Negative photosensitive resin compositions, cured films, patterned cured films and their applications

Abstract

This invention provides a negative photosensitive resin composition, a cured film, a patterned cured film, and their applications. The composition comprises: (A) a polybenzoxazole-imide resin, (B) a crosslinking agent as shown in structural formula (4), (C) a photosensitizer, and (D) an organic solvent; the polybenzoxazole-imide resin has photopolymerizable groups and contains benzoxazole or / and its precursor repeating units, and imide or / and its precursor repeating units. This invention, by combining a photopolymerizable polybenzoxazole-imide resin with a crosslinking agent of a specific structure, can reduce the fluidity of the film material during curing to reduce the porosity, thereby giving the film material advantages such as high heat resistance, solvent resistance, and minimal deformation of the pattern before and after curing.

Description

Technical Field

[0001] This invention relates to the field of optoelectronic display and semiconductor manufacturing technology, and more specifically, to a negative photosensitive resin composition, a cured film, a patterned cured film, and their applications. Background Technology

[0002] In the fabrication of semiconductor integrated circuits, there are generally two processes for preparing thin-film electrodes: ① Spray coating: A photosensitive resin composition is coated onto a substrate, followed by a series of processes such as drying, exposure, and development to obtain a resist film with an ideal pattern. The substrate with the resist film is then subjected to metal evaporation to fill the pits in the pattern. After evaporation, the resist film is removed, resulting in the substrate with the desired metal electrode thin-film pattern. ② Direct coating: A photosensitive resin composition is coated directly onto a metal thin film, followed by a series of processes such as drying, exposure, and development to obtain a resist film with an ideal pattern. The metal film is then subjected to dry / wet etching to obtain the desired metal thin-film electrode pattern. Similarly, in organic electroluminescent displays (organic EL) and liquid crystal displays (LCDs), it is also used to prepare insulating and light-shielding materials. If the spray coating method is used to prepare metal electrodes, when the resist pattern is an inverted trapezoid, the discontinuity between the metal evaporation film formed on the resist pattern and the metal evaporation film formed on the substrate is beneficial for the metal electrode.

[0003] Negative / positive photosensitive resin compositions are widely used in the production of devices such as semiconductor integrated circuits and organic electroluminescent displays. However, the production of these devices places extremely high demands on materials, thus limiting the number of photosensitive resin compositions suitable for the aforementioned methods. Consequently, researchers must select from a limited pool of photosensitive resin compositions, for example, by adjusting the preparation process and the exposure / development process / time to obtain satisfactory resist patterns.

[0004] Even with these numerous adjustments, the resulting resist patterns still have some drawbacks. For example, the resist patterns obtained using the negative photosensitive resin composition containing absorbable irradiated light and the method of using the composition, as invented in Japanese Patent 2989064, suffer from low heat resistance. To address this low heat resistance, the inventors in Patent JP-A 60-111240 added a ring-opening polymer of norbornene derivatives and an aromatic diazid compound. Patent JP-A 61-23618 added a photopolymerization initiator, a photosensitizer, and a copolymerizable monomer to the photosensitive resin composition. These improvements can enhance the heat resistance of the resist film to some extent. However, when using the spraying method and employing the resist film as an insulating material between the cathodes of an organic EL plate, a low-absorbency material is required in the insulating layer to prevent corrosion of the EL luminescent material by water / solvents. Furthermore, the material must not peel off during heating to avoid short circuits between adjacent electrodes, requirements that the aforementioned compositions cannot meet. In patent CN01805988.0, the inventors used a composition based on phenolic varnish and optimized it. However, with increasingly stringent environmental protection requirements, phenolic and aldehyde substances pose a threat to people's health. Summary of the Invention

[0005] One object of the present invention is to solve at least the above-mentioned problems and to provide at least the advantages that will be described later.

[0006] In order to achieve these objectives and other advantages according to the invention, a first aspect of the invention provides a polybenzoxazole-imide resin having photopolymerizable groups and containing benzoxazole and / or its precursor repeating units, and imide and / or its precursor repeating units.

[0007] A second aspect of the present invention provides a negative photosensitive resin composition comprising: (A) a polybenzoxazole-imide resin, (B) a crosslinking agent, (C) a photosensitizer, and (D) an organic solvent.

[0008] The polybenzoxazole-imide resin has photopolymerizable groups and contains benzoxazole and / or its precursor repeating units, as well as imide and / or its precursor repeating units.

[0009] The crosslinking agent is one or more of the compounds shown in structural formula (4):

[0010]

[0011] In equation (4), R1, R7, and R8 each independently represent the residues corresponding to amine compounds, R3 is the diamine residue corresponding to a diamine compound, R6 is the diphenol residue corresponding to a diphenol compound, x, y, z, k, and p each independently represent positive integers from 1 to 3, and R2, R4, R5, R9, and R6 represent the diamine residue corresponding to a diamine compound. 10Each of the following groups independently represents a hydrogen atom, an alkyl or alkoxy group having 1-30 carbon atoms, and any one of a hydroxyl, carboxyl, fluorine, chlorine, bromine, or aryl group.

[0012] The polybenzoxazole-imide resin is a polymer represented by the structure shown in the following general formula (1);

[0013]

[0014] In equation (1), m, n, and p represent positive integers from 1 to 50, and R 11 R 12 R 13 R 14 Each can be independently represented by a hydrogen atom or a monovalent organic group containing a double bond and having 1-20 carbon atoms, wherein R 11 -R 14 At least one of them is a monovalent organic group containing a double bond and having 1-20 carbon atoms.

[0015] In equation (1), K represents a structural unit containing the general formula (2) below;

[0016]

[0017] In formula (2), Y represents a tetravalent organic group with 2 to 60 carbon atoms, V represents a divalent organic group with 2 to 30 carbon atoms, and R represents a hydrogen atom or a monovalent organic group with 1 to 8 carbon atoms.

[0018] In equation (1), H represents a structural unit containing the following general equation (3);

[0019]

[0020] In formula (3), Q represents a tetravalent organic group with 2 to 30 carbon atoms, D represents a divalent organic group containing 2 to 60 carbon atoms, and R... 31 It represents a hydrogen atom or a monovalent organic group with 1 to 8 carbon atoms.

