KR101764734B1 - Fabrication of 0, 1, 2 dimensional carbon nanomaterials embedded polyimide film and flexible passivation film using the same - Google Patents
Fabrication of 0, 1, 2 dimensional carbon nanomaterials embedded polyimide film and flexible passivation film using the same Download PDFInfo
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- KR101764734B1 KR101764734B1 KR1020150051749A KR20150051749A KR101764734B1 KR 101764734 B1 KR101764734 B1 KR 101764734B1 KR 1020150051749 A KR1020150051749 A KR 1020150051749A KR 20150051749 A KR20150051749 A KR 20150051749A KR 101764734 B1 KR101764734 B1 KR 101764734B1
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- 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
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- 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
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Abstract
Embodiments of the present invention may include at least one carbon material selected from 0-dimensional, 1-dimensional, 2-dimensional carbon nanomaterials, a flexible substrate comprising a polyimide film layer incorporating uniformly embedded multidimensional complex carbon nanomaterials, Shielding protective film. Polyimide has excellent mechanical and chemical properties and high flexibility to protect flexible devices from external environments. Particularly, polyimide has a large surface area compared to its particle size and has a particle structure of a hollow shell (SHELL), which is very advantageous for adsorbing moisture and oxygen, and a two-dimensional carbon nanomaterial excellent in gas barrier ability By embedding the material uniformly, moisture and oxygen can be effectively blocked, and excellent protective film characteristics can be realized.
Description
Embodiments of the present invention relate to a method for manufacturing a polyimide film for a flexible device protective film in which 0-dimensional, 1-dimensional and 2-dimensional carbon nanomaterials are uniformly embedded, and a sandwich-type laminated protective film using the same. More specifically, a polyamic acid film in which at least one of 0-dimensional, 1-dimensional, and 2-dimensional carbon nanomaterials are uniformly dispersed is prepared and subjected to an imidization heat treatment process to produce a 0-dimensional and 1-dimensional carbon nanomaterial The present invention relates to a protective film capable of effectively blocking water and oxygen by forming a polyimide composite film having a uniformly built-in two-dimensional carbon nanomaterial having a wide surface area, and a manufacturing method thereof. The zero-dimensional, one-dimensional, and two-dimensional carbon nanomaterial-polyimide composite protective films have excellent multi-dimensional carbon nanostructures contained in the polyimide, and thus have superior oxygen / moisture barrier properties as moisture and oxygen have a long tortuosity It can be used as a protective film material.
With the arrival of wearable electronics such as computer wear, scrolling electronic paper, and bendable displays, various flexible devices with flexibility have been actively developed. In order to realize a flexible device, many element technologies are required. Among them, a passivation layer technology directly related to the stable operation and lifetime of the flexible device is indispensably required. Flexible devices are more flexible than non-flexible devices because of the high possibility of organic polymer materials used for driving flexible devices due to repetitive bending and twisting due to exposure to atmospheric oxygen and moisture and degradation. The protective film must effectively block oxygen / moisture permeation. However, since the high-order shielding film which stably protects the flexible device from the external environment without repeated bending and twisting, is a process requiring a very high level of technology from selection of materials to synthesis, a protective film And many companies, research institutes, and schools are actively conducting research.
Substrates for flexible devices are required to have high flexibility, light weight and small size, impact resistance, low thermal expansion rate, and high gas barrier properties. Especially, it is very important that the substrate has high flexibility, and a polymer material having high flexibility is mainly used as a substrate material. However, the polymer has drawbacks that it is vulnerable to oxygen / moisture interception because of its easy penetration of gas. Therefore, the protective film for flexible devices has been mainly studied with special coated polymer or modified polymer so as to have excellent flexibility and oxygen and moisture barrier properties. In recent years, studies have been made to solve the above problems by using a multilayer coating method including an organic / inorganic hybrid coating layer in the form of being combined with an inorganic gas barrier layer so that the barrier property can be further increased and an excellent surface hardness can be imparted. When a protective film composed of an organic / inorganic hybrid laminated structure is formed, the frequency of defect distribution in the inorganic material in the same space can be reduced vertically, and the pathway of moisture is significantly longer due to other materials in the middle, . Korean Patent Laid-Open Publication No. 1999-49287 discloses a method of applying a ceramic material such as Al 2 O 3 , MgO, BeO, SiC, TiO 2 , Si 3 N 4 and SiO 2 to a protective layer. When laminating such an inorganic material, a protective film is formed mainly by a vacuum deposition method such as sputtering or chemical vapor deposition. Since a polymer material used as a flexible substrate is vulnerable to a high temperature, the ceramic coating layer is generally Lt; RTI ID = 0.0 > 100 C < / RTI > However, the inorganic protective film deposited by the low temperature process contains many defects such as grain boundaries, pimples, microcracks, and inhomogeneity. Water defects which are generated when the (H 2 O) and oxygen (O 2) the molecular size is the respectively 0.26 nm, less than 0.35 nm protective film deposition than the smaller is the presence in the tens of nm in size can μm large, moisture and oxygen It is difficult to effectively block the above-mentioned problems. Therefore, it is more preferable to uniformly embed the oil / inorganic material in the flexible substrate or the polymeric protective film without the process of depositing the ceramic coating layer at low temperature to simultaneously satisfy the high flexibility and the high gas barrier property. In addition, when a ceramic coating layer is additionally deposited on a flexible substrate or a polymer protective film, it is essential to use a flexible substrate or a polymer protective film having excellent moisture and oxygen blocking effect capable of withstanding a high temperature of 300 ° C.
