CN117430848B - Heat-conducting polyimide film added with inorganic auxiliary agent and preparation method and application thereof - Google Patents
Heat-conducting polyimide film added with inorganic auxiliary agent and preparation method and application thereof Download PDFInfo
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- CN117430848B CN117430848B CN202311754309.5A CN202311754309A CN117430848B CN 117430848 B CN117430848 B CN 117430848B CN 202311754309 A CN202311754309 A CN 202311754309A CN 117430848 B CN117430848 B CN 117430848B
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- dianhydride
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 85
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052582 BN Inorganic materials 0.000 claims abstract description 35
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 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 26
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000004952 Polyamide Substances 0.000 claims abstract description 19
- 150000004985 diamines Chemical class 0.000 claims abstract description 19
- 229920002647 polyamide Polymers 0.000 claims abstract description 19
- 229920001709 polysilazane Polymers 0.000 claims abstract description 17
- 238000004100 electronic packaging Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000010345 tape casting Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 14
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011810 insulating material Substances 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 12
- 239000004642 Polyimide Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000003292 glue Substances 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract description 3
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000002019 doping agent Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 238000005266 casting Methods 0.000 description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 241000276425 Xiphophorus maculatus Species 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 4,4' -diaminodiphenyl ketone Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- 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
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the technical field of polyimide materials, in particular to a heat-conducting polyimide film added with an inorganic auxiliary agent, and a preparation method and application thereof. The preparation method of the heat-conducting polyimide film comprises the following steps: (1) Respectively adding diamine and dianhydride into a solvent, and stirring until the diamine and the dianhydride are completely dissolved; (2) Mixing diamine solution and dianhydride solution, and stirring to obtain polyamide acid gum; (3) Mixing the polyamic acid glue with an inorganic auxiliary agent, and uniformly stirring to obtain a mixture; (4) And (3) carrying out imidization on the mixture, and carrying out tape casting and biaxial stretching to obtain the polyimide film. The invention adds micro-scale boron nitride and nano-scale TiO with good dielectric property and excellent chemical stability 2 As doping agent, polysilazane is matched to enhance boron nitride and TiO 2 The bonding stability between the polyimide film and the adhesive improves the heat conduction performance and the mechanical performance of the polyimide film, thereby better meeting the use requirement of high-performance electronic packaging materials.
Description
Technical Field
The invention relates to the technical field of polyimide materials, in particular to a heat-conducting polyimide film added with an inorganic auxiliary agent, and a preparation method and application thereof.
Background
Polyimide is a rigid chain polymer with highly regular chemical structure and imide ring in the main chain of the polymer. The special imide ring structure of the flame retardant has excellent performances of thermal stability, mechanical property, dielectric property, mechanical property, radiation resistance, flame retardance, solvent resistance and the like.
In recent years, due to the requirement of electronic equipment on a higher-density and faster circuit, effective conduction of heat generated by discharging an electronic element and a battery is considered as one of key problems to be solved urgently, and polyimide is widely applied to industries such as microelectronics and power as an electronic packaging material and a battery insulating material due to excellent thermal stability, mechanical properties and low dielectric constant.
However, with the development of new energy industry technology, the heat conduction performance of polyimide films prepared from the existing polyimide materials cannot meet the increasing heat conduction use requirements of the new energy industry. Generally, a Flexible Copper Clad Laminate (FCCL) formed by bonding a copper foil and a multi-layer polyimide film can undergo multiple thermal cycling during the manufacturing and use processes, and structural internal stress can be generated due to the mismatch of high temperature coefficients of materials. When the internal stress is relatively large, warpage, cracking and stripping are caused between the inorganic base material and the high polymer coating, and even plastic deformation of welding spots is caused to cause fracture and the like, so that the reliability and stability of the FCCL are seriously affected. The same problem also occurs on the key problems of durability, insulativity and the like of the new energy power battery in the high-speed discharging process, and the insulativity between a battery PACK (PACK) and the cold liquid plate is required to be maintained, and the unimpeded performance of heat conduction of the battery to the cold liquid plate is required to be maintained. Therefore, polyimide films are required to have high temperature resistance similar to copper foil, and also to maintain effective conduction release of heat after the copper foil has been exposed to heat, which is now the most important issue.
