KR101972439B1 - Graphene oxide nanocomposite membrane for improved gas barrier and preparation method thereof - Google Patents

Abstract

The present invention relates to a graphene oxide nanocomposite film in which graphene oxide having a size of 3 mu m to 50 mu m is coated with a thickness of 10 nm or more on various supports or a graphene oxide nanocomposite film in which graphene oxide is embedded in a polymer Technology.
According to the graphene oxide nanocomposite film produced according to the present invention, graphene oxide having a size of 3 쨉 m to 50 쨉 m is coated with a nano-thick film on a variety of supports, or a simple film having graphene oxide inserted into a polymer It can be applied to display devices, food and medicine packaging and so on.

Description

TECHNICAL FIELD [0001] The present invention relates to a graphene oxide nanocomposite membrane having improved gas barrier properties,

The present invention relates to a graphene oxide nanocomposite film having improved gas barrier properties and a method of manufacturing the same, and more particularly, to a graphene oxide nanocomposite film having graphene oxide having a thickness of 3 탆 to 50 탆 and having a thickness of 10 nm or more, A nanocomposite film, or a graphene oxide nanocomposite film having a structure in which graphene oxide is inserted in a polymeric polymer. The present invention relates to a technology capable of being applied to a display device, a food, and a medicine packaging.

Graphene is a material consisting of a single carbon atom layer of hexagonal honeycomb structure, which is very interesting and has excellent physico-chemical properties due to the structural specificity of a two-dimensional nanocrystal structure. It became one. In other words, it is the thinnest substance in the world, but it has mechanical characteristics 200 times stronger than steel, 100 times more current permeability than copper and 100 times faster than silicon. In particular, it is known that the gas and ion molecular barrier properties are excellent with high mechanical strength despite being a single atom layer.

However, the fact that graphene has excellent gas and ion molecular interception characteristics is realized only in a defect-free graphene structure. When a defect occurs in graphene, gas and ion molecules easily permeate into a graphene defect portion, It is difficult to maintain the barrier properties of gas and ion molecules when the graphene is formed into a thin film.

Various techniques have been developed in relation to the blocking properties of gas and ion molecules of graphene. Recently, as a graphene laminated barrier film comprising at least one graphene laminate in which a hydrophilic graphene layer and a hydrophobic graphene layer are laminated, Attempts have been made to fabricate a graphene laminated film in which the thickness of the graphene layer is adjusted to 0.01 to 1,000 占 퐉 and to apply the graphene laminated film to food wrapping paper or the like by using the barrier properties. However, the structure is somewhat complicated, Data are presented, and the barrier properties of various gases are not known (Patent Document 1).

Also, a graphene / polymer composite protective film including a plurality of graphene layers and a plurality of polymer layers between each of the graphene layers is also known. However, the graphene / polymer composite protective film is also complicated in the structure of the graphene composite film, But the specific results regarding the gas barrier properties are not disclosed, and thus there is a limit to the application to actual industries (Patent Document 2).

Also known are gas diffusion barriers containing a polymer matrix and a functionalized graphene with a surface area of 300 to 2,600 m ² / g and a bulk density of 40 to 0.1 kg / m ³ , wherein the surface area and bulk density of the functionalized graphene It is difficult to predict the gas barrier properties in the case of a thin film and it is proved by the quantitative data on the gas barrier properties in practice that it is difficult to predict the gas barrier properties in the case of the thin film because it is a thick film in which the functionalized graphenes are dispersed in the polymer matrix, (Patent Document 3).

Further, studies on graphene / polyurethane nanocomposites and graphite barrier properties in which thermoplastic polyurethane contains graphite oxide as a nanofiller by melt mixing, solution blending, or co-polymerization are also known. As a filler for thermoplastic polyurethane The barrier properties of nitrogen gas have been clarified according to the content of graphene contained therein. However, the size of graphene oxide and the thickness of graphene oxide film have not been known to control various gas barrier properties (Non-Patent Document 1).

