KR101916659B1 - Manufacturing method of gas barrier film based on layered double hydroxide - Google Patents

Abstract

The present invention, (a) a first precursor of _{^{[M 2+] [A n- 2}} / n] · zH ₂ O and a second precursor _{^{[M 3+] [A n- 3}} / n] · zH 2 O (B) adding hexamethylenetetramine to the reaction vessel in which the first precursor and the second precursor are dissolved to form a precursor reaction solution, and (c) (D) selectively separating the layered double hydroxide formed by the hydrothermal reaction; and (e) separating the layered double hydroxide from the layered double hydroxide, (B) forming a layered double hydroxide layer on the organic substrate by coating the organic layer on the layered double hydroxide layer; and (g) (f) is repeated a plurality of times to form the layered double hydroxide layer And step (h) to group the organic layer is formed while alternately stacked hybrid film relates to a method for producing gas barrier film, which comprises forming an inorganic protective layer on the hybrid film thereon. The present invention is based on a layered double hydroxide having a high aspect ratio and exhibits a uniform gas barrier property because the deviation of the aspect ratio is small, and water permeation and oxygen permeation can be suppressed.

Description

[0001] The present invention relates to a method for producing a gas barrier film based on a layered double hydroxide,

More particularly, the present invention relates to a method for producing a gas barrier film, which is based on a layered double hydroxide having a high aspect ratio and has a small deviation in aspect ratio, And a method of manufacturing a gas barrier film.

Various barrier films have been attempted as barrier films of organic electronic materials. Conventionally, a barrier has been fabricated using a multilayer structure by depositing an inorganic material by using a vacuum process and coating an organic material. However, the process of depositing inorganic materials using a vacuum process not only has a high barrier to entry into the process, but also raises the overall process cost, which is one of the main factors that lowers the price competitiveness of the barrier film.

Various studies have been conducted to fabricate organic / inorganic hybrid barrier films in order to have a high moisture barrier ability and to reduce the process cost. Among them, a method of reducing the number of lamination and improving the barrier property by using a composite using inorganic nanoparticles and an organic material has been proposed. Recently, a method of using graphene or a layered silicate having a layered structure as an inorganic material has been studied for producing such an organic hybrid barrier film.

According to the method for producing a gas barrier film disclosed in Korean Patent Laid-Open Publication No. 10-2014-0071226, a layered silicate nanostructure is used to improve the barrier property, but the aspect ratio of the layered silicate material has a high deviation, There is a problem in that it is largely uneven.

Considering the above points, there is a need for research on controlling the barrier film properties by control of the aspect ratio of the layered inorganic material.

Korean Patent Publication No. 10-2014-0071226

A problem to be solved by the present invention is to provide a process for producing a gas barrier film for water permeation and oxygen permeation inhibition which is based on a layered double hydroxide having a high aspect ratio and has a small deviation in aspect ratio and thus exhibits uniform gas barrier properties have.

The present invention, (a) a first precursor of _{^{[M 2+] [A n- 2}} / n] · zH ₂ O and a second precursor _{^{[M 3+] [A n- 3}} / n] · zH 2 O (B) adding hexamethylenetetramine to the reaction vessel in which the first precursor and the second precursor are dissolved to form a precursor reaction solution, and (c) (D) selectively separating the layered double hydroxide formed by the hydrothermal reaction; and (e) separating the layered double hydroxide from the layered double hydroxide, (B) forming a layered double hydroxide layer on the organic substrate by coating the organic layer on the layered double hydroxide layer; and (g) (f) is repeated a plurality of times to form the layered double hydroxide layer And step (h) to group the organic layer is formed while alternately stacked hybrid film and forming an inorganic protective layer on the hybrid membrane, wherein M ²⁺ is ^{Ba 2+, Ca 2+ Co 2+,} Mn 2 ^+, Ni ^2+, Fe ^2+, Cu ^2+, Sn ^2+, and Zn ²⁺ and Mg ²⁺ group divalent metal ion at least one selected from consisting of the M ³⁺ is Al ^3+, Cr ^{3 +} , Fe ³⁺ , Co ³⁺ , Mn ³⁺ , Ni ³⁺ , Ce ^3+, and Ga ³⁺ , and A ^n- is at least one selected from the group consisting of hydroxide, Z is at least one anion selected from the group consisting of zirconium, zirconium, zirconium, zirconium, zirconium, zirconium, Of the gas barrier film. The present invention also provides a method for producing the gas barrier film.

The layered double hydroxide may be represented by the following formula (1).

[Chemical Formula 1]

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] [A ^n- ] _{x / n} zH ₂ O (0.2? X? 0.4)

The first precursor and the second precursor preferably form a molar concentration ratio of 1: 1 to 3: 1 in the precursor reaction solution.

Wherein the first precursor has a molar concentration of 10-200 mM in the precursor reaction solution and the second precursor has a molarity of 5-100 mM in the precursor reaction solution and the hexamethylenetetramine It is preferable that the precursor reaction solution has a molar concentration of 50 to 1000 mM.

