CN117384378A - Photosensitive polyamic acid ester resin, resin composition, preparation method and application thereof - Google Patents

Photosensitive polyamic acid ester resin, resin composition, preparation method and application thereof Download PDF

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CN117384378A
CN117384378A CN202311396951.0A CN202311396951A CN117384378A CN 117384378 A CN117384378 A CN 117384378A CN 202311396951 A CN202311396951 A CN 202311396951A CN 117384378 A CN117384378 A CN 117384378A
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bis
acid ester
polyamic acid
ester resin
solution
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贾斌
王富荣
范圣男
陈建俊
马嘉欣
任芳秀
李涛
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Minseoa Beijing Advanced Materials Development Co Ltd
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Minseoa Beijing Advanced Materials Development 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention discloses a photosensitive polyamic acid ester resin, a resin composition, a preparation method and application thereof. The structural formula of the photosensitive polyamic acid ester resin is shown as formula I, and the preparation method comprises the following steps: s1, carrying out esterification reaction on fluorine-containing aromatic dianhydride and an esterification reagent to obtain fluorine-containing aromatic diester diacid; s2, reacting fluorine-containing aromatic diester diacid with an acyl chloride reagent to obtain corresponding diester diacid chloride; s3, preparing a mixed diamine solution of diamine containing siloxane groups and aromatic diamine; s4, mixing diester diacid chloride, mixed diamine solution and molecular weight regulator,obtaining polyamic acid ester resin solution through polycondensation reaction; separating out solid resin from the polyamic acid ester resin solution. The resin composition solution obtained by the photosensitive polyamic acid ester resin can be obtained by adopting a secondary spin coating process, and a polyimide film with the thickness of more than 50um after pre-baking and more than 30um after thermal imidization can be obtained, so that the resin composition solution can be applied to a thick film photoetching process to realize finer wiring and higher packaging density.

Description

Photosensitive polyamic acid ester resin, resin composition, preparation method and application thereof
Technical Field
The invention relates to a photosensitive polyamic acid ester resin, a resin composition, a preparation method and application thereof, and belongs to the technical field of polymers.
Background
With the continuous upgrading and updating of electronic products, the emerging markets such as smart phones, 5G, AI and the like have put higher requirements on packaging technologies, and after the ultra-large scale integrated circuit (ULIC) manufacture is completed, many integrated circuit manufacturers continue to manufacture multi-layer metal interconnection circuits on the wafer surface so as to realize BGA, CSP, WLP, siP and other advanced IC packages. Due to the promotion of miniaturization and multilayer technology, the packaging density of hybrid circuits is higher and higher, the conductor lines are finer, the line spacing is narrower, thick film lithography (Thick Film Lithography) is the mainstream, and the thickness of films prepared from photoresist is generally required to be larger than 30um. The multilayer metal interconnection circuit can be manufactured on the surface of the wafer by adopting ultraviolet light technology, and the photosensitive polyimide resin (Photosensitive Polyimides, PSPI) interlayer dielectric insulating layers and the metal copper conductor wiring layers are alternately overlapped.
Because of the strong intermolecular and intramolecular interactions in the conventional polyimide molecular structure, a Charge Transfer Complex (CTC) is easily formed between an electron donor (diamine) and an electron acceptor (dianhydride), and thus, the thin film prepared therefrom has strong light absorption in the visible light region, poor light transmittance, and exhibits characteristic pale yellow or dark brown color. Hoyle et al (C.E.Hoyle, D.Creed, P.Subraamaian.Polym Prep, 1993, 34:369) report that the polymerization of a fluorine-containing diamine with a fluorine-containing dianhydride to form a PI resin decreases the dielectric constant of the polymer as the fluorine content increases. This is because the introduction of fluorine atoms in the PI resin backbone structure reduces the electron polarization effect, and as the fluorine content increases, the free volume fraction of the system increases, causing a linear decrease in the dielectric constant. However, perfluorinated polyimides can lead to polymers with reduced glass transition temperatures and mechanical properties and increased coefficients of thermal expansion.
When the thickness of the polyimide film after high-temperature curing is more than 30um, the thermal stress at high temperature can cause the stripping of the high polymer coating and the inorganic substrate with lower thermal expansion coefficient, and the subsequent packaging process is serious. Therefore, when the polyimide resin is used in an electronic component such as an interlayer insulating film or a cover film, and the electronic component is used in a heat treatment process such as a reflow soldering process, the polyimide resin should have good adhesion to metal and silicon, otherwise, molten tin flows at the delamination place of the dielectric film, resulting in failure of the whole product.
Disclosure of Invention
The invention aims to provide photosensitive polyamic acid ester resin, wherein a resin composition solution obtained by adopting the photosensitive polyamic acid ester resin adopts a secondary spin coating process, so that a polyimide film with the thickness of more than 50um after pre-baking and more than 30um after thermal imidization can be obtained, and the photosensitive polyamic acid ester resin can be applied to a thick film photoetching process to realize finer wiring and higher packaging density.
The polyimide film obtained by the photosensitive polyamic acid ester resin has the characteristics of low dielectric constant (Dk is less than or equal to 2.5) and low dielectric loss (Df is less than or equal to 0.006), and meanwhile, due to the introduction of fluorine atoms, the transparency of the polyimide film is improved, so that the film has excellent i-line transmittance and resolution is improved; the introduction of siloxane groups can reduce internal stress, increase the cohesiveness of polyimide films to metals (copper, aluminum and the like) and silicon, avoid the phenomenon that a high polymer coating and an inorganic substrate with a lower thermal expansion coefficient are peeled off due to thermal stress at high temperature, and ensure that molten tin does not flow when an electronic component is subjected to reflow soldering; a patterned resin film (patterned resin film) can be easily formed by introducing a photosensitive group into a polyimide precursor by an esterification reagent; the resin composition solution obtained by using the photosensitive polyamic acid ester resin can be subjected to a secondary spin coating process to obtain a polyimide film with the thickness of more than 50um after pre-baking and more than 30um after curing.
