CN114200775B - Positive polyimide resin composition - Google Patents

Positive polyimide resin composition Download PDF

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CN114200775B
CN114200775B CN202111562765.0A CN202111562765A CN114200775B CN 114200775 B CN114200775 B CN 114200775B CN 202111562765 A CN202111562765 A CN 202111562765A CN 114200775 B CN114200775 B CN 114200775B
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parts
compound
polyimide resin
fluorine
weight
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CN114200775A (en
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苏江华
王胜林
黎厚明
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Shenzhen Dalton Electronic Materials Co ltd
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Shenzhen Dalton Electronic Material Co ltd
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    • 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
    • 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
    • G03F7/008—Azides
    • G03F7/0085—Azides characterised by the non-macromolecular additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of material science, and discloses a positive polyimide resin composition which comprises the following components in parts by weight: 100 parts of polyimide resin, 1-50 parts of naphthoquinone diazide compound, 10-200 parts of thermal crosslinking compound, 0.01-5 parts of silane coupling agent, 10-15 parts of phenolic hydroxyl compound, 0-5 parts of auxiliary agent and 50-2000 parts of solvent. The positive polyimide resin composition prepared by the invention can keep high film retention rate and high resolution when used for developing, and can ensure that no residue exists on the edge of a pattern after developing.

Description

Positive polyimide resin composition
Technical Field
The invention relates to the technical field of material science, in particular to a positive polyimide resin composition.
Background
Conventionally, an interlayer insulating film and a surface protective film of a semiconductor device have been often produced using a polyimide resin or a polybenzoxazole resin which has excellent heat resistance, electrical characteristics and mechanical characteristics. In recent years, as higher integration and larger size of semiconductor devices have been carried out, thinning and miniaturization of sealing resin packages have been required, and therefore, methods such as LOC (lead on chip package) and surface mounting by reflow soldering have been often used, which has resulted in that polyimide resins having excellent mechanical properties and heat resistance have become a main raw material for producing interlayer insulating films and surface protective films of semiconductor devices.
It has been known that when an interlayer insulating film and a surface protective film of a semiconductor device are produced, the use of photosensitive polyimide can simplify the patterning process and shorten the complicated production process. Researchers have proposed that the performance of an interlayer insulating film and a surface protective film of a semiconductor device manufactured by using a positive photosensitive resin composition developed with an alkali aqueous solution is better, that is, diazonaphthoquinone is added to polyamic acid. However, diazonaphthoquinone has an inhibitory effect on the dissolution of alkali solution, and the solubility of the carboxyl group of polyamic acid increases, and then a desired pattern may not be obtained. In order to control the alkali solubility of polyamic acid, a polyamic acid derivative in which the carboxyl group of polyamic acid is protected with an ester group has been developed, however, when diazonaphthoquinone is added to the polyamic acid derivative, the dissolution-inhibiting effect of diazonaphthoquinone on an alkali solution becomes very large, and although a desired pattern can be obtained in many cases, the sensitivity is greatly reduced. In view of this problem, it has been considered that when various compounds having a phenolic hydroxyl group are added to the polyamic acid derivative to which diazonaphthoquinone is added, the sensitivity can be increased easily, but the film retention rate and the resolution cannot be achieved at the same time.
Therefore, it is an urgent problem for those skilled in the art to provide a positive polyimide resin composition that can satisfy both high resolution and high film retention.
Disclosure of Invention
In view of the above, the present invention provides a positive polyimide resin composition, which includes a fluorine-free polyimide resin and a fluorine-containing polyimide resin. By utilizing the polarity difference of the two resins, the problem that the film retention rate and the resolution of the conventional polyamic acid derivative cannot be considered at the same time can be effectively solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a positive polyimide resin composition comprises the following components in parts by weight: 100 parts of polyimide resin, 1-50 parts of naphthoquinone diazide compound, 10-200 parts of thermal crosslinking compound, 0.01-5 parts of silane coupling agent, 10-15 parts of phenolic hydroxyl compound, 0-5 parts of auxiliary agent and 50-2000 parts of solvent.
