CN113248708B - Polyimide adhesive film with excellent comprehensive performance and preparation method and application thereof - Google Patents
Polyimide adhesive film with excellent comprehensive performance and preparation method and application thereof Download PDFInfo
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- CN113248708B CN113248708B CN202110553594.9A CN202110553594A CN113248708B CN 113248708 B CN113248708 B CN 113248708B CN 202110553594 A CN202110553594 A CN 202110553594A CN 113248708 B CN113248708 B CN 113248708B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
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Abstract
The invention relates to a polyimide adhesive film with excellent comprehensive performance, a preparation method and application thereof, belongs to the technical field of polyimide, and solves the problems that the existing polyimide adhesive film has excellent heat resistance, good adhesive property, low dielectric constant at high frequency and low dielectric loss and is difficult to be compatible. The polyimide adhesive film is prepared from aromatic dianhydride, aromatic diamine containing diphenyl ether structure and diamine containing siloxane structure. The polyimide adhesive film has excellent heat resistance, high-frequency low dielectric property and good bonding property, the glass transition temperature is higher than 330 ℃, the dielectric constant under 10GHz is less than 3, the dielectric loss value is between 0.003 and 0.006, the peel strength after the polyimide adhesive film is in hot-pressing bonding with copper foil is more than 10N/cm, the application requirements of interlayer bonding and insulation in the manufacture of a flexible printed circuit board and the laminated wiring processing of a multilayer circuit board can be met, and the polyimide adhesive film can be widely applied to the fields of high-frequency flexible printed circuit boards, high-frequency film antennas and the like.
Description
Technical Field
The invention relates to the technical field of polyimide, in particular to a polyimide adhesive film with excellent comprehensive performance, a preparation method and application thereof, and more particularly relates to a polyimide adhesive film with excellent heat resistance, high-frequency dielectric property and good bonding property, a preparation method and application thereof.
Background
Polyimide materials have been widely used as high-performance insulating materials indispensable for the manufacture of flexible printed circuit boards in the microelectronics field because of their excellent heat resistance and insulating properties. In recent years, microelectronic products are becoming more compact, thinner, more flexible, more integrated, and more multifunctional, and electronic devices are increasingly manufactured by high-density multilayer wiring based on flexible printed circuit boards. With the development of the fifth generation mobile communication technology (5G), higher requirements are made on the reliability of electronic devices for fast transmission of large-capacity data in high-frequency and high-speed environments. In order to reduce signal interference caused by a wire current in a high-density multilayer wiring and to reduce an electronic signal transmission loss and delay at a high frequency, it is the most effective solution to use an insulating material having a lower dielectric constant (Dk) and a lower dielectric loss (Df), and thus development of a polyimide material having more excellent dielectric properties at a high frequency is urgently required. In addition, in both flexible printed circuit board manufacturing and multilayer circuit board laminated wiring processing, it is necessary to bond the polyimide insulating substrate and the conductive copper foil with an adhesive. Because electronic devices need to bear a high-temperature reflow soldering processing procedure of 260-280 ℃, the heat resistance of the current commercialized acrylic and epoxy adhesives is low, and the cracking of an adhesive layer is easy to occur in the processing process to cause bubbling and warping of a circuit board.
In the prior art, structural modification or blending modification is mainly carried out on polyimide to further improve the dielectric property of the material under high frequency. Introduction of fluorine-containing groups with low molar polarizability and large free volume into the polyimide backbone structure can significantly reduce the dielectric constant of the polyimide, but this approach has limitations for reducing the dielectric loss of the material at high frequencies. The prior art discloses a method for modifying fluorine-containing polyimide resin by further filling polytetrafluoroethylene with low dielectric property and low molecular weight polyphenylene ether, and Dk and Df values of the prepared film at 1GHz are respectively between 2.4-2.8 and 0.004-0.009. The prior art also discloses a method for adding fluorine-containing polymers such as polytetrafluoroethylene and the like into polyimide resin, and the Dk value of the prepared film at 10GHz is between 2.6 and 2.9, and the Df value is greatly reduced to be less than 0.0035. The prior art also discloses a method for preparing a copper-clad plate by using a mixture of polyimide and fluorine-containing polymer PFA and coating copper foil with the mixture for continuous rolling bonding, wherein a resin layer has lower Dk and Df values and higher bonding performance under 10GHz, and the peel strength of bonding with the copper foil is more than 1.0N/mm. Although the method for blending and modifying the polyimide by adopting the fluorine-containing polymer can improve the dielectric property of the resin under high frequency, the use temperature of the fluorine-containing polymer is usually not more than 250 ℃, so that the heat resistance is limited, and the comprehensive improvement of the heat resistance, the dielectric property and the bonding property of the polyimide cannot be realized.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a polyimide adhesive film with excellent overall performance, a preparation method thereof and an application thereof, so as to solve the problem that the existing polyimide adhesive film has excellent heat resistance, good adhesion performance, low dielectric constant at high frequency and low dielectric loss, which are difficult to achieve at the same time.