The organic material may be selected from the group consisting of poly (allylamine hydrochloride), poly (acrylic acid), polyethylenimine (PEI) and (3-aminopropyl) triethoxysilane (3-Aminopropyl) triethoxysilane).

The inorganic protective layer may include polysilazane.

The substrate may be at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyester (PES), polyimide (AryLite) and Cyclo-Olefin Copolymer (COC). ≪ / RTI >

Before the step (e), the step of peeling the layered double hydroxide to increase the aspect ratio of the layered double hydroxide may be further included.

The peeling is preferably performed by intercalating a surfactant, an organic solvent, and an amphoteric substance between the layer of the layered double hydroxide and the layer and subjecting the layer to ultrasonic treatment.

The surfactant may include at least one substance selected from the group consisting of phospholipid and sodium dodecylsulfate.

The organic solvent may include at least one material selected from the group consisting of dimethylformamide, dimethylsulfoxide, phenylethylformamide, and hydroxyethylformamide.

The amphoteric material may be selected from the group consisting of poly (methacrylic acid), poly (2- (ethylamino) ethyl poly (allylamine)), poly (Methacrylic acid), N-isopropylacrylamide, N- (3-aminopropyl) methacrylamide, and arylamine allylamine, acrylamide, (dimethylamino) ethylmethacrylate, and tetrahydropyranyl methacrylate. These materials may be used alone or in combination of two or more.

In the step (e), the solvent may be distilled water, and the layered double hydroxide may be dispersed in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the distilled water.

The first precursor may be Mg (NO ₃ ) ₂ .6H ₂ O, and the second precursor may be Al (NO ₃ ) ₃ .9H ₂ O.

The present invention is based on a layered double hydroxide having a high aspect ratio and exhibits a uniform gas barrier property because the deviation of the aspect ratio is small, and water permeation and oxygen permeation can be suppressed. When a gas barrier film is produced using a layered double hydroxide having a high aspect ratio, the diffusion distance can be greatly increased when water molecules are passed through compared to using general inorganic particles, thereby improving the moisture barrier property.

According to the present invention, it is possible to apply to a flexible substrate by a production method of a gas barrier film applicable to an organic electronic material, and to prevent contact with moisture and oxygen gas, thereby increasing the lifetime of the organic electronic material.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view schematically showing the structure of a gas barrier film based on a layered double hydroxide. Fig.
2A to 2C are scanning electron microscope (SEM) images of the layered double hydroxides prepared according to Experimental Example 1. FIG.
3A to 3C are scanning electron microscope (SEM) images of the layered double hydroxides prepared according to Experimental Example 1. Fig.
FIG. 4A is a scanning electron microscope (SEM) image of a layered double hydroxide having an aspect ratio controlled by using a Urea as a hydrolysis agent according to Experimental Example 1, and FIG. 4B is a scanning electron microscope This is a scanning electron microscope (SEM) image of layered double hydroxides with controlled aspect ratios using zero HMTA (Hexamethylenetetramine).
5A to 5C are optical microscope (OM) images of a layered double hydroxide layer coated by a drop casting method according to Experimental Example 4. FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not.

A method for producing a gas barrier film according to a preferred embodiment of the present invention comprises the steps of: (a) mixing a first precursor [M ²⁺ ] [A ^n- _{2 / n} ] .zH ₂ O and a second precursor [M ³⁺ ] Dissolving [A ^n- _{3 / n} ] .zH ₂ O in distilled water; and (b) adding hexamethylenetetramine to the reaction vessel in which the first precursor and the second precursor are dissolved to form a precursor Forming a reaction solution; (c) sealing the reaction vessel containing the precursor reaction solution and placing the reaction vessel in an autoclave vessel and performing a hydrothermal reaction; (d) forming a layered double hydroxide formed by the hydrothermal reaction; (E) dispersing the layered double hydroxide (LDH) in a solvent and coating it on an organic substrate to form a layered double hydroxide layer; (f) The organic material is coated on the double hydroxide layer, (G) repeating the steps (e) and (f) a plurality of times to form a hybrid film in which the layered double hydroxide layer and the organic material layer are alternately stacked, and (h) ^Wherein the M ²⁺ is selected from the group consisting of Ba ²⁺ , Ca ²⁺ Co ²⁺ , Mn ²⁺ , Ni ²⁺ , Fe ²⁺ , Cu ²⁺ , Sn ²⁺ , Zn ²⁺ and Mg ²⁺ , and M ³⁺ is at least one selected from the group consisting of Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Co ³⁺ , Mn ³⁺ , Ni ³⁺ , Ce ³⁺ and Ga ³⁺ , and A ^n- is at least one selected from the group consisting of a hydroxide, a carbonate, a bicarbonate, a nitrate, a chloride, a bromide, a sulfonate, a sulfate, At least one anion selected from the group consisting of zirconium, zirconium, zirconium, zirconium, zirconium, zirconium, zirconium, It may have a value of ten range.

The layered double hydroxide may be represented by the following formula (1).

[Chemical Formula 1]

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] [A ^n- ] _{x / n} zH ₂ O (0.2? X? 0.4)

The first precursor and the second precursor preferably form a molar concentration ratio of 1: 1 to 3: 1 in the precursor reaction solution.

