KR20160074245A - Transparent gas barrier film and method for manufacturing transparent gas barrier film - Google Patents

Abstract

Disclosed in the present invention are a transparent gas barrier film and a method for fabricating the same. According to one aspect of the present invention, the transparent gas barrier film includes: a base substrate; a first barrier layer disposed on the base substrate to prevent moisture from being infiltrated into the base substrate; an adhesive layer disposed on the first barrier layer to bond the first barrier layer to a second barrier layer, and formed of an organic material; and the second barrier layer disposed on the adhesive layer to prevent moisture, which is additionally produced, from being infiltrated into the adhesive layer. The second barrier layer is formed of an inorganic material having a hydrophobic property. According to one aspect of the present invention, an inorganic layer having the hydrophobic property is provided on the base substrate to effectively prevent moisture in air from being introduced.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent gas barrier film and a method of manufacturing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a gas barrier film and a method of manufacturing the same, and more particularly, to a transparent gas barrier film and a method of manufacturing the same.

The image display device that realizes various information on the screen is a core technology of the information communication age and it is becoming thinner, lighter, more portable and higher performance. An organic light emitting display (OLED) for displaying an image by controlling the amount of light emitted from the organic light emitting layer by using a flat panel display capable of reducing weight and volume, which is a disadvantage of a cathode ray tube (CRT) The organic light emitting display device is a self-luminous device using a thin light emitting layer between electrodes, and has an advantage that it can be made as thin as paper.

A general organic light emitting display has a structure in which a sub-pixel driver array and an organic electroluminescent array are formed on a substrate, and light emitted from the organic electroluminescent array of the organic electroluminescent array passes through the substrate or the barrier layer to display an image.

The organic light emitting device has deterioration due to internal factors such as deterioration of the electrode and the light emitting layer caused by oxygen, deterioration due to reaction between the light emitting layer and the interface, and deterioration easily due to external factors such as moisture, oxygen, ultraviolet rays, There are disadvantages that occur. In particular, it is very important to prevent penetration of oxygen and moisture in the organic electroluminescent display device because external oxygen and moisture have a critical effect on the lifetime of the device.

In general, an organic light emitting diode such as an organic light emitting diode (OLED) is a light emitting device that does not require an external light source and emits light by itself, and has an advantage of high luminous efficiency, excellent luminance and viewing angle, and high response speed. However, there is a disadvantage in that the gas such as moisture and oxygen in the air flows into the light emitting device to oxidize the electrodes or deteriorate the device itself, shortening the life span and gradually degrading the light emitting luminance, the light emitting efficiency, and the light emitting uniformity . In order to solve these problems, various techniques for sealing organic light emitting devices for suppressing contact between moisture and oxygen have been studied.

Korean Patent No. 10-1148144 (published on May 23, 2012)

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a transparent gas barrier film having an inorganic film layer having hydrophobic property and a method of manufacturing the same.

Other objects and advantages of the present invention will become apparent from the following description, and it will be understood by those skilled in the art that the present invention is not limited thereto. It will also be readily apparent that the objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.

According to an aspect of the present invention, there is provided a transparent gas barrier film comprising: a base substrate; A first barrier layer positioned above the base substrate to prevent penetration of moisture; An adhesive layer disposed on the first barrier layer and configured to adhere the first barrier layer and the second barrier layer; And a second barrier layer positioned above the adhesive layer and serving to prevent penetration of moisture that may be additionally generated, wherein the second barrier layer is made of an inorganic material having hydrophobicity.

Wherein the second barrier layer is comprised of hafnium oxide (HfO _x ), wherein the hafnium oxide (HfO _x ) may contain 32 to 37.5 at% of hafnium (Hf) and the remainder of 62.5 to 68 at% have.

The second barrier layer may form a contact angle of greater than 95 degrees.

The first barrier layer may be made of at least one of SiOx, SiNx, SiOxNy, AlxOy, AlxNy, NiOx, CoOx, and MgO.

