A positive photosensitive resin composition and its preparation method and application

Abstract

The present invention discloses a low-temperature curable positive photosensitive resin composition and its preparation method and application, belonging to the field of polymer material technology. The low-temperature curable positive photosensitive resin composition includes the following components by mass: 100 parts of phenolic hydroxyl polyamide resin; 3 to 40 parts of photoacid generator; 1 to 20 parts of reactive benzocyclobutene compound; 0.1 to 30 parts of thermal acid generator; 3 to 40 parts of cross-linking agent; 0.1 to 40 parts of adhesion promoter; 100 to 1000 parts of organic solvent; the reactive benzocyclobutene compound is a bisbenzocyclobutene compound with a specific imide structure or a bisbenzocyclobutene compound containing a saturated alkane and an unsaturated hydrocarbon structure. The resin composition solution of the present invention has excellent positive ultraviolet lithography process performance, can be cured at a temperature of 250°C or below, and the formed cured resin film has the characteristics of low dielectric constant, low dielectric loss, excellent heat resistance, low water absorption, high toughness, high adhesion and excellent photosensitivity, and is suitable for the use requirements of high-frequency and high-speed signal transmission circuits.

Description

Technical Field

[0001] The invention relates to a positive photosensitive resin composition and a preparation method and application thereof, belonging to the technical field of polymer materials. Background Art

[0002] Photosensitive polyimide / polybenzoxazole resin solution has excellent photolithography processability, and the cured resin has the advantages of high heat resistance, high electrical insulation, high strength and toughness. It is widely used in chip surface passivation and interlayer insulation of multi-layer metal interconnect structures in the semiconductor manufacturing process, multi-layer wiring and bump / micro-solder ball manufacturing processes of advanced electronic packaging (BGA, CSP, SiP, etc.) substrates, stress buffer inner coating protective layer films for plastic-encapsulated circuits, and multi-layer wiring processes for optoelectronic display devices.

[0003] With the rapid development of microelectronics manufacturing and packaging technology, the functionality of electronic devices continues to increase, while their size and dimensions continue to shrink. To maintain information transmission rates, reduce interference and inductive coupling between signals, and lower energy consumption and signal distortion during modulation, photosensitive polyimide / polybenzoxazole resin interlayer insulating films are required to have lower dielectric constants and dielectric losses. However, currently commonly used photosensitive polyimide / polybenzoxazole resins, due to the presence of numerous polar groups (such as ester groups and phenolic hydroxyl groups) in the resin backbone structure, result in a high dielectric constant, large dissipation factor, high moisture absorption, and poor reliability in the cured interlayer insulating films, making it difficult to meet the low dielectric performance requirements for high-frequency signal transmission.

[0004] To reduce the dielectric constant and dielectric loss of photosensitive polyimide / polybenzoxazole resins, various photosensitive fluorinated polyimide / polybenzoxazole resins have been prepared by introducing fluorinated groups into the resin backbone structure. Typically, patterns formed with these photosensitive resins require high-temperature curing at temperatures of 320°C or above. In advanced electronic packaging technologies, due to the low heat resistance of packaging materials, the resin curing temperature must not exceed 250°C.

[0005] Fengxi Zhidian et al. (CN 103502889A) and Songchuan Daisaku et al. (CN 108604059A) reported that adding a cross-linking agent containing methoxy and hydroxymethyl groups to a photosensitive polybenzoxazole resin can achieve low-temperature curing of the resin at 250°C or below. However, due to the addition of a large amount of nitrogen-containing and oxygen-containing cross-linking agents, the dielectric properties of the cured resin film were significantly reduced. Yang Jun et al. (CN 102520584A) provided a photosensitive benzocyclobutene resin with excellent photolithography processability and high heat resistance of the cured film; however, the photosensitive PS-BCB resin film has poor film-forming properties, a brittle texture, and a low elongation at break, which seriously limits the practical application of this type of material. Summary of the Invention

[0006] The present invention aims to provide a low-dielectric-loss, low-temperature-curing positive photosensitive resin composition. A solution of the positive photosensitive resin composition can form a positive photolithographic pattern after coating, exposure, and development. The cured resin film formed by curing the photolithographic pattern at 250° C. has the characteristics of low dielectric constant, low dielectric loss, high heat resistance, low water absorption, high toughness, and high adhesion, and is suitable for use in high-frequency and high-speed signal transmission circuits.

[0007] The positive photosensitive resin composition provided by the present invention comprises the following components in parts by weight:

[0008] 100 parts of phenolic hydroxyl-containing polyamide resin; 3-40 parts of photoacid generator; 1-20 parts of reactive benzocyclobutene compound; 0.1-30 parts of thermal acid generator; 3-40 parts of crosslinking agent; 0.1-40 parts of adhesion promoter; 100-1000 parts of organic solvent;

[0009] The reactive benzocyclobutene compound is a bisbenzocyclobutene compound having a specific imide structure or a bisbenzocyclobutene compound containing a saturated alkane and an unsaturated hydrocarbon structure.

[0010] The positive photosensitive resin composition has a viscosity of 500 to 5000 mPa.s and a solid content of 15 to 45%.

[0011] The structural formula of the bisbenzocyclobutene compound having a specific imide structure is as follows:

[0012]

[0013] The structural formula of the dibenzocyclobutene compound containing saturated alkane and unsaturated hydrocarbon structures is shown below:

[0014]

[0015] The reactive benzocyclobutene compound can undergo ring opening at 200-250°C to generate an o-dimethylquinone intermediate with high reactivity, which can undergo Diels-Alder reaction with the active double bond or triple bond at the end of the resin, or react with each other to form a cross-linked resin with a network structure. Wherein, the bisbenzocyclobutene compound containing an imide group improves the heat stability of the resin by introducing a rigid imide bond into the molecule, and preferably contains a fluorine-containing group (-CF3) with low atomic polarizability in the molecular structure or a large-volume benzene side group that can increase the free volume between molecules, which can reduce the dielectric constant, dielectric loss and water absorption of the resin; the bisbenzocyclobutene compound containing a saturated alkane and an unsaturated hydrocarbon structure is a full hydrocarbon chemical structure and does not contain polar groups, so the formed resin has excellent dielectric properties and good hydrophobicity.

