Photosensitive resin composition, cured film and application thereof

Abstract

The invention discloses a photosensitive resin composition which comprises alkali-soluble resin (A), a thermal crosslinking agent (B), a photopolymerization initiator (C) and an organic solvent (D), the alkali-soluble resin (A) comprises a structure as shown in a formula (I) and a structure as shown in a formula (II); in formula (I) and formula (II), R1 and R2 each independently represent a divalent to hexavalent organic group having 2 to 40 carbon atoms, R3 represents a hydrogen atom, a cyano group, a nitro group, a halogen, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group, n represents an integer of 1000 to 100000, m represents an integer of 100 to 10000, and p represents an integer of 0 to 2. The prepared photosensitive resin composition is small in exposure dose after film formation, low in film loss rate and good in thermal stability, and has a relatively good application prospect in the field of display devices.

Description

Technical Field

[0001] The present invention relates to the field of optoelectronic display and semiconductor manufacturing, and more specifically, to a photosensitive resin composition, a cured film and applications thereof. Background Art

[0002] In recent years, with the rapid development of display equipment and semiconductor industry in my country, and with the miniaturization of components in the relative field, high requirements have been put forward for the photosensitivity, heat resistance and high resolution of the photosensitive film materials on the surface of the device, and from the perspective of saving production time, high sensitivity requirements are placed on the pattern cured film. The prior art records the process of negative photosensitive polyimide film formation after exposure, development, retention of the exposed area, dissolution of the non-exposed area, and patterning. However, most negative photosensitive polyimides are developed using organic solvents such as cyclopentanone, which produces a lot of waste solvents and has a serious impact on the environment. There are few reports on the use of alkaline aqueous solution development, such as the negative photosensitive polyimide system of 2.38wt% TMAH. Therefore, it is urgent to develop a photosensitive resin material with stable performance, which can effectively reduce the photosensitivity dose of the cured film under the condition of excellent other properties. This is a technical challenge currently faced. Summary of the invention

[0003] An object of the present invention is to solve at least the above problems and to provide at least the advantages which will be described hereinafter.

[0004] Another object of the present invention is to provide a photosensitive resin composition, which has a small exposure dose after film formation, a low film loss rate, good thermal stability, and good application prospects in the field of display devices.

[0005] In order to achieve these objects and other advantages according to the present invention, the present invention provides a photosensitive resin composition in a first aspect, comprising: an alkali-soluble resin (A), a thermal crosslinking agent (B), a photopolymerization initiator (C) and an organic solvent (D);

[0006] The alkali-soluble resin (A) includes a structure represented by formula (I) and a structure represented by formula (II);

[0007]

[0008] In formula (I) and formula (II), R1 and R2 each independently represent a divalent to hexavalent organic group having 2 to 40 carbon atoms, R3 represents a hydrogen atom, a cyano group, a nitro group, a halogen, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, n represents an integer from 1000 to 100000, m represents an integer from 100 to 10000, and p represents an integer from 0 to 2.

[0009] Preferably, R1 in the structure represented by formula (I) further comprises at least two of the following structural formulas, and the structure represented by formula (2) accounts for 1 to 10 mol%;

[0010]

[0011] R 11 Each independently represents an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group or a halogen group, R 12 Each independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a fluoroalkyl group or an alkoxy group, and R3 represents a hydrogen atom, a cyano group, a nitro group, a halogen group, an alkyl group or an alkoxy group having 1 to 3 carbon atoms.

[0012] Preferably, the mass ratio of the structure represented by formula (I) to the structure represented by formula (II) is 80:(10-30).

[0013] Preferably, R2 in the structure represented by formula (I) and the structure represented by formula (II) also includes the following structural formula:

[0014]

[0015] R4 is independently an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group or a halogen group, and h and q are independently 0 or 1.

[0016] Preferably, the diamine residue with phenolic hydroxyl group in R2 of the structure represented by formula (I) and the structure represented by formula (II) accounts for 10 to 30 mol % respectively.

[0017] Preferably, the structure represented by formula (I) and the structure represented by formula (II) use fluorene structure as the end-capping group.

[0018] Specifically, the photosensitive resin composition includes 100 parts by mass of an alkali-soluble resin (A), 1 to 20 parts by mass of a thermal crosslinking agent (B), 1 to 10 parts by mass of a photopolymerization initiator (C), and 100 to 5000 parts by mass of an organic solvent (D).