The structural formula of the photosensitive polyamic acid ester resin provided by the invention is shown as formula I:
in the formula I, X is selected from one of fluorine-containing groups shown in formulas IIa to IId;
Y 1 one of the siloxane-containing groups shown in formulas IIIa to IIId;
Y 2 at least one selected from the groups shown in formulas VIa-VIg;
R 1 and R is 2 Each independently selected from at least one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, and monovalent organic groups having carbon-carbon unsaturated double bonds;
m and n represent polymerization degrees, the value range of m is 30-150, and the value range of n is 0-150, but not 0.
Preferably, R 1 And R is 2 Each independently selected from methyl, ethylAny one of n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, n-hexyl, cyclohexyl, ethyl acrylate, ethyl methacrylate, propyl acrylate and 2-hydroxy-n-propyl methacrylate.
The invention provides a preparation method of photosensitive polyamic acid ester resin, which comprises the following steps:
s1, carrying out esterification reaction on fluorine-containing aromatic dianhydride and an esterification reagent to obtain fluorine-containing aromatic diester diacid;
the fluorine-containing aromatic dianhydride is at least one of 4,4'- (hexafluoroisopropenyl) diphthalic anhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, (trifluoromethyl) pyromellitic anhydride, 2-bis [4- (3, 4 dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride and pentafluoroethyl pyromellitic anhydride;
The esterifying reagent is R 1 OH and R 2 OH, wherein R is 1 And R is 2 Each independently selected from at least one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, and monovalent organic groups having carbon-carbon unsaturated double bonds;
s2, reacting the fluorine-containing aromatic diester diacid with an acyl chloride reagent to obtain corresponding diester diacid chloride;
s3, preparing a mixed diamine solution of diamine containing siloxane groups and aromatic diamine;
s4, mixing the diester diacid chloride, the mixed diamine solution and a molecular weight regulator, and performing polycondensation reaction to obtain a polyamic acid ester resin solution;
the solid resin is separated out from the polyamic acid ester resin solution, namely the photosensitive polyamic acid ester resin.
In the above preparation method, in the step S1, the esterification reagent is an alcohol compound containing an unsaturated double bond, and the alcohol compound containing an unsaturated double bond is at least one of 2-acryloyloxy ethanol, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 1-acryloyloxy-3-propanol, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxy propyl acrylate, 1-methacryloyloxy-3-propanol, 2-methacryloyloxy ethanol, 2-isobutylamide ethanol, 2-hydroxy-3-butoxypropyl methacrylate, and 2-hydroxy-3-methoxypropyl methacrylate;
The esterification reaction is carried out under the action of an alkaline catalyst;
the alkaline catalyst is pyridine or triethylamine;
the esterification reaction is carried out in an organic solvent, wherein the organic solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the molar ratio of the fluorine-containing aromatic dianhydride to the esterifying reagent is 1:2;
the temperature of the esterification reaction is 20-150 ℃ and the time is 0.5-96 hours;
the esterification reaction is carried out under stirring.
In the above preparation method, in step S2, the molar ratio of the fluorinated aromatic diester diacid to the acid chloride reagent is 1:1.5 to 3;
the acyl chloride reagent is SOCl 2 、PCl 3 、PCl 5 Oxalyl chloride or COCl 2 ；
The reaction temperature is-30-50 ℃ and the reaction time is 1-48 h.
In the above preparation method, in step S3, the diamine containing siloxane groups is 1, 3-bis (3-aminobutyl) -1, 3-tetramethyl polysiloxane, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, 1, 3-bis (2-aminoethylaminomethyl) tetramethyl disiloxane at least one of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (3-aminobutyl) -1, 3-tetraphenyldisiloxane;
The aromatic diamine is p-phenylenediamine, 4 '-biphenyl diamine, 4' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane and 4, at least one of 4' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 1, 4-bis (4-amino-4, 4' -diisopropylbenzene), 4 '-bis (4-aminophenoxy) diphenyl sulfone, 2' -bis [4- (4-aminophenoxyphenyl) ] propane, 4 '-bis (4-aminophenoxy) diphenyl ether, and 4,4' -bis (4-aminophenoxy) benzophenone;
the molar ratio of the siloxane group-containing diamine to the aromatic diamine is 1:0.1 to 0.5;
the mixed diamine solution was formulated using the following organic solvents: at least one of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide and dimethylsulfoxide;
in the mixed diamine solution, the mass percentage concentration of the diamine containing siloxane groups and the aromatic diamine is 5-35%.
In the above preparation method, in step S4, the molecular weight regulator is at least one of phthalic anhydride, 4-phenylacetylene phthalic anhydride, hydrogenated 4-phthalic anhydride, 3-bromophthalic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, perchlorophthalic anhydride, 4-bromophthalic anhydride, perchlorophthalic anhydride, 3, 4-dibromophthalic anhydride, 3, 4-dichlorophthalic anhydride, 4-phenylethynyl aniline, aniline and 3-phenylethynyl aniline;
The mole ratio of the diester diacid chloride to the mixed diamine is 1:0.8 to 1.2;
the polycondensation reaction temperature is-30-10 ℃ and the time is 0.5-96 h;
the polycondensation reaction comprises the following steps: dripping the organic solution of the diester diacid chloride into the mixed diamine solution for reaction for 5-15 hours after the dripping is finished, and then adding the molecular weight regulator for continuous reaction for 0.5-2 hours to form a polyamic acid ester resin solution;
the molecular weight regulator is used in an amount such that the molar ratio of anhydride groups to amino groups in the final reaction solution is 1:1.
in the above preparation method, in step S4, the polycondensation reaction further includes the following processing steps:
mixing the polyamic acid ester resin solution with a poor solvent to precipitate a solid resin; washing and drying the solid resin to obtain the photosensitive polyamic acid ester resin;
the poor solvent can be deionized water, methanol, ethanol, hexane, butyl cellosolve, toluene, etc., preferably deionized water, methanol or ethanol;
the consumption of the poor solvent is 3-20 times of the mass of the polyamic acid ester resin solution;
the cleaning step is carried out by using the poor solvent used for the precipitation, and the amount of the poor solvent used for the cleaning is preferably 1 to 6 times by mass relative to the polymer; the more the number of times the polymer is washed, the less impurity of the polymer can be obtained. The number of washing is preferably 2 to 6.
