Polybenzoxazole photosensitive resin composition and application thereof

Abstract

The invention discloses a polybenzoxazole photosensitive resin composition and an application of the polybenzoxazole photosensitive resin composition. The photosensitive resin composition comprises resin, nitrogen heterocyclic polysiloxane, a silane coupling agent, a photosensitive auxiliary agent, a cross-linking agent and a solvent. By adding the nitrogen heterocyclic polysiloxane, the obtained photosensitive resin composition can show excellent dielectric properties.

Description

Technical Field

[0001] The present application relates to a polybenzoxazole photosensitive resin composition and application thereof, belonging to the technical field of organic silicon compounds. Background Art

[0002] With the development of aerospace and national defense military equipment, the high-end field has an increasingly strong demand for low-density, high-strength, high-modulus and high-temperature resistant polymer materials. The development of such materials is of great significance to enhancing the competitiveness of the country's high-end cutting-edge science and technology fields. Polybenzoxazole (PBO) is a high-performance resin material. Due to the alternating rigid benzoxazole rings and benzene rings in the PBO chain structure, it has extremely high tensile strength, stiffness, and relatively low density. Polybenzoxazole polymers are high-performance polymers with high-rigidity molecular chain segments. They are usually widely used in aerospace, navigation, military and other fields in the form of films, fibers, resin matrices and molecular reinforcement materials. They are important matrix materials for high-temperature resistant and high-strength composite materials.

[0003] Adhesion to the substrate is an important indicator of material quality. Semiconductor devices in different fields now use substrates of different materials, such as silicon, copper, copper alloy, titanium, titanium alloy, silver, aluminum, etc. A good product needs to show good adhesion to different substrates.

[0004] In addition, the interlayer insulation film used for multi-layer metal interconnect circuits in semiconductor packaging requires the lowest possible dielectric constant and dielectric loss to minimize parasitic capacitance, thereby preventing signal transmission delays, crosstalk, and noise. Polyimide materials themselves have good temperature resistance, mechanical properties, and insulation properties, and are important materials for interlayer insulation films. However, the dielectric constant of traditional polyimide is relatively high (about 3.4), which is difficult to meet the needs of next-generation semiconductor packaging materials, and low dielectric modification is required. Summary of the invention

[0005] One of the purposes of the present invention is to provide a photosensitive resin composition, wherein the resin used in the photosensitive resin composition is a polybenzoxazole resin, and a nitrogen-containing heterocyclic polysiloxane is introduced, which has strong dielectric properties and good adhesion to a substrate, and better meets the use requirements.

[0006] The present application provides a photosensitive resin composition, which has strong dielectric properties and can be used to form relief patterns such as passivation films, surface protection films and interlayer insulation films of semiconductor devices.

[0007] The photosensitive resin composition comprises resin, nitrogen-containing heterocyclic polysiloxane, silane coupling agent, photosensitive auxiliary agent, crosslinking agent and solvent.

[0008] Wherein, the nitrogen-containing heterocyclic polysiloxane is selected from at least one of the structural formulas shown in the following formula (1):

[0009]

[0010] Wherein, Y is an organic group containing a nitrogen heterocyclic ring. Optionally, Y is selected from at least one of the structures shown in the following formulas (2) to (5), and can be one, two or more than two, and * represents an accession site:

[0011]

[0012] In formula (2) to formula (5), R1 is selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Specifically, the alkyl group or alkoxy group having 1 to 20 carbon atoms may be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or an alkoxy group such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, or hydroxypropyl acrylate.

[0013] Preferably, R1 is selected from hydrogen atom, methyl group, ethyl group, butyl group, hydroxyethyl group of methacrylate.

[0014] In formula (2) to formula (5), the W group is selected from a nitrogen-containing heterocyclic structure, such as triazolyl, tetrazolyl, triazine, imidazole, oxazole, etc.

[0015] Preferably, W is selected from at least one of the following structures of formula (6), and * represents an insertion site:

[0016]

[0017] In formula (6), R2, R3, R4, R5, R6, R7, R8, and R9 are independently selected from at least one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, and an ester group. The hydrocarbon group having 1 to 10 carbon atoms may be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; a cycloalkyl group such as cyclopentyl and cyclohexyl; an aromatic group such as phenyl and tolyl; an aralkyl group such as benzyl, phenethyl, and phenylpropyl; or an unsaturated alkenyl group such as vinyl, allyl, butenyl, propenyl, isopropenyl, and phenylalkenyl.

[0018] Preferably, R2, R3, R4, R5, R6, R7, R8, and R9 are independently selected from hydrogen atom, alkyl group with 1 to 3 carbon atoms, carboxyl group with 1 to 5 carbon atoms, and ester group. More preferably, R2, R3, R4, R5, R6, R7, and R8 are independently selected from hydrogen atom, saturated alkyl group with 1 to 3 carbon atoms, and carboxyl group with 1 to 5 carbon atoms. More preferably, R2, R3, R4, R5, R6, R7, R8, and R9 are independently selected from hydrogen atom, methyl group, ethyl group, and carboxyl group.

[0019] Furthermore, the nitrogen-containing heterocyclic polysiloxane can be used alone or in combination of two or more, and has a significant promoting effect on the dielectric properties and adhesion of the polybenzoxazole precursor, the polybenzoxazole heat-resistant resin and the substrate.

[0020] Furthermore, the preparation method of the nitrogen-containing heterocyclic polysiloxane comprises the following steps:

[0021] Step 1: Under gas protection, the organic solvent, nitrogen-containing heterocyclic silane coupling agent monomer and catalyst are stirred and mixed uniformly;

[0022] Step 2: Control the temperature of the mixture in step 1 at 0-40°C, add water dropwise thereto, keep the mixture warm for reaction after the addition is complete, and then raise the temperature to 50-100°C to continue the reaction;

[0023] Step 3: After the reaction, the organic layer is separated and the volatile matter is removed by distillation to obtain polysiloxane.

[0024] Furthermore, in step 1, the nitrogen-containing heterocyclic silane coupling agent monomer is selected from at least one of the structures represented by the following formula (7):

[0025]

[0026] In formula (7), the definitions of R1 and W are consistent with the above definitions.

