WO2017116106A1 - High moisture- and gas-barrier flexible film of multilayer structure not using adhesive, and manufacturing method therefor - Google Patents

Abstract

The present invention relates to a barrier film and, more particularly, to a plastic nano composite film in which clay (clay tablets) particles are dispersed, a process for bonding a metal film or sheet to the plastic nano composite film without using an adhesive, and the manufacture of a high moisture- and gas-barrier flexible film formed into a multilayer structure of an organic composite-metal or (organic composite-metal-organic composite) film manufactured by the process. The high moisture- and gas-barrier flexible film according to the present invention causes a chemical reaction or exhibits a polar interaction between a matrix resin of a nanocomposite and a reactive group of having a metal surface, such that a metal film and the nanocomposite are uniformly bonded to the entire area, thereby removing a space for gas and moisture to penetrate therethrough.

Description

Multi-layered moisture and gas high barrier flexible film without adhesive and its manufacturing method

The present invention relates to a barrier film, and more particularly, to a plastic nanocomposite film in which nanoparticles, such as clay, are dispersed, and a process of bonding a metal film or sheet thereto without using an adhesive and an organo-metal prepared by using the same. Or it relates to a water and gas high barrier flexible film composed of a multilayer structure of an organic-metal-organic film and a method of manufacturing the same.

More specifically, the inorganic particles are dispersed in a polymer resin to prepare a composite film; Treating the metal film with an ion beam or plasma; And stacking and compressing the composite film and the surface treated metal film, and a display device using the same as an encapsulant or a backsheet packaging material, and a method of manufacturing a moisture and gas-high barrier multilayer composite film. It relates to a light emitting device or a solar cell device.

This application claims priority based on Korean Patent Application No. 10-2015-0191351, filed December 31, 2015 and Korean Patent Application No. 10-2016-0178090, filed December 23, 2016. All content disclosed in the specification and drawings of the present invention is integrated in this application.

Moisture and gas barrier films in which thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide are formed on the surface of a plastic substrate or film are used for packaging articles that require the blocking of various gases such as water vapor and oxygen. It is widely used for packaging to prevent alteration of food, industrial goods and pharmaceuticals, and is used in liquid crystal display devices, solar cells, organic electroluminescence substrates, electrode packaging materials and the like.

As a method of manufacturing such a gas barrier film, the method of forming a gas barrier layer mainly by plasma CVD method, apply | coating the coating liquid which has a polysilazane as a main component, and then apply a surface treatment method or them together Methods are known. In addition, the conventional plate glass used in the display field is easy to break, there is no bending, there is a large specific gravity, there is a limit to the thin and light, so that the plastic film is used as a substitute for the plate glass in the manufacture of flexible displays. Plastic film is a lightweight and flexible material that is easy to bend, hard to break, and easy to thin, so it is an effective material that is applied to large-sized display devices, but due to its own free volume, it is displayed due to high oxygen or water vapor transmission. There is a problem that the light emitting performance of the device is likely to be poor. The same is true for organic light emitting diodes (OLEDs), which are applied in various fields such as portable devices, monitors, notebooks, and TVs, and thus, low power consumption, fast response speed display, and easy thinning compared to conventional light sources. Although space utilization is excellent due to process application, organic materials and metal electrodes included in OLEDs are easily oxidized by external factors such as moisture, and products containing OLEDs are very sensitive to environmental factors. It causes problems in the durability of the equipment used.

OLEDs are becoming more versatile, ranging from small cell phones to 55-inch TVs. OLEDs are very sensitive to moisture, allowing a water vapor transmission rate (WVTR) of 10 ^-6 g / ㎡day (per day per square meter of substrate). Amount of moisture) At present, OLED uses glass substrate, so there is no problem of moisture permeation of the substrate itself, but this type of product is not flexible, and the latest flexible electronic products use plastic (polymer), not glass, as a substrate. That is, since the plastic substrate is composed of a structure having a free volume with low density between molecules, a large amount of moisture enters the device through the substrate itself, and the moisture permeation amount is more than 10 g / m 2 day. do. This figure is 10 ⁷ times the water permeability tolerance required for OLED displays. Therefore, technologies for preventing moisture transmittance (WVTR) by placing various types of barrier films on plastic substrates have been developed. For this purpose, a multilayer film structure manufactured by depositing a ceramic gas barrier layer having a composition such as SiO _x or AlO _y on a polymer film is used. This is a common problem in electrode materials and solar cell back sheets. Accordingly, there is a demand for developing a blocking material that effectively blocks the penetration of oxygen and moisture, thereby reducing damage to organic electronic devices and ensuring durability of the device.

