CN113121857A - Low-dielectric-property polyimide film and preparation method thereof - Google Patents

Low-dielectric-property polyimide film and preparation method thereof Download PDF

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CN113121857A
CN113121857A CN202110608855.2A CN202110608855A CN113121857A CN 113121857 A CN113121857 A CN 113121857A CN 202110608855 A CN202110608855 A CN 202110608855A CN 113121857 A CN113121857 A CN 113121857A
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resin solution
silver
film
silver salt
acid resin
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汪英
朱凌云
任小龙
王振宇
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Guilin Electrical Equipment Scientific Research Institute Co Ltd
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The invention discloses a low dielectric property polyimide film and a preparation method thereof, comprising the following steps: 1) preparing a polyamic acid resin solution; 2) adding silver salt dispersion liquid into polyamide acid resin solution, uniformly mixing, and carrying out constant-temperature thermal decomposition, imidization and shaping treatment on the obtained mixed resin solution after casting to form a film; the silver salt dispersion liquid is a solution formed by dispersing silver salt in a polar aprotic solvent, and the addition amount of the silver salt is controlled to be 0.1-10 wt% of the solid content of the polyamic acid resin solution; the silver salt is any one or the combination of more than two of silver nitrate, silver carbonate and silver oxalate; the constant temperature thermal decomposition treatment is thermal decomposition at 190-220 ℃, and the decomposition time is more than or equal to 5 min. The polyimide film with low dielectric property prepared by the method of the invention has good mechanical property while obtaining low dielectric property.

Description

Low-dielectric-property polyimide film and preparation method thereof
Technical Field
The invention relates to a polyimide material, in particular to a low-dielectric-property polyimide film and a preparation method thereof.
Background
Polyimide (PI) films have excellent high temperature resistance, chemical resistance, mechanical properties, and electrical properties, and are widely used as dielectric materials in the microelectronics industry. The molecular chain of the common PI film is a polar chain, and the dielectric constant (Dk) is usually 3.2-3.8.
With the rapid development of the microelectronic industry, the functions of microelectronic elements are continuously enhanced and the volume is continuously reduced, the integration level of very large scale integrated circuits is higher and higher, the size is also reduced, the parasitic resistance effect and the parasitic capacitance effect in the circuits are also more and more serious, and the resistance and capacitance delay of metal interconnection is increased in a nearly quadratic way, so that the capacitance in the resistance and the wiring is increased, the problems of signal transmission delay and crosstalk, noise interference, power loss increase and the like are caused, and the performance of devices is directly influenced. In order to reduce signal transmission delay, crosstalk and dielectric loss, to satisfy the requirement of high speed signal transmission and to further improve the function of electronic circuits, a dielectric interlayer insulating material is required to have lower dielectric properties, and generally, a dielectric constant of a polyimide material is required to be reduced from 3.2 to 3.8 to less than 3.0, and a dielectric loss factor (Df) is required to be reduced from 0.4 to 0.01 to less than 0.006, or even lower.
In the prior art, the method for reducing the dielectric property of polyimide mainly comprises the following steps: (1) the polyimide is subjected to fluorination modification, and the molecular polarizability is reduced by introducing fluorine-containing groups on the polyimide; (2) by adding bulky structural groups such as fluorene functional groups, poly cage siloxane structural groups; (3) adding fluoroplastic fillers such as polytetrafluoroethylene powder; (4) lowering the dielectricity by introducing a microporous structure in the polyimide molecular structure according to the minimum dielectric constant of air; and so on.
In the method for reducing the dielectric property of the polyimide, the polyimide porous film is prepared by introducing air holes, so that the method is an effective method for reducing the dielectric constant of the polyimide. At present, polyimide porous films are prepared at home and abroad mainly by adopting a chemical solvent method and a thermal degradation method:
a. the chemical solvent method is a method in which a composite material is prepared by adding a pore-forming agent (pore-forming substance), and then the pore-forming agent is removed by a chemical reaction or an extractive dissolution method to generate pores. Such as patent publications CN104910409A, CN1760241A or CN 104211980A.
