CN111793206A - Preparation method of polyimide film and polyimide film - Google Patents
Preparation method of polyimide film and polyimide film Download PDFInfo
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Abstract
A polyimide film and a preparation method thereof, wherein the preparation method of the polyimide film comprises the following steps: s1: preparing heat-conducting filler dispersion liquid, mixing clay treated by a first silane coupling agent and nano-scale inorganic filler treated by a second silane coupling agent in a solvent to form the heat-conducting filler dispersion liquid, wherein the particle size of the clay is micron-scale; s2: adding a diamine monomer and a dianhydride monomer into the heat-conducting filler dispersion liquid to generate a polyamic acid resin solution; the heat-conducting filler dispersion liquid forms a heat-conducting filler structure with a three-dimensional network structure in the polyamic acid resin solution; s3: and (3) casting the polyamic acid resin solution, imidizing and biaxially stretching to obtain the polyimide film. The heat-conducting filler structure with a three-dimensional network structure is formed in the polyimide film through the micron-sized clay and the nanoscale inorganic filler, so that the polyimide film keeps mechanical properties, the thermal expansion coefficient of the film is reduced, and the heat-conducting property of the film is improved.
Description
Technical Field
The application relates to the technical field of electronic information products, in particular to a preparation method of a polyimide film and the polyimide film.
Background
This section is intended to provide a background or context to the embodiments of the application that are recited in the claims. The description herein is not admitted to be prior art by inclusion in this section.
With the rapid development of the electronic information industry, the high integration, high density and high speed of electronic equipment enable a circuit or a chip to rapidly accumulate heat in a tiny limited space, and whether the circuit or the chip can dissipate heat in time becomes a key that affects the service life, the operation stability and the safety performance of components.
Polyimide (PI) has excellent thermal stability, electrical insulation and mechanical properties, and is widely applied to the fields of microelectronics, rail transit, aerospace and the like. However, the heat conductivity coefficient of the conventional PI film is only about 0.16W/(m · K), and the PI film is almost a thermal insulator, so that when the PI film is applied to a microelectronic device, a phenomenon of circuit overheating easily occurs, and the stability of a component and an integrated circuit is affected.
Filling an inorganic filler in a polyimide film is an effective method for improving its thermal conductivity, but has problems in that: if micron-sized filler with larger particle size is adopted for filling, the process is easy to realize, the heat-conducting property of the obtained polyimide film can be improved, but the surface of the prepared film is rough, and the mechanical and thermal properties can be reduced; if the nano-grade filler is adopted for filling, the phenomenon of particle agglomeration is easy to occur, the mechanical and thermal properties of the film can be influenced, and the popularization and the application are not facilitated.
Disclosure of Invention
In view of the above, there is a need for an improved method for preparing polyimide films.
The technical scheme provided by the application is as follows:
a preparation method of a polyimide film comprises the following steps:
s1: preparing heat-conducting filler dispersion liquid, mixing clay treated by a first silane coupling agent and nano-scale inorganic filler treated by a second silane coupling agent in a solvent to form the heat-conducting filler dispersion liquid, wherein the particle size of the clay is micron-scale;
s2: adding a diamine monomer and a dianhydride monomer into the heat-conducting filler dispersion liquid to generate a polyamic acid resin solution; the heat-conducting filler dispersion liquid forms a heat-conducting filler structure with a three-dimensional network structure in the polyamic acid resin solution;
s3: and (3) casting the polyamic acid resin solution, imidizing and biaxially stretching to obtain the polyimide film.
In some embodiments of the present application, the clay comprises at least one of montmorillonite, mica, and hectorite, and the clay has a particle size of < 15 μm.
In some embodiments of the present application, the nanoscale inorganic filler comprises at least one of silica, titania, zirconia, alumina, silicon carbide, silicon nitride, iron oxide, magnesium oxide, calcium oxide, boron oxide, zinc oxide, aluminum nitride, and boron nitride, and the nanoscale inorganic filler has a particle size of < 500 nm.