Filling the polyimide film with an inorganic auxiliary agent is an effective method for improving the thermal conductivity thereof. CN 111793206A provides a method for filling clay treated with a silane coupling agent and nanofiller treated with a silane coupling agent in a polyimide film, wherein the clay forms a skeleton as a carrier of the nanofiller and does not react with the nanofiller, and the clay in the polyimide film and the nanofiller cannot effectively link molecular chains, so that the structure is unstable, and the mechanical properties of the film are weak.
Disclosure of Invention
Aiming at the technical problem of poor high temperature resistance of polyimide films, the invention provides a heat conduction type polyimide film added with an inorganic auxiliary agent, and a preparation method and application thereof. In the polyimide film synthesis process, micron-sized boron nitride and nanometer-sized TiO with good dielectric property and excellent chemical stability are added 2 As a dopant, a Polysilazane (PSZ) is blended to enhance boron nitride and TiO 2 The bonding stability between the polyimide film and the adhesive improves the heat conduction performance and the mechanical performance of the polyimide film, thereby better meeting the use requirement of high-performance electronic packaging materials.
In a first aspect, the invention provides a method for preparing a heat-conducting polyimide film added with an inorganic auxiliary agent, which comprises the following steps:
(1) Respectively adding diamine and dianhydride into a solvent, and stirring until the diamine and the dianhydride are completely dissolved;
(2) Mixing the diamine solution and the dianhydride solution obtained in the step (1), and stirring to obtain polyamide acid gum;
(3) Mixing the polyamide acid gum obtained in the step (2) with an inorganic auxiliary agent, and uniformly stirring to obtain a mixture, wherein the inorganic auxiliary agent comprises the following components in percentage by mass of 2-5: 2-5: 2-5 micro-scale boron nitride and nano-scale TiO 2 The addition amount of the inorganic auxiliary agent and PSZ accounts for 20% -50% of the solid content of the mixture;
(4) And (3) carrying out imidization on the mixture obtained in the step (3), and then carrying out tape casting and biaxial stretching to obtain the polyimide film.
Further, the molar ratio of diamine to dianhydride is 1: 1.12-1.25.
Further, the diamine is selected from one or more of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, p-phenylenediamine, 4 '-diaminodiphenyl sulfone and 4,4' -diaminodiphenyl ketone.
Further, the dianhydride is selected from one or more of pyromellitic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride.
Further, the solvent is N, N-dimethylformamide or N, N-dimethylacetamide.
Further, the micron-sized boron nitride is in the form of a strip, and the strip-shaped boron nitride referred to in the present invention mainly comprises irregular polygonal boron nitride sheets, such as approximately rectangular boron nitride sheets, etc.
Further, nano-sized TiO 2 Is rod-shaped.
Further, in the step (4), the casting speed is 3-7 m/min, and the casting temperature is 185-195 ℃. The polyimide film can be formed in a mode that the tensile strength of the film is reduced when the film forming time is too long or too short, the tensile strength of the polyimide film is maximum when the film is formed under the casting parameters, and the peeling strength of the film can reach 1.2kgf/cm.
In a second aspect, the invention provides a heat-conducting polyimide film obtained by the preparation method.
In a third aspect, the present invention provides an application of the heat conductive polyimide film as an electronic packaging insulating material.
In a fourth aspect, the present invention further provides an application of the heat conductive polyimide film in the preparation of an electronic component, where the electronic component may be a flexible circuit board (FPC), an FCCL or a battery outer cladding.
