CN114230792B - Positive photosensitive polyimide resin, resin composition, and preparation method and application thereof - Google Patents

Positive photosensitive polyimide resin, resin composition, and preparation method and application thereof Download PDF

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CN114230792B
CN114230792B CN202210002412.3A CN202210002412A CN114230792B CN 114230792 B CN114230792 B CN 114230792B CN 202210002412 A CN202210002412 A CN 202210002412A CN 114230792 B CN114230792 B CN 114230792B
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dianhydride
bis
polyimide resin
positive photosensitive
photosensitive polyimide
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CN114230792A (en
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陈兴
贾斌
李涛
路延东
魏广彪
杨彦飞
李广凯
刘久琳
冯培龙
杨士勇
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Institute of Chemistry CAS
Minseoa Beijing Advanced Materials Development Co Ltd
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Institute of Chemistry CAS
Minseoa Beijing Advanced Materials Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers

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  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention discloses a positive photosensitive polyimide resin, a resin composition, a preparation method and application thereof. The positive photosensitive polyimide resin is prepared from total dianhydride, total diamine and a molecular weight regulator; the total dianhydride is any one of the following A1) -A2): a1 A norbornane dianhydride containing a siloxane structure shown in a formula I; a2 The composition comprises norbornane dianhydride containing siloxane structure and aromatic tetracarboxylic dianhydride without siloxane structure shown in formula I; the total diamine is any one of the following B1) -B2): b1 An aromatic diamine containing at least one phenolic hydroxyl group; b2 Consisting of an aromatic diamine containing at least one phenolic hydroxyl group and a diamine containing no phenolic hydroxyl group; the molar ratio of total dianhydride to total diamine is 0.9: 1-1: 1, a step of; the weight average molecular weight of the positive photosensitive polyimide resin is 15000-25000. The patterned polyimide film prepared by the invention has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high cohesiveness and the like.

Description

Positive photosensitive polyimide resin, resin composition, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a positive photosensitive polyimide resin, a resin composition, a preparation method and application thereof.
Background
Polyimide (PI) film has the advantages of high and low temperature resistance, corrosion resistance, high insulation, low dielectric constant, low dielectric loss, excellent mechanical property, chemical corrosion resistance, radiation resistance and the like, is widely used for chip surface passivation, stress absorption buffer and interlayer dielectric film of multilayer interconnection structure in the semiconductor manufacturing process, and has important application value in the aspects of package substrate signal wire distribution, alpha-particle shielding layer, micro solder ball making process, stress buffer layer of plastic package circuit, flexible package substrate and the like in the advance microelectronic package (BGA, CSP, siP, WLP and the like). In these applications, it is often necessary to make electronic circuitry on one or both sides of a polyimide film, and the electronic circuitry on both sides of the film is required to make conductive vias by making vias + copper plating on the film to make electrical connection to the electronic circuitry on both sides of the film. Currently, conductive vias are typically implemented through photo-induced vias using photosensitive polyimide resins. With the rapid development of high-tech fields such as mobile equipment, artificial intelligence, 5G communication and the like, microelectronic devices are developing toward high performance, multifunctional and miniaturized. In order to increase the information transmission rate, reduce interference and inductive coupling between signals, reduce energy consumption and signal distortion in the modulation process, further reduction of dielectric constant, dielectric loss and water absorption of polyimide materials is required. Meanwhile, in order to improve compatibility between different materials, it is also required that the photosensitive polyimide resin be able to further lower the curing temperature.
Traditional aromatic polyimides form higher packing densities due to stronger charge transfer complexation interactions and van der waals interactions, resulting in higher dielectric constants and dielectric losses of the thin film materials. In order to increase the distance between molecular chains and reduce the stacking density of the photosensitive polyimide resin, fluorine-containing groups are introduced into a main chain structure of the resin to form a fluorine-containing polyimide material, so that the fluorine-containing polyimide material becomes an effective means for reducing dielectric constants and dielectric losses. However, positive photosensitive polyimide resins are usually developed in alkaline developer, and too high a fluorine content in the resin main chain structure may cause a decrease in photolithography processability thereof. In addition, the aliphatic large steric hindrance side group is adopted to break the packing regularity of PI molecular chains, inhibit the interaction between the molecular chains and increase the free volume between the molecular chains, thus being an effective way for reducing the dielectric constant and dielectric loss.
X.Z.jin et al (X.Z.jin, H.Ishii,J. Appl. Polym. Sci.hydrogenated Homoanhydride (HPMDA) with 2, 2-bis [ 3-hydroxy-4-aminophenyl group, 2005, 98, 15)]Hexafluoropropane (6 FBIS) and 2, 2-bis [ 4-aminophenoxy-phenyl ]]The hexafluoropropane (6 FBAPP) mixture is formed into a hydroxyl-containing polyimide resin by polycondensation and then combined with a DNQ photoacid generator to form a positive photosensitive polyimide resin. However, the reported positive photosensitive polyimide resins have low adhesion and are difficult to meet the practical use requirements of IC chips.
Disclosure of Invention
The invention aims to provide a positive photosensitive polyimide resin, a resin composition and a preparation method and application thereof, wherein the positive photosensitive polyimide resin is phenolic hydroxyl group-containing polyimide resin, a silicon dianhydride structure containing aliphatic rings and diamine containing phenolic hydroxyl groups are introduced into the structure for polymerization, the aliphatic rings bring low dielectric constant, the silicon structure brings high adhesiveness, and the positive photosensitive polyimide resin composition can generate photochemical reaction after being exposed by ultraviolet rays (i and g lines), so that the solubility of an exposure area in alkaline developer is increased, the dissolution rate of a non-exposure area in the alkaline developer is slower, and a high-resolution pattern can be obtained; the polyimide film is formed by curing after heating to 180-300 ℃, has the characteristics of low-temperature curing, low dielectric constant, low water absorption, high chemical corrosion resistance, high heat resistance, high adhesiveness and the like, and can meet the use requirements of manufacturing high-frequency IC electronic devices.
It is a first object of the present invention to provide a positive photosensitive polyimide resin.
The positive photosensitive polyimide resin is prepared from total dianhydride, total diamine and a molecular weight regulator;
the total dianhydride is any one of the following A1) -A2):
A1 A norbornane dianhydride containing a siloxane structure shown in a formula I;
a2 The composition comprises norbornane dianhydride containing siloxane structure and aromatic tetracarboxylic dianhydride without siloxane structure shown in formula I;
i
In the formula I, n represents the number of the repeating units and is any natural number from 1 to 9; r is R 1 、R 2 、R 3 、R 4 The two are the same or different and are each independently selected from any one of methyl, phenyl, ethyl, propyl, isopropyl, butyl and methylphenyl;
the mass percentage of the norbornane dianhydride containing the siloxane structure shown in the formula I in the total dianhydride is 1% -100%;
the total diamine is any one of the following B1) -B2):
b1 An aromatic diamine containing at least one phenolic hydroxyl group;
b2 Consisting of an aromatic diamine containing at least one phenolic hydroxyl group and a diamine containing no phenolic hydroxyl group;
the mass percentage of the aromatic diamine containing at least one phenolic hydroxyl group in the total diamine is 1% -100%;
the molar ratio of the total dianhydride to the total diamine is 0.9: 1-1: 1, a step of;
the weight average molecular weight of the positive photosensitive polyimide resin is 15000-25000.
In the positive photosensitive polyimide resin, the mass percentage of the norbornane dianhydride containing a siloxane structure shown in the formula I in the total dianhydride is preferably 5-80%, more preferably 10-60%, for example 50% or 60%;
The aromatic diamine containing at least one phenolic hydroxyl group is preferably present in an amount of 30% to 100% by mass, more preferably 60% to 100% by mass, for example 60%, 80% or 100% by mass, based on the total diamine.
