KR101539828B1 - fabrication method of a multilayer by electrophoretic deposition - Google Patents

Abstract

(A) depositing a dispersion, suspension or solution of a first particle on a conductive substrate in the presence of an electric field to form a layer of a first particle; And
(b) electrodepositing a dispersion, suspension or solution of the second particles onto the layer of the first particle in the presence of an electric field to form a layer of the second particle
A multilayer film having various barrier properties is formed on a conductive substrate through an electrodeposition process satisfying a large area, processability, and low cost, and the formed multilayer film is formed into a multilayer film by a vacuum forming process By increasing the number of layers, a barrier film that maximizes moisture, oxygen, and electric field barrier properties is realized. The barrier film produced by the production method of the present invention exhibits a uniform and good film quality and can be improved to meet the respective characteristics such as heat resistance, water barrier property, gas barrier property, magnetic field barrier property and the like.
The present invention also relates to a multilayer film manufactured by the above manufacturing method and a gas barrier film using the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a multi-

The present invention relates to a multilayer film manufacturing method and a gas rupture film using the multilayer film by the electrodeposition process and / or the vacuum blank forming method, and more particularly, to a process for forming a multilayer film having a large area at low cost and at low cost, And more particularly to a method for forming a multilayer film having various functions, particularly gas barrier properties, through an electrodeposition process and / or a vacuum blank molding process.

Generally, an organic electronic device is a device that uses a phenomenon such as light emission or current generation according to the flow of electric charge when an electric field is applied to an organic layer provided between a cathode and an anode, and various devices functioning according to a selected organic material are manufactured . For example, organic electroluminescent devices (OLEDs), which are attracting attention as next-generation flat panel displays, are thin, light and have excellent color characteristics. They are not only used as inorganic substrates including conventional glass substrates and silicon, but also flexible substrates such as metal substrates and plastic substrates or metal foils It has an advantage that it can be manufactured on a substrate. However, unlike inorganic materials with high stability, organic electronic devices including organic materials are very susceptible to moisture and oxygen. Therefore, when moisture is exposed to the atmosphere including oxygen and water vapor or water vapor from the outside of the device, There is a problem that the device efficiency and lifetime are significantly reduced.

In order to solve these problems, there have been proposed a method in which a curable polymer material is coated on the surface of an organic layer or a metal layer and then a curing process is carried out to realize adhesiveness and sealing property, a method in which an inorganic material or metal cap such as glass is used or a laminating method Attempts have been made to block moisture and oxygen from the outside through the use of a gas barrier film or a method of depositing various materials.

However, each of the methods has advantages and disadvantages. When the film is formed using the lamination method, there is a problem such as the inflow of moisture and oxygen through the interface of the film adhesion surface. Inorganic materials and metal caps are difficult to apply to flexible displays because of their poor mechanical properties or due to the difference in thermal expansion coefficient between the substrates and the transparency of visible light. This has the drawback of being tricky. Further, in the case of the method of applying and curing the curable material, the by-products or unreacted residues generated in the curing reaction remain, which disadvantageously hinders the driving of the organic electronic device or shortens the service life. Even when a transparent material such as glass is used, it may cause a problem that it is easily broken by external pressure, and when the device is enlarged, the processing cost or sealing is incomplete, and the possibility of penetration of outside moisture or gas is increased.

In addition, various organic and inorganic materials have been known to form encapsulation films through chemical vapor deposition (CVD), spin coating, spray deposition, vacuum filtering, and the like (CW Chen, CC Huang, Goki Eda, Glovanni Fanchini (2010) 3308, Goki Eda, Kwon Chen, KC Chen, Diamond & Related Materials 14 (2005) 1126, Xu Y, Long G, Huang L, Huang Y, Wan X, and Manish Chowalla, Nature Nanotechnology 3 (2008), Korean Patent Laid-Open No. 10-2010-0121978, etc.). These methods are complicated in processes, waste of materials is high, demand for expensive equipment or quality of obtained film, , The presence of pinholes, and the like, resulting in problems in manufacturing a large-area film.