The purpose of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides a thermoplastic polyimide adhesive film with excellent comprehensive performance, which is prepared from the following raw materials of aromatic dianhydride, aromatic diamine containing diphenyl ether structure and diamine containing siloxane structure, wherein the polyimide adhesive film has the following general formula I:
wherein Ar is selected from any one of the following groups:
R1any one selected from the following groups:
R2any one selected from the following groups:
wherein x is 1-8, y is 0, 1;
at least one of the monomer of the aromatic dianhydride and the monomer of the aromatic diamine containing diphenyl ether structure contains fluorine, and trifluoromethyl is preferred.
Based on a further improvement of the above polyimide adhesive film, the aromatic dianhydride comprises at least one of 1,2,4, 5-pyromellitic dianhydride (PMDA), 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride (6FCDA), and 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride) (BPADA).
Based on the further improvement of the polyimide adhesive film, the aromatic diamine containing diphenyl ether structure comprises at least one of 1, 4-bis (4-aminophenoxy) benzene (1,4,4-APB), 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene (6FAPB), 4,4 '-bis (4-aminophenoxy) biphenyl (BAPB), 4,4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl (6FBAB), 2-bis (4-aminophenoxy phenyl) propane (BAPP) and 2, 2-bis [4- (4-aminophenoxy benzene) ] Hexafluoropropane (HFBAPP).
Based on the further improvement of the polyimide adhesive film, the diamine containing siloxane structure comprises at least one of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (SiDA), 3-aminopropyl bis-blocked hexamethyltrisiloxane (ATPDS), bis (3-aminopropyl) Polydimethylsiloxane (PDMS), bis (4-aminophenoxy) dimethylsilane (APDS) and 1, 3-bis (p-aminophenoxy) tetramethyldisiloxane (APTS).
Based on the further improvement of the polyimide adhesive film, the thickness of the polyimide adhesive film is 20-30 μm, the glass transition temperature is higher than 330 ℃, the dielectric constant Dk value under 10GHz is less than 3, and the dielectric loss Df value is 0.003-0.006.
Based on the further improvement of the polyimide adhesive film, the ratio of m to n in the general formula I is (9:1) - (9.9: 0.1).
Based on the further improvement of the polyimide adhesive film, the content of the imide in the molecular structure of the polyimide adhesive film is not more than 21 wt%, and the content of the siloxane is 0.2 wt% to 9.0 wt%.
On the other hand, the invention also provides a preparation method of the polyimide adhesive film, which is used for preparing the thermoplastic polyimide adhesive film with excellent comprehensive performance and comprises the following steps:
(1) dissolving aromatic diamine containing diphenyl ether structure and diamine containing siloxane structure in organic solvent, and stirring to obtain homogeneous solution;
(2) adding aromatic dianhydride into the homogeneous solution, and reacting to obtain a polyamic acid solution;
(3) and coating the polyamic acid solution, and obtaining the polyimide adhesive film after the first-stage hot drying and the second-stage hot drying.
Based on the further improvement of the preparation method, the method comprises the following steps:
(1) under the protection of inert gas, dissolving aromatic diamine containing diphenyl ether structure and diamine containing siloxane structure in organic solvent, and stirring at room temperature to obtain homogeneous solution;
(2) cooling to 0-5 ℃, adding aromatic dianhydride into the homogeneous phase solution obtained in the step (1), stirring until the aromatic dianhydride is completely dissolved, and continuously stirring at room temperature to react to obtain a polyamic acid solution with a certain solid content;
(3) and (3) filtering and defoaming the polyamic acid solution obtained in the step (2), coating the polyamic acid solution on a support, removing most of solvent through first-stage hot drying, peeling off the support, clamping the support by using a metal frame, and obtaining a polyimide adhesive film with a certain thickness through second-stage hot drying.