The process of minimizing the penetration of oxygen or water vapor through the deposition or addition of inorganic material on the well-known plastic film has been applied. In general, inorganic materials such as silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, and the like are mainly used as the gas barrier film. These gas barrier thin films are coated on the surface of the plastic film by a vacuum deposition method such as plasma chemical vapor deposition, sputtering, or the sol-gel method in a high vacuum state. In the form of such a gas barrier thin film, a multilayer structure in which the same structure is repeated many times is common, or in general, one or more inorganic layers are usually present in the gas barrier thin film. Here, the organic layer serves to prevent the defect of the thin film, which may occur in the inorganic layer, rather than the gas barrier property, from propagating to the next inorganic layer. In Korean Patent Laid-Open Publication No. 2009-0007590, a dry barrier layer deposited by an inorganic compound is provided on one side of a base film, and a gas barrier layer formed by a polyurethane resin is installed on the dry barrier layer, and on the gas barrier layer. Discloses a structure in which an overcoat layer formed of a polyester resin and / or a polyacrylic resin is provided. However, in the case of the overcoating layer using such a resin, deformation of the organic substrate and cracking and peeling of the inorganic thin film may occur due to a large linear expansion coefficient difference between the dry barrier layer and the overcoating layer. Therefore, the design of the appropriate multilayer structure and the adhesion between the coating layers is very important to minimize the stress at the interface of each layer. In addition, when the thickness is about 1 μm, the water vapor transmission rate is 0.3 g / m ² / day, which is not suitable for use as a gas barrier film. In US Patent No. 7,638,925, a process of manufacturing a dry barrier layer by sputtering on an organic layer was repeated to produce a multilayered plastic substrate, which showed excellent water vapor transmission rate. However, due to the multilayer structure, the process may be complicated, the thickness may be increased, and cracks may occur due to a difference in the coefficient of thermal expansion. Korean Patent Laid-Open Publication No. 2005-0010375 discloses a bonded plastic film, and a first organic-inorganic hybrid buffer layer, a gas barrier layer, and a second organic-inorganic hybrid buffer layer are sequentially stacked on both sides of the bonded plastic film. It provides a multi-layered plastic substrate forming a symmetrical structure around the center. However, this multilayer structure has a disadvantage in that a process such as coating or laminating is added. Japanese Patent Laid-Open No. 2011-161891 proposes a polysilazane film in many layers of two or more layers to complement pinholes and cracks in a gas barrier sheet, thereby minimizing the occurrence of pinholes or cracks that pass through all silica films and providing rapid gas barrier properties. It is mentioned that deterioration can be prevented. However, the method may cause cracks due to an increase in thickness compared to silazane monolayers. In addition, the coating process is increased and the water vapor transmission rate is 0.5 g / m ² / day, which is not suitable for use as a gas barrier film.

As described above, in order to make up for the shortcomings of pinholes and cracks, the conventional invention is to deposit and apply a multilayer coating of silazane or a mixture of an organic layer and an inorganic layer. However, the method is modified due to a large difference in coefficient of linear expansion of the dry barrier layer. Cracking and peeling of the inorganic thin film may occur. Therefore, the design of the appropriate multilayer structure and the adhesion between the coating layers is very important to minimize the stress at the interface of each layer. In the present invention, to bond a plastic film and a metal film dispersed with a nano-material without an adhesive to produce a flexible composite film having a high barrier of water and gas that conventional materials did not achieve.

