CN114656790A - Flexible printed circuit board containing polyimide material with low dielectric constant and high light transmittance - Google Patents
Flexible printed circuit board containing polyimide material with low dielectric constant and high light transmittance Download PDFInfo
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- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
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- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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Abstract
The invention provides a preparation method of a flexible printed circuit board containing a polyimide material with low dielectric constant and high light transmittance. The method mainly synthesizes a novel fluorine-containing dianhydride monomer 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydro-isobenzofuran-5-yl) -3- (trifluoromethyl) cyclohexyl-3-alkene-1-yl) -9,9' -spirobifluorene-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-diketone, and the polyimide performance is modified by utilizing the synthesis of the monomer. Due to the existence of the bulky fluorine-containing group, the dielectric constant of the material is greatly reduced. Meanwhile, fluorine has high electronegativity, so that the formation of a charge transfer complex can be inhibited, and the obtained material has excellent optical transmittance. The flexible printed circuit board prepared by the material has low dielectric constant and dielectric loss, and can be used in the field of high-frequency and high-speed communication.
Description
Technical Field
The invention relates to the field of material modification, in particular to preparation of a flexible circuit board containing polyimide with low dielectric constant and high light transmittance.
Background
The flexible printed circuit board is a flexible printed circuit board which is made of polyimide, polyester or polynaphthalene as an insulating layer and copper foil as a conductor layer and has high reliability. The high-density light-weight LED lamp has the characteristics of high wiring density, light weight, thin thickness and good bending property. Compared with another two insulating base materials, namely a polyester film and a polynaphthalene film, which are commonly used for the flexible printed circuit board, the Polyimide (PI) film has the characteristics of high strength, good toughness, excellent heat resistance and the like, can resist the high temperature of 500 ℃ in a short time, and can be used for a long time at the temperature of below 300 ℃. Therefore, polyimide materials used by printed circuit boards are hot spots for research, development and application in the field of printed circuit boards, and more than 90% of high-performance flexible copper clad laminates use polyimide as a heat-resistant base film.
Polyimide is a polymer containing imide rings on the main molecular chain, and has been widely applied to numerous fields of aviation, aerospace, machinery, electronic devices and the like due to excellent comprehensive properties. With the rapid development of science and technology, the performance of polyimide materials is also required to be higher. In recent years, the 5G technology has been rapidly advanced, and in order to meet the high-frequency and high-speed characteristics of the 5G field, the performance requirements of the substrate of the high-frequency printed circuit board are increased day by day, wherein the dielectric properties of the insulating material need to be further improved. The introduction of fluorine element with large volume and low electronic polarizability can reduce the dielectric constant and dielectric loss of the polyimide material (the dielectric constant is less than 3.0, and the dielectric loss factor is less than 0.001), and meet the requirements of high frequency and high speed of 5G communication. In addition, flexible OLED display is receiving wide attention from all the world as a new generation of display technology, and has a higher requirement for light transmittance. Because the charge transfer complex is generated in the polyimide, the light absorption enables the traditional polyimide film to be brown or yellow, and the fluorine element with higher electronegativity is introduced, so that the formation of the charge transfer complex can be inhibited, the light transmittance of the polyimide film is greatly improved, and the requirement for flexible OLED display can be met. Therefore, it is important to develop a polyimide material with low dielectric property and high light transmittance and to prepare a corresponding flexible printed circuit board.