In a further modification of the above preparation method, in the step (1), the organic solvent includes at least one of N-methylpyrrolidone (NMP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), and Dimethylsulfoxide (DMSO).
Based on a further improvement of the above preparation method, in the step (2), the reaction time is 12 to 24 hours, and the solid content of the polyamic acid solution is 12 to 20 wt.%.
Based on the further improvement of the preparation method, in the step (3), the polyamic acid solution is coated on a support body, and the support body is a glass plate, a stainless steel plate or a polytetrafluoroethylene plate; the metal frame is a stainless steel frame or a copper frame.
Based on the further improvement of the preparation method, in the step (3), the temperature of the first-stage hot baking is 60-80 ℃ and the time is 0.5-2 hours.
Based on the further improvement of the preparation method, in the step (3), the temperature of the second-stage heat drying is 250-350 ℃, and the time is 1-2 hours.
In addition, the invention also provides a method for bonding the polyimide adhesive film and the copper foil, which comprises the following steps: and (3) compounding the two sides of the polyimide adhesive film with copper foil, and carrying out hot pressing to obtain a bonding sample.
Based on the further improvement of the bonding method, the hot pressing temperature is 350-370 ℃, the pressure is 5-10MPa, and the hot pressing time is 5-20 minutes.
Based on a further improvement of the above bonding method, the peel strength of the bonded sample is greater than 10N/cm.
The polyimide adhesive film is applied to high-performance insulation bonding in the fields of high-frequency flexible printed circuit boards and high-frequency film antennas.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) the polyimide adhesive film with the flexible linear main chain structure is obtained by selecting specific types of dianhydride and diamine (such as aromatic dianhydride, aromatic diamine containing diphenyl ether structure and diamine containing flexible siloxane structure). Specifically, the introduction of the flexible diphenyl ether structure and the siloxane structure can not only enhance the hot melting of the adhesive film and ensure the bonding performance, but also destroy the conjugation of molecular chains due to the existence of the flexible chain segment, reduce the acting force among the molecular chains and reduce the motion relaxation time of the molecular chain segment under high frequency, thereby reducing the dielectric loss of the adhesive film under high frequency.
(2) The invention utilizes the characteristic that the aromatic diamine containing diphenyl ether structure and the diamine containing flexible siloxane structure have long chain segments to reduce the content of imide polar groups in the polyimide repeating unit, and further ensures the reduction of dielectric constant and dielectric loss of the polyimide adhesive film under high frequency by properly introducing trifluoromethyl with larger free volume and low molar polarization degree into a copolymerization structure. Specifically, the content of trifluoromethyl in the molecular structure of the polyimide adhesive film is 13-19 wt.%.
(3) According to the invention, the content of the siloxane structure in the copolymerization type polyimide adhesive film is controlled within 9.0 wt%, so that the adhesive film has excellent heat resistance, and can meet the application requirement of a high-temperature processing procedure of a flexible printed circuit board.
(4) The polyimide adhesive film provided by the invention has good adhesive property, excellent heat resistance, high frequency low dielectric constant and low dielectric loss characteristic (the glass transition temperature is more than 330 ℃, the dielectric constant Dk value under 10GHz is less than 3, the dielectric loss Df value is 0.003-0.006, and the peeling strength of the polyimide adhesive film and a copper foil adhesive sample is more than 10N/cm) while ensuring excellent heat resistance, and meets the application requirements of interlayer adhesion and insulation in the manufacture of a flexible printed circuit board and the laminated wiring processing of a multilayer circuit board.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The drawings, in which like reference numerals refer to like parts throughout, are for the purpose of illustrating particular embodiments only and are not to be considered limiting of the invention.
FIG. 1 is an IR spectrum of a polyimide adhesive film prepared in example 1;
FIG. 2 is a DMA curve of the polyimide adhesive film prepared in example 1;
FIG. 3 is a photograph showing the peel strength of the polyimide adhesive film prepared in example 1 after being tested with respect to a copper foil.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. Based on the preparation method and conditions of the present invention, the polyimide adhesive film prepared by changing the raw materials and monomers has the same effect as the present invention, and all of them belong to the protection scope of the present invention.