On the other hand, organic light emitting diodes (OLEDs), which have recently emerged as important in the display field, have low power consumption, fast response speed, and are advantageous for thinning a display device or lighting as compared to existing light sources. In addition, OLED is excellent in space utilization, and is applied in various fields including various portable devices, monitors, notebooks, and TVs, but in the commercialization and use of OLEDs, the main problem is durability.

Organic materials and metal electrodes included in OLEDs are easily oxidized by external factors such as moisture, and products including OLEDs are highly sensitive to environmental factors. In other words, OLEDs are very sensitive to moisture, so the water vapor transmission rate (WVTR) tolerance is less than 10 ^-6 g / m ² day (amount of moisture transmitted per day per square meter of substrate). Currently, OLED uses glass substrate, so there is no problem of moisture permeation of the substrate itself, and it solves the water permeation problem by improving the barrier property of the packaging material and the sealing material.

However, devices such as flexible displays and electronic papers, which are expected to occupy an important position in the market in the future, have a big problem because they use plastic (polymer) as a substrate rather than glass. In addition, the plate glass is easy to break, there is no bending, there is a limit in the specific gravity is large, thin and light. In order to manufacture flexible device substrates, plastic films having good flexibility instead of plate glass are attracting attention. Plastic films are lightweight and difficult to break, and are thin and easy to be flexible, which is an effective material that can cope with the increase in size of display devices. However, since the plastic film has a higher gas permeability than glass, the display device using the plastic film as a substrate has a problem in that the light emitting performance of the display device is easily degraded due to oxygen or water vapor permeation. That is, since the plastic substrate is composed of a structure having a free volume of low intermolecular density, a large amount of moisture enters the device through the substrate itself, and the moisture permeation amount may be more than 10 g / m 2 / day. do. This value is 10 ⁷ times the water permeability tolerance required for OLED display devices. Therefore, it is required to develop a moisture and gas high barrier flexible film that can effectively block the penetration of moisture while reducing damage to organic electronic devices and secure long-term reliability.

The present invention was developed to solve the above problems, by introducing a polar functional group on the surface by functionalizing the metal film surface and then thermally crimped without the adhesive and the polymer film dispersed nanoclay (clay plate) particles and organic-inorganic nano It is an object of the present invention to provide a method for producing a high barrier multilayer flexible film in which a composite film and a metal film are bonded, and thus, a multilayer organic-inorganic / metal flexible film having improved gas and moisture barrier properties.

In addition, in the present invention, after treating both sides of the metal film with an ion beam or plasma to which a reactive agent is added to generate functional groups on both sides of the metal film, the polymer film in which the metal film and the nanoclay (clay plate) particles are evenly dispersed is separated from the metal and the cross section or the like. The present invention provides a method of manufacturing a multilayer structure flexible film without using an adhesive by pressing the both sides using a thermal pressurization process and having no pin-hole and exhibiting high barrier against moisture and gas.

In the present invention, in order to solve the above problems by dispersing the inorganic particles in the polymer resin to produce a composite film; Treating the metal film with an ion beam or plasma; And it provides a method for producing a water and gas high barrier multi-layered composite film comprising the step of laminating and pressing the composite film and the surface treated metal film.

In the manufacturing method according to the present invention, before the pressing step may further comprise the step of treating the surface of the composite film with an ion beam or plasma.

In the production method according to the present invention, the inorganic particles include montmorillonite, bentonite, kaolinite, saponite, hectorite, baydelite, halosite, vermiculite, margite, sukconite, volconscote and kenyarite It may be selected from the group consisting of nano smectite clay, carbon material containing graphene, fullerene and carbon nanotubes, or nanometal plate mexene having a calcium carbonate or planar structure or a mixture thereof.

In the production method according to the present invention, the polymer is a polyester containing polyamide, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate or polyethylene naphthalate or maleic anhydride, amine, hydroxyl group Polystyrene, polyarylate, polycarbonate, polyacrylate, cyclic olefin copolymer, polynorbornene, aromatic florene polyester, polyisulfone, polyimide, epoxy resin or polyfunctional acrylic containing reactive functional groups, including Can be selected from among the rates.

In the manufacturing method according to the present invention, the step of preparing the composite film may use a polymer resin containing a polar group in the molecule or may further mix 5% by weight or less of a compatibilizer.