Wherein the first precursor has a molar concentration of 10-200 mM in the precursor reaction solution and the second precursor has a molarity of 5-100 mM in the precursor reaction solution and the hexamethylenetetramine It is preferable that the precursor reaction solution has a molar concentration of 50 to 1000 mM.

The organic material may be selected from the group consisting of poly (allylamine hydrochloride), poly (acrylic acid), polyethylenimine (PEI) and (3-aminopropyl) triethoxysilane (3-Aminopropyl) triethoxysilane).

The inorganic protective layer may include polysilazane.

The substrate may be at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyester (PES), polyimide (AryLite) and Cyclo-Olefin Copolymer (COC). ≪ / RTI >

Before the step (e), the step of peeling the layered double hydroxide to increase the aspect ratio of the layered double hydroxide may be further included.

The peeling is preferably performed by intercalating a surfactant, an organic solvent, and an amphoteric substance between the layer of the layered double hydroxide and the layer and subjecting the layer to ultrasonic treatment.

The surfactant may include at least one substance selected from the group consisting of phospholipid and sodium dodecylsulfate.

The organic solvent may include at least one material selected from the group consisting of dimethylformamide, dimethylsulfoxide, phenylethylformamide, and hydroxyethylformamide.

The amphoteric material may be selected from the group consisting of poly (methacrylic acid), poly (2- (ethylamino) ethyl poly (allylamine)), poly (Methacrylic acid), N-isopropylacrylamide, N- (3-aminopropyl) methacrylamide, and arylamine allylamine, acrylamide, (dimethylamino) ethylmethacrylate, and tetrahydropyranyl methacrylate. These materials may be used alone or in combination of two or more.

In the step (e), the solvent may be distilled water, and the layered double hydroxide may be dispersed in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the distilled water.

The first precursor may be Mg (NO ₃ ) ₂ .6H ₂ O, and the second precursor may be Al (NO ₃ ) ₃ .9H ₂ O.

Hereinafter, a method for producing a gas barrier film according to a preferred embodiment of the present invention will be described in more detail.

(WVTR) and oxygen permeability (OTR) values were 10 ^-2 g / m ² day and 10 ^- 10 g / m ² day, respectively, in the case of spherical inorganic nanoparticles and organic composite layer. ² cm ³ / m ² day, and the single layer alone is not suitable for organic electronic material.

The present invention implements a stable aspect ratio of a layered nanostructure through the synthesis of a layered double hydroxide and proposes a method of manufacturing an improved gas barrier film with increasing aspect ratio.

[M ²⁺ ] [A ^n- _{2 / n} ] .zH ₂ O and the second precursor [M ³⁺ ] [A ^n- ₃ ], which are the first precursor, are used for preparing the gas barrier film based on the layered double hydroxide. _{/ n} ] · zH ₂ O is dissolved in distilled water.

In the first precursor, [M ²⁺ ] [A ⁿ _{2 / n} ] 揃 zH ₂ O, the M ²⁺ is Ba ²⁺ , Ca ²⁺ Co ²⁺ , Mn ²⁺ , Ni ²⁺ , Fe ^{2 +} , Cu ²⁺ , Sn ²⁺ , Zn ²⁺ and Mg ²⁺ , and A ^n- is at least one selected from the group consisting of hydroxide, carbonate, bicarbonate, Z is at least one anion selected from the group consisting of halide, chloride, bromide, sulfonate, sulfate, bisulfate, vanadate, tungstate, borate and phosphate. For example, the first precursor may be Mg (NO ₃ ) ₂ .6H ₂ O.

In the second precursor, [M ³⁺ ] [A ^n- _{3 / n} ] .zH ₂ O, the M ³⁺ is Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Co ³⁺ , Mn ³⁺ , Ni ^{3 +} , Ce ³⁺ and Ga ³⁺ , and A ^n- is at least one selected from the group consisting of a hydroxide, a carbonate, a bicarbonate, a nitrate, a chloride, a bromide, a sulfonate At least one anion selected from the group consisting of sulfates, bisulfates, vanadates, tungstates, borates and phosphates, and z may have a value in the range of 0 to 10. For example, the second precursor may be an _{Al (NO 3) 3 · 9H} 2 O.

Hexamethylenetetramine (HMTA) is added to a reaction vessel in which the first precursor and the second precursor are dissolved to form a precursor reaction solution. The hexamethylenetetramine (HMTA) acts as a hydrolysis agent to assist in the hydroxylation reaction. The hexamethylenetetramine (HMTA) preferably has a molar concentration of 50-1000 mM in the precursor reaction solution. The hexamethylenetetramine (HMTA) has the advantage of increasing the aspect ratio of the layered double hydroxide synthesized by the hydrothermal reaction as compared with hydrolysis agents such as NH ₄ OH, NaOH, KOH, and Urea . When a gas barrier film is produced using a layered double hydroxide having a high aspect ratio, the diffusion distance can be greatly increased when water molecules are passed through compared to using general inorganic particles, thereby improving the moisture barrier property.

The reaction vessel may be a Teflon reaction vessel having excellent chemical resistance.