[0016] In the positive photosensitive resin composition, the phenolic hydroxyl group-containing polyamide resin is a condensation product of component 1 and component 2, and has a GPC weight-average molecular weight of 10,000 to 60,000;

[0017] The component 1 is a mixture of aromatic diacyl chloride or its derivatives and aliphatic diacyl chloride or its derivatives, wherein the molar content of the aromatic diacyl chloride or its derivatives is 20 to 100%;

[0018] The component 2 is a mixture of a phenolic hydroxyl-containing aromatic diamine and an aliphatic diamine, wherein the molar content of the phenolic hydroxyl-containing aromatic diamine is 80 to 100%;

[0019] The aromatic dicarboxylic acid chloride or its derivative is selected from at least one of diphenyl ether dicarboxylic acid chloride, isophthalic acid dichloride, terephthalic acid dichloride, biphenyl dicarboxylic acid chloride, diphenyl sulfone dicarboxylic acid chloride, diphenylmethane dicarboxylic acid chloride and benzophenone dicarboxylic acid chloride;

[0020] The aliphatic diacyl chloride or its derivative is selected from at least one of octanedicarboxylic acid chloride, adipic acid chloride, nonanedicarboxylic acid chloride, decanedicarboxylic acid chloride, dodecanedicarboxylic acid chloride, 1,4-cyclohexanedicarboxylic acid chloride and 1,3-cyclobutanedicarboxylic acid chloride;

[0021] The phenolic hydroxyl aromatic diamine is selected from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-di At least one of amino-3,3'-dihydroxydiphenyl ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxybenzophenone, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene;

[0022] The aliphatic diamine is at least one selected from 1,4-butanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, dodecanediamine, 1,4-cyclohexanediamine, 1,3-cyclobutanediamine, 2,2'-(ethylenedioxy)bis(ethylamine) and diethylene glycol di(3-aminopropyl) ether.

[0023] The polycondensation reaction of the component 1 and the component 2 is carried out in the following organic solvent:

[0024] N'N-dimethylformamide, N'N-dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethyl urea, phenol, m-cresol, methyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, ethyl acetate at least one of ester, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate;

[0025] The molecular weight regulator used in the polycondensation reaction of the component 1 and the component 2 is at least one of maleic anhydride, nadic anhydride, methylnadic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-vinylaniline, norbornenamine, allylamine, 4-ethynylaniline, 3-ethynylaniline, 3-phenylethynylaniline, 4-phenylethynylaniline, 4-(4-aminophenylethynyl)phenylacetylene, 4-[(trimethylsilyl)-ethynyl]aniline, 4-(4-amino-phenyl)-2-methyl-but-3-yn-2-ol, (E)-3-aminocinnamic acid and propargylamine;

[0026] The polycondensation reaction further comprises the following steps:

[0027] The reaction product is precipitated in a poor solvent to obtain a solid resin, which is then dried.

[0028] In the above-mentioned positive photosensitive resin composition, the photoacid generator may be at least one of a diazonaphthoquinone compound, an iodonium salt compound, and a sulfonium salt compound;

[0029] The naphthoquinone diazide compound is any one of the following 1)-3):

[0030] 1) Compounds produced by esterification of naphthoquinone diazides and polyhydroxy compounds;

[0031] 2) Compounds produced by sulfonylation of diazonaphthoquinone sulfonic acids with polyamine compounds;

[0032] 3) Compounds produced by esterification and / or sulfonylation of diazonaphthoquinone sulfonic acids with polyhydroxy polyamine compounds;

[0033] Wherein, the ratio of the polyhydroxy polyamine compound substituted by the diazonaphthoquinone sulfonic acid is 50% to 95%;

[0034] The naphthoquinone diazide compounds include 1,2-naphthoquinone diazide-5-sulfonyl compounds and 1,2-naphthoquinone diazide-4-sulfonyl compounds. The polyols include Bis-Z, BisP-EZ, BisP-AP, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35X L, TML-BP, TML-HQ, TML-PP-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (these are trade names, available from Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, Any one of 46DMOEP, TM-BIP-A (these are trade names, products of Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, pyrogallol acetone resin, m-cresol resin, and phenolic resin;

[0035] The iodonium salt compounds include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nitrate, [4-(trifluoromethyl)phenyl](2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, [3-(trifluoromethyl)phenyl](2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, iodonium trifluoromethanesulfonate, [(4-trifluoromethyl)phenyl](2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, phenyl(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, phenyl[3-(trifluoromethyl)phenyl]iodonium trifluoromethanesulfonate, (4-nitrophenyl)(phenyl)iodonium trifluoromethanesulfonate, (4-tolyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, (3-tolyl) (2,4,6-Trimethylphenyl)iodonium trifluoromethanesulfonate, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, diphenyliodonium hexafluorophosphate, Diphenyliodonium hexafluoroarsenate, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, (3-bromophenyl)(mesityl)iodonium trifluoromethanesulfonate, [4-(bromomethyl)phenyl](2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, bis(2,4,6-trimethylpyridinium)iodonium hexafluorophosphate, 4,4'-ditolyliodonium hexafluorophosphate, and mixtures thereof in any proportion;

[0036] The sulfonium salt compounds include 1,3-benzodithiopyrrole tetrafluoroboron salt, cyclopropyldiphenylsulfonium tetrafluoroborate, dimethyl (methylthio) sulfonium tetrafluoroborate, diphenyl (methyl) sulfonium tetrafluoroborate, (difluoromethyl) bis (2,5-dimethylphenyl) sulfonium tetrafluoroborate, 2-[4-(3-ethoxy-2-hydroxypropoxy)phenylcarbamoyl] ethyl dimethylthio toluenesulfonate, 4-hydroxyphenyldimethylsulfonium methanesulfonate, triphenylsulfonium tetrafluoroborate, tri (4-tolyl) sulfonium hexafluorophosphate, tri (4-tolyl) sulfonium trifluoromethanesulfonate, triethylsulfonium bis (trifluoromethylsulfonyl) imide and mixtures thereof in any proportion.

[0037] In the positive photosensitive resin composition, the thermal acid generator refers to a compound that can generate a strong acid when heated. It can promote the cyclization reaction of the phenolic hydroxyl polyamide resin at a lower temperature and promote the curing reaction between the phenolic hydroxyl polyamide resin and the crosslinking agent. The thermal acid generator preferably has a thermal decomposition starting temperature of 150°C to 250°C, such as pyridinium salts of alkylsulfonic acid, perfluoroalkylsulfonic acid or alkylsulfonic acid, alkylpyridinium salts, diaryliodonium salts, di(alkylaryl)iodonium salts, trialkylsulfonium salts, dialkylmonoarylsulfonium salts or diarylmonoalkyliodonium salts or ester compounds, including pyridinium p-toluenesulfonate, pyridinium 2,4,6-trimethylbenzenesulfonate, di(tert-butylphenyl)iodonium p-toluenesulfonate, trimethylsulfonium trifluorobenzenesulfonate, diphenylmethylsulfonium trifluoromethanesulfonate, 2-methoxyethyl p-toluenesulfonate, and mixtures thereof in any proportion.