b. Thermal degradation methods create holes by introducing thermally degradable components. As described in "research on porous PI film prepared from PAA/PU alloy and structure and performance" of the present invention, a porous PI film (i.e., liujie, published by advanced chemical schools, 2006, 1 month, p178-181.) is prepared by adding a PU (polyester polyurethane) solution to a PAA (polyamic acid) resin to form a film, and then imidizing the PAA and degrading the PU by heat treatment. It is pointed out that in the range of 0 to 20% by mass of PU, the dielectric constant of the obtained porous film gradually decreases with the increase of the PU content, and is minimized at 20% by mass of PU, while the tensile strength and water absorption of the obtained porous film both increase with the increase of the PU content, and is maximized at 20% by mass of PU; the reduction of the tensile strength is particularly obvious, and when the mass fraction of PU is 10%, the reduction of the tensile strength is more than 25% compared with the tensile strength when no PU is added. Also, for example, patent publication No. CN110358134A discloses a method for preparing a low dielectric constant polyimide film, in which aluminum triacetylacetonate is used as a pore-forming agent, and is dispersed in a polyamic acid resin solution, and the resulting mixed solution is subjected to a high-temperature heat treatment to sublimate and volatilize the aluminum triacetylacetonate in the thermal imidization process, so that holes are left in the polyimide matrix, thereby obtaining a polyimide film having a dielectric constant of 2.0 to 2.6. Although the method disclosed in the application can obtain the polyimide film with a relatively low dielectric constant, the tensile strength of the obtained film is only 89-121 MPa, and the elongation is low, and is only 8.1-11.2%. Therefore, the existing method for introducing the thermal degradable component to generate the holes has the problem of greatly reduced mechanical property.
Disclosure of Invention
The invention aims to provide a low dielectric polyimide film with good mechanical property while obtaining low dielectric property and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a low dielectric property polyimide film comprises the following steps:
1) preparing a polyamic acid resin solution;
2) adding silver salt dispersion liquid into polyamide acid resin solution, uniformly mixing, and carrying out constant-temperature thermal decomposition, imidization and shaping treatment on the obtained mixed resin solution after casting to form a film so as to obtain a low-dielectric polyimide film; wherein,
the silver salt dispersion liquid is a solution formed by dispersing silver salt in a polar aprotic solvent, wherein the silver salt is any one or the combination of more than two of silver nitrate, silver carbonate and silver oxalate;
the adding amount of the silver salt dispersion liquid is controlled to be 0.1-10 wt% of the solid content of the polyamic acid resin solution;
the constant temperature thermal decomposition treatment is thermal decomposition at 190-220 ℃, and the decomposition time is more than or equal to 5 min.
In step 2) of the method of the present invention, the polar aprotic solvent used for dispersing the silver salt is selected to be the same as the polar aprotic solvent used in the preparation of the polyamide-based resin solution in the art, and the amount of the polar aprotic solvent is preferably controlled such that the concentration of the silver salt in the silver salt dispersion can be 1 to 30 wt%, preferably 5 to 20 wt%. The silver salt is easy to dissolve in polar aprotic solvent, and the silver salt has excellent compatibility with polyamic acid resin solution, so that the problem that introduced components or fillers are difficult to disperse is solved. In order to further improve the dissolution or dispersion of the silver salt in the polar aprotic solvent, a dispersing device such as a homogenizer, a grinder, a sand mill, an emulsifying machine or an ultrasonic dispersing machine can be adopted to uniformly disperse the silver salt in the polar aprotic solvent. Similarly, the above conventional method and apparatus can be used to further improve the uniform dispersion degree of the silver salt dispersion in the polyamic acid resin solution. In this step, the addition amount of the silver salt dispersion is more preferably controlled to be 0.5 to 7.5 wt% of the solid content of the polyamic acid resin solution, and more preferably 1 to 5 wt% of the solid content of the polyamic acid resin solution. In this step, silver nitrate is more preferably used as the silver salt.
In step 2) of the method of the present invention, a self-supporting film (also referred to as a polyamic acid film in this application) obtained by casting is thermally decomposed at a specific temperature, so that silver salt therein is completely decomposed into silver oxide (wherein generated nitrogen dioxide, carbon dioxide or carbon monoxide continuously escapes from the self-supporting film, since the content of a solvent in the self-supporting film obtained by casting is usually about 30% (usually 20-40%), the escape of nitrogen dioxide, carbon dioxide or carbon monoxide from the self-supporting film during thermal decomposition does not cause formation of voids), the silver oxide is further decomposed into a nano-silver simple substance and oxygen by heating in a subsequent imidization treatment, and due to a small amount of oxygen generated, during the further decomposition by heating, oxygen generated during the decomposition of the silver oxide located in the self-supporting film expands in situ in a polyimide matrix obtained by simultaneous heating and imidization to form bubbles, oxygen generated during the decomposition of the silver oxide on the surface of the self-supporting film or close to the surface of the self-supporting film escapes from the surface of the polyimide base film obtained after the imidization is completed by heating, so that holes are left on the surface of the polyimide base film, the polyimide base film is a polyimide film which contains bubbles inside and has holes on the surface, and the existence of the bubbles and the holes ensures the low dielectric property of the polyimide base film. On the other hand, since the pores present inside the film are closed bubbles rather than pores communicating with the surface of the film, the degree of deterioration of the mechanical properties of the resulting film can be effectively suppressed.