The drying is preferably performed under vacuum at 20 to 70 ℃ to obtain a solid polyesteramide resin.
On the basis of the photosensitive polyamic acid ester resin, the invention also provides a resin composition which is prepared from the following components in parts by mass:
100 parts of photosensitive polyamic acid ester resin, 1-10 parts of photoinitiator, 0.01-30 parts of photosensitizer, 0.01-30 parts of polymerization inhibitor, 0.01-30 parts of crosslinking auxiliary agent and 100-1000 parts of organic solvent;
the resin composition preferably comprises the following components in parts by mass:
100 parts of photosensitive polyamic acid ester resin, 3-6 parts of photoinitiator, 1-5 parts of photosensitizer, 0.01-0.1 part of polymerization inhibitor, 5-15 parts of crosslinking auxiliary agent and 100-500 parts of organic solvent;
the resin composition most preferably comprises the following components in parts by mass:
100 parts of the photosensitive polyamic acid ester resin, 5 parts of a photoinitiator, 2 parts of a photosensitizer, 0.075 part of a polymerization inhibitor, 10 parts of a crosslinking auxiliary agent and 200 parts of an organic solvent;
wherein the photoinitiator is at least one of oxime ester compounds (such as 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, N '-tetramethyl-4, 4' -diaminobenzophenone, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime), benzophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone; oxime ester compounds and benzophenones are preferred; the oxime ester compound is preferably 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime;
The sensitizer is at least one of Michler's ketone, 4' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 4' -bis (diethylamino) chalcone, 4' -bis (dimethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 2- (p-dimethylaminophenyl-biphenylidene) -benzothiazole, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone and 2- (p-dimethylaminophenyl-vinylidene) benzothiazole;
the polymerization inhibitor is at least one of hydroquinone, 4-methoxyphenol, 2, 6-di-tert-butyl-p-methylphenol, phenothiazine, p-tert-butylcatechol, N-phenylnaphthylamine, 5-nitroso-8-hydroxyquinoline, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol, N-nitrosodiphenylamine and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol;
the cross-linking auxiliary agent is at least one of glycidyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, glycidyl acrylate, ethylene glycol diethyl ether methacrylate, glycidyl acrylate, ethylene glycol diethyl ether acrylate, polyethylene glycol methacrylate and glycidyl methacrylate;
The organic solvent is at least one of N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethyl acetamide and N, N-dimethyl formamide.
The resin composition may be prepared as follows:
and mixing the polyamic acid ester resin, the photoinitiator, the photosensitizer, the polymerization inhibitor, the crosslinking auxiliary agent and the organic solvent, and stirring until a uniform solution is formed, thus obtaining the resin composition.
Preferably, the preparation process is completed in a thousands of ultra-clean room equipped with a yellow light source;
preferably, the addition sequence of the raw materials is as follows: sequentially adding the photosensitive polyamic acid ester resin, the photoinitiator, the photosensitizer, the polymerization inhibitor and the crosslinking auxiliary agent into the organic solvent;
preferably, the preparation process is carried out at room temperature, for example 15-30 ℃, and further for example 25 ℃.
Preferably, the stirring time is 8-72 h;
the solid content of the resin composition provided by the invention is 10-30%, and the apparent viscosity at 25 ℃ is 2000-3 multiplied by 10 5 Cp。
The resin composition is subjected to secondary spin coating to obtain a polyimide film with the thickness of more than 50um after pre-baking and more than 30um after curing; the method comprises the following specific steps:
1) And (3) homogenizing: coating the resin composition on the surface of the substrate at a low rotational speed;
2) Pre-baking: evaporating the solvent in the resin composition to form a first resin coating film with a thickness of 25-35 um;
baking in a hot plate or oven at 80-130 ℃ for 1-60 min;
3) And (3) secondary spin coating: coating the resin composition on the first resin coating film at a high rotational speed;
4) And (5) pre-baking again: evaporating the solvent in the resin composition to form a second resin coating film with the thickness of 50-60 um;
5) Exposing, developing and curing: and exposing, developing and curing in sequence to obtain the polyimide film.
The speed difference between the high speed and the low speed is 1000-1500 rpm/s.
In the above method, the developer and the rinse solution can be used as auxiliaries conventionally used in the prior art. Among them, the developing solution is preferably a good solvent of the negative photosensitive resin composition or a combination of a good solvent and a poor solvent; the good solvent is preferably N-methylpyrrolidone, N-dimethylacetamide, N-cyclohexyl-2-pyrrolidone, cyclopentanone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone or gamma-butyrolactone; the poor solvent is preferably methanol, isopropanol, ethanol, ethyl lactate, butyl acetate, ethyl acetate, tetrahydrofuran, propylene glycol monomethyl ether or propylene glycol and methyl ether acetate dioxane; the rinsing liquid is preferably at least one of isopropanol, butyl acetate, ethyl acetate, propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether acetate, cyclopentanone and cyclohexanone.
After the resin composition is formed into a cured film, the resin composition layer forming step, the exposure step, and the development treatment step may be sequentially performed again. In particular, the resin composition layer forming step, the exposure step and the development treatment step are preferably performed 2 to 5 times in this order (i.e., 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be obtained. In the present invention, it is particularly preferable that after the cured film is provided and developed, a new metal line is formed by electroplating after the portion removed by the developer, so as to connect the original aluminum pad or gold pad, thereby completing the rewiring layer (Redistribution Layer, RDL).