The percentage contents in the invention are all mass percentages unless otherwise specified. The starting materials are commercially available from published sources unless otherwise specified. In the embodiment, the thickness of the siloxane-containing polyimide film can be regulated and controlled by adjusting the type of the coating roller and the solid content of the polyamic acid homogeneous solution.
Example 1
38.54 g (0.09 mol) of 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene (6FAPB), 8.00 g (0.01 mol) of bis (3-aminopropyl) Polydimethylsiloxane (PDMS) and 200 g of N, N-dimethylacetamide (DMAc) were put into a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, and stirred at room temperature under nitrogen atmosphere until completely dissolved to obtain a homogeneous solution. After the reaction system is cooled to 5 ℃, 21.81 g (0.1 mol) of 1,2,4, 5-pyromellitic anhydride (PMDA) and 187 g of DMAc are added, stirred for 3 hours until the mixture is completely dissolved, and then stirred and reacted for 14 hours at room temperature to obtain a polyamic acid solution with a solid content of 15 wt.%. And (3) filtering and defoaming the obtained polyamic acid solution in vacuum, coating the polyamic acid solution on a polytetrafluoroethylene plate with a smooth surface, removing most of solvent by hot baking at the temperature of 60 ℃/1.5 hours, peeling off the polytetrafluoroethylene plate, vertically clamping the polytetrafluoroethylene plate by a stainless steel frame, and hot baking at the temperature of 300 ℃/1 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 6MPa pressure at 370 ℃, and carrying out hot pressing for 15 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 2
In a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, 50.81 g (0.098 mol) of 2, 2-bis [4- (4-aminophenoxyphenyl) ] Hexafluoropropane (HFBAPP), 0.49 g (0.002 mol) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (SiDA) and 249 g of N, N-dimethylacetamide (DMAc) were introduced, and the mixture was stirred at room temperature under nitrogen protection until completely dissolved to obtain a homogeneous solution. After the temperature of the reaction system is reduced to 0 ℃, 21.81 g (0.1 mol) of 1,2,4, 5-pyromellitic dianhydride (PMDA) and 200 g of DMAc are added, stirred for 2 hours until the mixture is completely dissolved, and then stirred and reacted for 11 hours at room temperature to obtain a polyamic acid solution with a solid content of 14 wt.%. And filtering and vacuum defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by baking at the temperature of 80 ℃/1 hour, peeling off the polyamic acid solution from the glass plate, clamping the polyamic acid solution up and down by a stainless steel frame, and baking at the temperature of 350 ℃/1 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 5MPa pressure at 350 ℃, and carrying out hot pressing for 5 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 3
49.25 g (0.095 mol) of 2, 2-bis [4- (4-aminophenoxyphenyl) ] Hexafluoropropane (HFBAPP), 1.24 g (0.005 mol) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (SiDA) and 250 g of N, N-dimethylacetamide (DMAc) were charged into a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, and stirred at room temperature under nitrogen protection until completely dissolved to obtain a homogeneous solution. After the reaction system is cooled to 5 ℃, 21.81 g (0.1 mol) of 1,2,4, 5-pyromellitic anhydride (PMDA) and 129 g of DMAc are added, stirred for 2 hours until the PMDA and the DMAc are completely dissolved, and then stirred and reacted for 10 hours at room temperature to obtain a polyamic acid solution with a solid content of 16 wt.%. And filtering and vacuum defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by baking at 70 ℃/1.5 hours, peeling off the polyamic acid solution from the glass plate, clamping the polyamic acid solution up and down by a stainless steel frame, and baking at 350 ℃/1 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 7MPa pressure at 360 ℃, and carrying out hot pressing for 10 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 4
48.73 g (0.094 mol) of 2, 2-bis [4- (4-aminophenoxyphenyl) ] Hexafluoropropane (HFBAPP), 1.49 g (0.006 mol) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (SiDA) and 400 g of N, N-dimethylacetamide (DMAc) were charged in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, and stirred at room temperature under nitrogen protection until completely dissolved to obtain a homogeneous solution. After the reaction system is cooled to 5 ℃, 21.81 g (0.1 mol) of 1,2,4, 5-pyromellitic anhydride (PMDA) and 128 g of DMAc are added, stirred for 2 hours until the mixture is completely dissolved, and then stirred and reacted for 13 hours at room temperature to obtain a polyamic acid solution with a solid content of 12 wt.%. And filtering and vacuum defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a stainless steel plate with a smooth surface, removing most of solvent by baking at 60 ℃/2 hours, peeling off the polyamic acid solution from the stainless steel plate, clamping the polyamic acid solution from top to bottom by using a stainless steel frame, and baking at 300 ℃/1.5 hours to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 8MPa pressure at 350 ℃, and carrying out hot pressing for 15 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 5