The weight average molecular weight of the positive photosensitive polyimide resin can be 20000-25000, 24400, 22100, 21500, 21900, 22900, 21600, 22300 or 23400.
In the positive photosensitive polyimide resin, the norbornane dianhydride having a siloxane structure represented by formula I may be selected from exo-5,5'- (1, 3-tetramethyldisiloxane) norbornane dianhydride (TDNA), exo-5,5' - (1, 3-dimethyl 1, 3-diphenyldisiloxane) norbornane dianhydride (DMDPNA), exo-5,5'- (1, 3, 5-hexamethyltrisiloxane) norbornane dianhydride (HTNA), exo-5,5' - (1, 3, 5-trimethyl 1,3,5, -triphenyltrisiloxane) di-norbornane dianhydride (TMTPNA), exo-5,5'- (1, 3-tetraphenyldisiloxane) di-norbornane dianhydride (TPNA) and exo-5,5' - (1, 3, 5-hexaphenyltrisiloxane) di-norbornane dianhydride (HPNA) in any combination ratio. The listed norbornane dianhydrides containing siloxane structures have the following structural formula:
。
4,4 '-benzophenone tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride 4,4' -benzophenone tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 3',4,4' -diphenylmethane tetracarboxylic dianhydride, 2', 3' -diphenylmethane tetracarboxylic dianhydride, 3',4' -diphenylsulfone tetracarboxylic dianhydride, naphthalene-1, 4,5, 8-tetracarboxylic dianhydride, meso-butane-1, 2,3, 4-tetracarboxylic dianhydride, 1,2,3, 4-cyclobutane-tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane-tetracarboxylic dianhydride, 1,2,4, 5-cyclopentane-tetracarboxylic dianhydride, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride, dicyclohexyl-3, 4,3',4' -tetracarboxylic dianhydride, bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylic acid) 1, 4-phenylene ester and their mixture in any ratio. Meso-is known to those skilled in the art to represent meso.
In the above-described positive photosensitive polyimide resin, the aromatic diamine containing at least one phenolic hydroxyl group may be selected from the group consisting of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, 3 '-diamino-4, 4' -dihydroxydiphenyl ether 4,4 '-diamino-3, 3' -dihydroxydiphenyl ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxybenzophenone, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, 1, 3-diamino-4, 6-dihydroxybenzene, and mixtures thereof in any ratio.
In the positive photosensitive polyimide resin, the diamine containing no phenolic hydroxyl group may be aromatic diamine, aliphatic diamine or siliceous diamine; preferably, the method comprises the steps of, the aromatic diamine is selected from the group consisting of mercapto-containing aromatic diamines (e.g., dimercapto-phenylenediamine), 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl methane, 4' -diaminodiphenyl methane, 3, 4-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, benzidine m-phenylenediamine, p-phenylenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 1, 4-bis (4-aminophenoxy) benzene, 2' -dimethyl-4, 4' -diaminobiphenyl, 2' -diethyl-4, 4' -diaminobiphenyl, 3' -dimethyl-4, 4' -diaminobiphenyl, 3' -diethyl-4, 4' -diaminobiphenyl, 2', aromatic diamines such as 3,3' -tetramethyl-4, 4' -diaminobiphenyl, 3', 4' -tetramethyl-4, 4' -diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 1, 3-bis (aminomethyl) cyclohexane, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 1-bis (4-aminophenyl) cyclohexane, bis (aminomethyl) bicyclo [2.2.1] heptane, 1, 4-diaminocyclohexane, 4' -diamino-3, 3' -dimethyldicyclohexylmethane, 4' -diaminodicyclohexylmethane and mixtures thereof in any proportions.
In the positive photosensitive polyimide resin, the molecular weight modifier may be selected from phthalic anhydride, hydrogenated phthalic anhydride, 4-phenylacetylene phthalic anhydride, hydrogenated 4-cresyl anhydride, 3-chlorophthalic anhydride, 3-bromophenol, 4-chlorophthalic anhydride, 4-bromophenol, perchlorophthalic anhydride, perbromophthalic anhydride, 3, 4-dichlorophenolic anhydride, 3, 4-dibromophthalic anhydride, maleic anhydride, ethynylphthalic anhydride, trimellitic anhydride, 4-methylphthalic anhydride, phenylsuccinic anhydride, aniline, 2-aminoparacresol, 3-aminoparacresol, 4-aminoparacresol, 5-aminophthalol, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminophenylthiophenol, 4-aminophenylthiophenol, 2-aminotrifluorotoluene, 3-aminotoluene, 2-phenylethynyl aniline, 3-phenylethynyl aniline, noramine, butylamine, propyl amine, and a mixture thereof in any ratio. The amount of the molecular weight regulator used in the present application is not limited as long as the object of the present application can be achieved, and the molecular weight is controlled within the range of 15000 to 25000 weight average molecular weight, and the amount (molar amount) of the molecular weight regulator may be 0.005 to 0.3 times the molar amount of the above-mentioned total diamine.
A second object of the present invention is to provide a method for producing a positive photosensitive polyimide resin.
The preparation method of the positive photosensitive polyimide resin comprises the following steps:
(1) Dissolving the total diamine in an organic solvent to obtain a diamine solution;
(2) Adding the total dianhydride into the diamine solution, and then adding the molecular weight regulator for polycondensation reaction to obtain a polyamide resin solution;
(3) And adding a dehydrating agent into the polyamide resin solution, and imidizing the polyamide resin to obtain the positive photosensitive polyimide resin.
In the preparation method, in the step (1), the organic solvent is selected from N 'N dimethylformamide, N' N dimethylacetamide, N-methyl-epsilon-caprolactam, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, phenol, m-cresol, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, 3-ethoxypropionic acid ethyl ester, methyl ethyl ketone, cyclopentanone, cyclohexanone and a mixture thereof in any proportion.
In the step (2), the temperature of the polycondensation reaction may be 0 to 60 ℃, and specifically may be performed at room temperature; as known to those skilled in the art, the room temperature refers to a temperature of 10 to 30 ℃, for example 25 ℃; the polycondensation reaction time may be 1 to 24 hours, specifically may be 4 hours.
In the step (3), the dehydrating agent may be an aromatic hydrocarbon or substituted aromatic hydrocarbon dehydrating agent, preferably any one of benzene, toluene, o-xylene, m-xylene, p-xylene and ethylbenzene; the addition amount of the dehydrating agent is 1% -30% of the mass of the solvent, and preferably 4% -20%.
The imidization temperature is a reflux temperature, for example, 120-200 ℃, and the time can be 1-24 hours. The water generated during the reaction forms an azeotrope with the substituted aromatic hydrocarbon dehydrating agent and is removed by a dehydration device such as distillation, standing, layering and the like.
The preparation method, in the step (3), further comprises a step of separating the polyimide resin from the reacted system. The step of separating may specifically be as follows: pouring the polyimide resin solution after the reaction into a large amount of poor solvent to separate out solid resin; and washing and drying the solid resin to obtain the positive photosensitive polyimide resin. The poor solvent may specifically be deionized water.
It is a third object of the present invention to provide a positive photosensitive polyimide resin composition.
The positive photosensitive polyimide resin composition of the invention consists of the following components:
100 parts by mass of positive photosensitive polyimide resin, 1-50 parts by mass of photoacid generator, 0.01-50 parts by mass of sensitizer, 0.01-50 parts by mass of cross-linking agent, 0.01-30 parts by mass of adhesion promoter and 100-1000 parts by mass of organic solvent.
As an example, the positive photosensitive polyimide resin composition is composed of 100 parts by mass of a positive photosensitive polyimide resin, 10 parts by mass of a photoacid generator, 5 parts by mass of a sensitizer, 4 parts by mass of a crosslinking agent, 5 parts by mass of an adhesion promoter, and 240 parts by mass of an organic solvent.