The technical principle of the invention is as follows:
as with most polymers, polyimides belong to amorphous saturated systems, with neither free mobile electrons nor long range ordered crystal structures inside. In addition, polyimide has a broad molecular weight distribution due to the randomness of the polymerization reaction. In microcosmic, the defects of gaps, impurities and the like still exist in the molecular structure of the polyimide, so that phonons are easy to scatter in the transmission process, the average free path of phonons is greatly reduced, and the transmission efficiency of heat in a polyimide matrix is seriously influenced. Therefore, it is generally necessary to introduce a high heat conduction additive into the polyimide substrate, and to improve the heat conduction performance of the polyimide film by constructing a heat transfer network.
Boron nitride has good thermal conductivity, hardness inferior to that of diamond, and chemical resistance, and is not corroded by inorganic acid and water. The high-temperature stability of the boron nitride is good, the heat conductivity coefficient is high, the expansion coefficient is low, and the resistivity is high.TiO 2 Has super-strong flame retardant property, can improve the corrosion resistance of the organic coating to the film surface, and is more noble than TiO 2 Has certain catalytic action, and the activity is large, and the complexing ability is very strong.
The invention combines polyamide acid gum with micron-sized boron nitride and nano-sized TiO 2 Mixing, the micron-sized boron nitride can form a main heat conduction path in the polyamic acid glue, and the nanometer-sized TiO 2 Then the connection function is achieved between the micron-sized boron nitride, and the micron-sized boron nitride and the nanometer-sized TiO are adopted 2 The jointly formed heat conducting net increases the contact between the inorganic auxiliary agent and the polyamide acid glue, thereby improving the heat conducting performance of the polyimide film. PSZ is a relatively reactive resin product with high reactivity and capable of reacting boron nitride with TiO 2 Effectively combine with micron-sized boron nitride and rod-shaped nano TiO 2 The formed multidimensional heat conduction net is more stable, and the heat conduction efficiency is further improved; meanwhile, the polyimide resin is modified by adding PSZ, so that the viscosity of the resin is enhanced, the acid and alkali resistance of the resin is improved, the mechanical strength of the polyimide resin after film formation is improved, and the chemical stability is also enhanced.
The invention has the beneficial effects that:
the invention combines micron-sized boron nitride and TiO 2 The polyimide film is doped as an auxiliary agent to carry out surface treatment, so that effective bonding is formed at an interface, contact thermal resistance is reduced, and heat conduction performance is improved, thereby improving the heat conduction performance under the condition that effective dielectric property, flame retardance and insulating property are kept, ensuring dimensional stability under the condition of high temperature, improving voltage breakdown strength, ensuring safe, reliable and stable operation of used electronic equipment, and having important practical significance.
The heat-conducting polyimide film prepared by the invention has good heat-conducting property and lower thermal expansion coefficient, can effectively reduce the possibility of warping, cracking, stripping and other phenomena in the practical application process, can be used as an electronic packaging insulating material, and is widely applied to the fields of electronic components such as FPC, FCCL, battery outer cladding and the like.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The micron-sized strip-shaped platy boron nitride and spherical boron nitride used in the specific embodiment of the invention are all purchased from Suzhou Napozzolan materials science and technology Co., ltd; nanoscale rod-shaped TiO used 2 Is DuPont (Komu) 902+.
