CN114874441A - Chemical amplification type positive photosensitive polyimide coating adhesive and preparation method and application thereof - Google Patents

Chemical amplification type positive photosensitive polyimide coating adhesive and preparation method and application thereof Download PDF

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CN114874441A
CN114874441A CN202210811837.9A CN202210811837A CN114874441A CN 114874441 A CN114874441 A CN 114874441A CN 202210811837 A CN202210811837 A CN 202210811837A CN 114874441 A CN114874441 A CN 114874441A
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phenolic hydroxyl
methyl
polyimide resin
parts
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CN114874441B (en
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王立哲
贾斌
曹雪媛
孙朝景
杨士勇
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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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

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Abstract

The invention discloses a chemical amplification type positive photosensitive polyimide coating adhesive and a preparation method and application thereof. The chemical amplification type positive polyimide coating adhesive is prepared from the following components in parts by mass: 100 parts of partially-substituted polyimide resin containing phenolic hydroxyl, 5-25 parts of photoacid generator, 0-10 parts of photosensitive accelerator, 0-10 parts of adhesion promoter, 0-10 parts of alkaline inhibitor, 0-10 parts of cross-linking agent and 200-500 parts of organic solvent II. The chemical amplification type positive polyimide coating adhesive provided by the invention has the advantages of high photoetching pattern resolution ratio (less than 5 mm), low pattern section cone angle and controllability (15-45) o ) High film retention rate (>84 percent), good chemical corrosion resistance, good adhesion with different metal interfaces (peeling strength 70 MPa) and the like, and is suitable for photoelectric plane display, semiconductor chip packaging and the likeThe field of the technology.

Description

Chemical amplification type positive photosensitive polyimide coating adhesive and preparation method and application thereof
Technical Field
The invention relates to a chemical amplification type positive photosensitive polyimide coating adhesive and a preparation method and application thereof, belonging to the technical field of preparation of high polymer materials.
Background
Photosensitive polyimide coating (PSPI) can be coated on the surface of a substrate such as monocrystalline silicon to form a liquid glue film, and a three-dimensional precursor resin pattern can be formed on the surface of the substrate after the Photosensitive polyimide coating is processed by photoetching processes such as prebaking, exposure, development, rinsing and the like; polyimide resin formed by curing precursor resin for forming a photoetching pattern at high temperature has the advantages of high temperature resistance, high strength and toughness, high electrical insulation, high chemical corrosion resistance and the like, is widely applied to the manufacturing and packaging of ultra large scale integrated circuits (ULSI), and mainly comprises an interlayer insulation dielectric layer film of multilayer metal interconnection circuit (RDL), an alpha-Particle shielding layer (alpha-Particle Barrier), a Stress absorption and Buffer layer film (Stress Relief and Buffer Coating) and the like. Meanwhile, the method has wide application value in the preparation of photoelectric displays such as OLED, PLED and LCD.
In the process of manufacturing electro-optical displays (such as OLED, PLED, etc.), not only is the PSPI material required to have excellent physical properties and resolution, but also the cross section of the three-dimensional stereo pattern formed by photoetching has a lower taper angle (taper angle), i.e. the taper angle between the oblique side and the bottom side of the pattern cross section. Too high a pixel division layer taper angle can lead to anode layer faults and electrode fringe electric field concentrations in the device, which can cause device damage. Too low a cone angle results in low light emitting element density and reduced device display resolution. For the traditional photosensitive polyimide material, because the photoetching three-dimensional pattern is mainly influenced by the exposure range, the cone angle of the photoetching three-dimensional pattern is difficult to be effectively regulated and controlled. Chemical amplified photosensitive polyimide (CA-PSPI) can effectively regulate and control the cone angle of a stereo lithography pattern because the topography of the lithography pattern is influenced by the migration range of Lewis acid.
Jin zhi et al (CN 102893214B) discloses a positive photosensitive polyimide resin composition. Aromatic tetracid dianhydride or aromatic diacid chloride diester and aromatic diamine containing phenolic hydroxyl are polymerized to form polyimide resin containing phenolic hydroxyl; dissolving the positive photosensitive polyimide coating glue and a DNQ type photoacid generator in an organic solvent to form the positive photosensitive polyimide coating glue. The cross section of the photoetching three-dimensional graph formed after photoetching and drawing and high-temperature curing at 230 ℃ has a low taper angle, and the requirements of manufacturing an organic light-emitting diode (OLED) display device can be met. Tortoise et al (CN 108027562B) disclose a negative-type colored photosensitive resin composition, which is obtained by polymerizing an aromatic tetracarboxylic dianhydride with a phenolic hydroxyl group-containing aromatic diamine to form a phenolic hydroxyl group-containing polyimide resin or a polyimide precursor resin. Meanwhile, aromatic diacid derivative and aromatic diamine containing phenolic hydroxyl are polymerized to form polybenzoxazole resin or polybenzoxazole precursor resin containing phenolic hydroxyl. The resin is mixed with siloxane resin, Cardo resin or acrylic resin, and then added with photosensitizer, black toner, cross-linking agent and the like to be uniformly mixed to form photosensitive polyimide coating adhesive or polybenzoxazole coating adhesive. The coating glue is subjected to glue homogenizing, prebaking, exposure, alkaline water development and 250 ℃ curing on a substrate to form a photoetching three-dimensional pattern, and the photoetching three-dimensional pattern has the characteristics of high sensitivity, low section cone angle, excellent light shielding property and the like. On the basis of Guyuan Yougha et al (CN 111164512A), discloses a photosensitive polyimide resin composition and a preparation method thereof, wherein an epoxy cross-linking agent with a specific structure is additionally added to reduce the change of the size of a pattern opening before and after the resin composition is thermally cured, so that a lower cone angle is achieved, and the requirements of manufacturing an organic Electroluminescent (EL) display can be met. Therefore, the prior art means can not simultaneously meet the requirements on the stereo structure appearance, the photoetching resolution, the photoetching manufacturability and the physical performance in the process.
Disclosure of Invention
The invention aims to provide a chemical amplification type positive polyimide coating adhesive which has the characteristics of high resolution of a photoetching pattern, low and controllable taper angle of a section of the pattern, high film retention rate, high elongation at break, good chemical corrosion resistance, good adhesion with different interfaces and the like, and is suitable for being applied to the fields of photoelectric plane display, semiconductor chip packaging and the like.
The invention firstly provides a preparation method of partially-substituted polyimide resin containing phenolic hydroxyl, which comprises the following steps:
s1, in the presence of a blocking agent, carrying out polymerization reaction on aromatic tetracarboxylic dianhydride and aromatic diamine containing phenolic hydroxyl in an organic solvent I to obtain polyamic acid resin solution containing phenolic hydroxyl;
s2, adding a water-carrying agent and an organic base into the reaction system of the step S1, and carrying out an imide reaction to obtain a polyimide resin containing phenolic hydroxyl groups;
s3, stirring the polyimide resin containing phenolic hydroxyl, the hydroxyl protective agent and the catalyst in an organic solvent I; then dispersing in water, and filtering to obtain the partially substituted polyimide resin containing phenolic hydroxyl.
