CN107108926B - Method for producing polyimide film using porous particles and low dielectric constant polyimide film - Google Patents
Method for producing polyimide film using porous particles and low dielectric constant polyimide film Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08G73/1003—Preparatory processes
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
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Abstract
The present invention relates to a method for producing a polyimide film using particles having pores, and a low dielectric constant polyimide film produced by the method, wherein the polyimide film according to the present invention contains particles having an average particle diameter of 10 μm or less and pores having a particle density of 95% or less relative to the particle density of the particle-specific substance, and thus can exhibit a dielectric constant lower than that of a conventional polyimide film, and thus can be effectively used for production of electric/electronic devices and components such as printed wiring boards requiring a low dielectric constant.
Description
Technical Field
The present invention relates to a method for preparing a polyimide film using particles having pores, and a low dielectric constant polyimide film prepared according to the above method.
Background
Generally, a Polyimide (PI) resin is a high temperature resistant resin prepared by polymerizing an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, then subjecting the polyamic acid derivative to a ring-closing dehydration process under high temperature conditions, and then performing imidization.
Polyimide resins are insoluble and infusible, and have excellent properties such as thermal oxidation resistance, heat resistance, radiation resistance, low-temperature properties, and chemical resistance, and are widely used in the fields of heat-resistant materials such as automobile materials, aircraft materials, and spacecraft materials, and electronic materials such as insulating coating agents, insulating films, semiconductors, and electrode protective films for thin film transistor-liquid crystal displays (TFT-LCDs).
Recently, in electronic devices that accumulate a large amount of information corresponding to a highly information-oriented society to process the information at a high speed and transmit the information at a high speed, polyimide resins used for the above devices are also required to have high performance, and in particular, low dielectric constant and low dielectric constant are required as electrical characteristics corresponding to high frequency.
In order to realize a low dielectric constant of a polyimide resin, for example, japanese laid-open patent publication No. 2000-44719 discloses a method in which a hydrophilic polymer is dispersed in a precursor of a polyimide resin soluble in an organic solvent, and then the hydrophilic polymer is removed by plastic working or solvent extraction to perform a porous treatment, thereby obtaining a porous polyimide resin. However, in the case where the porous treatment is performed by removing the hydrophilic polymer as described above, it is preferable that the pores are formed while the shape of the fine separation structure of the hydrophilic polymer dispersed in the polyimide resin precursor is maintained, but if the hydrophilic polymer is removed by plastic working or solvent extraction as it is and then the imidization treatment is performed, the porosity is lowered to a desired value due to flattening or clogging of the pores, and the dielectric constant cannot be sufficiently lowered.
Korean patent No. 1299652 discloses a structure in which fluorine particles are used when a flexible metal laminate is manufactured, but this method is applicable to a single molecule of fluorine particles and has a disadvantage in that the fluorine particles are not easily dispersed.
Thus, the present inventors have developed a method for producing a polyimide film, in which the particles having pores exhibit electrical properties of air, and a dielectric constant lower than that of a conventional polyimide film, and the dispersion phenomenon and precipitation phenomenon of the particles having pores are improved in the production process, and have completed the present invention.
Disclosure of Invention
Technical problem
Accordingly, an object of the present invention is to provide a method for preparing a polyimide film using particles having pores and a low dielectric constant polyimide film prepared according to the above method.
Technical scheme
In order to achieve the above object, the present invention provides a method for producing a polyimide film, comprising:
step 1), preparing a polyimide precursor;
step 2) mixing the polyimide precursor and an imidization conversion solution containing particles having pores to prepare a gel film; and the number of the first and second groups,
step 3) of performing imidization treatment by heat-treating the gel film,
the particles having pores have an average particle diameter of 10 μm or less and a particle density of 95% or less with respect to a particle density (particle density) of a substance inherent to the particles having pores.
In order to achieve the above-described another object, the present invention provides a polyimide film containing particles having pores, wherein the average particle diameter of the particles having pores is 10 μm or less, and the particle density of the particles is 95% or less relative to the particle density of a substance specific to the particles having pores.
Advantageous effects
According to the present invention, a polyimide film having a minimum dielectric constant can be produced by using particles having pores, and thus the polyimide film can be used for internal insulators, buffer materials, circuit boards, and the like of electronic devices and the like.
Drawings
Fig. 1 is a picture of a Scanning Electron Microscope (SEM) showing a cross section of the polyimide film of the present invention.