In some embodiments of the present application, the solvent comprises at least one of N, N '-dimethylformamide, N' -dimethylacetamide, and N-methylpyrrolidone.
In some embodiments herein, the mass ratio of the clay to the nanoscale inorganic filler ranges from 10:90 to 40: 60.
In some embodiments of the present application, the diamine monomer comprises at least one of p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 4 '-diaminobenzophenone, and 3,4' -diaminodiphenyl ether.
In some embodiments of the present application, the dianhydride monomer includes at least one of pyromellitic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, and 3,3',4,4' -benzophenone tetracarboxylic dianhydride.
In some embodiments of the present application, the method of imidization is a chemical imidization or a thermal imidization method.
In some embodiments of the present application, a chemical imidizing agent consisting of an organic acid anhydride dehydrating agent, an organic base catalyst and an organic solvent is added during the chemical imidization.
Another object of the present invention is to provide a polyimide film, which is prepared by the above method for preparing a polyimide film, and includes a thermal conductive filler structure composed of clay of micron scale and inorganic filler of nanometer scale.
The application provides a preparation method of polyimide film, through with micron order clay and nanometer inorganic filler, fill in polyimide film, make the skeleton texture that forms heat conduction filler structure in polyimide ripples film through micron order clay, and nanometer inorganic filler fills between skeleton texture, in order to form the heat conduction filler structure that has three-dimensional network structure in polyimide film, thereby make polyimide film in the application, not only kept polyimide film's mechanical properties, reduced the coefficient of thermal expansion of film simultaneously, and improved its heat conductivility by a wide margin.
Detailed Description
In order that the manner in which the above-recited objects, features and advantages of the embodiments of the present application are obtained will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. In addition, the features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth to provide a thorough understanding of embodiments of the application, and the described embodiments are merely a subset of embodiments of the application, rather than all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without any creative effort belong to the protection scope of the embodiments in the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments of this application belong. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the present application.
The application provides a preparation method of a polyimide film, which comprises the following steps:
s1: preparing heat-conducting filler dispersion liquid, mixing clay treated by a first silane coupling agent and nano-scale inorganic filler treated by a second silane coupling agent in a solvent to form the heat-conducting filler dispersion liquid, wherein the particle size of the clay is micron-scale;
s2: adding a diamine monomer and a dianhydride monomer into the heat-conducting filler dispersion liquid to generate a polyamic acid resin solution; the heat-conducting filler dispersion liquid forms a heat-conducting filler structure with a three-dimensional network structure in the polyamic acid resin solution;
s3: and (3) casting the polyamic acid resin solution, imidizing and biaxially stretching to obtain the polyimide film.
Another object of the present invention is to provide a polyimide film, which is prepared by the above method for preparing a polyimide film, and includes a thermal conductive filler structure composed of clay of micron scale and inorganic filler of nanometer scale.
According to the preparation method of the polyimide film, micron-sized clay and nano-sized inorganic filler are filled in the polyimide film, so that the micron-sized clay forms a framework structure of a heat-conducting filler structure in the polyimide wave film, the nano-sized inorganic filler is filled between the framework structures, the heat-conducting filler structure with a three-dimensional network structure is formed in the polyimide film, the three-dimensional network is formed in the polyimide film, the mechanical property of the polyimide film is maintained in the application process of the polyimide film, the thermal expansion coefficient of the film is reduced, and the heat-conducting property of the polyimide film is greatly improved.
The following examples are presented in conjunction with the detailed description.
A preparation method of a polyimide film comprises the following steps:
s1: preparing a heat-conducting filler dispersion liquid: the clay and the nanoscale inorganic filler are mixed in a solvent to form a dispersion of thermally conductive filler.