In the above preparation method, in step S1, the aromatic tetracarboxylic dianhydride is selected from at least one of pyromellitic dianhydride (PMDA), 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (OPDA), 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride (BFDA), 2-bis (3, 4-phthalic dianhydride) propane (BAPPA), and 2, 2-bis (3, 4-phthalic dianhydride) -1,1,1,3,3, 3-hexafluoropropane (6 FDA);
the aromatic diamine containing phenolic hydroxyl is selected from p-Phenylenediamine (PDA), 4, 4-diaminodiphenyl ether (4,4-ODA), 3, 4-diaminodiphenyl ether (3,4-ODA), 1, 4-bis (4-aminophenoxy) -benzene (1,3,4-APB), 1, 4-bis (4-aminophenoxy) -benzene (1,4,4-APB), 2-bis (4-aminophenyl) propane (APP), 2-bis [4- (4-aminophenoxy) phenyl) ] propane (BAPP), 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP for short), 2-bis (3-amino-4-hydroxyphenyl) propane (BHAPP), 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 3 '-dihydroxybenzidine (p-HAB), 2-bis (4-aminophenyl) hexafluoropropane (6F-APP for short), 2-bis [4- (4-aminophenoxy) phenyl) ] hexafluoropropane (6F-BAPP), 3' -dihydroxybenzidine, at least one of 2,2' -bis (trifluoromethyl) diaminobiphenyl (TFMB), 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 1, 3-bis (3-aminopropyl) tetraphenyldisiloxane, 1, 3-bis (3-aminophenoxy) tetramethyldisiloxane and 1, 3-bis (4-aminophenoxy) tetramethyldisiloxane;
the end-capping reagent is selected from at least one of phthalic anhydride, 3-methyl phthalic anhydride, 4-methyl phthalic anhydride, acetic anhydride, propionic anhydride, aniline, 3-methylaniline, 4-methylaniline, 3-aminophenylacetylene, 4-ethynylaniline, 3-aminophenol, 4-aminophenol, cis-5-norbornene-exo-2, 3-dicarboxylic anhydride, methylamine, ethylamine and propylamine;
the molar ratio of the end-capping reagent to the aromatic diamine containing phenolic hydroxyl is 0-70: 100, wherein the using amount of the end capping agent is not zero;
the organic solvent I is at least one selected from N-methyl-2-pyrrolidone (NMP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), g-butyrolactone (GBL), beta-propiolactone, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, 3-methoxybutyl acetate, propylene glycol methyl ether acetate, tetrahydrofuran, dioxane, ethyl lactate, ethylene glycol diethyl ether, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether.
In the preparation method, in the step S1, the temperature of the polymerization reaction is 15-40 ℃ and the time is 0.5-96 hours.
In the above preparation method, in step S2, the organic base is at least one selected from triethylamine, pyridine, isoquinoline, 4-dimethylaminopyridine, 2, 6-dimethylpyridine, imidazole, piperazine, N-diisopropylethylamine, and N, N-dimethylformamide;
the temperature of the imidization reaction is 160-220 ℃, and the time is 1-24 h;
the water-carrying agent is toluene or xylene, and the weight ratio of the water-carrying agent to the polyamic acid resin containing phenolic hydroxyl is (0.1-10): 1;
the ratio of the molar weight of the organic base to the number of repeating units of the phenolic hydroxyl group-containing polyamic acid resin is 0.01-0.1: 1; the weight average molecular weight of the polyimide resin containing phenolic hydroxyl groups is 5000-100000 g/mol.
In the above preparation method, in step S3, the hydroxyl protecting agent is at least one selected from triphenylchloromethane, chloromethyl methyl ether, chloromethyl ethyl ether, benzyl bromide, p-methoxy benzyl chloride, dihydropyran, trifluoroacetic anhydride, di-tert-butyl dicarbonate, acetic anhydride, pivaloyl chloride, benzoyl chloride, tert-butyl alcohol, toluene, and xylene;
the catalyst is selected from at least one of triethylamine, pyridine, isoquinoline, 4-dimethylaminopyridine, 2, 6-dimethylpyridine, imidazole, piperazine, N-diisopropylethylamine, N-dimethylformamide, sodium hydride and p-toluenesulfonic acid;
the stirring temperature is 20-100 ℃, and the stirring time is 0.5-96 hours;
the molar ratio of the catalyst to the hydroxyl protective agent is 0.03-0.3: 1.
the partially substituted polyimide resin containing phenolic hydroxyl groups has a phenolic hydroxyl group protection rate of 20-100%, preferably 25-75%, 25-40%, 45-70%, 25%, 40% or 70%, and preferably a tert-butoxycarbonyl substituted partial hydroxyl group or a methoxymethyl ether substituted partial hydroxyl group.
On the basis of the partially substituted phenolic hydroxyl group-containing polyimide resin, the invention also provides a chemical amplification type positive polyimide coating adhesive which is prepared from the following components in parts by mass:
100 parts of partially-substituted polyimide resin containing phenolic hydroxyl, 1-30 parts of photoacid generator, 0-10 parts of photosensitive accelerator, 0-10 parts of adhesion promoter, 0-10 parts of alkaline inhibitor, 0-10 parts of cross-linking agent and 200-500 parts of organic solvent II;
preferably, the chemical amplification type positive polyimide coating adhesive comprises the following components:
1) the partially substituted polyimide resin containing phenolic hydroxyl, a photoacid generator and an organic solvent II, wherein the mass ratio of the polyimide resin containing phenolic hydroxyl to the photoacid generator to the organic solvent II can be 100: 5-30: 260. 100, and (2) a step of: 5: 260. 100, and (2) a step of: 15: 260 or 100: 30: 260 of a nitrogen atom;
2) the partially substituted polyimide resin containing phenolic hydroxyl, a photoacid generator, an adhesion promoter and an organic solvent II, wherein the mass ratio of the polyimide resin containing phenolic hydroxyl to the organic solvent II can be 100: 5-30: 5: 260. 100, and (2) a step of: 5: 5: 260. 100, and (2) a step of: 15: 5: 260 or 100: 30: 5: 260 of a nitrogen atom;
3) the partially substituted polyimide resin containing phenolic hydroxyl, a photoacid generator, an adhesion promoter, an alkaline inhibitor and an organic solvent II, wherein the mass ratio of the polyimide resin containing phenolic hydroxyl to the organic solvent II can be 100: 5-30: 5: 1.5: 260 or 100: 15: 5: 1.5: 260 of a nitrogen atom;
4) the partially substituted polyimide resin containing phenolic hydroxyl, a photoacid generator, an adhesion promoter, a photosensitive promoter and an organic solvent II, wherein the mass ratio of the polyimide resin containing phenolic hydroxyl to the photosensitive promoter can be 100: 5-30: 5: 1.5: 260 or 100: 15: 5: 1.5: 260 of a nitrogen atom;
5) the partially substituted polyimide resin containing phenolic hydroxyl, a photoacid generator, an adhesion promoter, a photosensitive promoter, a crosslinking agent and an organic solvent II, wherein the mass ratio of the polyimide resin containing phenolic hydroxyl to the photosensitive promoter to the organic solvent II can be 100: 5-30: 5: 1.5: 5: 260 or 100: 15: 5: 1.5: 5: 260.