According to another aspect of the present invention, there is provided a method of fabricating a transparent gas barrier film, including: forming a first barrier layer on an upper portion of a base substrate to prevent moisture from penetrating; Forming an adhesive layer made of an organic material on the first barrier layer and serving to adhere the first barrier layer and the second barrier layer; And forming a second barrier layer made of an inorganic material having hydrophobicity to prevent penetration of moisture, which may be additionally generated in the upper portion of the adhesive layer.

Wherein the second barrier layer is comprised of hafnium oxide (HfO _x ), wherein the hafnium oxide (HfO _x ) may contain 32 to 37.5 at% of hafnium (Hf) and the remainder of 62.5 to 68 at% have.

The second barrier layer may form a contact angle of greater than 95 degrees.

According to an aspect of the present invention, an inorganic film layer having hydrophobicity is provided on a base substrate to effectively prevent moisture from entering the atmosphere.

Further, it is possible to reduce the cost by performing the deposition in the chamber in which the adhesive layer and the barrier layer are deposited on the base substrate.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and, together with the description of the invention given below, serve to further the understanding of the technical idea of the invention. And should not be construed as limiting.
1 is a view showing a lamination structure of a transparent gas barrier film according to an embodiment of the present invention,
2 is a flow chart of a method for producing a transparent gas barrier film according to an embodiment of the present invention,
3 is a flow chart of a method for producing a transparent gas barrier film according to another embodiment of the present invention,
4 is a graph showing an experimental result of a transparent gas barrier film according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims are to be construed in accordance with the technical idea of the present invention based on the principle that the concept of a term can be properly defined in order to describe its own invention in the best way It must be interpreted as meaning and concept. Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

1 is a view showing a lamination structure of a transparent gas barrier film according to an embodiment of the present invention.

Referring to FIG. 1, the transparent gas barrier film according to the present embodiment may include a base substrate 100, a first barrier layer 200, an adhesive layer 300, and a second barrier layer 400.

The base substrate 100 may be a polymer plastic film, and may preferably be PET (polyethylene terephthalate), COP (Cyclo Olefin Polymer), PC (polycarbonate), or the like. However, the base substrate 100 is not limited thereto, and it is not necessary to be able to manufacture an OLED encapsulant, an OPV encapsulant, or the like. Generally, the base substrate 100 may have a thickness of 15 to 100 탆.

The first barrier layer 200 may be formed on the base substrate 100 to primarily prevent the penetration of moisture.

At this time, the first barrier layer 200 may be an inorganic film, and may be formed of at least one of SiOx, SiNx, SiOxNy, AlxOy, AlxNy, NiOx, CoOx, and MgO.

The adhesive layer 300 may be formed on the first barrier layer 200 to adhere the second barrier layer 400 and the first barrier layer 200 to each other. Preferably, the adhesive layer 300 may be formed of an organic material.

The second barrier layer 400 may be formed on the adhesive layer 300 to prevent moisture from penetrating into the second barrier layer 400.

The second barrier layer 400 may be an inorganic material having hydrophobicity. Generally, a hydrophobic substance has a contact angle with liquid of 90 degrees or more. Preferably, the hydrophobic inorganic material may be hafnium oxide (HfO _x ), wherein the hafnium oxide (HfO _x ) comprises 32 to 37.5 at% hafnium (Hf) and the remainder is 62.5 to 68 at% oxygen When it is contained, it has excellent effect of preventing moisture penetration. For example, according to this embodiment, the second barrier layer 400 formed of hafnium oxide (HfO _x ) containing the above range has a high contact angle of 95 degrees or higher, and thus has low wettability, that is, The effect of preventing moisture permeation is excellent. The contact angle is a measure of the wettability of a solid surface, and refers to an angle when the liquid equilibrates thermodynamically on a solid surface. The contact angle is measured by most of the fixed water droplets. When the value is low, the hydrophilic property is strong. When the value is high, the hydrophobic property is strong. A detailed description thereof will be given with reference to FIG.