Patent Document 1. Korean Patent Publication No. 10-2014-0015926 Patent Document 2: Korean Patent Publication No. 10-2013-0001705 Patent Document 3. US Patent Publication No. US 2010/0096595

Non-Patent Document 1. Hyunwoo Kim et al., Chem. Mater. 22, 3441-3450 (2010)

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a simple structure in which graphene oxide whose size is controlled on a support is coated with a nano-thick film or graphen oxide is inserted in a polymer The present invention also provides a graphene oxide nanocomposite membrane having excellent barrier properties against various gases even if it has a high thermal conductivity.

According to an aspect of the present invention, And a coating layer having nano-pores on which graphene oxide having a size of 3 mu m to 50 mu m is coated to a thickness of 10 nm or more on the support. The present invention also provides a gas barrier graphene oxide nanocomposite film.

The support may be any one selected from the group consisting of polymers, ceramics, glass, paper, and metal layers.

The polymer may be selected from the group consisting of polyester, polyolefin, polyvinyl chloride, polyurethane, polyacrylate, polycarbonate, polytetrafluoroethylene, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polyacrylonitrile, Cellulose acetate, cellulose triacetate, and polyvinylidene fluoride.

The ceramic is characterized by any one selected from the group consisting of alumina, magnesia, zirconia, silicon carbide, tungsten carbide, and silicon nitride.

The metal layer may be a metal foil, a metal sheet, or a metal film.

The material of the metal layer is any one selected from the group consisting of copper, nickel, iron, aluminum, and titanium.

The graphene oxide is a functionalized graphene oxide in which a hydroxyl group, a carboxyl group, a carbonyl group, or an epoxy group present in graphene oxide is converted into an ester group, an ether group, an amide group, or an amino group.

The nano pores have an average diameter ranging from 0.5 nm to 1.0 nm.

The coating layer is characterized in that it comprises a single layer or multiple layers of graphene oxide.

The single-layer graphene oxide has a thickness in the range of 0.6 nm to 1 nm.

The present invention also provides a gas barrier graphene oxide nanocomposite membrane having a structure in which graphene oxide is embedded in a polyethylene glycol diacrylate or polyethylene glycol dimethacrylate polymer.

The graphene oxide has a size of 100 to 1000 nm.

And the content of graphene oxide in the nanocomposite film is 5 wt% or less.

In addition, the present invention provides a display device comprising the gas barrier graphene oxide nanocomposite film.

The present invention also provides a food wrapper comprising the gas barrier granule oxide nanocomposite membrane.

The present invention also provides a pharmaceutical packaging sheet comprising the gas barrier granule oxide nanocomposite membrane.

The present invention also provides a method for preparing a graphene oxide dispersion, comprising the steps of: i) dispersing graphene oxide in distilled water and treating the graphene oxide with an ultrasonic mill for 0.1 to 6 hours to obtain a graphene oxide dispersion solution; ii) centrifuging the dispersion solution to form graphene oxide having a size of 3 탆 to 50 탆; iii) obtaining a solution in which graphene oxide formed in step ii) is dispersed again in distilled water; And iv) coating the dispersion solution of step iii) on a support to form a coating layer having nanopores. The present invention also provides a method for preparing a gas barrier graphene oxide nanocomposite membrane.

The graphene oxide is a functionalized graphene oxide in which a hydroxyl group, a carboxyl group, a carbonyl group, or an epoxy group present in graphene oxide is converted into an ester group, an ether group, an amide group, or an amino group.

The support may be any one selected from the group consisting of polymers, ceramics, glass, paper, and metal layers.

The polymer may be selected from the group consisting of polyester, polyolefin, polyvinyl chloride, polyurethane, polyacrylate, polycarbonate, polytetrafluoroethylene, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polyacrylonitrile, Cellulose acetate, cellulose triacetate, and polyvinylidene fluoride.

The ceramic is characterized by any one selected from the group consisting of alumina, magnesia, zirconia, silicon carbide, tungsten carbide, and silicon nitride.