The polyimide resin comprises the following components in a mass ratio of 20: 80-90: 10 a fluorine-free polyimide resin and a fluorine-containing polyimide resin; wherein the fluorine-free polyimide resin comprises a structural unit (1), and the fluorine-containing polyimide resin comprises a structural unit (2);
Figure BDA0003421078890000031
in the structural formulas of the structural units (1) and (2),
Figure BDA0003421078890000032
represents a dianhydride residue;
Figure BDA0003421078890000033
represents a non-fluorine-containing diamine residue,
Figure BDA0003421078890000034
represents a fluorine-containing diamine residue; n and m represent the number of repeating units, and n and m are independently integers between 50 and 1000.
The non-fluorine-containing polyimide resin and the fluorine-containing polyimide resin are both synthesized by raw materials containing tetracarboxylic dianhydride and diamine.
The naphthoquinone diazide compound is a compound obtained by performing ester bond bonding on sulfonic acid of naphthoquinone diazide and polyhydroxy compound, or a compound obtained by performing sulfonamide bond bonding on sulfonic acid of naphthoquinone diazide and polyamino compound, or a compound obtained by performing ester bond and/or sulfonamide bond bonding on sulfonic acid of naphthoquinone diazide and polyhydroxy polyamino compound.
The thermal crosslinking compound is one or more of a compound with a benzoxazine structure, a compound with an epoxy structure, a compound with an oxetane structure and a compound with an alkoxymethyl group.
The silane coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, trimethoxyepoxysilane, vinyl trimethoxysilane and mercaptopropyltrimethoxysilane.
The auxiliary agent is one or more of surfactant, ester, alcohol, ketone and ether.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the positive polyimide resin composition is prepared by blending the non-fluorine-containing polyimide resin and the fluorine-containing polyimide resin, the distribution that the content of fluorine-containing elements is increased from a substrate to the surface of the film in a gradient manner can be formed due to the polarity difference of the two resins, and the insulating film and the protective film prepared from the positive polyimide resin composition keep high film retention rate and high resolution during development by utilizing the hydrophobicity of the fluorine-rich atom surface and the alkali solubility of carboxylic acid, and ensure that no residue exists at the edge of the pattern after development.
Detailed Description
A positive polyimide resin composition comprises the following components in parts by weight: 100 parts of polyimide resin, 1-50 parts of naphthoquinone diazide compound, 10-200 parts of thermal crosslinking compound, 0.01-5 parts of silane coupling agent, 10-15 parts of phenolic hydroxyl compound, 0-5 parts of auxiliary agent and 50-2000 parts of solvent.
Preferably, 100 parts of polyimide resin, 10-40 parts of naphthoquinone diazide compound, 10-100 parts of thermal crosslinking compound, 1-3 parts of silane coupling agent, 12-15 parts of phenolic hydroxyl compound, 0-3 parts of auxiliary agent and 100-1500 parts of solvent.
The polyimide resin comprises the following components in a mass ratio of 20: 80-90: 10 a fluorine-free polyimide resin and a fluorine-containing polyimide resin; wherein the fluorine-free polyimide resin comprises a structural unit (1), and the fluorine-containing polyimide resin comprises a structural unit (2);
Figure BDA0003421078890000051
in the structural formulas of the structural units (1) and (2),
Figure BDA0003421078890000052
represents a dianhydride residue;
Figure BDA0003421078890000053
represents a non-fluorine-containing diamine residue,
Figure BDA0003421078890000054
represents a fluorine-containing diamine residue; n and m represent the number of repeating units, and n and m are independently an integer between 50 and 1000, preferably an integer between 100 and 500;
preferably, an end-capping reagent is further added during the synthesis of the polyimide resin, so as to improve the storage stability of the resin composition; the end capping agent is one or more of anilines, acid anhydrides, monocarboxylic acid and monoacyl chloride compounds;
the blocking agent is more preferably an aniline; more preferably one or more of aniline, 2-ethynylaniline, 3-ethynylaniline and 4-ethynylaniline.