Accordingly, there is a continuing need for a gas barrier material which has good transparency to visible light and does not exhibit the above problems, and a film using the same.

It is an object of the present invention to overcome the above-mentioned problems by simplifying a high-cost process used in the conventional multilayer film manufacturing. Another object of the present invention is to provide a barrier film having various characteristics such as transparency and gas barrier property at the same time.

The object of the present invention is achieved by using an electrodeposition process. In addition, in the present invention, by using the vacuum forming method in addition to the above electrodeposition step, formation of a multilayer film having a large area can be further facilitated.

A multilayer film manufacturing method of the present invention comprises:

(a) depositing a dispersion, suspension or solution of a first particle on a conductive substrate in the presence of an electric field to form a layer of a first particle; And

(b) electrodepositing a dispersion, suspension or solution of the second particles onto the layer of the first particle in the presence of an electric field to form a layer of the second particle

And a control unit. Preferred embodiments of the present invention further include the following steps (c) and (d) in addition to steps (a) and (b)

(c) peeling the multilayer film from the conductive substrate, and

(d) placing and separating two or more of the peeled multilayer films on the support, sealing, heating, and applying a vacuum.

Preferably, the first particles include at least one selected from the group consisting of polyimide, vinylidene halide, polypyrrole, and polyethylene dioxythiophene, and more preferably, the first particle is polyvinylidene chloride or Polyetherimide.

In a preferred embodiment, the second particles include at least one selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and boron nitride.

At least one of the steps (a) and (b) is performed under an electric field of 1 to 100 V / m, preferably 1 to 10 V / m, most preferably 1 to 3 V / m.

In a preferred embodiment, the content of the first particles in the dispersion, suspension or solution of the first particles is 0.01 to 50% by weight, preferably 0.01 to 10% by weight, most preferably 0.01 To 3% by weight. The content of the second particles in the dispersion, suspension or solution of the second particles is from 0.01 to 50% by weight, preferably from 0.01 to 10% by weight, most preferably from 1 to 6% by weight, based on the weight of the dispersion, suspension or solution .

At least one of the steps (a) and (b) may be performed at a temperature of 10 to 100 ° C, and at least one of the steps (a) and (b) Lt; / RTI > conditions. The step (d) may be performed at a temperature of 10 - 500 ° C for 1 - 24 hours.

In another preferred embodiment of the present invention, the manufacturing method of the present invention further comprises drying the multi-layered film peeled from the conductive substrate. Such a drying step may be carried out under suitable temperature and time conditions, as understood by those skilled in the art, and specifically at temperatures of from 10 to 500 DEG C for 1 to 24 hours.

Another aspect of the present invention relates to a multilayer film produced by the manufacturing method of the present invention.

Another aspect of the present invention is

(i) a first layer comprising at least one selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and boron nitride, and

(ii) a second layer comprising at least one selected from the group consisting of a polyimide, a halogenated polymer, an olefin polymer, and a conductive polymer

The present invention relates to a multi- Preferably, the polyimide can be prepared in accordance with the method of the present invention as long as it can be prepared as a polyetherimide (PEI) or a dispersion, suspension or solution even in the case of other polymers.

Another aspect of the present invention relates to a multilayer film produced according to the production method of the present invention, or a gas barrier film comprising the multilayer film comprising (i) the first layer and (ii) the second layer. Preferably, the gas barrier film has a water vapor transmission rate (WVTR) of 15 g · m ² / day or less and a visible light transmittance of 40% or more. In another embodiment, the number of the first layer and the second layer of the multilayer film in the gas barrier film is 2 or more, respectively.

Another aspect of the present invention relates to an electronic device including an electronic device including a multilayer film according to the present invention, and a gas barrier film including the multilayer film according to the present invention. Preferably, the electronic device is an active organic light emitting device (AM-OLED).