[0027] In formula (7), R 10 is selected from hydrocarbon groups having 1 to 10 carbon atoms. The hydrocarbon groups having 1 to 10 carbon atoms may be alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., cycloalkyl groups such as cyclopentyl and cyclohexyl, aromatic groups such as phenyl and tolyl, aralkyl groups such as benzyl, phenethyl, phenylpropyl, etc., and unsaturated alkenyl groups such as vinyl, allyl, butenyl, propenyl, isopropenyl, and phenylalkenyl. Preferably, R 10 is a saturated alkyl group having 1 to 10 carbon atoms, more preferably, R 10 It is methyl or ethyl.

[0028] Furthermore, the preparation method of the nitrogen-containing heterocyclic silane coupling agent monomer shown in formula (7) is:

[0029] Category 1: Amide-based nitrogen-containing heterocyclic silane coupling agent monomers:

[0030] The nitrogen-containing heterocyclic monoamine H is mixed with a solvent, and then a silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in a molar amount equal to one times the nitrogen-containing heterocyclic monoamine H is slowly added. After the addition is completed, the reaction is continued at 23-26° C. for 20-22 hours. After the reaction is completed, the nitrogen-containing heterocyclic silane coupling agent monomer of the amide acid type is obtained by distillation under reduced pressure and purification.

[0031] The second category: imide nitrogen-containing heterocyclic silane coupling agent monomer:

[0032] The nitrogen-containing heterocyclic monoamine H is mixed with a solvent, and then a silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in a molar amount of one times the nitrogen-containing heterocyclic monoamine H is slowly added. After the addition is completed, the reaction is continued at 23-26° C. for 20-22 hours, and then a base and anhydride are added to the reaction system for imidization. After the reaction is completed, the solvent, unreacted raw materials and by-products in the system are removed by reduced pressure distillation to obtain an imide-type nitrogen-containing heterocyclic silane coupling agent monomer.

[0033] Category 3: Amide ester nitrogen-containing heterocyclic silane coupling agent monomers:

[0034] The nitrogen-containing heterocyclic monoamine H is mixed with a solvent, and then a silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in a molar amount of one times the nitrogen-containing heterocyclic monoamine H is slowly added. After the addition is completed, the reaction is continued at 23-26° C. for 20-22 hours, and then an esterification agent (N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, etc.) is added to the system for esterification reaction. After the reaction is completed, reduced pressure distillation is performed to obtain an amide ester type nitrogen-containing heterocyclic silane coupling agent monomer.

[0035] Wherein, the nitrogen-containing heterocyclic monoamine H is selected from at least one of the structures shown in the following formula (8):

[0036]

[0037] In the above formula (8), the definitions of R2, R3, R4, R5, R6, R7, R8 and R9 are the same as those described above.

[0038] Optionally, in step 1, the organic solvent is at least one of hydrocarbons, ketones, esters, ethers, alcohols, etc. The hydrocarbons include, for example, toluene, xylene, etc.; the ketones include, for example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc.; the esters include, for example, ethyl acetate, n-butyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc.; the ethers include, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; the alcohols include, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, etc. The organic solvent is preferably one that is immiscible with water, and these organic solvents may be used alone or in combination of two or more.

[0039] Optionally, in step 1, the catalyst may be one of an acid, an alkali metal compound, an organic base, and the like. Examples of the acid include hydrochloric acid, p-toluenesulfonic acid, and the like; examples of the alkali metal compound include, for example, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, and the like; examples of the organic base include, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and diazacycloundecene; and quaternary organic amines such as tetramethylammonium hydroxide, and the like. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and tetramethylammonium hydroxide are preferred.

[0040] Optionally, in step 1, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to the organic solvent is 1:0.25-10, for example, 1:0.25, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, preferably 1:1-5.

[0041] Optionally, in step 1, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to the catalyst is 1:0.001-0.1, for example, 1:0.001, 1:0.002, 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, preferably 1:0.005-0.05.

[0042] Optionally, in step 2, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to water is 1:0.5-25, for example, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, preferably 1:1-10.

[0043] Optionally, in step 2, the water is added dropwise for 0.5 to 5 h, for example, 0.5 h, 1 h, 2 h, 3 h, 4 h, or 5 h.

[0044] Optionally, in step 2, water is added dropwise at 0-40°C, and the temperature can be 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C. After the water is added dropwise, the reaction is kept warm for 3-6 hours, such as 3 hours, 4 hours, 5 hours, 6 hours. After the reaction, the temperature is continued to rise to 50-100°C, such as 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, and the reaction is continued at this temperature for 6-12 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours.

[0045] Furthermore, in the above-mentioned photosensitive resin composition, the resin is a resin having a polybenzoxazole precursor structure and a polybenzoxazole structure as main components, the polybenzoxazole precursor structure is selected from at least one polymer having a structural formula represented by the following formula (9), and the polybenzoxazole structure is selected from at least one polymer having a structural formula represented by the following formula (10):

[0046]

[0047]

[0048] In formula (9) and formula (10), i1 and i2 are each independently selected from integers of 2 to 200, for example, 2, 5, 10, 30, 50, 80, 100, 120, 150, 180, 200, etc.

[0049] In the formula (9) and the formula (10), X1 and X2 are each independently selected from tetravalent organic groups having 4 to 40 carbon atoms.

[0050] Optionally, X1 and X2 are each independently selected from an organic group having 6 or more carbon atoms and containing an aromatic ring;

[0051] Optionally, X1 and X2 are each independently selected from at least one of the structures shown in formula (11), and * represents an insertion site:

[0052]

[0053] In formula (9) and formula (10), Y1 and Y2 are each independently selected from a divalent organic group having 2 to 40 carbon atoms.

[0054] Optionally, Y1 and Y2 are each independently selected from aromatic groups having 6 or more carbon atoms.

[0055] Optionally, Y1 and Y2 are each independently selected from at least one of the structures shown in formula (12), and * represents an insertion site:

[0056]

[0057] Furthermore, the resin of the present invention is selected from resins having a polybenzoxazole precursor structure and a polybenzoxazole structure as main components, and may also contain other resins as required.

[0058] Optionally, among all the structural units of the resin, more than 50 mol% of the structure is a structural unit represented by formula (9) or formula (10), for example, 51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, preferably, it contains more than 70 mol%, and more preferably, it contains more than 90 mol%.