Based on the good compatibility of silver salt and polar aprotic solvent, silver salt is uniformly distributed in the self-supporting film, and the subsequent thermal decomposition is carried out at a specific temperature, so that the particles of the obtained silver oxide are tiny, the silver oxide can be decomposed in the subsequent imidization to obtain nano-scale silver simple substance particles with the particle size of 10-150 nm, and the oxygen obtained by the decomposition is limited, therefore, the silver oxide positioned in the self-supporting film only expands in situ in a polyimide matrix to form bubbles, but not directly escapes from the polyimide matrix to form holes.
The time for constant-temperature thermal decomposition can be determined according to the thickness of the low-dielectric-property polyimide film to be prepared actually, and when the thickness of the film to be prepared is 7.5-12.5 mu m, the time for thermal decomposition is preferably controlled to be 5-10 min; when the thickness of the film to be prepared is 12.5 to 50 μm, the thermal decomposition time is preferably controlled to 10 to 30 min. . For thicker films, such as 75-150 μm films, 35-60 min is usually required.
In order to improve the dimensional stability of the obtained polyimide film, a stretching treatment is preferably added after the constant-temperature thermal decomposition treatment and before the imidization treatment, the operation of the stretching treatment is the same as that of the prior art, specifically, the stretching treatment comprises longitudinal stretching and/or transverse stretching of the self-supporting film obtained by casting, preferably, the longitudinal stretching and the transverse stretching are both carried out at 225-280 ℃, the time is both controlled at 0.1-6.0 h, and the stretching ratio is both preferably 0.8-2.5.
In step 2) of the method of the present invention, in actual production, the mixed resin solution obtained by mixing the polyamic acid resin solution and the silver salt dispersion liquid usually needs to be defoamed and then salivated to form a film. In the step, the operations of the salivation film forming, the imidization and the sizing treatment are the same as those of the prior art, specifically, the salivation film forming can be carried out at the temperature of between room temperature and 175 ℃, and the salivation drying treatment time is usually controlled to be between 0.1 and 3.0 hours; the thermal imidization is preferably carried out at 350-600 ℃, and the imidization time is controlled to be 0.1-9.0 h; the setting treatment is carried out at 180-360 ℃, and the time of the setting treatment is controlled to be 0.1-7.0 h.
The polyamic acid resin solution in step 1) of the present invention, also referred to as polyamic acid resin, polyamic acid solution, polyamic acid or polyimide precursor, is prepared by conventional in situ polymerization, such as known polycondensation reaction of diamine and dianhydride in polar aprotic solvent. Wherein, the selection and the dosage of the diamine, the dianhydride and the polar aprotic solvent are the same as those of the prior art, and the temperature and the time of the polycondensation reaction are also the same as those of the prior art. Specifically, the method comprises the following steps:
the diamine is preferably an aromatic diamine, which may be selected from 3,4' -diaminodiphenyl ether (3,4' -ODA), 4' -diaminodiphenyl ether (4,4' -ODA), 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2' -TFDB), 3' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (3,3' -TFDB), 4' -diaminobiphenyl, m-phenylenediamine (m-PDA), p-phenylenediamine (p-PDA), 2' -bistrifluoromethyl-4, 4' -diaminodiphenyl ether (TFODA), 3' -diamino-5, 5 ' -bistrifluoromethylbiphenyl (s-TFDB), 2, 2-bis (trifluoromethyl) -4,4 '-diaminophenylsulfone (SFTA), 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenylsulfone, 2- (4-aminophenyl) -5-aminobenzimidazole (APBIA), 4 '-bis (3-aminophenoxy) diphenylsulfone (M-BAPS), bis (3-aminophenyl) sulfone (3-DDS), bis (4-aminophenyl) sulfone (4-DDS), 4' -bis (4-aminophenoxy) biphenyl (BAPB), 1, 3-bis (3-aminophenoxy) benzene (TPE-M), 1, 3-bis (4-aminophenoxy) benzene (TPE-R), 1, 4-bis (4-aminophenoxy) benzene (TPE-Q), 2,2' -bis [4- (4-aminophenoxy phenyl) ] propane (BAPP), 2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane (HFBAPP), 9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA), 9-bis (3-methyl-4-aminophenyl) fluorene (BMAPF), 9-bis (4-aminophenyl) Fluorene (FDA), 1, 3-cyclohexanediamine, 1, 3-cyclobutanediamine, and the like. Further preferred are compounds selected from the group consisting of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (2,2' -TFDB), 3' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (3,3' -TFDB), 2' -bis (trifluoromethyl) -4,4' -diaminodiphenyl ether (TFODA), 3' -diamino-5, 5 ' -bis (trifluoromethyl) biphenyl (s-TFDB), 2-bis (trifluoromethyl) -4,4' -diaminophenylsulfone (SFTA), 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenylsulfone, 2' -bis [4- (4-aminophenoxyphenyl) ] propane (BAPP), 2, 2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane (HFBAPP), 9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA), 9-bis (3-methyl-4-aminophenyl) fluorene (BMAPF), 9-bis (4-aminophenyl) Fluorene (FDA), 1, 3-cyclohexanediamine, 1, 3-cyclobutanediamine, and the like.