38.97 g (0.091 mol) of 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene (6FAPB), 3.14 g (0.009 mol) of 1, 3-bis (p-aminophenoxy) tetramethyldisiloxane (APTS) and 228 g of N, N-dimethylacetamide (DMAc) were put into a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen gas introduction tube and a thermometer, and stirred at room temperature under nitrogen atmosphere until completely dissolved to obtain a homogeneous solution. After the reaction system was cooled to 0 ℃, 52.05 g (0.1 mol) of 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride) (BPADA) and 200 g of DMAc were added, and after stirring for 3 hours until complete dissolution, the reaction was continued at room temperature for 21 hours with stirring to obtain a polyamic acid solution having a solid content of 18 wt.%. And (3) filtering and defoaming the obtained polyamic acid solution in vacuum, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by baking at the temperature of 80 ℃/0.5 hour, peeling off the polyamic acid solution from the glass plate, clamping the polyamic acid solution from top to bottom by a stainless steel frame, and baking at the temperature of 300 ℃/1.5 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 8MPa pressure at 360 ℃, and carrying out hot pressing for 15 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 6
36.95 g (0.09 mol) of 2, 2-bis (4-aminophenoxy phenyl) propane (BAPP), 2.74 g (0.01 mol) of bis (4-aminophenoxy) dimethylsilane (APDS) and 348 g of N-methylpyrrolidone (NMP) were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, and stirred at room temperature under nitrogen atmosphere until completely dissolved to obtain a homogeneous solution. After the reaction system was cooled to 5 ℃, 45.82 g (0.1 mol) of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic dianhydride (6FCDA) and 101 g of NMP were added, and after stirring for 2 hours until completely dissolved, the reaction was continued at room temperature for 16 hours to obtain a polyamic acid solution with a solid content of 16 wt.%. And (3) filtering and defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by baking at 60 ℃/1 hour, peeling off the glass plate, clamping the glass plate up and down by a copper frame, and baking at 250 ℃/2 hours to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 8MPa pressure at 370 ℃, and carrying out hot pressing for 15 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in Table 1
Example 7
49.94 g (0.099 mol) of 4,4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl (6FBAB), 0.32 g (0.001 mol) of 3-aminopropyl-bis-blocked hexamethyltrisiloxane (ATPDS) and 308 g of N, N-Dimethylformamide (DMF) (DMF) were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer and stirred at room temperature under nitrogen atmosphere until completely dissolved to give a homogeneous solution. After the reaction system is cooled to 5 ℃, 21.81 g (0.1 mol) of 1,2,4, 5-pyromellitic anhydride (PMDA) and 100 g of DMF are added, stirred for 1 hour until the mixture is completely dissolved, and then stirred and reacted for 20 hours at room temperature to obtain a polyamic acid solution with a solid content of 15 wt.%. And (3) filtering and defoaming the obtained polyamic acid solution in vacuum, coating the polyamic acid solution on a stainless steel plate with a smooth surface, removing most of solvent by baking at the temperature of 80 ℃/0.5 hour, peeling off the polyamic acid solution from the stainless steel plate, clamping the polyamic acid solution from top to bottom by using a stainless steel frame, and baking at the temperature of 350 ℃/1 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 5MPa pressure at 350 ℃, and carrying out hot pressing for 10 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 8