[0059] The polybenzoxazole precursor of the present invention can be obtained by condensing a bisaminophenol compound of any structure with dicarboxylic acid or diacyl chloride by an acyl chloride method or an activated ester method in the presence of a dehydrating agent such as polyphosphoric acid or dicyclohexylcarbodiimide.

[0060] The polybenzoxazole of the present invention can be obtained by chemical or physical dehydration cyclization of any polybenzoxazole precursor.

[0061] Alternatively, representative examples of the bisaminophenol compounds include: 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis(4-amino-3-hydroxyphenyl)propane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 2,2'-bis(3-amino-4-hydroxy-2-trifluoromethyl)propane, 2,2'-bis(4-amino-3-hydroxy-2-trifluoromethyl)propane, 2,2'-bis(3-amino-4-hydroxy-5-trifluoromethyl)propane, 2,2'-bis(4-amino-3-hydroxy-5-trifluoromethyl)propane, 2,2'-bis(3-amino-4-hydroxy-6 2,2'-bis(4-amino-3-hydroxy-6-trifluoromethyl)propane, 2,2'-bis(3-amino-4-hydroxy-2-trifluoromethyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxy-2-trifluoromethyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxy-5-trifluoromethyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxy-5-trifluoromethyl)hexafluoropropane, 2,2'-bis(3-amino-4-hydroxy-6-trifluoromethyl)hexafluoropropane, 2,2'-bis(4-amino-3-hydroxy-2-trifluoromethyl)hexafluoropropane hexafluoropropane, 3,3'-diamino-4,4'-dihydroxy-2,2'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-2,2'-trifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-trifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-6,6'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-6,6'-trifluoromethylbiphenyl, etc.

[0062] Alternatively, the dicarboxylic acid and the dicarboxylic acid chloride include isophthaloyl chloride, terephthaloyl chloride, 4,4'-diphenyl ether dicarboxylic acid chloride, isophthalic acid, terephthalic acid, 4,4'-diphenyl ether dicarboxylic acid, and 4,4'-biphenyl dicarboxylic acid chloride.

[0063] In the present invention, it is desirable to cap the terminal groups from the perspective of improving storage stability. When capping, a derivative including an aliphatic group or a cyclic compound group having at least one alkenyl or alkynyl group can be introduced as an acid derivative or an amine derivative at the end of the polybenzoxazole precursor or polybenzoxazole.

[0064] After the condensation reaction is completed, the by-product of the dehydration condensation agent in the reaction solution is filtered out as needed, and the reaction solution is put into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof to precipitate the polymer. The polymer is purified by repeating the operations of re-dissolving and re-precipitating as needed, and vacuum drying is performed to obtain a precursor. In order to improve the purity of the polymer, the polymer solution can also be passed through a column filled with an anion and / or cation exchange resin soaked in a suitable organic solvent to remove ionic impurities.

[0065] From the perspective of heat resistance and mechanical properties after heat treatment, the weight average molecular weight (Mw) of the above resin is preferably 1000 or more, and more preferably 5000 or more, based on the polystyrene conversion value of gel permeation chromatography (GPC). From the perspective of solubility of the photosensitive resin composition in a developer, the weight average molecular weight of the above resin is preferably 60000 or less, and more preferably 40000 or less. As a developing solvent for gel permeation chromatography, N-methyl-pyrrolidone or tetrahydrofuran is recommended. The molecular weight is obtained by a standard curve made using standard monodisperse polystyrene.

[0066] Optionally, the weight average molecular weight of the resin is 10,000 to 40,000, for example, 10,000, 12,000, 15,000, 18,000, 20,000, 21,000, 22,000, 23,000, 24,000, 25,000, 28,000, 30,000, 32,000, 35,000, 38,000, or 40,000.

[0067] Optionally, the weight average molecular weight of the resin is 15,000 to 30,000.

[0068] Optionally, the weight average molecular weight of the resin is 15,000 to 25,000.

[0069] Optionally, the weight average molecular weight of the resin is 21,000 to 25,000.

[0070] Furthermore, in the above-mentioned photosensitive resin composition, the silane coupling agent includes at least one of a nitrogen-containing heterocyclic silane coupling agent, a urea-based silane coupling agent, a mercapto silane coupling agent, a vinyl silane coupling agent, and an epoxy-based silane coupling agent.

[0071] It can be mentioned that the nitrogen-containing heterocyclic coupling agent can be selected from at least one of the following structural formulas (13-1), (13-2), and (13-3):

[0072]

[0073]

[0074]

[0075] It can be mentioned that the urea-based silane coupling agent can be selected from 3-urea-based propyl triethoxysilane (Nanjing Xuanhao New Material Technology, XH-1160), 3-urea-based propyl trimethoxysilane (Nanjing Dimonte, DMT-116), 1-propyl-1-(triethoxysilyl) methyl urea (Nanjing Xuanhao New Material Technology, XH-712), etc., or at least one of the following structural formulas (14):

[0076]

[0077] The urea-based silane coupling agent of formula (14) can be prepared by referring to patent CN111825884B.

[0078] For example, the epoxy silane coupling agent can be selected from (3-glycidoxypropyl)trimethoxysilane (KH-560), (8-glycidoxyoctyl)trimethoxysilane (Japan Shin-Etsu Chemical, KBM-4803), (3-glycidoxypropyl)trimethoxysilane (Japan Shin-Etsu Chemical, KBM-403), etc.

[0079] It can be mentioned that the mercapto-based silane coupling agent can be selected from 3-(triethoxysilylthio)propyltrimethoxysilane (Japan Shin-Etsu Chemical, X-12-1056ES), 3-(trimethoxysilyl)-1-propanethiol (Momentive High-Tech Materials, A-189), γ-thiopropyltriethoxysilane (Nanjing Xuanhao New Materials Technology, KH-580), etc.;

[0080] For example, the vinyl silane coupling agent may be selected from vinyl triethoxysilane (Nanjing Demonte, KH-151), p-vinyl phenyl trimethoxy silane (Japan Shin-Etsu Chemical, KBM-1403), etc., but is not limited thereto.

[0081] It has been verified by experiments that the silane coupling agent is preferably one or two of a nitrogen-containing heterocyclic silane coupling agent and a mercapto silane coupling agent, and more preferably a nitrogen-containing heterocyclic silane coupling agent and a mercapto silane coupling agent are used in combination. At least one nitrogen-containing heterocyclic silane coupling agent can be selected, and at least one mercapto silane coupling agent can also be selected.