The metal layer may be a metal foil, a metal sheet, or a metal film.

The material of the metal layer is any one selected from the group consisting of copper, nickel, iron, aluminum, and titanium.

The coating is characterized in that it is carried out by any one method selected from the group consisting of a direct evaporation method, a transfer method, a spin coating method and a spray coating method.

The spin coating is performed three to ten times.

The nano pores have an average diameter ranging from 0.5 nm to 1.0 nm.

The coating layer is characterized in that it comprises a single layer or multiple layers of graphene oxide.

The single-layer graphene oxide has a thickness in the range of 0.6 nm to 1 nm.

According to the graphene oxide nanocomposite film produced according to the present invention, graphene oxide having a size of 3 탆 to 50 탆 is coated with a thin film of nano-thickness on various supports, or graphene oxide is inserted into a polymer Even if it has a simple structure, it can be applied to display devices, food and medicine packaging, etc. because of its excellent gas barrier properties.

Figure 1 shows the structure of graphene oxide and functionalized graphene oxide.
FIG. 2 is a transmission electron microscope (TEM) photograph of graphene oxide sized according to Example 1. FIG.
3 is a photograph of a graphene oxide nanocomposite film prepared from Example 1. Fig.
4 is a transmission electron microscope (TEM) photograph of a cross section of a graphene oxide film coated on a polymeric support (PES) according to Example 1. Fig.
FIG. 5 is a photograph (graphene oxide size: 270 nm) of a graphene oxide nanocomposite film according to the content of graphene oxide prepared in Example 2,
FIG. 6 is a scanning electron microscope (SEM) photograph (graphene oxide size: 270 nm) of the graphene oxide nanocomposite film according to the content of graphene oxide prepared in Example 2. FIG.
7 is a photograph (graphene oxide content: 4% by weight) of a graphene oxide nanocomposite film according to the size of graphene oxide prepared in Example 2,
8 is a schematic view of a constant pressure / volumetric volumetric measuring device equipped with gas chromatography.
9 is a graph showing the gas barrier properties and gas permeable pressure of an ultra-thin graphene oxide film according to the size of graphene oxide.
FIG. 10 is a scanning electron microscope (SEM) photograph of a graphene oxide film having a thickness of about 5 .mu.m prepared using a conventional vacuum filtration method. FIG.
11 is a graph showing various gas barrier properties according to the size of graphene oxide of a graphene oxide film produced by a conventional vacuum filtration method.
12 is a graph showing the theoretical gas barrier properties according to the size of graphene oxide and the thickness of the graphene oxide thin film.
13 is a graph of oxygen permeability (graphene oxide size: 270 nm) of the graphene oxide nanocomposite film according to the content of graphene oxide prepared in Example 2. FIG.
14 is a graph of oxygen permeability (graphene oxide content: 4 wt%) of the graphene oxide nanocomposite film according to the size of graphene oxide prepared in Example 2. Fig.

Hereinafter, a graphene oxide nanoparticle film in which graphene oxide having a size of 3 탆 to 50 탆 is coated to a thickness of 10 nm or more on various supports according to the present invention and a method for producing the same will be described in detail with reference to the accompanying drawings.

Firstly, the support can function as a reinforcing material for supporting the coating layer, and it is possible to use various materials in contact with the coating layer. The support may be any one selected from the group consisting of polymers, ceramics, glass, paper, have. In particular, examples of the polymer include polyolefins such as polyester, polyolefin, polyvinyl chloride, polyurethane, polyacrylate, polycarbonate, polytetrafluoroethylene, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polyacrylonitrile , Cellulose acetate, cellulose triacetate, and polyvinylidene fluoride. Among them, polyethersulfone is more preferably used, but is not limited thereto.

As the support for the ceramic material, any one selected from the group consisting of alumina, magnesia, zirconia, silicon carbide, tungsten carbide, and silicon nitride is preferably used, and alumina or silicon carbide is preferably used.