Example 1
The heat conducting polyimide film with the inorganic auxiliary agent is prepared by the following preparation method:
(1) Adding 4,4 '-diaminodiphenyl ether and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 25-30 ℃ to completely dissolve the 4,4' -diaminodiphenyl ether;
adding pyromellitic dianhydride and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 35-40 ℃ to completely dissolve the pyromellitic dianhydride;
(2) Mixing 4,4' -diaminodiphenyl ether solution and pyromellitic dianhydride solution according to diamine: dianhydride=1: mixing at a molar ratio of 1.2, and continuously and uniformly stirring for 4 hours at a temperature of 35-40 ℃ to obtain polyamide acid gum;
(3) Mixing the polyamide acid gum prepared in the step (2) with inorganic auxiliary agents, wherein the inorganic auxiliary agents comprise 30kg of micron-level bar-shaped platy boron nitride (D50 particle size is 8-11 mu m) and 18kg of nanoscale bar-shaped TiO 2 (60-80 nm) and 12kg of PSZ, uniformly stirring in an environment below 25 ℃, and then performing filter pressing to remove impurities to obtain 1500kg of a mixture with 20% of solid content, wherein the mass fraction of inorganic auxiliary agent in the solid content of the mixture is 20%;
(4) And (3) carrying out chemical imidization (mixing with about 312kg of isoquinoline and 46kg of acetic anhydride at the temperature of minus 5 ℃) on the mixture obtained in the step (3), casting and drying on a steel belt through a coating die head, controlling the speed of the steel belt to be 5m/min, heating upper and lower layers of heating pipes in a casting machine to be 185-195 ℃, carrying out longitudinal stretching, desolventizing and curing to obtain a polyimide film, and carrying out stretching through a transverse stretcher to obtain the biaxially oriented polyimide film, wherein the thickness of the polyimide film is about 12.5 mu m.
Example 2
The heat conducting polyimide film with the inorganic auxiliary agent is prepared by the following preparation method:
(1) Adding 4,4 '-diaminodiphenyl ether and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 25-30 ℃ to completely dissolve the 4,4' -diaminodiphenyl ether;
adding pyromellitic dianhydride and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 35-40 ℃ to completely dissolve the pyromellitic dianhydride;
(2) Mixing 4,4' -diaminodiphenyl ether solution and pyromellitic dianhydride solution according to diamine: dianhydride=1: mixing at a molar ratio of 1.2, and continuously and uniformly stirring for 4 hours at a temperature of 35-40 ℃ to obtain polyamide acid gum;
(3) Mixing the polyamide acid gum prepared in the step (2) with inorganic auxiliary agents, wherein the inorganic auxiliary agents comprise 12kg of micron-level bar-shaped platy boron nitride (D50 particle size is 8-11 mu m) and 18kg of nano-level bar-shaped TiO 2 (60-80 nm) and 30kg of PSZ, uniformly stirring in an environment below 25 ℃, and then performing filter pressing to remove impurities to obtain 1500kg of a mixture with 20% of solid content, wherein the mass fraction of inorganic auxiliary agent in the solid content of the mixture is 20%;
(4) And (3) carrying out chemical imidization (mixing with about 312kg of isoquinoline and 46kg of acetic anhydride at the temperature of minus 5 ℃) on the mixture obtained in the step (3), casting and drying on a steel belt through a coating die head, controlling the speed of the steel belt to be 5m/min, heating upper and lower layers of heating pipes in a casting machine to be 185-195 ℃, carrying out longitudinal stretching, desolventizing and curing to obtain a polyimide film, and carrying out stretching through a transverse stretcher to obtain the biaxially oriented polyimide film, wherein the thickness of the polyimide film is about 12.5 mu m.
Example 3
The heat conducting polyimide film with the inorganic auxiliary agent is prepared by the following preparation method:
(1) Adding 4,4 '-diaminodiphenyl ether and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 25-30 ℃ to completely dissolve the 4,4' -diaminodiphenyl ether;
adding pyromellitic dianhydride and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 35-40 ℃ to completely dissolve the pyromellitic dianhydride;
(2) Mixing 4,4' -diaminodiphenyl ether solution and pyromellitic dianhydride solution according to diamine: dianhydride=1: mixing at a molar ratio of 1.2, and continuously and uniformly stirring for 4 hours at a temperature of 35-40 ℃ to obtain polyamide acid gum;
(3) Mixing the polyamide acid gum prepared in the step (2) with inorganic auxiliary agents, wherein the inorganic auxiliary agents comprise 18kg of micron-sized bar-shaped platy boron nitride (D50 particle size is 8-11 mu m) and 12kg of nano-sized bar-shaped TiO 2 (60-80 nm) and 30kg of PSZ, uniformly stirring in an environment below 25 ℃, and then performing filter pressing to remove impurities to obtain 1500kg of a mixture with 20% of solid content, wherein the mass fraction of inorganic auxiliary agent in the solid content of the mixture is 20%;
(4) And (3) carrying out chemical imidization (mixing with about 312kg of isoquinoline and 46kg of acetic anhydride at the temperature of minus 5 ℃) on the mixture obtained in the step (3), casting and drying on a steel belt through a coating die head, controlling the speed of the steel belt to be 5m/min, heating upper and lower layers of heating pipes in a casting machine to be 185-195 ℃, carrying out longitudinal stretching, desolventizing and curing to obtain a polyimide film, and carrying out stretching through a transverse stretcher to obtain the biaxially oriented polyimide film, wherein the thickness of the polyimide film is about 12.5 mu m.