<Definition>

As used herein, the terms spatial, or directional, such as "inner,""outer,""above,""below," and the like, It should be understood, however, that the present invention may assume various alternative and alternative orientations, and thus, these terms are not to be considered as limiting. Also, as used in the specification and claims, It is to be understood that the numerical values set forth in the following specification and claims, unless otherwise indicated, are hereby incorporated by reference into the present invention. Unless the application is limited to the minimum and at least the same extent as the scope of the claims, each numerical parameter &lt; RTI ID = 0.0 &gt; It is to be understood that the scope of the invention is to be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements which fall within the true spirit and scope of the present invention. Quot; to 10 "refers to a range between a minimum value of 1 and a maximum value of 10 (including inclusive) and a range of values, that is, a range beginning at a minimum value of 1 or more and terminating at a maximum value of 10 or less, Quot; on "or" formed on, "as used herein, should be understood to include both on the surface Or " formed " on substrate "substrate " means that one or more of the same or different It should be understood that all references cited herein are incorporated by reference in their entirety for all purposes. By "visible region" or "visible light &quot;Quot; refers to electromagnetic radiation having a wavelength in the range of 380 nm to 780 nm. The term "film" refers to a region of the coating having a desired or selected composition. "Layer" includes one or more "films. &Quot; In addition, as used herein, the term " polymer "refers to oligomers, homopolymers, copolymers and terpolymers.

Electrodeposition electrophoretic deposition ) fair

The electrophoretic deposition process is a process that has been used in a variety of manufacturing industries. In the process of forming colloidal particles or ions dispersed in water or other suitable dispersion medium into a thin film on the surface of a conductive object, The particles and ions move to form a uniform thin film (see FIG. 1). As a result of the action of the electric field, ionized polymeric or inorganic particles go to the electrode surface of the opposite charge, lose charge, and solidify to form a thin film. This process is widely used in industry, and is often used in other processes as well as electrodeposition coating to form a paint film on a vehicle body for uniform coating of a vehicle. A uniform large-area thin film can be formed through electrodeposition of a polymer having desired characteristics. Unlike other conventional thin film forming methods, the electrodeposition process is advantageous in that a thin film can be manufactured at room temperature and atmospheric pressure without an expensive vacuum jammer, and uniform thinning of the thin film is easy.

A blank space  Molding Vacuum bag process , VBP )

The vacuum blank molding is a type of bag molding, in which one of the male or female molds is used, the laminated molding material is laid on its surface, the bag is covered with a soft rubber or plastic film bag, And the laminated molding material is brought into close contact with the surface of the mold, followed by curing and molding. When the laminated material is heated and press-cured by using an autoclave, it is called an autoclave molding method. The vacuum device used here is attached to the end product so as not to contain bubbles, and the pressure is applied and the densification and curing are performed. Depending on the molding process, the semi-finished product is put into the pressure vessel, and the structure is produced by pressurization and heating. Any number of structures having a complex shape and a desired size can be formed simultaneously within the allowable range of capacity. Therefore, it is used in cases where it is difficult to produce a mold because the size is large or the shape is complicated and it can not be manufactured by compression molding method or the quantity of product is not so large. It is widely used for manufacturing aerospace composite parts and prototypes and aircraft parts. There is an advantage that a high-quality large-sized molded article can be obtained, but it has a disadvantage in that it has a long curing cycle and a high production cost for operation because it is performed in a batch mode.

&Lt; Configuration of the Invention &

The present invention is characterized in that a multi-layered film having two or more layers is manufactured by using an electrodeposition method to provide a multilayered film having various properties, such as improved gas barrier properties, economically.

In the manufacturing method of the present invention, basically two layers are obtained through the following steps (a) and (b), and if necessary, steps (a) and / or have.

(a) depositing a dispersion, suspension or solution of a first particle on a conductive substrate in the presence of an electric field to form a layer of a first particle; And

(b) depositing a dispersion, suspension or solution of the second particles onto the layer of the first particles in the presence of an electric field to form a layer of the second particles. The substrate may be a "conductive" substrate or a "conductor &quot;. For example, the conductive substrate may have a resistivity of less than 10 ⁵ ohm-cm, for example less than 10 ¹ ohm-cm, for example less than 10 ^-2 ohm-cm.