The second barrier layer 400 may be formed on the adhesive layer 300 by using a chemical vapor deposition (CVD) method. In this case, the chemical vapor deposition (CVD) may be any one of CCP (Capacitively Coupled Plasma) chemical vapor deposition and ICP (Inductively Coupled Plasma) chemical vapor deposition.

When the light transmittance of the film including the second barrier layer 400 is low, the luminous efficiency of the light may be low and the reliability of the product may be reduced. Therefore, the transmittance of the film including the second barrier layer 400 is preferably 85% or more.

Each of the layers forming the above-described transparent barrier film is formed by sequentially performing a first barrier layer 200, an adhesive layer 300, and a second barrier layer 400 on a base substrate 100 in a chamber So that the process cost can be reduced.

In addition, the second barrier layer 400 may be formed by a vacuum deposition method such as a sputtering process. However, the second barrier layer 400 can not be formed directly on the adhesive layer 300 made of an organic material by using a deposition method such as sputtering. A more detailed description will be given later with reference to FIG.

2 is a flow chart of a method for producing a transparent gas barrier film according to an embodiment of the present invention.

Referring to FIG. 2, a first barrier layer 200 is formed on the prepared base substrate 100 (S210). In this case, the base substrate 100 may be a polymer plastic film, preferably PET (polyethylene terephthalate), COP (Cyclo Olefin Polymer), PC (polycarbonate), or the like.

Generally, the base substrate 100 may have a thickness of 15 to 100 탆.

The first barrier layer 200 may be formed on the upper surface of the base substrate 100 to primarily prevent moisture from penetrating the barrier layer. At this time, the first barrier layer 200 may be an inorganic film, and may be formed of at least one of SiOx, SiNx, SiOxNy, AlxOy, AlxNy, NiOx, CoOx, and MgO.

The first barrier layer 200 may be formed on the base substrate 100 by using a chemical vapor deposition (CVD) method. In this case, the chemical vapor deposition (CVD) may be any one of CCP (Capacitively Coupled Plasma) chemical vapor deposition and ICP (Inductively Coupled Plasma) chemical vapor deposition.

Thereafter, an adhesive layer 300 is formed on the first barrier layer 200 (S230).

The adhesive layer 300 serves to bond the first barrier layer 200 and the second barrier layer 400 to each other. Preferably, the adhesive layer 300 may be formed of an organic material.

The adhesive layer 300 may be formed on the first barrier layer 200 by using a chemical vapor deposition (CVD) method. In this case, the chemical vapor deposition (CVD) may be any one of CCP (Capacitively Coupled Plasma) chemical vapor deposition and ICP (Inductively Coupled Plasma) chemical vapor deposition.

Finally, a second barrier layer 400 is formed on the adhesive layer 300 (S250).

The second barrier layer 400 may be formed on the adhesive layer 300 to prevent moisture from penetrating into the second barrier layer 400.

The second barrier layer 400 may be an inorganic material having hydrophobicity. Generally, a hydrophobic substance has a contact angle with liquid of 90 degrees or more. Preferably, the hydrophobic inorganic material may be hafnium oxide (HfO _x ), wherein the hafnium oxide (HfO _x ) comprises 32 to 37.5 at% hafnium (Hf) and the remainder is 62.5 to 68 at% oxygen When it is contained, it has excellent effect of preventing moisture penetration. For example, according to the present embodiment, the second barrier layer 400 formed of hafnium oxide (HfO _x ) having the above range has a high contact angle of 95 degrees or higher, and thus has low wettability, that is, The effect of preventing moisture penetration is excellent. The contact angle is a measure of the wettability of a solid surface, and refers to an angle when the liquid equilibrates thermodynamically on a solid surface. The contact angle is measured by most of the fixed water droplets. When the value is low, the hydrophilic property is strong. When the value is high, the hydrophobic property is strong. A detailed description thereof will be given with reference to FIG.

The second barrier layer 400 may be formed on the adhesive layer 300 by using a chemical vapor deposition (CVD) method. In this case, the chemical vapor deposition (CVD) may be any one of CCP (Capacitively Coupled Plasma) chemical vapor deposition and ICP (Inductively Coupled Plasma) chemical vapor deposition.