Fig. 2 is a photograph showing a scanning electron microscope showing a state in which particles having pores are dispersed on the surface of the polyimide film of the present invention. Fig. 3 is a photograph showing a scanning electron microscope showing a particle state in which particles having pores are dispersed in a part of the surface of the polyimide film of the present invention.
Detailed Description
The invention provides a preparation method of a polyimide film, which is characterized by comprising the following steps: step 1) for preparing a polyimide precursor; step 2) mixing the polyimide precursor and an imidization conversion solution containing particles having pores to prepare a gel film; and a step 3) of subjecting the gel film to a heat treatment to perform imidization, wherein the average particle diameter of the particles having pores is 10 μm or less, and the particle density of the particles having pores is 95% or less of the particle density of the material specific to the particles having pores.
The method for preparing a polyimide film of the present invention includes the step of preparing a polyimide precursor.
As the polyimide precursor used in the present invention, any substance can be used as long as it can satisfy the conditions for preparing a polyimide resin by imidization treatment. For example, the polyamic acid can be obtained by copolymerizing an acid dianhydride component and a diamine component by a usual method under the condition of an organic solvent.
The acid dianhydride component and the diamine component may be each appropriately selected from those generally used for producing polyamic acid.
Examples of the acid dianhydride component include biphenyltetracarboxylic dianhydride or a derivative thereof, Pyromellitic dianhydride (PMDA), 3 ', 4' -benzophenone tetracarboxylic anhydride, and p-phenylene-bistrimellitic dianhydride, but the present invention is not limited thereto.
Examples of the diamine component include p-Phenylenediamine (pPDA), diaminophenyl ether, o-Phenylenediamine, m-Phenylenediamine, 4 ' -diaminodiphenyl ether (ODA), 3, 4 ' -diaminodiphenyl ether, and 2, 4 ' -diaminodiphenyl ether, but the present invention is not limited thereto.
The acid dianhydride component and the diamine component may be present in a ratio of 1: 0.9 to 1: 1.1 in a molar ratio.
Examples of the organic solvent include N, N '-Dimethylformamide (DMF), N' -Dimethylacetamide (DMAc), and N-methyl-pyrrolidone (NMP), but the present invention is not limited thereto.
The method for producing a polyimide film of the present invention includes a step of mixing the polyimide precursor and an imidization conversion solution containing particles having pores to produce a gel film.
First, an imidization resin is prepared by uniformly mixing an imidization conversion liquid with the polyimide precursor, that is, a polyamic acid, and uniformly dispersing and mixing particles having pores therein.
In the case of a substance generally used for chemical curing, any substance can be used as the above-mentioned imidization conversion solution. The imidization conversion liquid may be selected from the group consisting of, for example, a dehydrating agent, a catalyst, a polar organic solvent, and a mixture thereof, and preferably may be a mixed solution of a dehydrating agent, a catalyst, and a polar organic solvent.
More specifically, the imidization conversion solution may be a mixed solvent containing: a dehydrating agent such as acetic anhydride; a catalyst selected from tertiary amines of the group consisting of pyridine, beta-picoline, isoquinoline, and mixtures thereof; and a polar organic solvent selected from the group consisting of N-methylpyrrolidone, dimethylformamide, dimethylacetamide and mixtures thereof.
The above-mentioned imidization conversion solution may be used in an amount of 30 parts by weight to 70 parts by weight, preferably 40 parts by weight to 55 parts by weight, based on 100 parts by weight of the polyimide precursor, and may be varied depending on the kind of the polyimide precursor, the thickness of the polyimide film to be produced, and the like.
The average particle diameter of the particles having pores is 10 μm or less, and preferably, may be 1 to 10 μm, 1 to 7 μm, or 2 to 5 μm.
The particles having pores may have a particle density of 95% or less, preferably 30% to 95%, more preferably 50% to 90%, relative to the particle density of the material specific to the particles excluding the pores.
In the present invention, "particle density" refers to the weight per unit volume of the particle and to the density of the particle itself, and "particle-specific substance" refers to a substance having no pores in the particle.
The porous particles may be contained in an amount of 2 to 30 wt%, preferably 5 to 20 wt%, for example, 5 to 10 wt%, based on the total weight of the film. When the content of the particles having pores is 30% by weight or less, the mechanical properties of the polyimide film are not deteriorated, and when the content of the particles having pores is 2% by weight or more, the effect of low dielectric constant of the polyimide film can be exhibited.
