CN111630088B - Highly thermally conductive polyimide film containing two or more fillers - Google Patents
Highly thermally conductive polyimide film containing two or more fillers Download PDFInfo
- Publication number
- CN111630088B CN111630088B CN201880087103.2A CN201880087103A CN111630088B CN 111630088 B CN111630088 B CN 111630088B CN 201880087103 A CN201880087103 A CN 201880087103A CN 111630088 B CN111630088 B CN 111630088B
- Authority
- CN
- China
- Prior art keywords
- thermally conductive
- conductive filler
- polyimide film
- filler
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a polyimide film comprising a thermally conductive filler and a base film, wherein the thermally conductive filler comprises a first thermally conductive filler having an average particle diameter of 0.001 to 20 [ mu ] m, the first thermally conductive filler being a carbon-based filler or a boron-based filler, and a second thermally conductive filler having an average particle diameter of 0.1 to 20 [ mu ] m, the second thermally conductive filler being a metal oxide-based filler, the base film is prepared by imidizing a polyamic acid formed by a reaction of a dianhydride monomer and a diamine monomer, the polyimide film has a thermal conductivity of 0.5W/m.K or more in a thickness direction, and a thermal conductivity of 2.0W/m.K or more in a plane direction.
Description
Technical Field
The present invention relates to a highly thermally conductive polyimide film containing two or more types of fillers.
Background
Generally, a Polyimide (PI) resin refers to a high temperature resistant resin prepared by solution-polymerizing an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, followed by dehydration by ring closure at high temperature and by imidization.
Polyimide resins are insoluble and infusible, super heat-resistant resins and have excellent characteristics such as thermal oxidation resistance, heat resistance, radiation resistance, low-temperature characteristics, chemical resistance and the like, and thus are widely used for heat-resistant high-tech materials such as automobile materials, aviation materials, spacecraft materials and the like, and electronic materials such as insulating coating agents, insulating films, semiconductors, electrode protective films of thin film transistor liquid crystal displays (TFT-LCDs) and the like.
With the recent trend toward high degree of informatization, electronic devices are used to accumulate a large amount of information and rapidly process and communicate the information, and therefore polyimide resins used for electronic devices are required to have not only high electrical insulation properties but also improved thermal conductivity to effectively dissipate heat generated by the electronic devices.
Specifically, in order to further improve the heat dissipation performance, it is necessary to ensure a desired degree of thermal conductivity in the plane direction and the thickness direction of the polyimide film.
As a method for improving the thermal conductivity of a polyimide resin, a method is known in which a thermally conductive substance in a precursor solution is dispersed, and then a thin film is formed using the dispersion.
However, in the case of the polyimide film prepared in this way, the following problems may occur: a desired degree of thermal conductivity can be exhibited in the planar direction of the film, but a desired degree of thermal conductivity cannot be exhibited in the thickness direction.
Furthermore, generally, as the content of the filler increases, the thermal conductivity tends to increase, but in order to ensure the desired thermal conductivity, when the content of the filler is excessively applied, the excessive filler forms flocs, so that the flocs of the filler protrude from the surface of the film to cause poor appearance.
Furthermore, as the content of the filler in the film increases, there occurs a decrease in mechanical properties of the polyimide film or the film forming process itself cannot be performed.
Therefore, a technology capable of fundamentally solving these problems is urgently required.
Disclosure of Invention
Technical problem to be solved by the invention
The present invention is directed to solving the problems of the prior art as described above and the technical problems required in the past.
The inventors of the present application have made intensive studies and various experiments, and as described below, made that a filler having an average particle diameter of 0.001 μm to 20 μm in a polyimide film contains a carbon-based or boron-based filler and a metal oxide-based filler having an average particle diameter of 0.1 μm to 20 μm, and thus have confirmed that the in-plane direction thermal conductivity and the thickness direction thermal conductivity of the polyimide film can be improved, to complete the present invention.
Means for solving the problems
In order to achieve the object, the present invention provides a polyimide film comprising a thermally conductive filler and a base film, the thermally conductive filler comprising a first thermally conductive filler having an average particle diameter of 0.001 to 20 μm, the first thermally conductive filler being a carbon-based filler or a boron-based filler, and a second thermally conductive filler having an average particle diameter of 0.1 to 20 μm, the second thermally conductive filler being a metal oxide-based filler, the base film being prepared by imidizing a polyamic acid formed by a reaction of a dianhydride monomer and a diamine monomer, the polyimide film having a thickness direction thermal conductivity of 0.5W/m.k or more, and an in-plane direction thermal conductivity of 2.0W/m.k or more.
At this time, the dianhydride monomer may include one or more monomers selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), oxydiphthalic anhydride (ODPA), and benzophenonetetracarboxylic dianhydride (BTDA).
Also, the diamine monomer may include one or more monomers selected from the group consisting of 1,4-phenylenediamine (PPD), 4,4 '-Oxydianiline (ODA), 3,4' -oxydianiline, 2,2-bis [4'- (4-aminophenoxy) phenyl ] propane (BAPP), 4,4' -diaminodiphenylmethane (MDA), and 1,3-bis (4-aminophenoxy) benzene (TPE-R).
The carbon-based filler may be Graphene (Graphene) or Carbon Nanotubes (CNT), and the boron-based filler may be boron nitride (Boronnitride).