specifically, the photoacid generator is selected from the group consisting of Irgacure PAG103, Irgacure PAG 121, Irgacure PAG 169, Irgacure PAG250, Irgacure PAG290, diphenyliodonium hexafluorophosphate, tri-p-tolylsulfonium hexafluorophosphate, bis (3-methylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, 4' -ditolyl iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, (2-naphthyl) (2,4, 6-trimethylphenyl) iodonium hexafluorophosphate, (4-biphenyl) (2,4, 6-trimethylphenyl) iodonium hexafluorophosphate, bis (3-methylphenyl) iodonium hexafluorophosphate, bis (2-methylphenyl) iodonium hexafluorophosphate, 4-octyloxy diphenyliodonium hexafluoroantimonate, diphenyliodonium nitrate, diphenyl (trifluoromethyl) sulfonium trifluoromethanesulfonate, bis (trifluoromethyl) iodonium hexafluorophosphate, sodium diphenylphosphate, sodium salt, sodium hexafluorophosphate, sodium diphenylphosphate, sodium salt, Tri-p-tolylsulfonium trifluoromethanesulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, 1-naphthyldiphenylsulfonium trifluoromethanesulfonate, tris (4-tert-butylphenyl) sulfonium trifluoromethanesulfonate, (4-phenoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonate, bis [4- (1, 1-dimethylethyl) phenyl ] iodonium trifluoromethanesulfonate, (2-tolyl) (2,4, 6-trimethylphenyl) iodonium trifluoromethanesulfonate, phenyl (2,4, 6-trimethoxyphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, N-hydroxynaphthoylimide trifluoromethanesulfonate, N-naphthylimide trifluoromethanesulfonate, sodium hydrogen sulfonate, sodium salt, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, N-hydroxy-5-norbornene-2, 3-diamide nonafluorobutane sulfonic acid, perfluorobutylsulfonic acid triphenylsulfonium salt, bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonic acid, diphenyliodosyl chloride, and at least one salt of a weak acid consisting of an iodonium salt, a sulfonium salt, a phosphonium salt, an ammonium salt, and a diazonium salt;
the organic solvent II is at least one selected from N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, beta-propiolactone, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, 3-methoxybutyl acetate, propylene glycol methyl ether acetate, tetrahydrofuran, dioxane, ethyl lactate, ethylene glycol diethyl ether, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether;
the photosensitization accelerator is selected from at least one of 9, 10-diphenylanthracene, 9-anthracenealdehyde, anthracene-9, 10-dicarbaldehyde, 9, 10-diethoxyanthracene, xanthatine, curcumin, coumarin, 9, 10-bis (phenylethynyl) -2-ethylanthracene, 2-tert-butyl-9, 10-bis (naphthalen-2-yl) anthracene, 9, 10-dimethylanthracene, 9, 10-bis (1-naphthyl) anthracene, 9, 10-bis (2-naphthyl) anthracene, 9, 10-dibutoxyanthracene, 2-ethylanthracene and 2-isopropylthioxanthone;
the adhesion promoter is selected from gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatotrimethoxysilane, 3-isocyanatotriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydride, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatotriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydride, gamma-hydroxy-methyl-ethyl-3-isocyanatopropyl-3-isocyanato-methyl-trimethoxysilane, 3-isocyanato-methyl-ethyl-methyl-3-isocyanato-methyl-trimethoxysilane, and methyl-3-isocyanato-methyl-ethyl-trimethoxysilane, At least one of N- (3-diethoxymethylsilylpropyl) succinimide, N- (3-diethoxymethylsilylpropyl) phthalimide, benzophenone-3, 3 '-bis (N- [ 3-triethoxysilyl ] propylamide) -4,4' -dicarboxylic acid, and benzene-1, 4-bis (N- [ 3-triethoxysilyl ] propylamide) -2, 5-dicarboxylic acid;
the basic inhibitor is a non-photosensitive basic inhibitor or a photosensitive basic inhibitor, the non-photosensitive basic inhibitor is 2, 6-dimethylpiperidine, N-hydroxyethylpiperidine, imidazole, pyrazole or trioctylamine, and the photosensitive basic inhibitor is at least one of DNCDP, WPBG-300, WPBG-018, WPBG-027, WPBG-140 and WPBG-165 (trade name, manufactured by Fuji film, supra);
the cross-linking agent is selected from Bis-Z, BisP-EZ, 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-PTPTP, DML-34X, DML-BPA, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, ML-P, TriML-35XL, TML-BP, TML-HQ, TML-BPF, TML-pp-35-PFP, TMTML-TMBP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 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, manufactured by ASAHI YUKIZAI CORPORATION), 2, 6-dimethoxymethyl-4-tert-butylphenol, 2, 6-dimethoxymethyl-p-cresol, 2, 6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxyphenol, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, Bis-AP (trade name, manufactured by Honshu Industry Co., Ltd.), novolak resin, phenol novolak resin, novolak resin composition, and the like, At least one of glycerol propoxylate acid, polyoxyethylene glycerol ether, propoxylated pentaerythritol, tripentaerythritol, di (trimethylolpropane), 1,1, 1-tris (4-hydroxyphenyl) ethane, and 2-propenoic acid- (2-hydroxy-1, 3-propylene) bis [ oxy (2-hydroxy-3, 1-propylene) ] ester.
The chemical amplification type positive polyimide coating adhesive provided by the invention can be prepared according to the following method:
in a yellow light environment, taking the part of tert-butyl ester group substituted polyimide resin containing phenolic hydroxyl and the organic solvent II, and sequentially adding the polyimide resin containing phenolic hydroxyl and the organic solvent II into a reactor provided with a mechanical stirring device, an inert gas protection system and a temperature device; forming a homogeneous organic solution under stirring and inert gas protection; then, sequentially adding other auxiliary agents, and continuously stirring to obtain a chemical amplification type positive polyimide coating adhesive homogeneous phase solution with certain viscosity; filtering with 0.5 μm filter, and bottling.
The chemical amplification type positive polyimide coating adhesive provided by the invention can be applied to the fields of photoelectric plane display, semiconductor chip manufacturing and packaging and the like, and comprises a pixel definition layer, an organic insulating layer, an isolation column, a planarization layer, a TFT (thin film transistor) protective layer, a stress absorption-buffer protective film of a semiconductor chip and an alpha-particle shielding layer film of a photoelectric display.
The chemical amplification type positive polyimide coating adhesive provided by the invention has the advantages of high photoetching pattern resolution ratio (less than 5 mm), low pattern section cone angle and controllability (15-45) o ) High film retention rate (>84%), good chemical corrosion resistance, good adhesion with different metal interfaces (peeling strength 70 MPa) and the like, and is suitable for being applied to the fields of photoelectric plane display, semiconductor chip packaging and the like.
When the chemical amplification type positive polyimide coating adhesive is applied, the solution of the chemical amplification type positive polyimide coating adhesive can be coated on the surface of substrates such as monocrystalline silicon, ITO, glass and the like, a three-dimensional graph is formed through photoetching, and the chemical amplification type positive polyimide coating adhesive has the characteristics of high temperature resistance, high strength and toughness, chemical corrosion resistance, high electrical insulation, low dielectric constant, loss and the like after being cured at high temperature, and can be carried out by the following method, but is not limited to the following method: 1) coating: coating the chemical amplification type positive photosensitive polyimide coating adhesive on the surface of a substrate such as an indium tin oxide layer (ITO layer) in a spin coating and/or spraying manner; 2) pre-baking: in the range of 60 to 150 o C, pre-baking to form a solid adhesive film; 3) exposure: exposing through a photomask plate or a photomask by adopting an ultraviolet light source; 4) post-baking: in the range of 100 to 170 o C, carrying out postbaking treatment to promote acid catalytic reaction; 5) developing and rinsing: dissolving and removing the exposed resin layer by adopting a developing solution, and leaving the unexposed resin layer; rinsing to form a three-dimensional photoetching pattern; 6) heating and curing: placing the monocrystalline silicon or glass substrate with the three-dimensional photoetching pattern into an oven or a hot table, and heating and curing to convert the resin forming the three-dimensional photoetching pattern into high-temperature-resistant polyimide resin. 7) Forming pixels on the surface of the ITO substrate with the three-dimensional photoetching pattern by using conventional film coating methods such as vapor deposition, sputtering, electroplating, evaporation and the like; by the usual wayAnd coating a conductive layer on the pixel to form a light-emitting unit.