In addition, a layer of a third particle can be formed by using electrodeposition or other layer formation methods other than the first particle and the second particle (third particle). The multilayer film produced in the present invention may typically include two or more, preferably four or more, more preferably six or more different layers.

The multilayer film formed in accordance with the method of the present invention may further include (c) peeling the multilayer film from the conductive substrate in addition to the steps (a) and (b) for laminating a larger number of layers, and (d) (I.e., "vacuum forming method") in which two or more multi-layered films are stacked and positioned, followed by sealing, heating, and applying a vacuum. By carrying out the steps (c) and (d), the multilayer film of two or more layers is laminated, and a plurality of layers are closely contacted to form a multilayer film. The step (d) may be performed at a temperature of 10 to 500 ° C, preferably 50 to 300 ° C, more preferably 100 to 300 ° C, and most preferably 100 to 250 ° C for 1 to 24 hours. If the temperature at which the vacuum molding process is performed is less than 10 ° C, there is a high possibility that the two or more peeled multi-layer films are sufficiently close to each other to be unlikely to bond sufficiently. If the temperature exceeds 500 ° C, the multi- There is a high possibility that a problem such as the occurrence of problems occurs.

From the viewpoint of gas barrier properties, it is preferable to use a polymeric material such as polyimide, vinylidene halide, polypyrrole, polyethylene dioxythiophene, etc. as the material for use in the production method and multilayer film of the present invention, A polymeric material can be used as the first particle, and preferably polyvinylidene chloride, or polyetherimide and the like can be used. If desired, a mixture of two or more materials may be used.

A separate layer to be laminated to the layer comprising the above materials, i.e. the second particle, can be any material as long as it can exhibit optimal properties when combined with the above materials. Preferably, the second particle may comprise at least one of inorganic materials, more preferably selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and boron nitride. In one embodiment of the present invention, the graphene-based material as the second particle may be used in view of the gas barrier property. The graphene is sp ² Graphene is a hexagonal two-dimensional structure composed of carbon atoms bonded to each other and graphene has an extremely high carrier mobility. Recently, various types of graphene materials have been used through various processing processes. Examples thereof include graphene, graphene oxide, Treated graphene oxide, and the like.

At least one of the steps (a) and (b) is performed under an electric field of 1 to 100 V / m, preferably 1 to 10 V / m, most preferably 1 to 3 V / mV / m . If the electric field strength is lower than 1 V / m, the movement of the particles in the solvent is too slow or the quality of the formed film is lowered. If the electric field strength is higher than 100 V / m, There is a high possibility that a problem such as an increase will occur.

In a preferred embodiment, the content of the first particles in the dispersion, suspension or solution of the first particles is 0.01 to 50% by weight, preferably 0.01 to 10% by weight, most preferably 0.01 To 3% by weight. The content of the second particles in the dispersion, suspension or solution of the second particles is from 0.01 to 50% by weight, preferably from 0.01 to 10% by weight, most preferably from 1 to 6% by weight, based on the weight of the dispersion, suspension or solution . If the content of the first particles or the second particles is less than 0.01% by weight, it is difficult to obtain desired gas blocking effect due to these particles and the electrodeposition does not progress well. If the content of the first particles or the second particles exceeds 50% There is a high possibility that a solid lump that can not be mixed with a solvent in a dispersion liquid, a suspension or a solution is generated.

As the solvent in the dispersion, suspension or solution used in the present invention, any solvent which can uniformly form these dispersions, suspensions or solutions can be used, and as a non-limiting example, water and an aqueous Medium and the like. Useful coalescing solvents include hydrocarbons, alcohols, esters, ethers, and ketones. Suitable cohesive solvents include alcohols, polyols and ketones. Specific cohesive solvents include isopropanol, butanol, 2-ethylhexanol, isophorone, 2-methoxypentanone, ethylene and propylene glycol, and monoethyl, monobutyl and monohexyl ether of ethylene glycol . The amount of coalescent solvent is generally between 0.01 and 25% by weight, based on the total weight of the aqueous medium, if used, for example between 0.05 and 5% by weight. In addition to the solvent, various additives such as pigment compositions and, if desired, surfactants, wetting agents or catalysts, may be included in the dispersion, suspension or solution. The pigment composition may also comprise conventional pigments such as pigments such as iron oxide, strontium chromate, carabone black, coal dust, titanium dioxide, talc, barium sulphate, as well as color pigments such as cadmium yellow, cadmium red, chrome yellow, Lt; / RTI &gt;

At least one of the steps (a) and (b) may be performed at a temperature of 10 to 100 ° C, and at least one of the steps (a) and (b) Lt; / RTI &gt; conditions.