When the support is formed of a metal layer, it may be formed in various forms such as a metal foil, a metal sheet or a metal film. The material of the metal layer may be any one selected from the group consisting of copper, nickel, iron, aluminum and titanium .

  Next, a coating layer having nanopores in which graphene oxide having a size of 3 to 50 탆 is coated on the various supports according to the present invention in a thickness of 10 nm or more will be described in detail.

The graphene oxide used in the present invention can be produced in large quantities by oxidizing graphite using an oxidizing agent and includes a hydrophilic functional group such as a hydroxyl group, a carboxyl group, a carbonyl group, or an epoxy group. Currently, graphene oxide is mostly used in Hummers method [Hummers, WS & Offeman, RE Preparation of graphite oxide. J. Am. Chem. Soc. 80 . 1339 (1958)) or by the partially modified Hummers method. In the present invention, graphene oxide was obtained according to the Hummers method.

Also, the graphene oxide of the present invention can be chemically reacted with a compound having a hydrophilic functional group such as a hydroxyl group, carboxyl group, carbonyl group or epoxy group present in the graphene oxide to form an ester group, an ether group, an amide group or an amino group The converted functionalized graphene oxide may also be used. For example, the carboxyl group of graphene oxide reacts with an alcohol to convert to an ester group, the hydroxyl group of graphene oxide reacts with an alkyl halide to convert into an ether group, the carboxyl group of graphene oxide reacts with an alkylamine An amide group, or an epoxy group of graphene oxide is converted to an amino group by ring-opening reaction with an alkylamine.

With respect to the size of such graphene oxide, generally, the larger the size, the greater the barrier property with respect to the gas. When the thickness is less than 50 탆, the gas permeation property tends to be rather opposite to the barrier property. Even if the size of the graphene oxide layer is adjusted to less than 50 탆, the graphene oxide layer can be adjusted to a thickness of up to 50 탆. However, when the size of graphene oxide is too small, it is difficult to maintain a barrier property for various gases having different molecular sizes. Therefore, the size of graphene oxide should be adjusted to a minimum of 3 탆. That is, in order for the graphene oxide thin film according to the present invention to exhibit excellent barrier properties to gases having various molecular sizes, it is preferable to control the size of graphene oxide in the range of 3 탆 to 50 탆, especially 3 탆 to 10 탆 Is more preferable because it exhibits excellent gas barrier properties even when graphene oxide is formed into an ultra thin film. FIG. 1 shows the structure of the functionalized graphene oxide produced by reacting graphene oxide and graphene oxide obtained from the graphite with other compounds by the Hummers method.

According to the present invention, the graphene oxide coating layer formed on various supports includes a single layer or a plurality of graphene oxides, and the thickness of the single layer graphene oxide ranges from 0.6 nm to 1 nm. Further, a single layer of graphene oxide may be laminated to form multiple layers of graphene oxide. The interlayer distance of graphene oxide is as small as about 0.34 nm to 0.5 nm, and an additional movement path between grain boundaries And it is possible to improve the barrier property with respect to gases having various molecular sizes by adjusting the pore size and channel size of crystal grain boundary surface gaps. Therefore, it is preferable that the graphene oxide coating layer includes a plurality of laminated graphen oxide desirable.

It is a natural result that the gas barrier property is improved when the thickness of the graphene oxide coating layer is increased. However, in the present invention, when the size of the graphene oxide is controlled to be in the range of 3 탆 to 50 탆, The thickness of the graphene oxide coating layer is preferably 10 nm or more since an excellent effect of gas barrier properties can be obtained even when the coating layer is formed of an ultra-thin film having a minimum thickness of 10 nm. In addition, these graphene oxide coatings form nanopores with an average diameter in the range of 0.5 nm to 1.0 nm.

The present invention also relates to a gas barrier glycopyran oxide nanocomposite membrane prepared by coating graphene oxide on various supports including a support of a polymeric material as described above and a poly To provide a gas barrier graphene oxide nanocomposite film having a structure in which a pin oxide is inserted.