The first precursor and the second precursor preferably form a molar concentration ratio of 1: 1 to 3: 1 in the precursor reaction solution. The first precursor has a molar concentration of 10-200 mM in the precursor reaction solution, and the second precursor has a molarity of 5-100 mM in the precursor reaction solution.

The reaction vessel containing the precursor reaction solution is sealed, placed in an autoclave vessel, and hydrothermally reacted. Layered double hydroxides (LDH) are formed by the hydrothermal reaction.

The layered double hydroxide may be represented by the following formula (1).

[Chemical Formula 1]

[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] [A ^n- ] _{x / n} zH ₂ O (0.2? X? 0.4)

The M ²⁺ may be one selected from the group consisting of Ba ²⁺ , Ca ²⁺ Co ²⁺ , Mn ²⁺ , Ni ²⁺ , Fe ²⁺ , Cu ²⁺ , Sn ²⁺ , Zn ²⁺ and Mg ²⁺ And M ³⁺ is at least one selected from the group consisting of Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Co ³⁺ , Mn ³⁺ , Ni ³⁺ , Ce ³⁺ and Ga ³⁺ Wherein A ^n- is at least one selected from the group consisting of a hydroxide, a carbonate, a bicarbonate, a nitrate, a chloride, a bromide, a sulfonate, a sulfate, a bisulfate, a vanadate, a tungstate, a borate and a phosphate And z may have a value in the range of 0 to 10,

Layered Double Hydroxide (LDH) is a structure composed of a two-dimensional metal hydroxide film and consists of octahedral units composed of divalent or trivalent metal ions and hydroxide ions. The divalent metal ions are ^{Ba 2+, Ca 2+ Co 2+,} Mn 2+, Ni 2+, Fe 2+, Cu 2+, Sn 2+, Zn 2 + , and selected from the group consisting of Mg ^{2 +} 1 species may be more metal ions, wherein the three metal ions are Al ^{3 +,} Cr ^{3 +,} Fe ^{3 +,} Co ^{3 +,} Mn ^{3 +,} Ni ^{3 +,} Ce ^{3 +} and Ga ^{3 +} selected from the group consisting of May be one or more metal ions. The two-dimensional metal hydroxide film is totally positively charged by the presence of arbitrarily distributed trivalent metal ions.

The layered double hydroxides can be synthesized by hydrothermal synthesis and form a layered structure in which positive charge metal hydroxide films and anion molecules are alternately present due to negative charge molecules in the aqueous solution and electrostatic attraction. The layered double hydroxides are synthesized by an aqueous synthesis method in an aqueous solution consisting of precursor metal ions constituting the metal hydroxide and hydrolysis agent for the hydrolysis reaction. The temperature, pressure, precursor concentration, hydrolysis agent ) The shape of layered double hydroxides is determined by type and concentration, type of anion and concentration parameters.

Preferably, the hydrothermal reaction is performed at 100 ° C or higher (for example, 100 to 180 ° C) for 1 to 72 hours after the reaction vessel containing the precursor reaction solution is completely sealed and then placed in an autoclave vessel. After the hydrothermal reaction, the autoclave is preferably slowly cooled to room temperature.

The layered double hydroxide (LDH) formed by the hydrothermal reaction is selectively removed. For example, centrifugation is performed to selectively separate the reactants precipitated in the reaction vessel, and the supernatant is removed after the centrifugation. After the supernatant is removed, distilled water, anhydrous alcohol and the like are added thereto, washed and centrifuged, and the supernatant is removed at least once, followed by drying in an oven to obtain a layered double hydroxide (LDH).

The layered double hydroxide may be stripped to increase the aspect ratio of the layered double hydroxide. The synthesized layered double hydroxides can further increase the aspect ratio through the peeling process.

Preferably, the exfoliation is performed by intercalating a surfactant, an organic solvent and an amphoteric substance between the layer of the layered double hydroxide and the layer, and applying a physical force (for example, by ultrasonication).

The surfactant may include at least one substance selected from the group consisting of phospholipid and sodium dodecylsulfate.

The organic solvent may include at least one material selected from the group consisting of dimethylformamide, dimethylsulfoxide, phenylethylformamide, and hydroxyethylformamide.

The amphoteric material may be selected from the group consisting of poly (methacrylic acid), poly (2- (ethylamino) ethyl poly (allylamine); PAH) , Poly (methacrylic acid) (PMAA), N-isopropylacrylamide (NIPAm), N- (3-aminopropyl) methacrylamide (methacrylamide), allylamine (AA), acrylamide (AAm), (dimethylamino) ethylmethacrylate (DMAEMA) and tetrahydropyranyl methacrylate (THPMA) ≪ RTI ID = 0.0 > and / or < / RTI >

When a gas barrier film is produced using a layered double hydroxide having a high aspect ratio, the diffusion distance can be greatly increased when water molecules are passed through compared to using general inorganic particles, thereby improving the moisture barrier property.