In another preferred embodiment of the present invention, the manufacturing method of the present invention further comprises drying the multi-layered film peeled from the conductive substrate. This drying step may be carried out under suitable temperature and time conditions as will be understood by those skilled in the art, and is illustratively carried out at a temperature of from 10 to 500 DEG C for 1 to 24 hours.

Another aspect of the present invention relates to a multilayer film produced by the manufacturing method of the present invention.

Another aspect of the present invention is

(i) a first layer comprising at least one selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and boron nitride, and

(ii) a second layer comprising at least one selected from the group consisting of a polyimide, a halogenated polymer, an olefin polymer, and a conductive polymer

The present invention relates to a multi- Preferably the polyimide is a polyetherimide (PEI).

Another aspect of the present invention relates to a multilayer film produced according to the production method of the present invention, or a gas barrier film comprising the multilayer film comprising (i) the first layer and (ii) the second layer. Preferably, the gas barrier film has a water vapor transmission rate (WVTR) of 15 g · m ² / day or less, preferably 10 ^-2 g · m ² / day or less, and most preferably 10 ^-4 g · m ² / ). If the gas barrier film has a water vapor transmission rate exceeding 15 gm ² / day, the gas barrier effect is reduced and it is difficult to prevent deterioration of the device even when the barrier film is used. Further, the gas barrier film exhibits a visible light transmittance close to 40% or more, preferably 50% or more, more preferably 70% or more, and most preferably 100% or so. When the visible light transmittance of the gas barrier film is less than 40%, the light generated from the light emitting device is blocked by the film, resulting in a problem that the light efficiency is lowered. In another embodiment, the number of the first layer and the second layer of the multilayer film in the gas barrier film is 2 or more, respectively.

Another aspect of the present invention relates to an electronic device including an electronic device including a multilayer film according to the present invention, and a gas barrier film including the multilayer film according to the present invention. Preferably, the electronic device may be any organic electronic device including an organic layer and a metal layer. Examples of the electronic device include an OLED display, a backlight (OLED, TFT-LCD), a flat light source for illumination, an OLED display for a flexible flat panel, OLED lighting, organic photovoltaic (OPV) and dye-sensitized solar cells (DSSC), thin film solar cells, OTFTs (organic thin film transistors), and printed electronic materials. Among them, organic electroluminescent devices, and particularly active organic electroluminescent devices (AM-OLEDs), may be cited.

The organic light emitting device in which the multilayered film of the present invention is to be used is a complete solid device that self-luminesces by current conduction, and generally includes a light emitting layer (an organic semiconductor thin film capable of emitting fluorescence), a carrier transporting layer, Electrode, but it is also possible to use other configurations known in the relevant industry (see, for example, Japanese Patent Application Publication 2003-0031400). As a typical constitution, a transparent substrate made of glass, plastic or the like is used as a support for a light emitting device, and a transparent electrode material is an indium tin oxide (ITO) thin film or a tin oxide film, a metal having a large work function such as aluminum or gold, A conductive polymer such as copper, polyaniline, poly (3-methylthiophene), and polypyrrole may be used. The organic light emitting layer and the carrier transport layer are generally made of a p-channel organic semiconductor material. In some cases, the polymer light-emitting layer such as a fluorescent pigment molecule mixed with an amorphous polymer medium or a poly-p-phenylene derivative (PPV) Can be used.

The multilayer film according to the present invention is formed on the above-described electronic device to block moisture, oxygen, and the like from the outside and maintain an inert environment, thereby playing an important role in improving the lifetime of the electronic device.