The polyimide resin without fluorine and the polyimide resin with fluorine are both synthesized by tetracarboxylic dianhydride and diamine, wherein the tetracarboxylic dianhydride for synthesizing the polyimide resin without fluorine is preferably one or two of aromatic tetracarboxylic dianhydride of F-1-F-5 and F-12-F-17, and is further preferably one or two of F-5, F-14 and F-15; the tetracarboxylic dianhydride for synthesizing the fluorine-containing polyimide resin is preferably one or two kinds of alicyclic tetracarboxylic dianhydrides of F-6 to F-11, and more preferably one or two kinds of F-7, F-9 and F-11.
The structural formulas of F-1 to F-17 are as follows in sequence:
Figure BDA0003421078890000061
the diamine for synthesizing the fluorine-free polyimide resin is preferably one or two of H-1-H-8 non-fluorine-containing aromatic diamine, and is more preferably one or two of H4, H5 and H6; the diamine for synthesizing the fluorine-containing polyimide resin must contain one fluorine-containing aromatic diamine and one or two non-fluorine-containing aromatic diamines, wherein the fluorine-containing aromatic diamine preferably contains one or two of H-9-H-24, and more preferably contains one of H-15, H-16 and H-17; the non-fluorine-containing aromatic diamine is preferably one or two of H-1 to H-8, and more preferably one or two of H4, H5 and H6.
The structural formulas of H-1 to H-24 are as follows in sequence:
Figure BDA0003421078890000081
the diamine that can be used for synthesizing the polyimide resin containing the structural unit (2) preferably contains 10 to 90 mol% of a fluorine-containing aromatic diamine, and more preferably contains 20 to 50 mol%.
The diamine may be an aliphatic group having a siloxane structure, and copolymerization of the group can improve adhesion to a substrate; the diamine is preferably bis (3-aminopropyl) tetramethyldisiloxane and/or bis (p-aminophenyl) octamethylpentasiloxane.
The naphthoquinone diazide compound is a compound obtained by ester bond bonding of sulfonic acid of naphthoquinone diazide and polyhydroxy compound, or a compound obtained by sulfonamide bond bonding of sulfonic acid of naphthoquinone diazide and polyamino compound, or a compound obtained by ester bond and/or sulfonamide bond bonding of sulfonic acid of naphthoquinone diazide and polyhydroxy polyamino compound;
the polyhydroxy compound is one or more of Bis-Z, bisP-EZ, tekp-4HBPA, trisP-HAP, trisP-PA, trisP-SA, trisOCR-PA, bisOCHP-Z, bisP-MZ, bisP-PZ (trade name, manufactured by chemical industry Co., ltd., state), BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIR-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi organic material Co., ltd.), 2,6-dimethoxymethyl-4 tert-butylphenol, 3835 zxft 3935-dimethoxymethyl-p-cresol, diphenyl24 zxft 3924-diacetoxymethyl 3924-methyl ester, tetra-hydroxy methyl ester, bisphenol-3 zXP, bisphenol, and preferably BisP-34, bisP-HAP.
The polyamino compound is one or more of 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4-diaminodiphenyl ether, triethylamine, 4,4-diaminodiphenylmethane, 4,4-diaminodiphenyl sulfone, 4,4-diaminodiphenyl sulfide, and is preferably triethylamine.
The diazido quinone is diazido naphthoquinone-5-sulfonyl and/or diazido naphthoquinone-4-sulfonyl, preferably diazido naphthoquinone-5-sulfonyl.
The thermal crosslinking compound is one or more of a compound with a benzoxazine structure, a compound with an epoxy structure, a compound with an oxetane structure and a compound with an alkoxymethyl group.