Specifically, a certain amount of clay and nano-scale inorganic filler are weighed and are respectively treated by a first silane coupling agent and a second silane coupling agent, then the treated clay and nano-scale inorganic filler are added into a solvent to be mixed, and a uniform heat-conducting filler dispersion liquid is obtained through dispersion, wherein the mass of the nano-scale inorganic filler and the mass of the clay account for 1-20% of the whole mass of the heat-conducting filler dispersion liquid.
The first silane coupling agent and the second silane coupling agent are any one of N- (beta aminoethyl) -gamma-aminopropylmethyl-dimethoxysilane, vinyl tri (beta-methoxyethoxy) silane and vinyl triethoxysilane. The silane coupling agent is used as an adhesion promoter between a polymer and a filler.
The clay is at least one of montmorillonite, mica and lithium montmorillonite, and the particle size of the clay is less than 15 mu m. In one embodiment, the clay particle size is set to one of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm.
The nanoscale inorganic filler comprises at least one of silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, silicon carbide, silicon nitride, iron oxide, magnesium oxide, calcium oxide, boron oxide, zinc oxide, aluminum nitride and boron nitride, and the particle size of the nanoscale inorganic filler is less than 500 nm.
The solvent includes at least one of N, N '-dimethylformamide, N' -dimethylacetamide, and N-methylpyrrolidone.
The dispersion method is any one of ultrasonic, grinding and high-speed shearing. In other embodiments, the dispersion method may also be other known methods of uniformly dispersing a filler
The mass ratio of the clay to the nano inorganic filler is 1: 99-99: 1; preferably, the mass ratio of the clay to the nanoscale inorganic filler is 10: 90-40: 60.
S2: preparation of a polyamic acid resin solution: and adding a diamine monomer and a dianhydride monomer to the heat-conducting filler dispersion liquid to generate a polyamic acid resin solution.
Specifically, a diamine monomer and a dianhydride monomer are added into a heat-conducting filler dispersion liquid, and a polyamide acid resin solution is generated through a polycondensation reaction, wherein the viscosity of the polyamide acid resin solution is controlled to be 10-45 x 104mPa · s, and the fixed content of the resin in the polyamic acid resin solution is 10-35%.
The diamine monomer comprises at least one of p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 4 '-diaminobenzophenone and 3,4' -diaminodiphenyl ether.
The dianhydride monomer comprises at least one of pyromellitic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride and 3,3',4,4' -benzophenone tetracarboxylic dianhydride.
S3: preparing a polyimide film, casting a polyamic acid resin solution, imidizing and stretching to obtain the polyimide film.
Specifically, after the polyamic acid resin solution is defoamed in vacuum, a chemical imidization reagent is added into the polyamic acid resin solution, a polyamic acid adhesive film is cast, the polyamic acid adhesive film is heated at high temperature and is stretched in two directions to obtain a polyimide film, the addition amount of a heat-conducting filler in the prepared polyamic acid film accounts for 10-60% of the total mass of the polyimide film, and the polyamic acid film has a heat conductivity coefficient of more than 1.5 w/(m.k) and a thermal expansion coefficient of less than 20 ppm/DEG C.
The chemical imidization reagent is the combination of acetic anhydride and isoquinoline. In other embodiments, the polyamic acid resin solution may also be thermally imidized to form a polyimide film.
The scheme of the present application will be explained with reference to examples. Those skilled in the art will appreciate that the following examples are illustrative of the present application only and are not to be construed as limiting the present application.
Example 1
Taking 41.8g of montmorillonite treated by a silane coupling agent and 41.8g of aluminum nitride nanoscale inorganic filler modified by the silane coupling agent in total, wherein the particle size of the montmorillonite is 10 mu m, the particle size of the nanoscale inorganic filler is 300nm, the mass ratio of the montmorillonite to the aluminum nitride is 4:6, simultaneously adding the montmorillonite and the aluminum nitride nanoscale inorganic filler into 2.1kg of N, N-dimethylformamide, and performing ultrasonic dispersion for 1h to obtain uniform and stable heat-conducting filler dispersion liquid.