[0038] In the above-mentioned positive photosensitive resin composition, the crosslinking agent refers to a compound that can undergo a crosslinking reaction under heating conditions or under the action of a Lewis acid, including a compound containing an epoxy group, a compound containing a hydroxymethyl group or an alkoxymethyl group, etc.;

[0039] The epoxy group-containing compound includes any one of bisphenol A epoxy resin, bisphenol F epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl), and silicone containing epoxy groups, more preferably 3,3'-[oxybismethylene]bis[3-ethyl]oxetane, 1,4-butanediol diglycidyl ether, 2,2-bis(4-epoxypropyloxyphenyl)propane, 9,9-bis(4-epoxypropyloxy-3-methylphenyl)fluorene, 9,9-bis(4-epoxypropyloxyphenyl)fluorene, 1,3-bis[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 1,2,7,8-diepoxyoctane, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, triglycidyl isocyanurate, 4,4'-methylenebis(N,N-dicyclopropyloxyaniline), neopentyl glycol diglycidyl ether, 2,2'-(2,2,3,3,4,4,5,5-octafluorohexane-1,6-diyl)bis(ethylene oxide), pentaerythritol diglycidyl ether, vinylcyclohexene diglycidyl ether, polyethylene glycol diglycidyl ether ( degree of polymerization of 1-15), polypropylene glycol diglycidyl ether (degree of polymerization of 1-15), polydimethylsiloxane diglycidyl ether (degree of polymerization of 1-15), butanediol diglycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, 5,5-dimethyl-1,3-bis(oxiranylmethyl)imidazolidine-2,4-dione, 2,2',2"-[methylene-tris(phenyleneoxymethylene)]tri(oxirane), 1,1,1-tris(4-hydroxyphenyl)ethyl triglycidyl ether, bis(2,3-epoxycyclopentyl) ether, 3, 4-Epoxy-6-methylcyclohexylcarboxylic acid-3',4'-epoxy-6'-methylcyclohexyl ester, vinylcyclohexene and epoxy compound, 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexyl ester, diisoprene diepoxide, tetraphenylglycidyl ether ethane, triphenylglycidyl ether methane, triglycidyl-p-aminophenol, triglycidyl triisocyanate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl xylenediamine or tetraglycidyl-1,3-bisaminomethylcyclohexane; products with trade names include HP -850, HP-4032, HP-7200, HP-820, HP-4700, EXA-4710, HP-4770, EXA-859CRP, EXA-1514, EXA-4880, EXA-4850-150, EXA-4850-1000, EXA-4816, EXA-4822, BEO-60E, BPO-20E, HBE-100, DME-100, NC-3000, NC-6000 (Nippon Kayaku Co., Ltd.), and mixtures thereof in any proportion.

[0040] The compounds containing hydroxymethyl or alkoxymethyl include 46DMOC, 46DMOEP (the above are trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DMLMBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOMPTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML- pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (these are trade names, available from Honshu Chemical Industry Co., Ltd.), "NIKALAC" MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (Sanwa Chemical Co., Ltd.), and mixtures thereof in any proportion.

[0041] In the positive photosensitive resin composition, the adhesion promoter is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, isocyanatepropyltriethoxysilane, 3-isocyanatetrimethoxysilane, 3-isocyanatetriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyldimethoxysilane. At least one of silane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 3-(m-aminophenoxy)trimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane, and 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane;

[0042] In the above-mentioned positive photosensitive resin composition, the organic solvent is at least one of N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate.

[0043] The positive photosensitive resin composition of the present invention may further include a sensitizer, including a compound containing a phenolic hydroxyl group, a hydroxyl group or a carboxyl group, which can increase the solubility of the exposed portion in the developer, improve the photosensitivity and shorten the development time.

[0044] The compounds containing phenolic hydroxyl groups include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (the above are trade names, available from Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC- F (above are trade names, available from Asahi Organic Materials Industries, Ltd.), 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 9,9-bis(4-hydroxyphenyl)fluorene, 4,4'-dihydroxydiphenylcyclohexane, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,7-naphthalenediol, 2,6-naphthalenediol, bis(4-hydroxyphenyl)sulfide, spiro[fluorene-9,9'-xanthene]-3',6'-diol, and mixtures thereof in any proportions;

[0045] The organic compound containing hydroxyl group refers to a saturated or unsaturated fatty alcohol containing 2 to 16 carbon atoms, including ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, pentanol, n-hexanol, cyclopropylmethanol, cyclohexylmethanol, 4-methyl-1-cyclohexanol, 3,4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-tert-butylcyclohexanol, heptanol, octanol, cyclooctanol, 1-cyclohexyl-1-pentanol, 3,5,5-trimethylcyclohexanol, and cyclohexyl alcohol. 2-Heptene-2-methanol, cis-4-heptene-1-ol, cis-3-octen-1-ol, 2,7-octadienol, 2,4,4-methyl-2-pentanol, cyclohexylmethanol, cis-2-hexene-1-ol, n-hexanol, 1-hexadecanol, 2-ethyl-1-butanol, DL-2-methyl-1-butanol, isopentanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, isobutanol, neopentyl alcohol, and mixtures thereof in any proportion;

[0046] The organic compound containing a carboxyl group refers to a carboxylic acid compound containing 2 to 16 carbon atoms, including acetic acid, propionic acid, butyric acid, valeric acid, 2-methyl-4-pentenoic acid, 4-methyl-2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-n-pentanoic acid, 4-methyl-n-pentanoic acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-nonanoic acid, isononanoic acid, n-decanoic acid, 2-heptenoic acid, 2-octenoic acid, 2-nonenoic acid, 2-decenoic acid, 10-undecenoic acid, p-methoxybenzoic acid, m-methylbenzoic acid, benzoic acid, mandelic acid, trans-2-hexenoic acid, 3,7-dimethyl-6-octanoic acid, sorbic acid, 3,5,5-trimethylhexanoic acid, lauric acid, lauroleic acid and a mixture thereof in any proportion.

[0047] The added amount of the sensitizer is 3 to 40 parts per 100 parts of the phenolic hydroxyl-containing polyamide resin.