In the positive photosensitive polyimide resin composition, the photoacid generator (PAG) may be diazonaphthoquinone compound, iodonium salt compound, sulfonium salt compound, phosphonium salt compound, diazonium salt compound or iodonium salt compound;
in view of the effect of suppressing the solubility of the resin film in the unexposed region, the diazonaphthoquinone compound is preferable; the diazonaphthoquinone compound is preferably any one of the following C1) to C3):
c1 A compound generated by esterification reaction of diazonaphthoquinone sulfonic acid and polyhydroxy compound;
c2 A compound produced by a sulfonylation reaction of diazonaphthoquinone sulfonic acid and a polyamine-based compound;
c3 A compound generated by esterification and/or sulfonylation of diazonaphthoquinone sulfonic acid and polyhydroxy polyamine compound; the ratio of substitution by the diazonaphthoquinone sulfonic acid compound in the polyhydroxy polyamine compound is preferably 30% -90%, more preferably 50% -90%;
Preferably, the polyol is 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-26-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34-X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, triML-P, triML-35XL, TML-BP, TML-HQ, TML-PP-BPF, TML-BP, TML-TMOM-BP, HML-TPBA, PHTPL (trade name of PHTPP), available from Benzhou chemical industries, inc.), BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name above, available from Asahi organic materials industries, inc.), 2, 6-dimethoxymethyl-4-tert-butylphenol, 2, 6-dimethoxymethyl-p-cresol, 2, 6-diacetoxymethyl-p-cresol, naphthol, 2,3, 4-trihydroxybenzophenone, 2,3, 4' -tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, pyrogallol acetonide, any one of m-cresol formaldehyde resin, phenol formaldehyde resin and the like, but is not limited thereto;
It is also possible to consider that the composition contains two or more different photoacid generators to increase the difference in dissolution rate between the resin film in the exposed region and the resin film in the non-exposed region, so as to facilitate obtaining high-quality stereolithography patterns; more preferably, the diazonaphthoquinone compound is a 1, 2-diazonaphthoquinone-5-sulfonyl compound or a 1, 2-diazonaphthoquinone-4-sulfonyl compound, such as 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate;
preferably, the iodonium salt compound is bis (4-t-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, 4-isopropyl-4' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nitrate, [4- (trifluoromethyl) phenyl ] (2, 4, 6-trimethylphenyl) iodonium trifluoromethane sulfonate, [3- (trifluoromethyl) phenyl ] (2, 4, 6-trimethylphenyl) iodonium trifluoromethane sulfonate, [ (4-trifluoromethyl) phenyl ] (2, 4, 6-trimethoxyphenyl) iodonium p-toluene sulfonate, phenyl [3- (trifluoromethyl) phenyl ] iodonium trifluoromethane sulfonate, (4-nitrophenyl) (phenyl) iodonium trifluoromethane sulfonate, (4-methylphenyl) (2, 4, 6-trimethylphenyl) iodonium trifluoromethane sulfonate, [ 3-methylphenyl ] (2, 4, 6-trimethylphenyl) iodonium p-toluene sulfonate, [ 2,4, 6-trimethylphenyl ] iodonium (2, 4-trifluoromethane sulfonate, [ 2, 6-trimethylphenyl ] iodonium tetrafluorosulfonate, (-4-hydroxyphenyl) iodonium tetrafluorosulfonate (5-fluoro-2-nitrophenyl) (2, 4, 6-trimethoxyphenyl) iodonium p-toluenesulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsonate, (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-trimethylpyridine) iodonium hexafluorophosphate, 4' -xylyliodonium hexafluorophosphate, or a mixture thereof in any ratio;
Preferably, the sulfonium salt compound is selected from any one of 1, 3-benzodithiopyrrole boron tetrafluoride salt, cyclopropyl diphenyl sulfonium tetrafluoroborate, dimethyl (methylthio) sulfonium tetrafluoroborate, diphenyl (methyl) sulfonium tetrafluoroborate, (difluoromethyl) bis (2, 5-dimethylphenyl) sulfonium tetrafluoroborate, 2- [4- (3-ethoxy-2-hydroxypropoxy) phenylcarbamoyl ] ethyldimethyl sulfide p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium methanesulfonate, triphenylsulfonium tetrafluoroborate, tris (4-tolyl) sulfonium hexafluorophosphate, tris (4-tolyl) sulfonium trifluoromethanesulfonate, triethylsulfonium bis (trifluoromethanesulfonyl) imide or a mixture thereof in any ratio.
In the positive photosensitive polyimide resin composition, the sensitizer can be an organic compound containing phenolic hydroxyl groups, hydroxyl groups or carboxyl groups, so that the photosensitivity can be improved and the development time can be shortened.
Preferably, the organic compound containing a phenolic hydroxyl group is selected from 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 (trade name above, available from the chemical industry Co., present) BIP-PC, BIR-PTBP, BIR-BIPC-F (trade name above, available from the organic materials Co., asahi), any one of 2, 2-Bis (4-hydroxyphenyl) propane, 4' -dihydroxydiphenyl sulfone, 2-Bis (4-hydroxyphenyl) hexafluoropropane, 2-Bis (4-hydroxy-3, 5-dimethylphenyl) propane, 9-Bis (4-hydroxyphenyl) fluorene, 4' -dihydroxydiphenyl cyclohexane, 1, 4-naphthalene diphenol, 1, 5-naphthalene diphenol, 1, 6-naphthalene diphenol, 1, 7-naphthalene diphenol, 2, 3-naphthalene diphenol, 2, 7-naphthalene diphenol, 2, 6-naphthalene diphenol, bis (4-hydroxyphenyl) sulfide, spiro [ fluorene-9, 9' -xanthene ] -3',6' -diol or a mixture thereof in any ratio;
Preferably, the organic compound containing hydroxyl groups is a saturated or unsaturated fatty alcohol containing 2 to 16 carbons; more preferably, the organic compound containing hydroxyl groups is selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, t-butanol, pentanol, n-hexanol, cyclopropylmethanol, cyclohexylmethanol, 4-methyl-1-cyclohexylmethanol, 3, 4-dimethylcyclohexanol, 4-ethylcyclohexanol, 4-t-butylcyclohexanol, heptanol, octanol, cyclooctanol, 1-cyclohexyl-1-pentanol, 3, 5-trimethylcyclohexanol, norbornene-2-methanol, cis-4-hepten-1-ol, cis-3-octen-1-ol, 2, 7-octadienol, 2, 4-methyl-2-pentanol, cyclohexylmethanol, cis-2-hexen-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, and mixtures thereof in any ratio;
preferably, the organic compound containing carboxyl is a carboxylic acid compound containing 2-16 carbon atoms; more preferably, the organic compound containing a carboxyl group is selected from the group consisting of 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-valeric acid, 4-methyl-n-valeric 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-decanoic 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-trimethylhexanoic acid, lauric acid, myrcenic acid, and mixtures thereof in any ratio; the organic compound containing a carboxyl group may be a saturated or unsaturated organic acid.