In the present invention, it is possible to manufacture a multi-layered film including a plurality of layers using an electrodeposition process without complicated processes and expensive materials / equipments, and the multi-layered film thus manufactured is a barrier film maximizing moisture, oxygen, And exhibits excellent properties. In addition, by stacking a plurality of multilayer films through a vacuum forming process, a multilayer film including a larger number of layers can be manufactured to further improve the barrier properties. The present invention makes it possible to economically and easily manufacture a multi-layered film having a large area, thereby reducing the need for expensive materials and equipment, and is particularly useful in the manufacture of displays requiring a large area process.

1 is a schematic view of an electrodeposition processing apparatus according to the present invention.
2 is a schematic view showing a vacuum molding method.
3 is a scanning electron microscope (SEM) photograph of graphene formed on a metal electrode as a conductive substrate.
4 is a scanning electron microscope (SEM) image of the multi-layered film prepared by the vacuum forming method.
FIG. 5 is a photograph of a multi-layer film produced through electrodeposition and then peeled from a conductive substrate.
6 is a graph showing the transmittance in the visible light region according to the number of layers in the multilayer film including the polyetherimide and the reduced graphene oxide.
FIG. 7 is a graph showing the water barrier properties (WVTR) according to the number of layers in the multilayer including the polyetherimide and the reduced graphene oxide.

The present invention is illustrated by the following examples, which are intended to illustrate the invention in detail, but should not be construed as limiting the invention.

The process for producing a multilayer film according to the present invention was carried out in the following order.

(1) Preparation of colloidal suspension / dispersion for multi-layer film formation.

(2) Manufacturing the multilayer film by applying the suspension / dispersion liquid sequentially to the electrodeposition device and applying an electric field.

(3) Preparing a multi-layered film using the vacuum forming method after peeling the manufactured multi-layered film.

Example  One. Polyetherimide  Preparation of colloidal suspensions of particles

Ultram 1,000 (80 g) was placed in a mixed organic solvent of N-methylpyrrolidone (NMP, 165 g) and acetophenone (20.6 g) and completely dissolved at 85 to 90 ° C under nitrogen. N-methylpiperazine (18.9 g) and acetophenone (61.8 g) were simultaneously and slowly injected into the above solution of Ultem 1,000 for 2 hours while stirring (stirring rate: 150 rpm). After the injection was completed, the temperature of the mixed solution was heated to 110 ° C and allowed to react for 2 hours and 30 minutes. Then, lower the temperature of the mixed solution to room temperature, add acetophenone (6 g) and lytic acid (50%, 1.48 g) to the solution (30 g), slowly drop the distilled water (78 g).

Example  2. Reduction process Grapina  Preparation of dispersion of oxide particles

The graphite oxide (0.1 to 0.15 g) was placed in 100 ml of distilled water and subjected to ultrasonic pulverization through ultrasonic waves (700 W) for 4 hours to obtain a dispersion of graphene particles. At this time, in order to obtain a high-quality graphene dispersion, centrifugation was performed at 4,000 rpm for 10 to 15 minutes, and the graphene dispersion at the top was taken and used in the subsequent process. Hydrazine (35%, 5 ml) was mixed with distilled water (35 ml) at 0 ° C and then slowly dropped to the graphene dispersion obtained above at the same time as stirring, followed by reduction reaction at 100 ° C for 30 minutes.

Example  3. Through electrodeposition process Multilayer film  Produce

A dispersion of the reduced graphene oxide particles obtained in Example 2 was added to a container (7 cm x 4 cm) of a device for producing electrodeposited thin films provided with a stainless electrode and a copper / aluminum electrode at intervals of 1 cm, Was applied for about 30 seconds to 10 minutes to form a thin film of the reduced graphene oxide particles on the stainless steel anode or the cathode electrode. After the electrodeposition process was completed, the dispersion liquid was removed from the container, and the formed thin film was washed with distilled water several times and then dried at room temperature.