The composite film manufactured according to the manufacturing method of the present invention may be used as an encapsulant or a back sheet packaging material of a display device, an organic light emitting device, or a solar cell.

Although the polymer nanocomposite film itself has high gas and moisture barrier properties, gas and moisture are permeated after a long time. However, when used in a display, a battery electrode, or a solar cell, the life is affected. When the composite film and the metal film are laminated in a multi-layer structure, due to the synergistic effect (synergy), it shows a superior barrier property than the original metal film or nano composite film.

In addition, an object of the present invention can be produced a multi-layered film showing a high barrier properties and flexibility at the same time by showing excellent bonding properties.

In the case of nylon or polyester film in which nanoparticles are evenly dispersed, it shows excellent blocking properties, but it cannot satisfy the high barrier properties required in electronic devices, solar cells, batteries, and the like. It exhibits extreme moisture barrier and gas barrier properties much higher than nanocomposite or metal films. This process can be easily applied to a general polymer film or a metal film, it is possible to manufacture a high-breaking film in a continuous process without using an adhesive has the advantage of significantly reducing the time and cost of the processing process.

1 is a schematic diagram of a multi-layered composite film manufacturing process according to an embodiment of the present invention.

Figure 2 is a transmission electron micrograph showing a nano-composite film dispersed in clay according to an embodiment of the present invention.

3 is a scanning electron micrograph showing a bonding cross section of the nanocomposite film and the metal film according to an embodiment of the present invention.

Figure 4 is a result of measuring the water transmittance of the multi-layered film according to an embodiment of the present invention.

5 is a result showing the light emission of the same brightness when the multi-layered film according to an embodiment of the present invention is attached to the rear of the OLED display device as a blocking film when the switch is turned on 6 months after the performance.

Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

In the present invention, in order to solve the above problems by dispersing the inorganic particles in the polymer resin to produce a composite film; Treating the metal film with an ion beam or plasma; And it provides a method for producing a water and gas high barrier multi-layered composite film comprising the step of laminating and pressing the composite film and the surface treated metal film.

According to the invention 30% by weight (preferably up to 10% by weight, more preferably up to 5% by weight) of fillers (clay, talc (mica) as layer fillers) surface-treated in organic or inorganic crystalline and amorphous polymers, Graphene and other carbon nanotubes, calcium carbonate, fullerene, etc.) are extruded together with a compatibilizing agent in an extruder to produce a film, or mixed in an internal mixer, and then the composite is made into small particles and put into an extruder, followed by extrusion. After processing into a film to produce an organic composite film in which the filler is evenly dispersed, it is treated with a reaction ion beam or plasma and compressed to one side or both sides of a metal film containing a polar group on the surface to completely adhere the gas or water. Extremely different from water and gas due to the synergistic effect of infinitely extending or blocking passages Flexible organic compound showing a castle-metal compound or an organic-metal-organic composite structure may be composed.

In the manufacturing method according to the present invention, before the pressing step may further comprise the step of treating the surface of the composite film with an ion beam or plasma. After the metal film is bonded to the composite film after ion beam or plasma treatment in the connected vacuum chamber, it is possible to continuously manufacture a multi-layered composite film which is completed by winding on a roller. Figure 1 shows a schematic diagram of a multi-layered composite film manufacturing process according to an embodiment of the present invention, the metal film 10 is a vacuum chamber 40 with an ion beam generator 20 or a plasma generator 30 in succession The surface of the metal film is treated by ion beam or plasma by supplying argon 21 or oxygen 31 into the vacuum chamber. Thereafter, the composite film 40 prepared by dispersing the inorganic particles in the polymer resin is continuously supplied, pressed by the press 50, and then wound on a roller to obtain a multilayer structure composite film 60.

In the production method according to the present invention, the inorganic particles include montmorillonite, bentonite, kaolinite, saponite, hectorite, baydelite, halosite, vermiculite, margite, sukconite, volconscote and kenyarite It may be selected from the group consisting of nano smectite clay, carbon material containing graphene, fullerene and carbon nanotubes, or nanometal plate mexene having a calcium carbonate or planar structure or a mixture thereof.