The metal oxide filler may be alumina (Al) 2 O 3 )。
And, the thermally conductive filler may be contained in an amount of 5 to 20 wt% with respect to the total weight of the polyimide film, and the base film may be contained in an amount of 80 to 95 wt% with respect to the total weight of the polyimide film.
On the other hand, in the first thermally conductive filler and the second thermally conductive filler, the content (W) of the first thermally conductive filler 1 ) And content (W) of the second thermally conductive filler 2 ) Can satisfy 2W 1 ≤W 2 。
More specifically, the content of the second thermally conductive filler relative to the content of the first thermally conductive filler may be 200% to 1900% on a weight basis.
And, the first thermally conductive filler may be contained in an amount of 0.1 to 5 wt% with respect to the total weight of the polyimide film.
And, the content of the second thermally conductive filler may be 1 to 19 wt% with respect to the total weight of the polyimide film.
The polyimide film may have a light transmittance of 1% or less in a visible light region.
The invention also provides a preparation method of the polyimide film, wherein the polyamide acid is polymerized from the dianhydride monomer and the diamine monomer, the polyamide acid and the heat-conducting filler are mixed, and the film is formed on the carrier and is subjected to heat treatment to perform imidization.
The invention also provides an electronic device comprising the polyimide film.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of a cross section of the polyimide film of example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of a cross section of the polyimide film of example 3.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph of a cross section of the polyimide film of example 5.
Fig. 4 is a Scanning Electron Microscope (SEM) photograph of a cross section of the polyimide film of comparative example 1.
Fig. 5 is a Scanning Electron Microscope (SEM) photograph of a cross section of the polyimide film of comparative example 4.
Detailed Description
Hereinafter, the present invention is described in more detail.
The polyimide film according to the present invention is a polyimide film including a thermally conductive filler including a first thermally conductive filler having an average particle diameter of 0.001 to 20 μm, the first thermally conductive filler being a carbon-based filler or a boron-based filler, and a second thermally conductive filler having an average particle diameter of 0.1 to 20 μm, the second thermally conductive filler being a metal oxide-based filler, and a base film prepared by imidizing a polyamic acid formed by a reaction of a dianhydride monomer and a diamine monomer, the polyimide film having a thickness direction thermal conductivity of 0.5W/m.k or more, and a plane direction thermal conductivity of 2.0W/m.k or more.
When a polyimide film is used as the thermal conductive film, the physical properties required may differ depending on the specific position. For example, even if the heat radiator (e.g., heat radiation film) is of a single-layer structure or a multi-layer structure, and the thermal conductive film is located on the outermost side to increase only the in-plane direction thermal conductivity, an effect of improving the overall heat radiation performance can be obtained. On the contrary, in the case of a heat conductive film having a multilayer structure, which is interposed between the multilayer structures and is not the outermost heat conductive film, even if the in-plane direction heat conductivity is improved, the overall heat dissipation performance is hardly effective because the thickness direction heat conductivity is less than a predetermined level.
Due to the lack of recognition of the thermal conductivity in the specific position and thickness direction in the heat radiator as described above, the conventional thermal conductive film focuses only on improving the thermal conductivity in the planar direction, and such a conventional thermal conductive film can be expected to have an improved heat radiation performance only when it is located at the outermost side of the heat radiator.
In contrast, the polyimide film according to the present invention has excellent thermal conductivity in both the thickness direction and the planar direction, and can exhibit an effect of remarkably improving heat dissipation even if it is located at the outermost side or in the middle of the heat spreader. In particular, when the polyimide film is interposed in the middle of the heat radiator, the heat radiation can be further improved.
In a specific example, the thermally conductive filler may be 5 to 20 wt% with respect to the total weight of the polyimide film, and more specifically, may be 11 to 20 wt% with respect to the total weight of the polyimide film.
When the thermally conductive filler is less than the range with respect to the total weight of the polyimide film, the desired thermal conductivity cannot be achieved, and thus is not preferable.
In contrast, when the thermally conductive filler is more than the range with respect to the total weight of the polyimide film, an excessive amount of the filler forms flocs, so that the flocs of the filler protrude from the surface of the film to cause poor appearance, and the mechanical properties of the polyimide film are lowered, or the film forming process itself cannot be performed, and thus it is not preferable.
The polyimide film can have improved thermal conductivity and shielding properties by containing the first thermally conductive filler and the second thermally conductive filler in a specific content range and in a specific average particle diameter range. Specifically, the polyimide film may have a light transmittance of 1% or less in a visible light region.
More specifically, the first thermally conductive filler may be contained in an amount of 0.1 to 5 wt% with respect to the total weight of the polyimide film, and the second thermally conductive filler may be contained in an amount of 1 to 19 wt% with respect to the total weight of the polyimide film.
At this time, the first thermally conductive filler may be aligned in a planar direction of the polyimide film of the filler during the preparation of the polyimide film, for example, during the stretching of the polyimide film, and as a result, a heat transfer path is provided with respect to the planar direction of the polyimide film, so that the planar direction thermal conductivity of the polyimide film may be significantly improved.
On the other hand, when the first thermal conductive filler and the second thermal conductive filler are used together, not only the in-plane thermal conductivity of the polyimide film can be improved, but also a heat transfer path can be provided in the thickness direction of the polyimide film, so that the thickness direction thermal conductivity of the polyimide film can be improved.