[0082] Furthermore, in the above-mentioned photosensitive resin composition, the photosensitive auxiliary agent is at least one selected from diazoquinone compounds, onium salts, and halogen-containing compounds. From the viewpoint of solvent solubility and storage stability, it is preferably an ester compound obtained by ester-bonding a sulfonic acid of quinone diazide to a polyhydroxy compound, and examples of the polyhydroxy compound include, but are not limited to, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxy-p-cresol, 2,6-diacetoxymethyl-p-cresol, tetrahydroxybenzophenone, and the like. Commercially available quinonediazide compounds are preferred, such as NT-300 (esterification reaction product of 2,3,4-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid), 4NT-350, 4NT-300 (esterification reaction product of 2,3,4,4-tetrahydroxybenzophenone and 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid), tris(4-hydroxyphenyl)ethane (HP-190) and (esterification reaction product of 6-diazo-5,6-dihydroxy-5-oxy-1-naphthalenesulfonic acid) (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan).

[0083] Furthermore, in the above-mentioned photosensitive resin composition, the crosslinking agent includes at least one of DMOM-PTBP-MF, TMOM-BP, HMOM-TPHAP, DML-PC, DMOM-MBPC, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry), and MX-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.); the crosslinking agent can undergo a polymerization reaction or the addition polymerizable compound itself undergoes a polymerization reaction to form a crosslinked network structure. The addition polymerizable compound can further improve the heat resistance and chemical resistance of the cured film formed by the photosensitive resin composition.

[0084] Furthermore, in the above-mentioned photosensitive resin composition, the solvent is selected from at least one of N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.

[0085] Furthermore, the mass ratio of the resin to the nitrogen-containing heterocyclic polysiloxane is 100:0.01 to 10, for example, 100:0.01, 100:0.03, 100:0.05, 100:0.08, 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6,

[0087] Any value among 100:7, 100:8, 100:9, 100:10, or any range between them.

[0088] Optionally, the mass ratio of the resin to the nitrogen-containing heterocyclic polysiloxane is 100:0.1-5.

[0089] Optionally, the mass ratio of the resin to the nitrogen-containing heterocyclic polysiloxane is 100:1-5.

[0090] Furthermore, the mass ratio of the resin to the silane coupling agent is 100:0.1-5, for example, any value among 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5 or any range value between any two of them.

[0091] Optionally, the mass ratio of the resin to the silane coupling agent is 100:1-5.

[0092] Further, the mass ratio of the resin to the photosensitive auxiliary agent is 100:0.1-30, for example, 100:0.1, 100:0.3, 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, 100:21, 100:22, 100:23, 100:24, 100:25, 100:26, 100:27, 100:28,

[0094] Any value among 100:29, 100:30, or any range between them.

[0095] Optionally, the mass ratio of the resin to the photosensitizing agent is 100:0.5-25.

[0096] Optionally, the mass ratio of the resin to the photosensitizing agent is 100:0.5-20.

[0097] Further, the mass ratio of the resin to the cross-linking agent is 100:0.5-30, for example, 100:0.5, 100:0.8, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, 100:21, 100:22, 100:23, 100:24, 100:25, 100:26, 100:27, 100:28, 100:29, 100:30, 100:31 :14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20, 100:21, 100:22, 100:23, 100:24, 100:25, 100:26, 100:27, 100:28, 100:29, 100:30, or any range between them.

[0098] Optionally, the mass ratio of the resin to the cross-linking agent is 100:1-20.

[0099] Further, the mass ratio of the resin to the solvent is 100:80 to 5000, for example, 100:80, 100:100, 100:130, 100:150, 100:180, 100:200, 100:230, 100:250, 100:280, 100:300, 100:330, 100:350, 100:380, 100:4 00, 100:500, 100:600, 100:700, 100:800, 100:900, 100:1000, 100:1500, 100:2000, 100:2500, 100:3000, 100:3500, 100:4000, 100:4500, 100:5000, or any range between them.

[0100] Optionally, the mass ratio of the resin to the solvent is 100:100-1000.

[0101] Optionally, the mass ratio of the resin to the solvent is 100:150-400.

[0102] According to another aspect of the present application, a method for preparing the above-mentioned photosensitive resin composition is provided, comprising at least the following steps:

[0103] The resin, the nitrogen-containing heterocyclic polysiloxane, the silane coupling agent, the photosensitive auxiliary agent, the crosslinking agent and the solvent are mixed to obtain the photosensitive resin composition.

[0104] Optionally, it specifically includes:

[0105] In a three-necked flask equipped with a stirrer, the resin is dissolved in a solvent, a nitrogen-containing heterocyclic polysiloxane and a silane coupling agent are added, stirring is continued until completely dissolved, and then a photosensitive auxiliary agent and a cross-linking agent are added in sequence, stirring is continued until dissolved, and then filter-filtered (using a filter with a pore size of 0.1 μm to 5 μm) to obtain the photosensitive resin composition.

[0106] According to another aspect of the present application, a cured resin film is provided. The cured resin film is obtained by curing the above-mentioned photosensitive resin composition.

[0107] According to another aspect of the present application, a method for preparing the above-mentioned resin cured film is provided, comprising at least the following steps:

[0108] The photosensitive resin composition is applied to a surface of a substrate and heat-treated in an inert gas atmosphere to obtain the resin cured film.

[0109] Specifically, the steps include:

[0110] The photosensitive resin composition is coated on a 4-inch substrate by a coating machine, and then soft-baked at 120°C for 3 minutes using a heating table, and then the prepared resin cured film is placed in a vacuum oxygen-free oven to maintain nitrogen circulation for heat treatment. Specifically, after ensuring that the oxygen content in the oven cavity is reduced to below 50ppm, the temperature is first raised to 170°C and kept constant for 30 minutes, and then the temperature is raised to 350°C after 1 hour, and treated at 350°C for 1 hour to obtain a resin cured film.

[0111] The resin cured film exhibited excellent adhesion to a substrate in a PCT test.