[0019] A second aspect of the present invention provides a cured film prepared from a photosensitive resin composition.

[0020] A third aspect of the present invention provides a patterned cured film, which is prepared by using a cured film through exposure, development, and curing procedures.

[0021] A fourth aspect of the present invention provides a cured film for use in manufacturing an insulating layer, a pixel definition layer of an organic electroluminescent element, and a surface protection film and an insulating layer of a semiconductor element.

[0022] The present invention has at least the following beneficial effects:

[0023] 1. Adding the resin represented by the structure of formula (II) into the photosensitive resin composition can reduce the exposure dose of the cured film;

[0024] 2. By incorporating the structure represented by formula (2) into the structure represented by formula (I), the exposure dose of the cured film can be further reduced without affecting other properties of the cured film;

[0025] 3. When preparing the structure represented by formula (I) and the structure represented by formula (II), adding the diamine compound represented by formula (8) can reduce the film loss rate of the formed film during development;

[0026] 4. With the fluorene structure as the end-capping group, the obtained patterned cured film has suitable thermal stability.

[0027] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. DETAILED DESCRIPTION

[0028] Before the following detailed description of the present disclosure, it should be understood that the terminology used herein is provided for describing particular embodiments only.

[0029] Unless otherwise mentioned, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art.

[0030] In addition, the terms or words used in this specification are intended to be understood as having meanings and concepts consistent with the technical concepts of the present disclosure as described in this specification, based on the principle that the inventor can appropriately define the concepts of the terms in order to best describe the invention, and are not limited to the conventional meanings.

[0031] The present invention provides a photosensitive resin composition, comprising: an alkali-soluble resin (A), a thermal crosslinking agent (B), a photopolymerization initiator (C) and an organic solvent (D).

[0032] (A) Alkali-soluble resin

[0033] The alkali-soluble resin (A) includes a structure represented by formula (I) and a structure represented by formula (II);

[0034]

[0035]

[0036] In formula (I) and formula (II), R1 and R2 each independently represent a divalent to hexavalent organic group having 2 to 40 carbon atoms, R3 represents a hydrogen atom, a cyano group, a nitro group, a halogen, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, n represents an integer from 1000 to 100000, m represents an integer from 100 to 10000, and p represents an integer from 0 to 2.

[0037] In an embodiment of the present invention, the exposure dose of the cured film can be reduced by adding the resin represented by the structure of formula (II) into the photosensitive resin composition.

[0038] In some embodiments of the present invention, R1 is a residue of the following dianhydride structure, and the dianhydride structure can be selected from the following structural formulas: one or more of pyromellitic anhydride (PMDA), 3,3',4,4'-benzophenonetetracarboxylic anhydride (BTDA), 2,3,3',4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride (6FDA), 1,4-bis(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic anhydride (P6FDA), 2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride (BFDA) and 1,4-difluoropyromellitic anhydride (PA2DA).

[0039] In some embodiments of the present invention, R2 is a residue of the following diamine structure, and the diamine structure is selected from the following substances, for example, it can be: 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl (TFMB), 4,4'-diamino-2,2'-dimethylbiphenyl (m-TOL), 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane (HFBAPP), bis(4-(4-aminophenoxy)phenyl)sulfone (BAPS), bis(4-(3-aminophenoxy)phenyl)sulfone (BAPSM), 4,4'-diaminodiphenylsulfone (4DDS), 3,3'-diaminodiphenylsulfone (3DDS), 4,4'-diaminodiphenyl sulfide, At least one of 1,3-phenylenediamine (m-PDA), 1,2-phenylenediamine (o-PDA), 4,4'-diaminodiphenyl ether (44'ODA), 3,3'-diaminodiphenyl ether (33'ODA), 2,4-diaminodiphenyl ether (24'ODA), 3,4'-diaminodiphenyl ether (34'ODA), 4,4'-bis(3-aminophenoxy)biphenyl and 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 9,9-bis(4-aminophenyl)fluorene (FDA), 9,9-bis(3-fluoro-4-aminophenyl)fluorene (FFDA), fluoro-p-phenylenediamine, 2,2'-difluorobiphenylenediamine and 2,2'-dichlorobiphenylenediamine.