Drawings
FIG. 1 shows that the cone angle is controlled by adjusting the process conditions for the glue solution with the same formula.
FIG. 2 is a diagram showing a polyimide solid resin prepared in Synthesis example 1 of the present invention in which 40% of phenolic hydroxyl groups are protected with t-butoxycarbonyl group 1 H NMR hydrogen spectrum.
Detailed Description
The following evaluation methods were used for performance evaluation in the following examples: 1) photoetching manufacturability: spin-coating a chemical amplification type positive photosensitive polyimide coating adhesive solution on the surface of a silicon wafer; in the range of 60 to 150 o C, pre-baking to form a glue film to obtain a polyimide coating film with the thickness of about 3 mu m, placing a mask plate on the surface of the polyimide coating film, exposing by adopting an i-line or ultraviolet lamp (i and g lines), and then performing 100-170% of exposure o C, carrying out post-baking treatment to complete acid catalytic reaction; developing with 2.38wt% tetramethyl ammonium hydroxide aqueous solution developer, rinsing with deionized water, heating and curing in a forced air oven (230 ℃/30min) to obtain polyimide resin stereolithography pattern, and measuring the minimum resolution.
2) Cone angle: spin-coating a chemical amplification type positive photosensitive polyimide coating adhesive solution on the surface of a silicon wafer; in the range of 60 to 150 o C, pre-baking to form an adhesive film, placing a mask plate on the surface of the adhesive film, exposing by using an i-line or an ultraviolet lamp (i and g lines), and then performing 100-170% exposure o C, carrying out post-baking treatment to complete acid catalytic reaction; developing with 2.38wt% tetramethyl ammonium hydroxide aqueous solution developing solution, rinsing with deionized water, and heating and curing in a forced air oven (230 ℃/30min) to obtain the polyimide resin stereolithography pattern. Obtaining the polyimide photoetching three-dimensional graph section after heating and curing through a focused ion beam; and measuring an included angle between the pattern and the substrate.
3) Film retention rate: spin-coating a chemical amplification type positive photosensitive polyimide coating adhesive solution on the surface of a silicon wafer; in the range of 60-150 o C, pre-baking to form a glue film, and then baking at 100-170 deg.C o C, performing post-baking treatment, and measuring the film thickness D1 before development; by usingThe thickness D2 after curing was measured by developing with a 2.38wt% aqueous tetramethylammonium hydroxide solution, rinsing with deionized water, and heating in a forced air oven (230 ℃ C./30 min). The film retention rate was calculated as D2/D1.
4) Elongation at break: and cutting the polyimide film with the thickness of 10 mu m into sample strips with the width of 10mm and the length of 70mm, and measuring the elongation at break of the film by a stretching machine. The drawing rate of the drawing machine was 5 mm/min.
5) Adhesion to ITO surface: spin-coating a chemically amplified positive photosensitive polyimide coating adhesive solution on a glass surface covered with an (indium tin oxide) ITO film; in the range of 60 to 150 o C, pre-baking to form a glue film, and then baking at 100-170 deg.C o C, carrying out post-baking treatment; and heating and curing (230 ℃/30min) in a blast oven to obtain the polyimide layer film with the thickness of about 3 mu m. The adhesion between the film and copper was measured by measuring the chip bonding Strength (student Pull Die Bond Strength test) by the Quad Group pin method.
6) Chemical resistance: the polyimide photoetching three-dimensional graph after heating and curing is respectively soaked in a plurality of solutions (isopropylamine, propylene glycol methyl ether acetate, dimethylbenzene, ethyl lactate, gamma-butyrolactone, N-methyl pyrrolidone, concentrated sulfuric acid, hydrogen peroxide and 1% hydrofluoric acid) for 15 minutes at room temperature, and after washing and air drying, the chemical etching resistance of the polyimide film is evaluated by measuring the film thickness change and observing under an optical microscope: the thickness change of the polyimide layer after any solvent immersion was within. + -. 5% and no cracks or defects were generated, the evaluation was 10 points. Each solvent varied the film thickness by more than 5% minus one.
Synthesis example 1A 500ml three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a nitrogen blanket was charged with 31.02g (0.1 mol) of 3,3',4,4' -diphenylether tetracarboxylic dianhydride (OPDA), 32.97g (0.09 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP), 2.14g (0.02 mol) of 4-methylaniline and 250 ml of N-methylpyrrolidone (NMP), and stirred at room temperature (25 ℃ C.) for 12 hours or more. Then adding 25ml of dimethylbenzene and 0.01ml of isoquinoline, heating to 180 ℃, stirring for more than 6 hours, and evaporating most of water and dimethylbenzene to obtain the corresponding polyimide resin solution. The solution was naturally cooled to 80 ℃ to obtain a primary polyimide resin solution (A1, GPC Mw: 24472 g/mol).
50g A1, 6.8g (0.031mol) of di-tert-butyl dicarbonate (Boc2O) (corresponding to 40 mol of hydroxyl groups in the A1 resin), 0.37g (0.003mol) of DMAP and 200ml of NMP were placed in a 500ml three-necked round-bottomed flask equipped with a mechanical stirrer, thermometer, reflux condenser and nitrogen blanket and stirred at room temperature for 1 hour. And dispersing the reaction solution in 5L of deionized water, separating out a solid, filtering, and drying in vacuum to obtain the primary polyimide resin. Dissolving it in tetrahydrofuran to form a homogeneous solution, adsorbing with anion and cation resins to remove residual metal or nonmetal ions to obtain polyimide solid resin (A1-40, GPC Mw: 23974g/mol) with 40% phenolic hydroxyl groups protected by t-butyloxycarbonyl groups 1 The H NMR spectrum is shown in FIG. 2, and the protection ratio is 40% by calculating the ratio of the area of the alpha peak to the area of the beta peak.
Synthesis example 2, except for changing the Boc2O and DMAP parts in Synthesis example 1 to 12.6g (0.058mol) and 0.74g (0.006mol), respectively, the reaction was carried out in accordance with the method of resin Synthesis example 1 of the present invention to obtain a high purity polyimide resin solid (A1-75, GPC Mw: 245861 g/mol) having 75% of phenolic hydroxyl groups protected by t-butoxycarbonyl groups.
Synthesis example 3 and Boc in Synthesis example 1 2 The reaction was carried out in accordance with the method in resin Synthesis example 1 of the present invention except that the O and DMAP parts were changed to 4.1g (0.019mol) and 0.24g (0.002mol), respectively, to obtain a high purity polyimide resin solid (A1-25, GPC Mw:27845g/mol) having 25% of phenolic hydroxyl groups protected with t-butoxycarbonyl groups.
Synthesis example 4A high purity polyimide resin solid (A2-40, GPC Mw:25371g/mol) in which 40% of phenolic hydroxyl groups were protected with t-butoxycarbonyl groups was obtained by carrying out the reaction according to the method of Synthesis example 1 of the present invention except that 29.42 g (0.1 mol) of 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA) was used in place of 31.02g (0.1 mol) of 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (OPDA) in Synthesis example 1 of the present invention resin.
Synthesis example 5 the reaction was carried out in accordance with the method of Synthesis example 1 of the present invention except that 32.22g (0.1 mol) of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) was used in place of 31.02g (0.1 mol) of 3,3',4,4' -diphenylethertetracarboxylic dianhydride (OPDA) in Synthesis example 1 of the present invention to obtain a high purity polyimide resin solid (A3-40, GPC Mw:22531g/mol) having 40% of phenolic hydroxyl groups protected by t-butoxycarbonyl groups.