The dianhydride is preferably an aromatic dianhydride selected from the group consisting of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 3,4' -hexafluoroisopropylphthalic anhydride (a-6FDA), 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2, 3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA), 4' - (4,4' -isopropyldiphenoxy) bis (phthalic anhydride) (HBDA), 2,3,3',4' -biphenyltetracarboxylic dianhydride (a-BPDA), 4' -triphendiether tetracarboxylic dianhydride (HQDPA), diphenylsulfide tetracarboxylic dianhydride (3,4,3',4' -TDPA, 2,3,2',3'-TDPA, 2,3,3',4'-TDPA), 2,3,3',4 '-diphenylether tetracarboxylic dianhydride (a-ODPA), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA), 3,3',4,4 '-diphenylsulfone tetracarboxylic dianhydride, 2,3',4 '-diphenylsulfone tetracarboxylic dianhydride, pyromellitic acid (PMDA), 3,3',4,4 '-biphenyltetracarboxylic dianhydride (BPDA), 2',3,3 '-biphenyltetracarboxylic dianhydride (BPDA), 2,3,3',4 '-benzophenonetetracarboxylic dianhydride (a-BTDA), benzophenonetetracarboxylic dianhydride (BTDA), 4,4' -Oxydiphthalic Dianhydride (ODPA), 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride (CPDA) and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (HPMDA). More preferably, it is any one or a combination of two or more selected from 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 3,4' -hexafluoroisopropylphthalic anhydride (a-6FDA), 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride (CPDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (HPMDA), and the like.
The polar aprotic solvent may be specifically selected from the group consisting of N, N '-Dimethylacetamide (DMAC), N' -Dimethylformamide (DMF), N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphoric triamide, 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl ] ether, 1, 4-dioxane, dimethyl sulfoxide (DMSO), tetramethylsulfoxide, N '-dimethyl-N, N' -propyleneurea (DMPU), cyclopentanone, cyclohexanone, N-Dimethylolmethane (DMF), N-methylpyrrolidone (DMF), N-methylethyl, N-Dimethylolmethane (DMF), N-methylethyl-Dimethylolmethane (DMF), N-dimethyl, Dichloromethane, monochlorobenzene, dichlorobenzene, chloroform, tetrahydrofuran, 3-methyl-N, N-dimethylpropionamide, N dialkyl carboxyl amide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethylurea, phenol m-cresol and gamma-butyrolactone. Further preferred is N '-Dimethylacetamide (DMAC), N' -Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or γ -butyrolactone.
The polycondensation reaction of diamine and dianhydride is preferably carried out in an inert atmosphere (such as nitrogen, and the like) at the temperature of 10-80 ℃ under stirring, the dianhydride is preferably added in batches, and the molar ratio of the diamine to the dianhydride is generally controlled to be 0.9-1.1: 1, the reaction time is usually controlled to be 4-8 h. The solid content of the polyamic acid resin solution obtained by polymerization is preferably controlled to be 5 to 40 wt%, more preferably 10 to 30 wt%, and particularly preferably 12 to 22 wt%.
The invention also comprises the low dielectric property polyimide film prepared by the method, the dielectric loss factor of the film is less than or equal to 0.003, the dielectric constant is less than or equal to 2.8 (under the test frequency of 10 GHz), the tensile strength is more than or equal to 250MPa, the elongation is more than or equal to 45 percent, and the water absorption is less than or equal to 2.0 percent.
Compared with the prior art, the invention is characterized in that:
1. the obtained film is a polyimide film which contains bubbles inside and has holes on the surface, so that the film has lower dielectricity compared with the conventional nonporous film; secondly, by introducing soluble silver salt into the PAA resin, the introduction of silver salt (particularly silver nitrate) inhibits the deformation effect of a specific framework in the process of forming polyimide, namely, the relative displacement among atoms in a main chain structure is greatly reduced, and the atom polarization is inhibited; moreover, nanoscale simple substance silver particles obtained after imidization are uniformly dispersed in the PI matrix, and due to the fact that the simple substance silver particles are small in size, an effective dielectric network is not easily formed inside the composite film, and the inhibition on the interface polarization of polyimide molecules around the silver particles is more obvious (the uniform dispersion of the simple substance silver particles effectively promotes the quantum coulomb blocking effect of the simple substance silver particles, namely the migration of electrons in a system is hindered); the combination of these two effects further results in a reduction in the dielectric properties of the resulting film; the combined action of the three aspects can greatly reduce the overall dielectric property of the obtained film.
