CN116535708A - Ultralow-moisture-absorption low-dielectric high-performance polyimide film and preparation method thereof - Google Patents
Ultralow-moisture-absorption low-dielectric high-performance polyimide film and preparation method thereof Download PDFInfo
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- CN116535708A CN116535708A CN202310602325.6A CN202310602325A CN116535708A CN 116535708 A CN116535708 A CN 116535708A CN 202310602325 A CN202310602325 A CN 202310602325A CN 116535708 A CN116535708 A CN 116535708A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 70
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 54
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 31
- 239000011737 fluorine Substances 0.000 claims abstract description 31
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004185 ester group Chemical group 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 239000004642 Polyimide Substances 0.000 claims description 19
- -1 phenyl ester Chemical class 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 239000002313 adhesive film Substances 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- 150000002148 esters Chemical group 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000003880 polar aprotic solvent Substances 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000009719 polyimide resin Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- HGLWGKYCQGWMBR-UHFFFAOYSA-N bis(4-amino-2-fluorophenyl) benzene-1,4-dicarboxylate Chemical compound C(C1=CC=C(C(=O)OC2=C(C=C(C=C2)N)F)C=C1)(=O)OC1=C(C=C(C=C1)N)F HGLWGKYCQGWMBR-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- ZSYYLDVCLKJQKK-UHFFFAOYSA-N bis[4-amino-2-(trifluoromethyl)phenyl] benzene-1,4-dicarboxylate Chemical compound C(C1=CC=C(C(=O)OC2=C(C=C(C=C2)N)C(F)(F)F)C=C1)(=O)OC1=C(C=C(C=C1)N)C(F)(F)F ZSYYLDVCLKJQKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000013256 coordination polymer Substances 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 4
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- CXISKMDTEFIGTG-UHFFFAOYSA-N [4-(1,3-dioxo-2-benzofuran-5-carbonyl)oxyphenyl] 1,3-dioxo-2-benzofuran-5-carboxylate Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(OC=2C=CC(OC(=O)C=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)=O)=C1 CXISKMDTEFIGTG-UHFFFAOYSA-N 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- C08G73/1067—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a polyimide film with ultralow moisture absorption rate, low dielectric property and high performance and a preparation method thereof, wherein the preparation process is simple, and the prepared polyimide film has the advantages of low moisture absorption rate, dielectric constant, loss factor, low thermal expansion, high heat resistance, high strength and toughness and the like. The invention reduces the water absorption rate of the film and the thermal expansion coefficient of the film by introducing the fluorine-containing group and the aromatic diamine containing the ester chain segment and the aromatic dianhydride containing the ester group, and can realize the comprehensive performance optimization of the film with low dielectric constant and low dielectric loss factor by adjusting the balance of three powder additives of nanometer fluorine-containing polymer powder, aluminum oxide powder and silicon dioxide powder.
Description
Technical Field
The invention relates to the technical field of photoelectricity, in particular to a polyimide film with ultralow moisture absorption rate, low dielectric and high performance and a preparation method thereof.
Background
Low moisture absorption low dielectric high performance materials are widely used in integrated circuits due to their reduced electronic signal interference, power loss, and propagation delay. Polyimide (PI) film has excellent chemical and thermal stability, mechanical property, dielectric property and the like, and is one of the best candidate materials of low dielectric constant materials. However, for some application fields, commercial PI films have problems of high dielectric constant (about 3-4), high moisture absorption (about 1.5% -4.0%), and the like, which limit the application thereof in wider fields.
Disclosure of Invention
Therefore, based on the background, the invention provides the polyimide film with ultralow moisture absorption rate, low dielectric property and high performance and the preparation method thereof, the preparation process is simple, and the prepared polyimide film has low moisture absorption rate, dielectric constant and loss factor, and simultaneously has high performances such as low thermal expansion, high heat resistance, high strength and toughness and the like.