Polyimide, which has excellent mechanical properties and chemical properties and has transparency and is applied to many industrial fields, has recently been actively studied for use as a transparent substrate and protective film material for flexible devices.
Carbon nanomaterials (ketjen black, denka black, acetylene black, super-p, fullerene) and one-dimensional carbon materials (single wall carbon Wall carbon nanotubes (MWNTs), carbon nanofibers) are widely used as conductivity-imparting agents and have a surface area that is larger than that of the particle size, and hollow Shell (hollow SHELL) phase structure. This structure is a very advantageous structure for adsorbing oxygen / water.
Two-dimensional carbon nanomaterials (graphene oxide, reduced graphene oxide, doped graphene, and carbon nanoribbon) have been used as a substrate in a planar structure And due to their excellent electrical and mechanical properties, active research is underway in various fields. Particularly, it has been reported that a gas such as helium can not directly pass through a two-dimensional carbon nanomaterial monolayer, and thus two-dimensional carbon nanomaterials have attracted great interest as a gas barrier material.
One-dimensional, one-dimensional carbon nanomaterials and gases with a large surface area inside the polyimide substrate or polyimide protective film with excellent mechanical and chemical properties and having hollow shell (hollow SHELL) It is expected that if the two-dimensional carbon nanomaterials having excellent barrier ability are uniformly embedded, oxygen / moisture interception can be effectively expected.
Therefore, the embodiments of the present invention can provide a flexible polyimide film for a flexible device having a uniformly embedded 0-dimensional carbon nanomaterial and a 2-dimensional carbon nanomaterial, which is highly resistant to oxygen / moisture while having high flexibility, And to provide a substrate and a protective film material.
More specifically,
First, polyimide's excellent mechanical and chemical properties and high flexibility make it effective to protect flexible devices from repeated bending and twisting in exposed atmospheres of the atmosphere.
Second, uniformly embedding one or more carbon materials selected from 0-dimensional, 1-dimensional, and 2-dimensional carbon nanomaterials in the polyimide film enables the oxygen / moisture and oxygen path to be made significantly longer, will be.
Thirdly, based on the excellent heat resistance characteristics of the polyimide film including the 0-dimensional, 1-dimensional and 2-dimensional carbon nanomaterials, a ceramic protective film is further coated at a deposition temperature of about 300 ° C to form a polyimide / ceramic multilayer substrate or a protective film to provide.
The organic / inorganic composite structure is a polyimide composite film having a two-dimensional carbon nanomaterial embedded in a zero-dimensional carbon nanomaterial which is very easy to adsorb oxygen / moisture and an excellent gas barrier property, and is very suitable as a protective film material of a flexible device .
The present invention provides a polyimide film in which at least one of zero-dimensional, one-dimensional, and two-dimensional carbon nanomaterials is uniformly embedded, and a substrate and a protective film containing the same. The polyimide film is characterized by having excellent mechanical strength and chemical properties, while at the same time having high flexibility without deformation or damage in a wide temperature range. Therefore, when polyimide is used as a protective film for a flexible device, the flexible device can be safely protected from repetitive bending and twisting in an atmospheric environment. The zero-dimensional and one-dimensional carbon nanomaterials distributed evenly inside the polyimide film have a surface area larger than the particle size and have a hollow shell (hollow SHELL) particle structure, which is very effective in adsorbing oxygen / water. It is possible to provide effective oxygen and moisture barrier properties by significantly increasing the oxygen / water movement path.