200.2g of 4,4' -diaminodiphenyl ether and 218g of pyromellitic dianhydride were added to the heat conductive filler dispersion, and reacted for 2 hours to obtain a polyamic acid resin solution.
And (2) defoaming the polyamic acid resin solution in vacuum, adding 204.2g of acetic anhydride and 25.8g of isoquinoline, casting the polyamic acid resin solution to form a polyamic acid adhesive film, and heating the polyamic acid adhesive film at high temperature and performing biaxial tension to obtain the polyimide film. The main properties of the obtained polyimide film were as follows: the heat conductive filler accounts for 10 mass percent of the polyimide film, the tensile strength is 223MPa, the tensile modulus is 2.6GPa, the elongation at break is 70 percent, the thermal expansion coefficient is 19.8 ppm/DEG C, and the heat conductivity coefficient is 1.53 w/(m.k).
Example 2
Taking 125.5g of mica treated by a silane coupling agent and boron nitride nano-scale inorganic filler modified by the silane coupling agent in total, wherein the particle size of the mica is 10 mu m, the particle size of the boron nitride nano-scale inorganic filler is 300nm, the mass ratio of the mica to the boron nitride is 3:7, simultaneously adding the mica and the boron nitride nano-scale inorganic filler into 2.1kg of N, N-dimethylformamide, and performing ultrasonic dispersion for 1h to obtain uniform and stable heat-conducting filler dispersion liquid.
200.2g of 4,4' -diaminodiphenyl ether and 218g of pyromellitic dianhydride were added to the heat conductive filler dispersion, and reacted for 2 hours to obtain a polyamic acid resin solution.
And (2) defoaming the polyamic acid resin solution in vacuum, adding 204.2g of acetic anhydride and 25.8g of isoquinoline, casting the polyamic acid resin solution to form a polyamic acid adhesive film, and heating the polyamic acid adhesive film at high temperature and performing biaxial tension to obtain the polyimide film. The main properties of the obtained polyimide film were as follows: the thermal conductive filler accounts for 30 percent of the polyimide film, has the tensile strength of 234MPa, the tensile modulus of 2.8GPa, the elongation at break of 73 percent, the thermal expansion coefficient of 18.6 ppm/DEG C and the thermal conductivity of 1.72 w/(m.k).
Example 3
Taking 209.1g of montmorillonite treated by a silane coupling agent and boron nitride nano-scale inorganic filler modified by the silane coupling agent in total, wherein the particle size of the montmorillonite is 10 mu m, the particle size of the boron nitride nano-scale inorganic filler is 300nm, the mass ratio of the montmorillonite to the boron nitride is 2:8, simultaneously adding the montmorillonite and the boron nitride nano-scale inorganic filler into 2.1kg of N, N-dimethylformamide, and performing ultrasonic dispersion for 1h to obtain uniform and stable heat-conducting filler dispersion liquid.
200.2g of 4,4' -diaminodiphenyl ether and 218g of pyromellitic dianhydride were added to the heat conductive filler dispersion, and reacted for 2 hours to obtain a polyamic acid resin solution.
And (2) defoaming the polyamic acid resin solution in vacuum, adding 204.2g of acetic anhydride and 25.8g of isoquinoline, casting the polyamic acid resin solution to form a polyamic acid adhesive film, and heating the polyamic acid adhesive film at high temperature and performing biaxial tension to obtain the polyimide film. The main properties of the obtained polyimide film were as follows: the heat conductive filler accounts for 50 mass percent of the polyimide film, the tensile strength is 246MPa, the tensile modulus is 3.3GPa, the elongation at break is 67 percent, the thermal expansion coefficient is 16.7 ppm/DEG C, and the heat conductivity coefficient is 2.24w/(m & k).