The layered double hydroxide is dispersed in a solvent and coated on an organic substrate to form a layered double hydroxide layer. The solvent may be distilled water. Layered double hydroxides (LDH) dispersed in distilled water are positively charged and easily dispersed in distilled water. Layered double hydroxides (LDH) dispersed in distilled water have a pH between 6.0 and 7.0 depending on the dispersed amount. In the acidic state (~ pH 4.0), the dispersion is maintained for the longest, and in the basic state (pH 10 ~), the layered double hydroxide (LDH) easily precipitates and separates from the aqueous solution. It is desirable to disperse the layered double hydroxides (LDH) by adjusting the pH to a neutral or acidic state to obtain a uniform coated flat surface. The layered double hydroxide is preferably dispersed in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the distilled water. The coating may be dip coating, spin coating or the like. Drop casting, spray coating, inkjet, and layer-by-layer processes can be used.

The substrate may be at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyester (PES), polyimide (AryLite) and Cyclo-Olefin Copolymer (COC). ≪ / RTI >

An organic material is coated on the layered double hydroxide layer to form an organic layer. The organic material may be selected from the group consisting of poly (allylamine hydrochloride), poly (acrylic acid), polyethylenimine (PEI) and (3-aminopropyl) triethoxysilane (3-aminopropyl) triethoxysilane. The organic material may be coated by dip coating, spin coating, drop casting, spray coating or the like. ), Inkjet (inkjet), and layer-by-layer processes.

The step of forming the layered double hydroxide layer and the step of forming the organic material layer are repeated a plurality of times to form a hybrid film in which the layered double hydroxide layer and the organic material layer are alternately stacked. The layered double hydroxide and the organic material layer are alternately repeatedly laminated on the substrate to form a hybrid film.

The organic layer may be cured through ultraviolet (UV), heat and catalyst control.

As the number of layers and the aspect ratio of the layered double hydroxides increases, the diffusion of moisture increases, so that the barrier properties can be controlled by controlling the number of layers and the aspect ratio.

An inorganic protective layer is formed on the hybrid film. The inorganic protective layer may include polysilazane. For example, dip coating, spin coating. The polysilazane is coated on the upper part of the hybrid membrane by a coating method such as drop casting, spray coating, inkjet, or layer by layer to form an inorganic protective layer . Specific examples of the coating liquid for the polysilazane include Aqua Mica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140 and SP140 manufactured by AZ Electronic Materials Co.,

Curing is required depending on the organic material layer or the inorganic protective layer used. The curing method may be thermal curing, ultraviolet (UV) curing or thermal curing and ultraviolet (UV) curing sequentially or simultaneously. The curing conditions may vary depending on the type and amount of the polysilazane catalyst. In the case of curing using NN120, it is cured by irradiating for 30 minutes at 150 ° C for 30 minutes. The organic layer and the inorganic protective layer may be cured through a thermal compression process.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view schematically showing the structure of a gas barrier film based on a layered double hydroxide. Fig. 1, '10' denotes an organic substrate, '20' denotes a gas barrier film formed by coating on an organic substrate, '22' denotes a hybrid film in which a plurality of layered double hydroxide layers and organic layers are alternately stacked, '24 'Represents an inorganic protective layer.

Hereinafter, experimental examples according to the present invention will be specifically shown, and the present invention is not limited by the following experimental examples.

<Experimental Example 1>

A first precursor of Mg (NO _{3) 2} · 6H dissolved ₂ O in distilled water, and the second precursor of Al (NO _{3) 3} · was dissolved in distilled water 9H ₂ O, the Mg (NO _{3) 2} · 6H ₂ O and a solution in which Al (NO ₃ ) ₃ .9H ₂ O is dissolved are added to a Teflon reaction vessel and mixed to prepare a hydrolysis agent for hydrolysis reaction, Urea was added to the Teflon reaction vessel and stirred for 1 minute to form a precursor reaction solution. The molar concentration ratio of Mg (NO ₃ ) ₂ .6H ₂ O and Al (NO ₃ ) ₃ .9H ₂ O was 2: 1. The Mg (NO _{3) 2} · 6H molar concentration of ₂ O was fulfill each 200, 100, 10 mM in the precursor reaction mixture, the molar concentration of the _{Al (NO 3) 3 · 9H} 2 O is the precursor reaction solution 50, and 5 mM, respectively. The molar concentration of the urea was 1000 mM, 500 mM, and 50 mM in the precursor reaction solution, respectively.

The Teflon reaction vessel was completely sealed, placed in an autoclave vessel, and reacted at a temperature of 110 ° C or higher for 24 hours. After the hydrothermal reaction, the autoclave was slowly cooled to room temperature.

In order to separate the reaction product precipitated in the Teflon reaction vessel, centrifugation was carried out at 3500 rpm for 5 minutes. After the centrifugation, the supernatant was removed.

The supernatant was removed, washed with distilled water, centrifuged at 3500 rpm for 5 minutes, and then the supernatant was removed three times. Finally, the supernatant was removed, washed with anhydrous alcohol and washed at 3500 rpm After centrifugation for 5 minutes, the supernatant was removed and dried in an oven at 80 ° C to obtain a layered double hydroxide (LDH).