[0112] The substrate includes, but is not limited to, a copper sheet, a copper alloy sheet, a silicon sheet, a ceramic sheet, a titanium sheet, a glass sheet, an ITO glass, etc. As the coating method, there can be cited: a spray coating method, a spin coating method, a doctor blade method and the like. The coating film thickness will also be different due to the different coating methods, rotation speeds, viscosities, composition components, etc. In the present invention, a 4-inch copper sheet is preferably used as the substrate of the coating film, and the coating is preferably carried out by spin coating, and the thickness of the cured film on the copper sheet is controlled to be 10 to 20 μm.

[0113] Subsequently, the substrate coated with the photosensitive resin composition is heat-treated to obtain a resin cured film. The heat treatment method is usually an oven, a heating table, an infrared lamp, etc. Preferably, a heating table is used, preferably drying is performed at a temperature of 50 to 150° C. for 1 minute to 1 hour, and the thickness of the cured film is measured after natural cooling to 25° C. Preferably, the temperature is 100 to 130° C. and the time is 2 to 5 minutes for drying.

[0114] According to another aspect of the present application, there is provided use of the photosensitive resin composition or the cured resin film as a semiconductor interlayer insulating film, a semiconductor protective film, or an etching protective film.

[0115] According to another aspect of the present application, a semiconductor device is provided, comprising the above-mentioned cured resin film.

[0116] According to another aspect of the present application, a method for preparing the semiconductor device is provided, comprising at least the following steps:

[0117] The photosensitive resin composition is coated on the surface of a substrate, and a resin cured film is obtained after treatment. The resin cured film is exposed, developed, and heat-treated to obtain the semiconductor device.

[0118] Specifically, the steps include:

[0119] (1) coating a photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate;

[0120] (2) exposing the photosensitive resin layer;

[0121] (3) developing the exposed photosensitive resin layer to form a relief pattern;

[0122] (4) The relief pattern is subjected to a heat treatment to form a solidified relief pattern, thereby obtaining the semiconductor device.

[0123] Wherein, the substrate includes silicon, copper, copper alloy, titanium, titanium alloy, and aluminum.

[0124] The method for preparing the photosensitive resin layer in step (1) is the same as the method for preparing the above-mentioned resin cured film.

[0125] The exposure treatment is to expose the above-mentioned resin cured film to ultraviolet rays, X-rays, electron beams, etc. through a photomask or mask with a pattern or directly to a mask having a desired pattern on the above-formed resin film. Common active rays include ultraviolet rays, X-rays, electron beams, etc. In the present invention, a mercury lamp is preferably used, which includes i-line (365nm), h-line (405nm), and g-line (436nm).

[0126] In order to improve the sensitivity, etc., a post-exposure bake and / or a pre-development bake based on any combination of temperature and time may be performed as required. The baking conditions are a temperature of 40 to 120° C. and a time of 10 to 240 seconds, and are not limited to this range as long as the properties of the photosensitive resin composition of the present invention are not affected.

[0127] After exposure, a pattern is formed by removing the unexposed portion using a developer. Common developers include: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, isopropanol, ethyl lactate, butyl acetate, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, isobutyl ketone, tetramethylammonium hydroxide aqueous solution, etc. After development, it is preferably rinsed with deionized water, ethanol, isopropanol, ethyl lactate, propylene glycol monomethyl ether acetate, etc. For example, a developer and a rinse solution are poured into two glass culture dishes respectively. The developer temperature is controlled to be 25±1°C, the exposed resin film is immersed in the developer, and the timing is started immediately. After the unexposed part is completely exposed to the substrate, the development is completed, the timing is stopped, and the time required for the whole process is recorded.

[0128] Finally, the resin pattern obtained after development is thermally imidized at 200-500°C to convert it into a cured film. This heat treatment usually selects staged temperature increase and maintains a certain time at different temperatures or selects a certain temperature range for continuous temperature increase. For example, a heat treatment method is performed at 180°C, 240°C, and 350°C for 30 minutes respectively, or a method of linearly increasing the temperature from 25°C to 400°C over 2 hours.

[0129] The cured relief pattern can be used as a surface protection film, an interlayer insulating film, an insulating film for redistribution, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure.

[0130] The beneficial effects of this application include:

[0131] The photosensitive resin composition provided in the present application introduces a nitrogen-containing heterocyclic polysiloxane into the photosensitive resin composition, so that the resin cured film made from the photosensitive resin composition has excellent dielectric properties and excellent adhesion to the substrate. The cured film formed by the photosensitive resin composition can be used for semiconductor interlayer insulation films, semiconductor protective films, and protective films for etching, and has broad application prospects in semiconductor-related fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0132] Figure 1 These are the infrared spectra of polysiloxanes PS-11, PS-17, PS-19, and PS-20. DETAILED DESCRIPTION

[0133] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0134] Several specific synthesis examples and embodiments are given below to illustrate the present invention, which will help those skilled in the art to more fully understand the present invention, but the present invention is not limited to these examples. It should be noted that the evaluation of the products prepared in the following synthesis examples and embodiments is carried out according to the following method.

[0135] (1) Infrared spectrum test

[0136] The synthesized polysiloxane sample was tested by a KBr pellet method using an infrared spectrometer (Shimadzu, IRAffinity-1S) to detect whether the polysiloxane of the present invention was successfully prepared.

[0137] (2) Molecular weight test

[0138] The weight average molecular weight (Mw) of the resin was determined by gel permeation chromatography (standard polystyrene conversion). The gel permeation chromatograph used in the determination was LC-20AD of Shimadzu Corporation of Japan, the chromatographic column was KF-804 of Showa Denko, the detector was RID-20A of Shimadzu Corporation of Japan, and the mobile phase was N-methylpyrrolidone (NMP).

[0139] (3) Viscosity test

[0140] 0.5 mL of the resin composition sample was taken and placed in the sample cell of a rotational viscometer (BROOKFIELD DV2T RV), and a suitable measuring range was selected and the temperature was controlled at 25±0.1° C. to perform a viscosity test.