Synthesis example 6A reaction was carried out in the same manner as in Synthesis example 1 of the present invention except that 44.42g (0.1 mol) of 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) was used in place of 31.02g (0.1 mol) of 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (OPDA) in Synthesis example 1 of the resin of the present invention to obtain a high purity polyimide resin solid (A4-40, Mw GPC: 25542g/mol) in which 40% of phenolic hydroxyl groups were protected by t-butoxycarbonyl groups.
Synthesis example 7 the reaction was carried out in accordance with the method of Synthesis example 1 of the present invention except for using 23.25g (0.09 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) propane (BHAPP) in place of 0.09 mol (32.97g) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) in Synthesis example 1 of the resin of the present invention to obtain a high purity hydroxyl-protected polyimide resin solid (A5-40, GPC Mw:28293g/mol) having 40% of phenolic hydroxyl groups protected by t-butoxycarbonyl groups.
Synthesis example 8 the reaction was carried out in accordance with the method of Synthesis example 1 of the present invention except that 19.46g (0.09 mol) of 3,3' -dihydroxybenzidine (HAB) was used in place of 32.97g (0.09 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) in Synthesis example 1 of the present invention to obtain a high purity hydroxyl-protected polyimide resin solid (A6-40, GPC Mw:27830g/mol) having 40% of phenolic hydroxyl groups protected with t-butoxycarbonyl groups.
Synthesis example 9 Using 2.49g (0.01 mol) of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA) in place of 3.66g (0.01 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) in Synthesis example 1 of the resin of the present invention, the reaction was carried out in accordance with the procedure in Synthesis example 1 of the resin of the present invention to obtain a high purity hydroxyl-protected polyimide resin solid (A7-40, GPC Mw:27692g/mol) in which 40% of phenolic hydroxyl groups were protected with t-butoxycarbonyl groups.
Synthesis example 10 the reaction was carried out in accordance with the method of Synthesis example 1 of the present invention except for using 4.00g (0.02 mol) of 4, 4-diaminodiphenyl ether (4,4-ODA) in place of 7.32g (0.02 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) in Synthesis example 1 of the resin of the present invention to obtain a high purity hydroxyl-protected polyimide resin solid (A8-40, GPC Mw:29183g/mol) having 40% of phenolic hydroxyl groups protected by t-butoxycarbonyl groups.
Synthesis example 11A high purity polyimide resin solid (A9-40, GPC Mw:22912g/mol) having 40% of phenolic hydroxyl groups protected with methoxymethyl ether was obtained by carrying out the reaction according to the method of Synthesis example 1 of the present invention except that 6.8g (0.031mol) of di-tert-butyl dicarbonate (Boc2O) and 0.37g (0.003mol) of DMAP in Synthesis example 1 were replaced with 2.9g (0.031mol) of chloromethyl ethyl ether and 3.15(0.031mol) of triethylamine, respectively.
Synthesis example 12A high purity polyimide resin solid (A10-40, GPC Mw:25982g/mol) in which 40% of phenolic hydroxyl groups were protected with tetrahydropyran ether groups was obtained by carrying out the reaction according to the method of Synthesis example 1 of the present invention except that 6.8g (0.031mol) of di-tert-butyl dicarbonate (Boc2O) and 0.37g (0.003mol) of DMAP in Synthesis example 1 were replaced with 2.6g (0.031mol) of dihydropyran and 0.17g (0.001mol) of p-toluenesulfonic acid, respectively.
Synthesis example 13 the polyimide resin solution A8 obtained in Synthesis example 10 was poured into 5L of deionized water, and the resulting solution was precipitated as a solid, filtered and vacuum-dried to obtain a primary polyimide resin. It was redissolved in tetrahydrofuran to form a solution, and residual metal or nonmetal ions were removed by adsorption on anion and cation resins to obtain a high-purity polyimide resin solid (B1, GPC Mw:24058 g/mol).
Synthesis example 14A high-purity polyimide resin solid was obtained by conducting the reaction according to the method of Synthesis example 13 of the present invention except for using 2.96g (0.02 mol) of 1, 2-bis (2-aminoethoxy) ethane (EDEA) in place of 7.32g (0.02 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) in Synthesis example 13 of the present invention, and a high-purity polyimide resin solid was obtained (B2, GPC Mw:26339 g/mol).
Synthesis example 15 the polyimide resin solution A7 in Synthesis example 9 was poured into 5L of deionized water, and the resulting solution was precipitated as a solid, filtered, and vacuum-dried to obtain a primary polyimide resin. It was redissolved in tetrahydrofuran to form a solution, and residual metal or nonmetal ions were removed by adsorption on anionic and cationic resins to give a high-purity polyimide resin solid (C1, GPC Mw:25097 g/mol).
Synthesis example 16 the reaction was carried out in accordance with the method of Synthesis example 15 of the present invention except that 0.1 mol (31.02 g) of 3,3',4,4' -diphenylether tetracarboxylic dianhydride (OPDA) in Synthesis example 15 of the resin of the present invention was replaced with 0.1 mol (44.42g) of 3,3',4,4' -benzophenonetetracarboxylic dianhydride (6FDA), to obtain a high-purity polyimide resin solid (C2, GPC Mw:21572 g/mol).
Example 1 in an ultra clean room equipped with a yellow light lamp, 50g of polymer A1-40 was weighed and dissolved in 130g of GBL solvent to form a homogeneous solution; then 7.5g of (4-phenyl-thiophenyl) diphenyl sulfonium trifluoromethanesulfonic acid is added and stirred at room temperature for 1h to form a chemical amplification type positive photosensitive polyimide coating glue solution, the solid content is 26 +/-1%, and the viscosity is 400 mPa.s at room temperature.
Spin-coating the coating glue solution on the surface of the wafer; in the range of 60 to 150 o C, baking for 3min to form a solid adhesive film with the thickness of 3 mm, placing a mask plate on the surface of the adhesive film, and exposing by using i-line or ultraviolet lamps (i and g lines); then, 100 to 170 o C, baking for 2-6 min; developing with 2.38wt% tetramethyl ammonium hydroxide aqueous solution developer, rinsing with deionized water, and forming a three-dimensional photoetching pattern. Heating and curing in a forced air oven (230) o C/30min) to obtain a stereolithography pattern formed by the polyimide cured film.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 2 mm, the section taper angle is 23 degrees, the film retention rate is 86 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 65MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 2 the same procedure as described in example 1 of the present invention was repeated, except that 7.5g of [2- (propylsulfonyloxyimino) -2, 3-dihydrothiophen-3-ylidene ] -2- (2-methylphenyl) acetonitrile (PAG103) was used in place of 7.5g of (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonic acid in example 1.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 5 micrometers, the section taper angle is 46 degrees, the film retention rate is 86 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 65MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 3 the same procedure as described in example 1 of the present invention was repeated, except that 2.5g of gamma-mercaptopropyltrimethoxysilane was additionally added to example 1.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 2 mu m, the section taper angle is 23 degrees, the film retention rate is 86 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 4 was carried out in the same manner as in example 3 of the present invention except that 50g of the A1-75 resin in Synthesis example 2 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 4 mu m, the section taper angle is 37 degrees, the film retention rate is 84 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 5 was carried out in the same manner as in example 3 of the present invention except that 50g of the A1-25 resin in Synthesis example 3 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 2 mu m, the section taper angle is 19 degrees, the film retention rate is 59 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 6 the same procedure as described in example 3 of the present invention was repeated, except that 0.75g of 2, 6-Dimethylpiperidine (DMP) was additionally added to example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 2 micrometers, the section taper angle is 41 degrees, the film retention rate is 86 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 7 was carried out in the same manner as in example 3 of the present invention except that 0.75g of 2-isopropylthioxanthone was additionally added to example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 2 micrometers, the section taper angle is 21 degrees, the film retention rate is 86 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 8 the same procedure as described in example 3 of the present invention was repeated, except that 7.5g of (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonic acid in example 3 was reduced to 2.5 g.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 5 mu m, the section cone angle is 37 degrees, the film retention rate is 89 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 75MPa, and no film thickness change and no crack exist on the surface of the pattern in a chemical corrosion resistance test.