The polyimide film of the present invention can be used in A1) or A2) as follows:
a1 Preparing an insulating layer film, a dielectric layer film or a stress buffer protective layer film in the microelectronic packaging industry;
a2 Inter-layer dielectric or insulating membrane of the multilayer metal wiring interconnection structure;
specifically, the film is useful as a surface protective film, an interlayer insulating film of a multilayer wiring board, or the like of an electronic component. Among these, it can be particularly suitable for use in the redistribution layer (Redistribution Layer, RDL) process in a package.
The invention also provides an electronic component, comprising the polyimide film;
As the electronic component, there may be mentioned a semiconductor device, a multilayer wiring board, various electronic devices, etc., as shown in fig. 1, the above resin composition solution may be spin-coated on a semiconductor substrate 1 such as a Si substrate by spin coating, and after exposure and development, a polyimide film 2 is obtained, a conductor layer 3 is formed in the exposed window, a polyimide resin film as an interlayer insulating film 4 is formed on the upper surface of 2 by spin coating, etc., a new metal wiring 5 is formed by electroplating in the exposed window on the upper surface 4 after exposure and development, a polyimide resin film as an interlayer insulating film 6 is formed on the upper surface of 5 by spin coating, etc., and after exposure and development, an external connection terminal 7 called a bump is formed in the exposed window on the upper surface 6 by a known method, that is, the electronic component shown in fig. 1 is obtained.
The electronic component has a pattern cured film of the above resin composition solution containing a photosensitive polyamic acid ester resin. Examples of the electronic component include a semiconductor device, a multilayer wiring board, and various electronic devices. Specifically, the pattern cured film can be used as a surface protective film for electronic parts, an interlayer insulating film for a multilayer wiring board, and the like. Among these, it can be particularly suitable for use in the redistribution layer (Redistribution Layer, RDL) process in a package.
The invention has the following beneficial effects:
the resin composition solution obtained by the photosensitive polyamic acid ester resin used in the invention can be obtained by adopting a secondary spin coating process, and a polyimide film with the thickness of more than 50um after pre-baking and more than 30um after thermal imidization can be obtained, so that the resin composition solution can be applied to a thick film photoetching process to realize finer wiring and higher packaging density. The polyimide film has the characteristics of low dielectric constant (Dk is less than or equal to 2.5) and low dielectric loss (Df is less than or equal to 0.006), and meanwhile, due to the introduction of fluorine atoms, the transparency of the polyimide film is improved, so that the film has excellent i-line transmittance and resolution is improved; the introduction of siloxane groups can reduce internal stress, increase the cohesiveness of polyimide films to metals such as copper, aluminum and the like and silicon, avoid the phenomenon that a high polymer coating and an inorganic substrate with a lower thermal expansion coefficient are peeled off due to thermal stress at high temperature, and ensure that molten tin does not flow when an electronic component is subjected to reflow soldering; a photosensitive group is introduced into the polyimide precursor by an esterification reagent, so that a patterned resin film can be easily formed; by heating and curing the pattern resin film, a pattern cured film can be easily formed; meanwhile, through an esterification reagent, polyamide acid is changed into polyamide ester, so that self-degradation of a polyimide precursor is prevented, and the stability and practicability of polyimide are improved.
Drawings
FIG. 1 is a schematic view of the structure of an electronic component comprising a polyimide film of the present invention;
the marks are as follows: 1-a semiconductor substrate; a 2-polyimide layer; a 3-conductor layer; a 4, 6-interlayer insulating film polyimide layer; 5-metal wiring; 7 external connection terminals.
FIG. 2 is a graph showing the transmittance of the polyimide film prepared in example 1 of the present invention.
FIG. 3 is a graph showing the transmittance of the polyimide film prepared in comparative example 3 of the present invention.
Fig. 4 is an SEM image of the polyimide film prepared in example 1 of the present invention.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In the following examples, the glass transition temperature of polyimide films was measured using dynamic thermo-mechanical analysis (DMA). Dynamic thermo-mechanical analyzer: model Q800 of TA company in the united states.
In the following examples, the residual stress of the cured polyimide film was measured using a film stress measuring instrument (FLX-2320).
In the following examples, adhesion between a film and metal (copper, aluminum, etc.) and silicon was evaluated by a dicing method: every 100 dividing layers of films are stripped off 0 grid by the adhesive tape to be the best, and the films are stripped off 1 to 10 grids by the adhesive tape to be the best; the dicing layer film was peeled off by the tape by more than 11 cells per 100 cells as "bad".
In the following examples, the optical properties of the films were measured using ultraviolet-visible (UV-vis) absorption spectroscopy and a color difference meter, and the film samples were each greater than 50 μm thick, wherein lambda 0 For the initial transmission wavelength, T 365 For light transmittance at 365nm, T 500 Is light transmittance at 500 nm.
Example 1
1. Preparation of photosensitive Polyamic acid ester resins
(1) 89.12g of 4,4' - (hexafluoroisopropenyl) isophthalic anhydride (6 FDA), 52.24g of 2-hydroxyethyl methacrylate (HEMA), 28.44g of pyridine and 232g of N-methylpyrrolidone (NMP) are sequentially added into a 1L three-neck round bottom flask with electric stirring, and stirring is carried out at room temperature for 6-10 hours to generate corresponding 6 FDA-diacid dimethacrylate. The esterified liquid was cooled to below 10℃with an ice bath, and 43.60g SOCl was slowly added dropwise 2 After the dripping is completed for 30min, reacting for 2-4 h at the temperature of 10-20 ℃ to generate the corresponding diacyl chloride dimethacrylate.
(2) Into a 1L three-necked round bottom flask equipped with electric stirring, 39.76g of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 4.32g of p-phenylenediamine and 306g of NMP were successively added and stirred to dissolve to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting ice bath, and dropwise adding the prepared mixed diacid chloride dimethacrylate into the mixed diamine solution for 1h; then restoring the room temperature, and reacting for 12-16 hours at the room temperature; adding 12ml of ethanol, and continuously stirring for 1h; slowly pouring the reaction solution into 5L of deionized water to precipitate solid, and washing, filtering and vacuum drying to obtain the polyamic acid ester resin.