The compound with the benzoxazine structure is a benzoxazine addition product of polyhydroxystyrene resin and/or a novolac type dihydrobenzoxazine compound;
one or more of bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, biphenol type epoxy compounds, biphenyl type epoxy compounds, glycidyl amine type epoxy compounds and cyclic aliphatic epoxy compounds which are compounds with epoxy structures; preferably CYD-128, CYD-134, CYD-118, CYD-546, CYD-127, E-44, E-39D, CYD-011, CYD-011A, CYD-012, CYD-017, CYD-019, CYDCN-200, CYDCN-205, CYDCN-208 (trade name, manufactured by Zhongshimei Barlin petrochemical Co., ltd.), TTA21, TTA26, TTA22, TTA2083, and TTA2081 (trade name, manufactured by Jiangsu Tetel scientific and technology Co., ltd.).
The compound with an oxetane structure is one or more of OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (manufactured by east Asia synthetic Co., ltd), "ETERNACOLL" OXBP, "ETERNACOLL" OXTP (manufactured by Yu Shuixing Co., ltd.), preferably one or more of OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009 and RSOX.
The compound with an alkoxymethyl group is DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-Bisft Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTPC, DMOM-MBPC, triL-P, triML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPAF, TML-BPAP, TMPHBP, TML-PHBA, TML-BPAP, TML-PHBA, TML-BPA, HML-TPAP, HMBPA, HMBPOM and HMBPA; preferably one or more of DML-PC, DML-PEP, DML-OC, DML-OEP and DML-34X.
The silane coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, trimethoxyepoxysilane, vinyl trimethoxysilane and mercaptopropyl trimethoxysilane; gamma-glycidoxypropyltrimethoxysilane is preferable, and the adhesion of the resin composition to a substrate can be improved.
The solvent is a gamma-lactone polar aprotic solvent, and is selected from ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol and the like ketones, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, and other esters, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, ethyl lactate, and the like, other esters such as isopropyl butyrate, N-butyl butyrate, methyl pyruvate, ethyl pyruvate, N-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate, aromatic hydrocarbons such as toluene and xylene, and amides such as N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide; preferably gamma-butyrolactone.
The auxiliary agent is one or more of surfactant, ester, alcohol, ketone and ether, wherein the ester is preferably ethyl lactate or propylene glycol monomethyl ether acetate; the alcohol is preferably ethanol; the ketones are preferably cyclohexanone or methyl isobutyl ketone; the ethers are preferably tetrahydrofuran or dioxane.
The phenolic hydroxyl compound is one or more of Bis-Z, bisP-EZ, tekp-4HBPA, trisP-HAP, trisP-PA, trisP-SA, trisOCR-PA, bisOCHP-Z, bisP-MZ, bisP-PZ (trade name, manufactured by Nippon chemical industry Co., ltd.), BIR-OC, BIP-PC, BIR-PTBP, BIR-PCHP, BIR-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi organic materials industries Co., ltd.), and novolac resin; preferably TrisP-HAP.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The structures and abbreviations of the main compounds used in the following examples:
DG-1：BPDA
biphenyl tetracarboxylic dianhydride (294.22)
Figure BDA0003421078890000131
DG-2：ODPA
4,4-Biphenyl Ether dianhydride (310.21)
Figure BDA0003421078890000141
DG-3：CBDA(196.11)
Cyclobutanetetracarboxylic dianhydride
Figure BDA0003421078890000142
DG-4：HPMDA(224.17)
Hydrogenation of pyromellitic dianhydride
Figure BDA0003421078890000143
[ diamine Compound ]
DA-1：ODA
4,4-Diphenyl Ether diamine (200.24)
Figure BDA0003421078890000144
DA-2：BAPP
2,2-bis [4- (4-aminophenoxy) phenyl ] propane (410.51)
Figure BDA0003421078890000145
DA-3：HFBAPP
2,2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane (518.45)
Figure BDA0003421078890000151
[ SOLVENT ]
NMP: n-methyl-2-pyrrolidone
GBL: gamma-butyrolactone
[ other adjuvants ]
Compound having an alkoxymethyl group: HMOM-TPHAP (trade name, manufactured by chemical industries, ltd., japan);
compound having epoxy group: CYDCN-200 (trade name, manufactured by Zhongshijingbing petrochemical Co., ltd.);
compound having polyphenol hydroxyl group: trisP-HAP (trade name, manufactured by chemical industries, ltd., japan);
silane coupling agent: KH560, gamma-glycidoxypropyltrimethoxysilane.