The technical scheme of the invention is as follows:
a preparation method of a polyimide film with ultralow moisture absorption rate, low dielectric and high performance comprises the following steps:
(1) Adding the aromatic diamine with fluorine-containing groups and ester chain segments and the universal aromatic diamine monomer powder into a polar aprotic solvent, mixing, and stirring at room temperature to prepare an aromatic diamine solution;
(2) Mixing the aromatic dianhydride containing the ester group and the universal aromatic dianhydride monomer powder, adding the mixture into the aromatic diamine solution obtained in the step (1) in batches under the condition of stirring, and preparing a polyimide precursor resin solution through polycondensation reaction;
(3) Uniformly mixing fluorine-containing polymer powder, aluminum oxide powder and silicon dioxide powder, and then adding the mixture into a polar aprotic solvent to uniformly disperse to prepare slurry;
(4) Adding the slurry obtained in the step (3) into the polyimide precursor resin solution prepared in the step (2), adding a polar aprotic solvent, regulating and controlling the viscosity of a reaction product to 80000+/-1000 CP, performing suction filtration and vacuum defoaming, uniformly extruding and casting the reaction product to coat the surface of a stainless steel belt, heating the reaction product to 100-180 ℃ and keeping the reaction product for a certain time, and stripping the formed resin adhesive film containing part of the solvent from the surface of the steel belt to obtain a polyimide resin adhesive film;
(5) Fixing the periphery of the polyimide resin film in the step (4) on a frame of a metal mold, completing the two-way stretching and high-temperature imidization processes by adopting a temperature programming mode, and then obtaining the polyimide film through annealing treatment.
Further, the aromatic diamine having a fluorine-containing group and an ester-containing segment in the step (1) may be selected from at least one of bis (2-fluoro-4-aminophenyl) terephthalate and bis (2-trifluoromethyl-4-aminophenyl) terephthalate.
Further, the general aromatic diamine in the step (1) is selected from one or two of 4, 4-diaminodiphenyl ether, p-phenylenediamine, 4-diaminodiphenyl methane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane.
Further, the aromatic dianhydride containing an ester group in the step (2) is selected from one or two of bis (trimellitic anhydride) phenyl ester, methyl-bis (trimellitic anhydride) phenyl ester, methoxy-bis (trimellitic anhydride) phenyl ester.
Further, the general aromatic dianhydride in the step (2) is selected from one or two of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, 4 '-biphenyl ether dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
Further, the fluorine-containing polymer powder, the aluminum oxide powder and the silicon dioxide powder in the step (3) are all nano-scale;
the fluorine-containing polymer powder, the aluminum oxide powder and the silicon dioxide powder are added according to the weight ratio: 40% -60%: 20% -40%: 10% -30%.
The nano-scale aluminum oxide powder and the nano-scale silicon dioxide powder added in the invention can also play a role in reducing dielectric constant to a certain extent, can effectively reduce dielectric loss factors through filling, and simultaneously play a certain role in enhancing the whole matrix. The addition of the fluorine-containing polymer powder can reduce the water absorption and the dielectric constant.
Further, the fluorine-containing polymer powder is polytetrafluoroethylene powder.
Further, the total addition amount of the fluorine-containing polymer powder, the aluminum oxide powder and the silicon dioxide powder accounts for 10-50% of the polyimide precursor resin solution prepared in the step (2).
Further, the polar aprotic solvent used in steps (1) to (4) is selected from one or two of dimethylacetamide, N-methylpyrrolidone and dimethylformamide.
The invention also provides a polyimide film which is prepared by adopting the preparation method of the polyimide film with ultralow moisture absorption rate, low dielectric and high performance.
Further, the dielectric constant of the polyimide film is less than or equal to 2.6, the dielectric loss factor is less than or equal to 0.003, the moisture absorption rate is less than or equal to 0.02%, the glass transition temperature is more than 300 ℃, the tensile strength is more than 100MPa, the tensile modulus is more than 6.0GPa, and the thermal expansion coefficient is less than 20ppm/K.
According to the invention, the fluorine-containing group is introduced into the polyimide film resin main chain structure, the hydrophobicity of fluorine atoms is utilized, the water absorption rate of the film is reduced, and the water absorption expansion of the flexible packaging substrate in the alkaline etching process, the electronic component failure caused by moisture absorption in the use process and the like can be effectively reduced; and the dielectric constant can be reduced by introducing fluorine;
the ester-containing group is introduced into the main chain structure of the polyimide film resin, so that the secondary bond force effect among the main chain structure of the resin is enhanced, the main chain orientation of the polymer is enhanced, the inter-chain stacking is tight, the thermal expansion coefficient of the film is obviously reduced to be close to that of a metal copper foil (ETE: 17.8 ppm/K), and the mechanical property of the polyimide film is improved.