[0048] The composition of the low-temperature curing positive photosensitive resin composition of the present invention is as follows:

[0049] 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 3 to 40 parts by mass of a photoacid generator, 1 to 20 parts by mass of a reactive benzocyclobutene compound, 0.1 to 30 parts by mass of a thermal acid generator, 3 to 40 parts by mass of a crosslinking agent, 0.1 to 40 parts by mass of an adhesion promoter, and 100 to 1000 parts by mass of an organic solvent;

[0050] The composition of the low-temperature curing positive photosensitive resin composition of the present invention is specifically any one of the following:

[0051] 1) 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 12 to 15 parts by mass of a photoacid generator, 5 to 20 parts by mass of a reactive benzocyclobutene compound, 5 parts by mass of a thermal acid generator, 5 to 10 parts by mass of a crosslinking agent, 5 parts by mass of an adhesion promoter, and 200 parts by mass of an organic solvent;

[0052] 2) 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 15 parts by mass of a photoacid generator, 10 parts by mass of a reactive benzocyclobutene compound, 5 parts by mass of a thermal acid generator, 5 parts by mass of a crosslinking agent, 5 parts by mass of an adhesion promoter, and 200 parts by mass of an organic solvent;

[0053] 3) 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 12 parts by mass of a photoacid generator, 10 parts by mass of a reactive benzocyclobutene compound, 5 parts by mass of a thermal acid generator, 5 parts by mass of a crosslinking agent, 5 parts by mass of an adhesion promoter, and 200 parts by mass of an organic solvent;

[0054] 4) 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 15 parts by mass of a photoacid generator, 5 parts by mass of a reactive benzocyclobutene compound, 5 parts by mass of a thermal acid generator, 5 parts by mass of a crosslinking agent, 5 parts by mass of an adhesion promoter, and 200 parts by mass of an organic solvent;

[0055] 5) 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 15 parts by mass of a photoacid generator, 20 parts by mass of a reactive benzocyclobutene compound, 5 parts by mass of a thermal acid generator, 5 parts by mass of a crosslinking agent, 5 parts by mass of an adhesion promoter, and 200 parts by mass of an organic solvent;

[0056] 6) 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 15 parts by mass of a photoacid generator, 20 parts by mass of a reactive benzocyclobutene compound, 5 parts by mass of a thermal acid generator, 5 parts by mass of a crosslinking agent, 5 parts by mass of an adhesion promoter, and 200 parts by mass of an organic solvent;

[0057] 7) 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 15 parts by mass of a photoacid generator, 15 parts by mass of a reactive benzocyclobutene compound, 5 parts by mass of a thermal acid generator, 5 parts by mass of a crosslinking agent, 5 parts by mass of an adhesion promoter, and 200 parts by mass of an organic solvent;

[0058] 8) 100 parts by mass of a phenolic hydroxyl group-containing polyamide resin, 15 parts by mass of a photoacid generator, 10 parts by mass of a reactive benzocyclobutene compound, 5 parts by mass of a thermal acid generator, 5 parts by mass of a crosslinking agent, 10 parts by mass of an adhesion promoter, and 200 parts by mass of an organic solvent.

[0059] The low-temperature curing positive photosensitive resin composition of the present invention can be prepared according to the following method: in a Class 1000 clean room equipped with a yellow light source, the phenolic hydroxyl group-containing polyamide resin, the photoacid generator, the reactive benzocyclobutene compound, the thermal acid generator, the crosslinking agent, and the adhesion promoter are added in batches to the organic solvent under stirring to dissolve to form a homogeneous solution; after filtering, the solution is divided into packages to obtain a positive photosensitive polybenzoxazole resin precursor solution.

[0060] The low-temperature curable positive photosensitive resin composition of the present invention can form a patterned polybenzoxazole resin film after coating, exposure, development, and curing, which specifically includes the following steps:

[0061] 1) Spin-coating the positive photosensitive resin solution on a substrate surface such as a silicon wafer or glass to obtain a liquid adhesive film;

[0062] 2) baking at 80-130° C. for 1-30 min (pre-baking) to obtain a solid film;

[0063] 3) Cover the mask and expose under ultraviolet i-line, or expose under i-line and g-line;

[0064] 4) Developing with a developer to dissolve and remove the exposed area;

[0065] 5) washing with a rinse solution to obtain an uncured patterned resin film;

[0066] 6) low-temperature curing in an oxygen-free environment at 200° C. to 250° C. and with an oxygen content of less than 100 ppm to obtain a cured patterned polybenzoxazole resin film.

[0067] The developer and rinse solutions involved in the application method are conventional additives in the prior art. The developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, choline hydroxide, diethanolamine, diethylaminoethanol, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and 1,6-hexanediamine. The rinse solution is preferably water or an aqueous solution containing an alcohol such as methanol, ethanol, or isopropyl alcohol, or an ester such as ethyl lactate or propylene glycol monomethyl ether acetate.

[0068] The patterned polybenzoxazole resin film has the characteristics of low dielectric constant, low dielectric loss, excellent heat resistance, low water absorption, high toughness, high adhesion and excellent photosensitivity. Its main properties are shown in Table 1. It can be used for surface passivation protective layer films in integrated circuit manufacturing, interlayer insulation of multi-layer metal interconnect structures, or multi-layer wiring of advanced electronic packaging (BGA, CSP, SiP, etc.) substrates, etc., to meet the use requirements of high-frequency communications such as 5G.

[0069] Table 1 Main properties of positive photosensitive resin composition

[0070] DETAILED DESCRIPTION

[0071] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0072] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0073] Test or evaluation methods for various performance indicators of the embodiment:

[0074] (1) Molecular weight test

[0075] The resin weight-average molecular weight and molecular weight distribution were tested by GPC method. The eluent was LiBr (0.03 mol / l) and H3PO4 (0.06 mol / l) in NMP. The resin concentration was 1.0 mg / ml. The standard sample was polystyrene.

[0076] (2) Lithography performance evaluation

[0077] A. Film retention rate

[0078] A positive photosensitive resin composition solution was spin-coated onto a 6-inch silicon wafer and pre-baked at 80-130°C to form a solid film. A mask was placed on the surface and exposed to ultraviolet (i) light. The film was then developed with a 2.38wt% tetramethylammonium hydroxide aqueous solution and rinsed with deionized water to obtain an uncured patterned resin film. The film thickness of the unexposed portion after development was measured using an optical interferometer. The film retention rate was calculated by comparing the thickness of the unexposed portion to the thickness before development.

[0079] B. Resolution and Sensitivity

[0080] Observe the stereolithographic pattern after development with an optical microscope. The minimum size at which the pattern edge is smooth and free of scum is defined as the pattern resolution L / S (μm). The minimum exposure energy required for this resolution is the sensitivity (mJ / mm 2 ).