Example 4
250.9g of montmorillonite treated by a silane coupling agent and 250.9g of boron nitride nanoscale inorganic filler modified by the silane coupling agent are used in total, wherein the particle size of the montmorillonite is 10 mu m, the particle size of the boron nitride nanoscale inorganic filler is 300nm, the mass ratio of the montmorillonite to the boron nitride is 1:9, the montmorillonite and the boron nitride nanoscale inorganic filler are added into 2.1kg of N, N-dimethylformamide simultaneously, and the mixture is subjected to ultrasonic dispersion for 1h to obtain uniform and stable heat-conducting filler dispersion liquid.
200.2g of 4,4' -diaminodiphenyl ether and 218g of pyromellitic dianhydride were added to the heat conductive filler dispersion, and reacted for 2 hours to obtain a polyamic acid resin solution.
And (2) defoaming the polyamic acid resin solution in vacuum, adding 204.2g of acetic anhydride and 25.8g of isoquinoline, casting the polyamic acid resin solution to form a polyamic acid adhesive film, and heating the polyamic acid adhesive film at high temperature and performing biaxial tension to obtain the polyimide film. The main properties of the obtained polyimide film were as follows: the heat conductive filler accounts for 60 mass percent of the polyimide film, the tensile strength is 241MPa, the tensile modulus is 3.2GPa, the elongation at break is 65 percent, the thermal expansion coefficient is 18.5 ppm/DEG C, and the heat conductivity coefficient is 1.86w/(m & k).
Comparative example 1
Taking 20.9g of montmorillonite treated by a silane coupling agent and boron nitride nano-scale inorganic filler modified by the silane coupling agent in total, wherein the particle size of the montmorillonite is 10 mu m, the particle size of the boron nitride nano-scale inorganic filler is 300nm, the mass ratio of the montmorillonite to the boron nitride is 3:7, simultaneously adding the montmorillonite and the boron nitride nano-scale inorganic filler into 2.1kg of N, N-dimethylformamide, and performing ultrasonic dispersion for 1h to obtain uniform and stable heat-conducting filler dispersion liquid.
200.2g of 4,4' -diaminodiphenyl ether and 218g of pyromellitic dianhydride were added to the heat conductive filler dispersion, and reacted for 2 hours to obtain a polyamic acid resin solution.
And (2) defoaming the polyamic acid resin solution in vacuum, adding 204.2g of acetic anhydride and 25.8g of isoquinoline, casting the polyamic acid resin solution to form a polyamic acid adhesive film, and heating the polyamic acid adhesive film at high temperature and performing biaxial tension to obtain the polyimide film. The main properties of the obtained polyimide film were as follows: the heat conductive filler accounts for 5 mass percent of the polyimide film, the tensile strength is 220MPa, the tensile modulus is 2.5GPa, the elongation at break is 68 percent, the thermal expansion coefficient is 28.6 ppm/DEG C, and the heat conductivity coefficient is 0.34w/(m & k).
Comparative example 2
292.7g of montmorillonite treated by a silane coupling agent and 292.7g of boron nitride nanoscale inorganic filler modified by the silane coupling agent are used in total, wherein the particle size of the montmorillonite is 10 mu m, the particle size of the boron nitride nanoscale inorganic filler is 300nm, the mass ratio of the montmorillonite to the boron nitride is 2:8, the montmorillonite and the boron nitride nanoscale inorganic filler are added into 2.1kg of N, N-dimethylformamide simultaneously, and the mixture is subjected to ultrasonic dispersion for 1h to obtain uniform and stable heat-conducting filler dispersion liquid.
200.2g of 4,4' -diaminodiphenyl ether and 218g of pyromellitic dianhydride were added to the heat conductive filler dispersion, and reacted for 2 hours to obtain a polyamic acid resin solution.