Another aspect of the present invention is a substrate for a flexible device and a method for manufacturing a protective film using the polyimide in which at least one of 0-dimensional, 1-dimensional, and 2-dimensional carbon nanomaterials is uniformly embedded, comprising the steps of: (a) Preparing a solution; (b) dispersing one or more carbon nanomaterials selected from 0-dimensional, 1-dimensional and 2-dimensional carbon nanomaterials into the prepared polyamic acid solution; (c) coating a polyamic acid film on which a carbon nanomaterial is dispersed, on a glass substrate; (d) fabricating a polyimide film having a carbon nanomaterial embedded therein through an imidization heat treatment; And (e) separating a polyimide substrate or a protective film containing at least one carbon nanomaterial selected from the above-described zero-dimensional, one-dimensional and two-dimensional carbon nanomaterials from the glass substrate to form a flexible polyimide substrate .
According to the present invention, the polyimide film can be used as a substrate of high flexibility having excellent mechanical strength and chemical characteristics, and at the same time, when the carbon nanomaterial is dispersed evenly inside the polyimide film, excellent oxygen / Can be given. In addition, polyimide with high heat resistance can be used as a protective film for a flexible device requiring a high temperature process. In particular, it is possible to further coat the upper and lower layers of the polyimide film with a ceramic film layer having excellent film quality through high-temperature deposition.
The present invention eliminates the need for UV / ozone irradiation for the curing of organic materials in the hybrid structure of the organic / inorganic film that has been studied previously, and can be used as a protective film for a flexible device requiring high process temperature due to excellent heat resistance property of polyimide Do. At the same time, a two-dimensional carbon nanomaterial excellent in zero-dimensional and one-dimensional carbon nanomaterial and gas barrier ability having a large surface area and having a particle structure on a hollow shell (shell structure) Excellent oxygen / moisture barrier properties can be expected.
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a manufacturing method of a polyimide protective film structure in which Ketjen black nanoparticles (0-dimensional carbon nanomaterial) and graphene (2-dimensional carbon nanomaterial) It is a flowchart.
Fig. 2 is a schematic view of a polyimide protective film in which Ketjenblack nanoparticles according to Example 1 and graphenes are uniformly embedded.
Fig. 3 is a graph showing the results of measurement of a polyamic acid solution (left) prepared by stirring an anhydride and an amine in a solvent in Comparative Example 1 and a solution (right) in which Ketjenblack nanoparticles and graphene were dispersed in a polyamic acid solution in Example 1, .
4 is a photograph (left) of a polyimide protective film in Comparative Example 1 and a photograph (right) of a polyimide protective film containing Ketjenblack nanoparticles and graphene produced according to Example 1 (right).
5 is a cross-sectional scanning electron microscope photograph (left) and a high magnification photograph (right) of a Ketjenblack nanoparticle prepared according to Example 1 and a polyimide protective film containing graphene.
Hereinafter, with reference to the accompanying drawings, a method for manufacturing a polyimide protective film material in which at least one of 0-dimensional, 1-dimensional and 2-dimensional carbon nanomaterials are uniformly embedded will be described in detail.
As used herein, the term "zero-dimensional carbon nano material" is selected from ketjen black, denka black, acetylene black, Super-p, and fullerene, nm) to 50 nanometers (nm).
As used herein, the term "one-dimensional carbon nanomaterials" refers to single-wall carbon nanotubes (SWNTs), multi-wall carbon nanotubes (MWNTs), carbon nanofibers It should be understood that the size selected ranges from 1 nanometer (nm) to 50,000 nanometers (nm), and the diameter ranges from 1 nanometer (nm) to 100 nanometers (nm).
As used herein, the term "two-dimensional carbon nanomaterials" refers to graphene oxide, reduced graphene oxide, doped graphene, carbon nanoribbon , It should be understood that one or more layers are stacked, with the width and the length being in the range from 1 nanometer (nm) to a few micrometers (m), preferably from several tens to several hundred nanometers .
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view schematically showing a method of manufacturing a polyimide protective film (a Ketjenblack-graphene-polyimide composite substrate and a protective film) having Ketjenblack nanoparticles and graphene embedded therein according to an experimental example of the present invention. It is a schematic diagram.
The method of producing the Ketjen black nanoparticles of FIG. 1 and the polyimide protective film having graphene incorporated therein is merely to illustrate the present invention, and the present invention is not limited thereto.
As shown in FIG. 1, a method for producing a polyimide protective film having Ketjenblack nanoparticles and graphene embedded therein comprises the steps of: i) preparing a polyamic acid solution by stirring an anhydride and an amine (S10), ii) (S20) of dispersing the Ketjen black nanoparticles and the graphene in the step (S20), and iii) using the polyamic acid solution in which the Ketjen black nanoparticles and the graphene prepared in the step S20 are dispersed, (S30) of forming a polyimide high-k film composite film, iv) forming a polyimide high-blocking protective film film material in which polyamic acid is imidized with polyimide through heat treatment to incorporate Ketjenblack nanoparticles and graphene (S40 ).