In the positive photosensitive polyimide resin composition described above, the crosslinking agent may be a compound containing an epoxy group, a compound containing a hydroxymethyl group or an alkoxymethyl group;
preferably, the epoxy group-containing compound is selected from any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl), epoxy group-containing silicone, more preferably 1, 4-butanediol diglycidyl ether, 2-bis (4-glycidoxyphenyl) propane, 9-bis (4-glycidoxy-3-tolyl) fluorene, 9-bis (4-glycidoxyphenyl) fluorene 1, 3-bis [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] -1, 3-tetramethyldisiloxane, diglycidyl 1, 2-cyclohexanedicarboxylate, diglycidyl 1,2,7, 8-diglycidyl octane, diglycidyl 4-cyclohexene-1, 2-dicarboxylate, triglycidyl isocyanurate, 4 '-methylenebis (N, N-dicyclohexyl aniline), neopentyl glycol diglycidyl ether, 2' - (2, 3,4, 5-octafluorohexane-1, 6-diyl) bis (ethylene oxide), neopentyl glycol diglycidyl ether, vinylcyclohexene diglycidyl ether, polyethylene glycol diglycidyl ether (polymerization degree 1-15), polypropylene glycol diglycidyl ether (polymerization degree 1-15), polydimethylsiloxane diglycidyl ether (polymerization degree 1-15), butanediol diglycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, 5-dimethyl-1, 3-bis (oxiranylmethyl) imidazolidine-2, 4-dione, 2' ' - [ methylene-tris (phenoxymethylene) ] tris (ethylene oxide), 1-tris (4-hydroxyphenyl) ethyl triglycidyl ether, bis (2, 3-epoxycyclopentyl) ether, 3, 4-epoxy-6-methylcyclohexylmethyl formate-3 ',4' -epoxy-6 ' -methylcyclohexylmethyl ester, vinylcyclohexene and epoxide, 3, 4-epoxycyclohexylmethyl formate-3 ',4' -epoxycyclohexylmethyl ester, diprenediepoxide, tetraphenylglycidyl ether ethane, triphenylglycidyl ether-methane, triglycidyl-p-aminophenol, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl xylyldiamine or tetraglycidyl-1, 3-diaminomethylcyclohexane; as the product having trade names, HP-850, HP-4032, HP-7200, HP-820, HP-4700, EXA-4710, HP-4770, EXA-859CRP, EXA-1514, EXA-48180, EXA-4850-150, EXA-4850-1000, EXA-4816, EXA-4812, BEO-60E, BPO-20E, HBE-100, DME-100, NC-3000, NC-6000 (Japanese chemical Co., ltd.) and the like and a mixture thereof in any ratio can be mentioned;
Preferably, the hydroxymethyl or alkoxymethyl containing compound is selected from 46DMOC, 46DMOEP (trade name above, manufactured by Asahi organic materials industry Co., ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34-X, 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, DMLBisc-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-BPA, TMBPAF, TMOM-BPAP, HML-TPBA, HMPHA-TPOM, HMPHOM-TPP (trade name above), available from the present state chemical industry, inc.), NIKALAC MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (Sanand Chemie Co., ltd.) and the like, and combinations thereof in any ratio.
In the positive photosensitive polyimide resin composition, the adhesion promoter is selected from gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, 3-methacryloxypropyl dimethoxy methylsilane, 3-methacryloxypropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-isocyanato trimethoxysilane, 3-isocyanato triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyldimethoxy silane, 3-mercaptomethyl trimethoxysilane, 3-mercaptomethyl dimethoxy silane, 3-mercaptopropyl ethoxy dimethoxy silane, 3-mercaptopropyl tripropoxy silane, vinyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3- (triethoxysilyl) propyl succinic anhydride, 3- (m-aminophenoxy) trimethoxysilane, p-aminophenyl trimethoxysilane, vinyl diethoxy silane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl trimethoxy silane, 3-acryloxy propyl trimethoxysilane, 3-acryloxy trimethoxy silane, 3-acryloxy propyl trimethoxy silane, 3-piperazinyl propyl methyl dimethoxy silane and a mixture thereof according to any proportion.
In the positive photosensitive polyimide resin composition, the organic solvent is selected from the group consisting of N-methylpyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethylsulfoxide, γ -butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and a mixture thereof in any ratio.
It is a fourth object of the present invention to provide a method for preparing the above positive photosensitive polyimide resin composition.
The preparation method of the positive photosensitive polyimide resin composition comprises the following steps: and under the condition of irradiation of a yellow light source, mixing the positive photosensitive polyimide resin, the photoacid generator, the sensitizer, the adhesion promoter and the organic solvent to form a homogeneous solution, so as to obtain the positive photosensitive polyimide resin composition.
In the preparation method, the mixing can be that the positive photosensitive polyimide resin, the photoacid generator, the sensitizer and the adhesion promoter are sequentially added into the organic solvent under the stirring condition, and the mixture is stirred for 1-24 hours at room temperature.
A fifth object of the present invention is to provide a patterned polyimide film prepared from the positive photosensitive polyimide resin composition described above.
A sixth object of the present invention is to provide a method for preparing the patterned polyimide film.
The preparation method of the patterned polyimide film comprises the following steps:
(1) Coating the positive photosensitive polyimide resin composition on the surface of a substrate to obtain a coating film;
(2) Baking the coating film in the step (1) to obtain a pre-baked film;
(3) Covering a mask plate on the pre-baking film in the step (2), and then exposing under ultraviolet i line and g line;
(4) Dissolving and removing the exposed part in the step (3) by adopting a developer, and then cleaning to obtain the incompletely cured patterned resin;
(5) And (3) heating and curing the incompletely cured patterned resin in the step (4) to obtain the patterned polyimide film.
In the preparation method, in the step (1), the coating step may adopt a spin coating method, a dip coating method, a spray coating method, a screen printing method or the like.
In the preparation method, in the step (2), the baking temperature can be 100-130 ℃, and specifically can be 120 ℃; the baking time can be 1-15 min, and specifically can be 3min. The baking may evaporate a part of the solvent in the coating film to form a pre-baked film having a certain hardness.
In the above preparation method, in the step (3), the exposure dose may be 300 to 400mJ/cm 2 。
In the above preparation method, in step (4), the developer may be 2.38% (Wt) TMAH aqueous solution. The cleaning can be performed by deionized water.
In the preparation method, in the step (5), the temperature of the heating and curing is 180-300 ℃ for 0.5-4 hours, for example, the heating and curing are performed for 1 hour at 150 ℃ and then the heating and curing are performed for 1 hour at 200 ℃. The heat curing is carried out under anaerobic conditions having an oxygen content of less than 100 ppm.
The polyimide film has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high adhesiveness and the like, and the main performances are shown in table 1.
TABLE 1 principal Properties of polyimide layer film
。
Based on the above-mentioned properties, a seventh object of the present invention is to provide the use of the positive photosensitive polyimide resin, the positive photosensitive polyimide resin composition, and at least one of a passivation layer film and a stress buffer protective layer film on the surface of a chip in the manufacture and packaging of very large scale integrated circuits, an interlayer dielectric insulating layer film of a multi-layered metal interconnect circuit, an electronic packaging substrate, and an insulating protective layer film in an optoelectronic packaging substrate; and/or the number of the groups of groups,
the patterned polyimide film is applied to at least one of a chip surface passivation layer film and a stress buffer protection layer film in the manufacturing and packaging of a very large scale integrated circuit, an interlayer dielectric insulation layer film of a multi-layer metal interconnection circuit, an electronic packaging substrate and an insulation protection layer film in a photoelectric packaging substrate.
Glass transition temperature test: the test is carried out by using a DMA instrument of the American TA Q800 series, a film stretching mode is adopted, the heating rate is 5 ℃/min, and the heating range is 50-400 ℃.
5% weight loss temperature test: the test is carried out by utilizing a TA Q50 series thermal analyzer in the United states, the nitrogen flow is 20 ml/min, the heating rate is 20 ℃/min, and the heating range is 50-750 ℃. The 5% weight loss temperature was determined from the TGA curve.
Dielectric property test: dielectric constants and dielectric losses were tested using an Agilent PNA network analyzer with a 100 micron 350℃cured film at a frequency of 10GHz.
Mechanical property test: mechanical properties were tested using an Instron 5965 tensile machine, U.S. and a tensile sample bar of 1cm wide and 10cm long and 10 μm thick at a tensile rate of 2mm/min.
Molecular weight testing: the measurement conditions of the weight average molecular weight based on the GPC method are as follows.
LiBr (0.03 mol/l) and H were used 3 A solution of PO4 (0.06 mol/l) in NMP was used as a eluent, and the concentration of the polymer was measured as a solution of 0.5mg to 1 ml. The apparatus used was Waters 2695 GPC, molecular weight calibration was performed with PS standards.