[0081] (3) Thermal performance test

[0082] Preparation of thin film: A positive photosensitive resin composition solution was spin-coated on the surface of a 6-inch silicon wafer, heated at 140°C for 30 minutes in a nitrogen-protected blast oven, and then heated at 250°C for 1 hour. The silicon wafer with the film was immersed in 4% HF for 5-10 minutes, and then rinsed with water to obtain a polybenzoxazole resin film with a thickness of 10 μm.

[0083] a. Glass transition temperature (Tg): Tested using a dynamic mechanical analyzer (DMA) in tensile mode. The peak of the tanδ curve is the Tg. The DMA test frequency is 1 MHz, the heating rate is 5°C / min, and the heating range is 50-400°C.

[0084] b. 5% weight loss temperature (Td5%) test: The test was performed using a thermogravimetric analyzer (TGA) with a nitrogen flow rate of 20 mL / min, a heating rate of 20°C / min, and a heating range of 50-600°C.

[0085] c. Coefficient of Thermal Expansion (CTE) Test: Tested using a static thermomechanical analyzer (TMA). Film strips were 10 mm long, 4 mm wide, and 10 μm thick. The temperature was raised at a rate of 5°C / min over a temperature range of 30 to 500°C.

[0086] (4) Electrical performance test

[0087] Dielectric constant (ε) and dielectric loss (tanδ): Sample films were prepared according to the method for preparing films in the thermal performance test and tested using a vector network analyzer at a test frequency of 10 GHz.

[0088] Volume resistivity and surface resistivity: Sample films were prepared according to the method for preparing films in the thermal performance test, and tested using a volume and surface resistivity tester with a test voltage of 100V.

[0089] (5) Mechanical properties test

[0090] Tensile strength, tensile modulus and elongation at break: Sample films were prepared according to the film preparation method in the thermal performance test and tested using a universal testing machine. The film strips were 100 mm long, 10 mm wide, and 10 μm thick, and the tensile rate was 2 mm / min.

[0091] (6) Bond strength test

[0092] A positive photosensitive resin composition solution was spin-coated onto a 6-inch silicon wafer and heated in a nitrogen-protected forced-air oven at 140°C for 30 minutes, then at 250°C for 1 hour. A pin with epoxy resin was bonded to the cured film and then placed in an oven for curing at 150°C for 1 hour. The pin was stretched using an adhesion meter and the peeling state was visually observed. Pins that peeled from the interface between the cured film and the epoxy resin or from the interface between the epoxy resin and the aluminum pin and had a bond strength of less than 600 kg / cm were selected. 2 Rerun the test.

[0093] (7) Water absorption test

[0094] A positive photosensitive resin composition solution was evenly coated onto a glass plate using a coating machine. The plate was then heated in a nitrogen-protected forced-air oven at 140°C for 30 minutes and then at 250°C for 1 hour to produce a polybenzoxazole resin cured film approximately 30 μm thick. The cured film was then cut into 2 cm squares (the edges required to be smooth and flat) and immersed in water at 23°C ± 2°C for 24 hours. The mass of the cured film before and after immersion was measured using a balance (0.1 mg accuracy). The mass before immersion was recorded as m1, and the mass after immersion was recorded as m2. The water absorption was calculated using the formula (m2 - m1) / m1 × 100%. Each sample was measured three times in parallel, and the average of the measurements was taken as the water absorption of the cured film.

[0095] Synthesis Example 1: In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 23.24 g of 4,4'-diphenyl ether dicarboxylic acid (DPD) and 104 g of NMP were added in sequence and stirred at room temperature to form a homogeneous solution. The solution was then reacted with 21.41 g of SOCl2 at 0-10°C for 2 h and then at room temperature for 3 h to produce diphenyl ether dicarboxylic acid chloride.

[0096] In another 1L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 36.63g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 146.5g of NMP were added in sequence and stirred to dissolve to form a homogeneous transparent aromatic diamine solution; the solution was cooled to below 10°C in an ice bath, and the diphenyl ether dichloride solution prepared above was added dropwise to the aromatic diamine solution for 0.5h; then, the reaction was allowed to proceed at room temperature for 10h; 3.28g of nadic anhydride was added and stirring was continued for 1h; the reaction solution was poured into 5L of deionized water, the solid precipitated, filtered, and vacuum dried to obtain a benzoxazole precursor resin - a phenolic hydroxyl polyamide resin, with a weight average molecular weight Mw = 22000 and a molecular weight distribution of 1.9 as measured by GPC.

[0097] Synthesis Example 2: In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 10.36 g of dodecyl dicarboxylic acid, 11.62 g of 4,4'-diphenyl ether dicarboxylic acid, and 101 g of NMP were added in sequence and stirred at room temperature to form a homogeneous solution. The solution was then reacted with 21.41 g of SOCl2 at 0-10°C for 2 h and then at room temperature for 3 h to produce a corresponding dicarboxyl chloride mixture, wherein the molar ratio of dodecyl dicarboxyl chloride was 50%.

[0098] In another 1L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 36.63g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 146.5g of NMP were added in sequence and stirred to dissolve to form a homogeneous transparent aromatic diamine solution; the solution was cooled to below 10°C in an ice bath, and the diformyl chloride mixture prepared above was added dropwise to the aromatic diamine solution for 0.5h; then, the solution was reacted at room temperature for 10h; 3.28g of nadic anhydride was added and stirring was continued for 1h; the reaction solution was poured into 5L of deionized water, the solid precipitated, filtered, and vacuum dried to obtain a benzoxazole precursor resin - a phenolic hydroxyl group-containing polyamide resin. GPC analysis showed a weight average molecular weight Mw = 23800 and a molecular weight distribution of 2.3.

[0099] Synthesis Example 3: In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 16.58 g of dodecyl dicarboxylic acid, 4.65 g of 4,4'-diphenyl ether dicarboxylic acid, and 99 g of NMP were added in sequence and stirred at room temperature to form a homogeneous solution. The solution was then reacted with 21.41 g of SOCl2 at 0-10°C for 2 h and at room temperature for 3 h to produce a corresponding dicarboxyl chloride mixture, wherein the molar ratio of dodecyl dicarboxyl chloride was 80%.