[0021] In formula (4), R1, R7, and R8 are preferably residues corresponding to aromatic amine compounds; R3 is preferably a diamine residue corresponding to an aromatic diamine compound.

[0022] The crosslinking agent (B) is one or more of the following structures:

[0023]

[0024] The polybenzoxazole-imide resin has a weight-average molecular weight of 2000-7000, preferably 4000-6000.

[0025] The ratio of m to n is 0.20-10.00, preferably 0.50-2.00, and even more preferably 0.50-1.35.

[0026] The amount of the crosslinking agent relative to 100 parts by weight of polybenzoxazole-imide resin is 3-25 parts by weight, preferably 6-21 parts by weight, and further 10-15 parts by weight.

[0027] A third aspect of the present invention provides a cured film prepared from the above-described negative photosensitive resin composition.

[0028] A fourth aspect of the present invention provides a patterned curing film, which is prepared from the above-mentioned curing film through an exposure, development and curing process.

[0029] The fifth aspect of the present invention provides an application of a patterned curing film, which is used to manufacture an insulating layer and a pixel definition layer for organic electroluminescent elements, as well as a surface protective film and an insulating layer for semiconductor elements.

[0030] The present invention has at least the following beneficial effects:

[0031] This invention combines a polybenzoxazole-imide resin with photopolymerizable groups with a crosslinking agent of a specific structure, which can reduce the fluidity of the membrane material during curing to reduce the porosity, thereby giving the membrane material advantages such as high heat resistance, solvent resistance, and minimal deformation of the pattern before and after curing. Detailed Implementation

[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] <Polybenzoxazole-imide resin>.

[0034] The present invention provides a polybenzoxazole-imide resin having photopolymerizable groups and containing benzoxazole and / or its precursor repeating units, and imide and / or its precursor repeating units.

[0035] The polybenzoxazole-imide resin is a polymer represented by the structure shown in the following general formula (1);

[0036]

[0037] In equation (1), m, n, and p represent positive integers from 1 to 50, and R 11 -R 14Each represents a hydrogen atom or a monovalent organic group containing a double bond and having 1-20 carbon atoms, wherein at least one of them is a monovalent organic group containing a double bond and having 1-20 carbon atoms.

[0038] In equation (1), K represents a structural unit containing the following general equation (2):

[0039]

[0040] In formula (2), Y represents a tetravalent organic group with 2 to 60 carbon atoms, V represents a divalent organic group with 2 to 30 carbon atoms, and R represents a hydrogen atom or a monovalent organic group with 1 to 8 carbon atoms.

[0041] In equation (1), H represents a structural unit containing the following general formula (3):

[0042]

[0043] In formula (3), Q represents a tetravalent organic group with 2 to 30 carbon atoms, D represents a divalent organic group containing 2 to 60 carbon atoms, and R... 31 It represents a hydrogen atom or a monovalent organic group with 1 to 8 carbon atoms.

[0044] <Negative Photosensitive Resin Composition>

[0045] The present invention provides a negative photosensitive resin composition comprising: (A) a polybenzoxazole-imide resin; (B) a crosslinking agent; (C) a photosensitizer; and (D) an organic solvent.

[0046] (A) Polybenzoxazole-imide resin

[0047] The polybenzoxazole-imide resin has photopolymerizable groups and contains benzoxazole and / or its precursor repeating units, as well as imide and / or its precursor repeating units.

[0048] The polybenzoxazole-imide resin is a polymer represented by the structure shown in the above general formula (1).

[0049] The inventors discovered that introducing benzoxazole precursor groups into the polyimide precursor resin gives the film material advantages such as high heat resistance, solvent resistance, and resistance to deformation of the pattern before and after curing.

[0050] The polybenzoxazole-imide resin is first reacted with a diamine compound (M1) and at least one acid compound (M2) from a diacid compound and its derivatives. Then, a diamine compound (M3), a tetracarboxylic acid dianhydride, and at least one acid compound (M4) from a tetracarboxylic acid and its derivatives are added to continue the reaction. Finally, a compound containing a double bond (M5) is added to carry out the reaction. After post-treatment such as sedimentation and drying, a polybenzoxazole-imide resin with photopolymerizable groups is obtained.

[0051] That is, the structural unit shown in general formula (2) is formed by the reaction of a diamine compound (M1) with at least one acid compound (M2) among dicarboxylic acid compounds and their derivatives; the structural unit shown in general formula (3) is formed by the reaction of a diamine compound (M3) with at least one acid compound (M4) among tetracarboxylic acid dianhydride, tetracarboxylic acid and its derivatives.

[0052] Among them, the ratio of the total molar amount of diamine compound (M1) and diamine compound (M3) to the total molar amount of acid compound (M2) and acid compound (M4) is greater than 1. In the structure shown in general formula (1), m / n is the molar ratio of acid compound (M2) to acid compound (M4).

[0053] In the embodiments of the present invention, the molar ratio of diamine compound (M1) to acid compound (M2) is greater than 1, and the molar ratio of diamine compound (M3) to acid compound (M4) is greater than or equal to 1; in the structure shown in general formula (1), m / n is the molar ratio of acid compound (M2) to acid compound (M4), m / n = 0.10-15.00, preferably 0.20-10.00, more preferably 0.50-2.00, and even more preferably 0.50-1.35; the weight average molecular weight (Mw) of the polymer represented by the structure shown in general formula (1) is above 2000 and below 9000, preferably 2000-7000, and more preferably 4000-6000.

