KR101711965B1 - A method for fabricating a flexible gas barrier and a flexible gas barrier by the same - Google Patents

Abstract

The present invention relates to a flexible gas barrier film and a method of manufacturing the same. The present invention is characterized by comprising an organic layer comprising a first hydrophobic organic material and a composite layer comprising a second hydrophobic organic material and a stiffener. According to the present invention, it is possible to produce a gas barrier film that is more flexible and excellent in moisture permeation prevention performance.

Description

TECHNICAL FIELD [0001] The present invention relates to a flexible gas barrier film and a method of manufacturing the flexible gas barrier film.

The present invention relates to a flexible gas barrier film and a method of manufacturing the same, and more particularly, to a gas barrier film that is more flexible and excellent in moisture permeation prevention performance by using a hydrophobic organic material, and a method of manufacturing the same.

The inner light-emitting layer and other functional layers constituting the organic electronic device including the organic light-emitting device are composed of organic materials. Due to the nature of the organic material, the life span of the organic light- A sealing structure or sealing structure is required to prevent penetration of moisture and outside air in order to secure long life characteristics without changing color purity and characteristics.

Flexible displays have been recognized as the next generation technology because they can be deformed such as folding and bending while having excellent display characteristics, and many studies are being conducted.

Flexible plastic substrates are used because flexible displays can not be realized as rigid glass substrates conventionally used in general displays. However, in the case of a plastic substrate, there is a problem that the transmittance of water or oxygen is larger than that of the organic substrate, which is not suitable as a gas barrier film. When a gas barrier film having a large moisture or oxygen permeability is used as a gas barrier film, the organic material reacts with moisture due to moisture, shortening the overall lifetime of the display, and deteriorating the display quality due to deterioration of the device.

International Publication No. WO2007037358A1 discloses a method of alternately stacking inorganic and organic materials in a multilayer structure to deposit a gas barrier film in a vacuum state. However, since the inorganic layer is limited to a flexible display, it is also deposited in a vacuum state It is disadvantageous in that the process is complicated and the cost is high.

Korean Patent Laid-Open Publication No. 10-2012-0001163 discloses a method for producing a gas barrier film by vacuum deposition of an organic material, but also involves a problem in that the process is complicated and requires a large cost because of vacuum deposition.

1. International Patent Publication No. WO2007037358A1 2. Korean Patent Publication No. 10-2012-0001163

SUMMARY OF THE INVENTION The present invention provides a method for producing a flexible gas barrier film having a short process time, flexibility, and moisture barrier performance, and a flexible gas barrier film produced thereby.

One aspect of the present invention may be a flexible gas barrier film comprising a hydrophobic organic material.

Another aspect of the present invention may be a flexible gas barrier film comprising an organic layer comprising a first hydrophobic organic material and a composite layer having a second hydrophobic organic material and a stiffener.

According to still another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a first organic layer using a first hydrophobic organic material on a substrate; forming a first complex layer on the first organic layer using a mixed composition of a second hydrophobic organic material and a reinforcing material; And forming a flexible gas barrier film on the substrate.

According to the present invention, since the process of forming the gas barrier film can proceed in a non-vacuum state, the process control is easy and the process time can be remarkably shortened as compared with the conventional vacuum vapor deposition.

Further, since the gas barrier film according to the present invention is composed only of an organic material, it is superior in flexibility to a gas barrier film including an existing inorganic material layer and has a composite layer containing glass fiber or the like, so that gas permeability is remarkably low.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to more fully understand the drawings recited in the detailed description of the present invention, a detailed description of each drawing is provided.
1 is a schematic view showing a vertical section of a flexible gas barrier film according to one aspect of the present invention.
2 is a schematic view of a composite layer in which a hydrophobic organic material and glass fiber are mixed in a flexible gas barrier film according to an aspect of the present invention.
3 is a photograph of a surface of a gas barrier film produced according to an embodiment by a scanning electron microscope.
4 is a vertical cross-sectional photograph of the gas barrier film produced according to the embodiment.
FIG. 5 is a graph showing a measurement result of moisture permeability for a gas barrier film produced according to an embodiment.
Fig. 6 shows the contact angle measurement results for measuring the surface tension.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. The embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Furthermore, embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art. Accordingly, the shapes and sizes of the elements in the drawings may be exaggerated for clarity of description, and the elements denoted by the same reference numerals in the drawings are the same elements.