2. Preparation of polyamic acid ester resin composition solution
In a thousands grade super clean room equipped with a yellow light lamp, 40g of the above polyamide acid ester resin, 2.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 0.8g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-tert-butyl-p-methylphenol, 4.0g of 2-hydroxyethyl methacrylate were added in this order to 80g of NMP, and stirred at room temperature for 10 hours to form a homogeneous negative photosensitive polyamide acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the negative photosensitive polyamic acid ester resin composition solution on the surface of a 6 inch wafer by using a spin coater, baking at 110 ℃ for 4min to obtain a film with the thickness of 25-35 um, spin-coating again, baking at 110 ℃ for 4min to obtain a film with the thickness of 50-60 um,then placing a mask on the surface of the mask, and exposing for 30s by adopting an ultraviolet lamp (i and g lines); after development with cyclopentanone and ethyl acetate rinse, the temperature was programmed in a nitrogen-filled oven (60 o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film.
The transmittance curve of the polyimide film prepared in this example is shown in fig. 2, and the SEM image is shown in fig. 4.
Example 2
1. Preparation of photosensitive Polyamic acid ester resins
Into a 1L three-necked round bottom flask equipped with electric stirring, 32.31 g of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 7.56g of p-phenylenediamine and 306g of NMP were sequentially added and stirred to dissolve to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the mixed diacid chloride dimethacrylate prepared in the embodiment 1 into the mixed diamine solution for 1h; then restoring the room temperature, and reacting for 12-16 hours at the room temperature; adding 12ml of ethanol, and continuously stirring for 1h; slowly pouring the reaction solution into 5L of deionized water to precipitate solid, and washing, filtering and vacuum drying to obtain the polyamic acid ester resin.
2. Preparation of polyamic acid ester resin composition solution
In a thousands grade super clean room equipped with a yellow light lamp, 40g of the above polyamide acid ester resin, 2.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 0.8g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-tert-butyl-p-methylphenol, 4.0g of 2-hydroxyethyl methacrylate were added in this order to 80g of NMP, and stirred at room temperature for 10 hours to form a homogeneous negative photosensitive polyamide acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the negative photosensitive polyamic acid ester resin composition solution on the surface of a 6 inch wafer by using a spin coater, baking at 110 ℃ for 4min to obtain a film with a thickness of 25-35 um, spin-coating again, baking at 110 ℃ for 4min to obtain a film with a thickness of 50-60 um, and then coating on the surface of the filmPlacing a mask on the surface, and exposing for 30s by adopting an ultraviolet lamp (i and g lines); after development with cyclopentanone and ethyl acetate rinse, the temperature was programmed in a nitrogen-filled oven (60 o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film.
Example 3
1. Preparation of photosensitive Polyamic acid ester resins
Into a 1L three-neck round bottom flask with electric stirring, sequentially adding 24.9g of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 10.8g of p-phenylenediamine and 306g of NMP, and stirring to dissolve the mixture to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the mixed diacid chloride dimethacrylate prepared in the embodiment 1 into the mixed diamine solution for 1h; then restoring the room temperature, and reacting for 12-16 hours at the room temperature; adding 12ml of ethanol, and continuously stirring for 1h; slowly pouring the reaction solution into 5L of deionized water to precipitate solid, and washing, filtering and vacuum drying to obtain the polyamic acid ester resin.
2. Preparation of polyamic acid ester resin composition solution
In a thousands grade super clean room equipped with a yellow light lamp, 40g of the above polyamide acid ester resin, 2.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 0.8g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-tert-butyl-p-methylphenol, 4.0g of 2-hydroxyethyl methacrylate were added in this order to 80g of NMP, and stirred at room temperature for 10 hours to form a homogeneous negative photosensitive polyamide acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the negative photosensitive polyamic acid ester resin composition solution on the surface of a 6-inch wafer by using a spin coater, baking for 4min at 110 ℃ to obtain a film with the thickness of 25-35 um, spin-coating again, baking for 4min at 110 ℃ to obtain a film with the thickness of 50-60 um, placing a mask on the surface, and exposing for 30s by using an ultraviolet lamp (i and g lines); developing with cyclopentanone, washing with ethyl acetate, and heating in nitrogen-filled oven with programmed temperature(60 o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film.
Example 4
1. Preparation of photosensitive Polyamic acid ester resins
Into a 1L three-necked round bottom flask equipped with electric stirring, 40.48g of 1, 3-bis (3-aminobutyl) -1, 3-tetramethyldisiloxane, 4.32g of p-phenylenediamine and 306g of NMP were sequentially added, and stirred to dissolve to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting an ice bath, and dropwise adding the mixed diacid chloride dimethacrylate prepared in the embodiment 1 into the mixed diamine solution for 1h; then restoring the room temperature, and reacting for 12-16 hours at the room temperature; adding 12ml of ethanol, and continuously stirring for 1h; slowly pouring the reaction solution into 5L of deionized water to precipitate solid, and washing, filtering and vacuum drying to obtain the polyamic acid ester resin.
2. Preparation of polyamic acid ester resin composition solution
In a thousands grade super clean room equipped with a yellow light lamp, 40g of the above polyamide acid ester resin, 2.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 0.80g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-tert-butyl-p-methylphenol, 4.0g of 2-hydroxyethyl methacrylate were added in this order to 80g of NMP, and stirred at room temperature for 10 hours to form a homogeneous negative photosensitive polyamide acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the negative photosensitive polyamic acid ester resin composition solution on the surface of a 6-inch wafer by using a spin coater, baking for 4 min at 110 ℃ to obtain a film with the thickness of 25-35 um, spin-coating again, baking for 4 min at 110 ℃ to obtain a film with the thickness of 50-60 um, placing a mask on the surface, and exposing for 30s by using an ultraviolet lamp (i and g lines); after development with cyclopentanone and ethyl acetate rinse, the temperature was programmed in a nitrogen-filled oven (60 o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film.