[0054] The diamine compounds in this invention include, but are not limited to, conventional diamine compounds in the art. These conventional diamine compounds refer to those that can be directly purchased commercially or obtained through other means. That is, the diamine compounds used in the synthesis of structural formula (2) and structural formula (3) may be the same or different, and include one or more combinations of the following: p-phenylenediamine, m-phenylenediamine, bis[N-(3-aminophenyl)-3-amino-4-hydroxyphenyl]thione, 2,2'-diamino-4,4'-(cyclohexyl-1,1'-diyl)diol, 3,3'-dihydroxybenzidine, and 2,2'-bis(4-hydroxy-3-aminophenyl) Propane, 4,4'-oxybis(2-aminophenol), 2,2'-bis(4-hydroxy-3-aminophenyl)-4-methylpentane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 5,5'-diamino-3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirodi[indene]-6,6'-diol, 5(6)-amino-1-(4-aminophenyl)-1,3',3''-trimethylindene, 1,3'-bis(3-aminopropyl)tetramethyldisiloxane, bis(4-aminophenoxy)dimethylsilane, bis(ethylamino)dimethylsilane, 4 4′-Diaminodiphenyl ether, 3,4′-Diaminodiphenyl ether, 3,4′-Diaminodiphenyl sulfone, 4,4′-Diaminodiphenyl sulfone, 3,4′-Diaminodiphenyl sulfide, 4,4′-Diaminodiphenyl sulfide, 1,4-Di(4-aminophenoxy)benzene, bis(4-aminophenoxyphenyl)sulfone, bis(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 Products obtained from the above aromatic compounds, such as 4′-diaminobiphenyl and cycloalkyl or halogen-substituted compounds.

[0055] Furthermore, V in the structural formula (2) represents one or more combinations of residues of diacid compounds or diacid compound derivatives, including but not limited to phthalic acid, terephthalic acid, isophthalic acid, biphenyl acid, 2,2'-biphenyl acid, 4,4'-biphenyl acid, 2-methyl-1,4-phthalic acid, 1,4-naphthalenedicarboxylic acid, and their corresponding diacid ester compounds and diacid derivatives.

[0056] Furthermore, Q in the structural formula (3) represents one or more combinations of residues comprising, but not limited to, the following tetracarboxylic dianhydrides or tetracarboxylic acids and their derivatives, such as 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 Tetracarboxyphenyl)fluorene dianhydride, cyclobutanetetracarboxylic dianhydride (CBDA), cyclohexanetetracarboxylic dianhydride and other tetracarboxylic dianhydride compounds and their corresponding tetracarboxylic acids and derivatives.

[0057] Specific examples of compounds containing double bonds may be, but are not limited to, one or more combinations of the following example compounds: glycidyl acrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, itaconic anhydride, maleic anhydride, acrylic anhydride, dimethylmaleic anhydride, methacrylic anhydride, citraconic anhydride, nadic anhydride, norbornene, etc.

[0058] In this invention, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polybenzoxazole-imide resin (A) are determined using gel permeation chromatography (GPC), light scattering, small-angle X-ray scattering, etc., in the form of polystyrene equivalents. The polystyrene equivalents determined by gel permeation chromatography (GPC) have a weight-average molecular weight (Mw) between 2000 and 9000, preferably between 2000 and 7000. To ensure adequate solubility of the resin in alkaline developing solution and good heat resistance and elongation after heat treatment, a resin molecular weight (Mw) of 4000-6000 is preferred.

[0059] Furthermore, in order to better adjust the molecular weight of the 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 above-mentioned capping agent is added in a proportion of 0 to 0.3% of the total molar amount of all the diamine compounds added, and more specifically, 0 to 0.15%. Within the above range, a resin composition with moderate solution viscosity and excellent film properties can be obtained.

[0064] (B) Crosslinking agent

[0065] In this invention, the added crosslinking agent can not only form a crosslinking structure with the resin during the curing process of the adhesive film, thereby reducing the fluidity of the film material during curing and reducing the porosity, but also self-crosslink to form resin, improving the heat resistance and water absorption resistance of the adhesive film. Its self-crosslinking has the advantages of low shrinkage rate and no leakage of small molecule compounds.

[0066] The crosslinking agent is one or more of the compounds shown in the following structural formula (4).

[0067]

[0068] In equation (4), R1, R7, and R8 each independently represent the residues corresponding to amine compounds, R3 is the diamine residue corresponding to diamine compounds, R6 is the diphenol residue corresponding to diphenol compounds, x, y, z, k, and p are each independently represented as positive integers from 1 to 3, and R2, R4, R5, R9, and R6 are also represented as positive integers from 1 to 3. 10 Each can be independently represented as any one of hydrogen atom, alkyl or alkoxy group with 1-30 carbon atoms, hydroxyl group, carboxyl group, fluorine, chlorine, bromine or aryl group.

[0069] In the compound represented by structural formula (4), R1, R7, and R8 are preferably residues corresponding to aromatic amine compounds, such as residues corresponding to aromatic amine compounds containing 6 to 30 carbon atoms; R3 is preferably a diamine residue corresponding to an aromatic diamine compound, such as a diamine residue corresponding to an aromatic diamine compound containing 6 to 60 carbon atoms.

[0070] For ease of understanding, examples of crosslinking agents shown in structural formula (4) are provided by way of example, but are not limited thereto.

[0071]

[0072] The compound represented by structural formula (4) is a reaction product obtained by the Mannich reaction of an amine compound and a phenolic compound.

[0073] Furthermore, the diamine compounds described by R3 in formula (4) include, but are not limited to, conventional diamine compounds in the art. These conventional diamine compounds refer to those that can be directly purchased commercially or obtained through other means, such as p-phenylenediamine, m-phenylenediamine, 3-carboxy-m-phenylenediamine, 3-hydroxy-m-phenylenediamine benzidine, 4,4′-diaminodiphenyl ether, bis[N-(3-aminophenyl)-3-amino-4-hydroxyphenyl]thione, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol, 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,4′-diaminodiphenyl ether, 4,4'-oxybis(2-aminophenol), 3,4′-diaminodiphenyl sulfone, 2,2-bis(4-hydroxy-3-aminophenyl)-4-methylpentane, 4,4′ -Diaminodiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 5,5'-diamino-3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirodi[indene]-6,6'-diol, 4,4'-diaminodiphenyl sulfide, 5(6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindene, 1,4-di(4-aminophenoxy)benzene, 5(6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindene, di(4-aminophenoxyphenyl)sulfone, 6,6'-diamino-3,3'-methylenedibenzoic acid, di(3-aminophenoxyphenyl)sulfone, 1,4-di(4-aminophenoxyphenyl)sulfone (Aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, bis(4-aminophenoxy)dimethylsilane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-(1,3-propanedioxy)diphenylamine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis[4-(3-aminophenoxy)phenyl)]propane, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis[4-(4-aminophenoxyphenyl)]propane, 2,2,3,3′-tetramethyl-4,4′-diaminobiphenyl, 4,4′-diaminodicyclohexylmethane, 3,3′,4,4′-tetramethyl-4,4′ Products obtained from diaminobiphenyl and the above aromatic compounds substituted with cycloalkyl or halogen atoms.