The present invention relates to a technique for producing a gas barrier film by using a hydrophobic organic substance to produce a gas barrier film which is more flexible and excellent in moisture permeation prevention performance.

One aspect of the present invention may be a flexible gas barrier film comprising a hydrophobic organic material.

The main function of the gas barrier film used in the display is to protect the electronic device from moisture penetration from the outside to the electronic device side. In order to improve the effect of the moisture barrier, a hydrophobic material can be used.

Examples of the hydrophobic organic material include organic materials having hydrophilic properties such as poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxole-co-tetrafluoroethylene], Polytetrafluoroethylene and Ethylene tetrafluoro At least one selected from the group can be used. In particular, poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxole-co-tetrafluoroethylene] is preferable. Since it can be dissolved in Fluorine and Carbon series solutions, Because. Its chemical structure is shown in the following chemical formula (1).

Here, m and n are integers.

In addition, flexibility is required for a gas barrier film applied to a flexible display, such as warping, but only an organic material can be used for securing flexibility. However, if only organic materials are used, it is easy to penetrate water due to pinholes or the like. Therefore, a reinforcing material may be added to prevent this. When a reinforcing material is added, there is a possibility that flexibility is reduced. An appropriate amount of a material that does not cause problems in securing flexibility can be added. The reinforcing material may be glass fiber, glass powder, silicon oxide (SiOx), silicon nitride (SiNx) or the like, though not limited thereto.

The content of the reinforcing material is preferably 0.1 to 1 part by weight based on 100 parts by weight of the hydrophobic organic material. If the content is within the above range, the flexibility of the membrane can be ensured and the moisture permeability can be remarkably reduced.

Another aspect of the present invention may be a flexible gas barrier film having a multilayer structure. The flexible gas barrier film according to this aspect may include an organic layer 20 comprising a first hydrophobic organic material and a composite layer 30 having a second hydrophobic organic material and a stiffener 40. [

This aspect further includes a composite layer 30 including a hydrophobic organic material and a reinforcing material 40 as well as the organic layer 20 made of a hydrophobic organic material.

Here, the expressions "first" and "second" and the like are used to simply distinguish the hydrophobic organic material contained in the organic layer 20 from the hydrophobic organic material contained in the complex layer 30, It does not have the meaning of.

By forming the gas barrier film from an organic material, the stability of the membrane can be assured even with tension and attractive force due to external force. However, since the organic material basically forms a porous structure, it may be very vulnerable to water penetrating from the outside. In order to overcome such disadvantages, a feature of the present invention is that a flexible gas barrier film is formed by using a hydrophobic organic substance that pushes moisture.

Fig. 1 schematically shows a cross section of a flexible gas barrier film having a multilayer structure. FIG. 2 is a schematic view of a composite layer in which a hydrophobic organic material and glass fiber are mixed in a flexible gas barrier film according to an aspect of the present invention. 1 and 2, an organic layer 20 including a hydrophobic organic material is formed on a substrate 10, a hydrophobic organic material and a glass fiber 40 are mixed on the organic layer 20, And the organic layer 20 and the composite layer 30 are alternately and repeatedly laminated.

As the substrate 10, a flexible substrate can be used. Specific examples thereof include polyethylene naphthalate, acrylate resin, polyester resin, styrene resin, transparent teflon resin, polyimide resin, A polyimide resin, a polyamide resin, a polyesterimide resin, a cellulose acylate resin, a polyurethane resin, a polyether ether ketone resin ( polyetherether ketone resins, polycarbonate resins, polyolefin resins, polyarylate resins, polyethersulfone resins, polysulfone resins, cycloolefin resins, resin, polyethylene resin and the like can be used as a flexible substrate material.

Poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxo le-co-tetrafluoroethylene] is preferable as the hydrophobic organic material, and its chemical structure is shown in the following chemical formula 2.

Here, m and n are integers.

The gas barrier film made of only the organic layer 20 may have a pinhole 50 or the like and may have a high gas permeability. By additionally providing the composite layer 30, the gas permeability can be remarkably reduced.

The organic layer 20 is made of a hydrophobic organic material. The composite layer 30 is an extension of the organic layer 20 in that it is based on a hydrophobic organic material like the organic layer 20. However, it is different only in that it further includes a reinforcing member 40.