And (2) defoaming the polyamic acid resin solution in vacuum, adding 204.2g of acetic anhydride and 25.8g of isoquinoline, casting the polyamic acid resin solution to form a polyamic acid adhesive film, and heating the polyamic acid adhesive film at high temperature and performing biaxial tension to obtain the polyimide film. The main properties of the obtained polyimide film were as follows: the heat conductive filler accounts for 70 mass percent of the polyimide film, the tensile strength is 192MPa, the tensile modulus is 2.9GPa, the elongation at break is 47 percent, the thermal expansion coefficient is 12.3 ppm/DEG C, and the heat conductivity coefficient is 0.62w/(m & k).
Comparative example 3
Taking 125.5g of montmorillonite treated by a silane coupling agent and boron nitride nano-scale inorganic filler modified by the silane coupling agent in total, wherein the particle size of the montmorillonite is 10 mu m, the particle size of the boron nitride nano-scale inorganic filler is 300nm, the mass ratio of the montmorillonite to the boron nitride is 5:5, simultaneously adding the montmorillonite and the boron nitride nano-scale inorganic filler into 2.1kg of N, N-dimethylformamide, and performing ultrasonic dispersion for 1h to obtain uniform and stable heat-conducting filler dispersion liquid.
200.2g of 4,4' -diaminodiphenyl ether and 218g of pyromellitic dianhydride were added to the heat conductive filler dispersion, and reacted for 2 hours to obtain a polyamic acid resin solution.
And (2) defoaming the polyamic acid resin solution in vacuum, adding 204.2g of acetic anhydride and 25.8g of isoquinoline, casting the polyamic acid resin solution to form a polyamic acid adhesive film, and heating the polyamic acid adhesive film at high temperature and performing biaxial tension to obtain the polyimide film. The main properties of the obtained polyimide film were as follows: the heat conductive filler accounts for 30 mass percent of the polyimide film, the tensile strength is 228MPa, the tensile modulus is 2.8GPa, the elongation at break is 66 percent, the thermal expansion coefficient is 22.8 ppm/DEG C, and the heat conductivity coefficient is 0.42 w/(m.k).
Comparative example 4
Taking 125.5g of montmorillonite treated by a silane coupling agent and boron nitride nano-scale inorganic filler modified by the silane coupling agent in total, wherein the particle size of the montmorillonite is 10 mu m, the particle size of the boron nitride nano-scale inorganic filler is 300nm, the mass ratio of the montmorillonite to the boron nitride is 5:95, simultaneously adding the montmorillonite and the boron nitride nano-scale inorganic filler into 2.1kg of N, N-dimethylformamide, and performing ultrasonic dispersion for 1h to obtain uniform and stable heat-conducting filler dispersion liquid.
200.2g of 4,4' -diaminodiphenyl ether and 218g of pyromellitic dianhydride were added to the heat conductive filler dispersion, and reacted for 2 hours to obtain a polyamic acid resin solution.
And (2) defoaming the polyamic acid resin solution in vacuum, adding 204.2g of acetic anhydride and 25.8g of isoquinoline, casting the polyamic acid resin solution to form a polyamic acid adhesive film, and heating the polyamic acid adhesive film at high temperature and performing biaxial tension to obtain the polyimide film. The main properties of the obtained polyimide film were as follows: the heat conductive filler accounts for 30 mass percent of the polyimide film, the tensile strength is 231MPa, the tensile modulus is 2.8GPa, the elongation at break is 64 percent, the thermal expansion coefficient is 23.7 ppm/DEG C, and the heat conductivity coefficient is 0.28w/(m & k).