First, in step S10, an anhydride and an amine are stirred to prepare a mixed solution of a polymer. The mixed solution includes an anhydride, an amine and a solvent. In this case, solvents such as N, N-dimethylacetamide, N-methylpyrrolidinone, 1,3-dimethyl-5-imidazolidinone, N, N-dimethylformamide, 1,1,3,3-tetramethylurea and N-cyclohexylpyrrolidinone And anhydrides and amines must be soluble at the same time.
The anhydride used in step S10 is an anhydride capable of synthesizing polyamic acid. The anhydride may be 4,4'-oxydiphthalic dianhydride (ODPA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride DSDA), 4'-biphenyl tetracarboxylic acid dianhydride (BPDA), 4,4'- (4,4'-isopropylidenediphenoxy) bis (phthalic anhydride), 4,4'- (hexafluoroisopropylidene) diphthalic anhydride May include at least one selected from 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 1,2,3,4-cyclobutanetetracaroxylic dianhydride (CBDA), 1,4-cyclohexanedicarboxylic acid (CHDA), and also polyamic acid If an anhydride is present, it does not impose any restriction on the specific substance.
The amine used in step S10 is an amine capable of synthesizing a polyamic acid. The amines include 3,3'-bis (4-aminophenoxy) biphenyl (M-BAPB), 1,3- BAPB), ammonium persulfate (APS), (9-fluorenylidene) dianiline (BAPF), para-aminobiphenylsulfone (m-BAPS), 2,2- bis (4-aminophenyl) hexafluoropropane at least one of amino-bis metabisaminophenoxy diphenyl sulfone (p-BAPS), 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane (BAMF) In addition, if the amine is capable of synthesizing polyamic acid, it does not limit the specific substance.
In step S20, Ketjenblack nanoparticles and graphene are dispersed in the polyamic acid solution synthesized in step S10. Ketjenblack has a particle size of 0.1 to 50 nanometers (nm), and graphene has a particle size of 1 nanometer (μm) to several micrometers (μm), preferably several tens to several hundred nanometers (nm). If the diameter of the graphene is very small, the water and oxygen blocking effect is deteriorated. If the diameter of the graphene is increased to several tens of micrometers or more, dispersion becomes difficult. In order to disperse the Ketjen black nanoparticles and the graphene in the polyamic acid solution, the dispersion is firstly dispersed in another solvent through a sonication process, and then stirred with the polyamic acid solution to be uniformly dispersed in the polyamic acid solution.
The dispersion solvent of Ketjenblack nanoparticles and graphene used in step S20 may be selected from the group consisting of N, N-dimethylacetamide, N-methylpyrrolidinone, 1,3-dimethyl-5-imidazolidinone, 3-tetramethylurea, N-cyclohexylpyrrolidinone, and the like.
In step S20, a surfactant may be added to prevent agglomeration of Ketjenblack nanoparticles and graphene when the Ketjenblack nanoparticles and the graphene are dispersed in a solvent. The surfactant may be sodium dodecylsulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium myreth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, octenidine dihydrochloride, cetyl trimethylammonium bromide, cetyl trimethylammonium chloride, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, 5-bromo- It may contain at least one surfactant selected from the group consisting of -dioxane, dimethyldioctadecylammonium chloride, cetrimonium bromide, dioctadecyldimethylammonium bromide, and Triton-X. The hydrophilic lipophile balance value may range from 7 to 9 HLB And the Ketjen black nanoparticles and the graphene are embedded in the polyimide matrix The surfactant is not limited to a specific substance.
In step S30, a polyamic acid solution in which Ketjenblack nanoparticles and graphene are uniformly dispersed is prepared by spin coating using the spin coating method. , It is possible to control the thickness of the film formed through the control of the viscosity of the polyamic acid solution and the revolution per minute (RPM) of the spin coating. Although spin coating is used in the present invention, there is no restriction on a specific method as long as a method capable of producing a polyamic acid film having carbon nanomaterials of 0, 1, and 2 dimensions. When a polyimide substrate containing 0, 1, or 2 dimensional carbon nanomaterials is to be manufactured, a substrate of several micrometers or more can be manufactured using a screen printing process instead of the spin coating method. Here, the spin coating process can be easily understood by a person skilled in the art, so that a detailed description thereof will be omitted.