Example 9 the same procedure as described in example 3 of the present invention was repeated except that 7.5g of (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonic acid in example 3 was increased to 15 g.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 2 mu m, the section taper angle is 16 degrees, the film retention rate is 77 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 10 the same procedure as described in example 7 of the present invention was repeated, except that 2.5g of ditrimethylolpropane was additionally added to example 7.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 4 mu m, the section taper angle is 23 degrees, the film retention rate is 88 percent, the elongation at break is 40 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 11 was carried out in the same manner as in example 7 of the present invention except that in example 7, 2.5g of polyoxyethylene glyceryl ether was additionally added.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 4 mu m, the section taper angle is 22 degrees, the film retention rate is 89 percent, the elongation at break is 50 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 12 was carried out in the same manner as in example 7 of the present invention except that 2.5g of TMOM-BP was additionally added to example 7.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 5 mu m, the section taper angle is 23 degrees, the film retention rate is 87 percent, the elongation at break is 40 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 13 was carried out in the same manner as in example 3 of the present invention except that 50g of the A2-40 resin in Synthesis example 4 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 5 micrometers, the section taper angle is 38 degrees, the film retention rate is 84 percent, the elongation at break is 25 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 14 was carried out in the same manner as in example 3 of the present invention except that 50g of the A3-40 resin in Synthesis example 5 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 4 micrometers, the section taper angle is 29 degrees, the film retention rate is 85 percent, the elongation at break is 27 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 15 was carried out in the same manner as in example 3 of the present invention except that 50g of the A4-40 resin in Synthesis example 6 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 3 mu m, the section taper angle is 23 degrees, the film retention rate is 86 percent, the elongation at break is 27 percent, the stripping strength of the ITO surface is 65MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 16 was carried out in the same manner as in example 3 of the present invention except that 50g of the A5-40 resin in Synthesis example 7 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 5 micrometers, the section taper angle is 34 degrees, the film retention rate is 85 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 17 was carried out in the same manner as in example 3 of the present invention except that 50g of the A6-40 resin in Synthesis example 8 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 4 micrometers, the section taper angle is 37 degrees, the film retention rate is 86 percent, the elongation at break is 20 percent, the stripping strength of the ITO surface is 65MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 18 was carried out in the same manner as in example 3 of the present invention except that 50g of the A7-40 resin in Synthesis example 9 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 3 mu m, the section taper angle is 28 degrees, the film retention rate is 86 percent, the elongation at break is 25 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 19 was carried out in the same manner as in example 3 of the present invention except that 50g of the A8-40 resin in Synthesis example 10 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 4 micrometers, the section taper angle is 22 degrees, the film retention rate is 85 percent, the elongation at break is 35 percent, the stripping strength of the ITO surface is 75MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 20 was carried out in the same manner as in example 3 of the present invention except that 50g of the A9-40 resin in Synthesis example 11 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 2 mu m, the section taper angle is 26 degrees, the film retention rate is 84 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 65MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Example 21 was carried out in the same manner as in example 3 of the present invention except that 50g of the A10-40 resin in Synthesis example 12 was used in place of the A1-40 resin in example 3.
The resolution of a photoetching pattern of the chemical amplification type positive photosensitive polyimide coating adhesive is 2 micrometers, the section taper angle is 29 degrees, the film retention rate is 86 percent, the elongation at break is 30 percent, the stripping strength of the ITO surface is 65MPa, and the chemical corrosion resistance test has no film thickness change and no crack on the surface of the pattern.
Comparative example 1 in an ultraclean room equipped with a yellow light lamp, 50g of the hydroxyl group-containing polyimide resin B1 prepared in resin synthesis example 13 of the present invention was dissolved in 130g of gbl to form a homogeneous solution; then, diazonaphthoquinone ester (diazonaphthoquinone ester) compound (TPPA 320: OH or OD given selectively according to the ratio OD/(OD + OH) = 2/3) was added as photoactive compound 33g, and stirred at room temperature for 1h to form a positive PSPI coating gum solution. Baking at about 110 deg.C to 145 deg.C for 1 to 2 minutes to form a film. The film is exposed through a light-shielding mask forming a pattern, developed by using 2.38wt% of tetramethylammonium hydroxide aqueous solution developing solution, rinsed by deionized water, and then a positive stereo lithography pattern is formed. Thereafter, the resultant film was heated at 230 ℃ for 30 minutes to obtain a positive pattern.
The positive photosensitive polyimide coating adhesive has the advantages that the resolution of a photoetching pattern is 4 mu m, the section taper angle is 48 degrees, the film retention rate is 72 percent, the elongation at break is 5 percent, the stripping strength of the ITO surface is 45MPa, no film thickness change exists in a chemical corrosion resistance test, and no crack exists on the surface of a pattern.
Comparative example 2 the same procedure as described in example 12 of the present invention was carried out, except that 50g of the B-2 resin in Synthesis example 14 was used in place of the B1 resin in comparative example 1.
The positive photosensitive polyimide coating adhesive has the advantages that the resolution of a photoetching pattern is 5 mu m, the section taper angle is 28 degrees, the film retention rate is 70 percent, the elongation at break is 5 percent, the ITO surface peeling strength is 65MPa, no film thickness change exists in a chemical corrosion resistance test, and no crack exists on the surface of a pattern.
Comparative example 3 in an ultraclean room equipped with a yellow light lamp, 50g of the hydroxyl group-containing polyimide resin C1 prepared in Synthesis example 15 of a resin of the present invention was dissolved in 380g of 3-methoxybutyl acetate (MBA) and 150g of Propylene Glycol Methyl Ether Acetate (PGMEA) to form a homogeneous solution; then, 9.2g of an oxime ester photopolymerization initiator (NCI-831), 26.9g of a radically polymerizable compound dipentaerythritol hexaacrylate (DPHA), and 7.7g of a crosslinking agent 9, 9-bis (4-glycidoxyphenyl) fluorene (FR-201) were added in this order, and stirred to prepare a uniform solution. Prebaking at 110 ℃ for 120 seconds, developing by using 2.38wt% of tetramethylammonium hydroxide aqueous solution developing solution after exposure, and rinsing by deionized water to form a negative stereolithography pattern. A negative pattern was obtained after thermal curing at 250 c for 30 minutes.
The negative photosensitive polyimide coating adhesive has the photoetching pattern resolution of 12 microns, the section taper angle of 22 degrees, the film retention rate of 79 percent, the elongation at break of 40 percent, the ITO surface peeling strength of 75MPa, no film thickness change in a chemical corrosion resistance test and no crack on the surface of a pattern.
Comparative examples 4,
The same procedure as described in comparative example 3 of the present invention was repeated, except that 50g of the C2 resin in Synthesis example 16 was used in place of the C1 resin in comparative example 3.
The negative photosensitive polyimide coating adhesive has the photoetching pattern resolution of 9 microns, the section taper angle of 22 degrees, the film retention rate of 80 percent, the elongation at break of 40 percent, the ITO surface peeling strength of 65MPa, no film thickness change in a chemical corrosion resistance test and no crack on the surface of a pattern.
The comparative data of the properties of the coating pastes prepared in the above examples and comparative examples are shown in table 1.