That is, in the process of polymerizing the polyethylene glycol diacrylate or polyethylene glycol dimethacrylate macromer having a carbon-carbon double bond at its end with a polymer and forming a crosslinked structure, graphen oxide is inserted as a kind of filler into the polymer, Thereby further improving the blocking effect. At this time, the number average molecular weight (Mn) of the polyethylene glycol diacrylate or polyethylene glycol dimethacrylate macromer is preferably in the range of 250 to 1000 in the polymerization reaction, particularly in the ultraviolet (UV) polymerization reaction using a photoinitiator and in the formation of the crosslinking structure Suitable.

If the size of the graphene oxide is less than 100 nm, gas barrier properties may be deteriorated. If the size of the graphene oxide is more than 1000 nm, polyethylene glycol having a crosslinked structure Diacrylate, or polyethylene glycol dimethacrylate polymer.

When the content of graphene oxide in the gas barrier glycoxide oxide nanocomposite membrane having the structure in which graphene oxide is embedded in the polyethylene glycol diacrylate or polyethylene glycol dimethacrylate polymer is 5 wt% or less, the effect of decreasing the gas permeability Can be maximized.

The present invention also provides a method for preparing a graphene oxide dispersion, comprising the steps of: i) dispersing graphene oxide in distilled water and treating the graphene oxide with an ultrasonic mill for 0.1 to 6 hours to obtain a graphene oxide dispersion solution; ii) centrifuging the dispersion solution to form graphene oxide having a size of 3 탆 to 50 탆; iii) obtaining a solution in which graphene oxide formed in step ii) is dispersed again in distilled water; And iv) coating the dispersion solution of step iii) on a support to form a coating layer having nanopores. The present invention also provides a method for preparing a gas barrier graphene oxide nanocomposite membrane.

The graphene oxide in step i) may be a functionalized graphene oxide in which the hydroxyl group, carboxyl group, carbonyl group, or epoxy group present in graphene oxide is converted to an ester group, an ether group, an amide group, or an amino group.

In the step i), the dispersibility of the graphene oxide in the dispersion solution can be improved by dispersing the graphene oxide in distilled water and treating the dispersion with an ultrasonic pulverizer for 0.1 to 6 hours. The dispersion solution obtained in the step iii) is 0.01 to 0.5% by weight of a graphene oxide aqueous solution adjusted to pH 10.0 by using 1 M aqueous sodium hydroxide solution. When the concentration of the aqueous graphene oxide solution is less than 0.01% by weight, It is difficult to obtain a coating layer. If the concentration exceeds 0.5% by weight, the viscosity becomes too high to achieve a smooth coating. Therefore, the concentration of the graphene oxide aqueous solution is preferably 0.01 to 0.5% by weight.

In addition, the support in step iv) can function as a reinforcing material for supporting the coating layer, and various materials can be in contact with the coating layer. The support may be selected from the group consisting of polymer, ceramic, glass, paper and metal layer It can be either one. In particular, examples of the polymer include polyolefins such as polyester, polyolefin, polyvinyl chloride, polyurethane, polyacrylate, polycarbonate, polytetrafluoroethylene, polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polyacrylonitrile , Cellulose acetate, cellulose triacetate, and polyvinylidene fluoride. Among them, polyethersulfone is more preferably used, but is not limited thereto.

As the support for the ceramic material, any one selected from the group consisting of alumina, magnesia, zirconia, silicon carbide, tungsten carbide, and silicon nitride is preferably used, and alumina or silicon carbide is preferably used.

When the support is formed of a metal layer, it may be formed in various forms such as a metal foil, a metal sheet or a metal film. The material of the metal layer may be any one selected from the group consisting of copper, nickel, iron, aluminum and titanium .