The beneficial effects achieved by adopting the invention are as follows:
(1) The invention adopts at least two different diamines and dianhydrides to introduce fluorine-containing groups and ester groups through copolymerization, thereby being convenient for regulating and controlling the film performance and ensuring that the product has excellent mechanical properties;
(2) The polyimide film prepared by the invention has a single-layer structure, and the preparation process is simple;
(3) The invention reduces the water absorption rate of the film and the thermal expansion coefficient of the film by introducing the fluorine-containing group and the aromatic diamine containing the ester chain segment and the aromatic dianhydride containing the ester group, and can realize the comprehensive performance optimization of the film with low dielectric constant and low dielectric loss factor by adjusting the balance of three powder additives of nanometer fluorine-containing polymer powder, aluminum oxide powder and silicon dioxide powder.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention. The invention is further illustrated below with reference to examples.
The invention provides a preparation method of a polyimide film with ultralow moisture absorption rate, low dielectric and high performance, which comprises the following steps:
(1) Adding the aromatic diamine with fluorine-containing groups and ester chain segments and the universal aromatic diamine monomer powder into a polar aprotic solvent, mixing, and stirring at room temperature to prepare an aromatic diamine solution;
the aromatic diamine having a fluorine-containing group and an ester-containing segment may be at least one selected from the group consisting of bis (2-fluoro-4-aminophenyl) terephthalate (F-BPTP) and bis (2-trifluoromethyl-4-aminophenyl) terephthalate (CF 3-BPTP).
The general aromatic diamine is selected from one or two of 4, 4-diaminodiphenyl ether, p-phenylenediamine, 4-diaminodiphenyl methane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane.
The molar ratio of the fluorine-containing group and the ester segment-containing aromatic diamine to the general aromatic diamine is 5/95 to 30/70.
(2) Mixing the aromatic dianhydride containing the ester group and the universal aromatic dianhydride monomer powder, adding the mixture into the aromatic diamine solution obtained in the step (1) in batches under the condition of stirring, and preparing a polyimide precursor resin solution through polycondensation reaction;
the aromatic dianhydride containing an ester group is selected from one or two (MeO-TAHQ) of bis (trimellitic anhydride) phenyl ester (TAHQ), methyl-bis (trimellitic anhydride) phenyl ester (CH 3-TAHQ) and methoxy-bis (trimellitic anhydride) phenyl ester.
The general aromatic dianhydride is selected from one or two of pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 4 '-biphenyl ether dianhydride (ODPA) and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride (6 FPA).
The molar ratio of the aromatic dianhydride containing an ester group to the general aromatic dianhydride in this step is 5/95 to 10/90.
(3) Uniformly mixing fluorine-containing polymer powder, aluminum oxide powder and silicon dioxide powder, and then adding the mixture into a polar aprotic solvent to uniformly disperse to prepare slurry;
the fluorine-containing polymer powder, the aluminum oxide powder and the silicon dioxide powder are all nano-scale;
the fluorine-containing polymer powder, the aluminum oxide powder and the silicon dioxide powder are added according to the weight ratio: 40% -60%: 20% -40%: 10% -30%.
The total addition amount of the fluorine-containing polymer powder, the aluminum oxide powder and the silicon dioxide powder accounts for 10% -50% of the polyimide precursor resin solution prepared in the step (2).
(4) Adding the slurry obtained in the step (3) into the polyimide precursor resin solution prepared in the step (2), adding a polar aprotic solvent, regulating and controlling the viscosity of a reaction product to 80000+/-1000 CP, performing suction filtration and vacuum defoaming, uniformly extruding and casting the reaction product to coat the surface of a stainless steel belt, heating the reaction product to 100-180 ℃ and keeping the reaction product for a certain time, and stripping the formed resin adhesive film containing part of the solvent from the surface of the steel belt to obtain a polyimide resin adhesive film;
(5) Fixing the periphery of the polyimide resin film in the step (4) on a frame of a metal mold, completing the two-way stretching and high-temperature imidization processes by adopting a temperature programming mode, and then obtaining the polyimide film through annealing treatment.