[0141] (4) Peel test of adhesion between cured film and different substrates

[0142] The resin composition samples were evenly coated on silicon wafers and aluminum wafers using a coating machine, and then placed on a heating table at 120°C for 3 minutes for soft baking to obtain a resin film with a film thickness of 10 to 20 μm. The resin film was scored into 10 rows × 10 columns of squares using a grid marker (BYK-Gardner A-5125), and then the film was placed in a vacuum oxygen-free oven (MOLZK-32D1) for heat treatment: heat treatment at 170°C for 30 minutes, then the temperature was raised to 350°C after 1 hour, and treated at 350°C for 1 hour to finally obtain a cured film. The cured film was placed in a PCT test chamber for a 400-hour PCT aging test (121°C, 2 atmospheres of saturated steam; PCT-30 of Dongguan Hongjin Technology). After the PCT test was completed, a peeling test was performed using tape (special transparent 3M tape) in accordance with the national standard GB / T 9286-1998 for the cross-cutting test of paint and varnish films. The number of cross-cuttings peeled off was recorded as the peeling condition after the PCT test.

[0143] In the adhesive peeling test, the number of peeled pieces was considered "best" when it was less than 5, "good" when it was less than 10, "slightly good" when it was less than 30, and "poor" when it was 30 or more.

[0144] (5) Dielectric constant

[0145] Referring to the national standard GB / T 31838.6-2021 dielectric and resistance properties of solid insulating materials, the dielectric constant was measured at 25°C using a DMS2000 high and low temperature dielectric resistance thermometer, and the value at a frequency of 1 MHz was recorded.

[0146] The abbreviations of ingredients used in this application are as follows:

[0147] NMP: N-methylpyrrolidone

[0148] MIBK: Methyl isobutyl ketone

[0149] ODPA: 4,4-oxydiphthalic anhydride

[0150]

[0151] BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane silane coupling agent SCA:

[0152] SCA-1:

[0153]

[0154] SCA-2:

[0155]

[0156] SCA-3:

[0157]

[0158] SCA-4:

[0159]

[0160] SCA-5:

[0161]

[0162] SCA-6:

[0163]

[0164] SCA-7:

[0165]

[0166] SCA-8:

[0167]

[0168] SCA-9:

[0169]

[0170] SCA-10:

[0171]

[0172] SCA-11:

[0173]

[0174] SCA-12:

[0175]

[0176] SCA-13:

[0177]

[0178] SCA-14:

[0179]

[0180] SCA-15:

[0181]

[0182] SCA-16:

[0183]

[0184] SCA-17:

[0185]

[0186] SCA-18:

[0187]

[0188] SCA-19:

[0189]

[0190] SCA-20:

[0191]

[0192] SCA-21:

[0193]

[0194] Preparation of silane coupling agent SCA-1~SCA-21:

[0195] Preparation of SCA-1:

[0196] To a 500 mL three-necked flask equipped with a stirrer and a thermometer, 250.00 g of solvent N-methylpyrrolidone and 0.1 mol of 4-aminotriazole were added in sequence, and stirring was started. After 4-aminotriazole was fully dissolved, 0.1 mol of silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride was slowly added. After the addition was completed, the reaction was continued at 25° C. for 20 hours. After the reaction was completed, the reaction was purified by vacuum distillation to obtain SCA-1.

[0197] Preparation of SCA-2:

[0198] To a 500 mL three-necked flask equipped with a stirrer and a thermometer, 250.00 g of solvent N-methylpyrrolidone and 0.1 mol of 4-aminotriazole were added in sequence, and stirring was started. After 4-aminotriazole was fully dissolved, 0.1 mol of silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride was slowly added. After the addition was completed, the reaction was continued at 25° C. for 20 hours. Then, 0.2 mol of pyridine was added to the reaction system. After stirring evenly, 0.2 mol of acetic anhydride was slowly added. The reaction was carried out at 25° C. for 20 hours. After the reaction was completed, the solvent, acetic anhydride, and the generated acetic acid and pyridine in the system were removed by reduced pressure distillation to obtain SCA-2.

[0199] Preparation of SCA-3:

[0200] The same as SCA-1 except that 0.1 mol of 3-(trimethoxysilyl)propyl succinic anhydride was replaced by 0.1 mol of silane coupling agent SANAH (Shin-Etsu Chemical Co., Ltd.).

[0201] Preparation of SCA-4:

[0202] The preparation method is the same as SCA-2 except that 0.1 mol of 3-(trimethoxysilyl)propyl succinic anhydride is replaced by 0.1 mol of silane coupling agent SANAH.

[0203] Preparation of SCA-5:

[0204] The preparation method is the same as SCA-1 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 3-amino-1,2,4-triazole.

[0205] Preparation of SCA-6:

[0206] The preparation method is the same as SCA-1 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 5-amino-1H-1,2,4-triazole-3-carboxylic acid.

[0207] Preparation of SCA-7:

[0208] The preparation method is the same as SCA-1 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 5-aminotetrazolyl.

[0209] Preparation of SCA-8:

[0210] The preparation method is the same as SCA-2 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 5-aminotetrazolyl.

[0211] Preparation of SCA-9:

[0212] The preparation method is the same as SCA-3 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 5-aminotetrazolyl.

[0213] Preparation of SCA-10:

[0214] The same as SCA-4 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 5-aminotetrazolyl.

[0215] Preparation of SCA-11:

[0216] The same method as SCA-1 was used except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 1-methyl-5-aminotetrazolyl.

[0217] Preparation of SCA-12:

[0218] The reaction was the same as SCA-1 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 2-aminoimidazole.

[0219] Preparation of SCA-13:

[0220] The preparation method is the same as SCA-3 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 2-aminoimidazole.

[0221] Preparation of SCA-14:

[0222] The reaction was the same as SCA-1 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 2-aminooxazole.

[0223] Preparation of SCA-15:

[0224] The reaction was the same as SCA-3 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 2-aminooxazole.

[0225] Preparation of SCA-16:

[0226] To a 500 mL three-necked flask equipped with a stirrer and a thermometer, 250.00 g of solvent N-methylpyrrolidone and 0.1 mol of 2-aminoimidazole were added in sequence, and stirring was started. After the 2-aminoimidazole was fully dissolved, 0.1 mol of silane coupling agent SANAH was slowly added. After the addition was completed, the reaction was continued at 25° C. for 20 hours, and then 0.2 mol of N,N-dimethylformamide dimethyl acetal was added to the system, and the reaction was continued at 25° C. for 4 hours. After the reaction was completed, it was distilled under reduced pressure to obtain SCA-16.