TABLE 1 Properties of the coating pastes of the examples and comparative examples
Examples Fringe resolution Angle of taper angle Film retention rate Elongation at break Adhesion of ITO Resistance to chemicals
1 2μm 23° 86% 30% 65MPa 10 minutes
2 5μm 46° 86% 30% 65MPa 10 minutes
3 2μm 23° 86% 30% 75MPa 10 minutes
4 4μm 19° 84% 30% 75MPa 10 minutes
5 2μm 37° 59% 30% 75MPa 10 minutes
6 2μm 41° 86% 30% 75MPa 10 minutes
7 2μm 21° 86% 30% 75MPa 10 minutes
8 5μm 37° 89% 30% 75MPa 10 minutes
9 2μm 16° 77% 30% 75MPa 10 minutes
10 4μm 23° 88% 40% 75MPa 10 minutes
11 4μm 22° 89% 50% 75MPa 10 minutes
12 5μm 23° 87% 40% 75MPa 10 minutes
13 5μm 38° 84% 25% 75MPa 10 minutes
14 4μm 29° 85% 27% 75MPa 10 minutes
15 3μm 23° 86% 27% 65MPa 10 minutes
16 5μm 34° 85% 30% 75MPa 10 minutes
17 4μm 37° 86% 20% 65MPa 10 minutes
18 3μm 28° 86% 25% 75MPa 10 minutes
19 4μm 22° 85% 35% 75MPa 10 minutes
20 2μm 26° 84% 30% 65MPa 10 minutes
21 2μm 29° 86% 30% 65MPa 10 minutes
Comparative example1 4μm 48° 72% 5% 45MPa 10 minutes
Comparative example 2 5μm 28° 70% 5% 65MPa 10 minutes
Comparative example 3 12μm 22° 79% 40% 75MPa 10 minutes
Comparative example 4 9μm 22° 80% 40% 65MPa 10 minutes
As can be seen from the data in Table 1, the chemically amplified positive photosensitive polyimide coating adhesive provided by the invention has better comprehensive properties including high resolution, proper taper angle, high film retention, high elongation at break, high adhesion, chemical corrosion resistance and the like.
Compared with the positive PSPI added with the diazonaphthoquinone ester compound, the PSPI provided by the invention has good cone angle, film retention rate and elongation at break; compared with the negative PSPI containing a specific epoxy cross-linking agent, the PSPI disclosed by the invention has higher resolution and film retention rate; meanwhile, under the condition that the formula is not adjusted, the PSPI disclosed by the invention can adjust the angle of the taper angle of the graph within a certain range (40 ℃) by adjusting the process conditions, as shown in figure 1 (the formula 11 can freely adjust the angle of the taper angle under different process conditions, namely 58.7 degrees, 35.7 degrees and 22.3 degrees in sequence).
The chemical amplification type positive photosensitive polyimide coating adhesive prepared by the method has excellent performance, and can meet the requirements of preparation of a pixel partition layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT (thin film transistor) planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer, an electrode protective layer, a wiring protective layer and a grid electrode insulating layer in display equipment; and can be used for preparing a redistribution layer (RDL), an alpha-Particle Barrier layer (alpha-Particle Barrier), a Stress absorption and Buffer layer (Stress Relief and Buffer Coating) in a circuit (ULSI), an Interlayer dielectric insulating layer (Interlayer Dielectrics) of a multilayer metal interconnection circuit and the like.

Claims (10)

1. A method for preparing partially substituted polyimide resin containing phenolic hydroxyl comprises the following steps:
s1, in the presence of a blocking agent, carrying out polymerization reaction on aromatic tetracarboxylic dianhydride and aromatic diamine containing phenolic hydroxyl in an organic solvent I to obtain polyamic acid resin solution containing phenolic hydroxyl;
s2, adding a water-carrying agent and an organic base into the reaction system of the step S1, and carrying out an imide reaction to obtain a polyimide resin containing phenolic hydroxyl groups;
s3, stirring the polyimide resin containing phenolic hydroxyl, the hydroxyl protective agent and the catalyst in an organic solvent I; then dispersing in water, and filtering to obtain the partially substituted polyimide resin containing phenolic hydroxyl.
2. The method of claim 1, wherein: in step S1, the aromatic tetracarboxylic dianhydride is selected from at least one of pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride, 2-bis (3, 4-phthalic dianhydride) propane, and 2, 2-bis (3, 4-phthalic dianhydride) -1,1,1,3,3, 3-hexafluoropropane;
the aromatic diamine containing phenolic hydroxyl group is selected from p-phenylenediamine, 4-diaminodiphenyl ether, 3, 4-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) -benzene, 2-bis (4-aminophenyl) propane, 2-bis [4- (4-aminophenoxy) phenyl) ] propane, 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 3' -diamino-4, 4' -dihydroxydiphenylsulfone, 3' -dihydroxybenzidine, 2-bis (4-aminophenyl) hexafluoropropane, At least one of 2, 2-bis [4- (4-aminophenoxy) phenyl) ] hexafluoropropane, 3 '-dihydroxybenzidine, 2' -bis (trifluoromethyl) diaminobiphenyl, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 1, 3-bis (3-aminopropyl) tetraphenyldisiloxane, 1, 3-bis (3-aminophenoxy) tetramethyldisiloxane and 1, 3-bis (4-aminophenoxy) tetramethyldisiloxane;
the end-capping reagent is selected from at least one of phthalic anhydride, 3-methyl phthalic anhydride, 4-methyl phthalic anhydride, acetic anhydride, propionic anhydride, aniline, 3-methylaniline, 4-methylaniline, 3-aminophenylacetylene, 4-ethynylaniline, 3-aminophenol, 4-aminophenol, cis-5-norbornene-exo-2, 3-dicarboxylic anhydride, methylamine, ethylamine and propylamine;
the molar ratio of the end-capping reagent to the aromatic diamine containing phenolic hydroxyl is 0-70: 100, wherein the using amount of the end capping agent is not zero;
the organic solvent I is at least one selected from N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, g-butyrolactone, beta-propiolactone, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, 3-methoxybutyl acetate, propylene glycol methyl ether acetate, tetrahydrofuran, dioxane, ethyl lactate, ethylene glycol diethyl ether, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether.
3. The production method according to claim 1 or 2, characterized in that: in step S1, the temperature of the polymerization reaction is 15-40 ℃ and the time is 0.5-96 h.
4. The production method according to claim 3, characterized in that: in step S2, the organic base is at least one selected from triethylamine, pyridine, isoquinoline, 4-dimethylaminopyridine, 2, 6-dimethylpyridine, imidazole, piperazine, N-diisopropylethylamine, and N, N-dimethylformamide;
the temperature of the imidization reaction is 160-220 ℃, and the time is 1-24 h;
the water-carrying agent is toluene or xylene, and the weight ratio of the water-carrying agent to the polyamic acid resin containing phenolic hydroxyl is (0.1-10): 1;
the ratio of the molar weight of the organic base to the number of repeating units of the phenolic hydroxyl group-containing polyamic acid resin is 0.01-0.1: 1;
the weight average molecular weight of the polyimide resin containing phenolic hydroxyl groups is 5000-100000 g/mol.