[0040] In some preferred embodiments of the present invention, R1 in the structure represented by formula (I) comprises at least two of the following structural formulas, and the structure represented by formula (2) accounts for 1 to 10 mol%, preferably 1 to 8 mol%, and more preferably 2 to 6 mol%. The incorporation of the structure represented by formula (2) into the structure represented by formula (I) can further reduce the exposure dose of the cured film without affecting other properties of the photosensitive resin composition. If the molar proportion of the structure represented by formula (2) in R1 of the structure represented by formula (I) exceeds 10 mol%, it will affect other properties of the cured film, such as adhesion.

[0041]

[0042] In the above structure, R 11 Each independently represents an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group or a halogen group, R 12 Each independently represents an alkyl group, a fluoroalkyl group or an alkoxy group having 1 to 5 carbon atoms, and R3 represents a hydrogen atom, a cyano group, a nitro group, a halogen group, an alkyl group or an alkoxy group having 1 to 3 carbon atoms;

[0043] In some preferred embodiments of the present invention, the molecular weight of the structure represented by formula (I) is 10,000 to 100,000.

[0044] In some preferred embodiments of the present invention, the molecular weight of the structure represented by formula (II) is 10,000 to 30,000.

[0045] In some preferred embodiments of the present invention, R2 in the structure represented by formula (I) and the structure represented by formula (II) is selected from the following structural formulas:

[0046]

[0047] R4 is independently an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group or a halogen group, and h and q are independently 0 or 1.

[0048] Preferably, the diamine residue structure with phenolic hydroxyl group in R2 of the structure shown in formula (I) accounts for 10-30 mol%. The diamine residue structure with phenolic hydroxyl group in R2 of the structure shown in formula (II) accounts for 10-30 mol%. Exceeding 30 mol% will affect the performance of the membrane. In the present invention, adding a diamine compound of the above structural formula within a certain molar range to the diamine component forming the alkali-soluble resin can reduce the membrane loss rate.

[0049] The present invention provides a method for preparing a diamine structure corresponding to R2 as a residue, which has the advantages of simple route, mild synthesis conditions of reaction intermediates, easy post-treatment and purification, easy scale-up production and low preparation cost.

[0050] The preparation route of the diamine structure is:

[0051]

[0052] The preparation method of the diamine structure comprises the following steps:

[0053] Step S1, dissolving the compound of the structure shown in formula (4) in an organic solvent, which can usually be a common organic solvent such as dichloromethane, acetonitrile, toluene, tetrahydrofuran, etc., preferably tetrahydrofuran; and controlling the temperature to 0-26°C, preferably, cooling to 0-5°C; and then fully reacting with carbonyldiimidazole to obtain a suspension containing the intermediate.

[0054] Step S2, adding an organic solution of the compound of formula (6) to the system of step S1 under stirring, controlling the system temperature to 0-26°C, preferably to 0-5°C, after the addition is completed, the main reaction is completed, and the remaining unreacted or unreacted substrate is precipitated by the reaction substrate and needs to be heated for further conversion.

[0055] After the reaction in step S2 is completed, the crude residue is filtered to obtain a crude residue, which is then added to a single organic solvent including methanol, ethanol, acetonitrile, toluene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylmorpholine, etc., or a system including but not limited to the above two organic solvents for slurrying, preferably a mixed solvent with a solvent ratio of N,N-dimethylformamide / ethanol of 1 / 1 to 1 / 5 for slurrying and purification, so as to dissolve impurities as much as possible while reducing product loss, and then filtered and dried to obtain a refined compound represented by formula (7).

[0056] Step S3, dissolving the compound represented by formula (7) obtained in step S2 in an organic solvent, which is usually ethanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylmorpholine, dimethyl sulfoxide, etc., which are polar and miscible with water, preferably N,N-dimethylformamide; at a temperature of 26 to 60° C., preferably 60° C. considering the thermal solubility and safety of the product, and at a hydrogen pressure of 1 to 3 MPa, preferably 1.5 MPa considering the reaction conversion efficiency and reaction safety; and adding a catalyst palladium carbon with a mass ratio of 1 / 100 to 1 / 10, preferably 1 / 30; after the reaction is complete, filter out the catalyst, add the reaction solution into ice water, and stir and filter to obtain the target product.