[0100] In another 1L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 36.63g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 146.5g of NMP were added in sequence and stirred to dissolve to form a homogeneous transparent aromatic diamine solution; the solution was cooled to below 10°C in an ice bath, and the diformyl chloride mixture prepared above was added dropwise to the aromatic diamine solution for 0.5h; the solution was then reacted at room temperature for 10h; 3.44g of 4-ethynylphthalic anhydride was then added and stirring continued for 1h; the reaction solution was poured into 5L of deionized water, the solid precipitated, filtered, and vacuum dried to obtain a benzoxazole precursor resin - a phenolic hydroxyl group-containing polyamide resin. GPC analysis showed a weight average molecular weight Mw = 24600 and a molecular weight distribution of 2.4.

[0101] Synthesis Example 4: In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 3.10 g of 1,4-cyclohexanedicarboxylic acid, 18.59 g of 4,4'-diphenyl ether dicarboxylic acid, and 101 g of NMP were added in sequence and stirred at room temperature to form a homogeneous solution. The solution was then reacted with 21.41 g of SOCl2 at 0-10°C for 2 h and at room temperature for 3 h to produce the corresponding dicarboxyl chloride mixture, wherein the molar ratio of 1,4-cyclohexanedicarboxylic acid was 20%.

[0102] In another 1L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 36.63g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 146.5g of NMP were added in sequence and stirred to dissolve to form a homogeneous transparent aromatic diamine solution; the solution was cooled to below 10°C in an ice bath, and the diformyl chloride mixture prepared above was added dropwise to the aromatic diamine solution for 0.5h; then, the solution was reacted at room temperature for 10h; 3.28g of nadic anhydride was added and stirring was continued for 1h; the reaction solution was poured into 5L of deionized water, the solid precipitated, filtered, and vacuum dried to obtain a benzoxazole precursor resin - a phenolic hydroxyl group-containing polyamide resin. GPC analysis showed a weight average molecular weight Mw = 22500 and a molecular weight distribution of 2.3.

[0103] Synthesis Example 5: In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 23.24 g of 4,4'-diphenyl ether dicarboxylic acid (DPD) and 104 g of NMP were added in sequence and stirred at room temperature to form a homogeneous solution. The solution was then reacted with 21.41 g of SOCl2 at 0-10°C for 2 h and then at room temperature for 3 h to produce diphenyl ether dicarboxylic acid chloride.

[0104] In another 1L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 29.30g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2.96g of 2,2'-(ethylenedioxy)bis(ethylamine), and 129g of NMP were added in sequence and stirred to dissolve to form a homogeneous transparent diamine solution. The solution was cooled to below 10°C in an ice bath, and the prepared diphenyl ether diformyl chloride solution was added dropwise to the diamine solution for 0.5h. The solution was then reacted at room temperature for 10h. 3.44g of 4-ethynylphthalic anhydride was then added and stirring continued for 1h. The reaction solution was poured into 5L of deionized water, the precipitated solid was filtered, and vacuum dried to obtain a benzoxazole precursor resin - a phenolic hydroxyl group-containing polyamide resin. GPC analysis showed a weight average molecular weight Mw = 23000 and a molecular weight distribution of 2.2.

[0105] Other components for the resin composition:

[0106] Reactive benzocyclobutene compounds:

[0107]

[0108] BCB-1, BCB-2, and BCB-5 were prepared according to the methods described in patent application CN200310100717 and the doctoral dissertation "Synthesis and Properties of Low Dielectric Constant Benzocyclobutene Resins" from the Graduate School of the Chinese Academy of Sciences. BCB-3 was prepared according to the method described in US Pat. 5,136,069, and BCB-4 and BCB-6 were prepared according to the method described in US Pat. 4,540,763.

[0109] Photoacid generator: 2,3,4-trihydroxybenzophenone-1,2-diazonaphthoquinone-5-sulfonate.

[0110] Crosslinking agent:

[0111]

[0112] Thermal acid generators: pyridinium p-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate.

[0113] Adhesion promoter: γ-glycidyloxypropyltrimethoxysilane, (4-vinylphenyl)trimethoxysilane.

[0114] Solvent: GBL, PGMEA.

[0115] Example 1. In a Class 1000 clean room equipped with a yellow light, 20 g of the phenolic hydroxyl polyamide resin in Synthesis Example 1, 3.0 g of 2,3,4-trihydroxybenzophenone-1,2-diazonaphthoquinone-5-sulfonate, 2.0 g of the reactive benzocyclobutene compound BCB-1, 1.0 g of MX-270, 1.0 g of pyridinium p-toluenesulfonate, and 1.0 g of γ-glycidyloxypropyltrimethoxysilane were added sequentially to a mixed solvent of 40 g of GBL and PGMEA (mass ratio of 9 / 1), and stirred at room temperature for 6 h to form a positive photosensitive polybenzoxazole resin solution. The amount of the mixed solvent added can be adjusted so that the solid content of the final solution is 40±2% and the viscosity at 25°C is 2000±200 mPa.s (wherein the mass ratio of phenolic hydroxyl polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinking agent: adhesion promoter is 100:15:10:5:5:5).

[0116] Example 2: The amount of 2,3,4-trihydroxybenzophenone-1,2-diazonaphthoquinone-5-sulfonate added in Example 1 was adjusted to 2.4 g. Except for this, the same method as described in Example 1 of the present invention was followed (wherein the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter is 100:12:10:5:5:5).

[0117] Examples 3-4: The addition amounts of the reactive benzocyclobutene compound BCB-1 in Example 1 were adjusted to 1.0 g and 4.0 g, respectively. The same method as described in Example 1 of the present invention was followed except that the mass ratios of the phenolic hydroxyl group-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter were 100:15:(5,20):5:5:5.

[0118] Examples 5-6: The same method as in Example 1 was used, except that the reactive benzocyclobutene compound BCB-1 (2.0 g) in Example 1 was replaced with BCB-3 and BCB-4, each added in 2.0 g amounts. (The mass ratio of phenolic hydroxyl group-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter was 100:15:10:5:5:5.)

[0119] Example 7: The cross-linking agent 1.0 g MX-270 in Example 1 was replaced with 1.0 g TMOM-BP. Other than that, the same method as described in Example 1 of the present invention was followed (wherein the mass ratio of phenolic hydroxyl group-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: cross-linker: adhesion promoter is 100:15:10:5:5:5).

[0120] Example 8. The thermal acid generator pyridinium p-toluenesulfonate in Example 1 was replaced with 2-methoxyethyl p-toluenesulfonate. Other than that, the same method as described in Example 1 of the present invention was followed (wherein the mass ratio of phenolic hydroxyl group-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter is 100:15:10:5:5:5).