After completion of the drying, the stainless electrode having the thin film formed thereon was placed back into the container of the electrodeposited thin film production apparatus, and a colloidal suspension of the polyetherimide particles obtained in Example 1 was added. A voltage of 5 to 7 V was applied to the suspension at a rate of about 2 to 3 Min to form a thin film of polyetherimide particles. The multilayer film (film of reduced graphene oxide + film of polyetherimide) formed on the stainless electrode was washed several times with distilled water and dried at a temperature of 200 to 300 ° C. A scanning electron microscope photograph of the dried multilayer film is shown in Fig.

Example  4. From the metal electrode Multilayer film  detach

The multilayer film prepared in Example 3 was separated from a stainless electrode using a support. The separated multilayer film showed a film shape with high transparency as shown in FIG.

Example  5. Formation of multilayer structure of organic / inorganic double film by vacuum forming

The multilayer film prepared in Example 4 was superposed and placed in two vacuum forming molds, and a release film and a breather were added. The sealant was then applied to the rim, covered with a vacuum blank film, and vacuum applied using a vacuum pump. After the vacuum state was formed, the temperature was increased to 200 ~ 250 ° C, and then maintained for 30 minutes to prepare a multi-layered film. A scanning electron microscope photograph of the prepared multilayer structure film is shown in Fig.

The obtained multilayered film exhibited excellent water barrier properties as compared with other materials while maintaining a good transmittance in the visible light region as shown in Figs. 6 and 7.

The present invention can manufacture a thin film of a large-area multilayer structure by manufacturing the multilayer film through an electrodeposition and a vacuum forming process economically and easily, and is useful in manufacturing a large-area display without the need for expensive materials and equipment.

It will be readily apparent to those skilled in the art that modifications may be made to the invention without departing from the principles disclosed in the foregoing specification. Accordingly, the specific embodiments described in detail herein are illustrative only and are not intended to limit the scope of the invention, which fall within the full scope of the appended claims and their specific and all equivalents.

Claims (21)

(a) depositing a dispersion, suspension or solution of a first particle on a conductive substrate in the presence of an electric field to form a layer of a first particle; And
(b) electrodepositing a dispersion, suspension or solution of the second particles onto the layer of the first particle in the presence of an electric field to form a layer of the second particle
/ RTI &gt;
Wherein the first particles include at least one selected from the group consisting of a polyimide, a halogenated polymer, an olefin polymer, and a conductive polymer,
Wherein the second particle comprises at least one selected from the group consisting of graphene, graphene oxide, reduced graphene oxide, and boron nitride.
A method for producing a multilayered film. The method according to claim 1,
(c) peeling the multilayer film from the conductive substrate, and
(d) placing and separating two or more of the peeled multilayer films on the support, sealing, heating and applying a vacuum
Wherein the method further comprises: delete 3. The method according to claim 1 or 2, wherein the first particle comprises polyvinylidene chloride, or polyetherimide. delete 3. The method according to claim 1 or 2,
Is carried out under an electric field of 1 to 100 V / m in at least one of the steps (a) and (b). 3. The method according to claim 1 or 2,
Wherein the content of the first particles in the dispersion, suspension or solution of the first particles is from 0.01 to 50% by weight, based on the weight of the dispersion, suspension or solution of the first particles. 3. The method according to claim 1 or 2,
Wherein the content of the second particles in the dispersion, suspension or solution of the second particles is from 0.01 to 50% by weight, based on the weight of the dispersion, suspension or solution of the second particles. 3. The method according to claim 1 or 2,
Wherein at least one of the steps (a) and (b) is carried out at a temperature between 10 and 100 ° C. 3. The method according to claim 1 or 2,
Wherein at least one of the steps (a) and (b) is performed at 10-30% relative humidity. The method according to claim 1,
And drying the multi-layered film peeled off from the conductive substrate. 12. The method of claim 11,
Wherein the drying step is carried out at a temperature of 10 - 500 캜 for 1 - 24 hours. 3. The method of claim 2,
Wherein the step (d) is performed at a temperature of 10 to 500 ° C for 1 to 24 hours. delete delete delete delete delete delete delete delete

Images