In the present invention, in order to obtain a polyimide film that exhibits a desired level of in-plane thermal conductivity and thickness-direction thermal conductivity, the content (W) of the first thermally conductive filler is the content of the first thermally conductive filler in the first thermally conductive filler and the second thermally conductive filler 1 ) And content (W) of the second thermally conductive filler 2 ) Can satisfy 2W 1 ≤W 2 The relationship (2) of (c).
And, the content ratio of the second thermally conductive filler to the first thermally conductive filler may be 200% to 1900% by weight, more specifically, the content ratio of the second thermally conductive filler to the second thermally conductive filler may be 200% to 1000% by weight.
When the content (W) of the first thermally conductive filler 1 ) And content (W) of the second thermally conductive filler 2 ) Does not satisfy the relationship of (2W) 1 ≤W 2 Or when the content of the first thermally conductive filler and the content of the second thermally conductive filler exceed the above ranges, the thickness direction thermal conductivity and the plane direction thermal conductivity cannot be attained to a desired degree, which is not preferable.
Wherein the first thermally conductive filler may be defined as a carbon-based filler or a boron-based filler having an average particle diameter of 0.001 to 20 μm.
When the average particle diameter of the first thermally conductive filler is smaller than the range, thermal conductivity, particularly in the in-plane direction of the polyimide film, is difficult to achieve a desired degree, and thus it is not preferable.
In contrast, when the average particle diameter of the first thermally conductive filler is larger than the range, the dispersion degree is decreased when mixing with polyamic acid in the production process, and the filler protrudes from the surface to cause poor appearance, so that it is not preferable.
The carbon-based filler may be, for example, multi-layer Graphene (Graphene) and/or Carbon Nanotubes (CNT), but is not limited thereto.
The boron-based filler may be, for example, boron nitride (Boronnitride), but is not limited thereto.
On the other hand, the second thermally conductive filler may be defined as a metal oxide-based filler having an average particle diameter of 0.1 μm to 20 μm.
When the average particle diameter of the second thermally conductive filler is smaller than the range, thermal conductivity, particularly thickness direction thermal conductivity of the polyimide film, is difficult to achieve a desired degree, and thus it is not preferable.
In contrast, when the average particle diameter of the second thermally conductive filler is larger than the above range, since the dispersibility is reduced when mixing with polyamic acid during the production process, the mechanical properties are reduced and it is difficult to form a film, and appearance defects such as protrusion of the filler from the surface of the film occur even if the film is produced, which is not preferable.
The metal oxide-based filler may be alumina (Al 2O 3), but is not limited thereto.
On the other hand, the dianhydride monomer may include one or more monomers selected from the group consisting of pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), oxydiphthalic anhydride (ODPA), and benzophenonetetracarboxylic dianhydride (BTDA), but is not limited thereto.
Also, the diamine monomer may include one or more monomers selected from the group consisting of 1,4-phenylenediamine (PPD), 4,4 '-Oxydianiline (ODA), 3,4' -oxydianiline, 2,2-bis [4'- (4-aminophenoxy) phenyl ] propane (BAPP), 4,4' -diaminodiphenylmethane (MDA), and 1,3-bis (4-aminophenoxy) benzene (TPE-R), but is not limited thereto.
The invention also provides a preparation method of the polyimide film, wherein the polyimide film is prepared by polymerizing polyamic acid from dianhydride monomer and diamine monomer, mixing the polyamic acid and heat-conducting filler, forming a film on a carrier, and performing heat treatment to perform imidization.
Specifically, the polyamic acid may be prepared by polymerizing a dianhydride monomer and a diamine monomer in an organic solvent.
The organic solvent may be an amide solvent, and specifically, may be an aprotic polar solvent. The organic solvent may be, for example, one or more selected from the group consisting of N, N '-Dimethylformamide (DMF), N' -dimethylacetamide, N-methyl-pyrrolidone (NMP), gamma-butyrolactone (GBL), and Diglyme (Diglyme), but is not limited thereto, and may be used alone or in combination of two or more according to need.
Also, the dianhydride monomer and the diamine monomer may be added in the form of powder (powder), lump (lump) and solution, preferably, in the initial stage of the reaction, in the form of powder to perform the reaction and in the form of solution to adjust the polymerization viscosity.
For example, the dianhydride monomer and the diamine monomer are added in powder form for reaction for a period of time, and then the dianhydride is added in solution form to react the viscosity of the polyamic acid composition to a prescribed range.
On the other hand, the polyamic acid containing the thermally conductive filler may be applied to a support after further adding a catalyst.
In this case, as the catalyst, a dehydration catalyst composed of an anhydrous acid such as acetic anhydride, a tertiary amine such as isoquinoline, β -picoline, pyridine, or the like, and the like can be used, and the catalyst can be used in the form of an anhydrous acid/amine mixture or an anhydrous acid/amine/solvent mixture.
The amount of the anhydrous acid to be added can be calculated from the molar ratio of the o-carboxyamide functional group in the polyamic acid solution, and may be 1.0 mol to 5.0 mol, and the amount of the tertiary amine to be added can be calculated from the molar ratio of the o-carboxyamide functional group in the polyamic acid, specifically, may be 0.2 mol to 3.0 mol.