Comparative example 1,
1. Preparation of Polyamic acid ester resins
(1) Into a 1L three-necked round bottom flask equipped with electric stirring, 62.05g of 3,3', 4' -biphenylene oxide tetracarboxylic dianhydride (ODPA), 52.24g of 2-hydroxyethyl methacrylate (HEMA), 28.44g of pyridine and 232g of N-methylpyrrolidone (NMP) were successively added, and stirred at room temperature for 6 hours to give the corresponding ODPA-diacid dimethacrylate. The esterified liquid was cooled to below 10℃with an ice bath, and 43.60g SOCl was slowly added dropwise 2 After the dripping is completed for 30min, reacting for 2-4 h at the temperature of 10-20 ℃ to generate the corresponding diacyl chloride dimethacrylate.
(2) Into a 1L three-necked round bottom flask equipped with electric stirring, 39.76g of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 4.32g of p-phenylenediamine and 306g of NMP were successively added and stirred to dissolve to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting ice bath, and dropwise adding the prepared mixed diacid chloride dimethacrylate into the mixed diamine solution for 1h; then restoring the room temperature, and reacting for 12-16 hours at the room temperature; adding 12ml of ethanol, and continuously stirring for 1h; slowly pouring the reaction solution into 5L of deionized water to precipitate solid, and washing, filtering and vacuum drying to obtain the polyamic acid ester resin.
2. Preparation of polyamic acid ester resin composition solution
In a thousands grade super clean room equipped with a yellow light lamp, 40g of the above polyamide acid ester resin, 2.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 0.8g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-tert-butyl-p-methylphenol, 4.0g of 2-hydroxyethyl methacrylate were added in this order to 80g of MP, and stirred at room temperature for 10 hours to form a homogeneous negative photosensitive polyamide acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the negative photosensitive polyamic acid ester resin composition solution on the surface of a 6 inch wafer by using a spin coater, baking at 110deg.C for 4 min to obtain a film with a thickness of 25-35 um, spin-coating again, and heating at 110deg.CBaking for 4 min to obtain a film with the thickness of 50-60 um, then placing a mask on the surface of the film, and exposing for 30s by adopting an ultraviolet lamp (i and g lines); after development with cyclopentanone and ethyl acetate rinse, the temperature was programmed in a nitrogen-filled oven (60 o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film.
Comparative example 2,
1. Preparation of photosensitive Polyamic acid ester resins
(1) Into a 1L three neck round bottom flask equipped with electric stirring, 89.12g of 4,4' - (hexafluoroisopropenyl) isophthalic anhydride (6 FDA), 52.24g of 2-hydroxyethyl methacrylate (HEMA), 28.44g of pyridine and 232g of N-methylpyrrolidone (NMP) were sequentially added, and stirred at room temperature for 6 hours to yield the corresponding 6 FDA-diacid dimethacrylate. The esterified liquid was cooled to below 10℃with an ice bath, and 43.60g SOCl was slowly added dropwise 2 After the dripping is completed for 30min, reacting for 2-4 h at the temperature of 10-20 ℃ to generate the corresponding diacyl chloride dimethacrylate.
(2) Into a 1L three-necked round bottom flask equipped with an electric stirring and compressed air (CDA) inlet and outlet, 36.06g of 4,4' -diaminodiphenyl ether (ODA), 2.16g of p-phenylenediamine and 306g of NMP were sequentially added, and stirred to dissolve to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting ice bath, and dropwise adding the prepared mixed diacid chloride dimethacrylate into the mixed diamine solution for 1h; then restoring the room temperature, and reacting for 12-16 hours at the room temperature; adding 12ml of ethanol, and continuously stirring for 1h; slowly pouring the reaction solution into 5L of deionized water to precipitate solid, and washing, filtering and vacuum drying to obtain the polyamic acid ester resin.
2. Preparation of polyamic acid ester resin composition solution
In a thousands grade super clean room equipped with a yellow light lamp, 40g of the above polyamide acid ester resin, 2.0g of 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 0.8g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-tert-butyl-p-methylphenol, 4.0g of 2-hydroxyethyl methacrylate were added in this order to 80g of NMP, and stirred at room temperature for 10 hours to form a homogeneous negative photosensitive polyamide acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the negative photosensitive polyamic acid ester resin composition solution on the surface of a 6-inch wafer by using a spin coater, baking for 4min at 110 ℃ to obtain a film with the thickness of 25-35 um, spin-coating again, baking for 4min at 110 ℃ to obtain a film with the thickness of 50-60 um, placing a mask on the surface, and exposing for 30s by using an ultraviolet lamp (i and g lines); after development with cyclopentanone and ethyl acetate rinse, the temperature was programmed in a nitrogen-filled oven (60 o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film.
Comparative example 3,
1. Preparation of Polyamic acid ester resins
(1) Into a 1L three-necked round bottom flask equipped with an electric stirring and compressed air (CDA) inlet and outlet were successively charged 62.05g of 3,3', 4' -biphenylene oxide tetracarboxylic dianhydride (ODPA), 52.24g of 2-hydroxyethyl methacrylate (HEMA), 28.44g of pyridine and 232g of N-methylpyrrolidone (NMP), and stirred at room temperature for 6 hours to give the corresponding ODPA-diacid dimethacrylate. The esterified liquid was cooled to below 10℃with an ice bath, and 43.60g SOCl was slowly added dropwise 2 After the dripping is completed for 30min, reacting for 2-4 h at the temperature of 10-20 ℃ to generate the corresponding diacyl chloride dimethacrylate.