The Ketjenblack nanoparticles prepared in step S30 and the polyamic acid film having graphene incorporated therein may have a thickness ranging from 0.1 to 100 mu m and preferably have a thickness ranging from 1 to 20 mu m. In the present invention, Ketjen black nanoparticles are exemplified. However, carbon nanomaterials such as denka black, acetylene black, Super-p, and carbon black nanoparticles and one-dimensional carbon nanomaterials Wall carbon nanotubes (SWNTs), multi-wall carbon nanotubes (MWNTs), carbon nanofibers), or combinations thereof, are embedded in the interior of the polyamic acid membrane. The graphene is a two-dimensional carbon nanomaterial, specifically, a non-oxidized graphene oxide, a reduced graphene oxide, a reduced graphene oxide, Doped graphene, carbon nanoribbon, or a combination thereof is embedded in the inside of the polyamic acid film to finally form the polyimide film.
In step S40, the Ketjen black nanoparticles and the polyamic acid film with graphene embedded therein are heat-treated. In this step, when the polyamic acid mixed by an anhydride and amine polymerization is heat-treated at 100 to 300 ° C., imidization occurs to form polyimide, and finally Ketjenblack nanoparticles and graphene are uniformly Thereby forming a built-in polyimide protective film.
Hereinafter, the present invention will be described in detail by way of examples. The present invention will be described by way of examples. The embodiments are merely intended to illustrate the present invention, and the present invention is not limited thereto.
Comparative Example 1: Production of polyimide protective film
Hereinafter, a method for producing a polyimide film according to the present invention will be described in detail.
Polyamic acid production step
The polyamic acid solution is first prepared as a precursor before making the polyimide polymer. The polyamic acid is composed of an anhydride and an amine bond, and the imidization reaction occurs during the heat treatment at 100 to 300 ° C to produce polyimide.
In the present invention, 6FDA (4,4 '- (hexafluoroisopropylidene) diphthalic anhydride) having a trifluoromethyl group as an anhydride and APS (ammonium persulfate) containing a sulfone structure as an amine were selected and N, N-dimethylformamide DMF) organic solvent at low temperature for about 5 to 10 hours to form a liquid polyamic acid.
A spin coating process was performed to prepare a liquid polyamic acid solution as a film. In the process of spin-coating, the glass substrate is first fixed in a vacuum on a spin coater, and then a polyamic acid solution in which a sufficient amount of Ketjenblack nanoparticles and graphene are dispersed in a glass substrate is dropped, And the uniform film was coated over the entire area of the substrate. Spin coating can control spin speed and spin time, so that the thickness of the film can be controlled. In this comparative example, the spin coating method has been described as an example, but there is no restriction on the specific coating method.
Production process of polyimide film by heat treatment
The polyimide film prepared by spin coating may be subjected to an imidization heat treatment to produce a polyimide film. When the polyamic acid prepared by polymerization of anhydride and amine is heat treated at 100 ° C, 200 ° C and 300 ° C for 1 hour each, imidization occurs and polyimide is produced.
Example 1: Preparation of a polyimide protective film uniformly incorporating Ketjenblack nanoparticles and graphene
Hereinafter, a method for producing a polyimide film in which the Ketjen black nanoparticles and graphene are uniformly embedded according to the present invention will be described in detail.
Ketjen black nanoparticles and polyamic acid with homogeneously embedded graphene
The polyamic acid solution is first prepared as a precursor before making the polyimide polymer. The polyamic acid is composed of an anhydride and an amine bond, and the imidization reaction occurs during the heat treatment at 100 to 300 ° C to produce polyimide.
In the present invention, 6FDA (4,4 '- (hexafluoroisopropylidene) diphthalic anhydride) having a trifluoromethyl group as an anhydride and APS (ammonium persulfate) containing a sulfone structure as an amine were selected and N, N-dimethylformamide DMF) organic solvent at low temperature for about 5 to 10 hours to form a liquid polyamic acid.
In order to disperse the Ketjenblack nanoparticles and the graphene in the liquid polyamic acid, Ketjenblack nanoparticles and graphene were dispersed in the same organic solvent, N, N-dimethylformamide (DMF). N, N-dimethylformamide (DMF), Ketjenblack nanoparticles and graphene were mixed at a ratio of 100: 10: 5. The size of Ketjenblack nanoparticles was 0.1 to 50 nm and the size of graphene was 1 to 500 nm It is preferable to use Ketjen black having a nanoparticle size of 50 nm or less and graphene having a size of 500 nm or less. In the present invention, Ketjen black nanoparticles having a size of 10 nm and graphenes having a size of 500 nm were used. In this experiment, Ketjenblack nanoparticles were used, but it is also possible to incorporate denca black, acetylene black, Super-p, carbon black nanoparticles, or a combination thereof in a polyimide film. Also, instead of graphene, a combination of graphene oxide and graphene and graphene oxide may be embedded within the polyimide film.