[0074] Furthermore, the diphenol compounds described by R6 in formula (4) include, but are not limited to, conventional diphenol compounds in the art. These conventional diphenol compounds are those that can be directly purchased through commercial channels or obtained through other channels, such as bisphenol A, bisphenol F, bisphenol AF, etc.

[0075] In this invention, the amount of (B) crosslinking agent relative to 100 parts by weight of (A) polybenzoxazole-imide resin is 1-30 parts by weight, preferably 3-25 parts by weight in the embodiments of this invention, more preferably 6-21 parts by weight, and even more preferably 10-15 parts by weight.

[0076] (C) Photoinitiator.

[0077] The negative photosensitive resin composition of the present invention contains a photoinitiator. Under the action of the photoinitiator, the double bonds in the polybenzoxazole-imide resin undergo free radical cross-linking, resulting in differences in the solubility of the photosensitive resin composition.

[0078] Specific examples of photoinitiators include carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α-aminoalkylphenyl ketone-based photopolymerization initiators. Among these, considering excellent sensitivity and the acquisition of good patterns, oxime ester compounds are preferred. Specific examples include: 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, bis(α-isonitrosophenylacetone oxime) isophthaloyl, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyl oxime), "IRGACURE OXE01" (manufactured by BASF Corporation), "IRGACURE OXE02" (manufactured by BASF Co., Ltd.), N-1818, N-1919, NCI-831 (manufactured by ADEKA Co., Ltd.), etc.

[0079] In this invention, there is no particular limitation on the amount of photoinitiator (C), but it is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of polybenzoxazole-imide resin (A). When the amount of component (C) added is greater than or equal to 0.01 parts by weight, the crosslinking of the exposed portion can be more complete, and the photosensitivity, resolution, residual film rate, and other photosensitivity properties of the composition become better. When the amount of component (C) added is less than or equal to 10 parts by weight, the photoinitiator residue in the cured film is reduced, and the resulting cured film has better heat resistance and lower gas escape rate. Furthermore, the above-mentioned "photoinitiator" can be used alone or in combination of two or more.

[0080] (D) Organic solvents

[0081] Furthermore, the present invention also contains component (D) solvent. Considering the solubility of the photosensitive resin composition, polar solvents are preferred, including the following: 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-imidazolinone, etc. Among these, γ-butyrolactone, propylene glycol monomethyl ether acetate, 3-methoxybutanol, 3-methoxybutanol acetate, and ethyl lactate are preferred; they can be used alone or in combination of two or more. The content of component (D) in the photosensitive resin composition of the present invention is not particularly limited, and is 100 to 5000 parts by mass relative to 100 parts by mass of component (A), 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.

[0082] (E) Other additives

[0083] To improve the adhesion between the resin and the substrate, the negative photosensitive resin composition of the present invention further includes an adhesion promoter. Preferably, it is a silane-based coupling agent, whose hydrolyzed silanol or silyl groups can bind to the substrate to improve the adhesion between the film and the substrate during development and inhibit pattern detachment during development. Preferred examples include vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-trimethoxysilylpropylpropylsuccinic acid, 3-trimethoxysilylpropylpropylsuccinic anhydride, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl) The following are some combinations of the following: -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-(4-aminophenyl)propyltrimethoxysilane, 1-[4-(3-trimethoxysilylpropyl)phenyl]urea, 1-(3-trimethoxysilylpropyl)urea, 3-triethoxysilyl-N-(1,3-dimethylbutenyl)propylamine, 3-ylpropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 1,3,5-tris(3-trimethoxysilylpropyl)isocyanuric acid, N-tert-butyl-2-(3-trimethoxysilylpropyl)succinimide or N-tert-butyl-2-(3-trizoxysilylpropyl)succinimide.

[0084] To improve the flatness of the coated film surface, the negative photosensitive resin composition of the present invention may contain various surfactants, such as various organosilicon surfactants and various fluorinated surfactants. There are no special limitations on the type of surfactant.

[0085] To improve storage stability, the negative photosensitive resin composition of the present invention may contain various polymerization inhibitors, such as phenolic polymerization inhibitors, quinone polymerization inhibitors, free radical polymerization inhibitors, etc. There are no restrictions on the type of polymerization inhibitor.

[0086] To improve the exposure and development effect, the negative photosensitive resin composition of the present invention may contain various sensitizers, and there is no limitation on the type of sensitizer.

[0087] <Cured film>

[0088] The present invention provides a curing film, wherein the curing film in some embodiments of the present invention is formed by curing the photosensitive resin composition in some embodiments of the present invention.

[0089] <Pattern Curing Film>

[0090] This invention provides a patterned curable film. In some embodiments of this invention, the patterned curable film is prepared by the following steps: coating, drying, exposure, and development. Specifically, on a smooth and even substrate such as glass or silicon wafer, spin coating, spraying, roller coating, slot coating, screen printing, etc., can be used. Depending on the coating method and the composition, viscosity, and solid content of the composition used, the thickness of the dried film is typically 0.1-30 μm. The freshly coated film can be dried using an oven, hot plate, infrared furnace, etc., at 40-150°C for several minutes to several hours. After drying, the substrate is irradiated with photochemical rays through a mask to photocur the exposed area of ​​the photosensitive layer. The photochemical rays mentioned here include electromagnetic waves and particle beams, such as ultraviolet light, 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, an ambient lamp, a carbon rod arc lamp, or a metal halide lamp. Alternatively, exposure can be performed directly by laser irradiation without using a mask.