Synthesis example 1 Synthesis of resin (A-1)
DA-1 (10.01g, 0.05mol), DA-2 (16.42g, 0.04mol) and NMP (230.96 g) were charged into a three-necked flask under a nitrogen atmosphere at room temperature, and stirred at room temperature for 30min to confirm complete dissolution. Then, DG-1 (14.71g, 0.05mol) and DG-2 (15.51g, 0.05mol) were added thereto, and the mixture was stirred at room temperature for reaction for 3 hours, and then 3-aminophenol (1.09g, 0.01mol) was added thereto and reacted at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of water for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure for 12 hours at 60 ℃ in a vacuum oven to obtain the fluorine-free polyimide resin powder A-1 (non-fluorine PAA).
Synthesis example 2 Synthesis of resin (A-2)
DA-1 (2.00g, 0.01mol), DA-3 (32.84g, 0.08mol) and NMP (227.80 g) were added to a three-necked flask under a nitrogen atmosphere at room temperature, and stirred at room temperature for 30min to confirm complete dissolution. Then, DG-3 (9.81g, 0.05mol) and DG-4 (11.21g, 0.05mol) were added thereto, and the mixture was stirred at room temperature for reaction for 3 hours, and then 3-aminophenol (1.09g, 0.01mol) was added thereto and reacted at room temperature for 2 hours. After the reaction is finished, pouring the reaction solution into a large amount of water for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure for 12 hours at 60 ℃ in a vacuum oven to obtain fluorine-containing polyimide resin powder A-2 (fluorine PAA (1:8)).
Synthesis example 3 Synthesis of resin (A-3)
DA-1 (10.01g, 0.05mol), DA-2 (16.42g, 0.04mol) and NMP (194.16 g) were added to a three-necked flask under a nitrogen atmosphere at room temperature, and stirred at room temperature for 30min to confirm complete dissolution. Then, DG-3 (9.81g, 0.05mol) and DG-4 (11.21g, 0.05mol) were added thereto, and the mixture was stirred at room temperature for reaction for 3 hours, and then 3-aminophenol (1.09g, 0.01mol) was added thereto and reacted at room temperature for 2 hours.
Acetic anhydride (16.33 g) and pyridine (12.66 g) were further added to the above polyamic acid solution, and the mixture was reacted at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure in a vacuum oven at 60 ℃ for 12 hours to obtain fluorine-free polyimide solid powder A-3 (non-fluorine PI).
Synthesis example 4 Synthesis of resin (A-4)
DA-1 (16.02g, 0.08mol), DA-3 (5.18g, 0.01mol) and NMP (173.24 g) were charged into a three-necked flask under a nitrogen atmosphere at room temperature, and the mixture was stirred at room temperature for 30min to confirm complete dissolution. Then, DG-3 (9.81g, 0.05mol) and DG-4 (11.21g, 0.05mol) were added thereto, and the mixture was stirred at room temperature for reaction for 3 hours, and then 3-aminophenol (1.09g, 0.01mol) was added thereto and reacted at room temperature for 2 hours.
Acetic anhydride (17.56 g) and pyridine (13.61 g) were further added to the above polyamic acid solution, and the mixture was reacted at room temperature for 2 hours. After the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure for 12 hours at 60 ℃ in a vacuum oven to obtain fluorine-containing polyimide solid powder A-4 (fluorine PI (8:1)).
Synthesis example 5 Synthesis of resin (A-5)
DA-1 (10.01g, 0.05mol), DA-3 (25.92g, 0.04mol) and NMP (232.16 g) were added to a three-necked flask under a nitrogen atmosphere at room temperature, and stirred at room temperature for 30min to confirm complete dissolution. Then, DG-3 (9.81g, 0.05mol) and DG-4 (11.21g, 0.05mol) were added thereto, and the mixture was stirred at room temperature for reaction for 3 hours, and then 3-aminophenol (1.09g, 0.01mol) was added thereto and reacted at room temperature for 2 hours.