In order to uniformly disperse the Ketjen black nanoparticles and the graphene in a solvent, a small amount of a Triton-X surfactant was added and the mixture was stirred for 10 minutes by sonication. The Ketjenblack nanoparticles dispersed in the solvent and the graphene were mixed with the liquid polyamic acid to prepare a polyamic acid solution in which the final Ketjenblack nanoparticles and graphene were uniformly dispersed.
FIG. 3 is a photograph of a solution prepared through the above process. On the left side is a photograph of a Ketjen black nanoparticle of Example 1 and a transparent polyamic acid solution not containing graphene and on the right is a photograph of a solution of Ketjenblack nanoparticles and graphene dispersed in a polyamic acid solution of Comparative Example 1 and dispersed therein to be. The addition of Ketjenblack nanoparticles and graphene confirmed that the polyamic acid solution became a dark suspension. The amount of the Ketjenblack nanoparticles to be dispersed in the polyamic acid solution is 0.1 to 4 wt%, preferably 2 wt%, based on the polyamic acid solution. The addition amount of graphene is 0.1-1 wt%, preferably 1 wt%, based on the polyamic acid solution.
Steps for fabricating polyamic acid films with Ketjenblack nanoparticles and graphene
A spin coating process was performed to prepare a liquid polyamic acid solution in which the Ketjen black nanoparticles and graphene shown in FIG. 3 were uniformly dispersed in a film. In the process of spin-coating, the glass substrate is first fixed in a vacuum on a spin coater, and then a polyamic acid solution in which a sufficient amount of Ketjenblack nanoparticles and graphene are dispersed in a glass substrate is dropped, And the uniform film was coated over the entire area of the substrate. Thereafter, evaporation of the solvent produces a polyamic acid film in which Ketjenblack nanoparticles and graphene are distributed. Spin coating can control spin speed and spin time, so that the thickness of the film can be controlled. In this embodiment, the spin coating method has been described as an example, but the specific coating method is not limited.
Manufacturing process of polyimide film with Ketjenblack nanoparticles and graphene evenly embedded by heat treatment
The polyimide film can be prepared by imidizing heat treatment of Ketjen black nanoparticles prepared by spin coating and a polyamic acid film containing graphene. When the polyamic acid prepared by polymerization of anhydride and amine is heat treated at 100 ° C, 200 ° C and 300 ° C for 1 hour each, imidization occurs and polyimide is produced.
4 is an actual photograph (left) of a polyimide film produced according to Comparative Example 1 in the present invention and a real photo (right) of a polyimide protective film containing Ketjenblack nanoparticles and graphene prepared according to Example 1 . The Ketjen black nanoparticles prepared according to Example 1 on the right side and the polyimide protective film having graphene incorporated therein show that Ketjenblack nanoparticles and graphene are uniformly embedded and dark.
FIG. 5 is a cross-sectional view (left) and an enlarged view (right) of a scanning electron microscope of a polyimide film having Ketjenblack nanoparticles and graphene manufactured in the present invention. FIG. It can be seen that Ketjenblack nanoparticles having a thickness of 20 μm and a polyimide film with graphene incorporated on the glass substrate are manufactured very uniformly. SEM images of the right side show that Ketjen black nanoparticles having a size of about 50 nm and graphene having a size of about 500 nm are uniformly distributed in the polyimide film.
Table 1 shows the water vapor transmission rates (WVTR) of the polyimide films prepared according to Comparative Example 1 and the Ketjenblack nanoparticles prepared according to Example 1 and the graphene-containing polyimide films prepared in the present invention will be. As shown in Table 1, the Ketjenblack nanoparticles and the graphene-embedded polyimide films had a water permeability (WVTR) much lower than the polyimide film's water permeability (WVTR) It can be confirmed that the built-in polyimide film acts effectively as a flexible protective film.
In the present invention, Ketjenblack nanoparticles and graphene were selected as nanoparticles uniformly embedded in the polyimide. However, the present invention further includes a one-dimensional carbon nanotube material having excellent water barrier properties, Heat-resistant polyimide substrate and protective film, which have built-in dimensional, one-dimensional and two-dimensional composite carbon materials.
In addition, in the present invention, a polyimide flexible protective film in which Ketjenblack nanoparticles and graphene are uniformly embedded in a polyimide is prepared in order to enhance the water and oxygen barrier properties. However, in order to further enhance water and oxygen barrier properties, (SiO 2 , SiN, MgO, ZnO, SnO 2 , WO 3 , Fe 2 O 3 , Fe 3 O 4 , NiO, TiO 2 , and the like) are formed on the upper and lower portions of the polyimide film having black nano- ZrO 2, Al 2 O 3, B 2 O 3, Cr 3 O 4, Cr 2 O 3, CeO 2, Nd 2 O 3, Sm 2 O 3, Eu 2 O 3, Gd 2 O 3, Tb 4 O 7 , At least one of Dy 2 O 3 , Er 2 O 3 , Yb 2 O 3, and Lu 2 O 3 ) at a temperature of 300 ° C. is applied to the substrate by RF sputtering, Pulsed Laser Deposition (PLD), thermal evaporation, Deposited using any of E-beam evaporation, chemical vapor deposition, and atomic layer deposition to form a dense thin film structure A protective film which can be a flexible oxygen / water barrier protective film naejineun substrate including a carbon nano composite material is built-in multi-dimensional polyimide film layer, characterized in that it further comprises.