[0091] After exposure, the substrate is developed in a developer solution, where unexposed areas are dissolved to form a pattern. The developer solution can be a polar organic solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, g-butyrolactone, etc., or a mixture thereof with water; however, from an environmental perspective, an alkaline aqueous solution is preferred. The selected alkaline aqueous solution developer includes, but is not limited to, aqueous solutions of tetramethylammonium hydroxide, triethylamine, diethanolamine, dimethylaminoethanol, ethylenediamine, cyclohexylamine, hexamethylenediamine, diethylaminoethanol, methylamine, dimethylamine, etc., with a further preferred option being a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. Development can be performed by directly or by misting the developer solution onto the coated surface, or by immersion in the developer solution. The development time varies from 5 to 600 seconds depending on the film thickness, preferably from 5 to 300 seconds. After development, when using an alkaline aqueous solution as the developer, it is preferable to use water as the rinsing agent to clean the patterned film and then perform fixing treatment.

[0092] The developed film is then subjected to heat treatment, specifically by heat-treating it in a curing oven to completely transform the composition into a heat-resistant film. The heat treatment temperature is preferably 100–400°C; more preferably 150–300°C. The heat treatment time is controlled from 10 minutes to several hours, more preferably 30 minutes or more and 300 minutes or less; particularly preferably 30 minutes or more and 200 minutes or less. Simultaneously, multi-stage heat treatment can be performed, such as heat-curing at 150°C for 30 minutes, followed by heat-curing at 250°C for 30 minutes.

[0093] <Applications of Patterned Curing Films>

[0094] This invention provides an application of a patterned curing film, which is applied to the insulating layer, pixel definition layer, planarization layer of an organic electroluminescent element, and / or the surface protection layer and insulating layer of a semiconductor device.

[0095] Example

[0096] The following embodiments illustrate the present invention, but the present invention is not limited to the following embodiments.

[0097] Synthesis of Crosslinking Agents

[0098] Synthesis Example 1: Synthesis of Crosslinking Agent B1

[0099] Weigh 1.86 g of aniline (20 mmol) into a three-necked flask, add 80 mL of tetrahydrofuran to dissolve it, and slowly add 3.25 g (40 mmol) of formaldehyde solution (37% concentration) dropwise at 5 °C. Stir at room temperature (23 °C) for 1 h, add 2.00 g (10 mmol) of bisphenol F, raise the temperature to 75 °C and reflux for 6 h, lower the solution to room temperature (23 °C), remove the THF phase, add ethyl acetate and deionized water, extract, take the organic phase, wash three times with saturated sodium carbonate and saturated sodium bicarbonate, wash once with saturated brine, dry with anhydrous sodium sulfate, concentrate, and obtain crosslinking agent B1.

[0100] Synthesis Example 2: Synthesis of Crosslinking Agent B2

[0101]

[0102] Weigh 1.86 g (20 mmol) of aniline into a three-necked flask, add 80 mL of tetrahydrofuran to dissolve it, and slowly add 3.25 g (40 mmol) of formaldehyde solution (37% concentration) dropwise at 5 °C. Stir at room temperature (23 °C) for 1 h, add 3.50 g (10 mmol) of bisphenol fluorene, raise the temperature to 75 °C and reflux for 6 h, lower the solution to room temperature (23 °C), remove the THF phase, add ethyl acetate and deionized water, extract, take the organic phase, wash three times with saturated sodium carbonate and saturated sodium bicarbonate, wash once with saturated brine, dry with anhydrous sodium sulfate, concentrate, and obtain crosslinking agent B2.

[0103] Synthesis Example 3: Synthesis of Crosslinking Agent B3

[0104]

[0105] Weigh 1.98 g (10 mmol) of 4,4'-diaminodiphenylmethane into a three-necked flask, add 80 mL of tetrahydrofuran to dissolve it, and slowly add 3.25 g (40 mmol) of formaldehyde solution (37% concentration) dropwise at 5 °C. Stir at room temperature (23 °C) for 1 h, add 2.20 g (20 mmol) of resorcinol, raise the temperature to 75 °C and reflux for 6 h, lower the solution to room temperature (23 °C), remove the THF phase, add ethyl acetate and deionized water, extract, take the organic phase, wash three times with saturated sodium carbonate and saturated sodium bicarbonate, wash once with saturated brine, dry with sodium sulfate, concentrate, and obtain crosslinking agent B3.

[0106] Synthesis Example 4: Synthesis of Crosslinking Agent B4

[0107]

[0108] Weigh 2.30 g of polyetheramine (D230) (10 mmol) into a three-necked flask, add 80 mL of tetrahydrofuran to dissolve it, and slowly add 3.25 g (40 mmol) of formaldehyde solution (37% concentration) dropwise at 5 °C. Stir at room temperature (23 °C) for 1 h, add 2.20 g (20 mmol) of resorcinol, raise the temperature to 75 °C and reflux for 6 h, lower the solution to room temperature (23 °C), remove the THF phase, add ethyl acetate and deionized water, extract, take the organic phase, wash three times with saturated sodium carbonate and saturated sodium bicarbonate, wash once with saturated brine, dry with sodium sulfate, concentrate, and obtain crosslinking agent B4.

[0109] Synthesis Example 5: Synthesis of Crosslinking Agent B5

[0110]

[0111] Weigh 2.48 g (10 mmol) of 1,3-bis(aminopropane)tetramethyldisiloxane into a three-necked flask, add 80 mL of tetrahydrofuran to dissolve it, and slowly add 3.25 g (40 mmol) of formaldehyde solution (37% concentration) dropwise at 5 °C. Stir at room temperature (23 °C) for 1 h, add 2.20 g (20 mmol) of resorcinol, raise the temperature to 75 °C and reflux for 6 h, lower the solution to room temperature (23 °C), remove the THF phase, add ethyl acetate and deionized water, extract, take the organic phase, wash three times with saturated sodium carbonate and saturated sodium bicarbonate, wash once with saturated brine, dry with sodium sulfate, concentrate, and obtain crosslinking agent B5.