[0227] Preparation of SCA-17:

[0228] The same as SCA-16 except that 0.1 mol 2-aminoimidazole was replaced by 0.1 mol 2-aminooxazole.

[0229] Preparation of SCA-18:

[0230] The reaction mixture was the same as that of SCA-1 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 3-aminophenol.

[0231] Preparation of SCA-19:

[0232] The process is the same as SCA-1 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of p-aminobenzoic acid.

[0233] Preparation of SCA-20:

[0234] SCA-20 was prepared according to the method of Example 3 in patent ZL202111145299.6.

[0235] Preparation of SCA-21:

[0236] SCA-21 was prepared according to the method of Example 2 in patent ZL202111145299.6.

[0237] The silane coupling agent was characterized by hydrogen nuclear magnetic resonance spectroscopy. Some hydrogen spectrum information is as follows:

[0238]

[0239]

[0240] Synthesis example 1

[0241] Under nitrogen protection, 100 g of methyl isobutyl ketone (MIBK), 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1, and 0.5 g of p-toluenesulfonic acid were added to a 250 ml three-necked flask, and the mixture was stirred and mixed evenly, and the system temperature was maintained at 10° C. (reaction temperature 1) to obtain a mixed solution; 150 g of deionized water was dropped into the above mixed solution within 4 hours. After the addition was completed, the mixture was kept at 10° C. for 4 hours, and then the temperature was raised to 70° C. (reaction temperature 2) and the reaction was continued for 10 hours; after the reaction was completed, the organic layer was taken out, and the volatiles were evaporated off using a rotary evaporator to obtain polysiloxane PS-1.

[0242] Synthesis example 2-23

[0243] The synthesis of polysiloxanes PS-2 to PS-23 was carried out by referring to the steps of Synthesis Example 1, except that the reaction conditions used were selected according to Table 1 below.

[0244] Table 1

[0245]

[0246]

[0247] The synthesized polysiloxane sample was tested by the KBr pellet method using an infrared spectrometer (Shimadzu, IRAffinity-1S) to detect whether the polysiloxane of the present invention was successfully prepared. From the infrared characterization results, it can be seen that the 1035-1160cm -1 The Si-O-Si stretching vibration peak appears, indicating that the alkoxy group has been successfully converted into a Si-O-Si structure by hydrolysis. Among them, the infrared spectra of PS-11, PS-17, PS-19, and PS-20 are as follows: Figure 1 shown.

[0248] Comparative Synthesis Example 1

[0249] Polysiloxane PS-24 was prepared according to the method of Synthesis Example 1, except that 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 was replaced with 20 g of silane coupling agent monomer SCA-18.

[0250] Comparative Synthesis Example 2

[0251] Polysiloxane PS-25 was prepared according to the method of Synthesis Example 1, except that 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 was replaced with 20 g of silane coupling agent monomer SCA-19.

[0252] Synthesis example 24

[0253] Synthesis of polybenzoxazole precursor C-1:

[0254] Under nitrogen flow, add 36.63g (0.10mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 100.00g of N-methylpyrrolidone (NMP) and 52.87g (0.6mol) of glycidyl methyl ether into a 500ml three-necked flask. After fully dissolved, cool the solution to -15°C. Add 29.51g (0.10mol) of 4,4'-diphenyl ether diformyl chloride dissolved in 50.00g of N-methylpyrrolidone to the flask, and control the reaction material below 0°C during the addition. After the addition is completed, continue stirring the reaction at -10 to -15°C for 6 hours, and the reaction is completed. Pour the reaction solution into 3L of 10wt% methanol aqueous solution, and the polymer is precipitated to obtain a white precipitate. After filtering, the mixture was washed with deionized water three times, placed in a vacuum oven, and dried at 50°C for 72 hours to obtain polybenzoxazole precursor resin C-1. The molecular weight of the polymer powder was measured by gel permeation chromatography (standard polystyrene conversion), and the result showed that the weight average molecular weight (Mw) was 21,000 to 25,000.

[0255] Synthesis example 25

[0256] Synthesis of polybenzoxazole precursor C-2:

[0257] Under nitrogen flow, add 36.63g (0.10mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 100.00g of N-methylpyrrolidone (NMP) and 52.87g (0.6mol) of glycidyl methyl ether into a 500ml three-necked flask. After fully dissolved, cool the solution to -15°C. Add 27.91g (0.10mol) of 4,4'-biphenyl dicarboxylic acid chloride dissolved in 50.00g of N-methylpyrrolidone to the flask, and control the reaction material below 0°C during the addition. After the addition is completed, continue stirring the reaction at -10 to -15°C for 6 hours, and the reaction is completed. Pour the reaction solution into 3L of 10wt% methanol aqueous solution, and the polymer is precipitated to obtain a white precipitate. After filtering, the mixture was washed with deionized water three times, placed in a vacuum oven, and dried at 50°C for 72 hours to obtain polybenzoxazole precursor resin C-2. The molecular weight of the polymer powder was measured by gel permeation chromatography (standard polystyrene conversion), and the result showed that the weight average molecular weight (Mw) was 21,000 to 25,000.

[0258] Synthesis Example 26

[0259] Synthesis of polybenzoxazole C-3:

[0260] Under nitrogen flow, 40 g of polybenzoxazole precursor C-1 was placed in a 500 mL three-necked flask, and 100.00 g of NMP was added. The mixture was stirred to dissolve at room temperature. Then, 22.46 g (0.22 mol) of acetic anhydride and 17.40 g (0.22 mol) of pyridine were added and reacted at 30°C for 2 h.

[0261] The obtained reaction solution was added into 5L of deionized water to precipitate a polymer, and the obtained precipitate was filtered out, washed three times with deionized water, and vacuum dried at 50°C for 72 hours to obtain a polymer powder, i.e., polybenzoxazole C-3. The molecular weight of the polymer powder was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 21,000 to 25,000.