[0121] Example 9. The cross-linking agent 1.0 g MX-270 in Example 1 was replaced by 1.0 g TMOM-BP, and the coupling agent 1.0 g γ-glycidyloxypropyltrimethoxysilane was replaced by 1.0 g (4-vinylphenyl)trimethoxysilane. Except for this, the same method as described in Example 1 of the present invention was followed (wherein the mass ratio of phenolic hydroxyl group-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: cross-linker: adhesion promoter is 100:15:10:5:5:5).

[0122] Example 10. The mixed solvent GBL / PGMEA ratio in Example 1 was adjusted to 8 / 2 (mass ratio). Other than that, the same method as described in Example 1 of the present invention was followed (wherein the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter was 100:15:10:5:5:5).

[0123] Example 11. The phenolic hydroxyl-containing polyamide resin in Synthesis Example 1 used in Example 1 is replaced by the phenolic hydroxyl-containing polyamide resin in Synthesis Example 2, and the reactive benzocyclobutene compound BCB-1 is replaced by BCB-2. The added amounts remain unchanged. Except for this, the same method as described in Example 1 of the present invention is followed (wherein the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: cross-linking agent: adhesion promoter is 100:15:10:5:5:5).

[0124] Example 12: The phenolic hydroxyl-containing polyamide resin in Synthesis Example 2 used in Example 11 is replaced by the phenolic hydroxyl-containing polyamide resin in Synthesis Example 3, and the added amount remains unchanged; the added amount of the reactive benzocyclobutene compound BCB-2 is adjusted to 3.0 g; except for this, the same method as described in Example 11 of the present invention is followed (wherein, the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: cross-linking agent: adhesion promoter is 100:15:15:5:5:5).

[0125] Example 13. The phenolic hydroxyl-containing polyamide resin in Synthesis Example 1 used in Example 1 is replaced by the phenolic hydroxyl-containing polyamide resin in Synthesis Example 4, and the added amount remains unchanged; except for this, the same method as described in Example 1 of the present invention is followed (wherein, the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: cross-linking agent: adhesion promoter is 100:15:10:5:5:5).

[0126] Example 14: The phenolic hydroxyl-containing polyamide resin in Synthesis Example 1 used in Example 1 is replaced by the phenolic hydroxyl-containing polyamide resin in Synthesis Example 5, and the added amount remains unchanged; other than that, the same method as described in Example 1 of the present invention is followed (wherein, the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: cross-linking agent: adhesion promoter is 100:15:10:5:5:5).

[0127] Example 15. Based on the formula of Example 14, 1.0 g of TMOM-BP was added as the crosslinker. Other than that, the same method as described in Example 14 of the present invention was followed (wherein the mass ratio of phenolic hydroxyl group-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter is 100:15:10:5:10:5).

[0128] Comparative Example 1: The amount of the reactive benzocyclobutene compound BCB-1 in Example 1 was adjusted to 6.0 g. Except for this, the same method as described in Example 1 of the present invention was followed (wherein the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter is 100:15:30:5:5:5).

[0129] Comparative Examples 2 to 3: The same method as described in Example 1 of the present invention was followed except that 2.0 g of the reactive benzocyclobutene compound BCB-1 in Example 1 was replaced with 2.0 g of BCB-5 and 2.0 g of BCB-6, respectively (wherein the mass ratios of the phenolic hydroxyl group-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter were all 100:15:10:5:5:5).

[0130] Comparative Example 4: The amount of the reactive benzocyclobutene compound BCB-1 added in Example 1 was adjusted to 0 g. Other than that, the same method as described in Example 1 of the present invention was followed (wherein the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: crosslinker: adhesion promoter is 100:15:0:5:5:5).

[0131] Comparative Example 5: The phenolic hydroxyl-containing polyamide resin in Synthesis Example 1 used in Example 1 was replaced by the phenolic hydroxyl-containing polyamide resin in Synthesis Example 3, and the amount of the reactive benzocyclobutene compound BCB-1 added was adjusted to 0 g. Except for this, the same method as described in Example 1 of the present invention was carried out (wherein, the mass ratio of phenolic hydroxyl-containing polyamide resin: photoacid generator: reactive benzocyclobutene compound: thermal acid generator: cross-linking agent: adhesion promoter is 100:15:0:5:5:5).

[0132] The positive photosensitive polybenzoxazole resin solutions described in the above examples and comparative examples were spin-coated onto a 6-inch wafer and baked at 120°C for 3 minutes to produce an 8μm pre-baked film. A mask was placed on the pre-baked film and exposed using UV i-rays. The film was then developed with a 2.38 wt.% TMAH aqueous solution and rinsed with deionized water to create a stereolithographic pattern on the silicon wafer. The film was then cured at low temperatures (140°C / 30 minutes, 250°C / 1 hour) in an oxygen-free forced-air oven with an oxygen content below 100 ppm to produce a cured, patterned polybenzoxazole film.

[0133] Examples 1 to 15 and Comparative Examples 1 to 5 were evaluated according to the photolithography performance evaluation method, and the results are listed in Table 2.

[0134] Table 2 Lithography performance evaluation results

[0135]

[0136]

[0137] Note: The solution prepared in Comparative Example 2 contained suspended matter and was not a uniform solution, so photolithography was not performed.

[0138] It can be seen from Examples 1 to 15 and Comparative Examples 1 to 5 that when the amount of the reactive benzocyclobutene compound added is ≤ 20 parts by mass relative to 100 parts by mass of the resin, the positive photosensitive polybenzoxazole resin solution prepared by the present invention has excellent lithographic performance.

[0139] The evaluation results of various performance indicators of Examples 1 to 15 and Comparative Examples 1 to 5 are listed in Table 3 and Table 4.

[0140] Table 3 Evaluation results of various performance indicators of the embodiment

[0141]

[0142] Table 4 Evaluation results of various performance indicators of comparative examples

[0143]

[0144] Note: Comparative Example 2 was not a homogeneous solution, so its performance was not tested.

[0145] It can be seen from Examples 1 to 15 and Comparative Examples 1 to 4 that the present invention greatly improves the dielectric properties of the polybenzoxazole film by adding a reactive benzocyclobutene resin compound to the positive photosensitive polybenzoxazole resin solution. The polybenzoxazole film not only has a low dielectric constant, low dielectric loss, and high heat resistance, but also has low water absorption, high adhesion, and high toughness. It has significant beneficial effects and can meet the use requirements of high-frequency communications such as 5G.