[0112] Synthesis Example 6: Synthesis of Crosslinking Agent B6

[0113]

[0114] Weigh 0.93 g of aniline (10 mmol) into a three-necked flask, add 80 mL of tetrahydrofuran to dissolve it, and slowly add 1.62 g (20 mmol) of formaldehyde solution (37% concentration) dropwise at 5 °C. Stir at room temperature (23 °C) for 1 h, add 0.94 g (10 mmol) of phenol, raise the temperature to 75 °C and reflux for 6 h, lower the solution to room temperature (23 °C), remove the THF phase, add ethyl acetate and deionized water, extract, take the organic phase, wash three times with saturated sodium carbonate and saturated sodium bicarbonate, wash once with saturated brine, dry with sodium sulfate, concentrate, and obtain crosslinking agent B6.

[0115] Synthesis Example 7: Synthesis of Crosslinking Agent B7

[0116]

[0117] Weigh 0.87 g of 1-aminopentane (10 mmol) into a three-necked flask, add 80 mL of tetrahydrofuran to dissolve it, and slowly add 1.62 g (20 mmol) of formaldehyde solution (37% concentration) dropwise at 5 °C. Stir at room temperature (23 °C) for 1 h, add 0.94 g (10 mmol) of phenol, raise the temperature to 75 °C and reflux for 6 h, lower the solution to room temperature (23 °C), remove the THF phase, add ethyl acetate and deionized water, extract, take the organic phase, wash three times with saturated sodium carbonate and saturated sodium bicarbonate, wash once with saturated brine, dry with sodium sulfate, concentrate, and obtain crosslinking agent B7.

[0118] Synthesis of diacid derivatives.

[0119] Synthesis Example 8: Synthesis of diacid derivative P1

[0120]

[0121] Weigh 14.92 g (92 mmol) of 1,1'-dicarbonylimidazoline and dissolve it in a 500 mL three-necked flask. Add an appropriate amount of N-methylpyrrolidone and dissolve it completely. Purge with nitrogen for protection. Slowly add an N-methylpyrrolidone solution containing 10.33 g (40 mmol) of 4,4'-dicarboxylic acid diphenyl ether. After the addition is complete, raise the temperature to 65 °C and react for 2 h. Lower the temperature to below 5 °C and add an appropriate amount of 0 °C ice-water mixture (pure water). Stir thoroughly and filter to obtain the diacid derivative P1.

[0122] Synthesis Example 9: Synthesis of diacid derivative P2

[0123]

[0124] Weigh 14.92 g of 1,1'-dicarbonylimidazoline and dissolve it in a 500 mL three-necked flask. Add an appropriate amount of N-methylpyrrolidone and dissolve it completely. Purge with nitrogen for protection and slowly add an N-methylpyrrolidone solution containing terephthalic acid dropwise. After the addition is complete, raise the temperature to 65 °C and react for 2 h. Lower the temperature to below 5 °C and add an appropriate amount of 0 °C ice-water mixture (pure water). Stir thoroughly and filter to obtain the diacid derivative P2.

[0125] Synthesis of Polybenzoxazole-imide Resins

[0126] Synthesis Example 10: Synthesis of Polybenzoxazole-imide Resin A1

[0127] Weigh 23.78 g (110 mmol) of 3,3'-dihydroxybenzidine, 5.84 g (100 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 16.02 g (80 mmol) of 4,4'-diaminodiphenyl ether, and stir for 2 h. Add 15.27 g (70 mmol) of pyromellitic dianhydride, and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate, and stir for 5 h. Add 2.96 g (20 mmol) of phthalic acid, and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A1 containing double bonds. The molecular weight (Mw) was 3684 according to GPC testing.

[0128] Synthesis Example 11: Synthesis of Polybenzoxazole-imide Resin A2

[0129] Weigh 23.78 g (110 mmol) of 3,3'-dihydroxybenzidine, 5.84 g (100 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 16.02 g (80 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 16.36 g (75 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Add 1.48 g (10 mmol) of phthalic acid and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A2 containing double bonds. The molecular weight (Mw) was 4938 according to GPC testing.

[0130] Synthesis Example 12: Synthesis of Polybenzoxazole-imide Resin A3

[0131] Weigh 23.78 g (110 mmol) of 3,3'-dihydroxybenzidine, 5.84 g (100 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 16.02 g (80 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 17.45 g (80 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C and add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A3 containing double bonds. The molecular weight (Mw) was 6742 according to GPC testing.

[0132] Synthesis Example 13: Synthesis of Polybenzoxazole-imide Resin A4

[0133] Weigh 23.78 g (110 mmol) of 3,3'-dihydroxybenzidine, 226.63 g (100 mmol) of diacid derivative P2, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 16.02 g (80 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 15.27 g (70 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Add 2.96 g (20 mmol) of phthalic acid and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A4 containing double bonds. The molecular weight (Mw) was 3201 according to GPC testing.

[0134] Synthesis Example 14: Synthesis of Polybenzoxazole-imide Resin A5

[0135] Weigh 8.65 g (40 mmol) of 3,3'-dihydroxybenzidine, 0.75 g (30 mmol) of diacid derivative P11, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 16.02 g (80 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 17.45 g (80 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C and add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A5 containing double bonds. The molecular weight (Mw) was 4739 according to GPC testing.

[0136] Synthesis Example 15: Synthesis of Polybenzoxazole-imide Resin A6

[0137] Weigh 12.97 g (60 mmol) of 3,3'-dihydroxybenzidine, 17.92 g (50 mmol) of diacid derivative P1, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 16.02 g (80 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 17.01 g (78 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Add 0.59 g (4 mmol) of phthalic acid and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A6 containing double bonds. The molecular weight (Mw) was 4861 according to GPC testing.

[0138] Synthesis Example 16: Synthesis of Polybenzoxazole-imide Resin A7

[0139] Weigh 17.30 g (80 mmol) of 3,3'-dihydroxybenzidine, 5.09 g (70 mmol) of diacid derivative P12, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 16.02 g (80 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 16.80 g (77 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Add 0.89 g (6 mmol) of phthalic acid and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A7 containing double bonds. The molecular weight (Mw) was 4673 according to GPC testing.

[0140] Synthesis Example 17: Synthesis of Polybenzoxazole-imide Resin A8

[0141] Weigh 21.62 g (100 mmol) of 3,3'-dihydroxybenzidine, 2.25 g (90 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 16.02 g (80 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 16.36 g (75 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Add 1.48 g (10 mmol) of phthalic acid and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A8 containing double bonds. The molecular weight (Mw) was 4885 according to GPC testing.