In the production method according to the present invention, the polymer is a polyester containing polyamide, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate or polyethylene naphthalate or maleic anhydride, amine, hydroxyl group Polystyrene, polyarylate, polycarbonate, polyacrylate, cyclic olefin copolymer, polynorbornene, aromatic florene polyester, polyisulfone, polyimide, epoxy resin or polyfunctional acrylic containing reactive functional groups, including Can be selected from among the rates.

In the manufacturing method according to the present invention, the step of preparing the composite film may use a polymer resin containing a polar group in the molecule or may further mix 5% by weight or less of a compatibilizer. The polymer may contain a polar group in the molecule or, in the case of a non-polar polymer, 5 wt% or less (preferably 1 wt% or less) of a compatibilizer to prepare a crystalline or amorphous thermoplastic polymer composite so that the filler is evenly dispersed. Can be. Organic complexes containing fillers act as barriers to the passage of gases and moisture, increasing the passage of these permeable molecules indefinitely, and blocking the extremely small amount of permeation by bonding metal films without pinholes to one or both sides. It becomes a barrier flexible film. In order to manufacture the flexible film, the organic nanocomposite film and the metal film are compressed at room temperature or below the glass transition temperature of the mother resin, and the film is compressed evenly in all areas to block pinholes through which gas or moisture can pass.

According to the present invention, the flexible composite film is formed by applying an ion beam or plasma process to generate a polar group on the surface of the organic composite film, and has a covalent bond by interacting with or reacting with a polar group present on the surface of the metal film treated in this manner. This causes adhesion on both sides, which blocks the path for gas or moisture to pass through.

The composite film manufactured according to the manufacturing method of the present invention may be used as an encapsulant or a back sheet packaging material of a display device, an organic light emitting device, or a solar cell.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. In particular, the technical spirit of the present invention and its core configuration and operation are not limited by this. In addition, the content of the present invention may be implemented in various other forms of equipment, not limited to the embodiments and embodiments described herein.

It is an object of the present invention described above that less than 50% by weight (preferably less than 20% by weight more preferably less than 5% by weight) of clay particles is preferably less than 10% by weight (more preferably less than 5% by weight) Emulsifiers or compatibilizers may be mixed in a mixer and then injected into a film in which nanoclay particles are evenly dispersed. Both sides of the metal film or sheet are added with reactive gases (oxygen, ammonia, etc.) in small portions on the film, treated with an ion beam or plasma-treated to generate a reactor on the metal surface. After attaching the nanocomposite film in which the above-mentioned nanoclay particles are dispersed on both sides or the cross-section of the functionalized metal film, and then bonding by pressing with a pressing roller at a temperature lower than the glass transition temperature of the polymer resin or the two-layer or three-layer structure Prepare a multilayer film. The distribution state of nanoparticles was measured by scanning electron microscope, transmission electron microscope, and incineration X-ray scattering apparatus. The above-mentioned clay particles are characterized in that they are selected from the group consisting of montmorillonite, bentonite, kaolinite, mica, hectorite, stevensite, vermiculite, halosite, volconcite, marganite, kenyalite, and mixtures thereof. . The compatibilizer interacts with the ionic groups of the clay organicized in the polymer backbone or side chains to open up the clay layers and at the same time allow the high pressure foam fluid to enter between these open clays and easily adsorb on the clay surface. Works. Reactors formed on the metal surface were measured by X-ray spectroscopy (XPS), and moisture and gas permeability were measured by a mocon meter and a moisture permeability meter of the Institute of Standards and Science.

An important process variable in achieving the object of the present invention is the adhesion strength of the metal surface and the nanocomposite. In the present invention, the adhesive is not used at all, but the reactor generated on the metal surface reacts with the reactor of the nanocomposite resin or has strong interaction (hydrogen interaction), thereby uniformly bonding all the surfaces. By removing the space through which gas or moisture can permeate, high fluidity is exhibited by preventing the diffusion of the fluid. In the embodiment of the present invention is an environmentally friendly by not using an adhesive and by using oxygen as a reaction gas, the reaction occurs well, but the reaction occurs only on the surface is almost no change in the properties of the metal film itself. Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are only illustrative of the present invention, and it is intended that the present invention is not limited to these examples.