The invention has the following beneficial effects:
the photosensitive polyimide resin composition of the invention can form a stereolithography pattern formed by polyimide films on the surfaces of substrates such as silicon wafers after being coated on the surfaces of the substrates to form liquid adhesive films, and the stereolithography pattern has high pattern resolution and sharpness, and the polyimide films forming the stereolithography pattern have the characteristics of low dielectric constant, low dielectric loss, low water absorption, high cohesiveness and the like, and can meet the use requirements of manufacturing high-frequency IC circuits.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The reaction temperatures in the examples below were carried out at room temperature unless otherwise specified.
1. Synthesis of monomeric TDNA
65.66g (400 mmol) of cis-5-norbornene-2, 3-endo-dianhydride and 150g of dimethylchlorosilane were dissolved in 1000ml of dry toluene, 330. Mu.L of Pt (DVS) solution (800. Mu.L/mol double bond Karstedt catalyst) were added, the mixture was reacted at 110℃under a nitrogen pressure of 5atm for 48h and cooled, the excess dimethylchlorosilane was removed, and the product was dried at 0.4mm Hg for 6h to give 185g A as a white powder in 100% yield. 103.51 g (400 mmol) A was added to 8.35g (464 mmol) of water in 1000ml THF at 0deg.C, stirred at room temperature for 2h, the solvent was removed and the product dried at 160deg.C, 0.4mmHg for 3h to give 92.52g TDNA.
2. Synthesis of monomeric DMDPNA
65.66g (400 mmol) of cis-5-norbornene-2, 3-endo-dianhydride and 250g of methylphenyl chlorosilane were dissolved in 1000ml of dry toluene, 330. Mu.L of Pt (DVS) solution (800. Mu.L/mol double bond Karstedt catalyst) were added, the mixture was reacted at 110℃under a nitrogen pressure of 5atm for 48h and cooled, the excess of methylphenyl chlorosilane was removed, and the product was dried at 0.4mm Hg for 6h to give 128.34B as a white powder in 100% yield. 128.34g (400 mmol) of B are taken up in 1000ml of THF, 8.35g (464 mmol) of water are added at 0℃and stirred at room temperature for 2h, the solvent is removed and the product is dried at 160℃for 3h at 0.4mmHg to give 117.36g of DMDPNA.
EXAMPLE 1 preparation of hydroxyl-containing polyimide resin, composition and polyimide film
220. 220g N-methylpyrrolidone (NMP), 21.50g of 1, 3-diamino-4, 6-dihydroxybenzene, was added in sequence to a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen blanket, and dissolved by stirring at room temperature to form a homogeneous hydroxyl-containing diamine solution. Then, 18.56g TDNA,18.61g 4,4' -oxydiphthalic anhydride and 1.48g phthalic anhydride are weighed and added into the hydroxyl-containing diamine solution under stirring, and the stirring reaction is continued for 4 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain a hydroxyl group-containing polyimide resin A1, which had a weight average molecular weight mw= 24400 by GPC.
50g of the above-mentioned hydroxyl-containing polyimide resin A1, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-scale ultra clean room equipped with a yellow light, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer to form a liquid adhesive film with a certain thickness; baking at 120deg.C for 3min, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) (exposure dose 300-400 mJ/cm) 2 ) Developing with 2.38% (Wt) aqueous solution of tetramethylammonium hydroxide (TMAH), washing with deionized water, and baking in an oxygen-free blast oven with oxygen content lower than 100 ppm (150 ℃/1h+200 ℃/1 h) to obtain polyimide film stereolithography pattern with pattern resolution of 10 μm. The dielectric constant of the prepared polyimide film is 2.70, the dielectric loss is 0.0050, the water absorption is 0.70%, and the Tg is 240 ℃.
EXAMPLE 2 preparation of hydroxyl-containing polyimide resin, composition and polyimide film
220gNMP,36.57g 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added in sequence to a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen blanket, and dissolved by stirring at room temperature to form a diamine solution. Then adding 18.56gTDNA,18.61g 4,4' -oxydiphthalic anhydride and 0.76g phthalic anhydride into the diamine solution, and stirring for 4 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction was completed, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried under vacuum to obtain a hydroxyl group-containing polyimide resin A2, and the weight average molecular weight mw=22100 was measured by GPC.
50g of the above polyimide resin A2, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-grade ultra clean room equipped with a yellow light, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer; baking at 120deg.C for 3min to obtain a pre-baked film with thickness of 6 μm, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) at exposure dose of 300-400mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing by using 2.38% (Wt) TMAH aqueous solution, flushing by deionized water, and baking (150 ℃/1h,200 ℃/1 h) in an anaerobic blast oven with oxygen content lower than 100ppm to obtain polyimide film photoetching patterns, wherein the pattern resolution is 10 mu m. The polyimide film obtained had a dielectric constant of 2.5, a dielectric loss of 0.004, a water absorption of 0.7% and a Tg of 226 ℃.
EXAMPLE 3 preparation of hydroxyl-containing polyimide resin, composition and polyimide film
220g NMP,21.51g 1,3-diamino-4, 6-dihydroxybenzene was added sequentially to a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen blanket and dissolved by stirring at room temperature to form a diamine solution. Then adding 23.47g DMDPNA,18.61g 4,4' -oxydiphthalic anhydride and 0.83g phthalic anhydride into the diamine solution, and continuously stirring for 4 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain a polyimide resin A3 having a weight average molecular weight mw=21500 by GPC measurement.
50g of the above polyimide resin A3, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-scale ultra clean room equipped with a yellow light, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer; baking at 120deg.C for 3min to obtain a pre-baked film with thickness of 6 μm, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) at exposure dose of 300-400mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing by using 2.38% (Wt) TMAH aqueous solution, flushing by deionized water, and baking (150 ℃/1h,200 ℃/1 h) in an anaerobic blast oven with oxygen content lower than 100ppm to obtain polyimide film photoetching patterns, wherein the pattern resolution is 10 mu m. The resulting polyimide film had a dielectric constant of 2.9, a dielectric loss of 0.007, a water absorption of 0.6% and a Tg of 230 ℃.
EXAMPLE 4 preparation of hydroxyl-containing polyimide resin, composition and polyimide film
Into a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 220g NMP,27.92g 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone was added in sequence, and stirred and dissolved at room temperature to form a diamine solution. Then adding 23.47g of DMDPNA and 18.61g of 4,4' -oxydiphthalic anhydride into the diamine solution, adding 1.12g of phthalic anhydride as a molecular weight regulator, and stirring for 4 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain polyimide resin A4, which had a weight average molecular weight mw=21900 by GPC test.
50g of the above polyimide resin A4, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-scale ultra clean room equipped with a yellow light, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer; baking at 120deg.C for 3min to obtain a pre-baked film with thickness of 6 μm, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) at exposure dose of 300-400mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing by using 2.38% (Wt) TMAH aqueous solution, flushing by deionized water, and baking (150 ℃/1h,200 ℃/1 h) in an anaerobic blast oven with oxygen content lower than 100ppm to obtain polyimide film photoetching patterns, wherein the pattern resolution is 10 mu m. The polyimide film obtained had a dielectric constant of 2.8, a dielectric loss of 0.005, a water absorption of 0.8% and a Tg of 232 ℃.
EXAMPLE 5 preparation of hydroxyl-containing polyimide resin, composition and polyimide film
Into a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 220g NMP,14.14g 1,3 diamino-4, 6 dihydroxybenzene was added in sequence, and stirred and dissolved at room temperature to form a diamine solution. Then adding 18.56g TDNA,18.61g 4,4' -oxydiphthalic anhydride and 1.35g phthalic anhydride into the diamine solution, and continuously stirring for 4 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain polyimide resin A5, which had a weight average molecular weight mw= 22900 by GPC test.