5. The method of manufacturing according to claim 4, characterized in that: in step S3, the hydroxyl protecting agent is at least one selected from triphenylchloromethane, chloromethylmethyl ether, chloromethylethyl ether, benzyl bromide, p-methoxybenzyl chloride, dihydropyran, trifluoroacetic anhydride, di-tert-butyl dicarbonate, acetic anhydride, pivaloyl chloride, benzoyl chloride, and tert-butyl alcohol;
the catalyst is selected from at least one of triethylamine, pyridine, isoquinoline, 4-dimethylaminopyridine, 2, 6-dimethylpyridine, imidazole, piperazine, N-diisopropylethylamine, N-dimethylformamide, sodium hydride and p-toluenesulfonic acid;
the stirring temperature is 20-100 ℃, and the stirring time is 0.5-96 hours;
the molar ratio of the catalyst to the hydroxyl protective agent is 0.03-0.3: 1.
6. a partially substituted phenolic hydroxyl group-containing polyimide resin prepared by the method of any one of claims 1 to 5;
the phenolic hydroxyl protection rate of the partially substituted polyimide resin containing phenolic hydroxyl is 20-100%.
7. A chemical amplification type positive polyimide coating adhesive is prepared from the following components in parts by mass:
the partially substituted phenolic hydroxyl group-containing polyimide resin composition according to claim 6, wherein the partially substituted phenolic hydroxyl group-containing polyimide resin composition comprises 100 parts of a partially substituted phenolic hydroxyl group-containing polyimide resin, 5-25 parts of a photoacid generator, 0-10 parts of a photosensitive accelerator, 0-10 parts of an adhesion promoter, 0-10 parts of an alkaline inhibitor, 0-10 parts of a crosslinking agent and 200-500 parts of an organic solvent II.
8. The chemically amplified positive polyimide coating paste according to claim 7, wherein: the photoacid generator is selected from Irgacure PAG103, Irgacure PAG 121, Irgacure PAG 169, Irgacure PAG250, Irgacure PAG290, diphenyliodonium hexafluorophosphate, tri-p-tolylsulfonium hexafluorophosphate, bis (3-methylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, 4' -ditolyl iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, (2-naphthyl) (2,4, 6-trimethylphenyl) iodonium hexafluorophosphate, (4-biphenyl) (2,4, 6-trimethylphenyl) iodonium hexafluorophosphate, bis (3-methylphenyl) iodonium hexafluorophosphate, bis (2-methylphenyl) iodonium hexafluorophosphate, 4-octyloxy diphenyliodonium hexafluoroantimonate, diphenyliodonitrate, diphenyl (trifluoromethyl) sulfonium trifluoromethanesulfonate, sodium iodonium, Tri-p-tolylsulfonium trifluoromethanesulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, 1-naphthyldiphenylsulfonium trifluoromethanesulfonate, tris (4-tert-butylphenyl) sulfonium trifluoromethanesulfonate, (4-phenoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonate, bis [4- (1, 1-dimethylethyl) phenyl ] iodonium trifluoromethanesulfonate, (2-tolyl) (2,4, 6-trimethylphenyl) iodonium trifluoromethanesulfonate, phenyl (2,4, 6-trimethoxyphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, N-hydroxynaphthoylimide trifluoromethanesulfonate, N-naphthylimide trifluoromethanesulfonate, sodium hydrogen sulfonate, sodium salt, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, N-hydroxy-5-norbornene-2, 3-diamide nonafluorobutane sulfonic acid, perfluorobutylsulfonic acid triphenylsulfonium salt, bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonic acid, diphenyliodosyl chloride, and at least one salt of a weak acid consisting of an iodonium salt, a sulfonium salt, a phosphonium salt, an ammonium salt, and a diazonium salt;
the organic solvent II is at least one selected from N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolactone, beta-propiolactone, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, 3-methoxybutyl acetate, propylene glycol methyl ether acetate, tetrahydrofuran, dioxane, ethyl lactate, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol and tert-butanol;
the photosensitization accelerator is selected from at least one of 9, 10-diphenylanthracene, 9-anthracenealdehyde, anthracene-9, 10-dicarbaldehyde, 9, 10-diethoxyanthracene, xanthatine, curcumin, coumarin, 9, 10-bis (phenylethynyl) -2-ethylanthracene, 2-tert-butyl-9, 10-bis (naphthalen-2-yl) anthracene, 9, 10-dimethylanthracene, 9, 10-bis (1-naphthyl) anthracene, 9, 10-bis (2-naphthyl) anthracene, 9, 10-dibutoxyanthracene, 2-ethylanthracene and 2-isopropylthioxanthone;
the adhesion promoter is selected from gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatotrimethoxysilane, 3-isocyanatotriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydride, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatotriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydride, gamma-hydroxy-methyl-ethyl-3-isocyanatopropyl-3-isocyanato-methyl-trimethoxysilane, 3-isocyanato-methyl-ethyl-methyl-3-isocyanato-methyl-trimethoxysilane, and methyl-3-isocyanato-methyl-ethyl-trimethoxysilane, At least one of N- (3-diethoxymethylsilylpropyl) succinimide, N- (3-diethoxymethylsilylpropyl) phthalimide, benzophenone-3, 3 '-bis (N- [ 3-triethoxysilyl ] propylamide) -4,4' -dicarboxylic acid, and benzene-1, 4-bis (N- [ 3-triethoxysilyl ] propylamide) -2, 5-dicarboxylic acid;
the alkaline inhibitor is a non-photosensitive alkaline inhibitor or a photosensitive alkaline inhibitor, the non-photosensitive alkaline inhibitor is 2, 6-dimethylpiperidine, N-hydroxyethylpiperidine, imidazole, pyrazole or trioctylamine, and the photosensitive alkaline inhibitor is at least one of DNCDP, WPBG-300, WPBG-018, WPBG-027, WPBG-140 and WPBG-165;
the cross-linking agent is selected from Bis-Z, BisP-EZ, 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-PTPTP, DML-34X, DML-BPA, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, ML-P, TriML-35XL, TML-BP, TML-HQ, TML-BPF, TML-pp-35-PFP, TMTML-TMBP, HML-TPPHBA, HML-TPHAP, BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A, 2, 6-dimethoxymethyl-4-t-butylphenol, 2, 6-dimethoxymethyl-p-cresol, 2, 6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxyphenol, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, Bis-AP (trade name, manufactured by Honshu chemical Industry Co., Ltd.), novolak resin, glycerol propoxylated acid, polyoxyethylated glycerol ether, propoxylated pentaerythritol, tripentaerythritol, di (trimethylolpropane), 1,1, 1-tris (4-hydroxyphenyl) ethane, and 2-propenoic acid- (2-hydroxy-1, 3-propylene) bis [ oxy (2-hydroxy-3, 1-propylene) ] ester.
9. A pixel defining layer, an organic insulating layer, an isolation pillar, a planarization layer, a TFT protective layer, or a stress absorbing-buffering protective film, an α -particle barrier film of a semiconductor chip of an electro-optical display, which is obtained by curing the partially substituted phenolic hydroxyl group-containing polyimide resin according to claim 6 or the chemically amplified positive polyimide coating paste according to claim 7 or 8.
10. Use of the partially substituted phenolic hydroxyl group-containing polyimide resin of claim 6 or the chemically amplified positive polyimide coating paste of claim 7 or 8 in the manufacture and packaging of optoelectronic flat panel displays, semiconductor chips;
the partially substituted phenolic hydroxyl group-containing polyimide resin or the chemical amplification type positive polyimide coating adhesive is used for preparing a pixel defining layer, an organic insulating layer, an isolation column, a planarization layer, a TFT (thin film transistor) protective layer, a stress absorption-buffer protective film of a semiconductor chip and an alpha-particle shielding layer film of a photoelectric display.
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CN116149140A (en) * 2023-04-19 2023-05-23 明士(北京)新材料开发有限公司 Positive photosensitive resin composition with high chemical resistance and preparation method and application thereof

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