<Example 1>

Mitsubishi's nylon resin MXD6 (Metaxylene diamine 6 nylon, glass transition temperature = 85 ^o C, melting point = 237 ^o C) 95% by weight of clay clay's Closite 93A (treated with methyl, dihydrgenated tallow, quaternary ammonium) 5% by weight After mixing in advance, the mixture is melt-mixed in a single screw extruder, and stretched by 2 to 3 times during T die extrusion to prepare an extrusion film in which clay is dispersed. The film thus prepared is annealed at 180 ° C. for 10 minutes and then dried in a vacuum oven. The aluminum film was washed with ethyl alcohol and dried in a vacuum oven at 80 ° C. for 24 hours, and then mounted in an ion beam plasma reactor. On the buffer layer to gel, it reacted in the DC / RF ion / plasma reactor 5x10 ^- under a vacuum of ² Torr to generate oxygen plasma with RF (13.56MHz) power of 120 Watt processes the aluminum film for 10 minutes. In the vacuum reactor, the ion beam is injected at a constant flow rate of 3 ml / min in a vacuum chamber equipped with a cold-hollow cathode ion gun to generate an ion beam having a low energy of about 1 keV. Generates an ion beam with energy as low as 1 keV and scans the ion beam under high precision (300 microamperes per unit cm ² ). The reactive gas added with the ion beam uses oxygen or ammonia and the injection amount is 0.2 to 6 ml. / min, preferably about 3 ml / min is suitable. The clay / nylon composite film prepared on both sides of the treated aluminum film or prior to the cross-section is put together in a press (compress), pressed at 150 ° C for 10 minutes to 30 minutes, taken out, stored in a vacuum oven, and then sized as needed. The oxygen permeability and water vapor transmission rate were measured by cutting. Oxygen permeability was measured using MOCON's OX-TRAN instrument at a relative humidity of 0% at room temperature using the method of ASTM D 3985. Water vapor transmission rate was measured at 100% relative humidity using the method of ASTM F 1249 using Illinois Instrument Inc 7001. For 48 hours at room temperature, the values below 10 ^-4 g / m ² / day were measured using a standard measuring instrument. In addition, the measurement was performed twice about two test pieces about each Example, and the average value of four measured values in total was obtained.

<Example 2>

The nylon composite film of Example 1 was placed on both sides of an aluminum film (12 μm), pressed at 150 ° C. for about 20 minutes, taken out, stored in a vacuum oven, and cut to an appropriate size as needed to measure oxygen permeability and water vapor transmission rate. .

Figure 2 is a transmission electron micrograph showing a nano-composite film dispersed in clay prepared according to Example 1 of the present invention. In the case of the nylon composite prepared in Examples of the present invention, it can be seen from the transmission electron microscope that the clay particles are well dispersed at a single monolayer particle level and are oriented regularly.

In addition, Figure 3 is a scanning electron micrograph showing the bonding cross section of the nanocomposite film and the metal film according to an embodiment of the present invention when the fracture surface of the bilayer composite film is observed with a scanning electron microscope, the two films are perfectly attached to each other You can see it.

Figure 4 is a graph of the results of measuring the water transmittance of the multi-layered film according to an embodiment of the present invention. Examining this as shown in Table 1, which summarizes the barrier properties of the nylon composite film in which the clay particles are dispersed, the oxygen permeability is reduced to less than 1% and the moisture permeability is also reduced by more than 70%. You can see the evenly distributed effect. Aluminum film has excellent self-shielding properties and hardly differs depending on aluminum thickness. In the case of a double layer film in which a nylon composite film and aluminum are bonded, a range of performances suitable for most applications is shown. In particular, the composite film has a water transmittance of 3x10 ^-3 g / mm / m ² day or less, and in the case of the double-sided bonded film of Example 2, 1x10 ^-7 g / mm / m ² day or less (measured by the Institute) (Figure 4). Among the currently measured films, it shows the world's highest level of flexible film blocking performance.