In forming the coating layer in the step iv), any known coating method may be used without limitation, but any one method selected from the group consisting of direct evaporation, transfer, spin coating and spray coating may be used Among them, the spin coating method is more preferable because a uniform coating layer can be easily obtained.

The spin coating is preferably performed three to ten times. If spin coating is performed less than three times, it is difficult to expect a function as a gas barrier layer. If spin coating is performed 10 times or more, the thickness of the coating layer becomes too thick, It is difficult to obtain a coating layer.

In the step iv), the coating layer may include a single layer or a plurality of layers of graphene oxide. The single layer of graphene oxide has a thickness ranging from 0.6 nm to 1 nm. The graphene oxide coating layer has an average diameter Form nanopores in the range of 0.5 nm to 1.0 nm.

Hereinafter, specific examples will be described in detail.

(Example 1)

The graphene oxide prepared by the Hummers method was dispersed in distilled water and treated with an ultrasonic mill for 3 hours to obtain a graphene oxide dispersion solution. The dispersion solution was centrifuged, After forming graphene oxide adjusted to 3 탆, it was dispersed again in distilled water to obtain a 0.1% by weight graphene oxide aqueous solution adjusted to pH 10.0 using 1 M sodium hydroxide aqueous solution. 1 mL of the graphene oxide aqueous solution was spin-coated on the porous polyethersulfone (PES) support 5 times to prepare a graphene oxide nanocomposite film having a 10 nm thick graphene oxide coating layer.

(Example 2)

Polyethylene glycol diacrylate (PEGDA) macromer (number average molecular weight 250) and deionized water were mixed in a ratio of 7: 3 (weight ratio) and stirred for 12 hours to obtain a homogeneous solution. To the solution, 1 wt% of graphene oxide prepared by the Hummers method was added to PEGDA macromer and 0.1 wt% of 1-hydroxycyclohexyl phenyl ketone was added as a photoinitiator, and the mixture was ultrasonicated for 2 hours and then stirred for 24 hours A precursor solution was obtained. The precursor solution was cast on a glass plate and irradiated with 312 nm UV for 5 minutes under a nitrogen atmosphere to prepare a graphene oxide nanocomposite film having a size of 270 nm and 800 nm, And its content was also changed to 1, 2, 3, and 4% by weight based on PEGDA Macromolymer).

(Test Example)

The gas barrier properties of the graphene oxide nanocomposite membranes prepared in Examples 1 and 2 were measured by a constant pressure / volumetric volumetric device equipped with gas chromatography.

FIG. 2 shows a transmission electron microscope (TEM) photograph of graphene oxide obtained by centrifuging a graphene oxide dispersion solution according to an embodiment of the present invention. The size of the graphene oxide was adjusted to about 3 .mu.m.

3, it can be seen that the graphene oxide nanocomposite film produced according to the embodiment forms a graphene oxide coating layer on the polyethersulfone support.

FIG. 4 is a transmission electron microscope (TEM) photograph of a cross section of a graphene oxide film coated on a porous polyethersulfone (PES) support to a thickness of 10 nm according to an embodiment of the present invention. It can be seen that they are laminated.

On the other hand, it was confirmed from the photograph (graphene oxide size: 270 nm) of the graphene oxide nanocomposite film according to the content of graphene oxide prepared in Example 2 of FIG. 5 that a darker color was exhibited as the content of graphene oxide increased Graphene oxide is uniformly dispersed and inserted in the PEGDA polymer having a crosslinked structure while the content of graphene oxide is increased.

FIG. 6 shows a scanning electron microscope (SEM) photograph (graphene oxide size: 270 nm) of the graphene oxide nanocomposite film according to the content of graphene oxide prepared in Example 2, (2 wt.% Of GO, 4 wt.% Of GO) shows a layered structure due to graphene oxide, while the surface of the untreated PEGDA polymer (pristine PEG) film is smooth.

7 shows photographs (graphene oxide content: 4% by weight) of the graphene oxide nanocomposite film according to the size of the graphene oxide prepared in Example 2, wherein the size of the graphene oxide is 270 nm to 800 nm, graphene oxide is uniformly dispersed and inserted in the PEGDA polymer having a crosslinked structure.