[0057] It should be noted that the implementation of steps S1 and S2 must be carried out under nitrogen protection to prevent the system from contacting with water vapor in the external environment during the reaction; in addition, the solvents used in the implementation of steps S1 and S2 are all commercially available anhydrous solvents, but the water content of the solvent must be <50ppm; the above requirements are all to prevent the generated active acyl imidazole from reacting with water and decomposing.

[0058] In addition, implementing step S3 to control the temperature of the post-treatment water to 0-5°C (ice water) helps to improve the yield of the refined product while maintaining stable product quality.

[0059] The structure represented by formula (I) and the structure represented by formula (II) use fluorene structure as the end-capping group. The end-capping group is provided by a monoacid compound such as fluorene-4-carboxylic acid, 9-fluorenecarboxylic acid, fluorene-1-carboxylic acid as an end-capping agent. The monoacid compound is in the range of 1 to 60 mol% of the molar number of the dicarboxylic acid or dianhydride structure, and more preferably 1 to 50 mol%, 1 to 40 mol%, 1 to 30 mol%, 1 to 20 mol%. The photosensitive resin composition obtained by using the above-mentioned end-capping agent has suitable thermal stability.

[0060] (B) Thermal crosslinking agent

[0061] When the photosensitive resin is heat-treated, the thermal crosslinking agent can form a crosslinked structure between the resins, which can not only reduce the shrinkage rate of the film during curing, but also improve the chemical resistance of the film after thermal curing. The thermal crosslinking agent generally uses a compound with a photopolymerizable group, such as an ethylene unsaturated group. The content of the component (B) is 1 to 20 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A).

[0062] In some embodiments of the present invention, the ethylenically unsaturated group is selected from the following group: vinyl, propenyl, methacryl, n-butenyl, isobutenyl, vinylphenyl, propenylphenyl, propenyloxymethyl, propenyloxyethyl, propenyloxypropyl, propenyloxybutyl, propenyloxypentyl, propenyloxyhexyl, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, methacryloxybutyl, methacryloxypentyl, and methacryloxyhexyl.

[0063] The compound having a photopolymerizable group includes an ethylene-based unsaturated compound, specifically trimethylolpropane trimethacrylate, (meth)acrylamide, (meth)acryloylmorpholine, (meth)acrylate-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (meth)acrylamide, (meth)acrylate isobornyloxyethyl ester, (meth)acrylate isobornyl ester, (meth)acrylate-2-ethylhexyl ester, ethyl diethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acrylate dimethylaminoethyl ester, (meth)acrylate dodecyl ester, (meth)acrylate dicyclopentenyloxyethyl ester, (meth)acrylate dicyclopentenyl ester, nitrogen, nitrogen-dimethyl (meth)acrylate The compounds having one ethylenically unsaturated group may be used alone or in combination of two or more.

[0064] (C) Photopolymerization initiator

[0065] The component C in the resin precursor composition of the present invention is a photopolymerization initiator.

[0066] The photopolymerization initiator may be any substance that can initiate polymerization of the alkali-soluble resin (A) component and the crosslinking agent (B) component by irradiation with active light such as laser, ultraviolet light, X-ray, electron beam, etc. There is no particular limitation on the photopolymerization initiator, and any known photopolymerization initiator used for photocuring of resins can be used.

[0067] The light used in the light irradiation can be appropriately selected according to the photopolymerization initiator used, and usually, visible light, ultraviolet light, electron beam, etc. can be used.

[0068] The content of the photopolymerization initiator component C in the resin precursor composition of the present invention varies depending on the type of component C used and the type of light to be irradiated.

[0069] Specific examples of the photopolymerization initiator include aromatic ketone compounds such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone; quinones formed by condensation of an aromatic ring such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether; oxime ester compounds; benzyl derivatives such as benzyl dimethyl ketal, and the like.

[0070] Among them, from the perspective of excellent sensitivity and obtaining a good pattern, oxime ester compounds are preferred, and specific examples include: "IRGACURE OXE-01" (Formula 9), "IRGACURE OXE 02" (Formula 10) produced by BASF, DFI-091 (Formula 11) produced by Daito Chemix, etc.;

[0071]

[0072] The content of component (C) is 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, further preferably 1 to 20 parts by mass, and further preferably 1 to 10 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A). When the addition amount of component (C) is greater than or equal to 0.01 parts by mass, the crosslinking of the exposed part can be more fully carried out, and the photosensitivity, resolution, residual film rate and other photosensitive properties of the composition become better. When the addition amount of component (C) is less than or equal to 30 parts by mass, the photopolymerization initiator in the film after curing can be less, and the obtained cured film has better heat resistance and low outgassing. In addition, the above "photopolymerization initiator" can be used alone or in combination of two or more.