film	Oxygen transmittance (cc / m 2 day)	Moisture permeability (g / mm / m 2 day)
Nylon (MXD6)	One	1.9
Nylon Composite (+ 5wt% Clay)	0.002	0.58
Aluminum film (12μm)	0.0008 or less	0.001
Aluminum film (18μm)	0.0009 or less	0.001
Nylon Composite (+ 5wt% Clay) + Aluminum Film (12μm)	1x10 -4 or less	0.0003
Nylon Composite (+ 5wt% Clay) + Aluminum Film (18μm)	1x10 -4 or less	0.0003
Nylon composite (+5 wt% clay) + Aluminum film (12 μm) + Nylon composite (+5 wt% clay) (Example 2)	~ 0 (1x10 -5 or less)	1x10 -7 or less (Standard Institute Measurement)

As described above, according to the present invention, a polyamide (nylon) system in which clay (clay plate) particles are evenly dispersed without using an adhesive by functionalizing both surfaces of a metal film or sheet to generate reactive polar groups on the surface thereof. Nanocomposite films, polyester films such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate or polyethylene naphthalate, or polystyrene containing reactive functional groups (such as maleic hydride, amine, hydroxyl group), Nano, such as polyacrylates, polycarbonates, polyacrylates such as polymethacrylates, cyclic olefin copolymers, polynorbornenes, aromatic florene polyesters, polyesulfones, polyimides, epoxy resins or polyfunctional acrylates Composite film and thermocompression In turn, due to the interaction and reaction between the reactors on the whole surface, it is possible to prepare a multilayered composite film having an organic composite-metal film (or organic composite-metal-organic composite film) structure bonded evenly without pinholes on the front surface. Multi-layered composite films have superior barrier properties to water and gases than the original polymeric nanocomposite films or metal sheets.

5 is attached to the back of the OLED display device (FIG. 5 a, b) with a blocking film according to an embodiment of the present invention (Fig. 5 c) by attaching epoxy to the edge UV curing (Fig. 5d) 6 months later, when the switch is turned on again, the result shows the same brightness of light emission (FIG. 5 e). The multi-layered composite film produced from the above results has excellent barrier properties against moisture and gas, and it can be seen that it can be used as a flexible substrate material without deterioration in performance even when used as a back substrate material of the OLED for a long time.

Claims (7)

1. Dispersing inorganic particles in a polymer resin to prepare a composite film;

   Treating the metal film with an ion beam or plasma; And

   The method of manufacturing a water and gas high barrier multi-layer composite film, characterized in that it comprises the step of laminating the composite film and the surface treated metal film.
2. The method according to claim 1,

   The method of manufacturing a water and gas high barrier multi-layer composite film, characterized in that further comprising the step of treating the surface of the composite film with an ion beam or plasma before the pressing step.
3. The method according to claim 1,

   The inorganic particles may be montmorillonite, bentonite, kaolinite, saponite, hectorite, baydelite, halosite, vermiculite, margotite, sukconite, volconscote and kenyarite, including nanosmectite clay, graphene, A method of manufacturing a water and gas high barrier multi-layered composite film, wherein the carbon material comprises fullerene and carbon nanotubes, or is selected from the group consisting of calcium carbonate or nanometal plate mexene having a planar structure or a mixture thereof.
4. The method according to claim 1,

   The polymer is a polyester containing polyamide, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate or polyethylene naphthalate or a polystyrene containing reactive functional group containing maleic hydride, amine, hydroxyl group Water, characterized in that selected from polyarylates, polycarbonates, polyacrylates, cyclic olefin copolymers, polynorbornenes, aromatic florene polyesters, polythersulfones, polyimides, epoxy resins or polyfunctional acrylates And a method for manufacturing a gas barrier layered composite film.
5. The method according to claim 1,

   The preparing of the composite film may include using a polymer resin containing a polar group in a molecule or further mixing 5 wt% or less of a compatibilizer.
6. An electronic device using the composite film produced according to any one of claims 1 to 5 as an encapsulant or a backsheet packaging material.
7. The method according to claim 6,

   The electronic device is any one of a display device, an organic light emitting device or a solar cell.

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