Disclosure of Invention
The invention provides a preparation method of a flexible printed circuit board containing a polyimide material with a low dielectric constant and high light transmittance, aiming at the improvement of material requirements in the fields of high-frequency high-speed communication, flexible OLED display and the like. Researchers in this project found that to achieve the objects of the present invention, the following preparation method can be used: a novel fluorine-containing dianhydride monomer 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydro-isobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9 '-spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione is synthesized from 2, 7-dibromo-9, 9' -spirobifluorene, 4-bromo-3- (trifluoromethyl) phenylboronic acid and the like, and is dried to remove water. Dissolving the dried diamine monomer in the polar aprotic solution at normal temperature. After complete dissolution, the ice-water bath was adjusted to 5-10 ℃ and 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione and other dianhydride monomers were added in five portions by a one-half addition. And after the last time of dosing is finished, continuously stirring for 12 hours to obtain the fluorine-containing polyamide acid solution with certain viscosity. The polyamic acid solution is vacuumed to remove bubbles for 0.5h, then coated on a glass plate or a steel plate, the thickness is adjusted to about 35 microns, the solvent is removed at 80-150 ℃, and imidization treatment is carried out at 180-300 ℃. And after imidization is completed, cooling to room temperature, boiling in water to remove a film, thus obtaining a polyimide film with low dielectric constant and high light transmittance, dissolving the film in N-methylpyrrolidone again under the action of ultrasound, quickly and uniformly stirring to form a solution with solid content of 15-20%, then coating the solution on the rough surface of the electrolytic copper foil with the thickness of 12 microns, and drying in a vacuum oven at 50-170 ℃ for 1-3 hours to obtain the flexible printed circuit board.
In the preparation process, 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione is used in an amount of 5% -20% of the total moles of dianhydride monomers, and the ratio of the total moles of dianhydride to the total moles of diamine is 1.02: about 1 and a solid content (the total mass of all monomers of dianhydride and diamine accounts for the total mass of the polyamic acid) of 20 percent. The polar aprotic solvent used is one of N-methylpyrrolidone, N-dimethylacetamide and N, N-dimethylformamide. The diamine monomer is one or more of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, 4 '-diaminodiphenylmethane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 3' -diaminodiphenylsulfone, 4 '-diaminobiphenyl, 4- (hexafluoroisopropyl) bis (p-phenoxy) diphenylamine, 4' -diaminophenyl ether and p-phenylenediamine. The other dianhydride monomer is one or more of 4,4 '-hexafluoroisopropyl phthalic anhydride, 2,3,3', 4-biphenyl tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride and 3,3',4,4' -biphenyl tetracarboxylic dianhydride.
The invention has the beneficial effects that: because the novel dianhydride monomer synthesized by the invention contains fluorine-containing groups, the dielectric constant and the dielectric loss of the obtained polyimide material and the finally obtained flexible printed circuit board are reduced, and the requirement of the field of 5G high-frequency high-speed communication can be met. Meanwhile, the monomer contains larger side group groups and fluorine elements, and the formation of a charge transfer complex is effectively inhibited under the synergistic effect, so that the light transmittance of the obtained polyimide material is greatly improved, and the requirements of the flexible OLED display field can be met. The preparation process of the flexible printed circuit board is simple, and the energy consumption and the process flow are greatly reduced.
Drawings
FIG. 1 is a synthetic route diagram of the present invention.
Detailed Description
In order to make the technical means, the characteristics, the objectives and the functions of the present invention easy to understand, the present invention will be further described with reference to the following embodiments.
Example 1
Dissolving the dried 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl and 4,4' -diaminophenyl ether in a polar aprotic solution at room temperature in a molar ratio of 5: 5. n-methylpyrrolidone was added and dissolved at room temperature with stirring for about 0.5 h. After complete dissolution, the ice-water bath was adjusted to 5-10 ℃ and 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione and 3,3',4,4' -benzophenone tetracarboxylic dianhydride were added in five portions by a one-half addition in a molar ratio of 2: 8. and after the last time of dosing is finished, continuously stirring for 12 hours, and controlling the solid content to be about 20 percent through the solvent to obtain the fluorine-containing polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed under vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, heat-treated at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour to remove the solvent, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour. And cooling to room temperature after imidization is complete, and boiling in water to remove the film, thus obtaining the polyimide film with low dielectric constant and high light transmittance, wherein the thickness of the dry film is 25 micrometers. Cutting the film into pieces, dissolving the cut film in N-methylpyrrolidone again, quickly and uniformly stirring the cut film to form a solution with the solid content of 15%, coating the solution on the rough surface of an electrolytic copper foil with the thickness of 12 microns, and drying the rough surface of the electrolytic copper foil in a vacuum oven at 50 ℃, 120 ℃ and 170 ℃ for 1 hour respectively to obtain the flexible printed circuit board.