Acetic anhydride (18.18 g) and pyridine (14.08 g) were further added to the above polyamic acid solution, and the mixture was reacted at room temperature for 2 hours. After the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure for 12 hours at 60 ℃ in a vacuum oven to obtain fluorine-containing polyimide solid powder A-5 (fluorine PI (5:4)).
Synthesis example 6 Synthesis of resin (A-6)
DA-1 (2.00g, 0.01mol), DA-3 (32.84g, 0.08mol) and NMP (227.80 g) were added to a three-necked flask under a nitrogen atmosphere at room temperature, and stirred at room temperature for 30min to confirm complete dissolution. Then, DG-3 (9.81g, 0.05mol) and DG-4 (11.21g, 0.05mol) were added thereto, and the mixture was stirred at room temperature for reaction for 3 hours, and then 3-aminophenol (1.09g, 0.01mol) was added thereto and reacted at room temperature for 2 hours.
Acetic anhydride (19.40 g) and pyridine (15.03 g) were further added to the above polyamic acid solution, and the mixture was reacted at room temperature for 2 hours. After the reaction is finished, pouring the reaction liquid into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure in a vacuum oven at 60 ℃ for 12 hours to obtain fluorine-containing polyimide solid powder A-6 (fluorine PI (1:8)).
Synthesis example 7 Synthesis of naphthoquinone diazide Compound (B)
TrisP-PA (21.22g, 0.05mol) (trade name, manufactured by chemical industries, ltd., japan) and diazanaphthoquinone-5-sulfonyl chloride (26.8g, 0.1mol) were dissolved in 1,4-dioxane (450 g) under a dry nitrogen stream. While maintaining the solution at 40 ℃,1,4-dioxane (50 g) and triethylamine (12.65 g) were mixed uniformly, and then added dropwise, followed by stirring at 40 ℃ for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. The precipitated precipitate was collected, washed with 1L of 1% hydrochloric acid aqueous solution, and washed 2 times with 2L of water. The precipitate was dried in a vacuum drier to obtain naphthoquinone diazide compound (B) shown by the following formula.
Figure BDA0003421078890000191
Example 1
A positive polyimide resin composition was prepared by mixing 50 parts by weight of the resin (A-1) obtained in the above synthesis example, 50 parts by weight of the resin (A-5), 25 parts by weight of the naphthoquinone diazide compound (B), 10 parts by weight of HMOM-TPHAP, 10 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as a solvent.
Example 2
A positive polyimide resin composition was prepared by mixing 50 parts by weight of the resin (A-1) obtained in the above synthesis example, 50 parts by weight of the resin (A-5), 25 parts by weight of the naphthoquinone diazide compound (B), 20010 parts by weight of CYDCN-20010 parts by weight, 10 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as a solvent.
Example 3
A positive polyimide resin composition was prepared by mixing 20 parts by weight of the resin (A-1) obtained in the above synthesis example, 80 parts by weight of the resin (A-4), 25 parts by weight of the naphthoquinone diazide compound (B), 10 parts by weight of HMOM-TPHAP, 10 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as a solvent.
Example 4
A positive polyimide resin composition was prepared by mixing 90 parts by weight of the resin (A-1) obtained in the above synthesis example, 10 parts by weight of the resin (A-6), 25 parts by weight of the naphthoquinone diazide compound (B), 10 parts by weight of HMOM-TPHAP, 10 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as a solvent.
Example 5
A positive polyimide resin composition was prepared by mixing 50 parts by weight of the resin (A-1) obtained in the above synthesis example, 50 parts by weight of the resin (A-5), 30 parts by weight of the naphthoquinone diazide compound (B), 200 parts by weight of CYDCN, 15 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 232 parts by weight of gamma-butyrolactone as a solvent.