Next, as a step of heat-treating and gelling the polyamic acid applied to the support, the gelling temperature condition may be 100 to 250 ℃.
As the carrier, a glass plate, an aluminum foil, a circulating stainless steel belt, a stainless steel drum, or the like can be used.
The treatment time required for gelation may be 5 to 30 minutes, but is not limited thereto, and may vary depending on the gelation temperature, the type of support, the coating amount of the polyamic acid solution, and the mixing conditions of the catalyst.
After the gelled film is separated from the support, heat treatment is performed to complete drying and imidization.
The heat treatment temperature may be 100 to 500 deg.c, and the heat treatment time may be 1 to 30 minutes. The gelled film may be fixed on a fixable supporter, for example, a pin-type frame or a clip-type supporter, when being heat-treated, to be heat-treated.
And, when heat treatment is performed by using a drier or the like after fixing to the pin type frame, in order to prevent the film from being cracked in the heat treatment process, the heat treatment may be performed at a temperature of 50 to 150 c lower than the highest heat treatment temperature standard in preparing a yellow polyimide film of the same thickness.
Finally, the imidized film can be made into a thin film by a cooling treatment at a temperature of 20 ℃ to 30 ℃.
The polyimide film produced by the production method may have a thickness direction thermal conductivity of 0.5W/m · K or more, as described above.
The polyimide film has a thermal conductivity in the in-plane direction of 2.0W/mK or more and a light transmittance in the visible light region of 1%.
As described above, the polyimide film of the present invention has excellent thermal conductivity in the plane direction of the polyimide film, and also excellent thermal conductivity in the thickness direction of the polyimide film, and has low light transmittance in the visible light region, and thus can be effectively used for electronic devices including polyimide films.
The present invention will be described in more detail below with reference to specific examples and comparative examples. The following examples are intended to illustrate the present invention more specifically, but the present invention is not limited to the following examples.
Example 1
Preparation examples 1 to 1: polymerization of the first Polyamic acid
As a polyamic acid solution polymerization process, 407.5g of dimethylformamide was added as a solvent in a 0.5L reactor under a nitrogen atmosphere.
After setting the temperature to 25 ℃, 44.27g of ODA was added as diamine monomer and stirred for about 30 minutes, after confirming the monomer dissolution, 46.78g of PMDA was added as dianhydride monomer and added after adjusting the final addition amount so that the final viscosity was 100000 centipoise to 150000 centipoise.
After the addition was completed, 4.625g of graphene having an average particle size of 15 μm was added as a first thermally conductive filler to the solvent, and 9.25g of alumina (Al) having an average particle size of 15 μm was mixed 2 O 3 ) As the second thermally conductive filler, the amic acid solution was polymerized while maintaining the temperature while stirring for 1 hour.
Preparation examples 1 to 2: preparation of polyimide film
To 40g of the polyamic acid solution prepared in the production example 1-1, 0.81g of Isoquinoline (IQ), 7.07g of Acetic Anhydride (AA), and 0.13g of DMF were added as catalysts, uniformly mixed, cast to 50 μm on a stainless steel (SUS) plate (100 SA, a product of Sandvik, sweden) using a doctor blade, and further dried at a temperature ranging from 100 ℃ to 200 ℃.
Then, the film was peeled from the SUS plate and fixed on a pin-type frame, and then transferred to a high-temperature tenter.
After heating the film from 200 ℃ to 600 ℃ on a high-temperature tenter, it was cooled at a temperature of 25 ℃ and then separated from the pin frame, thereby preparing a polyimide film comprising 80 wt% of a base film, 1 wt% of a first thermally conductive filler, and 19 wt% of a second thermally conductive filler, relative to the total weight of the polyimide film.
A Scanning Electron Microscope (SEM) photograph of a cross section of the polyimide film thus prepared is shown in FIG. 1.
Example 2
A polyimide film was produced in the same manner as in example 1, except that 89 wt% of the base film, 1 wt% of the first thermally conductive filler, and 10 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film in example 1.
Example 3
A polyimide film was produced in the same manner as in example 1, except that in example 1, 80 wt% of the base film, 5 wt% of the first thermally conductive filler, and 15 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
A SEM photograph of a cross section of the polyimide film thus prepared is shown in FIG. 2.
Example 4
A polyimide film was prepared in the same manner as in example 1, except that the polyimide film in example 1 was made to include 85 wt% of the base film, 5 wt% of the first thermally conductive filler, and 10 wt% of the second thermally conductive filler, relative to the total weight of the polyimide film.
Example 5
A polyimide film was produced in the same manner as in example 1, except that 80 wt% of the base film, 3 wt% of the first thermally conductive filler, and 17 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film in example 1.
An SEM photograph of a cross section of the polyimide film thus prepared is shown in FIG. 3.
Example 6
A polyimide film was produced in the same manner as in example 1, except that in example 1, alumina having an average particle diameter of 5 μm was used as the second thermally conductive filler instead of alumina having an average particle diameter of 15 μm, and that 80 wt% of the base film, 5 wt% of the first thermally conductive filler, and 15 wt% of the second thermally conductive filler were included, based on the total weight of the polyimide film.