Example 2
Dissolving dried 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl and 4,4' -diaminophenyl ether in a molar ratio of 5: 5. n-methylpyrrolidone was added and dissolved with stirring at room temperature for about 0.5 h. After complete dissolution, the ice-water bath was adjusted to 5-10 ℃ and 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione and 3,3',4,4' -benzophenone tetracarboxylic dianhydride were added in five portions by a one-half addition in a molar ratio of 3: 7. and after the last time of dosing is finished, continuously stirring for 12 hours, and controlling the solid content to be about 20 percent through the solvent to obtain the fluorine-containing polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed under vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, heat-treated at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour to remove the solvent, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour. And cooling to room temperature after imidization is complete, and boiling in water to remove the film, thus obtaining the polyimide film with low dielectric constant and high light transmittance, wherein the thickness of the dry film is 25 micrometers. Cutting the film into pieces, dissolving the cut film in N-methylpyrrolidone again, quickly stirring the cut film uniformly to form a solution with the solid content of 15%, coating the solution on the rough surface of an electrolytic copper foil with the thickness of 12 microns, and drying the rough surface of the electrolytic copper foil in a vacuum oven at 50 ℃, 150 ℃ and 170 ℃ for 1 hour respectively to obtain the flexible printed circuit board.
Example 3
Dissolving the dried 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl and 4,4' -diaminophenyl ether in a polar aprotic solution at room temperature in a molar ratio of 5: 5. n-methylpyrrolidone was added and dissolved with stirring at room temperature for about 0.5 h. After complete dissolution, the ice-water bath was adjusted to 5-10 ℃ and 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione and 3,3',4,4' -benzophenone tetracarboxylic dianhydride were added in five portions by a one-half addition in a molar ratio of 1: 9. and after the last time of dosing is finished, continuously stirring for 12 hours, and controlling the solid content to be about 20 percent through the solvent to obtain the fluorine-containing polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed under vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, heat-treated at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour to remove the solvent, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour. And cooling to room temperature after imidization is complete, and boiling in water to remove the film, thus obtaining the polyimide film with low dielectric constant and high light transmittance, wherein the thickness of the dry film is 25 micrometers. Cutting the film into pieces, dissolving the cut film in N-methylpyrrolidone again, quickly stirring the cut film uniformly to form a solution with the solid content of 20%, coating the solution on the rough surface of an electrolytic copper foil with the thickness of 12 microns, and drying the rough surface of the electrolytic copper foil in a vacuum oven at 50 ℃, 150 ℃ and 170 ℃ for 1 hour respectively to obtain the flexible printed circuit board.
Comparative example 1
Dissolving the dried 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl and 4,4' -diaminophenyl ether in a polar aprotic solution at room temperature in a molar ratio of 5: 5. n-methylpyrrolidone was added and dissolved at room temperature with stirring for about 0.5 h. After the solution is completely dissolved, the temperature is adjusted to 5-10 ℃ in an ice water bath, and 3,3',4,4' -benzophenone tetracarboxylic dianhydride is added five times by a half-feeding method. And after the last time of dosing is finished, continuously stirring for 12 hours, and controlling the solid content to be about 20 percent through the solvent to obtain the fluorine-containing polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed under vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, heat-treated at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour to remove the solvent, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour. And cooling to room temperature after imidization is complete, and boiling in water to remove the film to obtain the corresponding polyimide film, wherein the thickness of the dry film is 25 micrometers. Cutting the film into pieces, dissolving the cut film in N-methylpyrrolidone again, quickly and uniformly stirring the cut film to form a solution with the solid content of 15%, coating the solution on the rough surface of an electrolytic copper foil with the thickness of 12 microns, and drying the rough surface of the electrolytic copper foil in a vacuum oven at 50 ℃, 120 ℃ and 170 ℃ for 1 hour respectively to obtain the flexible printed circuit board.