[0142] Synthesis Example 18: Synthesis of Polybenzoxazole-imide Resin A9

[0143] Weigh 23.78 g (110 mmol) of 3,3'-dihydroxybenzidine, 5.84 g (100 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 2.00 g (10 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 2.18 g (10 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C and add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A9 containing double bonds. The molecular weight (Mw) was 4639 according to GPC testing.

[0144] Synthesis Example 19: Synthesis of Polybenzoxazole-imide Resin A10

[0145] Weigh 23.78 g (110 mmol) of 3,3'-dihydroxybenzidine, 5.84 g (100 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 6.01 g (30 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 6.11 g (28 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Add 0.59 g (4 mmol) of phthalic acid and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A10 containing double bonds. The molecular weight (Mw) was 4857 according to GPC testing.

[0146] Synthesis Example 20: Synthesis of Polybenzoxazole-imide Resin A11

[0147] Weigh 23.78 g (110 mmol) of 3,3'-dihydroxybenzidine, 5.84 g (100 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 10.01 g (50 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 10.25 g (47 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Add 0.89 g (6 mmol) of phthalic acid and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A11 containing double bonds. The molecular weight (Mw) was 4772 according to GPC testing.

[0148] Synthesis Example 21: Synthesis of Polybenzoxazole-imide Resin A12

[0149] Weigh 23.78 g (110 mmol) of 3,3'-dihydroxybenzidine, 5.84 g (100 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 14.01 g (70 mmol) of 4,4'-diaminodiphenyl ether and stir for 2 h. Add 14.18 g (65 mmol) of pyromellitic dianhydride and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate and stir for 5 h. Add 1.48 g (10 mmol) of phthalic acid and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A12 containing double bonds. The molecular weight (Mw) was 4890 according to GPC testing.

[0150] Synthesis Example 22: Synthesis of Polybenzoxazole-imide Resin A13

[0151] Weigh 28.42 g (110 mmol) of 2,2'-bis(4-hydroxy-3-aminophenyl)propane, 5.84 g (100 mmol) of diacid derivative P13, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, and stir for 3 h. Add 17.30 g (80 mmol) of 3,3'-dihydroxybenzidine, and stir for 2 h. Add 20.60 g (70 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and stir for 5 h. Cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate, and stir for 5 h. Add 2.96 g (20 mmol) of phthalic acid, and stir for 5 h. Pour into 2 L of ethanol, filter, and collect the polymer precipitate. Heat the obtained polymer at 50 °C. The resin A13 containing double bonds was obtained by drying in a vacuum drying oven at ℃ for 24 hours. The molecular weight (Mw) was 3513 after GPC testing.

[0152] Synthesis Example 23: Synthesis of Polyimide Resin A14

[0153] Weigh 40.04 g (200 mmol) of 4,4'-diaminodiphenyl ether into a 500 mL round-bottom flask, add 200 mL of N-methylpyrrolidone, purge with nitrogen, stir to dissolve, add 39.26 g (180 mmol) of pyromellitic dianhydride, stir at 85 °C for 5 h, cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate, stir for 5 h, add 2.96 g (20 mmol) of phthalic acid, stir for 5 h, pour into 2 L of ethanol, filter and collect the polymer precipitate, dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A14 containing double bonds, and the molecular weight (Mw) was 3298 according to GPC test.

[0154] Synthesis Example 24: Synthesis of Polybenzoxazole Resin A15

[0155] Weigh 43.24 g (200 mmol) of 3,3'-dihydroxybenzidine, 4.51 g (180 mmol) of diacid derivative P16, and 0.3 g of p-toluenesulfonic acid into a 500 mL round-bottom flask. Add 200 mL of N-methylpyrrolidone, purge with nitrogen, heat to 85 °C, stir for 3 h, cool to 23 °C, add 2.84 g (20 mmol) of glycidyl methacrylate, stir for 5 h, add 2.96 g (20 mmol) of phthalic acid, stir for 5 h, pour into 2 L of ethanol, filter and collect the polymer precipitate, and dry the obtained polymer in a vacuum drying oven at 50 °C for 24 h to obtain resin A15 containing double bonds. The molecular weight (Mw) was 3718 according to GPC testing.

[0156] Example 1

[0157] 1.0 g of resin precursor A1, 0.12 g of crosslinking agent B1, 0.025 g of photoinitiator IRGACURE OXE01 and 0.025 g of TPS-TF, 0.01 g of surfactant "TEGO GLIDE 300" and 0.03 g of silane coupling agent vinyltrimethoxysilane were dissolved in a mixed solution of 2.39 g of propylene glycol methyl ether acetate and 4.79 g of γ-butyrolactone. After stirring at room temperature for 6 h, the mixture was filtered through an organic filter membrane with a pore size of 0.25 micrometers. The filtered mixed solution is the negative photosensitive resin composition.

[0158] The photosensitive resin composition slurry is coated onto a silicon wafer or glass substrate, baked at 120 °C for 3 min, exposed, developed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 s, and then washed with water for 30 s to obtain a patterned film. After ultraviolet bleaching, it is then heat-treated at 240 °C for 1 h to obtain the final film used for performance evaluation.

[0159] Examples 2-27, Comparative Examples 1-5

[0160] The synthesis methods of Examples 2-27 and Comparative Examples 1-5 are the same as those of Example 1, except that the selection and proportioning of raw materials are different. The specific formulations are shown in Table 1. The surfactants, silane coupling agents, and organic solvents in the Examples and Comparative Examples are the same.

[0161] Table 1

[0162]

[0163] The photosensitive resin compositions prepared in Examples 1-27 and Comparative Examples 1-5 were evaluated for their imaging ability, chamfer change rate, heat resistance, water absorption, and other properties. The results are shown in Table 2.

[0164] <Evaluation Methods>

[0165] (1) Imaging capability

[0166] The developed film was inspected using SEM (JEOL JSM-6510) to check the etched lines. Excellent results were achieved when lines less than 5 mm wide were 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 mm wide were clearly etched, without bending or defects, and the linewidth ratio was consistent with the mask design. Poor results were achieved when lines greater than 10 mm wide were clearly etched, without bending or defects, and the linewidth ratio was consistent with the mask design.