(2) Into a 1L three-necked round bottom flask equipped with an electric stirring and compressed air (CDA) inlet and outlet, 36.06g of 4,4' -diaminodiphenyl ether (ODA), 2.16g of p-phenylenediamine and 306g of NMP were sequentially added, and stirred to dissolve to form a homogeneous transparent mixed diamine solution; cooling the mixed diamine solution to below 10 ℃ by adopting ice bath, and dropwise adding the prepared mixed diacid chloride dimethacrylate into the mixed diamine solution for 1h; then restoring the room temperature, and reacting for 12-16 hours at the room temperature; adding 12ml of ethanol, and continuously stirring for 1h; slowly pouring the reaction solution into 5L of deionized water to precipitate solid, and washing, filtering and vacuum drying to obtain the polyamic acid ester resin.
2. Preparation of polyamic acid ester resin composition solution
In a thousands of ultra clean room equipped with a yellow light lamp, 40g of the above polyamic acid ester resin, 0.6g of 2-propanedione-2- (O-methoxycarbonyl) oxime, 0.10g of 2, 6-bis (4' -diethylaminobenzylidene) cyclohexanone, 0.03g of 2, 6-di-t-butyl-p-methylphenol, 4.0g of 2-hydroxyethyl methacrylate were successively added to 80g of NMP, and stirred at room temperature for 3 hours to form a homogeneous negative photosensitive polyamic acid ester resin composition solution.
3. Preparation of polyimide film
Spin-coating the negative photosensitive polyamic acid ester resin composition solution on the surface of a 6-inch wafer by using a spin coater, baking for 4min at 110 ℃ to obtain a film with the thickness of 25-35 um, spin-coating again, baking for 4min at 110 ℃ to obtain a film with the thickness of 50-60 um, placing a mask on the surface, and exposing for 30s by using an ultraviolet lamp (i and g lines); after development with cyclopentanone and ethyl acetate rinse, the temperature was programmed in a nitrogen-filled oven (60 o C/1h，80 o C/1h，120 o C/1h，170 o C/1h，250 o C/1h，300 o C/1h，350 o C/1 h) to obtain a polyimide film.
The transmittance curve of the polyimide film prepared in this comparative example is shown in fig. 3.
As can be seen from examples 1 to 4, comparative examples 1, 2, 3 and tables 1 and 2, as the proportion of diamine containing siloxane groups in the resin decreases (examples 1 to 3 decrease in order), the stress of the resin film gradually increases and the adhesion to metal and silicon becomes poor. The resin film containing only the fluorine aromatic dianhydride and the aromatic diamine has a low dielectric constant, but the film has high stress and poor adhesion to metal and silicon; the resin film which is composed of the fluorine-free aromatic dianhydride, the siloxane group-containing diamine and other aromatic diamines has small stress and good adhesion with metal and silicon, but has a dielectric constant higher than 3. The fluorine-containing resin film has high light transmittance at 365nm and 500nm and low yellow index.

Claims (14)

1. A photosensitive polyamic acid ester resin has a structural formula shown in a formula I:
；
in the formula I, X is selected from one of fluorine-containing groups shown in formulas IIa to IId;
；
Y 1 one of the siloxane-containing groups shown in formulas IIIa to IIId;
；
Y 2 at least one selected from the groups shown in formulas VIa-VIg;
；
R 1 and R is 2 Each independently selected from at least one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, and monovalent organic groups having carbon-carbon unsaturated double bonds;
m and n represent polymerization degrees, the value range of m is 30-150, and the value range of n is 0-150, but not zero.
2. The photosensitive polyamic acid ester resin according to claim 1, wherein: r is R 1 And R is 2 Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, t-butyl, n-hexyl, cyclohexyl, ethylene acrylateAny one of an ester group, an ethyl methacrylate group, a propyl acrylate group, and a 2-hydroxy-n-propyl methacrylate group.
3. The method for preparing the photosensitive polyamic acid ester resin according to claim 1 or 2, comprising the steps of:
s1, carrying out esterification reaction on fluorine-containing aromatic dianhydride and an esterification reagent to obtain fluorine-containing aromatic diester diacid;
the fluorine-containing aromatic dianhydride is at least one of 4,4'- (hexafluoroisopropenyl) diphthalic anhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4' - (hexafluoroisopropylidene) diphthalic anhydride, (trifluoromethyl) pyromellitic anhydride, 2-bis [4- (3, 4 dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride and pentafluoroethyl pyromellitic anhydride;
The esterifying reagent is R 1 OH and R 2 OH, wherein R is 1 And R is 2 Each independently selected from at least one of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, and monovalent organic groups having carbon-carbon unsaturated double bonds;
s2, reacting the fluorine-containing aromatic diester diacid with an acyl chloride reagent to obtain corresponding diester diacid chloride;
s3, preparing a mixed diamine solution of diamine containing siloxane groups and aromatic diamine;
s4, mixing the diester diacid chloride, the mixed diamine solution and a molecular weight regulator, and performing polycondensation reaction to obtain a polyamic acid ester resin solution;
the solid resin is separated out from the polyamic acid ester resin solution, namely the photosensitive polyamic acid ester resin.
4. A method of preparation according to claim 3, characterized in that: in the step S1, the esterifying reagent is an alcohol compound containing unsaturated double bonds, and the alcohol compound containing unsaturated double bonds is at least one of 2-acryloyloxy ethanol, 2-acrylamide ethanol, hydroxymethyl vinyl ketone, 1-acryloyloxy-3-propanol, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxy propyl acrylate, 1-methacryloyloxy-3-propanol, 2-methacryloyloxy ethanol, 2-isobutylamide ethanol, 2-hydroxy-3-butoxypropyl methacrylate and 2-hydroxy-3-methoxypropyl methacrylate;
The esterification reaction is carried out under the action of an alkaline catalyst;
the alkaline catalyst is pyridine or triethylamine;
the esterification reaction is carried out in an organic solvent, wherein the organic solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the molar ratio of the fluorine-containing aromatic dianhydride to the esterifying reagent is 1:2;
the temperature of the esterification reaction is 20-150 ℃ and the time is 0.5-96 hours;
the esterification reaction is carried out under stirring.