Comparative example 2
Dissolving the dried 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl and 4,4' -diaminophenyl ether in a polar aprotic solution at room temperature in a molar ratio of 5: 5. n-methylpyrrolidone was added and dissolved at room temperature with stirring for about 0.5 h. After complete dissolution, the temperature was adjusted to 5-10 ℃ in an ice water bath, and 4,4' -hexafluoroisopropyl phthalic anhydride was added five times by a one-half addition method. And after the last time of dosing is finished, continuously stirring for 12 hours, and controlling the solid content to be about 20 percent through the solvent to obtain the fluorine-containing polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed in vacuum for 0.5 hour, then applied on a glass plate with a wet film thickness adjusted to about 35 μm, heat-treated at 80 deg.C, 120 deg.C and 150 deg.C, respectively, for 1 hour to remove the solvent, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C, respectively, for 1 hour. And cooling to room temperature after imidization is complete, and boiling in water to remove the film to obtain the polyimide film, wherein the thickness of a dry film is 25 microns. Cutting the film into pieces, dissolving the cut film in N-methylpyrrolidone again, quickly stirring the cut film uniformly to form a solution with the solid content of 15%, coating the solution on the rough surface of an electrolytic copper foil with the thickness of 12 microns, and drying the rough surface of the electrolytic copper foil in a vacuum oven at 50 ℃, 120 ℃ and 170 ℃ for 0.5 hour respectively to obtain the flexible printed circuit board.
Comparative example 3
Dissolving the dried 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl and 4,4' -diaminophenyl ether in a polar aprotic solution at room temperature in a molar ratio of 5: 5. n-methylpyrrolidone was added and dissolved at room temperature with stirring for about 0.5 h. After the solution is completely dissolved, the temperature is adjusted to 5-10 ℃ in an ice-water bath, and the 2,3,3', 4-biphenyl tetracarboxylic dianhydride is added five times by a one-half feeding method. And after the last time of dosing is finished, continuously stirring for 12 hours, and controlling the solid content to be about 20 percent through the solvent to obtain the fluorine-containing polyamide acid solution with certain viscosity. The polyamic acid solution obtained was defoamed under vacuum for 0.5 hour, then applied to a glass plate, the wet film thickness was adjusted to about 35 μm, heat-treated at 80 deg.C, 120 deg.C and 150 deg.C for 1 hour to remove the solvent, and imidized at 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C and 300 deg.C for 1 hour. And cooling to room temperature after imidization is complete, and boiling in water to remove the film to obtain the polyimide film, wherein the thickness of a dry film is 25 microns. Cutting the film into pieces, dissolving the cut film in N-methylpyrrolidone again, quickly stirring the cut film uniformly to form a solution with the solid content of 15%, coating the solution on the rough surface of an electrolytic copper foil with the thickness of 12 microns, and drying the rough surface of the electrolytic copper foil in a vacuum oven at 50 ℃, 120 ℃ and 170 ℃ for 0.5 hour respectively to obtain the flexible printed circuit board.