[0167] (2) Chamfer change rate

[0168] The developed film was inspected using a SEM (JEOL JSM-6510) to measure the chamfer angle of a 5mm wide line cross-section. After inspection, the film was baked in a 260℃ oven for 1.5 hours, and then the chamfer angle of the 5mm wide line cross-section was inspected again using a SEM (JEOL JSM-6510). An angle change rate of less than 2° is considered excellent; a line spacing change rate of 2°-5° is considered good; and a line spacing change rate greater than 5° is considered poor.

[0169] (3) Heat resistance

[0170] 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% ≤ R 400 ≤80% is considered good, R 400 <75% is considered poor.

[0171] (4) Water absorption rate

[0172] The heat-treated film (area greater than 5*5 cm, thickness 2 mm) was left to stand for 72 h, and the film thickness change before and after immersion in pure water at 40 °C for 120 s 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. < 1% is considered excellent, 1% ≤ ΔTHK ≤2% is considered good, ΔTHK>2% is considered poor.

[0173] Table 2

[0174]

[0175] 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 polybenzoxazole-imide resin, characterized by, The polybenzoxazole-imide resin is a polymer represented by the structure represented by the following general formula (1): ， In formula (1), m, n, p each represent a positive integer of 1 to 50, R 11 , R 12 , R 13 , R 14 each independently represent a hydrogen atom or a monovalent organic group having a double bond and a carbon atom number of 1 to 20, wherein R 11 -R 14 at least one is a monovalent organic group having a double bond and a carbon atom number of 1 to 20; the monovalent organic group having a double bond and a carbon atom number of 1 to 20 is selected from one or more of the residues of acrylic acid glycidyl ester, methacrylic acid glycidyl ester, acrylic acid, methacrylic acid, itaconic anhydride, maleic anhydride, acrylic anhydride, dimethyl maleic anhydride, methacrylic anhydride, citraconic anhydride, nadic anhydride, norbornene diacid anhydride; In formula (1), K represents a structural unit represented by the following general formula (2): ， In formula (2), Y represents one or more kinds of residues selected from 2,2'-diamino-4,4'-(cyclohexyl-1,1'-diyl)diphenol, 3,3'-dihydroxybenzidine, 2,2'-bis(4-hydroxy-3-aminophenyl)propane, 4,4'-oxybis(2-aminophenol), 2,2'-bis(4-hydroxy-3-aminophenyl)-4-methylpentane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, or 5,5'-diamino-3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobis[indene]-6,6'-diol, V represents one or more kinds of residues of a diacid compound or a diacid compound derivative, and R represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms. In formula (1), H represents a structural unit represented by the following general formula (3): ， In formula (3), Q represents a tetravalent organic group having 2 to 30 carbon atoms, D represents a divalent organic group having 2 to 60 carbon atoms, R 31 represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.

2. A negative photosensitive resin composition, characterized by comprising: The composition comprises: (A) the polybenzoxazole-imide resin according to claim 1, (B) a crosslinking agent, (C) a photosensitizer, and (D) an organic solvent. The crosslinking agent is one or more kinds of compounds represented by the following structural formula (4): ， In formula (4), R1, R7, and R8 each independently represent a residue corresponding to the amine compound, R3 is a diamine residue corresponding to the diamine compound, R6 is a diphenol residue corresponding to the diphenol compound, x, y, z, k, and p each independently represent a positive integer of 1 to 3, R2, R4, R5, R9, and R10 each independently represent a hydrogen atom, an alkyl or alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, fluorine, chlorine, bromine, or an aryl group. 10 each independently represents any one of a hydrogen atom, an alkyl or alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group, fluorine, chlorine, bromine, or an aryl group.

3. The negative-working photosensitive resin composition according to claim 2, wherein In formula (4), R1, R7, and R8 each independently represent a residue corresponding to an aromatic amine compound; and R3 is a diamine residue corresponding to an aromatic diamine compound.

4. The negative-working photosensitive resin composition of claim 2, wherein The crosslinking agent (B) is one or more kinds of the following structures: 。 5. The negative-working photosensitive resin composition of claim 2, wherein The crosslinking agent (B) is one or more kinds of the following structures: 。 6. The negative-working photosensitive resin composition of claim 2, wherein The ratio of m to n is 0.20 to 10.00; and / or, the weight average molecular weight of the polybenzoxazole-imide resin is 2000 to 7000.

7. The negative-working photosensitive resin composition of claim 2, wherein The ratio of m to n is 0.50 to 2.00, and / or, the weight average molecular weight of the polybenzoxazole-imide resin is 4000 to 6000.

8. The negative-working photosensitive resin composition of claim 2, wherein The ratio of m to n is 0.50 to 1.35; and / or, the weight average molecular weight of the polybenzoxazole-imide resin is 4000 to 6000.

9. The negative-working photosensitive resin composition of claim 2, wherein The amount of the crosslinking agent is 3 to 25 parts by mass relative to 100 parts by mass of the polybenzoxazole-imide resin.

10. The negative-working photosensitive resin composition of claim 2, wherein The amount of the crosslinking agent is 6 to 21 parts by mass relative to 100 parts by mass of the polybenzoxazole-imide resin.

11. The negative-working photosensitive resin composition of claim 2, wherein The amount of the crosslinking agent is 10 to 15 parts by mass relative to 100 parts by mass of the polybenzoxazole-imide resin.

12. A cured film characterized by, A negative photosensitive resin composition according to any one of claims 2 to 11 is prepared.

13. A patterned cured film characterized by, A cured film is prepared by using the cured film according to claim 12 through an exposure, development, and curing process.

14. Use of a patterned solidification film according to claim 13, characterized in that The cured film is applied to a surface protective layer or an insulating layer of a semiconductor device.

15. Use of the patterned solidification film according to claim 13, characterized in that The cured film is applied to an insulating layer, a pixel definition layer, or a planarization layer of an organic electroluminescent element. The cured film is applied to an insulating layer, a pixel definition layer, or a planarization layer of an organic electroluminescent element.

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