50g of the above polyimide resin A5, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-grade ultra clean room equipped with a yellow light, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
The positive photosensitive material is preparedSpin-coating the solution of the polyimide resin composition on the surface of a 6-inch wafer; baking at 120deg.C for 3min to obtain a pre-baked film with thickness of 6 μm, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) at exposure dose of 300-400mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing by using 2.38% (Wt) TMAH aqueous solution, flushing by deionized water, and baking (150 ℃/1h,200 ℃/1 h) in an anaerobic blast oven with oxygen content lower than 100ppm to obtain polyimide film photoetching patterns, wherein the pattern resolution is 15 mu m. The resulting polyimide film had a dielectric constant of 2.6, a dielectric loss of 0.007, a water absorption of 0.7% and a Tg of 204 ℃.
EXAMPLE 6 preparation of hydroxyl-containing polyimide resin, composition and polyimide film
220g of NMP,21.57g of bis (3-amino-4-hydroxy) biphenyl were successively introduced into a 500ml three-necked round-bottomed flask equipped with a mechanical stirrer, thermometer and nitrogen protection, and dissolved by stirring at room temperature to form a diamine solution. Then 18.56g TDNA and 18.38g dicyclohexyl-3, 4,3',4' -tetracarboxylic dianhydride were added to the diamine solution, followed by 0.70g phthalic anhydride, and stirring was continued for 4 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain polyimide resin A6, which had a weight average molecular weight mw=21600 by GPC test.
50g of the above polyimide resin A6, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-grade ultra clean room equipped with a yellow light, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer; baking at 120deg.C for 3min to obtain a pre-baked film with thickness of 6 μm, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) at exposure dose of 300-400mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Using 2.38% (Wt) TMAAnd (3) developing by using an aqueous solution H, flushing by using deionized water, and then baking (150 ℃/1H,200 ℃/1H) in an oxygen-free blast oven with the oxygen content lower than 100ppm to obtain the polyimide film photoetching pattern, wherein the pattern resolution is 15 mu m. The polyimide film obtained had a dielectric constant of 2.4, a dielectric loss of 0.003, a water absorption of 0.6% and a Tg of 274 ℃.
EXAMPLE 7 preparation of hydroxyl-containing polyimide resin, composition and polyimide film
Into a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 220g NMP,21.56g1,3 diamino-4, 6 dihydroxybenzene was added in sequence, and stirred and dissolved at room temperature to form a diamine solution. Then 18.56g TDNA and 17.65g 3,3', 4' -biphenyl tetracarboxylic dianhydride are added to the diamine solution, 1.3g phthalic anhydride is added, and stirring is continued for 4 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain polyimide resin A7 having a weight average molecular weight mw=22300 in GPC test.
50g of the above polyimide resin A7, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-grade ultra clean room equipped with a yellow light, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer; baking at 120deg.C for 3min to obtain a pre-baked film with thickness of 6 μm, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) at exposure dose of 300-400mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing by using 2.38% (Wt) TMAH aqueous solution, flushing by deionized water, and baking (150 ℃/1h,200 ℃/1 h) in an anaerobic blast oven with oxygen content lower than 100ppm to obtain polyimide film photoetching patterns, wherein the pattern resolution is 15 mu m. The dielectric constant of the obtained polyimide film is 2.9, the dielectric loss is 0.006, and the water absorption rate is high0.6% and Tg of 263 ℃.
EXAMPLE 8 preparation of hydroxyl-containing polyimide resin, composition and polyimide film
220. 220g N-methylpyrrolidone (NMP), 15.14g of 1, 3-diamino-4, 6-dihydroxybenzene, 10.03g of 2, 2-bis (4-aminophenyl) hexafluoropropane were successively added to a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and stirred at room temperature to dissolve to form a homogeneous hydroxyl-containing diamine solution. Then, 18.56g TDNA,18.61g 4,4' -oxydiphthalic anhydride and 1.6g phthalic anhydride are weighed and added into the hydroxyl-containing diamine solution under stirring, and the stirring reaction is continued for 4 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain a hydroxyl group-containing polyimide resin A8, which had a weight average molecular weight mw=23400 by GPC.
50g of the above-mentioned hydroxyl-containing polyimide resin A8, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-scale ultra clean room equipped with a yellow light, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer to form a liquid adhesive film with a certain thickness; baking at 120deg.C for 3min, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) (exposure dose 300-400 mJ/cm) 2 ) Developing with 2.38% (Wt) aqueous solution of tetramethylammonium hydroxide (TMAH), washing with deionized water, and baking in an oxygen-free blast oven with oxygen content lower than 100 ppm (150 ℃/1h+200 ℃/1 h) to obtain polyimide film stereolithography pattern with pattern resolution of 13 μm. The dielectric constant of the prepared polyimide film is 2.60, the dielectric loss is 0.0040, the water absorption is 0.70%, and the Tg is 247 ℃.
Comparative example 1
In a 500ml three neck round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection was charged 21.81g of pyromellitic dianhydride (PMDA), 14.82g of n-butanol, 14.24g of pyridine and 95g of NMP and stirred at room temperature for 6h to yield the corresponding dibutyl phthalate. The product was combined with 23.79g SOCl 2 Reacting for 2h at 0-10 ℃ and 4h at room temperature to obtain the corresponding dibutyl isophthaloyl dichloride.
In a 1L three neck round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen protection device, 23.22g of 3,3 '-diamino-4, 4' -dihydroxydiphenyl ether and 84g of NMP were added and stirred to dissolve to form a homogeneous transparent solution; cooling the mixture to below 10 ℃ by adopting ice bath, and dropwise adding the prepared dibutyl isophthaloyl dichloride into a 3,3 '-diamino-4, 4' -dihydroxydiphenyl ether solution for 0.5h; then, reacting for 10 hours at room temperature; then adding 1.48g phthalic anhydride and stirring for 1h; the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried under vacuum to obtain polyimide resin A8.
50g of the above-mentioned polyacid ester resin, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane and 2.5g of gamma-glycidoxypropyl trimethoxysilane were successively added to 80g of NMP in a thousands-class ultra clean room equipped with a yellow light lamp, and stirred at room temperature for 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer; baking at 120deg.C for 3min to obtain a pre-baked film with thickness of 6 μm, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) at exposure dose of 300-400mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Developing by using 2.38% (Wt) TMAH aqueous solution, flushing by deionized water, and baking (150 ℃/1h,200 ℃/4 h) in an anaerobic blast oven with oxygen content lower than 100ppm to obtain polyimide film photoetching patterns, wherein the pattern resolution is 10 mu m. The polyimide film obtained had a dielectric constant of 3.6, a dielectric loss of 0.030, a water absorption of 2.40% and a Tg of 240 ℃.
Comparative example 2
220. 220g N-methylpyrrolidone (NMP), 36.70g of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, was successively introduced into a 500ml three-necked round bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, and dissolved by stirring at room temperature to form a homogeneous hydroxyl group-containing diamine solution. Then, 31.02g of 4,4' -oxydiphthalic anhydride and 1.48g of phthalic anhydride are weighed and added into the hydroxyl-containing diamine solution under stirring, and the stirring reaction is continued for 2 hours; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain a hydroxyl group-containing polyimide resin A9.
50g of the above-mentioned hydroxyl-containing polyimide resin A9, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-scale ultra clean room equipped with a yellow light, and stirred at room temperature for 1 to 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer to form a liquid adhesive film with a certain thickness; baking at 120deg.C for 3min, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) (exposure dose 300-400 mJ/cm) 2 ) Developing with 2.38% (Wt) aqueous solution of tetramethylammonium hydroxide (TMAH), washing with deionized water, and baking in an oxygen-free blast oven with oxygen content lower than 100 ppm (150 ℃/1h+200 ℃/1 h) to obtain polyimide film stereolithography pattern with pattern resolution of 30 μm. The dielectric constant of the prepared polyimide film is 3.20, the dielectric loss is 0.01, the water absorption rate is 1.30%, and the Tg is 256 ℃.
