl group, and a fluorine, chlorine or bromine substituent; R3 represents a hydrogen atom, an alkyl group or alkoxy group having 1 to 3 carbon atoms, and a fluorine, chlorine or bromine substituent; p represents an integer of 0 to 2.

5. A photosensitive resin composition as described in claim 2 or 3, characterized in that, In the structural formula (2), Q represents one or more combinations of dianhydride residues corresponding to the following tetracarboxylic dianhydrides: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-tetracarboxylic diphenyl ether dianhydride, 3,3',4,4'-tetracarboxylic dibenzophenone dianhydride, 3,3',4,4'-tetracarboxylic diphenylsulfonyl dianhydride, 4,4'-hexafluoroisopropylphthalic anhydride (6FDA), 4,4'-isopropylphthalic anhydride, 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclobutanetetracarboxylic dianhydride (CBDA), and cyclohexanetetracarboxylic dianhydride.

6. A photosensitive resin composition as described in claim 1 or 2, characterized in that, In the macromolecular crosslinking agent with the structure shown in formula (1), R5 is one or more combinations of the following structural formula (5): 。 7. A photosensitive resin composition as described in claim 1 or 2, characterized in that, The amount of the macromolecular crosslinking agent (B) is 0.1-20 parts by weight relative to 100 parts by weight of the hydroxyl-containing polyimide precursor resin (A).

8. A method for manufacturing a patterned cured material, characterized in that, Forming a pattern with a resin coating from the photosensitive resin composition according to any one of claims 1 to 7 comprises the following steps: Step 1: Coat the photosensitive resin composition onto the substrate to form a photosensitive resin coating, and then pre-bake it on a hot plate at 80-120℃ for 2-60 minutes to form a photosensitive film. Step 2: Expose the above-mentioned photosensitive film using an exposure mask; Step 3: Use an alkaline developing solution to remove the exposed portions of the above-mentioned photosensitive film and then develop it. Step 4: Cure the developed film at a temperature of 100-300℃ to obtain the cured film.

9. A cured product, characterized in that, The product is cured from the photosensitive resin composition according to any one of claims 1 to 7, and is a patterned cured product.

10. An application of the cured material as described in claim 9, characterized in that, The cured material is applied to the insulating layer, pixel definition layer, planarization layer of organic electroluminescent elements, and / or the surface protection layer and insulating layer of semiconductor devices.

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