The number of the organic layers 20 and the number of the multiple layers 30 are preferably 1 to 30 and 1 to 30, respectively.

When there are a plurality of organic layers 20 and multiple layers 30, there may be various ways of laminating them. For example, organic layer / organic layer / organic layer / inorganic layer / organic layer / organic layer / Inorganic layer / inorganic layer / organic layer / inorganic layer / inorganic layer / inorganic layer / inorganic layer / inorganic layer / inorganic layer / inorganic layer / inorganic layer / As shown in Fig. However, since the composite layer 30 can compensate for the problem of the organic layer 20, the organic layer 20 and the composite layer 30 are alternately formed, that is, the organic layer / the multiple layer / the organic layer / Are stacked in this order.

The first and second hydrophobic organic materials each contain a Flurion functional group such as Poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-ioxole-co-tetrafluoroethylene], Polytetrafluoroethylene, Ethylene tetrafluoroetylene, And organic materials having a high melting point and a high melting point. However, the present invention is not limited thereto, and any material having a hydrophobic property can be used.

The first hydrophobic organic material and the second hydrophobic organic material may be the same material. If the hydrophobic material of the adjacent organic layer 20 is the same as the hydrophobic material of the complex layer 30, the compatibility between the organic layer 20 and the composite layer 30 is good, so that problems such as delamination can be remarkably reduced.

As the reinforcing material 40, any material can be used as long as it can compensate for the disadvantages of the organic layer 20, that is, it can reduce the gas permeability. However, the flexibility of the reinforcing material 40 should not be deteriorated by the addition of the reinforcing material 40. Examples of the reinforcing material 40 include glass fiber, glass powder, silicon oxide (SiOx) Silicon nitride (SiNx), or a combination thereof. In the case of using glass fiber, the glass fiber serves as a bridge for enhancing the bonding force between the organic materials and can fill the porous structure such as the pin hole 50 which may be formed in the organic layer 20.

Since the gas barrier film of this aspect has a multi-layered structure in which only an organic layer is laminated (the reinforcing material is further included but the multiple layer is also an extension of the organic layer), a conventional gas barrier film structure having a multilayer structure in which an organic layer and an inorganic layer are repeatedly laminated .

Further, since the gas barrier film of the present invention is made of only an organic material, the organic layer / inorganic layer / organic layer / inorganic layer ... Which is superior in flexibility to the conventional gas barrier film.

Another aspect of the present invention is a method of manufacturing a semiconductor device comprising the steps of forming a first organic layer 20 using a first hydrophobic organic material on a substrate 10 and forming a second hydrophobic organic material and a stiffener 40) to form the first composite layer (30). The method of manufacturing the flexible gas barrier film of the present invention includes the steps of:

Further, the method may further include forming the second organic layer 21 on the first complex layer 30 using the first hydrophobic organic material or the second hydrophobic organic material.

That is, the organic layer 20 may be formed first on the substrate 10, and then the composite layer 30, the organic layer 21, and the composite layer 31 may be formed thereon. In this case, the first organic layer 20 / the first composite layer 30 / the second organic layer 21 / the second composite layer 31 ... , That is, a film having a structure in which the organic layer 20 is disposed at the outermost position.

Here, the reason why the organic layer is divided into the first organic layer 20 and the second organic layer 21 is that the hydrophobic organic materials used in the respective organic layers may be different. However, if the hydrophobic organic materials used in each organic layer are the same, it is not necessary to distinguish them, and the organic layer / multiple layer / organic layer / multiple layer ... In particular, since one organic material is used, the process can be easily managed and the process can be simplified.

The step of forming the first organic layer 20, the first composite layer 30, or the second organic layer 21 may be performed by a non-vacuum solution process. As the solution process, one or more methods selected from the group consisting of spraying, dipping, spin coating, and drop casting may be used. This aspect is characterized in that it forms a film in a non-vacuum state rather than a vacuum deposition.

Since the film is formed using a simple solution process in a non-vacuum state, it is possible to simplify the process, facilitate the process control, and improve the productivity by reducing the management cycle time, compared with the conventional case using the vacuum deposition process have. However, the present invention is not limited thereto, and any solution process capable of forming a film can be used.