Comparative example 3
220. 220g N-methylpyrrolidone (NMP), 21.63g of 1, 3-diamino-4, 6-dihydroxybenzene, was added in sequence to a 500ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and nitrogen blanket, and dissolved by stirring at room temperature to form a homogeneous hydroxyl-containing diamine solution. Then, 44.42g of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride and 1.48g of phthalic anhydride are weighed, added into the hydroxyl-containing diamine solution under stirring, and the reaction is continued for 2 hours under stirring; then, 30g of toluene was added to the above reaction solution, heated to reflux temperature (120 to 200 ℃ C.), and reacted for 12 hours to distill off a part of toluene and carry out the produced water. After the reaction, the reaction solution was poured into 5L of deionized water to precipitate a solid, which was then filtered and dried in vacuo to obtain a hydroxyl group-containing polyimide resin A10.
50g of the above-mentioned hydroxyl-containing polyimide resin A9, 5g of 2,3, 4-trihydroxybenzophenone-1, 2-diazonaphthoquinone-5-sulfonate, 2.5g of 2, 2-bis (4-hydroxyphenyl) propane, 2g of 2, 2-bis (4-glycidoxyphenyl) propane and 2.5g of gamma-aminopropyl triethoxysilane were sequentially added to 120g of NMP in a thousands-scale ultra clean room equipped with a yellow light, and stirred at room temperature for 1 to 6 hours to form a homogeneous positive photosensitive polyimide resin composition solution.
Spin-coating the positive photosensitive polyimide resin composition solution on the surface of a 6-inch wafer to form a liquid adhesive film with a certain thickness; baking at 120deg.C for 3min, placing mask on its surface, exposing with ultraviolet lamp (i and g lines) (exposure dose 300-400 mJ/cm) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Developing with 2.38% (Wt) tetramethyl ammonium hydroxide (TMAH) aqueous solution, washing with deionized water, and baking (150 ℃/1h+200 ℃/1 h) in an oxygen-free blast oven with oxygen content lower than 100 ppm to obtain polyimide film stereolithography pattern with pattern resolution of 20 μm. The dielectric constant of the prepared polyimide film is 3.2, the dielectric loss is 0.01, the water absorption is 1.10%, and the Tg is 275 ℃.
The evaluation results of examples 1 to 7 and comparative examples 1 to 3 are shown in Table 2.
Table 2 performance tables of examples and comparative examples
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Although the above embodiments illustrate the present invention, the present invention is not limited to this embodiment, and it will be understood by those skilled in the art that modifications and variations may be made thereto without departing from the spirit and scope of the invention. The scope of the invention is defined by the claims.

Claims (10)

1. A positive photosensitive polyimide resin composition is composed of the following components:
100 parts by mass of positive photosensitive polyimide resin, 1-50 parts by mass of photoacid generator, 0.01-50 parts by mass of sensitizer, 0.01-50 parts by mass of cross-linking agent, 0.01-30 parts by mass of adhesion promoter and 100-1000 parts by mass of organic solvent;
the positive photosensitive polyimide resin is prepared from total dianhydride, total diamine and a molecular weight regulator;
the total dianhydride consists of norbornane dianhydride containing a siloxane structure and aromatic tetracarboxylic dianhydride without the siloxane structure;
the norbornane dianhydride containing siloxane structure is selected from exo-5,5'- (1, 3-tetramethyl disiloxane) norbornane dianhydride, exo-5,5' - (1, 3-dimethyl 1,3 diphenyl disiloxane) norbornane dianhydride, exo-5,5'- (1, 3, 5-hexamethyltrisiloxane) norbornane dianhydride, exo-5,5' - (1, 3, 5-trimethyl 1,3,5, -triphenyltrisiloxane) di-norbornane dianhydride, exo-5,5'- (1, 3-tetraphenyldisiloxane) di-norbornane dianhydride, exo-5,5' - (1, 3, 5-hexaphenyltrisiloxane) di-norbornane dianhydride, and mixtures thereof in any ratio;
The mass percentage of the norbornane dianhydride containing the siloxane structure in the total dianhydride is 10% -60%;
the total diamine is any one of the following B1) -B2):
b1 An aromatic diamine containing at least one phenolic hydroxyl group;
b2 Consisting of an aromatic diamine containing at least one phenolic hydroxyl group and a diamine containing no phenolic hydroxyl group;
the mass percentage of the aromatic diamine containing at least one phenolic hydroxyl group in the total diamine is 1% -100%;
the molar ratio of the total dianhydride to the total diamine is 0.9: 1-1: 1, a step of;
the weight average molecular weight of the positive photosensitive polyimide resin is 15000-25000;
the photoacid generator is diazonaphthoquinone compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, diazonium salt compounds or iodonium salt compounds;
the sensitizer is an organic compound containing phenolic hydroxyl, hydroxyl or carboxyl;
the cross-linking agent is a compound containing epoxy groups, and a compound containing hydroxymethyl or alkoxymethyl;
the adhesion promoter is selected from gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, 3-methacryloxypropyl dimethoxy methylsilane, 3-methacryloxypropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-isocyanatotrimethoxysilane, 3-isocyanatotriethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyldimethoxy silane, 3-mercaptomethyl trimethoxysilane, 3-mercaptomethyl dimethoxy silane, 3-mercaptopropyl ethoxy dimethoxy silane, 3-mercaptopropyl tripropoxy silane, vinyltrimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3- (triethoxysilyl) propyl succinic anhydride, 3- (m-aminophenoxy) trimethoxysilane, p-aminophenyl trimethoxysilane, aminophenyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-acetoxypropyl trimethoxysilane, 3-mercaptomethyl propyl trimethoxysilane, piperazine, and any combination of these three methoxypropyl silanes.
2. The positive photosensitive polyimide resin composition according to claim 1, characterized in that: the aromatic tetracarboxylic dianhydride not containing a siloxane structure is selected from pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 4' -oxydiphthalic anhydride, 3,4' -oxydiphthalic anhydride, 4' -terephthaloyl diphthalic anhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 3',4,4' -diphenylmethane tetracarboxylic dianhydride, 2', 3' -diphenylmethane tetracarboxylic dianhydride, 3',4' -diphenylsulfone tetracarboxylic dianhydride, naphthalene-1, 4,5, 8-tetracarboxylic dianhydride, bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylic acid) 1, 4-phenylene ester and a mixture thereof combined according to any proportion;
the aromatic diamine containing at least one phenolic hydroxyl group is selected from the group consisting of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methane, 3 '-diamino-4, 4' -dihydroxydiphenyl ether 4,4 '-diamino-3, 3' -dihydroxydiphenyl ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxybenzophenone, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, 1, 3-diamino-4, 6-dihydroxybenzene, and mixtures thereof in any ratio;
The aromatic diamine containing no phenolic hydroxyl group is selected from mercapto-containing aromatic diamine, 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl methane, 4' -diaminodiphenyl methane, 3, 4-diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 1, 4-bis (4-aminophenoxy) benzene, benzidine m-phenylenediamine, p-phenylenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 1, 4-bis (4-aminophenoxy) benzene, 2' -dimethyl-4, 4' -diaminobiphenyl, 2' -diethyl-4, 4' -diaminobiphenyl, 3' -dimethyl-4, 4' -diaminobiphenyl, 3' -diethyl-4, 4' -diaminobiphenyl, 2',3,3' -tetramethyl-4, 4' -diaminobiphenyl, 3', 4' -tetramethyl-4, 4' -diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 1-bis (4-aminophenyl) cyclohexane, and mixtures thereof in any ratio;
the molecular weight regulator is selected from phthalic anhydride, hydrogenated phthalic anhydride, 4-phenylacetylene phthalic anhydride, hydrogenated 4-creosol, 3-chlorophthalic anhydride, 3-bromophthalic anhydride, 4-chlorophthalic anhydride, 4-bromophthalic anhydride, perchlorophthalic anhydride, 3, 4-dichlorophthalic anhydride, 3, 4-dibromophthalic anhydride, maleic anhydride, ethynylphthalic anhydride, trimellitic anhydride, 4-methylphthalic anhydride, phenylsuccinic anhydride, aniline, 2-amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-m-cresol, 5-amino-o-cresol, 2-amino-phenol, 3-amino-phenol, 4-amino-thiophenol, 2-amino-benzotrifluoride, 3-amino-benzol, 2-amino-toluene, 4-phenylethynyl aniline, norborneneamine, butylamine, propargylamine, and mixtures thereof in any combination thereof.