Claims (23)
The particle size of the zero-dimensional carbon nanomaterial ranges from 0.1 nanometers (nm) to 50 nanometers (nm)
The length of the one-dimensional carbon nanomaterial ranges from 0.1 nanometers (nm) to 50,000 nanometers (nm), the diameter ranges from 0.1 nanometers (nm) to 100 nanometers (nm)
The two-dimensional carbon nanomaterial has a lateral length and a longitudinal length ranging from 1 nanometer (nm) to 500 nanometer (nm)
Wherein the two-dimensional carbon nanomaterial is a laminate of a plurality of layers.
The zero-dimensional carbon nanomaterial is uniformly embedded in the polyimide film and is preferably selected from the group consisting of ketjen black, denka black, acetylene black, super-p, Wherein the polyimide film comprises at least one selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol, and fullerene.
The one-dimensional carbon nanomaterial may be uniformly embedded in the polyimide film and may be a single-wall carbon nanotube (SWNT), a multi-wall carbon nanotube (MWNT) Wherein the polyimide film is composed of at least one selected from carbon nanofibers.
Wherein the two-dimensional carbon nanomaterial is uniformly embedded in the polyimide film and is composed of a non-oxidized graphene oxide, a reduced graphene oxide, a doped graphene doped graphene, and carbon nanoribbon. < Desc / Clms Page number 13 >
And a protective film having a dense thin film structure by depositing an inorganic thin film layer at a temperature of 300 캜.
Wherein the thickness of the polyimide film ranges from 0.1 micrometers (μm) to 100 micrometers (μm).
The anhydride used in the production of the polyamic acid film layer may be selected from the group consisting of 4,4'-Oxydiphthalic Dianhydride (ODPA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'- diphenylsulfonetetracarboxylic dianhydride, 4'-biphenyl tetracarboxylic acid dianhydride, BPADA, 4,4'-isopropylidenediphenoxy bis (phthalic anhydride), 6FDA (4,4 '- (hexafluoroisopropylidene) diphthalic wherein the polyimide film comprises one selected from the group consisting of anhydride, 4,4'-benzophenonetetracarboxylic dianhydride, 1,2,4-cyclobutanetetracaroxylic dianhydride, and 1,4-cyclohexanedicarboxylic acid. .
The amines used in the production of the polyamic acid film layer are amines which can be synthesized from polyamic acid, such as M-BAPB (3,3'-bis (4-aminophenoxy) biphenyl), p-BAPB -aminophenoxy) benzene), BAHFP (2,2-bis (4-aminophenyl) hexafluoropropane), m-BAPS (meta-amino- bis metabisaminophenoxy diphenyl sulfone), APS (ammonium persulfate), BAPF , p-BAPS (para-amino-bis metabisaminophenoxy diphenyl sulfone), BAMF (2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane) and TFB Lt; RTI ID = 0.0 > polyimide < / RTI >
The solvent used in the preparation of the polyamic acid film layer may be selected from the group consisting of N, N-dimethylacetamide, N-methylpyrrolidinone, 1,3-dimethyl-5-imidazolidinone, N, N-dimethylformamide, 1,1,3,3-tetramethylurea, N -cyclohexylpyrrolidinone. < RTI ID = 0.0 > 8. < / RTI >
The inorganic thin film layer is comprised of SiO 2, SiN, MgO, ZnO , SnO 2, WO 3, Fe 2 O 3, Fe 3 O 4, NiO, TiO 2, ZrO 2, Al 2 O 3, B 2 O 3, Cr 3 O 4, Cr 2 O 3, CeO 2, Nd 2 O 3, Sm 2 O 3, Eu 2 O 3, Gd 2 O 3, Tb 4 O 7, Dy 2 O 3, Er 2 O 3, Yb 2 O 3 and polyimide film comprises at least one of Lu 2 O 3.