The particles having pores may be hollow particles or mesoporous (mesoporus) particles selected from the group consisting of silica, alumina, titania, zeolite, and a mixture thereof, and preferably may be hollow silica, as the particles having pores.
The particles having pores may be charged, and preferably, the particles are dispersed and mixed more uniformly in the imide resin, and thus, the particles may be charged in a dispersion state or a colloidal state dispersed in the polar organic solvent.
Next, after uniformly mixing the imidization conversion liquid with the polyamic acid and uniformly dispersing and mixing the above-mentioned particles having pores therein, the imidization resin may be prepared into a gel film.
Specifically, the above-mentioned imidized resin is applied to a support (for example, a stainless steel plate, a glass plate, an aluminum foil, a circulating stainless steel belt, a stainless steel tub, or the like), and then subjected to a first heat treatment and drying, thereby preparing a gel film which is partially chemically imidized.
The above-mentioned first heat treatment process in which a part of the above-mentioned chemical imidization treatment is performed may be performed at a temperature of 100 to 200 c for a time of 5 to 15 minutes.
The method for preparing a polyimide film according to the present invention includes a step of performing imidization treatment by heat-treating the above gel film.
The gel film chemically partially imidized as prepared above may be subjected to a second heat treatment after being separated from the support in order to perform a complete imidization treatment.
The second heat treatment process for performing the complete imidization treatment as described above may be performed at a temperature of 250 to 850 c for a time of 5 to 25 minutes. When the second heat treatment is performed, it is preferable to perform the heat treatment under a certain tension so as to be able to remove residual stress inside the film generated during the film formation.
According to one embodiment of the present invention, there is provided a method for producing a polyimide film, including: a step of preparing a polyamic acid as a polyimide precursor; a step of mixing the polyamic acid and an imidization conversion solution in which particles having pores are uniformly dispersed to prepare an imidization resin; a step of applying the imidized resin to a support, and then performing a first heat treatment and drying to prepare a gel film; and a step of preparing a polyimide film by subjecting the gel film to a second heat treatment, wherein the average particle diameter of the particles having pores is 10 μm or less, and the particle density of the particles having pores is 95% or less of the particle density of the material specific to the particles having pores.
On the other hand, the present invention provides a polyimide film containing particles having pores, wherein the average particle diameter of the particles having pores is 10 μm or less, and the particle density of the particles having pores is 95% or less of the particle density of the particles inherent in the particles having pores.
Specifically, the polyimide film containing the particles having pores may be obtained from a polyimide resin synthesized from a conversion solution of an imidization reaction including a polyamic acid and the particles having pores, and the average particle diameter of the particles having pores may be 10 μm or less, and the polyimide film may have a particle density of 95% or less relative to the particle density of the material specific to the particles having pores.
The thickness of the polyimide film of the present invention is in a thin state of 5 μm to 200 μm.
The polyimide film of the present invention has a dielectric constant of 3.0 or less at 1GHz, preferably a low dielectric constant in the range of 2.0 to 2.9, and an induced dielectric tangent of less than 0.002, preferably in the range of 0.0005 to 0.001, and thus can be effectively used for internal insulators, buffer materials, circuit boards, and the like of electronic devices and the like.
Detailed description of the preferred embodiments
The present invention will be described in more detail below with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
[ PREPARATION EXAMPLES ]
Preparation example 1: preparation of polyamic acid solution
After 320g of Dimethylformamide (DMF) was charged into a 0.5L reactor, the temperature was set at 20 ℃, 27.59g of diaminodiphenyl ether (ODA) was charged and dissolved, and Pyromellitic dianhydride (PMDA) was charged in two portions in 20.03g units and dissolved. After completion of the dissolution, 3.97g of p-phenylenediamine was charged therein and reacted for 30 minutes, and then the molecular weight was measured using the solution as a sample. After the reaction was completed, the temperature of the reactor was raised to 30 ℃, and then 1.00g of p-phenylenediamine was charged to adjust the molar ratio of diamine/acid dianhydride to 1: 1. after the completion of charging of the raw materials, the reaction was carried out at 40 ℃ for 2 hours, and then a polyamic acid solution was obtained.