The gas barrier properties of the graphene oxide film according to the present invention were evaluated using a constant pressure / volumetric volumetric device equipped with gas chromatography as shown in FIG. 8, and it was found from FIG. 9 that the size of graphene oxide The pressure at which the gas begins to permeate gradually increases with increasing the pressure. Particularly, when a thin film is prepared using graphene oxide having a size of 3.0 μm (= 3000 nm), a relatively high pressure (180 mbar) It can be seen that the gas can not permeate at all.

On the other hand, in order to investigate the size of graphene oxide and the thickness of the graphene oxide thin film affecting the gas barrier properties of the graphene oxide thin film with or without support, a graphene oxide film without support was formed by a conventional vacuum filtration method . FIG. 10 is a scanning electron microscope (SEM) image of a graphene oxide film having a thickness of about 5 .mu.m produced by a conventional vacuum filtration method. It can be seen that graphene oxide, which is a two-dimensional structure, is laminated tightly.

Also, Figure 11 shows the gas barrier properties of a graphene oxide film that was controlled to have a specific size (0.5, 1.0, and 5.0 쨉 m) by preparing a graphene oxide film without support by conventional vacuum filtration As the size of graphene oxide increases, it becomes clear that gas permeation characteristics change to barrier properties. Particularly, it can be confirmed that graphen oxide has excellent gas barrier properties at a size of 3.0 μm or more. By controlling the size of the oxide, the gas barrier properties can be improved.

FIG. 12 is a graph that the gas permeation channel length at the same thickness of a film of various sizes of graphene oxide is theoretically calculated. As the size of graphene oxide increases at the same thickness, the gas permeation channel length gradually increases And that when the film is produced using graphene oxide having a specific size (3.0 μm), the gas permeation channel length increases to show an excellent blocking characteristic. As a result, the measurement result of the test example according to the present invention It shows the agreement.

13 shows graphs of oxygen permeability (graphene oxide size: 270 nm) of the graphene oxide nanocomposite membrane according to the content of graphene oxide prepared in Example 2. As the content of graphene oxide increases, oxygen In particular, when the content of graphene oxide in the graphene oxide nanocomposite membrane is 4% by weight, the oxygen permeability is 83% as compared with the graphene oxide-free pristine PEG film. %, Respectively.

14 shows graphs of oxygen permeability (graphene oxide content: 4% by weight) of the graphene oxide nanocomposite membrane according to the size of the graphene oxide prepared in Example 2. As the size of graphene oxide increases The gas barrier property is improved. In particular, when the size of the graphene oxide inserted into the graphene oxide nanocomposite film is 800 nm, the oxygen permeability is higher than that of the graphene oxide-free pristine PEG film And it decreases to 90%.

Therefore, according to the graphene oxide nanocomposite film produced according to the present invention, graphene oxide having a size of 3 탆 to 50 탆 is coated on a variety of supports with a nano-thick film, or graphen oxide is embedded in a polymer It can be applied to display devices, food and medicine packaging and so on.

Claims (28)

delete delete delete delete delete delete delete delete delete delete A gas-barrier graphene oxide nanocomposite membrane having a structure in which graphene oxide having a size of 100 to 1000 nm is inserted in a polyethylene glycol diacrylate or polyethylene glycol dimethacrylate polymer. delete The gas-barrier graphene oxide nanocomposite membrane according to claim 11, wherein the content of graphene oxide in the nanocomposite membrane is 5 wt% or less. delete delete delete delete delete delete delete delete delete delete delete delete 12. A display device comprising a gas barrier layered graphene oxide nanocomposite membrane according to claim 11. A food wrapper comprising the gas barrier nature graphene oxide nanocomposite membrane according to claim 11. A pharmaceutical packaging sheet comprising a gas barrier granule oxide nanocomposite membrane according to claim 11.

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