The polar aprotic solvent used in the steps (1) to (4) is one or two selected from dimethylacetamide, N-methylpyrrolidone and dimethylformamide.
The polyimide film prepared by the method has the dielectric constant less than or equal to 2.6, the dielectric loss factor less than or equal to 0.003, the moisture absorption rate less than or equal to 0.02 percent, the glass transition temperature more than 300 ℃, the tensile strength more than 100MPa, the tensile modulus more than 6.0GPa and the thermal expansion coefficient less than 20ppm/K.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are for illustrative purposes only and are not to be construed as limiting the invention.
Example 1:
(1) taking the aromatic diamine and the general aromatic diamine monomer powder (the molar ratio is 5/95 to 30/70) which are simultaneously provided with fluorine-containing groups and ester chain segments according to a proportion, adding the powder into a reaction kettle, and dissolving the powder by using dimethylacetamide;
the aromatic diamine containing a fluorine group and an ester segment of this example was bis (2-fluoro-4-aminophenyl) terephthalate (F-BPTP);
the general aromatic diamine monomer was 4, 4-diaminodiphenyl ether (ODA) (1 mol 120 g);
(2) taking and mixing the aromatic dianhydride containing ester groups and the general aromatic dianhydride (the molar ratio is 5/95 to 10/90) according to the proportion, adding the mixture into an upper reaction kettle in batches, and stirring to prepare polyimide precursor resin solution;
the ester group-containing aromatic dianhydride of this example was bis (trimellitic anhydride) phenyl ester (TAHQ);
the general aromatic dianhydride of this example was pyromellitic dianhydride (PMDA) (1 mol 182 g);
(3) uniformly mixing nano Polytetrafluoroethylene (PTFE) (25 g), nano aluminum oxide powder (15 g) and nano silicon dioxide powder (10 g), then adding the mixture into a polar aprotic solvent dimethylacetamide, and fully stirring to prepare slurry;
(4) adding the prepared slurry into the reaction kettle for preparing the polyimide precursor resin solution, adding a dimethylacetamide solvent to regulate and control the viscosity of a final reaction product, performing suction filtration and vacuum defoamation, casting into a film, heating to 100-180 ℃ and keeping for a certain time, and stripping the formed resin adhesive film containing part of the solvent from the surface of a steel belt to obtain a polyimide resin adhesive film;
(5) fixing the periphery of the polyimide resin adhesive film on a frame of a metal mold, adopting a temperature programming mode (200-380 ℃) to finish the two-way stretching and high-temperature imidization process, and then carrying out annealing treatment to obtain the polyimide film. The polyimide film obtained in this example had a moisture absorption of 0.02%, a dielectric constant of 2.6, a dielectric dissipation factor of 0.003, a glass transition temperature of 375℃and a tensile strength of 162MPa, a tensile modulus of 6.9GPa and a thermal expansion coefficient of 9.5ppm/K.
Example 2:
(1) taking the aromatic diamine and the general aromatic diamine monomer powder (the molar ratio is 10/90 to 30/70) which are simultaneously provided with fluorine-containing groups and ester chain segments according to a proportion, adding the powder into a reaction kettle, and dissolving the powder by using dimethylacetamide;
the aromatic diamine containing a fluorine group and an ester segment of this example was bis (2-fluoro-4-aminophenyl) terephthalate (F-BPTP);
the general aromatic diamine monomer was 4, 4-diaminodiphenyl ether (ODA) (1 mol 120 g);
(2) taking and mixing the aromatic dianhydride containing ester groups and the general aromatic dianhydride (the molar ratio is 5/95 to 10/90) according to the proportion, adding the mixture into an upper reaction kettle in batches, and stirring to prepare polyimide precursor resin solution;
the ester group-containing aromatic dianhydride of this example was bis (trimellitic anhydride) phenyl ester (TAHQ);
the general aromatic dianhydride of this example was pyromellitic dianhydride (PMDA) (1 mol 182 g);
(3) uniformly mixing nano Polytetrafluoroethylene (PTFE) (25 g), nano aluminum oxide powder (15 g) and nano silicon dioxide powder (10 g), then adding the mixture into a polar aprotic solvent dimethylacetamide, and fully stirring to prepare slurry;
(4) adding the prepared slurry into the reaction kettle for preparing the polyimide precursor resin solution, adding a dimethylacetamide solvent to regulate and control the viscosity of a final reaction product, performing suction filtration and vacuum defoamation, casting into a film, heating to 100-180 ℃ and keeping for a certain time, and stripping the formed resin adhesive film containing part of the solvent from the surface of a steel belt to obtain a polyimide resin adhesive film;
(5) fixing the periphery of the polyimide resin adhesive film on a frame of a metal mold, adopting a temperature programming mode (200-380 ℃) to finish the two-way stretching and high-temperature imidization process, and then carrying out annealing treatment to obtain the polyimide film.