Claims

1. A positive photosensitive resin composition comprising the following components in parts by weight: 100 parts of phenolic hydroxyl-containing polyamide resin; 3-40 parts of photoacid generator; 1-20 parts of reactive benzocyclobutene compound; 0.1-30 parts of thermal acid generator; 3-40 parts of crosslinking agent; 0.1-40 parts of adhesion promoter; 100-1000 parts of organic solvent; The reactive benzocyclobutene compound is a bisbenzocyclobutene compound having a specific imide structure or a bisbenzocyclobutene compound containing a saturated alkane and an unsaturated hydrocarbon structure; The structural formula of the bisbenzocyclobutene compound having a specific imide structure is as follows: The structural formula of the dibenzocyclobutene compound containing saturated alkane and unsaturated hydrocarbon structures is shown below: 。 2. The positive photosensitive resin composition according to claim 1, wherein: The phenolic hydroxyl-containing polyamide resin is a condensation product of component 1 and component 2, and has a GPC weight average molecular weight of 10,000 to 60,000; The component 1 is a mixture of an aromatic diacyl chloride or a derivative thereof and an aliphatic diacyl chloride or a derivative thereof, the molar content of the aromatic diacyl chloride or a derivative thereof is 20 to 100%; The component 2 is a mixture of phenolic hydroxyl aromatic diamine and aliphatic diamine, the molar content of the phenolic hydroxyl aromatic diamine is 80 to 100%; The aromatic dicarboxylic acid chloride or its derivative is selected from at least one of diphenyl ether dicarboxylic acid chloride, isophthalic acid dichloride, terephthalic acid dichloride, biphenyl dicarboxylic acid chloride, diphenyl sulfone dicarboxylic acid chloride, diphenylmethane dicarboxylic acid chloride and benzophenone dicarboxylic acid chloride; The aliphatic diacyl chloride or its derivative is selected from at least one of octanedicarboxylic acid chloride, adipic acid chloride, nonanedicarboxylic acid chloride, decanedicarboxylic acid chloride, dodecanedicarboxylic acid chloride, 1,4-cyclohexanedicarboxylic acid chloride and 1,3-cyclobutanedicarboxylic acid chloride; The phenolic hydroxyl aromatic diamine is selected from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-di At least one of amino-3,3'-dihydroxydiphenyl ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxybenzophenone, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene; The aliphatic diamine is at least one selected from 1,4-butanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, dodecanediamine, 1,4-cyclohexanediamine, 1,3-cyclobutanediamine, 2,2'-(ethylenedioxy)bis(ethylamine) and diethylene glycol di(3-aminopropyl) ether.

3. The positive photosensitive resin composition according to claim 2, wherein: The polycondensation reaction of the component 1 and the component 2 is carried out in the following organic solvent: N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-ε-caprolactam, N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylurea, phenol, m-cresol, methyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone , ethyl acetate, butyl acetate, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, ethyl 3-ethoxypropionate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate; The molecular weight regulator used in the polycondensation reaction of the component 1 and the component 2 is at least one of maleic anhydride, nadic anhydride, methylnadic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-vinylaniline, norbornenamine, allylamine, 4-ethynylaniline, 3-ethynylaniline, 3-phenylethynylaniline, 4-phenylethynylaniline, 4-(4-aminophenylethynyl)phenylacetylene, 4-[(trimethylsilyl)-ethynyl]aniline, 4-(4-amino-phenyl)-2-methyl-but-3-yn-2-ol, (E)-3-aminocinnamic acid and propargylamine; The polycondensation reaction further comprises the following steps: The reaction product is precipitated in a poor solvent to obtain a solid resin, which is then dried.

4. The positive photosensitive resin composition according to any one of claims 1 to 3, characterized in that: The photoacid generator is at least one of a diazonaphthoquinone compound, an iodonium salt compound, and a sulfonium salt compound; The naphthoquinone diazide compound is any one of the following 1)-3): 1) Compounds produced by esterification of naphthoquinone diazides and polyhydroxy compounds; 2) Compounds produced by sulfonylation of diazonaphthoquinone sulfonic acids with polyamine compounds; 3) A compound produced by esterification and / or sulfonylation of a diazonaphthoquinone sulfonic acid with a polyhydroxy polyamine compound; wherein the proportion of the polyhydroxy polyamine compound substituted by the diazonaphthoquinone sulfonic acid is 50% to 95%.

5. The positive photosensitive resin composition according to claim 4, wherein: The thermal acid generator is at least one of an alkylsulfonate pyridinium salt, a perfluoroalkylsulfonate pyridinium salt, an alkylpyridinium salt, a diaryliodonium salt, a di(alkylaryl)iodonium salt, a trialkylsulfonium salt, a dialkylmonoarylsulfonium salt, and a diarylmonoalkyliodonium salt or an ester compound; The cross-linking agent is a compound containing an epoxy group, a compound containing a hydroxymethyl group or an alkoxymethyl group; The organic solvent is at least one of N-methylpyrrolidone, N,N'-dimethylacetamide, N,N'-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monomethyl ether acetate.

6. The positive photosensitive resin composition according to claim 5, wherein: The adhesion promoter is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, isocyanatepropyltriethoxysilane, 3-isocyanatetrimethoxysilane, 3-isocyanatetriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyldimethoxysilane. At least one of oxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 3-(m-aminophenoxy)trimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane and 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane.

7. A patterned polybenzoxazole resin film obtained by coating, exposing, developing and curing the positive photosensitive resin composition according to any one of claims 1 to 6.

8. The patterned polybenzoxazole resin film according to claim 7, wherein: The patterned polybenzoxazole resin film was prepared according to the following steps: 1) Spin-coating the positive photosensitive resin composition on the surface of a substrate to obtain a liquid adhesive film; 2) baking at 80-130° C. for 1-30 min to obtain a solid film; 3) Cover the mask and expose under ultraviolet i-line, or expose under i-line and g-line; 4) Developing with a developer to dissolve and remove the exposed area; 5) washing with a rinse solution to obtain an uncured patterned resin film; 6) low-temperature curing in an oxygen-free environment at 200° C. to 250° C. and with an oxygen content of less than 100 ppm to obtain the cured patterned polybenzoxazole resin film.

9. Use of the positive photosensitive resin composition according to any one of claims 1 to 6 in preparing surface passivation protective layer films in integrated circuit manufacturing and packaging, and interlayer insulating layer films of multi-layer metal interconnection circuits.

10. Use of the patterned polybenzoxazole resin film according to claim 7 or 8 as a surface passivation protective layer film in integrated circuit manufacturing and packaging, or an interlayer insulating layer film in a multi-layer metal interconnection circuit.

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