Example 7
A polyimide film was produced in the same manner as in example 1, except that graphene having an average particle size of 10 μm was used as the first thermally conductive filler instead of graphene having an average particle size of 15 μm in example 1, and that 80 wt% of the base film, 5 wt% of the first thermally conductive filler, and 15 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Example 8
A polyimide film was produced in the same manner as in example 1, except that boron nitride having an average particle size of 15 μm was used as the first thermally conductive filler instead of graphene having an average particle size of 15 μm in example 1, and that 80 wt% of the base film, 5 wt% of the first thermally conductive filler, and 15 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Example 9
A polyimide film was prepared in the same manner as in example 1, except that in example 1, the first thermally conductive filler was formed of carbon nanotubes having an average particle diameter of 15 μm instead of graphene having an average particle diameter of 15 μm, and the base film was contained in an amount of 80 wt%, the first thermally conductive filler was contained in an amount of 5 wt%, and the second thermally conductive filler was contained in an amount of 15 wt%, based on the total weight of the polyimide film.
Comparative example 1
A polyimide film was prepared in the same manner as in example 1, except that the thermally conductive filler was not mixed in example 1.
A SEM photograph of a cross section of the polyimide film thus prepared is shown in FIG. 4.
Comparative example 2
A polyimide film was produced in the same manner as in example 1, except that no alumina was added in example 1 so that 85 wt% of the base film and 15 wt% of the first thermally conductive filler were contained, relative to the total weight of the polyimide film.
Comparative example 3
A polyimide film was prepared in the same manner as in example 1, except that graphene was not added in example 1 so that 85 wt% of the base film and 15 wt% of the first thermally conductive filler were included, relative to the total weight of the polyimide film.
Comparative example 4
A polyimide film was produced in the same manner as in example 1, except that in example 1, 85 wt% of the base film, 7.5 wt% of the first thermally conductive filler, and 7.5 wt% of the second thermally conductive filler were included, relative to the total weight of the polyimide film.
A SEM photograph of a cross section of the polyimide film thus prepared is shown in FIG. 5.
Comparative example 5
A polyimide film was produced in the same manner as in example 1, except that graphene having an average particle size of 10 μm was used as the first thermally conductive filler instead of graphene having an average particle size of 15 μm, and alumina having an average particle size of 30 μm was used as the second thermally conductive filler instead of alumina having an average particle size of 15 μm in example 1, and that 85 wt% of the base film, 5 wt% of the first thermally conductive filler, and 10 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Comparative example 6
A polyimide film was produced in the same manner as in example 1, except that graphene having an average particle size of 28 μm was used as the first thermally conductive filler instead of graphene having an average particle size of 15 μm in example 1, and the base film was contained in an amount of 85 wt%, the first thermally conductive filler was contained in an amount of 5 wt%, and the second thermally conductive filler was contained in an amount of 10 wt%, based on the total weight of the polyimide film.
Comparative example 7
A polyimide film was produced in the same manner as in example 1, except that no alumina was added in example 1 so that only 99 wt% of the base film and 1 wt% of the first thermally conductive filler were contained, relative to the total weight of the polyimide film.
Comparative example 8
A polyimide film was prepared in the same manner as in example 1, except that graphene was not added in example 1 so that only 81 wt% of the base film and 19 wt% of the second thermally conductive filler were included, relative to the total weight of the polyimide film.
Comparative example 9
A polyimide film was prepared in the same manner as in example 1, except that alumina having an average particle diameter of 25 μm was used as the second thermally conductive filler in example 1 instead of alumina having an average particle diameter of 15 μm.
Comparative example 10
A polyimide film was prepared in the same manner as in example 1, except that alumina having an average particle diameter of 0.01 μm was used as the second thermally conductive filler instead of alumina having an average particle diameter of 15 μm in example 1.
Comparative example 11
A polyimide film was prepared in the same manner as in example 1, except that graphene having an average particle size of 25 μm was used as the first thermally conductive filler instead of graphene having an average particle size of 15 μm in example 1.
Comparative example 12
A polyimide film was produced in the same manner as in example 1, except that in example 1, 98.9 wt% of the base film, 1 wt% of the first thermally conductive filler, and 0.1 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Comparative example 13
A polyimide film was prepared in the same manner as in example 1, except that 80.999 wt% of the base film, 0.001 wt% of the first thermally conductive filler, and 19 wt% of the second thermally conductive filler were contained, relative to the total weight of the polyimide film, in example 1.
Comparative example 14
A polyimide film was prepared in the same manner as in example 1, except that silicon nitride having an average particle diameter of 15 μm was used as the first thermally conductive filler instead of graphene in example 1.
Comparative example 15
A polyimide film was prepared in the same manner as in example 1, except that carbon black (carbon black) having an average particle diameter of 15 μm was used as the second thermally conductive filler instead of alumina in example 1.
Reference example 1
It was evaluated whether or not a film can be produced in the same manner as in example 1 except that in example 1, 70 wt% of the base film, 15 wt% of the first thermally conductive filler, and 15 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Reference example 2
It was evaluated whether or not a film can be produced in the same manner as in example 1 except that in example 1, 74 wt% of the base film, 1 wt% of the first thermally conductive filler, and 25 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Reference example 3
It was evaluated whether or not a film can be produced in the same manner as in example 1 except that in example 1, 71 wt% of the base film, 10 wt% of the first thermally conductive filler, and 19 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Reference example 4
It was evaluated whether or not a film can be produced in the same manner as in example 1 except that in example 1, 60 wt% of the base film, 20 wt% of the first thermally conductive filler, and 20 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Reference example 5
It was evaluated whether or not a film can be produced in the same manner as in example 1 except that in example 1, 50 wt% of the base film, 25 wt% of the first thermally conductive filler, and 25 wt% of the second thermally conductive filler were included with respect to the total weight of the polyimide film.