Example 4
The heat conducting polyimide film with the inorganic auxiliary agent is prepared by the following preparation method:
(1) Adding 4,4 '-diaminodiphenyl sulfone and N, N-dimethylacetamide into a dissolution kettle, and uniformly stirring for 20min at 25-30 ℃ to completely dissolve the 4,4' -diaminodiphenyl sulfone;
adding 3,3',4' -benzophenone tetracarboxylic dianhydride and N, N-dimethylacetamide into a dissolution kettle, and uniformly stirring for 20min at 35-40 ℃ to completely dissolve the 3,3',4' -benzophenone tetracarboxylic dianhydride;
(2) The solution of 4,4' -diaminodiphenyl sulfone and the solution of 3,3',4' -benzophenone tetracarboxylic dianhydride are mixed according to diamine: dianhydride=1: mixing at a molar ratio of 1.12, and continuously and uniformly stirring for 4 hours at a temperature of 35-40 ℃ to obtain polyamide acid gum;
(3) Mixing the polyamide acid gum prepared in the step (2) with inorganic auxiliary agents, wherein the inorganic auxiliary agents comprise 21kg of micron-level bar-shaped platy boron nitride (D50 particle size is 8-11 mu m) and 52.5kg of nano-level bar-shaped TiO 2 (60-80 nm) and 31.5kg of PSZ, uniformly stirring in an environment below 25 ℃, and then performing filter pressing to remove impurities to obtain 1500kg of a mixture with 20% of solid content, wherein the mass fraction of inorganic auxiliary agent in the mixture is 35%;
(4) And (3) carrying out chemical imidization (mixing with about 312kg of isoquinoline and 46kg of acetic anhydride at the temperature of minus 5 ℃) on the mixture obtained in the step (3), casting and drying on a steel belt through a coating die head, controlling the speed of the steel belt to be 3m/min, heating upper and lower layers of heating pipes in a casting machine to be 185-195 ℃, carrying out longitudinal stretching, desolventizing and curing to obtain a polyimide film, and carrying out stretching through a transverse stretcher to obtain the biaxially oriented polyimide film, wherein the thickness of the polyimide film is about 15 mu m.
Example 5
The heat conducting polyimide film with the inorganic auxiliary agent is prepared by the following preparation method:
(1) Adding 3,4 '-diaminodiphenyl ether and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 25-30 ℃ to completely dissolve the 3,4' -diaminodiphenyl ether;
adding 2, 3',4' -diphenyl ether tetracarboxylic dianhydride and N, N-dimethylacetamide into a dissolution kettle, and uniformly stirring for 20min at 35-40 ℃ to completely dissolve the 2, 3',4' -diphenyl ether tetracarboxylic dianhydride;
(2) Mixing 3,4' -diaminodiphenyl ether solution and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride solution according to diamine: dianhydride=1: mixing at a molar ratio of 1.25, and continuously and uniformly stirring for 4 hours at a temperature of 35-40 ℃ to obtain polyamide acid gum;
(3) Mixing the polyamide acid gum prepared in the step (2) with inorganic auxiliary agents, wherein the inorganic auxiliary agents comprise 75kg of micron-sized bar-shaped platy boron nitride (D50 particle size is 8-11 mu m) and 30kg of nanoscale bar-shaped TiO 2 (60-80 nm) and 45kg of PSZ, uniformly stirring in an environment below 25 ℃, and then performing filter pressing to remove impurities to obtain 1500kg of a mixture with 20% of solid content, wherein the mass fraction of inorganic auxiliary agent in the mixture is 50%;
(4) And (3) carrying out chemical imidization (mixing with about 312kg of isoquinoline and 46kg of acetic anhydride at the temperature of minus 5 ℃) on the mixture obtained in the step (3), casting and drying on a steel belt through a coating die head, controlling the speed of the steel belt to be 7m/min, heating upper and lower layers of heating pipes in a casting machine to be 185-195 ℃, carrying out longitudinal stretching, desolventizing and curing to obtain a polyimide film, and carrying out stretching through a transverse stretcher to obtain the biaxially oriented polyimide film, wherein the thickness of the polyimide film is about 10 mu m.