In a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, 40.25 g (0.094 mol) of 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene (6FAPB), 1.65 g (0.006 mol) of bis (4-aminophenoxy) dimethylsilane (APDS) and 305 g of N, N-dimethylacetamide (DMAc) were introduced and stirred at room temperature under nitrogen protection until completely dissolved to obtain a homogeneous solution. After the reaction system was cooled to 0 ℃, 52.05 g (0.1 mol) of 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride) (BPADA) and 70 g of DMAc were added, and after stirring for 2 hours until complete dissolution, the reaction was continued at room temperature for 16 hours with stirring to obtain a polyamic acid solution having a solid content of 20 wt.%. And filtering and vacuum defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by 60 ℃/1 hour of heat drying, peeling off the glass plate, clamping the glass plate by a stainless steel frame up and down, and obtaining the polyimide adhesive film by 300 ℃/1.5 hour of heat drying. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 6MPa pressure at 350 ℃, and carrying out hot pressing for 15 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 9
49.26 g (0.095 mol) of 2, 2-bis [4- (4-aminophenoxyphenyl) ] Hexafluoropropane (HFBAPP), 4.00 g (0.005 mol) of bis (3-aminopropyl) Polydimethylsiloxane (PDMS) and 240 g of N, N-dimethylacetamide (DMAc) were charged into a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, and stirred at room temperature under nitrogen atmosphere until completely dissolved to obtain a homogeneous solution. After the reaction system was cooled to 5 ℃, 21.81 g (0.1 mol) of 1,2,4, 5-pyromellitic anhydride (PMDA) and 102 g of DMAc were added, stirred for 2 hours until completely dissolved, and then stirred at room temperature for reaction for 12 hours to obtain a polyamic acid solution having a solid content of 18 wt.%. And filtering and vacuum defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by means of 80 ℃/1 hour of heat drying, peeling off the polyamic acid solution from the glass plate, clamping the polyamic acid solution by means of a stainless steel frame up and down, and performing heat drying at 300 ℃/1 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 5MPa pressure at 370 ℃, and carrying out hot pressing for 10 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 10
38.99 g (0.095 mol) of 2, 2-bis (4-aminophenoxyphenyl) propane (BAPP), 1.24 g (0.005 mol) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (SiDA) and 387 g of dimethyl sulfoxide (DMSO) were put into a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen guide tube and a thermometer, and stirred at room temperature under nitrogen atmosphere until completely dissolved to obtain a homogeneous solution. After the reaction system is cooled to 0 ℃, 45.82 g (0.1 mol) of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride (6FCDA) and 100 g of DMSO are added, stirred for 3 hours until the materials are completely dissolved, and then the stirring reaction is continued for 18 hours at room temperature, so that a polyamic acid solution with a solid content of 15 wt.% is obtained. And filtering and vacuum defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by baking at 70 ℃/1.5 hours, peeling off the polyamic acid solution from the glass plate, clamping the polyamic acid solution from top to bottom by a copper frame, and baking at 300 ℃/2 hours to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 6MPa pressure at 360 ℃, and carrying out hot pressing for 10 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 11
33.89 g (0.092 mol) of 4,4' -bis (4-aminophenoxy) biphenyl (BAPB), 1.99 g (0.008 mol) of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane (SiDA) and 300 g of N-methylpyrrolidone (NMP) were put into a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, and stirred at room temperature under nitrogen atmosphere until completely dissolved to obtain a homogeneous solution. After the reaction system was cooled to 5 ℃, 45.82 g (0.1 mol) of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic dianhydride (6FCDA) and 99 g of NMP were added, and after stirring for 3 hours until completely dissolved, the reaction was continued at room temperature for 15 hours to obtain a polyamic acid solution with a solid content of 17 wt.%. And filtering and vacuum defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by 60 ℃/2 hours of heat drying, peeling off the glass plate, clamping the glass plate by a stainless steel frame up and down, and performing heat drying at 350 ℃/1 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 8MPa pressure at 360 ℃, and carrying out hot pressing for 15 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Example 12