The properties of the materials tested in this example and comparative example are shown in the following table:
Claims (8)
1. a preparation method of a polyimide film with low dielectric constant and high light transmittance is characterized by comprising the following steps: synthesizing novel fluorine-containing dianhydride monomer 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydro-isobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9 '-spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione from raw materials such as 2, 7-dibromo-9, 9' -spirobifluorene and 4-bromo-3- (trifluoromethyl) phenylboronic acid, drying to remove water, dissolving the dried diamine monomer in a polar aprotic solution at normal temperature until the diamine monomer is completely dissolved, adjusting the solution to 5-10 ℃ in an ice water bath, and adding 5- (4- (2- (4-) (trifluoromethyl) five times according to a one-half feeding method 1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione and other dianhydride monomers. And after the last dosing is finished, continuously stirring for 12 hours to obtain a fluorine-containing polyamide acid solution with certain viscosity, removing bubbles of the obtained polyamide acid solution in vacuum for 0.5 hour, then coating the polyamide acid solution on a glass plate or a steel plate, adjusting the thickness to be about 35 micrometers, removing the solvent at the temperature of 80-150 ℃, carrying out imidization treatment at the temperature of 180-300 ℃, cooling to room temperature after the imidization is complete, and boiling in water to remove the film, thus obtaining the polyimide film with low dielectric constant and high light transmittance.
2. The method for preparing a polyimide film with low dielectric constant and high transmittance as claimed in claim 1, wherein the novel fluorine-containing dianhydride monomer 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione is synthesized by the following steps: under the protection of nitrogen, 2, 7-dibromo-9, 9 '-spirobifluorene (2.36g,5.0mmol), 4-bromo-3- (trifluoromethyl) phenylboronic acid (3.22g,12.0mmol), Pd (PPh3)2Cl2(72mg,0.10mmol) and PPh3(52mg,0.20mmol) were added to a reaction flask containing toluene (60mL) and water (20mL), and after mixing and heating reflux reaction for 24 hours, after completion of the reaction, the system was cooled, toluene was removed by a rotary evaporator, extraction was performed with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate, filtered, dried, and purified by column chromatography using petroleum ether-dichloromethane as an eluent to give 2, 7-bis (4-bromo-3- (trifluoromethyl) phenyl) -9,9' -spirobifluorene (3.20g,4.21mmol), yield 84.1%, under the protection of nitrogen, the obtained 2, 7-bis (4-bromo-3- (trifluoromethyl) phenyl) -9,9 '-spirobifluorene (3.05g,4.0mmol), 3, 4-dimethylphenylboronic acid (1.44g,9.6mmol), Pd (PPh3)2Cl2(58mg,0.08mmol) and PPh3(42mg,0.16mmol) were added to a reaction flask containing toluene (50mL) and water (16mL), mixed and heated under reflux for 24 hours, after completion of the reaction, the system was cooled, toluene was removed by a rotary evaporator, extraction was performed with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, dried by spin-drying, and purified by column chromatography using petroleum ether-dichloromethane as an eluent to give 2, 7-bis (3',4 '-dimethyl-2- (trifluoromethyl) - [1,1' -biphenyl ] -4-yl) -9,9' -spirobifluorene (2.58g,3.17mmol), yield 79.2%, 2, 7-bis (3',4' -dimethyl-2- (trifluoromethyl) - [1,1' -biphenyl ] -4-yl) -9,9' -spirobifluorene (1.87g,2.0mmol), potassium permanganate (3.16g,20.0mmol) were added to a dry reaction flask containing t-butanol (20mL) and water (20mL) under nitrogen protection, reaction was carried out at 78 ℃ for 3h, after completion of the reaction, 10mL of a sodium thiosulfate solution was added to the system, t-butanol was removed by a rotary evaporator, hydrochloric acid was added to make pH 1, extraction was carried out with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, column chromatography was carried out, dichloromethane-methanol was used as an eluent, and purification was carried out to give 4', 4' ″ - (9), adding 0.93g and 1.00mmol of 9', 4' - (9,9' -spiro [ fluorene ] -2, 7-diyl) bis (2' - (trifluoromethyl) - [1,1' -biphenyl ] -3, 4-dicarboxylic acid) into a dry reaction bottle filled with acetic anhydride (1.633g and 16mmol) under the protection of nitrogen, heating and refluxing for 3h, cooling the mixture after the reaction is finished, filtering and drying to obtain 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-ene) (1.16g and 1.24mmol) -1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione (0.86g,0.95 mmol).