<Experimental Example 2>

A first precursor of Mg (NO _{3) 2} · 6H dissolved ₂ O in distilled water, and the second precursor of Al (NO _{3) 3} · was dissolved in distilled water 9H ₂ O, the Mg (NO _{3) 2} · 6H ₂ O and a solution in which Al (NO ₃ ) ₃ .9H ₂ O is dissolved are added to a Teflon reaction vessel and mixed to prepare a hydrolysis agent for hydrolysis reaction, Hexamethylenetetramine (HMTA) was added to the Teflon reaction vessel and stirred for 1 minute to form a precursor reaction solution. The molar concentration ratio of Mg (NO ₃ ) ₂ .6H ₂ O and Al (NO ₃ ) ₃ .9H ₂ O was 2: 1. The Mg (NO _{3) 2} · 6H molar concentration of ₂ O was fulfill each 200, 100, 10 mM in the precursor reaction mixture, the molar concentration of the _{Al (NO 3) 3 · 9H} 2 O is the precursor reaction solution 50, and 5 mM, respectively. The molar concentration of the hexamethylenetetramine (HMTA) was adjusted to 1000 mM, 500 mM, and 50 mM in the precursor reaction solution, respectively.

The Teflon reaction vessel was completely sealed, placed in an autoclave vessel, and reacted at a temperature of 110 ° C or higher for 24 hours. After the hydrothermal reaction, the autoclave was slowly cooled to room temperature.

In order to separate the reaction product precipitated in the Teflon reaction vessel, centrifugation was carried out at 3500 rpm for 5 minutes. After the centrifugation, the supernatant was removed.

The supernatant was removed, washed with distilled water, centrifuged at 3500 rpm for 5 minutes, and then the supernatant was removed three times. Finally, the supernatant was removed, washed with anhydrous alcohol and washed at 3500 rpm After centrifugation for 5 minutes, the supernatant was removed and dried in an oven at 80 ° C to obtain a layered double hydroxide (LDH).

FIGS. 2A to 2C show scanning electron microscope (SEM) images of the layered double hydroxides prepared according to Experimental Example 1. FIG. FIG. 2A is a graph showing the relationship between the molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O and the molar concentration of Al (NO ₃ ) ₃ .9H ₂ O of 5 mM, Urea molar concentration of 50 mM at 110 ° C. for 24 hours (NO ₃ ) ₂ .6H ₂ O molar concentration of 100 mM, Al (NO ₃ ) ₃ .9H ₂ O molar concentration of 50 mM, Urea molar concentration of 500 mM at 110 ℃ a scanning electron microscope (SEM) image of a layered double hydroxide, a synthetic sequence for 24 hours, Figure 2c _{Mg (NO 3) 2 · 6H} 2 O molar concentration of _{200mM, Al (NO 3) 3} · 9H 2 O mole (SEM) image of a layered double hydroxide hydrothermally synthesized at 110 캜 for 24 hours at a concentration of 100 mM and a concentration of urea (Urea) of 1000 mM.

Figs. 3A to 3C show scanning electron microscope (SEM) images of the layered double hydroxides prepared according to Experimental Example 1. Fig. 3A shows the results of hydrothermal synthesis at a molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O of 100 mM, a molar concentration of Al (NO ₃ ) ₃ .9H ₂ O of 50 mM, a molar concentration of Urea of 500 mM and a reaction temperature of 110 ° C. for 24 hours FIG. 3B is a scanning electron microscope (SEM) image of one layered double hydroxide. FIG. 3B is a graph showing the relationship between the molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O of 100 mM, the molar concentration of Al (NO ₃ ) ₃ .9H ₂ O of 50 mM, (NO ₃ ) ₂揃 6H ₂ O molar concentration of 100 mM, Al (NO ₃ ) ₂ O 6, and a concentration of 500 mM, and a hydrothermal synthesis at 130 ° C for 24 hours. FIG. 3c is a scanning electron microscope (SEM) image of a layered double hydroxide obtained by hydrothermal synthesis at a reaction temperature of 150 ° C for 24 hours at a molar concentration of ₃ · 9H ₂ O of 50 mM and a molar concentration of urea of 500 mM.

FIG. 4A shows a scanning electron microscope (SEM) image of a layered double hydroxide having an aspect ratio controlled using a Urea as a hydrolysis agent according to Experimental Example 1, and FIG. (SEM) image of layered double hydroxides in which the aspect ratio is controlled using HMTA (Hexamethylenetetramine) as a hydrolyzing agent. FIG. 4A is a graph showing the relationship between the molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O of 100 mM, the molar concentration of Al (NO ₃ ) ₃ .9H ₂ O of 50 mM and the molar concentration of urea, (NO ₃ ) ₂ .6H ₂ O molar concentration of 100 mM, Al (NO ₃ ) ₃ .9H ₂ O molar concentration of 50 mM, hydrolysis (Hexamethylenetetramine) molar concentration of 130 mM and hydrothermal synthesis at 150 ℃ for 24 hours.

<Experimental Example 3>

The layered double hydroxides (LDH) prepared using Urea according to Experimental Example 1 were added to distilled water and dispersed. The layered double hydroxide (LDH) was added in an amount of 1, 0.5, 0.25, and 0.1 parts by weight based on 100 parts by weight of the distilled water.