27.58 g (0.095 mol) of 1, 4-bis (4-aminophenoxy) benzene (1,4,4-APB), 4.00 g (0.005 mol) of bis (3-aminopropyl) Polydimethylsiloxane (PDMS) and 250 g of N, N-dimethylacetamide (DMAc) were charged into a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, and stirred at room temperature under a nitrogen atmosphere until completely dissolved to obtain a homogeneous solution. After the reaction system was cooled to 0 ℃, 45.82 g (0.1 mol) of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic dianhydride (6FCDA) and 102 g of DMAc were added, and after stirring for 3 hours until completely dissolved, the reaction was continued at room temperature for 20 hours to obtain a polyamic acid solution having a solid content of 18 wt.%. And (3) filtering and defoaming the obtained polyamic acid solution in vacuum, coating the polyamic acid solution on a polytetrafluoroethylene plate with a smooth surface, removing most of solvent by baking at 60 ℃/2 hours, peeling off the polytetrafluoroethylene plate, clamping the polytetrafluoroethylene plate by a stainless steel frame up and down, and baking at 300 ℃/2 hours to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 10MPa pressure at 370 ℃, and carrying out hot pressing for 20 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Comparative example 1
42.82 g (0.1 mol) of 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene (6FAPB) and 239 g of N, N-dimethylacetamide (DMAc) were added to a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, and stirred at room temperature under nitrogen protection until completely dissolved to obtain a homogeneous solution. After the reaction system is cooled to 5 ℃, 21.81 g (0.1 mol) of 1,2,4, 5-pyromellitic anhydride (PMDA) and 100 g of DMAc are added, stirred for 2 hours until the PMDA and the DMAc are completely dissolved, and then stirred and reacted for 14 hours at room temperature to obtain a polyamic acid solution with a solid content of 16 wt.%. And filtering and vacuum defoaming the obtained polyamic acid solution, coating the polyamic acid solution on a glass plate with a smooth surface, removing most of solvent by baking at 60 ℃/1.5 hours, peeling off the polyamic acid solution from the glass plate, clamping the polyamic acid solution from top to bottom by a stainless steel frame, and baking at 300 ℃/1 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 6MPa pressure at 370 ℃, and carrying out hot pressing for 15 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
Comparative example 2
In a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen introduction tube and a thermometer, 29.98 g (0.07 mol) of 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene (6FAPB), 24.00 g (0.03 mol) of bis (3-aminopropyl) Polydimethylsiloxane (PDMS) and 260 g of N, N-dimethylacetamide (DMAc) were introduced, and the mixture was stirred at room temperature under a nitrogen atmosphere until completely dissolved to obtain a homogeneous solution. After the reaction system is cooled to 5 ℃, 21.81 g (0.1 mol) of 1,2,4, 5-pyromellitic anhydride (PMDA) and 110 g of DMAc are added, stirred for 2 hours until the PMDA and the DMAc are completely dissolved, and then stirred and reacted for 16 hours at room temperature to obtain a polyamic acid solution with a solid content of 17 wt.%. And (3) filtering and defoaming the obtained polyamic acid solution in vacuum, coating the polyamic acid solution on a polytetrafluoroethylene plate with a smooth surface, removing most of solvent by hot baking at the temperature of 60 ℃/1.5 hours, peeling off the polytetrafluoroethylene plate, vertically clamping the polytetrafluoroethylene plate by a stainless steel frame, and hot baking at the temperature of 300 ℃/1 hour to obtain the polyimide adhesive film. And (3) compounding the two surfaces of the polyimide adhesive film with copper foil, applying 6MPa pressure at 370 ℃, and carrying out hot pressing for 15 minutes to obtain a firm bonding sample. The main properties of the polyimide adhesive film prepared in this example are shown in table 1.
TABLE 1 Main Properties of Silicone-containing polyimide adhesive films
The thickness of the polyimide adhesive film is 20-30 mu m;
glass transition temperature (T)g) Dynamic mechanical analysis is adopted for determination;
the dielectric constant (Dk) and dielectric loss (Df) were measured using a split dielectric resonator at a frequency of 10 GHz;
the adhesive property of the adhesive film and the copper foil is 90-degree peel strength according to IPC-TM-650 standard test.
It is apparent from table 1 that, in comparative example 1, when the content of the imide polar group exceeds 21 wt.%, the content of the trifluoromethyl group is higher than 0.2 wt.%, and the siloxane structure is not contained, the dielectric constant of the obtained polyimide adhesive film is higher than 3, the dielectric loss is as high as 0.0102, the dielectric property is obviously deteriorated, the peel strength is also reduced to 6.5N/cm, and the adhesive property is obviously reduced. In comparative example 2, the content of siloxane was more than 9.0 wt.%, and the glass transition temperature of the obtained polyimide adhesive film was only 256 ℃, and the heat resistance was poor.