2. Based on the polyimide with covalent bond connection as a main chain structure, in the presence of lone pair electrons of silver atoms (metal) and nitrogen atoms in silver salts, through chemical bond actions such as metal-carboxylic acid coordination bonds, hydrogen bonds and the like, the crystallization and orientation of polyimide molecules with a conjugated structure are greatly improved, so that the stacking among the polyimide molecular chains is further enhanced under the influence of van der Waals force, and the interlayer distance of the polyimide molecular chains is reduced; in addition, the simple substance silver nanoparticles obtained by reduction are uniformly dispersed in the polyimide matrix and are not separated from the inside of the film (at least, the simple substance silver nanoparticles in the film are not separated from the inside of the film), and because the simple substance silver particles are small in size and uniform in distribution, a supporting framework in the polyimide matrix is effectively formed, so that the obtained polyimide film has good mechanical properties; on the other hand, since the pores present inside the film are bubbles rather than pores communicating with the surface of the film, the degree of deterioration of the mechanical properties of the resulting film can be effectively suppressed. Meanwhile, silver nitrate and nano-scale decomposition products thereof effectively inhibit molecular chain distortion in the imidization process of the polyamic acid, so that the arrangement of polyimide molecular chains is more linear, and in addition, simple substance silver particles reduced in situ are uniformly dispersed in a polyimide substrate, so that the obtained polyimide film keeps lower water absorption under the comprehensive action.
3. The dielectric loss factor of the film prepared by the method is less than or equal to 0.003, the dielectric constant is less than or equal to 2.8 (under the test frequency of 10 GHz), the tensile strength is more than or equal to 250MPa, the elongation is more than or equal to 45 percent, and the water absorption is less than or equal to 2.0 percent.
Drawings
FIG. 1 is an electron micrograph of the surface of a low dielectric polyimide film obtained in example 1 of the present invention.
FIG. 2 is an electron micrograph of a cross section of a low dielectric polyimide film obtained in example 1 of the present invention.
FIG. 3 is a DTA curve of the polyamic acid resin solution obtained in step 1) and the mixed resin solution obtained in step 2) in example 1, wherein curve A represents the polyamic acid resin solution and curve B represents the mixed resin solution.
FIG. 4 is an XRD pattern of the self-supporting film obtained in step 2) in example 1 of the present invention.
FIG. 5 is an electron micrograph of a pure polyimide film obtained in comparative example 1 of the present invention.
FIG. 6 is an electron micrograph of a polyimide film obtained in comparative example 2 of the present invention without constant temperature thermal decomposition treatment.
Detailed Description
In order to better explain the technical solution of the present invention, the present invention is further described in detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.
When a polyimide film is produced by using the process described in the following examples, the thickness of the polyimide film is not limited, and may be various thicknesses such as 12.5 μm, 25 μm, 38 μm, 50 μm, 75 μm, 100 μm, 125 μm, or 150 μm.
In the following examples and comparative examples, the purity of the monomer is 99.5% or more, and the solvent for forming the silver salt dispersion in each example is the same as the solvent for preparing the polyamic acid resin solution in the examples.
The dielectric loss factor and dielectric constant of the films in Table 1 were tested according to the Standard GB/T13542.2-2006 "film for Electrical insulation part 6: polyimide film for electrical insulation "6.1 properties independent of thickness were tested.
The mechanical properties (tensile strength and elongation) of the film in table 1 are tested by using an electronic universal tensile machine (model KD111-0.2, qian li test instrument ltd, shenzhen), specifically referring to standard GB/T13542.2-2009 part 2 of film for electrical insulation: test methods.
In Table 1, the water absorption properties are as described in GB/T13542.6-2006 part 6 of film for electrical insulation: polyimide film for electrical insulation "6.1 properties independent of thickness were tested.