When the light transmittance of the film including the second barrier layer 400 is low, the luminous efficiency of the light may be low and the reliability of the product may be reduced. Therefore, the transmittance of the film including the second barrier layer 400 is preferably 85% or more.

Each of the layers forming the above-described transparent barrier film is formed by sequentially performing a first barrier layer 200, an adhesive layer 300, and a second barrier layer 400 on a base substrate 100 in a chamber So that the process cost can be reduced.

3 is a flow chart of a method for producing a transparent gas barrier film according to another embodiment of the present invention.

The transparent gas barrier film according to another embodiment of the present invention may be formed using a deposition method such as sputtering in addition to the above-described chemical vapor deposition (CVD). Since the function and effect of each layer are the same in addition to the deposition method used in the manufacturing method of the film according to the present embodiment, only the manufacturing method using the sputtering will be described.

3 (a) to 3 (e), a first barrier layer 320 is formed on the base substrate 310 using a sputtering method (FIG. 3A) The first barrier layer 320 and the second barrier layer 360 are coated with an adhesive layer 330 to form a first film (FIG. 3 (b)).

Thereafter, a second barrier layer 360 is formed on one side of the base substrate 350 using a sputtering method to produce a second film (FIG. 3 (c)).

Next, the portion of the first film on which the adhesive layer 330 is formed and the portion of the second film on which the second barrier layer 360 is formed are butted against each other (FIG. 3 (d)).

Thereafter, the base material 350 formed on the second film is removed by etching (Fig. 3 (e)).

The first barrier layer 320 is formed on the top of the base substrate 310 in a vacuum chamber by sputtering in addition to the above-described method of manufacturing the transparent gas barrier film using a deposition method such as sputtering, The film formed up to the layer 320 may be taken out of the vacuum chamber to apply an adhesive layer formed of an organic material and then put into the vacuum chamber to form the second barrier layer 360 by a sputtering method.

Hereinafter, the present invention will be described in more detail with reference to the following experimental examples.

Evaluation sample preparation

1. A first barrier layer, an adhesive layer and a second barrier layer are sequentially deposited on a base substrate (for example, a polymer plastic film) by vacuum deposition. At this time, the deposition may be performed using chemical vapor deposition (CVD). The chemical vapor deposition (CVD) may be any one of capacitively coupled plasma (CCP) chemical vapor deposition and inductively coupled plasma (ICP) chemical vapor deposition. In addition, the deposition may be performed by a vacuum deposition method such as a sputtering process. Silane, HMDSO, nitrogen, oxygen and ammonia gas were used for CVD, and RF was used as the source. The thickness of the deposited first barrier layer was 100 nm, and the thickness of the second barrier layer was 500 nm.

Test

1. Measurement of Water Vapor Transmission Rate (WVTR)

: 10cm X 10cm After maintaining the vacuum state of the chamber in the sample area, measure the water permeability of the lower chamber (Techmoloc deltaperm) by passing the moisture through the sample while maintaining the environment at 40 ° C and 90% humidity.

2. Measurement of permeability

: Measurement of the transmittance of visible light (0.35 탆 to 0.7 탆) light in a region of 30 mm X 30 mm (using Konica Minolta, CM-5)

3. Contact angle measurement

: Use contact angle / surface energy analyzer (using Phoenix 300)

result

The results for the test are as shown in FIG.

4 is a graph showing an experimental result of a transparent gas barrier film according to an embodiment of the present invention.

The superiority of the transparent gas barrier film according to this embodiment will be described with reference to FIG.

The transparent gas barrier film according to this embodiment sequentially forms a first barrier layer, an adhesive layer, and a second barrier layer on the base substrate.