Examples of the first hydrophobic organic substance and the second hydrophobic organic substance include Flurion functional groups such as Poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-ioxole-co-tetrafluoroethylene], Polytetrafluoroethylene and Ethylene tetrafluoroethylene, And an organic material having hydrophobic properties, may be used. In particular, the same material may be used as the first hydrophobic organic material and the second hydrophobic organic material, and in this case, the bonding property between adjacent layers can be improved.

As the reinforcing material 40, at least one selected from the group consisting of glass fiber, glass powder, silicon oxide (SiOx), and silicon nitride (SiNx) may be used although not limited thereto. The reinforcing material 40 may serve to remove the porous structure or to prevent the occurrence of the porous structure by, for example, filling the pin holes 50 formed in the organic layer. Therefore, any substance can be used as long as it can perform the above function. For example, when PTFE is used as the hydrophobic organic material, the glass fiber can be added as a reinforcing material to significantly reduce the permeability of moisture and the like, and even if glass fiber is added, the flexibility of the film is not deteriorated.

The organic layer 20 is first formed on the substrate 10 but the present invention is not limited thereto and the organic layer 20 may be formed on the substrate 10 by first forming the composite layer 30 on the substrate 10, May be formed. In this case, multiple layers / organic layers / ... That is, a structure in which the multiple layers are disposed at the outermost positions.

In this aspect, the organic layer, the composite layer, and the materials constituting the organic layer, the composite layer and the material constituting the organic layer,

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

<Examples>

First, 0.5 g of Poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxo le-co-tetrafluoroethylene] (Sigma Aldrich) was added to 100 g of solvent FC- g, and the mixture was agitated in air for 24 hours to immerse the PES substrate in the organic layer coating solution. The PES substrate was held for 5 minutes, and then taken out and dried. This immersion and drying step was repeated 10 times and 30 times to form an organic layer on the PES substrate.

Next, 0.5 g of Poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxo le-co-tetrafluoroethylene] was added to 100 g of the solvent FC-72 0.5 g of a fiber (purchased from Sanlú) was added and stirred in air for 24 hours. The substrate was immersed in the coating solution for a layer, and the substrate was held for 5 minutes, and then taken out and dried. This immersion and drying step was repeated 10 times and 30 times to form a composite layer on the organic layer.

The above process was repeated to produce a gas barrier film having a total of 15-layer structure in which an organic layer and a multiple layer were alternately laminated.

<Microstructure observation>

FIG. 3 shows a photograph of the surface of the gas barrier film prepared according to the embodiment by scanning electron microscope. Referring to FIG. 3, a hydrophobic organic material layer is formed on the surface of the film, and it is confirmed that pinholes of a small size are rarely formed. The water can easily permeate through the pinhole, but the composite layer formed immediately adjacent to the pinhole includes a reinforcing material, whereby the passage of moisture and the like can be effectively blocked.

FIG. 4 is a vertical cross-sectional photograph of a gas barrier film manufactured according to an embodiment of the present invention. Referring to FIG. 4, it can be seen that the total thickness of the gas barrier film composed of 15 layers is about 30 .mu.m.

<Evaluation of water permeability rate>

The gas barrier film prepared according to the example was measured for moisture permeability using a calcium test. As a measuring instrument, a Keithley 2400 voltage-current meter was used. The measurement was performed at a temperature of 20 ° C and a relative humidity of 50%, and the result is shown in FIG. The moisture permeability can be calculated by the following formula.

는 칼슘의 밀도, M[X] 는 X 물질의 몰랄 질량, R는 시간 t 가 지난 후 칼슘의 저항, R_i는 초기 칼슘 저항, h_i는 초기 칼슘 높이를 의미한다.Here, WVTR refers to the moisture permeability of the gas barrier,

Is the density of calcium, M [X] is the moral mass of the X material, R is the resistance of calcium after time t, R _i is the initial calcium resistance and h _i is the initial calcium height.

As a result of the test, the gas barrier film of the examples had a water vapor permeability of 1.98x10 ^-2 g / m ² / day. Generally, the moisture permeability of the gas barrier film required in the flexible electronic device is 10 ^-1 to 10 ^-6 g / m ² / day. Since the moisture barrier rate of the gas barrier film of the embodiment is within this range, the gas barrier film according to the present invention is flexible It can be utilized as a gas barrier film of an electronic device.