Example 1
1) 850.00kg of N-methyl-2-pyrrolidone (NMP) is added into a reaction kettle under the nitrogen atmosphere and the temperature of a synthesis system is controlled to be 30 ℃, then 60.745kg of 4,4 '-diaminodiphenyl ether (4,4' -ODA) is added, after stirring and dissolving, dianhydride 3,3',4,4' -biphenyltetracarboxylic acid dianhydride (s-BPDA, 89.255kg, added by 12 times) with the molar ratio of 1:1 to diamine is added, and stirring and reacting are carried out for 24 hours, so that a polyamic acid resin solution with the solid content of 15 wt% is obtained (the solid content in the solution (M, the same below) is 150.0 kg);
2) keeping the polyamic acid resin solution at 15 ℃, adding silver nitrate dispersion liquid (the silver nitrate concentration is 10 wt%), wherein the addition amount of the silver nitrate dispersion liquid is 2 wt% of the solid content of the polyamic acid resin solution, and uniformly stirring and mixing to obtain a mixed resin solution; coating the obtained mixed resin solution on an annular steel belt through an extrusion molding die, controlling the thickness of a liquid film on the steel belt to be 300 mu m, and then drying and curing at 200 ℃ to remove 70 wt% of solvent to obtain a self-supporting film; and (3) the obtained self-supporting film is sent to an environment at 200 ℃ for heat preservation and decomposition for 20min, then sent to a longitudinal and transverse biaxial stretching machine for longitudinal stretching at 225 ℃ for 1.2 times of stretching for 0.5h and transverse stretching at 250 ℃ for 1.15 times of stretching for 1.0h, then imidized at 600 ℃ for 2h, finally shaped at 360 ℃ for 1.5h, and rolled to obtain the polyimide film with the thickness of 25 mu m. The surface and cross-section of the polyimide film are shown in fig. 1 and 2, respectively, and it can be seen from fig. 1 and 2 that the film contains nano-silver simple substance particles, and the film contains bubbles inside and has holes on the surface.
The polyamic acid resin solution obtained in step 1) and the mixed resin solution obtained in step 2) were subjected to DTA (Differential Thermal Analysis) Analysis, respectively, and their DTA curves are shown in fig. 3. As can be seen from fig. 3, the endothermic peak of the mixed resin solution at 190.2 ℃ is significantly different from that of the pure polyamic acid resin, and the endothermic peak of the mixed resin solution at 190.2 ℃ also includes the reaction of the silver nitrate decomposing into silver oxide by comparison with the pure silver nitrate, so the DTA curve is different as above.
Sampling from the self-supporting film obtained in the step 2), and carrying out XRD analysis on the sample by using an X-ray diffractometer, wherein an X-ray diffraction pattern is shown in figure 4. As can be seen from fig. 4, the diffraction peak of the self-supporting film sample appears at 38.5 °, which is the characteristic diffraction peak of silver oxide, indicating that silver nitrate is decomposed to form silver oxide (nitrogen dioxide gas escapes from the matrix) after the mixed resin solution is coated with a film and heat treated at 200 ℃.
Comparative example 1
The comparative example is different from example 1 in that the polyamic acid resin solution obtained in step 1) was directly applied to an endless steel belt through an extrusion molding die without adding a silver nitrate dispersion in step 2). Finally, a pure (intrinsic) polyimide film with a thickness of 25 μm was obtained, and an electron micrograph thereof is shown in FIG. 5.
Comparative example 2
The difference between the comparative example and the example 1 is that the self-supporting film obtained in the step 2) is directly sent to a longitudinal and transverse biaxial stretching machine for subsequent operation (i.e. the process of thermal decomposition in an environment of 200 ℃ for 20min is not carried out). Finally, a polyimide film having a thickness of 25 μm was obtained, and an electron micrograph thereof is shown in FIG. 6. The polyimide film obtained contained silver particles of nanometer order, but no pores were formed.
Comparative example 3
This comparative example is different from example 1 in that the amount of silver nitrate dispersion added was controlled to be 0.05 wt% of the solid content of the polyamic acid resin solution.
Comparative example 4
This comparative example is different from example 1 in that the amount of silver nitrate dispersion added was controlled to be 12.0wt of the solid content of the polyamic acid resin solution.
Example 2
This example is different from example 1 in that the silver nitrate dispersion was added in an amount of 10.0 wt% based on the solid content of the polyamic acid resin solution.
Example 3
This example is different from example 1 in that the silver nitrate dispersion was added in an amount to control the silver nitrate to be added in an amount of 0.5 wt% based on the solid content of the polyamic acid resin solution.
Example 4
This example is different from example 1 in that the amount of silver nitrate dispersion added was controlled to be 7.5 wt% of the solid content of the polyamic acid resin solution.
Example 5
This example is different from example 1 in that the silver nitrate dispersion was added in an amount of 1.0 wt% based on the solid content of the polyamic acid resin solution.
Example 6
This example is different from example 1 in that the silver nitrate dispersion was added in an amount to control the silver nitrate to be added in an amount of 5.0 wt% based on the solid content of the polyamic acid resin solution.