The polyimide film obtained in this example had a moisture absorption of 0.015%, a dielectric constant of 2.6, a dielectric dissipation factor of 0.003, a glass transition temperature of 324℃and a tensile strength of 148MPa, a tensile modulus of 6.7GPa and a thermal expansion coefficient of 11.3ppm/K.
Example 3:
(1) taking the aromatic diamine and the general aromatic diamine monomer powder (the molar ratio is 5/95 to 30/70) which are simultaneously provided with fluorine-containing groups and ester chain segments according to a proportion, adding the powder into a reaction kettle, and dissolving the powder by using dimethylacetamide;
the aromatic diamine containing a fluorine group and an ester segment of this example was bis (2-fluoro-4-aminophenyl) terephthalate (F-BPTP);
the general aromatic diamine monomer was 4, 4-diaminodiphenyl ether (ODA) (1 mol 120 g);
(2) taking and mixing the aromatic dianhydride containing ester groups and the general aromatic dianhydride (the molar ratio is 5/95 to 10/90) according to the proportion, adding the mixture into an upper reaction kettle in batches, and stirring to prepare polyimide precursor resin solution;
the ester group-containing aromatic dianhydride of this example was bis (trimellitic anhydride) phenyl ester (TAHQ);
the general aromatic dianhydride of this example was pyromellitic dianhydride (PMDA) (1 mol 182 g);
(3) uniformly mixing three additives, namely nano Polytetrafluoroethylene (PTFE) (20 g), nano aluminum oxide powder (10 g) and nano silicon dioxide powder (5 g), and then adding the three additives into a polar aprotic solvent dimethylacetamide, and fully stirring to prepare slurry;
(4) adding the prepared slurry into the reaction kettle for preparing the polyimide precursor resin solution, adding a dimethylacetamide solvent to regulate and control the viscosity of a final reaction product, performing suction filtration and vacuum defoamation, casting into a film, heating to 100-180 ℃ and keeping for a certain time, and stripping the formed resin adhesive film containing part of the solvent from the surface of a steel belt to obtain a polyimide resin adhesive film;
(5) fixing the periphery of the polyimide resin adhesive film on a frame of a metal mold, adopting a temperature programming mode (200-380 ℃) to finish the two-way stretching and high-temperature imidization process, and then carrying out annealing treatment to obtain the polyimide film.
The polyimide film prepared in this example had a moisture absorption of 0.02%, a dielectric constant of 2.9, a dielectric dissipation factor of 0.005, a glass transition temperature of 370℃and a tensile strength of 160MPa, a tensile modulus of 6.9GPa, and a thermal expansion coefficient of 9.5ppm/K.
Comparative example 1:
(1) adding general aromatic diamine monomer powder 4, 4-diaminodiphenyl ether (ODA) (1 mol 120 g) into a reaction kettle, dissolving with dimethylacetamide, then adding a mixture of general aromatic dianhydride monomer powder pyromellitic dianhydride (PMDA) (1 mol 182 g) into the reaction kettle in batches, and stirring to prepare polyimide precursor resin solution;
(2) adding the prepared polyamic acid solution into dimethylacetamide solvent to regulate and control the final viscosity, then carrying out suction filtration and vacuum defoamation, extruding and casting to 100-180 ℃ on a steel belt, drying at high temperature, biaxially stretching and imidizing at high temperature of 260-380 ℃ to obtain the polyimide film.