&Lt; Evaluation of surface tension &

The surface energy can be used to determine the degree of hydrophobicity of the gas barrier film. The smaller the surface tension, the stronger the hydrophobicity. This surface tension can be calculated using the following Owen's equation.

는 가스배리어의 표면장력,

는 도포하는 용액의 표면장력,

는 가스베리어의 표면 수소결합 힘,

는 도포하는 용액의 표면 수소결합 힘을 나타낸다. Here, &amp;thetas; is a contact angle,

The surface tension of the gas barrier,

The surface tension of the solution to be coated,

The surface hydrogen bond strength of the gas barrier,

Represents the surface hydrogen bonding force of the solution to be applied.

Fig. 6 shows the contact angle measurement results for measuring the surface tension. 6 is a photograph of droplets dropped onto the base plastic, and the right photograph is a photograph of droplets falling on the gas barrier film of the example. Referring to FIG. 6, the contact angle between the basic plastic film and the water droplet was about 29.3 DEG, and the calculated surface tension was 64.229 mN / m. The contact angle between the gas barrier film and the water droplet in the example was 98.6 占 and the calculated surface tension was 17.24 mN / m. Generally, when the contact angle is 90 ° to 150 °, it is evaluated as a hydrophobic film, and it can be confirmed that the gas barrier film of the embodiment is a hydrophobic film.

The terms used in the present invention are intended to illustrate specific embodiments and are not intended to limit the present invention. The singular presentation should be understood to include plural meanings, unless the context clearly indicates otherwise. The word &quot; comprises &quot; or &quot; having &quot; means that there is a feature, a number, a step, an operation, an element, or a combination thereof described in the specification. The present invention is not limited by the above-described embodiments and the accompanying drawings, but is intended to be limited only by the appended claims. It will be apparent to those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. something to do.

10: substrate
20: Organic layer
30: multiple layers
40: glass fiber
50: pin hole

Claims (15)

delete delete An organic layer comprising a first hydrophobic organic material; And
A composite layer having a second hydrophobic organic material and a stiffener,
The content of the reinforcing material is 0.1 to 1 part by weight based on 100 parts by weight of the second hydrophobic organic material,
Wherein the first hydrophobic organic material and the second hydrophobic organic material are the same material,
Flexible gas barrier film. The method of claim 3,
Wherein the first and second hydrophobic organic materials are selected from the group consisting of Poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxole- co- tetrafluoroethylene], Polytetrafluoroethylene and Ethylene tetrafluoro Or more. The method of claim 3,
Wherein the reinforcing material comprises at least one selected from the group consisting of glass fiber, glass powder, and silicon nitride (SiNx). The method of claim 3,
Wherein the number of the organic layers and the number of the multiple layers are each a plurality, and the organic layer and the multiple layers are alternately stacked. The method according to claim 6,
Wherein the number of the organic layers is 1 to 30 and the number of the multiple layers is 1 to 30. delete Forming a first organic layer on the substrate using a first hydrophobic organic material; And
And forming a first composite layer on the first organic layer using a mixed composition of a second hydrophobic organic material and a reinforcing material,
The content of the reinforcing material is 0.1 to 1 part by weight based on 100 parts by weight of the second hydrophobic organic material,
Wherein the first hydrophobic organic material and the second hydrophobic organic material are the same material,
A method for manufacturing a flexible gas barrier film. 10. The method of claim 9,
And forming a second organic layer using the first hydrophobic organic material or the second hydrophobic organic material on the first complex layer. 10. The method of claim 9,
The first hydrophobic organic material and the second hydrophobic organic material may be poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxole-co-tetrafluoroethylene], polytetrafluoroethylene and ethylene tetrafluoroethylene Wherein at least one selected from the group consisting of the fluorine-containing gas barrier film and the fluorine-containing gas barrier film is used. 10. The method of claim 9,
Wherein the reinforcing material is at least one selected from the group consisting of glass fiber, glass powder, and silicon nitride (SiNx). delete 11. The method according to claim 9 or 10,
Wherein the step of forming the first organic layer, the first complex layer, or the second organic layer is performed by a non-vacuum solution process. 15. The method of claim 14,
Wherein the solution process comprises using at least one method selected from the group consisting of spraying, dipping, spin coating, and drop casting.

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