Layered double hydroxides (LDH) are positively charged and are easily dispersed in distilled water. Layered double hydroxides (LDH) dispersed in distilled water have a pH between 6.0 and 7.0 depending on the dispersed amount.

A layered double hydroxide dispersion in which layered double hydroxide (LDH) was dispersed in distilled water was coated on a substrate by a drop casting method to form a layered double hydroxide layer. Polyethylene terephthalate (PET) was used as the substrate.

<Experimental Example 4>

The layered double hydroxide (LDH) prepared using HMTA (Hexamethylenetetramine) according to Experimental Example 2 was added to distilled water and dispersed. The layered double hydroxide (LDH) was added in an amount of 1, 0.5, 0.25, and 0.1 parts by weight based on 100 parts by weight of the distilled water.

Layered double hydroxides (LDH) are positively charged and are easily dispersed in distilled water. Layered double hydroxides (LDH) dispersed in distilled water have a pH between 6.0 and 7.0 depending on the dispersed amount.

A layered double hydroxide dispersion in which layered double hydroxide (LDH) was dispersed in distilled water was coated on a substrate by a drop casting method to form a layered double hydroxide layer. Polyethylene terephthalate (PET) was used as the substrate.

5A to 5C show an optical microscope (OM) image of a layered double hydroxide layer coated by a drop casting method according to Experimental Example 4. FIG. 5A is a graph showing the relationship between the molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O, the concentration of Al (NO ₃ ) ₃ .9H ₂ O molar concentration of 50 mM, the concentration of HMTA (hexamethylenetetramine) molar concentration of 130 mM, Hydroxide, and 0.1 part by weight of a layered double hydroxide is added to distilled water is coated by a drop casting method. FIG. 5B is a graph showing the relationship between the molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O and the molar concentration of Al (NO ₃ ) ₃ .9H ₂ O of 50 mM and HMTA (hexamethylenetetramine) A layered double hydroxide is coated by a drop casting method, and a layered double hydroxide dispersion in which 0.25 parts by weight of a layered double hydroxide is added to distilled water is coated by a drop casting method. FIG. 5C is a graph showing the relationship between the molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O, the concentration of Al (NO ₃ ) ₃ .9H ₂ O molar concentration of 50 mM and the concentration of HMTA (hexamethylenetetramine) molar concentration of 130 mM, Hydroxide and 0.5 part by weight of a layered double hydroxide in distilled water was coated by a drop casting method.

<Experimental Example 5>

The layered double hydroxides (LDH) prepared using Urea according to Experimental Example 1 were added to distilled water and dispersed. The layered double hydroxide (LDH) had a molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O of 100 mM, a molar concentration of Al (NO ₃ ) ₃ .9H ₂ O of 50 mM, a molar concentration of urea as a hydrolyzing agent of 500 mM, The layered double hydroxides hydrothermally synthesized at 150 ° C for 24 hours were used. The layered double hydroxide (LDH) was added in an amount of 1, 0.5, 0.25, and 0.1 parts by weight based on 100 parts by weight of the distilled water.

A layered double hydroxide dispersion in which layered double hydroxide (LDH) was dispersed in distilled water was coated on a substrate by a drop casting method to form a layered double hydroxide layer. Polyethylene terephthalate (PET) was used as the substrate.

After the layered double hydroxide (LDH) coating, the organic material was coated to form an organic material layer. The organic material used was poly (acrylic acid) (PAA).

The layered double hydroxide (LDH) and the organic material were alternately repeatedly coated to form a hybrid film. The hybrid film has a multilayer structure in which a layered double hydroxide layer and an organic layer are alternately stacked.

<Experimental Example 6>

The layered double hydroxide (LDH) prepared using HMTA (Hexamethylenetetramine) according to Experimental Example 2 was added to distilled water and dispersed. The layered double hydroxide (LDH) had a molar concentration of Mg (NO ₃ ) ₂ .6H ₂ O of 100 mM, a molar concentration of Al (NO ₃ ) ₃ .9H ₂ O of 50 mM, a molar concentration of HMTA (Hexamethylenetetramine) The layered double hydroxides hydrothermally synthesized at 150 ° C for 24 hours were used. The layered double hydroxide (LDH) was added in an amount of 1, 0.5, 0.25, and 0.1 parts by weight based on 100 parts by weight of the distilled water.

A layered double hydroxide dispersion in which layered double hydroxide (LDH) was dispersed in distilled water was coated on a substrate by a drop casting method to form a layered double hydroxide layer. Polyethylene terephthalate (PET) was used as the substrate.

After the layered double hydroxide (LDH) coating, the organic material was coated to form an organic material layer. The organic material used was poly (acrylic acid) (PAA).

The layered double hydroxide (LDH) and the organic material were alternately repeatedly coated to form a hybrid film. The hybrid film has a multilayer structure in which a layered double hydroxide layer and an organic layer are alternately stacked.

Table 1 below shows water permeation (WVTR) and oxygen permeability (OTR) characteristics according to the number of laminated layered double hydroxides of hybrid membranes prepared according to Experimental Example 5.