Preparation example 2: preparation of an imidization conversion solution to which particles having air holes were added (1)
To a mixed solution of 2.8g of β -picoline (boiling point: 144 ℃ C.) as a curing catalyst for the imide-conversion solution, 21.2g of acetic anhydride as a dehydrating agent, and 13.4g of dimethylformamide as a polar organic solvent, 13.4g of a dispersion of Hollow silica (Hollow silica) (a dimethylformamide mixed solution containing 6% of solid content of Hollow silica (Korea Baishan Steel VHSN-1000, having an average particle diameter of 3 μm and an average pore diameter of 200nm) was added and stirred, thereby obtaining 50.8g of the imide-conversion solution to which particles having pores were added.
Preparation example 3: preparation of Imidization conversion solution to which particles having air holes were added (2)
26.7g of a dispersion of hollow silica (a dimethylformamide mixed solution containing 6% of solid content of hollow silica (Korea Baishan Steel VHSN-1000, average particle diameter of particles of 6 μm, and average pores of particles of 200 nm)) was added to a mixed solution of 2.8g of beta-picoline (having a boiling point of 144 ℃ C.) as a curing catalyst for an imidization conversion liquid, 21.2g of acetic anhydride as a dehydrating agent, and 0.9g of dimethylformamide as a polar organic solvent, and stirred, thereby obtaining 51.6g of an imidization conversion liquid to which particles having pores were added.
Preparation example 4: preparation of Imidization conversion solution to which pore-free silica particles were added (1)
To a mixed solution of 2.8g of β -picoline (having a boiling point of 144 ℃ C.) as a curing catalyst for the imide-conversion solution, 21.2g of acetic anhydride as a dehydrating agent, and 13.4g of dimethylformamide as a polar organic solvent, 13.3g of a dispersion liquid of spherical silica (a dimethylformamide mixed solution containing 6% of spherical silica (Japanese catalyst KEP-250, having an average particle diameter of 3 μm and having no pores) as a solid component) was added and stirred, thereby obtaining 50.8g of the imide-conversion solution to which spherical silica particles were added.
Preparation example 5: preparation of Imidization conversion solution to which pore-free silica particles were added (2)
26.7g of a spherical silica dispersion (a dimethylformamide mixed solution containing 6% of spherical silica (Japanese catalyst KEP-250, particle having an average particle diameter of 3 μm and no pores) as a solid content was added to a mixed solution of 2.8g of beta-picoline (having a boiling point of 144 ℃ C.) as a curing catalyst for an imidization conversion solution, 21.2g of acetic anhydride as a dehydrating agent, and 0.9g of dimethylformamide as a polar organic solvent, followed by stirring, whereby 51.6g of an imidization conversion solution to which spherical silica particles were added was obtained.
Preparation example 6: preparation of Imidization conversion solution to which pore-free fluorine particles were added
A dispersion of Polytetrafluoroethylene (PTFE, Polytetrafluoroethylene) (a dimethylformamide mixed solution containing 6% of fluorine particles (having an average particle diameter of 22 μm and no pores)) in an amount of 26.7g was added to a mixed solution of 2.8g of isoquinoline (having a boiling point of 242 ℃ C.) as a curing catalyst for an imidization conversion solution, 21.2g of acetic anhydride as a dehydrating agent, and 0.9g of dimethylformamide as a polar organic solvent, and then stirred to obtain 51.6g of an imidization conversion solution to which fluorine particles were added.
Preparation example 7: preparation of imidization conversion solution without addition of particles
After 3.3g of beta-picoline (having a boiling point of 144 ℃ C.) as a curing catalyst for the imidization conversion liquid, 21.5g of acetic anhydride as a dehydrating agent, and 25.2g of dimethylformamide as a polar organic solvent were mixed and stirred, 50g of the imidization conversion liquid was obtained.
[ examples ] A method for producing a compound
Example 1: preparation of polyimide film suitable for particles having air holes (1)
50.8g of the imidization conversion liquid obtained in production example 2 was mixed with 100g of the polyamic acid solution obtained in production example 1, and then applied to a stainless steel plate, and dried in an oven at a temperature of 120 ℃ for 3 minutes by hot air, to prepare a gel film.
After removing the gel film prepared by such a method from a stainless steel plate, fixing with a frame pin, followed by removing the film after heat treatment at a temperature of 450 ℃ for 7 minutes to the gel film-fixed frame, a polyimide film having an average thickness of 25 μm was obtained.
A scanning electron microscope picture of a cross section of the polyimide film prepared by such a method is shown in fig. 1.