[0073] (D) Organic solvents

[0074] The present invention further contains an organic solvent as component (D). From the perspective of dissolving the photosensitive resin composition, a polar solvent is preferred, and the following solvents may be cited: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, 3-methoxybutanol, γ-butyrolactone, 3-methoxybutanol acetate, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, etc. Among them, γ-butyrolactone, propylene glycol monomethyl ether acetate, 3-methoxybutanol, 3-methoxybutanol acetate, and ethyl lactate are preferred, and they may be used alone or in combination of two or more. The content of the component (D) in the photosensitive resin composition of the present invention is not particularly limited, but is 100 to 5000 parts by mass, preferably 200 to 4000 parts by mass, more preferably 200 to 3000 parts by mass, and even more preferably 300 to 2000 parts by mass, based on 100 parts by mass of the component (A).

[0075] <Cured film>

[0076] The present invention provides a cured film. The cured film in some embodiments of the present invention is formed by curing the photosensitive resin composition in some embodiments of the present invention.

[0077] <Pattern Cured Film>

[0078] The present invention provides a pattern-cured film. The pattern-cured film in some embodiments of the present invention is prepared by the following preparation method, including the steps of coating film, drying, exposure, and development. Specifically, on a smooth and neat substrate such as glass or silicon wafer, spin coating, spray coating, roller coating, slit coating, screen printing, etc. can be used. Depending on the coating method and the composition, viscosity, solid content, etc. of the composition used, the thickness of the film after drying is usually 0.1 to 30 μm. The film drying just after coating can be dried at 40 to 150° C. for several minutes to several hours using an oven, a hot plate, an infrared furnace, etc.; the dried substrate is irradiated with actinic rays through a mask to shield it, thereby photocuring the exposed area of ​​the photosensitive layer. The actinic rays described here include electromagnetic waves and particle beams, such as ultraviolet rays, X-rays, electron beams, radiation rays, and ion beams. The light source is not particularly limited, and can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a vapor lamp, a carbon rod arc lamp, or a metal halide lamp. It is also possible to expose directly by laser irradiation without using a mask.

[0079] The exposed substrate is developed in a developer, and the unexposed portion is dissolved in the developer to form a pattern. The developer can use polar organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, g-butyrolactone, r-butyrolactone, etc. and solvents mixed with water, but from an environmental protection perspective, an alkaline aqueous solution is more preferably used as a developer. The selected alkaline aqueous developer includes but is not limited to aqueous solutions of tetramethylammonium hydroxide, triethylamine, diethanolamine, dimethylaminoethanol, ethylenediamine, cyclohexylamine, hexamethylenediamine, diethylaminoethanol, methylamine, dimethylamine, etc., among which a 2.38wt% aqueous solution of tetramethylammonium hydroxide is further preferred. The development method can be carried out by spraying the developer directly or in a mist form on the coating surface, or soaking in the developer. The development time is controlled to be between 5s and 600s, preferably between 5s and 300s, depending on the film thickness. When an alkaline aqueous solution is used as a developer, the film after development is preferably rinsed with water as a rinse agent to wash the obtained patterned thin film and perform a fixing treatment.

[0080] The developed film is heat treated, specifically: the developed film is heat treated in a curing furnace to completely convert the composition into a heat-resistant film. The heat treatment temperature is preferably 100-400°C; more preferably 150-300°C; and particularly preferably 150-250°C. The heat treatment time is controlled to be from 10 minutes to several hours, more preferably more than 30 minutes and less than 300 minutes; and particularly preferably more than 30 minutes and less than 200 minutes. The heat treatment can be performed in multiple stages, such as heat curing it at 150°C for 30 minutes, and then heat curing it at 250°C for 30 minutes.

[0081] <Application of Cured Film>

[0082] The present invention provides an application of a cured film, wherein the cured film is applied to an insulating layer, a pixel definition layer, a planarization layer of an organic electroluminescent element, or / and a surface protection layer and an insulating layer of a semiconductor device.