Experimental example 1: evaluation of thermal conductivity
The thermal diffusivities in the thickness direction and the plane direction of the polyimide films were measured by a laser flash photolysis (laser flash) method using a thermal diffusivity measuring apparatus (model: LFA447, manufactured by Netsch corporation) with respect to the polyimide films prepared in examples 1 to 9 and comparative examples 1 to 15, respectively, and the thermal diffusivities were calculated by multiplying the measured values of the thermal diffusivities by the density (weight/volume) and the specific heat (measured value of the specific heat using Differential Scanning Calorimetry (DSC)) to calculate the thermal conductivities, and the results are shown in table 1.
TABLE 1
* In the case of example 8, boron nitride was added as the first thermally conductive filler.
* In the case of example 9, carbon nanotubes were added as the first thermally conductive filler.
* In the case of comparative example 14, silicon nitride was added as the first thermally conductive filler.
* In the case of comparative example 15, carbon black (carbon black) was added as the second thermally conductive filler.
Referring to table 1, it can be confirmed that the polyimide films of examples 1 to 7 include the first thermally conductive filler having an average particle diameter of 0.001 to 20 μm and the second thermally conductive filler having an average particle diameter of 0.1 to 20 μm, so that the polyimide film has a thickness direction thermal conductivity of 0.5W/m · K or more and an in-plane direction thermal conductivity of 2.0W/m · K or more.
In contrast, the polyimide films of comparative examples 1, 2, 3, 7, and 8, which did not contain the first and second thermally conductive fillers or contained the first and second thermally conductive fillers alone, were confirmed to have significantly lower thermal conductivities, particularly thickness direction thermal conductivities, than those of examples 1 to 7.
In addition, it was confirmed that the thermal conductivity, particularly the thickness direction thermal conductivity, of the polyimide films of comparative examples 4, 6, and 9 to 13 in which the particle diameters or the contents of the first and second thermally conductive fillers are larger than the range of the present invention is significantly lower than those of examples 1 to 7.
On the other hand, in example 8 and comparative example 9, it was confirmed that the thickness direction thermal conductivity and the plane direction thermal conductivity of the desired degree can be achieved even when Boron nitride (Boron nitride) and carbon nanotubes are used as the first thermal conductive filler in addition to graphene.
In contrast, in comparative examples 14 and 15, silicon nitride was used as the first thermally conductive filler instead of the carbon-based filler or the boron-based filler, and carbon black (carbon black) was used as the second thermally conductive filler instead of the metal oxide-based filler, and the thickness direction thermal conductivity and the plane direction thermal conductivity were not achieved to a desired degree.
Experimental example 2: evaluation of light transmittance
Light transmittance was measured in the visible light region by the American society for testing and materials Standard ASTM D1003 method using a transmittance measuring apparatus (model: colorQuesetXE, manufacturer: hunter Lab., USA) with respect to the polyimide films prepared in examples 1 to 9 and comparative examples 1 to 15, respectively, and the results thereof are shown in Table 2 below.
TABLE 2
* In the case of example 8, boron nitride was added as the first thermally conductive filler.
* In the case of example 9, carbon nanotubes were added as the first thermally conductive filler.
* In the case of comparative example 14, silicon nitride was added as the first thermally conductive filler.
* In the case of comparative example 15, carbon black (carbon black) was added as the second thermally conductive filler.
Referring to table 2, it was confirmed that the polyimide films of examples 1 to 9 had a light transmittance of 1% or less, and that comparative examples 1,3, 7 to 10 and comparative examples 12 to 14 did not contain a thermally conductive filler or contained a first thermally conductive filler less than the content, and had a light transmittance of more than 1%, and thus had a reduced shielding property.
Experimental example 3: evaluation of film Forming Property
Whether or not a polyimide film can be prepared in the same manner as in example 1 was evaluated as described in reference examples 1 to 5, and the results thereof are shown in table 3 below.
TABLE 3
Referring to table 3, with reference to reference examples 1 to 5, the film contained an excessive amount of the thermally conductive filler, and in the process of curing to prepare the film, the film was damaged due to the decrease in physical properties of the film, and it was confirmed that the polyimide film could not be finally prepared.
Although the invention has been described in detail with reference to the embodiments thereof, those skilled in the art can make various applications and modifications within the scope of the invention based on the above description.
Industrial availability
As described above, the polyimide film according to the present invention includes the thermally conductive filler and the base film such that the thermally conductive filler includes the carbon-based or boron-based filler having the average particle diameter of 0.001 μm to 20 μm and the metal oxide-based filler having the average particle diameter of 0.1 μm to 20 μm, thereby providing the polyimide film in which the in-plane direction thermal conductivity and the thickness direction thermal conductivity are improved.