3. The positive photosensitive polyimide resin composition according to claim 1 or 2, characterized in that: the preparation method of the positive photosensitive polyimide resin comprises the following steps:
(1) Dissolving the total diamine in an organic solvent to obtain a diamine solution;
(2) Adding the total dianhydride into the diamine solution, and then adding the molecular weight regulator for polycondensation reaction to obtain a polyamide resin solution;
(3) And adding a dehydrating agent into the polyamide resin solution, and imidizing the polyamide resin to obtain the positive photosensitive polyimide resin.
4. The positive photosensitive polyimide resin composition according to claim 3, characterized in that: in the step (1), the organic solvent is selected from N 'N dimethylformamide, N' N dimethylacetamide, N-methyl-epsilon-caprolactam, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, phenol, m-cresol, sulfolane, p-cresol, 3-chlorophenol, 4-chlorophenol, tetrahydrofuran, 3-ethoxypropionic acid ethyl ester, methyl ethyl ketone, cyclopentanone, cyclohexanone and a mixture formed by combining the same according to any proportion;
In the step (2), the temperature of the polycondensation reaction is 0-60 ℃ and the time is 1-24 hours;
in the step (3), the dehydrating agent is an aromatic hydrocarbon or substituted aromatic hydrocarbon dehydrating agent; the addition amount of the dehydrating agent is 1% -30% of the mass of the solvent; the imidization temperature is 120-200 ℃ and the imidization time is 1-24 h.
5. The positive photosensitive polyimide resin composition according to claim 4, wherein: the dehydrating agent is any one of benzene, toluene, o-xylene, m-xylene, p-xylene and ethylbenzene.
6. The positive photosensitive polyimide resin composition according to claim 5, characterized in that: the diazonaphthoquinone compound is selected from any one of the following C1) -C3): c1 A compound generated by esterification reaction of diazonaphthoquinone sulfonic acid and polyhydroxy compound; c2 A compound produced by a sulfonylation reaction of diazonaphthoquinone sulfonic acid and a polyamine-based compound; c3 A compound generated by esterification and/or sulfonylation of diazonaphthoquinone sulfonic acid and polyhydroxy polyamine compound;
the organic solvent is selected from N-methylpyrrolidone, N '-dimethylacetamide, N' -dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, ethyl acetate, butyl acetate, N-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydrofuran, tetrahydropyran, dioxane, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate and a mixture formed by combining the same according to any proportion.
7. The method for preparing a positive photosensitive polyimide resin composition according to any one of claims 1 to 6, comprising the steps of: and under the condition of irradiation of a yellow light source, mixing the positive photosensitive polyimide resin, the photoacid generator, the sensitizer, the adhesion promoter and the organic solvent to form a homogeneous solution, so as to obtain the positive photosensitive polyimide resin composition.
8. A patterned polyimide film prepared from the positive photosensitive polyimide resin composition of any one of claims 1 to 6.
9. The method for preparing the patterned polyimide film according to claim 8, comprising the steps of:
(1) Coating the positive photosensitive polyimide resin composition according to any one of claims 1 to 6 on the surface of a substrate to obtain a coating film;
(2) Baking the coating film in the step (1) to obtain a pre-baked film;
(3) Covering a mask plate on the pre-baking film in the step (2), and then exposing under ultraviolet i line and g line;
(4) Dissolving and removing the exposed part in the step (3) by adopting a developer, and then cleaning by using a rinsing liquid to obtain the incompletely cured patterned resin;
(5) And (3) heating and curing the incompletely cured patterned resin in the step (4) to obtain the patterned polyimide film.
10. Use of the positive photosensitive polyimide resin composition according to any one of claims 1 to 6 or the patterned polyimide film according to claim 8 for the preparation of at least one of a passivation layer film and a stress buffer protective layer film on the surface of a chip in the fabrication and packaging of very large scale integrated circuits, an interlayer dielectric insulating layer film of a multi-layered metal interconnect circuit, an electronic packaging substrate, and an insulating protective layer film in an optoelectronic packaging substrate.
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CN114920934B (en) * 2022-06-29 2024-03-22 深圳职业技术学院 Preparation method and application of photosensitive polyimide resin
CN114874441B (en) * 2022-07-12 2022-11-01 明士(北京)新材料开发有限公司 Chemical amplification type positive photosensitive polyimide coating adhesive and preparation method and application thereof
CN114995061B (en) * 2022-08-01 2022-11-01 明士(北京)新材料开发有限公司 Low-water-absorption positive photosensitive resin composition and preparation method and application thereof
CN117964897A (en) * 2024-01-10 2024-05-03 上海八亿时空先进材料有限公司 Alkali-soluble resin and application thereof
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423606A (en) * 2007-10-31 2009-05-06 比亚迪股份有限公司 Negative photosensitive polyimide material and preparation method thereof
JP2011236283A (en) * 2010-05-07 2011-11-24 Shin-Etsu Chemical Co Ltd New polyimide and method for producing the same
JP2012004200A (en) * 2010-06-15 2012-01-05 Shin Etsu Chem Co Ltd Thin wafer manufacturing method
CN110016136A (en) * 2017-12-05 2019-07-16 信越化学工业株式会社 Novel tetracarboxylic dianhydride, polyimide resin and its manufacturing method, photosensitive resin composition, pattern forming method
CN111142332A (en) * 2018-11-01 2020-05-12 信越化学工业株式会社 Photosensitive resin composition and photosensitive dry film
CN112175182A (en) * 2020-09-30 2021-01-05 明士(北京)新材料开发有限公司 Positive photosensitive polyesteramide resin and composition using same
JP2021117330A (en) * 2020-01-24 2021-08-10 信越化学工業株式会社 Photosensitive resin composition, photosensitive dry film, and pattern formation method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7335217B2 (en) * 2020-09-24 2023-08-29 信越化学工業株式会社 Photosensitive resin composition, pattern forming method, cured film forming method, interlayer insulating film, surface protective film, and electronic component

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423606A (en) * 2007-10-31 2009-05-06 比亚迪股份有限公司 Negative photosensitive polyimide material and preparation method thereof
JP2011236283A (en) * 2010-05-07 2011-11-24 Shin-Etsu Chemical Co Ltd New polyimide and method for producing the same
JP2012004200A (en) * 2010-06-15 2012-01-05 Shin Etsu Chem Co Ltd Thin wafer manufacturing method
CN110016136A (en) * 2017-12-05 2019-07-16 信越化学工业株式会社 Novel tetracarboxylic dianhydride, polyimide resin and its manufacturing method, photosensitive resin composition, pattern forming method
CN111142332A (en) * 2018-11-01 2020-05-12 信越化学工业株式会社 Photosensitive resin composition and photosensitive dry film
JP2021117330A (en) * 2020-01-24 2021-08-10 信越化学工業株式会社 Photosensitive resin composition, photosensitive dry film, and pattern formation method
CN112175182A (en) * 2020-09-30 2021-01-05 明士(北京)新材料开发有限公司 Positive photosensitive polyesteramide resin and composition using same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
何天白 等.《功能高分子与新技术》.化学工业出版社,2000,(第1版),第304-305页. *

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