Example 6
The heat conducting polyimide film with the inorganic auxiliary agent is prepared by the following preparation method:
(1) Adding 4,4 '-diaminodiphenyl ether and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 25-30 ℃ to completely dissolve the 4,4' -diaminodiphenyl ether;
adding pyromellitic dianhydride and N, N-dimethylformamide into a dissolution kettle, and uniformly stirring for 20min at 35-40 ℃ to completely dissolve the pyromellitic dianhydride;
(2) Mixing 4,4' -diaminodiphenyl ether solution and pyromellitic dianhydride solution according to diamine: dianhydride=1: mixing at a molar ratio of 1.2, and continuously and uniformly stirring for 4 hours at a temperature of 35-40 ℃ to obtain polyamide acid gum;
(3) Mixing the polyamide acid gum prepared in the step (2) with inorganic auxiliary agents, wherein the inorganic auxiliary agents comprise 30kg of 500-mesh spherical boron nitride and 18kg of nano-rod-shaped TiO 2 (60-80 nm) and 12kg of PSZ, uniformly stirring in an environment below 25 ℃, and then performing filter pressing to remove impurities to obtain 1500kg of a mixture with 20% of solid content, wherein the mass fraction of inorganic auxiliary agent in the solid content of the mixture is 20%;
(4) And (3) carrying out chemical imidization (mixing with about 312kg of isoquinoline and 46kg of acetic anhydride at the temperature of minus 5 ℃) on the mixture obtained in the step (3), casting and drying on a steel belt through a coating die head, controlling the speed of the steel belt to be 5m/min, heating upper and lower layers of heating pipes in a casting machine to be 185-195 ℃, carrying out longitudinal stretching, desolventizing and curing to obtain a polyimide film, and carrying out stretching through a transverse stretcher to obtain the biaxially oriented polyimide film, wherein the thickness of the polyimide film is about 12.5 mu m.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that nano-sized CaO of the same particle size is used instead of nano-sized TiO 2 。
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that the same scale of micron-sized boron oxide is used instead of micron-sized boron nitride.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that montmorillonite treated with a silane coupling agent is used instead of PSZ.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that the inorganic auxiliary agent composition is different, and the inorganic auxiliary agent of comparative example 4 comprises 30kg of micron-sized bar-shaped flake boron nitride (D50 particle diameter of 8-11 μm) and 18kg of nano-sized bar-shaped TiO 2 （60~80nm）。
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that the inorganic auxiliary agent composition is different, and the inorganic auxiliary agent of comparative example 5 comprises 12kg PSZ and 18kg nano-rod-like TiO 2 （60~80nm）。
Comparative example 6
Comparative example 6 is substantially the same as example 1 except that the casting speed is 1m/min.
Comparative example 7
Comparative example 7 is substantially the same as example 1 except that the casting speed was 10m/min.