As can be seen from the experimental data of examples 1 to 12 in Table 1, the polyimide adhesive films obtained by the present invention have glass transition temperatures of more than 330 ℃ and even as high as 385 ℃, dielectric constants of less than 3 at a high frequency of 10GHz, dielectric loss values of 0.0030 to 0.0059, and peel strengths of more than 10.0N/cm and even as high as 13.1N/cm, by controlling the content of the imide polar groups to not more than 21 wt.%, while controlling the content of the siloxane to 0.2 wt.% to 9.0 wt.%, and the content of the trifluoromethyl group to 0.13 wt.% to 0.19 wt.%. Compared with the prior art that the Dk value of a film obtained by adding a fluorine-containing polymer into polyimide resin is 2.6-2.9 at 10GHz and the Df value is less than 0.0035, the polyimide adhesive film disclosed by the invention has low dielectric constant and low dielectric loss at high frequency, has excellent heat resistance and good adhesive property, and is a polyimide adhesive film with excellent comprehensive properties.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The polyimide adhesive film with excellent comprehensive performance is characterized in that the preparation raw materials consist of aromatic dianhydride, aromatic diamine containing diphenyl ether structure and diamine containing siloxane structure, and the polyimide adhesive film has the following general formula I:
wherein Ar is selected from any one of the following groups:
R1any one selected from the following groups:
R2any one selected from the following groups:
wherein x is 1-8, y is 0, 1;
at least one of the monomer of the aromatic dianhydride and the monomer of the aromatic diamine containing diphenyl ether structure contains fluorine;
the content of trifluoromethyl in the molecular structure of the polyimide adhesive film is 13-19 wt.%, the content of siloxane is 0.2-9.0 wt.%, and the content of imide is not more than 21 wt.%;
the thickness of the polyimide adhesive film is 20-30 μm.
2. The polyimide adhesive film according to claim 1, wherein the aromatic dianhydride comprises at least one of 1,2,4, 5-pyromellitic anhydride, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride, and 4,4'- (4,4' -isopropyldiphenoxy) bis (phthalic anhydride).
3. The polyimide film according to claim 1, wherein the aromatic diamine containing diphenyl ether structure comprises at least one of 1, 4-bis (4-aminophenoxy) benzene, 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 2-bis (4-aminophenoxyphenyl) propane and 2, 2-bis [4- (4-aminophenoxy benzene) ] hexafluoropropane.
4. The polyimide film according to any one of claims 1 to 3, wherein the diamine having a siloxane structure comprises at least one of 1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, 3-aminopropyl-bis-terminated hexamethyltrisiloxane, bis (3-aminopropyl) polydimethylsiloxane, bis (4-aminophenoxy) dimethylsilane and 1, 3-bis (p-aminophenoxy) tetramethyldisiloxane.
5. The polyimide adhesive film according to claim 4, wherein the polyimide adhesive film has a glass transition temperature of more than 330 ℃ and a dielectric constant Dk value of less than 3 at 10GHz, and a dielectric loss Df value of 0.003-0.006.
6. A method for preparing a polyimide adhesive film, which is used for preparing the polyimide adhesive film of any one of claims 1 to 5, comprising the following steps:
(1) dissolving aromatic diamine containing diphenyl ether structure and diamine containing siloxane structure in organic solvent, and stirring to obtain homogeneous solution;
(2) adding aromatic dianhydride into the homogeneous phase solution, and reacting to obtain polyamic acid solution;
(3) and coating the polyamic acid solution, and obtaining the polyimide adhesive film after the first-stage hot drying and the second-stage hot drying.
7. The method according to claim 6, wherein in the step (1), the organic solvent comprises at least one of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide and dimethylsulfoxide.
8. A method for bonding a polyimide adhesive film and a copper foil is characterized by comprising the following steps: and (3) compounding the two sides of the polyimide adhesive film as described in any one of claims 1 to 5 with copper foil, and performing hot pressing to obtain a bonding sample.
9. The bonding method of claim 8, wherein the peel strength of the bonded sample is greater than 10N/cm.
10. The polyimide adhesive film according to any one of claims 1 to 5 is used for insulation bonding in the fields of flexible printed circuit boards and thin film antennas.
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