(a) preparing a polyamic acid solution by stirring an anhydride and an amine;
(b) dispersing at least one carbon nanomaterial selected from a zero-dimensional carbon nanomaterial and a one-dimensional carbon nanomaterial and a two-dimensional carbon nanomaterial in a solvent using a surfactant, mixing the solution with a polyamic acid solution, Preparing a dispersed polyamic acid solution;
(c) coating the polyamic acid solution on a glass substrate;
(d) preparing a polyimide film in which the multi-dimensional composite carbon nanomaterial is uniformly embedded through heat treatment of the glass substrate coated with the polyamic acid solution
Lt; / RTI >
The particle size of the zero-dimensional carbon nanomaterial ranges from 0.1 nanometers (nm) to 50 nanometers (nm)
The length of the one-dimensional carbon nanomaterial ranges from 0.1 nanometers (nm) to 50,000 nanometers (nm), the diameter ranges from 0.1 nanometers (nm) to 100 nanometers (nm)
The two-dimensional carbon nanomaterial has a lateral length and a longitudinal length ranging from 1 nanometer (nm) to 500 nanometer (nm)
Wherein the two-dimensional carbon nano material is a laminate of a plurality of layers.
The step (c)
Wherein the thickness of the polyimide film is controlled by adjusting a rotation speed and a spin time using a spin coating process. ≪ RTI ID = 0.0 > 8. < / RTI >
The step (c)
Wherein the polyamic acid solution is coated on the glass substrate using one process selected from the group consisting of spin coating, spin coating, and screen printing coating.
Wherein the heat treatment process comprises heat treating the polyamic acid film formed by coating the polyamic acid solution on the glass substrate at a temperature of 300 ° C.
The surfactant may be selected from the group consisting of sodium dodecylsulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium myreth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, octenidine dihydrochloride, cetyl trimethylammonium bromide, cetyl trimethylammonium chloride, cetylpyridinium chloride, benzalkonium chloride, A range including at least one surfactant selected from the group consisting of Bromo-5-nitro-1,3-dioxane, dimethyldioctadecylammonium chloride, cetrimonium bromide, dioctadecyldimethylammonium bromide and Triton-X and used as a dispersant in the hydrophilic lipophile balance value Wherein the carbon nanotubes have an HLB value of 7 to 9, inclusive.
Wherein the amount of the at least two selected carbon nanomaterials is in the range of 0.1 wt% to 4 wt% with respect to the amount of the polyamic acid solution.
(f) separating the polyimide film from the glass substrate
Further comprising:
The polyimide film has a structure in which at least one carbon nanomaterial selected from the zero-dimensional carbon nanomaterial and the one-dimensional carbon nanomaterial and the two-dimensional carbon nanomaterial are uniformly embedded in the polyimide film and have a blocking power against moisture and oxygen Wherein the multi-dimensional complex carbon nanomaterial is embedded in the polyimide film.
The polyimide film further includes a protective film having a dense thin film structure by depositing an inorganic thin film layer at a temperature of 300 ° C,
The inorganic thin film layer is comprised of SiO 2, SiN, MgO, ZnO , SnO 2, WO 3, Fe 2 O 3, Fe 3 O 4, NiO, TiO 2, ZrO 2, Al 2 O 3, B 2 O 3, Cr 3 O 4, Cr 2 O 3, CeO 2, Nd 2 O 3, Sm 2 O 3, Eu 2 O 3, Gd 2 O 3, Tb 4 O 7, Dy 2 O 3, Er 2 O 3, Yb 2 O 3 and And Lu 2 O 3. The method of manufacturing a polyimide film according to claim 1, wherein the multi-dimensional composite carbon nanomaterial comprises at least one of Lu 2 O 3 and Lu 2 O 3 .
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| JP2013221150A (en) * | 2012-04-13 | 2013-10-28 | Mortech Corp | Polyimide film and method for manufacturing the same |
| JP5636135B1 (en) | 2013-03-04 | 2014-12-03 | 積水化学工業株式会社 | Fine particle-exfoliated graphite composite, negative electrode material for lithium ion secondary battery, production method thereof, and lithium ion secondary battery |
| KR101482491B1 (en) * | 2014-01-15 | 2015-01-16 | 한국과학기술원 | Fabrication of mgo nanoparticles embedded colorless polyimide film as encapsulation and it's multi-stacking passivation film |
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| JP2013221150A (en) * | 2012-04-13 | 2013-10-28 | Mortech Corp | Polyimide film and method for manufacturing the same |
| JP5636135B1 (en) | 2013-03-04 | 2014-12-03 | 積水化学工業株式会社 | Fine particle-exfoliated graphite composite, negative electrode material for lithium ion secondary battery, production method thereof, and lithium ion secondary battery |
| KR101482491B1 (en) * | 2014-01-15 | 2015-01-16 | 한국과학기술원 | Fabrication of mgo nanoparticles embedded colorless polyimide film as encapsulation and it's multi-stacking passivation film |
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