Comparative example 1
A positive polyimide resin composition was prepared from 100 parts by weight of the resin (A-1) obtained in the above synthesis example, 25 parts by weight of naphthoquinone diazide compound (B), 10 parts by weight of HMOM-TPHAP, 10 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as a solvent.
Comparative example 2
A positive polyimide resin composition was prepared by using 100 parts by weight of the resin (A-2) obtained in the above synthesis example, 25 parts by weight of naphthoquinone diazide compound (B), 10 parts by weight of HMOM-TPHAP, 10 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as a solvent.
Comparative example 3
A positive polyimide resin composition was prepared by mixing 50 parts by weight of the resin (A-1) obtained in the above synthesis example, 50 parts by weight of the resin (A-2), 25 parts by weight of the naphthoquinone diazide compound (B), 10 parts by weight of HMOM-TPHAP, 10 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as a solvent.
Comparative example 4
A positive polyimide resin composition was prepared from 50 parts by weight of the resin (A-2), 50 parts by weight of the resin (A-5), 25 parts by weight of the naphthoquinone diazide compound (B), 10 parts by weight of HMOM-TPHAP, 10 parts by weight of trisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as the solvent.
Comparative example 5
A positive polyimide resin composition was prepared by mixing 50 parts by weight of the resin (A-2) obtained in the above synthesis example, 50 parts by weight of the resin (A-3), 25 parts by weight of the naphthoquinone diazide compound (B), 10 parts by weight of HMOM-TPHAP, 10 parts by weight of TrisP-HAP, 5 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 225 parts by weight of gamma-butyrolactone as a solvent.
The positive polyimide resin compositions prepared in examples 1 to 5 and comparative examples 1 to 5 were evaluated as follows:
(1) The polyimide imidization rate determination method comprises the following steps:
the polyimide was dried at room temperature, dissolved in DMSO-d6, and 1H-NMR was measured at room temperature using tetramethylsilane as a reference substance, and the value was determined by the following formula (i):
imidization rate (%) = (1-A1/A2. Times. Alpha.) X100 (i)
A1: peak area of proton derived from NH group (10 ppm)
A2: peak area derived from other protons
α: the ratio of the number of other protons to 1 proton of the NH group in the precursor of the polymer (polyamic acid) was determined.
(2) Evaluation of resolution:
the positive polyimide resin composition was coated on a 6-inch silicon wafer by a spin coating method, and pre-baked at 110 ℃ for 2min to give a pre-baked adhesive film having a thickness of 5.0 to 5.5 μm. And performing exposure treatment on the silicon wafer by using an i-line stepper as an exposure machine. After exposure, the substrate was developed in a 2.38 wt% aqueous tetramethylammonium hydroxide solution for 90 seconds, and then rinsed with pure water and then blown dry to obtain a positive pattern. The pattern was observed with a microscope, and the minimum size of the resolvable lines and spaces (lines and spaces) was taken as the resolution. Therefore, the smaller the width, the denser the pattern can be obtained, and the better the resolution can be judged.
(3) Evaluation of film remaining rate:
the film retention rate is calculated according to the following formula:
film deposition rate (%) = film thickness after development ÷ film thickness after prebaking × 100
(4) Evaluation of residual film rate:
the prepared photosensitive polyimide adhesive film is processed at 150 ℃ for 30min, heated to 200 ℃ for 30min and then processed at 350 ℃ for 60min to prepare a cured film. The residual film rate is calculated according to the following formula:
residual film ratio (%) = film thickness after curing ÷ film thickness after development × 100.
The evaluation results are shown in the following table:
Figure BDA0003421078890000231
Figure BDA0003421078890000241
as can be seen from the above table, in comparison with example 1, in comparative examples 1 and 2, no pattern was obtained after development of the positive polyimide resin composition containing only the fluorine-containing polyimide resin or only the fluorine-free polyimide resin. As is clear from comparison of comparative example 3 with example 1, when the fluorine content in the positive polyimide resin composition is low, both the film retention rate and the resolution are lowered. As is clear from comparison of comparative example 4 with example 1, when the fluorine content in the positive polyimide resin composition is high, the film-remaining rate is high, but the resolution is degraded and the pattern edge is seriously remained. As is clear from comparison of comparative example 5 with example 1, in the positive polyimide resin composition, fluorine atoms were removed from the polyimide resin component containing the structural unit (2) and introduced into the polyimide resin component containing the structural unit (1), the resolution and the film-remaining rate were both lowered, and the pattern edge remained.