Example 7
1) 960.00kg of N, N-Dimethylformamide (DMF) is added into a reaction kettle under the nitrogen atmosphere and at the temperature of a synthesis system controlled to be 25 ℃, 114.871kg of 4,4 '-diaminodiphenyl ether (4,4' -ODA) is added, stirring is carried out to dissolve the DMF, dianhydride pyromellitic diacid (PMDA, 125.129kg, added in 8 times) with the molar ratio of 1:1 to diamine is added into the mixture, stirring is carried out for reaction for 30 hours, and a polyamic acid resin solution with the solid content of 20 wt% is obtained (M is 240.0 kg);
2) keeping the polyamic acid resin solution at 20 ℃, adding silver nitrate dispersion liquid (the silver nitrate concentration is 20 wt%), wherein the addition amount of the silver nitrate dispersion liquid is 5 wt% of the solid content of the polyamic acid resin solution, and uniformly stirring and mixing to obtain a mixed resin solution; coating the obtained mixed resin solution on an annular steel belt through an extrusion molding die, controlling the thickness of a liquid film on the steel belt to be 220 mu m, and then drying and curing at 150 ℃ to remove 80 wt% of solvent to obtain a self-supporting film; and (3) putting the obtained self-supporting film into an environment with the temperature of 190 ℃ for heat preservation and decomposition for 30min, then carrying out imidization treatment for 3h at the temperature of 350 ℃, finally carrying out setting treatment for 0.5h at the temperature of 200 ℃, and rolling to obtain a polyimide film with the thickness of 25 mu m. The obtained film contains bubbles inside and holes on the surface.
Example 8
1) 410.00kg of N, N '-Dimethylacetamide (DMAC) is added into a reaction kettle under the nitrogen atmosphere and the temperature of a synthesis system is controlled to be 25 ℃, then 15.418kg of 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (2,2' -TFDB) and 21.112kg of 1, 3-bis (4-aminophenoxy) benzene (TPE-R) are added, after stirring and dissolving, dianhydride 3,3',4,4' -biphenyltetracarboxylic dianhydride (s-BPDA, 53.471kg, added in 8 times) with the molar ratio of 1:1 to diamine is added into the mixture, and stirring and reacting are carried out for 24 hours to obtain a polyamic acid resin solution (M is 90.0kg) with the solid content of 18 wt%;
2) keeping the polyamic acid resin solution at 10 ℃, adding silver nitrate dispersion liquid (the silver nitrate concentration is 5 wt%), wherein the addition amount of the silver nitrate dispersion liquid is 1.0 wt% of the solid content of the polyamic acid resin solution, and uniformly stirring and mixing to obtain a mixed resin solution; coating the obtained mixed resin solution on an annular steel belt through an extrusion molding die, controlling the thickness of a liquid film on the steel belt to be 250 mu m, and then drying and curing at 173 ℃ to remove 80 wt% of solvent to obtain a self-supporting film; and (3) the obtained self-supporting film is sent to a longitudinal and transverse biaxial stretching machine for longitudinal stretching at 250 ℃ and 1.5 times of stretching for 0.2h and transverse stretching at 280 ℃ and 1.3 times of stretching for 0.3h in sequence, imidization treatment is carried out for 0.5h at 350 ℃, setting treatment is carried out for 0.5h at 200 ℃, and rolling is carried out to obtain the polyimide film with the thickness of 25 mu m.
Example 9
The difference between this example and example 8 is that the self-supporting film in step 2) is decomposed for 5min under the condition of 220 ℃.
Comparative example 5
The difference between this example and example 8 is that the self-supporting film in step 2) is decomposed for 3min under the condition of 220 ℃.
Example 10
1) 600.00kg of N, N '-Dimethylacetamide (DMAC) is added into a reaction kettle under the nitrogen atmosphere and the temperature of a synthesis system is controlled to be 35 ℃, then 83.289kg of 2,2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl (2,2' -TFDB) is added, after stirring and dissolving, dianhydride 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA, 116.711 kg) with the molar ratio of 1:0.99 to diamine is added in 6 times, and stirring reaction is carried out for 36 hours to obtain a polyamic acid resin solution with the solid content of 25 wt% (M is 200.0 kg);
2) keeping the polyamic acid resin solution at 10 ℃, adding silver nitrate dispersion liquid (the silver nitrate concentration is 5 wt%), wherein the addition amount of the silver nitrate dispersion liquid is 1.0 wt% of the solid content of the polyamic acid resin solution, and uniformly stirring and mixing to obtain a mixed resin solution; coating the obtained mixed resin solution on an annular steel belt through an extrusion molding die, controlling the thickness of a liquid film on the steel belt to be 180 mu m, and then drying and curing at 140 ℃ to remove 70 wt% of solvent to obtain a self-supporting film; and (3) the obtained self-supporting film is sent to a vertical and horizontal biaxial stretching machine to be subjected to longitudinal stretching at 280 ℃ for 3.0h by 1.3 times and transverse stretching at 280 ℃ for 6.5h by 1.4 times in sequence after being subjected to heat preservation and decomposition for 25min at 200 ℃, then is subjected to imidization treatment for 4.5h at 400 ℃, finally is subjected to sizing treatment for 7.0h at 300 ℃, and is rolled to obtain the polyimide film with the thickness of 25 mu m.