[0083] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0084] It should be noted that the experimental methods described in the following embodiments are conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0085] <Synthesis example 1>

[0086] The synthetic route of compound H is as follows:

[0087]

[0088] (1) Add 100 g (387.25 mmol) of 4,4'-diphenyl ether dicarboxylic acid to a three-necked flask, then add 1000 g of anhydrous tetrahydrofuran, introduce nitrogen protection, start stirring, control the temperature at 0-5°C, add 126 g (774.51 mmol) of carbonyl diimidazole in batches, raise the temperature to room temperature after addition, react for 12 hours, and obtain a white turbid liquid, which is directly used in the next step. (A small amount of the turbid liquid is sampled and filtered, the filter residue is washed with water and dried, and the clean 1,1'-(4,4'-oxydibenzoyl) diimidazole is obtained by nuclear magnetic resonance identification.

[0089] (2) The temperature of the white turbid liquid was controlled to 0-5°C, and stirring was maintained. 119.37 g (774.48 mmol) of 2-amino-5-nitrophenol was dissolved in 1000 g of anhydrous tetrahydrofuran, and the mixture was dripped into the white turbid liquid obtained by the above reaction at a controlled speed. At the same time, the above-prepared tetrahydrofuran reaction liquid was dripped into the white turbid liquid. The dripping was completed in two hours, and the white turbid liquid turned into a yellow solution. The temperature was raised to 50°C, and stirring was continued for 5 hours to obtain an orange-red suspension. The suspension was filtered and washed with water to obtain a yellow residue. The yellow residue was transferred to 700 ml of a mixed solvent of N,N-dimethylformamide / ethanol 1 / 5, heated to 70°C, stirred for 5 hours, cooled, filtered, and washed with ethanol to obtain 144.37 g (272.17 mmol) of a yellow solid 4,4'-oxybis(N-(2-hydroxy-4-nitrophenyl)benzamide).

[0090] (3) 60.1 g (113.30 mmol) of 4,4'-oxybis(N-(2-hydroxy-4-nitrophenyl)benzamide) was added to a 2000 mL high pressure hydrogenation kettle, followed by 720 g of N,N-dimethylformamide, and finally 2 g of wet palladium carbon (mass fraction 10%) was added to the high pressure hydrogenation kettle. The nitrogen in the kettle was replaced twice with 0.2 MPa, and then replaced twice with 0.2 MPa of hydrogen. Finally, 1.5 MPa of hydrogen was added to the kettle. The temperature outside the high pressure hydrogenation kettle was raised to 60°C. After stirring for 2 hours, hydrogen was added to the autoclave to 1.5 MPa, and stirring was continued for 12 hours to stop the reaction. The brown-red reaction liquid was filtered and slowly added dropwise into 2000 g of ice water. During the dropwise addition, an off-white solid slowly precipitated and settled from the water. After the dropwise addition was completed, a gray suspension was obtained. The suspension was filtered and rinsed twice with 100 g of ethanol to obtain an off-white solid. The solid was dried to obtain 43.15 g of gray powder.

[0091] <Preparation Example 1>

[0092] Under a dry nitrogen stream, the compound 4,4'-diaminodiphenyl ether (10.12 g, 0.05 mol), pyromellitic anhydride (6.55 g, 0.03 mol), and 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride (8.88 g, 0.02 mol) were dissolved in 50 g of N,N-dimethylpyrrolidone (NMP) and stirred at room temperature for 24 hours. The solution was then poured into 2 liters 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 hours and used as the alkali-soluble resin I-1.

[0093] The preparation method of Preparation Example 2-8 is the same as that of Preparation Example 1, except for the specific ingredients. The specific preparation ingredients of Preparation Example 2-8 are shown in Table 1. 6FCDA is the abbreviation of 9,9-bis(trifluoromethyl)-2,3,6,7-oxanthene tetracarboxylic dianhydride.

[0094] Table 1

[0095]

[0096] <Example 1>

[0097] Prepare 15g of γ-butyrolactone (as solvent D-1) and 25g of ethyl lactate (as solvent D-2), add 7.00g of alkali-soluble resin I-1, 3.00g of alkali-soluble resin II-1, 1.00g of trimethylolpropane trimethacrylate (as crosslinking agent B), and 0.3g of OXE-01 (as photoinitiator C), stir and mix well to obtain a photosensitive resin composition.