As is clear from comparison of the data in examples 1 and 5, the increase in the amount of naphthoquinone diazide compound increases the film remaining rate and decreases the residual film rate. As can be seen from a comparison of the data in examples 1 and 3 with those in example 4, the higher the content of the polyimide resin containing the structural unit (2) in the positive polyimide resin composition, the higher the film remaining rate and the film residue rate.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (3)

1. A positive polyimide resin composition is characterized by comprising the following components in parts by weight: 100 parts of polyimide resin, 1-50 parts of naphthoquinone diazide compound, 10-200 parts of thermal crosslinking compound, 0.01-5 parts of silane coupling agent, 10-15 parts of phenolic hydroxyl compound, 0-5 parts of assistant and 50-2000 parts of solvent;
the polyimide resin comprises the following components in a mass ratio of 20: 80-90: 10 a fluorine-free polyimide resin and a fluorine-containing polyimide resin; wherein the fluorine-free polyimide resin comprises a structural unit (1), and the fluorine-containing polyimide resin comprises a structural unit (2);
Figure FDA0003904074630000011
in the structural formulas of the structural units (1) and (2),
Figure FDA0003904074630000012
represents a dianhydride residue;
Figure FDA0003904074630000013
Figure FDA0003904074630000014
represents a non-fluorine-containing diamine residue,
Figure FDA0003904074630000015
represents a fluorine-containing diamine residue; n and m represent the number of repeating units, and n and m are independently integers between 50 and 1000;
the non-fluorine-containing polyimide resin and the fluorine-containing polyimide resin are both synthesized by raw materials containing tetracarboxylic dianhydride and diamine;
the naphthoquinone diazide compound is a compound obtained by performing ester bond linkage on sulfonic acid of naphthoquinone diazide and polyhydroxy compound, or a compound obtained by performing sulfonamide bond linkage on sulfonic acid of naphthoquinone diazide and polyamino compound, or a compound obtained by performing ester bond linkage and/or sulfonamide bond linkage on sulfonic acid of naphthoquinone diazide and polyhydroxy polyamino compound;
the thermal crosslinking compound is one or more of a compound with a benzoxazine structure, a compound with an epoxy structure, a compound with an oxetane structure and a compound with an alkoxymethyl group.
2. The positive polyimide resin composition according to claim 1, wherein the silane coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, trimethoxycyclosilane, vinyltrimethoxysilane and mercaptopropyltrimethoxysilane.
3. The positive polyimide resin composition according to claim 1, wherein the auxiliary agent is one or more of a surfactant, an ester, an alcohol, a ketone, and an ether.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000241640A (en) * 1998-12-24 2000-09-08 Hitachi Chem Co Ltd Optical element, its manufacture, and optical module
CN102292675A (en) * 2009-12-28 2011-12-21 东丽株式会社 Positive-type photosensitive resin composition
CN110028670A (en) * 2019-04-11 2019-07-19 明士新材料有限公司 Low-dielectric loss negative light-sensitive poly amic acid ester resin, resin combination, preparation method and application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003029899A1 (en) * 2001-09-26 2003-04-10 Nissan Chemical Industries, Ltd. Positive photosensitive polyimide resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000241640A (en) * 1998-12-24 2000-09-08 Hitachi Chem Co Ltd Optical element, its manufacture, and optical module
CN102292675A (en) * 2009-12-28 2011-12-21 东丽株式会社 Positive-type photosensitive resin composition
CN110028670A (en) * 2019-04-11 2019-07-19 明士新材料有限公司 Low-dielectric loss negative light-sensitive poly amic acid ester resin, resin combination, preparation method and application

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