Number of layers 20 30 40 WVTR (g / m2day) 0.01 0.006 0.004 OTR (cm3 / m2day) One 0.02 0.006

Table 2 below shows the water permeation (WVTR) and oxygen permeability (OTR) characteristics according to the aspect ratio of the layered double hydroxides of the hybrid membranes prepared according to Experimental Example 6.

Aspect ratio 20 100 200 600 WVTR (g / m2day) 0.01 0.01 0.008 0.007 OTR (cm3 / m2day) 8 One 0.03 0.005

Table 1 shows a case where a hybrid membrane was formed using a layered double hydroxide prepared using urea and Table 2 shows a case where a hybrid membrane was formed using a layered double hydroxide prepared using HMTA (hexamethylenetetramine) The aspect ratio of HMTA (Hexamethylenetetramine) was higher than that of Urea.

As the number of layers and the aspect ratio of the layered double hydroxides increases, the diffusion of moisture increases, so that the barrier properties can be controlled by controlling the number of layers and the aspect ratio.

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, but, on the contrary, This is possible.

10: organic substrate
20: Gas barrier film
22: Hybrid membrane
24: inorganic protective layer

Claims (12)

(a) The first precursor, [M ²⁺ ] [A ⁿ _{2 / n} ] 揃 zH ₂ O and the second precursor, [M ³⁺ ] [A ^n- _{3 / n} ] 揃 zH ₂ O are dissolved in distilled water ;
(b) adding hexamethylenetetramine to the reaction vessel in which the first precursor and the second precursor are dissolved to form a precursor reaction solution;
(c) sealing the reaction vessel containing the precursor reaction solution and subjecting the reaction vessel to the hydrothermal reaction in an autoclave vessel;
(d) selectively separating the layered double hydroxides formed by the hydrothermal reaction;
(e) dispersing the layered double hydroxide in a solvent and coating the organic layer on the organic substrate to form a layered double hydroxide layer;
(f) coating an organic material on the layered double hydroxide layer to form an organic layer;
(g) repeating the steps (e) and (f) a plurality of times to form a hybrid film in which the layered double hydroxide layer and the organic material layer are alternately laminated; And
(h) forming an inorganic protective layer on the hybrid film,
^Wherein M ²⁺ is at least one divalent metal ion selected from the group consisting of Ba ²⁺ and Sn ²⁺ ,
^Wherein M ³⁺ is at least one trivalent metal ion selected from the group consisting of Ce ³⁺ and Ga ³⁺ ,
Wherein A ^n- is at least one anion selected from the group consisting of vanadate, tungstate and borate,
And z has a value in the range of 0 to 10.
The method for producing a gas barrier film according to claim 1, wherein the layered double hydroxide is represented by the following formula (1).
[Chemical Formula 1]
[M ²⁺ _1-x M ³⁺ _x (OH) ₂ ] [A ^n- ] _{x / n} zH ₂ O (0.2? X? 0.4)
The method of claim 1, wherein the first precursor and the second precursor have a molar concentration ratio of 1: 1 to 3: 1 in the precursor reaction solution.
The method of claim 1, wherein the first precursor has a molar concentration of 10 to 200 mM in the precursor reaction solution,
The second precursor has a molar concentration of 5 to 100 mM in the precursor reaction solution,
Wherein the hexamethylenetetramine has a molar concentration of 50-1000 mM in the precursor reaction solution.
The method of claim 1, wherein the organic material is selected from the group consisting of poly (allylamine hydrochloride), poly (acrylic acid), polyethylenimine (PEI) (3-aminopropyl) triethoxysilane). &Lt; / RTI &gt;
The method of claim 1, wherein the inorganic protective layer comprises polysilazane.
The method of claim 1, wherein the substrate is at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyester (PES), polyimide (PI), AryLite, and Cyclo-Olefin Copolymer (COC). &Lt; / RTI &gt;
2. The method of claim 1, wherein before step (e)
Further comprising peeling the layered double hydroxide to increase the aspect ratio of the layered double hydroxide,
Wherein the exfoliation is carried out by intercalating a surfactant, an organic solvent and an amphoteric substance between the layer of the layered double hydroxide and the layer and subjecting the layer to ultrasonic treatment.
9. The composition of claim 8, wherein the surfactant comprises at least one material selected from the group consisting of phospholipids and sodium dodecylsulfate,
Wherein the organic solvent comprises at least one substance selected from the group consisting of dimethylformamide, dimethylsulfoxide, phenylethylformamide, and hydroxyethylformamide. A method for producing a gas barrier film.
The method of claim 8, wherein the amphoteric material is selected from the group consisting of poly (methacrylic acid), poly (2- (ethylamino) ethyl poly (arylamine) allylamine)), poly (methacrylic acid), N-isopropylacrylamide, N- (3-aminopropyl) methacrylamide, one or more substances selected from the group consisting of methacrylamide, allylamine, acrylamide, (dimethylamino) ethylmethacrylate, and tetrahydropyranyl methacrylate. Wherein the gas barrier film is formed of a metal.
The method according to claim 1, wherein, in the step (e), the solvent is distilled water,
Wherein the layered double hydroxide is dispersed in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the distilled water.
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