Table 1 compares the main properties of the polyimide films prepared in the respective examples and comparative examples. The thermal expansion coefficient of the polyimide film used for the flexible wiring board is matched with that of a copper foil (about 18 ppm/DEG C), and the value is generally 15-20 ppm/DEG C. In the application, as shown in the examples, if the total filling amount of the heat-conducting filler is 10-60% and the ratio of the clay to the nano-scale inorganic filler is 10: 90-40: 60, the film has a low thermal expansion coefficient and a high thermal conductivity coefficient while maintaining the mechanical properties; if the total amount of the thermal conductive filler is less than 10% (comparative example 1), or the ratio of the clay to the nano-sized inorganic filler is greater than 4:6 (comparative example 3), or the ratio of the clay to the nano-sized inorganic filler is less than 1:9 (comparative example 4), a thermal conductive filler structure having a three-dimensional network structure cannot be formed in the polyimide film, and the thermal conductivity of the film is low; if the total filling amount of the heat conductive filler is more than 60% (comparative example 2), the heat conductive filler is agglomerated, the thermal expansion coefficient of the film is difficult to match with the copper foil, and the heat conductivity is low.
TABLE 1 Main Properties of high thermal conductivity and low thermal expansion polyimide film
Through the clay and the inorganic filler of nanometer with micron order in this application, fill in the polyimide film, make the skeleton texture that forms heat conduction filler structure in polyimide ripples film through the clay of micron order, and the inorganic filler of nanometer fills between skeleton texture, in order to form the heat conduction filler structure that has three-dimensional network structure in the polyimide film, thereby make the polyimide film in the application, the mechanical properties of polyimide film has not only been kept, the coefficient of thermal expansion of film has been reduced simultaneously, and its heat conductivility has been improved by a wide margin. And the clay has low cost and the whole preparation process of the film is simple, so the method is easy to industrialize.
Although the embodiments of the present application have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the embodiments of the present application.
Claims (10)
1. The preparation method of the polyimide film is characterized by comprising the following steps:
s1: preparing heat-conducting filler dispersion liquid, mixing clay treated by a first silane coupling agent and nano-scale inorganic filler treated by a second silane coupling agent in a solvent to form the heat-conducting filler dispersion liquid, wherein the particle size of the clay is micron-scale;
s2: adding a diamine monomer and a dianhydride monomer into the heat-conducting filler dispersion liquid to generate a polyamic acid resin solution; the heat-conducting filler dispersion liquid forms a heat-conducting filler structure with a three-dimensional network structure in the polyamic acid resin solution;
s3: and (3) casting the polyamic acid resin solution, imidizing and biaxially stretching to obtain the polyimide film.
2. The method for producing a polyimide film according to claim 1, wherein: the clay comprises at least one of montmorillonite, mica and hectorite, and the particle size of the clay is less than 15 mu m.
3. The method for producing a polyimide film according to claim 1, wherein: the nanoscale inorganic filler comprises at least one of silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, silicon carbide, silicon nitride, iron oxide, magnesium oxide, calcium oxide, boron oxide, zinc oxide, aluminum nitride and boron nitride, and the particle size of the nanoscale inorganic filler is less than 500 nm.
4. The method for producing a polyimide film according to claim 1, wherein: the solvent includes at least one of N, N '-dimethylformamide, N' -dimethylacetamide, and N-methylpyrrolidone.
5. The method for producing a polyimide film according to claim 1, wherein: the mass ratio of the clay to the nanoscale inorganic filler ranges from 10:90 to 40: 60.
6. The method for producing a polyimide film according to claim 1, wherein: the diamine monomer comprises at least one of p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 4 '-diaminobenzophenone and 3,4' -diaminodiphenyl ether.
7. The method for producing a polyimide film according to claim 1, wherein: the dianhydride monomer comprises at least one of pyromellitic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride and 3,3',4,4' -benzophenone tetracarboxylic dianhydride.
8. The method for producing a polyimide film according to claim 1, wherein: the imidization method is a chemical imidization method or a thermal imidization method.
9. The method for producing a polyimide film according to claim 8, wherein: in the chemical imidization process, a chemical imidization reagent consisting of an organic anhydride dehydrating agent, an organic base catalyst and an organic solvent is added.
10. A polyimide film characterized by: the polyimide film according to any one of claims 1 to 9, which comprises a thermally conductive filler structure composed of clay of a micro size and an inorganic filler of a nano size.
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