At this time, the second barrier layer may function to prevent moisture penetration secondarily, and the second barrier layer may be formed of an inorganic material having hydrophobicity. Preferably, the hydrophobic inorganic material may be hafnium oxide (HfO _x ), wherein the hafnium oxide (HfO _x ) comprises 32 to 37.5 at% hafnium (Hf) and the remainder is 62.5 to 68 at% oxygen (Examples 1 to 3). ≪ tb >< TABLE >

That is, in the case where the second barrier layer is made of hafnium oxide (HfO _x ), which is an inorganic material having hydrophobicity, and contains hafnium (Hf) in an amount of 32 to 37.5 at% and the remainder in an amount of 62.5 to 68 at% to 3, the laminated structure is the same but the oxidation Chemistry peunyum (HfO _x) of hafnium (Hf) and a large contact angle content compared to the comparative examples 1 to 3 fall outside the conditions of the oxygen (O) (95 degrees or more contained in the ), And as a result, the water permeability (WVTR) is lowered to 10 ^-4 or less, which shows that the water penetration prevention effect is more excellent. Generally, a hydrophobic substance has a contact angle with liquid of 90 degrees or more. The contact angle is a measure of the wettability of a solid surface, and refers to an angle when the liquid equilibrates thermodynamically on a solid surface. The contact angle is measured by most of the fixed water droplets. When the value is low, the hydrophilic property is strong. When the value is high, the hydrophobic property is strong. In addition, the water permeability (WVTR) is a factor indicating the degree of permeation of water, and the lower the value, the better the property. The transmittance is a factor for indicating the extent to which the film passes through the light. When the transmittance is low, the efficiency of light emission is low and the reliability of the product is reduced. Therefore, it is preferable that the transmittance is 85% .

As described above, a first barrier layer made of an inorganic material is formed on the base substrate, an adhesive layer made of an organic material is formed on the first barrier layer, and an inorganic substance having hydrophobicity When the second barrier layer containing hafnium (HfO _x ) in an amount of 32 to 37.5 at% of hafnium (Hf) and oxygen (O) in the remaining amount of 62.5 to 68 at% is formed, a transparent barrier film having excellent transmittance and water permeability (WVTR) A barrier film can be obtained.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It will be understood that various modifications and changes may be made without departing from the scope of the appended claims.

100: base substrate
200: first barrier layer
300: adhesive layer
400: second barrier layer

Claims (7)

A base substrate;
A first barrier layer positioned above the base substrate to prevent penetration of moisture;
An adhesive layer disposed on the first barrier layer and configured to adhere the first barrier layer and the second barrier layer; And
And a second barrier layer positioned above the adhesive layer and serving to prevent further infiltration of moisture,
Wherein the second barrier layer is made of an inorganic material having hydrophobicity. The method according to claim 1,
Wherein the second barrier layer is made of hafnium oxide (HfO _x ), the hafnium oxide (HfO _x ) contains 32 to 37.5 at% hafnium (Hf) and the remainder contains 62.5 to 68 at% oxygen Wherein the transparent gas barrier film is a transparent gas barrier film. 3. The method according to claim 1 or 2,
Wherein the second barrier layer forms a contact angle of at least 95 degrees. The method according to claim 1,
Wherein the first barrier layer is made of an inorganic film selected from the group consisting of SiOx, SiNx, SiOxNy, AlxOy, AlxNy, NiOx, CoOx and MgO. A method for producing a transparent gas barrier film,
Forming a first barrier layer on the top of the base substrate to prevent penetration of moisture;
Forming an adhesive layer made of an organic material on the first barrier layer and serving to adhere the first barrier layer and the second barrier layer; And
And forming a second barrier layer made of an inorganic material having hydrophobicity to prevent penetration of moisture that may be additionally generated in the upper portion of the adhesive layer. 6. The method of claim 5,
Wherein the second barrier layer is made of hafnium oxide (HfO _x ), the hafnium oxide (HfO _x ) contains 32 to 37.5 at% hafnium (Hf) and the remainder contains 62.5 to 68 at% oxygen Wherein the transparent gas barrier film is a transparent gas barrier film. The method according to claim 5 or 6,
Wherein the second barrier layer forms a contact angle of 95 deg. Or more.

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