[0262] Examples and Comparative Examples

[0263] In a three-necked flask equipped with a stirrer, 25.00 g of the synthesized polybenzoxazole resin was dissolved in 60.00 g of N-methylpyrrolidone (NMP). After the resin was completely dissolved, polysiloxane and silane coupling agent were added according to the ratio in Table 2, and stirring was continued until completely dissolved. Then, 4 g of photosensitive auxiliary agent quinone diazide compound NT-300 (manufactured by Toyo Gosei Kogyo Co., Ltd., Japan) and 2.00 g of thermal crosslinking agent TMOM-BP (manufactured by Honshu Chemical Industry) were added in sequence. After sufficient dissolution, filter pressure was performed using a 1.0 μm filter membrane to obtain photosensitive resin compositions P-1 to P-41, and the viscosity measured at 25°C was 1800 to 2200 cP.

[0264] Table 2

[0265]

[0266]

[0267]

[0268] The photosensitive resin composition prepared above was evaluated according to the test method described above. The results are shown in Table 3.

[0269] Table 3

[0270]

[0271]

[0272] From the above table we can see that:

[0273] From the experimental results of Example 1, Examples 11 to 33, Comparative Example 5 and Comparative Example 8, it can be seen that the polybenzoxazole photosensitive resin composition to which the nitrogen-containing heterocyclic polysiloxane compound of the present invention is added exhibits better dielectric properties than that without the addition, and also has a significant improvement effect on the adhesion on silicon and aluminum substrates.

[0274] It can be seen from the experimental results of Example 1 and Comparative Examples 1-2 that the photosensitive composition containing the nitrogen-containing heterocyclic polysiloxane compound of the present invention has a more obvious effect on improving adhesion and dielectric properties than the photosensitive composition containing the non-nitrogen-containing heterocyclic polysiloxane compound.

[0275] It can be seen from the experimental results of Examples 1 and 4 to 8 that in terms of the effect of improving the adhesion to the substrate, the nitrogen-containing heterocyclic polysiloxane compound, the nitrogen-containing heterocyclic silane coupling agent, and the mercapto silane coupling agent perform best when used in combination.

[0276] From the experimental results of Example 1 and Examples 16 to 33, it can be seen that different types of nitrogen-containing heterocyclic polysiloxane compounds have slightly different effects on improving adhesion and dielectric properties, among which oxazoles and imidazoles perform better, and a mixture of two different types of nitrogen-containing heterocyclic polysiloxane compounds performs best.

[0277] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A photosensitive resin composition, characterized in that Including resin, nitrogen-containing heterocyclic polysiloxane, silane coupling agent, photosensitive auxiliary agent, crosslinking agent and solvent; The nitrogen-containing heterocyclic polysiloxane is selected from at least one of the structural formulas shown in the following formula (1): Wherein, Y is an organic group containing a nitrogen heterocyclic ring.

2. The photosensitive resin composition according to claim 1, characterized in that In formula (1), Y is selected from at least one of the structures shown in formulas (2) to (5), and * represents an insertion site: Wherein, R1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms; wherein W is selected from at least one of the following structures of formula (6), and * represents an insertion site: Here, R2, R3, R4, R5, R6, R7, R8, and R9 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, or an ester group.

3. The photosensitive resin composition according to claim 2, characterized in that: R1 is selected from a hydrogen atom, a methyl group, an ethyl group, a butyl group, and a hydroxyethyl group of methacrylate; R2, R3, R4, R5, R6, R7, R8, and R9 independently represent a hydrogen atom, a methyl group, an ethyl group, and a carboxyl group.

4. The photosensitive resin composition according to claim 1, characterized in that The resin is selected from a resin having a polybenzoxazole precursor structure and a polybenzoxazole structure as a main component, the polybenzoxazole precursor structure is selected from at least one polymer having a structural formula represented by the following formula (9), and the polybenzoxazole structure is selected from at least one polymer having a structural formula represented by the following formula (10); Wherein, i1 and i2 are each independently selected from integers of 2 to 200; X1 and X2 are each independently selected from a tetravalent organic group having 4 to 40 carbon atoms; Y1 and Y2 are each independently selected from a divalent organic group having 2 to 40 carbon atoms; Preferably, the sum of the polybenzoxazole precursor structure and the polybenzoxazole structure accounts for more than 50 mol % of the entire resin structure, more preferably more than 70 mol %, and even more preferably more than 90 mol %; Preferably, the weight average molecular weight of the resin is 10,000 to 40,000, preferably 15,000 to 30,000, more preferably 15,000 to 25,000, and even more preferably 21,000 to 25,000.

5. The photosensitive resin composition according to claim 4, characterized in that: X1 and X2 are each independently selected from at least one of the structures shown in formula (11), and * represents an insertion site: Y1 and Y2 are each independently selected from at least one of the structures shown in formula (12), and * represents an insertion site:

6. The photosensitive resin composition according to claim 1, characterized in that: The silane coupling agent is selected from at least one of a nitrogen-containing heterocyclic silane coupling agent, a urea-based silane coupling agent, a mercapto silane coupling agent, a vinyl silane coupling agent, and an epoxy-based silane coupling agent, and is preferably a combination of a nitrogen-containing heterocyclic silane coupling agent and a urea-based silane coupling agent; The photosensitizer is selected from at least one of diazoquinone compounds, onium salts, and halogen-containing compounds; The cross-linking agent is selected from at least one of DMOM-PTBP-MF, TMOM-BP, HMOM-TPHAP, DML-PC, DMOM-MBPC, HMOM-TPHAP, and MX-100LM; The solvent is selected from at least one of N-methylpyrrolidone, γ-butyrolactone, tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.

7. The photosensitive resin composition according to claim 4, characterized in that: The mass ratio of the resin to the nitrogen-containing heterocyclic polysiloxane is 100:0.01-10, preferably 100:0.1-5, more preferably 100:1-5; The mass ratio of the resin to the silane coupling agent is 100:0.1-5, preferably 100:1-5; The mass ratio of the resin to the photosensitive auxiliary agent is 100:0.1-30, preferably 100:0.5-25, more preferably 100:0.5-20; The mass ratio of the resin to the cross-linking agent is 100:0.5-30, preferably 100:1-20; The mass ratio of the resin to the solvent is 100:80-5000, preferably 100:100-1000, and more preferably 100:150-400.

8. A cured resin film, characterized in that: The method is obtained by curing the photosensitive resin composition according to any one of claims 1 to 7.

9. A semiconductor device, characterized in that: The cured resin film according to claim 8 is included.

10. Use of the cured resin film according to claim 8 as a semiconductor interlayer insulating film, a semiconductor protective film, or an etching protective film.

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