[0098] The preparation methods of the photosensitive compositions of Examples 2 to 8 and Comparative Examples 1 to 3 are the same as those of Example 1, except that the preparation ingredients are different. The preparation ingredients of the photosensitive compositions of Examples 2 to 8 and Comparative Examples 1 to 3 are shown in Table 2 below.

[0099] The evaluation methods of the photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3 refer to the evaluation methods described below, and the test results are shown in Table 2.

[0100] Table 2

[0101]

[0102] <Evaluation method is as follows>

[0103] (1) Exposure dose evaluation

[0104] The dried 2um thick coating was obtained by drying at 120℃ for 120s, and different doses of exposure were performed under the mask using a high-pressure mercury lamp. Then, it was immersed in 2.38wt% tetramethylammonium hydroxide (TMAH) for development for 60s and washed with water for 30s. The minimum exposure amount at which the 7um size lines of the mask could be replicated 1:1 after development was the optimal dose.

[0105] (2) Evaluation of film loss rate during development

[0106] The change of film thickness in the exposed area after immersion in 2.38% TMAH (tetramethylammonium hydroxide) for 60 seconds was measured by ellipsometer, and the difference between the film thickness before development and the film thickness after development was taken as the film loss rate during development.

[0107] (3) Thermal stability

[0108] Take a small amount of patterned film sample and use a thermal gravimetric analyzer (TGA) to measure the 1% thermal weight loss temperature (T d1 ).

[0109] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the embodiments shown and described herein.

Claims

1. A photosensitive resin composition, characterized in that: include: Alkali-soluble resin (A), thermal crosslinking agent (B), photopolymerization initiator (C) and organic solvent (D); The alkali-soluble resin (A) includes a structure represented by formula (I) and a structure represented by formula (II); In formula (I) and formula (II), R1 and R2 each independently represent a divalent to hexavalent organic group having 2 to 40 carbon atoms, R3 represents a hydrogen atom, a cyano group, a nitro group, a halogen, an alkyl group or an alkoxy group having 1 to 3 carbon atoms, n represents an integer from 1000 to 100000, m represents an integer from 100 to 10000, and p represents an integer from 0 to 2.

2. The photosensitive resin composition according to claim 1, characterized in that R1 in the structure represented by formula (I) comprises at least two of the following structural formulas, and the structure represented by formula (2) accounts for 1 to 10 mol%; R 11 Each independently represents an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group or a halogen group, R 12 Each independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a fluoroalkyl group or an alkoxy group, and R3 represents a hydrogen atom, a cyano group, a nitro group, a halogen group, an alkyl group or an alkoxy group having 1 to 3 carbon atoms.

3. The photosensitive resin composition according to claim 1, characterized in that The mass ratio of the structure represented by formula (I) to the structure represented by formula (II) is 80:(10-30).

4. The photosensitive resin composition according to claim 1, characterized in that R2 in the structure represented by formula (I) and the structure represented by formula (II) includes the following structural formulas: R4 is independently an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, a fluoroalkyl group, an alkoxy group, an ester group, a nitro group, a cyano group or a halogen group, and h and q are independently 0 or 1.

5. The photosensitive resin composition according to claim 1, characterized in that The diamine residue with phenolic hydroxyl group in R2 of the structure represented by the formula (I) and the structure represented by the formula (II) accounts for 10 to 30 mol % respectively.

6. The photosensitive resin composition according to claim 1, characterized in that The structure represented by formula (I) and the structure represented by formula (II) use fluorene structure as the end-capping group.

7. The photosensitive resin composition according to claim 1, characterized in that: The photosensitive resin composition includes 100 parts by mass of an alkali-soluble resin (A), 1 to 20 parts by mass of a thermal crosslinking agent (B), 1 to 10 parts by mass of a photopolymerization initiator (C), and 100 to 5000 parts by mass of an organic solvent (D).

8. A cured film, characterized in that: The photosensitive resin composition according to any one of claims 1 to 7 is prepared.

9. A patterned cured film, characterized in that: The method comprises using the cured film as claimed in claim 8 and subjecting the cured film to exposure, development and curing procedures.

10. The cured film according to claim 8 is used for manufacturing an insulating layer, a pixel definition layer of an organic electroluminescent element, and a surface protection film and an insulating layer of a semiconductor element.

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