The polyimide films prepared in examples 1 to 6 and comparative examples 1 to 7 were tested for mechanical properties and heat conductive properties, tensile strength, elongation at break and Young's modulus according to ASTM D882, thermal expansion coefficient at 200℃according to ASTM D696, heat preservation at 200℃for 2 hours according to ASTM D5213-04, shrinkage rate, and heat conductive coefficient of the films tested by a flash thermal conductive instrument. The detection results are shown in tables 1 and 2 below.
Table 1 shows performance data of polyimide films prepared in examples 1 to 6
Table 2 Table of Performance data of polyimide films prepared in comparative examples 1 to 7
As can be seen from Table 1, the polyimide films of examples 1 to 6 have good heat conduction and mechanical properties, can meet the use requirements of electronic packaging insulating materials, and can be used for preparing electronic components. Example 6 using 500 mesh spherical boron nitride, the thermal and mechanical properties were slightly inferior to examples 1-5 using micron-sized strip-shaped platelet-shaped boron nitride, indicating that micron-sized strip-shaped platelet-shaped boron nitride can better form a thermal conduction path within the polyamic acid gel and act as a backbone.
The properties of the polyimide films of comparative example 1 and comparative examples 1 to 5 can be found that the micro-sized boron nitride and nano-sized TiO 2 When the polyimide film is matched with PSZ, the heat conduction performance of the polyimide film can be improved, and meanwhile, the mechanical strength of the polyimide film is enhanced, so that the stability and the reliability of the polyimide film when the polyimide film is used as an electronic component material are ensured. Lack of micro-sized boron nitride and nano-sized TiO 2 The performance of the polyimide film prepared from the polyimide film and any one of PSZ materials is weakened, which shows the interaction relation among three inorganic auxiliary agents, so that the combination among molecules is tighter, the stability of a heat conducting net is ensured, and better heat conducting performance and better heat conducting capability are further provided for the polyimide filmThe chemical properties.
The properties of the polyimide films of comparative example 1 and comparative examples 6 to 7 can be found that the casting speed affects the mechanical properties of the films to some extent. According to the invention, the casting speed is controlled to be 3-7 m/min, and the mechanical properties of the obtained film are better by matching with the casting temperature of 185-195 ℃.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.
Claims (6)
1. The preparation method of the heat conduction type polyimide film added with the inorganic auxiliary agent is characterized by comprising the following steps of:
(1) Respectively adding diamine and dianhydride into a solvent, and stirring until the diamine and the dianhydride are completely dissolved;
(2) Mixing the diamine solution and the dianhydride solution obtained in the step (1), and stirring to obtain polyamide acid gum, wherein the molar ratio of diamine to dianhydride is 1: 1.12-1.25;
(3) Mixing the polyamide acid gum obtained in the step (2) with an inorganic auxiliary agent, and uniformly stirring to obtain a mixture, wherein the inorganic auxiliary agent comprises the following components in percentage by mass of 2-5: 2-5: 2-5 micro-scale boron nitride and nano-scale TiO 2 The inorganic auxiliary agent accounts for 20% -50% of the solid content of the mixture, the micron-sized boron nitride is strip-shaped sheet, and the nanometer-sized TiO is prepared by mixing the inorganic auxiliary agent with polysilazane 2 Is bar-shaped;
(4) And (3) carrying out imidization on the mixture obtained in the step (3), and then carrying out tape casting and biaxial stretching to obtain the polyimide film, wherein the tape casting speed is 3-7 m/min, and the tape casting temperature is 180-200 ℃.
2. The process according to claim 1, wherein the diamine is one or more selected from the group consisting of 4,4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, p-phenylenediamine, 4 '-diaminodiphenyl sulfone, and 4,4' -diaminobenzophenone;
the dianhydride is selected from one or more of pyromellitic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride.