5. The method according to claim 3 or 4, wherein: in the step S2, the molar ratio of the fluorinated aromatic diester diacid to the acid chloride reagent is 1:1.5 to 3;
the acyl chloride reagent is SOCl 2 、PCl 3 、PCl 5 Oxalyl chloride or COCl 2 ；
The reaction temperature is-30-50 ℃ and the reaction time is 1-48 h.
6. The method of manufacturing according to claim 5, wherein: in the step S3 of the process, the diamine containing siloxane groups is 1, 3-bis (3-aminobutyl) -1, 3-tetramethyl polysiloxane, 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, 1, 3-bis (2-aminoethylaminomethyl) tetramethyl disiloxane at least one of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane and 1, 3-bis (3-aminobutyl) -1, 3-tetraphenyldisiloxane;
The aromatic diamine is p-phenylenediamine, 4 '-biphenyl diamine, 4' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane, 4' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, and at least one of 1, 4-bis (4-amino-4, 4' -diisopropylbenzene), 4 '-bis (4-aminophenoxy) diphenylsulfone, 2' -bis [4- (4-aminophenoxyphenyl) ] propane, 4 '-bis (4-aminophenoxy) diphenylether, and 4,4' -bis (4-aminophenoxy) benzophenone;
the molar ratio of the siloxane group-containing diamine to the aromatic diamine is 1:0.1 to 0.5;
the mixed diamine solution was formulated using the following organic solvents: at least one of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide and dimethylsulfoxide;
in the mixed diamine solution, the mass percentage concentration of the diamine containing siloxane groups and the aromatic diamine is 5-35%.
7. The method of manufacturing according to claim 6, wherein: in the step S4, the molecular weight regulator is at least one of phthalic anhydride, 4-phenylacetylene phthalic anhydride, hydrogenated 4-methylaniline, 3-bromophthalic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, perchlorophthalic anhydride, 4-bromophthalic anhydride, perchlorophthalic anhydride, 3, 4-dibromophthalic anhydride, 3, 4-dichlorobenzoic anhydride, 4-phenylethynyl aniline, aniline and 3-phenylethynyl aniline;
The mole ratio of the diester diacid chloride to the mixed diamine is 1:0.8 to 1.2;
the polycondensation reaction temperature is-30-10 ℃ and the time is 0.5-96 h;
the polycondensation reaction comprises the following steps: dripping the organic solution of the diester diacid chloride into the mixed diamine solution for reaction for 5-15 hours after the dripping is finished, and then adding the molecular weight regulator for continuous reaction for 0.5-2 hours to form a polyamic acid ester resin solution;
the molecular weight regulator is used in an amount such that the molar ratio of anhydride groups to amino groups in the final reaction solution is 1:1.
8. a resin composition is prepared from the following components in parts by mass:
100 parts of the photosensitive polyamic acid ester resin according to claim 1 or 2, 1 to 10 parts of a photoinitiator, 0.01 to 30 parts of a sensitizer, 0.01 to 30 parts of a polymerization inhibitor, 0.01 to 30 parts of a crosslinking auxiliary agent and 100 to 1000 parts of an organic solvent.
9. The resin composition according to claim 8, wherein: the photoinitiator is at least one of oxime ester compound, diphenyl ketone and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-acetone;
the sensitizer is at least one of Michler's ketone, 4' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 4' -bis (diethylamino) chalcone, 4' -bis (dimethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 2- (p-dimethylaminophenyl-biphenylidene) -benzothiazole, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone and 2- (p-dimethylaminophenyl-vinylidene) benzothiazole;
The polymerization inhibitor is at least one of hydroquinone, 4-methoxyphenol, 2, 6-di-tert-butyl-p-methylphenol, phenothiazine, p-tert-butylcatechol, N-phenylnaphthylamine, 5-nitroso-8-hydroxyquinoline, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol, N-nitrosodiphenylamine and 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol;
the cross-linking auxiliary agent is at least one of glycidyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, glycidyl acrylate, ethylene glycol diethyl ether methacrylate, glycidyl acrylate, ethylene glycol diethyl ether acrylate, polyethylene glycol methacrylate and glycidyl methacrylate;
the organic solvent is at least one of N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethyl acetamide and N, N-dimethyl formamide.
10. A method for producing the resin composition according to claim 8 or 9, comprising the steps of:
mixing the photosensitive polyamic acid ester resin according to claim 1 or 2, the photoinitiator, the photosensitizer, the polymerization inhibitor, the crosslinking auxiliary agent and the organic solvent, and stirring to form a uniform solution, thus obtaining the resin composition.
11. A polyimide film obtained from the resin composition according to claim 8 or 9 by secondary spin coating.
12. The method for producing a polyimide film according to claim 11, comprising the steps of:
1) And (3) homogenizing: coating the resin composition on the surface of the substrate at a low rotational speed;
2) Pre-baking: evaporating the solvent in the resin composition to form a first resin coating film with a thickness of 25-35 um;
3) And (3) secondary spin coating: coating the resin composition on the first resin coating film at a high rotational speed;
4) And (5) pre-baking again: evaporating the solvent in the resin composition to form a second resin coating film with the thickness of 50-60 um;
5) Exposing, developing and curing: sequentially exposing, developing and curing to obtain a polyimide film;
the speed difference between the high speed and the low speed is 1000-1500 rpm/s.
13. Use of the polyimide film according to claim 11 in A1) or A2) as follows:
a1 Preparing an insulating layer film, a dielectric layer film or a stress buffer protective layer film in the microelectronic packaging industry;
a2 Inter-layer dielectric or insulating separator for multilayer metal wiring interconnection structure.
14. An electronic component comprising the polyimide film of claim 11.
CN202311396951.0A 2023-10-26 2023-10-26 Photosensitive polyamic acid ester resin, resin composition, preparation method and application thereof Pending CN117384378A (en)

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CN117384378A true CN117384378A (en) 2024-01-12

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