Example 2: preparation of polyimide film suitable for particles having air holes (2)
The same procedure as in example 1 was carried out except that 51.6g of the imidization conversion liquid obtained in production example 3 was used instead of the imidization conversion liquid obtained in production example 2 to obtain a polyimide film having an average thickness of 25 μm.
Comparative example 1: preparation of polyimide film suitable for pore-free particles (1)
The same procedure as in example 1 was carried out except that 50.8g of the imidization conversion liquid obtained in production example 4 was used instead of the imidization conversion liquid obtained in production example 2 to obtain a polyimide film having an average thickness of 25 μm.
Comparative example 2: preparation of polyimide film suitable for pore-free particles (2)
The same procedure as in example 1 was carried out except that 51.6g of the imidization conversion liquid obtained in production example 5 was used instead of the imidization conversion liquid obtained in production example 2 to obtain a polyimide film having an average thickness of 25 μm.
Comparative example 3: preparation of polyimide film suitable for pore-free fluorine particles
The same procedure as in example 1 was carried out except that 51.6g of the imidization conversion liquid obtained in production example 6 was used instead of the imidization conversion liquid obtained in production example 2 to obtain a polyimide film having an average thickness of 25 μm.
Comparative example 4: preparation of particle-free polyimide film
The same procedure as in example 1 was carried out except that 50.0g of the imidization conversion liquid obtained in production example 7 was used instead of the imidization conversion liquid obtained in production example 2 to obtain a polyimide film having an average thickness of 25 μm.
Test example 1: determination of the Density ratio
In the present invention, the particle densities of the particles (a) added when the polyimide film was prepared and the intrinsic substance (B) of the particles thereof were measured based on the specification (KSM 6020:2010), respectively. In this case, natural silica which is a material unique to the hollow silica used in examples 1 and 2 and the spherical silica used in comparative examples 1 and 2 was measured by using a catalyst (model name: EP-250) purchased from Japan.
Next, the particle density ratio (%) of the particles having pores with respect to the inherent substances of the particles was calculated by the following calculation formula 1, and the results are shown in table 1 below.
[ calculation formula 1]
Test example 2: measurement of average particle diameter of particles having pores
The average Particle Size of the particles having pores used in the present invention was measured by a Laser Diffraction Particle Size Analyzer (model name of SALD-2201, shi madzu corporation), and the average Particle Size values of the particles having pores are shown in table 1 below.
Test example 3: determination of the particle content of the film
The particle contents of the polyimide films prepared in examples 1 and 2 and comparative examples 1 to 4 were measured by an ASH content (ASH) method. The ash method is carried out by measuring the content by measuring the residual amount remaining in the crucible after burning at 900 ℃ for 3 hours after placing the film in the crucible. The measured particle contents (in weight%) are shown in table 1 below.
Test example 4: confirmation of distribution state in average film of particles having pores
The distribution state of the particles having the pores in the polyimide film according to example 1 of the present invention was observed using a field emission scanning electron microscope (FE-SEM, field emission scanning electron microscope) (JEOL, model name JSM-6700F), and a picture on the scanning electron microscope was shown.
Fig. 1 shows a scanning electron microscope photograph of a cross section of a polyimide film of example 1 of the present invention.
Fig. 2 shows a state in which particles having pores are dispersed on the surface of the film, and fig. 3 shows an enlarged view of a state in which particles having pores are dispersed on the surface of the film, showing a particle state.
As shown in fig. 2, it was confirmed that the particles having pores used in the polyimide film of the present invention were uniformly distributed throughout the film, and a good dispersion state was exhibited.
Test example 5: determination of dielectric constant and dielectric Positive connection
The dielectric constant and the dielectric positive contact at 1GHz of the polyimide films prepared in examples 1 and 2 and comparative examples 1 to 4 were measured by an SPDR measuring instrument of agilent (Keysight). The measured dielectric constant and dielectric positive values are shown in table 1.
[ Table 1]
As shown in table 1 above, the polyimide films of examples 1 and 2 containing hollow silica particles having pores exhibit a low dielectric constant of 3 or less.
Further, the polyimide films according to examples 1 and 2 were compared with the case where the densification ratio was higher than 95%, the case where fluorine particles were included, or the case where particles were not included in comparative examples 1 to 4, and they were also found to have low dielectric constants and dielectric positive contact, and thus to have excellent electrical characteristics. Therefore, the method can be effectively used for manufacturing electric/electronic devices and parts such as printed circuit boards requiring a low dielectric constant.