3. The process according to claim 1, wherein the solvent is N, N-dimethylformamide or N, N-dimethylacetamide.
4. A heat conductive polyimide film obtained by the production method according to any one of claims 1 to 3.
5. Use of the thermally conductive polyimide film of claim 4 as an insulating material for electronic packaging.
6. Use of the thermally conductive polyimide film of claim 4 in the manufacture of electronic components.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243715A (en) * | 2016-08-15 | 2016-12-21 | 中国科学院宁波材料技术与工程研究所 | A kind of high heat conduction polyimides/boron nitride composite and preparation method thereof |
| CN107189092A (en) * | 2017-06-22 | 2017-09-22 | 莱芜中天绝缘材料有限公司 | A kind of preparation method of high heat conduction type Kapton |
| CN110791200A (en) * | 2019-11-05 | 2020-02-14 | 中国航发北京航空材料研究院 | High-temperature-resistant coating protected by polyimide composite material and preparation method of coating |
| CN110885556A (en) * | 2019-11-07 | 2020-03-17 | 安徽国风塑业股份有限公司 | Heat-conducting cross-linked polyimide film and preparation method thereof |
| CN111234459A (en) * | 2020-01-14 | 2020-06-05 | 山东德钧智能科技服务有限公司 | Modified resin, composite material and heat protection plate |
| CN111793206A (en) * | 2020-06-09 | 2020-10-20 | 中天电子材料有限公司 | Preparation method of polyimide film and polyimide film |
| CN113512214A (en) * | 2021-03-30 | 2021-10-19 | 浙江中科玖源新材料有限公司 | Transparent polyimide film with good barrier property and preparation method thereof |
| CN115044205A (en) * | 2022-06-21 | 2022-09-13 | 太湖方舟新材料科技有限公司 | High-mechanical-strength heat-conducting polyimide film and preparation method thereof |
| CN115894998A (en) * | 2022-12-28 | 2023-04-04 | 江西有泽新材料科技有限公司 | High-thermal-conductivity polyimide film and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621234B (en) * | 2021-08-04 | 2022-08-30 | 深圳瑞华泰薄膜科技股份有限公司 | Ultrahigh-modulus high-transmittance polyimide film and preparation method and application thereof |
-
2023
- 2023-12-20 CN CN202311754309.5A patent/CN117430848B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243715A (en) * | 2016-08-15 | 2016-12-21 | 中国科学院宁波材料技术与工程研究所 | A kind of high heat conduction polyimides/boron nitride composite and preparation method thereof |
| CN107189092A (en) * | 2017-06-22 | 2017-09-22 | 莱芜中天绝缘材料有限公司 | A kind of preparation method of high heat conduction type Kapton |
| CN110791200A (en) * | 2019-11-05 | 2020-02-14 | 中国航发北京航空材料研究院 | High-temperature-resistant coating protected by polyimide composite material and preparation method of coating |
| CN110885556A (en) * | 2019-11-07 | 2020-03-17 | 安徽国风塑业股份有限公司 | Heat-conducting cross-linked polyimide film and preparation method thereof |
| CN111234459A (en) * | 2020-01-14 | 2020-06-05 | 山东德钧智能科技服务有限公司 | Modified resin, composite material and heat protection plate |
| CN111793206A (en) * | 2020-06-09 | 2020-10-20 | 中天电子材料有限公司 | Preparation method of polyimide film and polyimide film |
| CN113512214A (en) * | 2021-03-30 | 2021-10-19 | 浙江中科玖源新材料有限公司 | Transparent polyimide film with good barrier property and preparation method thereof |
| CN115044205A (en) * | 2022-06-21 | 2022-09-13 | 太湖方舟新材料科技有限公司 | High-mechanical-strength heat-conducting polyimide film and preparation method thereof |
| CN115894998A (en) * | 2022-12-28 | 2023-04-04 | 江西有泽新材料科技有限公司 | High-thermal-conductivity polyimide film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Pyrolysis behavior of polysilazane and polysilazane-coated-boron nitride for high thermal conductive composite;Kiho Kim et al.;《Composites Science and Technology》;20170106;全文 * |
| 无机掺杂改性聚酰亚胺薄膜的制备及表征;吴大青;;材料科学与工艺;20060830(04);全文 * |
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