The basic performance index data for examples 1, 2, 3 and comparative example 1 are shown in table 1.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
Claims (10)
1. A preparation method of a polyimide film with ultralow moisture absorption rate, low dielectric and high performance is characterized in that,
the method comprises the following steps:
(1) Adding the aromatic diamine with fluorine-containing groups and ester chain segments and the universal aromatic diamine monomer powder into a polar aprotic solvent, mixing, and stirring at room temperature to prepare an aromatic diamine solution;
(2) Mixing the aromatic dianhydride containing the ester group and the universal aromatic dianhydride monomer powder, adding the mixture into the aromatic diamine solution obtained in the step (1) in batches under the condition of stirring, and preparing a polyimide precursor resin solution through polycondensation reaction;
(3) Uniformly mixing fluorine-containing polymer powder, aluminum oxide powder and silicon dioxide powder, and then adding the mixture into a polar aprotic solvent to uniformly disperse to prepare slurry;
(4) Adding the slurry obtained in the step (3) into the polyimide precursor resin solution prepared in the step (2), adding a polar aprotic solvent, regulating and controlling the viscosity of a reaction product to 80000+/-1000 CP, performing suction filtration and vacuum defoaming, uniformly extruding and casting the reaction product to coat the surface of a stainless steel belt, heating the reaction product to 100-180 ℃ and keeping the reaction product for a certain time, and stripping the formed resin adhesive film containing part of the solvent from the surface of the steel belt to obtain a polyimide resin adhesive film;
(5) Fixing the periphery of the polyimide resin film in the step (4) on a frame of a metal mold, completing the two-way stretching and high-temperature imidization processes by adopting a temperature programming mode, and then obtaining the polyimide film through annealing treatment.
2. The method for producing a polyimide film having an ultra-low moisture absorption and a low dielectric constant as claimed in claim 1, wherein the aromatic diamine having a fluorine-containing group and an ester segment in the step (1) is at least one selected from the group consisting of bis (2-fluoro-4-aminophenyl) terephthalate and bis (2-trifluoromethyl-4-aminophenyl) terephthalate.
3. The method for producing a polyimide film having an ultra-low moisture absorption and a low dielectric constant as claimed in claim 1, wherein the general aromatic diamine in the step (1) is at least one selected from the group consisting of 4, 4-diaminodiphenyl ether, p-phenylenediamine, 4-diaminodiphenyl methane, and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane.
4. The method for producing a polyimide film having an ultra-low moisture absorption and a low dielectric constant as claimed in claim 1, wherein the aromatic dianhydride containing an ester group in the step (2) is at least one selected from the group consisting of bis (trimellitic anhydride) phenyl ester, methyl-bis (trimellitic anhydride) phenyl ester and methoxy-bis (trimellitic anhydride) phenyl ester.
5. The method for producing a polyimide film having a low moisture absorption and a low dielectric constant as claimed in claim 1, wherein the general aromatic dianhydride in the step (2) is selected from pyromellitic dianhydride, 3', at least one of 4,4' -biphenyl tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, 4 '-biphenyl ether dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
6. The method for preparing the polyimide film with ultralow moisture absorption rate and low dielectric property according to claim 1, wherein the fluorine-containing polymer powder, the aluminum oxide powder and the silicon dioxide powder in the step (3) are all nano-scale;
the fluorine-containing polymer powder, the aluminum oxide powder and the silicon dioxide powder are added according to the weight ratio: 40% -60%: 20% -40%: 10% -30%.
7. The method for preparing a polyimide film with ultralow moisture absorption and low dielectric constant and high performance according to claim 6, wherein the total amount of fluorine-containing polymer powder, aluminum oxide powder and silicon dioxide powder is 10% -50% of the polyimide precursor resin solution prepared in the step (2).
8. The method for producing a polyimide film having an ultra low moisture absorption and a low dielectric constant according to claim 1, wherein the polar aprotic solvent used in steps (1) to (4) is one or two selected from dimethylacetamide, N-methylpyrrolidone and dimethylformamide.
9. A polyimide film, characterized in that it is produced by the process for producing a polyimide film of ultra-low moisture absorption and low dielectric and high performance according to any one of claims 1 to 8.
10. The polyimide film according to claim 9, wherein the polyimide film has a dielectric constant of 2.6 or less, a dielectric dissipation factor of 0.003 or less, a moisture absorption of 0.02% or less, a glass transition temperature of > 300 ℃, a tensile strength of > 100MPa, a tensile modulus of > 6.0GPa, and a thermal expansion coefficient of < 20ppm/K.
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