Example 11
1) 410.00kg of N, N' -Dimethylformamide (DMF) is added into a reaction kettle under the nitrogen atmosphere and at the temperature of a synthesis system controlled to be 15 ℃, then 19.288kg of 9, 9-bis (3-fluoro-4-aminophenyl) fluorene (FFDA) is added into the reaction kettle, the mixture is stirred and dissolved, then 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA, 10.712kg, added in 4 times) with the molar ratio of 1.05:1 to diamine is added into the mixture, and the mixture is stirred and reacted for 48 hours to obtain a polyamic acid resin solution with the solid content of 10 weight percent (M is 30.0 kg);
2) keeping the polyamic acid resin solution at 10 ℃, adding silver nitrate dispersion liquid (the silver nitrate concentration is 5 wt%), wherein the addition amount of the silver nitrate dispersion liquid is 0.1 wt% of the solid content of the polyamic acid resin solution, and uniformly stirring and mixing to obtain a mixed resin solution; coating the obtained mixed resin solution on an annular steel belt through an extrusion molding die, controlling the thickness of a liquid film on the steel belt to be 380 mu m, and then drying and curing at 120 ℃ to remove 85 wt% of solvent to obtain a self-supporting film; and (3) the obtained self-supporting film is sent to an environment with the temperature of 200 ℃ for heat preservation and decomposition for 45min, then sent to a longitudinal and transverse biaxial stretching machine for longitudinal stretching with the temperature of 200 ℃ and the stretching time of 1.18 times for 0.6h and transverse stretching with the temperature of 250 ℃ and the stretching time of 1.25 times for 0.4h, then sent to a high-temperature imidization oven for imidization treatment for 3.0h at the temperature of 550 ℃, finally subjected to setting treatment for 0.5h at the temperature of 320 ℃, and rolled to obtain the polyimide film with the thickness of 75 mu m.
Example 12
This example differs from example 1 in that silver carbonate is used as the silver salt instead of silver nitrate.
Example 13
This example differs from example 10 in that silver oxalate was used instead of silver nitrate as the silver salt.
The properties of the low dielectric polyimide films obtained in the above examples and comparative examples were measured, and the results are shown in table 1 below.
TABLE 1
Figure BDA0003094729160000101
Figure BDA0003094729160000111
As shown in Table 1, the low dielectric polyimide films prepared in examples 1-13 have relatively low dielectric constant, dielectric loss and low water absorption characteristics, and also exhibit high mechanical properties (e.g., high tensile strength and high elongation). In the case of preparing a film having a relatively large thickness, a polyimide film having low dielectric properties can also be obtained by increasing the time of the isothermal thermal decomposition treatment (as in example 11); furthermore, polyimide films with low dielectric properties can also be prepared by selecting different silver salt compounds (examples 12 to 13, such as silver carbonate and silver oxalate).
On the other hand, the polyimide film prepared in comparative example 1 without adding silver salt compound silver nitrate as shown in table 1 did not have the desired dielectric properties; the polyimide film prepared in comparative example 2, to which silver salt compound silver nitrate was added but which was not subjected to the isothermal thermal decomposition treatment, also did not have the desired dielectric properties, whereas in comparative examples 3 to 5, when the amount of silver salt added or the isothermal thermal decomposition treatment process was not within the range defined in the present application, the polyimide film prepared had poor dielectric properties and/or mechanical properties.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A preparation method of a low dielectric property polyimide film comprises the following steps:
1) preparing a polyamic acid resin solution;
2) adding silver salt dispersion liquid into polyamide acid resin solution, uniformly mixing, and carrying out constant-temperature thermal decomposition, imidization and shaping treatment on the obtained mixed resin solution after casting to form a film so as to obtain a low-dielectric polyimide film; wherein,
the silver salt dispersion liquid is a solution formed by dispersing silver salt in a polar aprotic solvent, wherein the silver salt is any one or the combination of more than two of silver nitrate, silver carbonate and silver oxalate;
the adding amount of the silver salt dispersion liquid is controlled to be 0.1-10 wt% of the solid content of the polyamic acid resin solution;
the constant temperature thermal decomposition treatment is thermal decomposition at 190-220 ℃, and the decomposition time is more than or equal to 5 min.
2. The method according to claim 1, wherein in the step 2), the decomposition time is 10 to 30min in the isothermal thermal decomposition treatment.
3. The method according to claim 1, wherein the silver salt dispersion is added in the step 2) in an amount of 0.5 to 7.5 wt% based on the solid content of the polyamic acid resin solution.
4. The method according to claim 1, wherein the silver salt dispersion is added in the step 2) in an amount of 1 to 5 wt% based on the solid content of the polyamic acid resin solution.
5. The process according to any one of claims 1 to 4, wherein in the step 2), the stretching treatment is performed after the constant-temperature thermal decomposition treatment and before the imidization treatment.
6. The low dielectric polyimide film prepared by the method according to any one of claims 1 to 5.
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