Claims (11)
1. A polyimide film comprising a thermally conductive filler and a base film,
the thermally conductive filler contains a first thermally conductive filler having an average particle diameter of 0.001 to 20 [ mu ] m and a second thermally conductive filler having an average particle diameter of 0.1 to 20 [ mu ] m,
the thermally conductive filler is contained in an amount of 5 to 20 wt% with respect to the total weight of the polyimide film,
the base film is contained in an amount of 80 to 95 wt% with respect to the total weight of the polyimide film,
the first thermally conductive filler is contained in an amount of 0.1 to 5 wt% with respect to the total weight of the polyimide film,
the second thermally conductive filler is contained in an amount of 1 to 19 wt% with respect to the total weight of the polyimide film,
the first thermally conductive filler is a carbon-based filler or a boron-based filler,
the second thermally conductive filler is a metal oxide-based filler,
the base film is prepared by imidizing a polyamic acid formed by a reaction of a dianhydride monomer and a diamine monomer,
the polyimide film has a thermal conductivity in the thickness direction of 0.5W/mK or more and a thermal conductivity in the in-plane direction of 2.0W/mK or more.
2. The polyimide film according to claim 1, wherein the dianhydride monomer comprises one or more monomers selected from the group consisting of pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, oxydiphthalic anhydride, and benzophenonetetracarboxylic dianhydride.
3. The polyimide film of claim 1 wherein the diamine monomer comprises one or more monomers selected from the group consisting of 1,4-phenylenediamine, 4,4 '-oxydianiline, 3,4' -oxydianiline, 2,2-bis [4'- (4-aminophenoxy) phenyl ] propane, 4,4' -diaminodiphenylmethane, and 1,3-bis (4-aminophenoxy) benzene.
4. The polyimide film according to claim 1, wherein the carbon-based filler is multi-layer graphene and/or carbon nanotubes.
5. The polyimide film according to claim 1, wherein the boron-based filler is boron nitride.
6. The polyimide film according to claim 1, wherein the metal oxide-based filler is alumina.
7. The polyimide film according to claim 1, wherein a content W of the first thermally conductive filler in the first thermally conductive filler and the second thermally conductive filler is 1 And the content W of the second thermally conductive filler 2 Satisfies the relation of (2W) 1 ≤W 2 。
8. The polyimide film according to claim 1, wherein a content of the second thermally conductive filler is 200 to 1900% on a weight basis with respect to a content of the first thermally conductive filler.
9. The polyimide film according to claim 1, wherein the polyimide film has a light transmittance of 1% or less in a visible light region.
10. The method for producing a polyimide film according to claim 1,
polymerizing polyamic acid from dianhydride monomer and diamine monomer,
the polyamic acid and the thermally conductive filler are mixed,
and forming a film of the mixture of the polyamic acid and the thermally conductive filler on a support, and performing heat treatment to perform imidization.
11. An electronic device comprising the polyimide film according to claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2018-0007836 | 2018-01-22 | ||
| KR1020180007836A KR102069709B1 (en) | 2018-01-22 | 2018-01-22 | High Thermal Conductive Polyimide Film Comprising At Least Two Kinds of Fillers |
| PCT/KR2018/011401 WO2019143000A1 (en) | 2018-01-22 | 2018-09-27 | Highly thermally conductive polyimide film comprising two or more types of fillers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111630088A CN111630088A (en) | 2020-09-04 |
| CN111630088B true CN111630088B (en) | 2023-02-17 |
Family
ID=67302249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880087103.2A Active CN111630088B (en) | 2018-01-22 | 2018-09-27 | Highly thermally conductive polyimide film containing two or more fillers |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7003276B2 (en) |
| KR (1) | KR102069709B1 (en) |
| CN (1) | CN111630088B (en) |
| WO (1) | WO2019143000A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230174837A1 (en) * | 2020-03-30 | 2023-06-08 | Toyobo Co., Ltd. | Thermally conductive resin composition and molded article comprising same |
| KR20220160166A (en) | 2021-05-26 | 2022-12-06 | 주식회사 테라하임 | A heat-transfer composition with excellent heat-transferring property |
| CN114316328B (en) * | 2022-01-19 | 2023-01-24 | 东莞市鸿亿导热材料有限公司 | High-thermal-conductivity insulating radiating fin for new energy battery and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004123867A (en) * | 2002-10-01 | 2004-04-22 | Kanegafuchi Chem Ind Co Ltd | Polyimide resin composition, polyimide film, and polyimide tube |
| CN101960929A (en) * | 2008-03-06 | 2011-01-26 | 新日铁化学株式会社 | Laminate for flexible board and heat conductive polyimide film |
| CN102149542A (en) * | 2008-09-08 | 2011-08-10 | 新日铁化学株式会社 | Highly heat conductive polyimide film, highly heat conductive metal-clad laminate and method for producing same |
| JP2011211190A (en) * | 2010-03-10 | 2011-10-20 | Nippon Steel Chem Co Ltd | Laminated structure, and method for manufacturing the same |