Claims (5)
1. A method for producing a polyimide film, comprising:
step 1), preparing a polyimide precursor;
step 2) mixing the polyimide precursor and an imidization conversion solution containing particles having pores to prepare a gel film; and
step 3) of performing imidization treatment by heat-treating the gel film,
the particles having pores have an average particle diameter of 1 to 10 [ mu ] m and a particle density of 95% or less relative to the particle density of a substance specific to the particles having pores; the particles with air holes are hollow silicon dioxide;
the imidization conversion solution is a mixed solvent containing the following components: acetic anhydride is used as a dehydrating agent; a catalyst of a tertiary amine selected from the group consisting of pyridine, beta-picoline, isoquinoline, and mixtures thereof; and a polar organic solvent selected from the group consisting of N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof;
the imidization conversion solution is used in an amount of 40 to 55 parts by weight based on 100 parts by weight of the polyimide precursor.
2. The method for producing a polyimide film according to claim 1, wherein the particles having pores have a particle density of 30% to 95% with respect to a particle density of a substance inherent to the particles having pores.
3. The method for producing a polyimide film according to claim 1, wherein the particles having pores are contained in an amount of 2 to 30 wt% based on the total weight of the film.
4. A polyimide film containing particles having pores, characterized in that,
the particles having pores have an average particle diameter of 1 to 10 [ mu ] m and a particle density of 95% or less relative to the particle density of a substance specific to the particles having pores; the particles with air holes are hollow silicon dioxide.
5. The polyimide film according to claim 4, wherein the polyimide film has a dielectric constant of 3.0 or less at 1 GHz.
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| KR1020150010092A KR101728100B1 (en) | 2015-01-21 | 2015-01-21 | Method for preparation of polyimide film using porous particles and polyimide film having low permittivity |
| KR10-2015-0010092 | 2015-01-21 | ||
| PCT/KR2016/000131 WO2016117856A1 (en) | 2015-01-21 | 2016-01-07 | Method for preparing polyimide film using porous particles, and low dielectric constant polyimide film |
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| CN109689745B (en) * | 2016-09-01 | 2021-12-10 | 聚酰亚胺先端材料有限公司 | High-heat-dissipation graphene-polyimide composite film with insulating property and preparation method thereof |
| KR102019928B1 (en) * | 2016-09-01 | 2019-09-11 | 에스케이씨코오롱피아이 주식회사 | Graphene-polyimide composite film with improved heat dissipating and insulating properties and preparation method thereof |
| KR101851752B1 (en) * | 2016-10-21 | 2018-04-24 | 에스케이씨 주식회사 | Method for preparing graphite sheet |
| KR20190025072A (en) * | 2017-08-02 | 2019-03-11 | 에스케이씨코오롱피아이 주식회사 | Method for preparation of polyimide film using fumed silica particles and polyimide film having low permittivity |
| KR102416346B1 (en) * | 2017-11-08 | 2022-07-06 | 한국전자통신연구원 | Flexible polyimide substrate and manufacturing method thereof |
| CN108079803A (en) * | 2017-11-21 | 2018-05-29 | 浙江德清科赛塑料制品有限公司 | A kind of microporous teflon membran |
| KR102160552B1 (en) * | 2018-02-28 | 2020-09-28 | 최영준 | Manufacturing method of insulator film and insulator film making apparatus |
| KR102164458B1 (en) * | 2018-05-18 | 2020-10-13 | 피아이첨단소재 주식회사 | Polyimide Film Having Low Permittivity and Low Hygroscopicity And Manufacturing Method thereof |
| KR102167968B1 (en) | 2018-08-31 | 2020-10-20 | 한국자동차연구원 | A low dielectric constant polyimide film using nanosilicate particles and a method of manufacturing the same |
| KR102378209B1 (en) | 2020-04-24 | 2022-03-23 | 연세대학교 원주산학협력단 | Low dielectric constant polyimide film by high internal phase emulsion and manufacturing method thereof |
| US20230257580A1 (en) | 2020-06-23 | 2023-08-17 | Lg Electronics Inc. | Polyimide and method of preparing the same |
| CN115803385A (en) * | 2020-07-10 | 2023-03-14 | 可隆工业株式会社 | Polyimide-based film having excellent filler dispersibility and display device including the same |
| CN112266260B (en) * | 2020-10-21 | 2022-11-15 | 安徽国风新材料股份有限公司 | Preparation method of polyimide graphite film |
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