3. The method for preparing a polyimide film with low dielectric constant and high transmittance as claimed in claim 1, wherein the novel fluorine-containing dianhydride monomer 5- (4- (2- (4- (1, 3-dioxy-1, 3-dihydroisobenzofuran-5-yl) -3- (trifluoromethyl) cyclohex-3-en-1-yl) -9,9' -spirobifluoren-7-yl) -2- (trifluoromethyl) phenyl) isobenzofuran-1, 3-dione is used in an amount of 5% to 20% based on the total molar amount of dianhydride monomer.
4. The method of claim 1, wherein the polar aprotic solvent is one of N-methylpyrrolidone, N-dimethylacetamide, or N, N-dimethylformamide.
5. The method for preparing a polyimide film having a low dielectric constant and a high transmittance as claimed in claim 1, wherein the diamine monomer is one or more selected from the group consisting of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, 4 '-diaminodiphenylmethane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 3' -diaminodiphenylsulfone, 4 '-diaminobiphenyl, 4- (hexafluoroisopropyl) bis (p-phenoxy) diphenylamine, 4' -diaminophenyl ether and p-phenylenediamine.
6. The method for preparing a polyimide film having a low dielectric constant and a high transmittance as claimed in claim 1, wherein the other dianhydride monomer is one or more selected from the group consisting of 4,4 '-hexafluoroisopropyl phthalic anhydride, 2,3,3', 4-biphenyltetracarboxylic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, and 3,3',4,4' -biphenyltetracarboxylic dianhydride.
7. The method of claim 1, wherein the ratio of the total moles of dianhydride to the total moles of diamine in the polyamic acid solution is from 1.02: about 1 and a solid content (the total mass of all the dianhydride and diamine monomers accounts for the total mass of the polyamic acid) of 20 percent.
8. A method for preparing a flexible printed circuit board using the polyimide film having a low dielectric constant and a high light transmittance obtained in claim 1, comprising the steps of: the polyimide material with low dielectric constant and high light transmittance obtained in the method of claim 1 is dissolved in N-methylpyrrolidone again under the action of ultrasound, the mixture is rapidly and uniformly stirred to form a solution with solid content of 15-20%, then the solution is coated on the rough surface of an electrolytic copper foil with the thickness of 12 microns, and the rough surface is dried for 1-3 hours in a vacuum oven at the temperature of 50-170 ℃, so that the flexible printed circuit board disclosed by the invention is obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115537027A (en) * | 2022-10-19 | 2022-12-30 | 天津泰合利华材料科技有限公司 | Preparation method of boron-doped fluorinated polyimide film applied to supercapacitor |
| CN115612098A (en) * | 2022-07-28 | 2023-01-17 | 江西有泽新材料科技有限公司 | Intrinsic low-dielectric low-water-absorption polymer and preparation method and application thereof |
| CN115819761A (en) * | 2022-08-04 | 2023-03-21 | 南京理工大学 | Preparation of polyimide material with high light transmittance and high heat resistance |
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2022
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115612098A (en) * | 2022-07-28 | 2023-01-17 | 江西有泽新材料科技有限公司 | Intrinsic low-dielectric low-water-absorption polymer and preparation method and application thereof |
| CN115612098B (en) * | 2022-07-28 | 2023-10-03 | 江西有泽新材料科技有限公司 | Intrinsic low-dielectric low-water-absorption polymer and preparation method and application thereof |
| CN115819761A (en) * | 2022-08-04 | 2023-03-21 | 南京理工大学 | Preparation of polyimide material with high light transmittance and high heat resistance |
| CN115537027A (en) * | 2022-10-19 | 2022-12-30 | 天津泰合利华材料科技有限公司 | Preparation method of boron-doped fluorinated polyimide film applied to supercapacitor |
| CN115537027B (en) * | 2022-10-19 | 2024-03-29 | 天津泰合利华材料科技有限公司 | Preparation method of boron doped fluorinated polyimide film applied to super capacitor |
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