| CN106062049A (en) * | 2013-12-18 | 2016-10-26 | 韩国爱思开希可隆Pi股份有限公司 | Polyimide film and manufacturing method therefor |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4337991B2 (en) * | 1997-12-22 | 2009-09-30 | 日東電工株式会社 | Thermally conductive pressure-sensitive adhesive sheets and methods of fixing electronic components and heat radiating members using the same |
| JP2003321554A (en) | 2002-04-26 | 2003-11-14 | Polymatech Co Ltd | Heat-conductive molding and method for producing the same |
| KR101268185B1 (en) * | 2008-08-22 | 2013-05-27 | 코오롱인더스트리 주식회사 | polyimide resin and film |
| JP5646823B2 (en) * | 2009-05-27 | 2014-12-24 | 株式会社カネカ | High thermal conductivity polyimide film |
| JP6069112B2 (en) | 2013-06-19 | 2017-02-01 | デクセリアルズ株式会社 | Thermally conductive sheet and method for producing the thermally conductive sheet |
| JP2015076356A (en) | 2013-10-11 | 2015-04-20 | ユニチカ株式会社 | Heat radiation structure and manufacturing method of the same |
| JP6126524B2 (en) | 2013-12-16 | 2017-05-10 | 旭化成株式会社 | Organic-inorganic composite composition, molded body and sheet |
| CN107257837A (en) | 2015-02-26 | 2017-10-17 | 帝斯曼知识产权资产管理有限公司 | High heat transport apparatus |
-
2018
- 2018-01-22 KR KR1020180007836A patent/KR102069709B1/en active IP Right Grant
- 2018-09-27 JP JP2020537735A patent/JP7003276B2/en active Active
- 2018-09-27 WO PCT/KR2018/011401 patent/WO2019143000A1/en active Application Filing
- 2018-09-27 CN CN201880087103.2A patent/CN111630088B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004123867A (en) * | 2002-10-01 | 2004-04-22 | Kanegafuchi Chem Ind Co Ltd | Polyimide resin composition, polyimide film, and polyimide tube |
| CN101960929A (en) * | 2008-03-06 | 2011-01-26 | 新日铁化学株式会社 | Laminate for flexible board and heat conductive polyimide film |
| CN102149542A (en) * | 2008-09-08 | 2011-08-10 | 新日铁化学株式会社 | Highly heat conductive polyimide film, highly heat conductive metal-clad laminate and method for producing same |
| JP2011211190A (en) * | 2010-03-10 | 2011-10-20 | Nippon Steel Chem Co Ltd | Laminated structure, and method for manufacturing the same |
| CN106062049A (en) * | 2013-12-18 | 2016-10-26 | 韩国爱思开希可隆Pi股份有限公司 | Polyimide film and manufacturing method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111630088A (en) | 2020-09-04 |
| JP7003276B2 (en) | 2022-01-20 |
| JP2021510388A (en) | 2021-04-22 |
| KR20190089397A (en) | 2019-07-31 |
| KR102069709B1 (en) | 2020-01-23 |
| WO2019143000A1 (en) | 2019-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2867276B1 (en) | Polyimide and polyimide film comprising the same | |
| KR20190067600A (en) | Polyimide Film Having Low Dielectric Constant And High Thermal Conductivity | |
| CN101168598B (en) | Method for preparing ultra-thick polyimide film with high heat conductivity and low thermal expansion coefficient | |
| CN111278898B (en) | Ultrathin black polyimide film and preparation method thereof | |
| KR101227317B1 (en) | Polyimide film with improved thermal stability | |
| CN111630088B (en) | Highly thermally conductive polyimide film containing two or more fillers | |
| JP2016017169A (en) | Graphite sheet polyimide film and production method thereof | |
| JP2010065064A (en) | Thermally conductive material, thermally conductive sheet, inter-laminar insulation film, and manufacturing method thereof | |
| Zhang et al. | Molecular design, synthesis and characterization of intrinsically black polyimide films with high thermal stability and good electrical properties | |
| JP2013189568A (en) | Highly thermally conductive polyimide film containing graphite powder | |
| Hamciuc et al. | Thermal and electrical behaviour of some hybrid polyimide films containing barium and titanium oxides | |
| JP6763115B2 (en) | Ultra-thin black polyimide film and its manufacturing method (ULTRA THIN BLACK POLYIMIDE FILM AND METHOD FOR PREPARING THE SAME) | |
| CN112585198B (en) | Polyimide film containing crystalline polyimide resin and thermally conductive filler, and method for producing same | |
| JPH0733875A (en) | Highly crystalline polyimide powder and its production | |
| CN116063676A (en) | Polyimide film | |
| CN113501984B (en) | Graphene in-situ modified polyimide film and preparation method thereof | |
| CN112689656A (en) | Method for producing polyamideimide film and polyamideimide film produced thereby | |
| KR102136679B1 (en) | Thermal Conductive film inculding carbon nanotube | |
| CN113166454B (en) | Polyimide film with improved thermal conductivity and method for preparing same | |
| TWI545013B (en) | Polyimide metal laminate and a method of fabricating the same | |
| TW201821490A (en) | Method for manufacturing polyimide film and polyimide film | |
| KR101240955B1 (en) | Polyimide film having excellent high temperature stability and substrate for display device using the same | |
| KR101258432B1 (en) | Polyimide film having excellent high temperature stability and substrate for display device using the same | |
| KR102644735B1 (en) | Aqueous polyamic acid composition | |
| KR102644736B1 (en) | Aqueous polyamic acid composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: North Chungcheong Province Applicant after: Polyimide Advanced Materials Co.,Ltd. Address before: North Chungcheong Province Applicant before: SKCKOLON PI Inc. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |