Preparation method of water-oxygen barrier film and water-oxygen barrier film

Abstract

The invention provides a preparation method of a water-oxygen barrier film and the water-oxygen barrier film, and belongs to the technical field of materials.The method comprises the steps that a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is prepared on a metal substrate; the surface of the amorphous hexagonal boron nitride layer with the composite structure is coated with an organic glue layer, so that the surface of the amorphous hexagonal boron nitride layer with the composite structure is adhered to the flexible substrate, and a composite combination body is obtained; removing the metal substrate of the composite combination body, and taking the exposed surface of the hexagonal boron nitride layer as a material connection surface to obtain a composite structure film; the two-dimensional material layer is coated on the material connecting surface of one composite structure film so as to be attached to the material connecting surface of the other composite structure film, so that the water-oxygen barrier film is obtained. By means of the method, the problems that in the prior art, when a transfer medium is removed, residues exist, the barrier film is damaged, and the performance of the barrier film is reduced can be solved.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and more specifically, to a preparation method of a water-oxygen barrier film and the water-oxygen barrier film. Background Art

[0002] Hexagonal boron nitride thin films prepared by chemical vapor deposition (CVD) can be used as packaging materials for organic optoelectronic devices due to their unique structure, excellent mechanical properties, high transparency and other advantages. The lattice difference between hexagonal boron nitride and graphene is only about 1.8%, so it is called "white graphite" and is expected to replace graphene, effectively protect the organic functional layer and electrodes of the device, and improve the life of the device. The preparation of hexagonal boron nitride thin films by chemical vapor deposition has gradually matured, but it is still rare to uniformly grow amorphous hexagonal boron nitride on the surface of hexagonal boron nitride. If the hexagonal boron nitride-amorphous hexagonal boron nitride composite film grown by CVD is applied to the field of low-dimensional composite material preparation technology, it still needs to be transferred to the target substrate and the integrity of the hexagonal boron nitride-amorphous hexagonal boron nitride film and the functionality of the composite material should be maintained; the transfer technology directly affects the quality of the hexagonal boron nitride-amorphous hexagonal boron nitride composite film after transfer, as well as the subsequent characterization and application. The interface cleanliness and fit between the hexagonal boron nitride-amorphous hexagonal boron nitride composite film and other components in the composite material during the transfer will also directly affect the barrier properties of the composite film. At present, the technology of hexagonal boron nitride-amorphous hexagonal boron nitride composite water and oxygen barrier film has not been reported.

[0003] The performance of the hexagonal boron nitride-amorphous hexagonal boron nitride composite structure barrier film is not only related to the integrity of the hexagonal boron nitride-amorphous hexagonal boron nitride composite structure, but also closely related to the interlayer spacing of the hexagonal boron nitride-amorphous hexagonal boron nitride composite structure, the spacing between the hexagonal boron nitride-amorphous hexagonal boron nitride composite structure and the substrate, and the interface cleanliness. In the process of transferring the hexagonal boron nitride-amorphous hexagonal boron nitride composite structure from the growth substrate to the functional substrate to prepare the barrier film, the traditional preparation process involves transfer methods mainly including polymer transfer medium assisted transfer, thermal release tape assisted transfer, etc. These methods will have many problems in large-scale production. For example: when the polymer assists the transfer of hexagonal boron nitride to the target substrate, the polymer transfer medium has a poor conformal bonding effect on the surface of the hexagonal boron nitride film. The removal of the substrate will cause damage to the hexagonal boron nitride film and poor surface cleanliness, resulting in its barrier performance of only 0.6g / (m 2.day). On the other hand, the separation principle of the thermal release tape is that the heat-expandable microspheres in the adhesive layer expand when heated, squeeze out of the adhesive layer surface, reduce the contact area between the adhesive layer and the sample, and thus reduce the bonding force. However, when peeling, the microspheres expand when heated, and the stress generated will cause the bonded hexagonal boron nitride-amorphous hexagonal boron nitride composite structure film to wrinkle and break, and the quality will decrease; and there will still be a small area of ​​adhesive layer remaining that cannot be completely removed. All these will cause the barrier performance of the hexagonal boron nitride-amorphous hexagonal boron nitride composite film to decrease.

[0004] It should be noted that the information disclosed in the above background technology section is only used to enhance the understanding of the background of the present invention, and therefore may include information that does not constitute the prior art known to ordinary technicians in the field. Summary of the invention

[0005] In view of the above problems, the purpose of the present invention is to provide a method for preparing a water and oxygen barrier film and a water and oxygen barrier film, so as to solve the problem in the prior art that the traditional barrier film preparation method needs to transfer the prepared barrier film to the target substrate. Regardless of whether the polymer transfer medium assisted transfer method or the thermal release tape assisted transfer method is used, there are problems such as residues when the transfer medium is removed, damage to the barrier film, and degradation of the barrier film performance.

[0006] The present invention provides a method for preparing a water-oxygen barrier film, comprising the following steps:

[0007] Preparing a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate; wherein the hexagonal boron nitride layer in the composite structure is located on the surface of the metal substrate;

[0008] The organic glue layer is coated on the surface of the amorphous hexagonal boron nitride layer of the composite structure to adhere the surface of the amorphous hexagonal boron nitride layer of the composite structure to the flexible substrate to obtain a composite body; wherein the composite body comprises a metal substrate, a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic glue layer and a flexible substrate in order from bottom to top;

[0009] The metal substrate of the composite body is removed, and the exposed surface of the hexagonal boron nitride layer is used as a material connection surface to obtain a composite structure membrane; wherein the composite structure membrane includes a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic glue layer and a flexible substrate in order from bottom to top;

[0010] A water and oxygen barrier film is obtained by coating a two-dimensional material layer on the material connection surface of a composite structure film so as to fit it with the material connection surface of another composite structure film.

[0011] In addition, a preferred solution is that the preparation of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on the metal substrate comprises:

[0012] By chemical vapor deposition technology, in a tube furnace, using a boron-ammine complex as a precursor, hexagonal boron nitride and amorphous hexagonal boron nitride are grown on the metal substrate to prepare a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on the metal substrate; wherein,

[0013] During the growth of hexagonal boron nitride and amorphous hexagonal boron nitride on the metal substrate, argon is used as a carrier gas for transporting the precursor, and hydrogen is used as a protective gas for the deposition and growth of the precursor on the metal substrate.

[0014] In addition, a preferred solution is that the metal substrate is any one of copper, iron and nickel, or an alloy substrate made by mixing at least two of these metals in any proportion.

[0015] In addition, a preferred solution is that in the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride, the thickness of the amorphous hexagonal boron nitride is 0.5 nm to 500 nm.

[0016] In addition, a preferred solution is that the surface of the amorphous hexagonal boron nitride layer of the composite structure is coated with an organic glue layer to adhere the surface of the amorphous hexagonal boron nitride layer of the composite structure to the flexible substrate to obtain a composite combination, comprising:

[0017] Spin coating an organic glue material on the surface of the amorphous hexagonal boron nitride layer of the composite structure to form an organic glue layer on the surface of the amorphous hexagonal boron nitride layer;

[0018] The flexible substrate is adhered to the surface of the organic adhesive layer, and the flexible substrate and the surface of the amorphous hexagonal boron nitride layer are rolled and laminated by rolling to obtain a primary composite body; wherein the flexible substrate is a composite film structure composed of a polymer layer and a polyacrylic acid layer; the polyacrylic acid layer is in contact with the organic adhesive layer; and the rolling temperature is 40°C to 100°C;

[0019] The primary composite body is subjected to a hot pressing treatment to obtain a composite body; wherein the hot pressing treatment temperature is 40°C to 100°C, the pressure is 300Pa to 500Pa, and the treatment time is 60min to 240min.

[0020] In addition, a preferred solution is that the polymer layer is made of any one of polyethylene naphthalate, polyethylene terephthalate, polyimide, polytetrafluoroethylene, biaxially oriented polypropylene, polyethylene, and polyolefin elastomer, or is made by mixing at least two of the above polymers in any proportion, or is made by stacking at least two of the above polymers in any order; and / or,

[0021] The thickness of the polymer layer is 50 μm to 150 μm; and / or,

[0022] The acrylic acid modified part of the polyacrylic acid material used in the polyacrylic acid layer contains any one or at least two of the elements C, H, O, N, S, P, Si, F, and Cl; and / or,

[0023] The thickness of the polyacrylic acid layer is 1 μm to 30 μm, and the peel strength of the polyacrylic acid layer is 1 to 200 g / 25 mm; and / or,

[0024] The thickness of the organic glue layer is 500nm to 10μm; and / or,

[0025] The organic adhesive layer is made of any one of ethylene vinyl acetate, polyvinylidene fluoride, polystyrene, and polyolefin elastomer, or is made by mixing at least two of the above materials in any proportion, or is made by stacking at least two of the above materials in any order.

[0026] In addition, a preferred solution is to use etching or electrochemical bubbling to remove the metal substrate of the composite body; wherein,

[0027] When the metal substrate of the composite body is removed by etching;

[0028] The etching solution is any one of cupric chloride solution, ferric chloride solution, potassium ferrocyanide solution, hydrochloric acid solution or nitric acid solution, or at least two of them mixed in any proportion;

[0029] The concentration of the etching solution is 0.5 mol / L to 2.0 mol / L;

[0030] When the metal substrate of the composite body is removed by electrochemical bubbling, platinum or graphite is used as an anode and the metal substrate is used as a cathode to carry out an electrochemical reaction; wherein,

[0031] The electrolyte is one of sodium hydroxide solution, potassium hydroxide solution, sodium nitrate solution, potassium nitrate solution, and ammonium nitrate solution, or at least two of them mixed in any proportion;

[0032] The concentration of the electrolyte is 0.5 mol / L to 2.0 mol / L.

[0033] In addition, a preferred solution is that the water and oxygen barrier film is obtained by coating a two-dimensional material layer on the material connection surface of a composite structure film to fit with the material connection surface of another composite structure film, including:

[0034] Spin coating a two-dimensional material on a material connection surface of a composite structure film to form a two-dimensional material layer on the material connection surface;

[0035] Laying the material connection surface of another composite structure film on the surface of the two-dimensional material layer, and laminating the two composite structures by rolling, to obtain a primary water and oxygen barrier film; wherein the rolling temperature is 40° C. to 100° C.;

[0036] The primary water-oxygen barrier film is subjected to a hot pressing treatment to obtain a water-oxygen barrier film; wherein the hot pressing treatment temperature is 40° C. to 100° C., the pressure is 300 Pa to 500 Pa, and the treatment time is 60 min to 240 min.

[0037] In addition, a preferred solution is that the thickness of the two-dimensional material layer is 0.5 nm to 5 μm;

[0038] The two-dimensional material layer is made of any one of the two-dimensional materials of hexagonal boron nitride, hydroxyboron nitride, and molybdenum disulfide, or is made by mixing at least two of the above two-dimensional materials in any proportion, or is made by stacking at least two of the above two-dimensional materials in any order.

[0039] The present invention also provides a water-oxygen barrier film, which is prepared by the method for preparing the water-oxygen barrier film as described above.

[0040] It can be seen from the above technical scheme that the preparation method of the water-oxygen barrier film and the water-oxygen barrier film provided by the present invention realize the modification of the surface of the hexagonal boron nitride by preparing a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate. Compared with the artificially bonded hexagonal boron nitride composite film, the directly prepared composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is more tightly bonded, without bubbles, wrinkles, impurities and damage, thereby greatly improving the water-oxygen barrier performance of the barrier film; the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is isolated by an organic adhesive layer so as to be in direct contact with the flexible substrate, so that the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is perfectly bonded to the organic adhesive layer, and it is not easy to produce gaps, thereby ensuring that the hexagonal boron nitride and amorphous hexagonal boron nitride are bonded to each other. The integrity of the composite structure of boron; the strong friction of water molecules on the surface of hexagonal boron nitride and other characteristics slow down the slip of water molecules on the surface of boron nitride; the organic adhesive layer is retained as a functional layer to avoid the damage of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride caused by stress when the organic adhesive layer is removed. The support strength of the organic adhesive layer can be improved by a flexible substrate, and the operating requirements for workers in the process of transferring the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride are reduced, thereby improving the transfer efficiency, making the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride complete after transfer, and bonding the two composite structure films together through a two-dimensional material layer. The hydrogen bonding between the two-dimensional material and water molecules is used to further improve the barrier properties of water molecules, thereby making the barrier properties of the water-oxygen barrier film even better.

[0041] In order to achieve the above and related purposes, one or more aspects of the present invention include the features that will be described in detail later. The following description and the accompanying drawings describe some exemplary aspects of the present invention in detail. However, these aspects indicate only some of the various ways in which the principles of the present invention can be used. In addition, the present invention is intended to include all these aspects and their equivalents. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] By referring to the following description in conjunction with the accompanying drawings, and with a more complete understanding of the present invention, other objects and results of the present invention will become more apparent and easily understood.

[0043] Figure 1 is a flow chart of a method for preparing a water and oxygen barrier film according to an embodiment of the present invention;

[0044] Figure 2 Schematic diagram of the layer structure of a water and oxygen barrier film according to an embodiment of the present invention;

[0045] Figure 3 An optical microscope photograph of a hexagonal boron nitride-amorphous boron nitride film transferred to a SiO2 substrate according to Example 1 of the present invention;

[0046] Figure 4 The Raman spectrum of the hexagonal boron nitride-amorphous boron nitride film transferred to the SiO2 substrate according to Example 1 of the present invention;

[0047] Figure 5 This is a graph showing the water permeability test results of the water-oxygen barrier film in Example 1 of the present invention;

[0048] Figure 6 This is a graph showing the water permeability test results of the barrier film in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0049] In the following description, for the purpose of explanation, numerous specific details are set forth in order to provide a thorough understanding of one or more embodiments. However, it is apparent that these embodiments may also be implemented without these specific details.

[0050] In view of the above-mentioned prior art, a traditional barrier film preparation method is adopted, and the prepared barrier film needs to be transferred to a target substrate. Regardless of whether a polymer transfer medium assisted transfer method or a thermal release tape assisted transfer method is adopted, there are problems such as residues when the transfer medium is removed, damage to the barrier film, and degradation of the barrier film performance. A preparation method of a water-oxygen barrier film and a water-oxygen barrier film are proposed.

[0051] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0052] In order to illustrate the preparation method of the water-oxygen barrier film and the water-oxygen barrier film provided by the present invention, Figure 1 The process of the method for preparing the water and oxygen barrier film according to the embodiment of the present invention is shown; Figure 2 shows the layer structure of the water and oxygen barrier film according to an embodiment of the present invention; Figure 3 The optical microstructure of the hexagonal boron nitride-amorphous boron nitride film transferred to the SiO2 substrate according to Example 1 of the present invention is shown; Figure 4 The Raman spectrum of the hexagonal boron nitride-amorphous boron nitride film transferred to the SiO2 substrate in Example 1 of the present invention is shown; Figure 5 The water permeability test results of the water and oxygen barrier film in Example 1 of the present invention are shown; Figure 6 The water permeability test results of the barrier film in Comparative Example 1 according to the present invention are shown.

[0053] like Figure 1 Combination Figure 2 As shown in the figure, the method for preparing the water and oxygen barrier film provided by the present invention comprises the following steps:

[0054] Step S1, preparing a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate; wherein the hexagonal boron nitride layer in the composite structure is located on the surface of the metal substrate.

[0055] Specifically, it is preferred but not limited to using a deposition method such as chemical vapor deposition to directly prepare a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate, and the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is grown on the metal substrate by controlling the growth time. The process is to first grow a hexagonal boron nitride layer on the metal substrate, and as the growth time goes by, an amorphous hexagonal boron nitride layer is grown on the surface of the hexagonal boron nitride, thereby obtaining a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride.

[0056] As a preferred embodiment of the present invention, a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is prepared on a metal substrate, comprising:

[0057] By chemical vapor deposition technology, in a tube furnace, using a boron-ammine complex as a precursor, hexagonal boron nitride and amorphous hexagonal boron nitride are grown on a metal substrate to prepare a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on the metal substrate; wherein,

[0058] In the process of growing hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate, argon gas is used as a carrier gas for transporting the precursor, and hydrogen gas is used as a protective gas for depositing and growing the precursor on the metal substrate.

[0059] Specifically, in the process of growing hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate, it is preferred but not limited to use argon as a carrier gas for transporting the precursor and hydrogen as a protective gas for depositing and growing the precursor on the metal substrate.

[0060] As a preferred embodiment of the present invention, the metal substrate is any one of copper, iron and nickel or an alloy substrate prepared by mixing at least two of these metals in any proportion.

[0061] Specifically, when the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is grown on a metal substrate by chemical vapor deposition, the metal substrate is preferably, but not limited to, a metal foil of Cu, Fe, Ni or an alloy thereof that catalyzes the growth of hexagonal boron nitride and amorphous hexagonal boron nitride.

[0062] As a preferred embodiment of the present invention, in the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride, the thickness of the amorphous hexagonal boron nitride is 0.5 nm to 500 nm.

[0063] Specifically, the thickness of the amorphous hexagonal boron nitride layer is controllable within the range of 0.5 nm to 500 nm. In an embodiment of the present invention, the thickness of the amorphous hexagonal boron nitride layer is preferably but not limited to 0.5 nm to 500 nm, such as 3 nm, 4 nm, 5 nm, 100 nm, etc.

[0064] Step S2, by coating an organic adhesive layer on the surface of the amorphous hexagonal boron nitride layer of the composite structure, so as to adhere the surface of the amorphous hexagonal boron nitride layer of the composite structure to the flexible substrate to obtain a composite body; wherein the composite body includes a metal substrate, a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic adhesive layer and a flexible substrate from bottom to top.

[0065] As a preferred embodiment of the present invention, an organic adhesive layer is coated on the surface of the amorphous hexagonal boron nitride layer of the composite structure to adhere the surface of the amorphous hexagonal boron nitride layer of the composite structure to the flexible substrate to obtain a composite body, comprising:

[0066] Spin coating an organic glue material on the surface of the amorphous hexagonal boron nitride layer of the composite structure to form an organic glue layer on the surface of the amorphous hexagonal boron nitride layer;

[0067] The flexible substrate is adhered to the surface of the organic adhesive layer, and the flexible substrate and the surface of the amorphous hexagonal boron nitride layer are rolled and laminated by rolling to obtain a primary composite body; wherein the flexible substrate is a composite film structure composed of a polymer layer and a polyacrylic acid layer; the polyacrylic acid layer is in contact with the organic adhesive layer; and the rolling temperature is 40°C to 100°C;

[0068] The primary composite body is subjected to hot pressing treatment to obtain a composite body; wherein the temperature of the hot pressing treatment is 40°C to 100°C, the pressure is 300Pa to 500Pa, and the treatment time is 60min to 240min.

[0069] As a preferred embodiment of the present invention, the polymer layer is made of any one of polyethylene naphthalate, polyethylene terephthalate, polyimide, polytetrafluoroethylene, biaxially oriented polypropylene, polyethylene, and polyolefin elastomer, or is made by mixing at least two of the above polymers in any proportion, or is made by stacking at least two of the above polymers in any order; and / or,

[0070] The thickness of the polymer layer is 50 μm to 150 μm; and / or,

[0071] The acrylic acid modified part of the polyacrylic acid material used in the polyacrylic acid layer contains any one or at least two of the elements C, H, O, N, S, P, Si, F, and Cl; and / or,

[0072] The thickness of the polyacrylic acid layer is 1 μm to 30 μm, and the peel strength of the polyacrylic acid layer is 1 to 200 g / 25 mm; and / or,

[0073] The thickness of the organic glue layer is 500nm to 10μm; and / or,

[0074] The organic adhesive layer is made of any one of ethylene vinyl acetate, polyvinylidene fluoride, polystyrene, and polyolefin elastomer, or is made by mixing at least two of the above materials in any proportion, or is made by stacking at least two of the above materials in any order.

[0075] Specifically, an organic polymer (organic glue raw material) is first dissolved in an organic solvent to form a solution, and then the organic polymer solution is coated on the upper surface of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride, and then heated on a hot plate to volatilize the solvent to form an organic glue layer. The coating method of the organic glue can be any appropriate method, such as scraping, spin coating, spraying, etc., and the present invention is not particularly limited to this.

[0076] The organic glue layer is preferably, but not limited to, made of any one of ethylene-vinyl acetate, polyvinylidene fluoride, polystyrene, and polyolefin elastomer, or made of at least two of the above materials mixed in any proportion, or made of at least two of the above materials stacked in any order. The appropriate solvent and solution concentration can be selected according to the selected organic polymer (organic glue raw material) and the coating method, and the specific parameters can be set according to actual needs. The present invention does not make any special restrictions on this. The purpose of configuring the organic polymer solution is to form an organic glue layer, as long as the organic polymer solution can achieve the above purpose. The thickness of the organic glue layer is preferably, but not limited to, 500nm to 10μm. When the thickness of the organic glue layer is less than 500nm, the isolation effect of the organic glue layer on the support layer formed by the flexible substrate cannot reach the best; but those skilled in the art should understand that as long as the organic glue layer is added between the flexible substrate and the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride, the pollution of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride by the flexible substrate can be reduced. The thickness is limited to not less than 500nm only to reduce the pollution to the ideal standard, and is not used to limit the present invention. When the thickness of the organic glue layer is greater than 10 μm, the thickness of the barrier film will increase and the light transmittance will be reduced. Therefore, the thickness of the organic glue layer is preferably 500 nm to 10 μm.

[0077] In a preferred embodiment of the present invention, the organic adhesive layer can be a composite layer including multiple layers. For example, when two organic adhesive layers are included, the first organic adhesive layer is in direct contact with the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride, and the second organic adhesive layer is adhered to the surface of the first organic adhesive layer away from the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride. The first organic adhesive layer is in direct contact with and fully combined with the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride to ensure that the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride will not be damaged during transfer. If the thickness of the first organic adhesive layer is too thin, the bonding force is insufficient, and the composite structure film of hexagonal boron nitride and amorphous hexagonal boron nitride cannot be completely transferred. If it is too thick, it will affect the thickness and light transmittance of the overall composite film. The first organic adhesive layer is preferably made of a material with a large force on the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride to increase the bonding between the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride and the polymer film. For example, the first organic glue layer is preferably, but not limited to, one or at least two of ethylene vinyl acetate, polyvinylidene fluoride, polystyrene, and polyolefin elastomer.

[0078] It should be noted that the organic adhesive layer in the present invention can be a multi-layer or a single layer. According to the above introduction, the skilled person in the art should know that when the organic adhesive layer is a single layer, the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride can be tightly combined with the flexible substrate, and the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride remains intact and clean during the transfer process.

[0079] A flexible substrate is adhered to the surface of the organic adhesive layer. The flexible substrate is a composite film structure composed of a polymer layer and a polyacrylic acid layer; the polyacrylic acid layer is in contact with the organic adhesive layer. The composite film structure composed of a polymer layer and a polyacrylic acid layer has stronger mechanical properties than the organic adhesive layer, which can reduce the operating requirements for the staff during the transfer process of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride, and can achieve the bonding of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride with the target substrate, improve the transfer efficiency, and make the transfer of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride easier to achieve. The organic adhesive layer and the flexible substrate are both part of the barrier film, and the conformal bonding between the two helps to improve the performance of the barrier film.

[0080] The acrylic acid used in the polyacrylic acid layer may be a modified group containing one or more of the functional groups such as methyl, ethyl, fluorine, chlorine, and amino. Those skilled in the art can select a suitable specific type of polyacrylic acid according to the performance of the acrylic acid to be used. The thickness of the polyacrylic acid layer is preferably but not limited to 1μm to 30μm, and the peel strength is preferably but not limited to 1 to 200g / 25mm; if the peel strength of the polyacrylic acid layer is too high, the mechanical force used to separate the polyacrylic acid from the release film will be too large, causing the flexible substrate to deform and affecting the bonding with the composite structure. The stress generated by the organic glue layer is released to the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride. If the peel strength of the acrylic acid layer is too low, the bonding force is weak, and the bonding between the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride and the flexible substrate cannot be achieved. Those skilled in the art can select a polyacrylic acid layer of appropriate thickness and peel strength according to actual needs. For example, the thickness of the acrylic layer is 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, etc.; the peel strength is 1 g / 25 mm, 10 g / 25 mm, 20 g / 25 mm, 30 g / 25 mm, 50 g / 25 mm, 70 g / 25 mm, 90 g / 25 mm, 110 g / 25 mm, 130 g / 25 mm, 150 g / 25 mm, 170 g / 25 mm, 200 g / 2 mm, etc. The polymer film is composed of one or more of PEN, PET, PI, PTFE, BOPP, PE, and POE. The above polymers have good strength and can play a supporting role to prevent the polyacrylic acid layer from deforming; the thickness of the polymer film is 50 to 150 μm. Those skilled in the art can select a suitable polymer film thickness according to actual needs, such as 50 μm, 70 μm, 90 μm, 110 μm, 130 μm, 150 μm, etc.

[0081] Step S3, removing the metal substrate of the composite body, and using the exposed surface of the hexagonal boron nitride layer as a material connection surface to obtain a composite structure membrane; wherein the composite structure membrane includes a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic glue layer and a flexible substrate from bottom to top.

[0082] As a preferred embodiment of the present invention, the metal substrate of the composite body is removed by etching or electrochemical bubbling; wherein,

[0083] When the metal substrate of the composite combination is removed by etching;

[0084] The etching solution is any one of cupric chloride solution, ferric chloride solution, potassium ferrocyanide solution, hydrochloric acid solution or nitric acid solution, or at least two of them mixed in any proportion;

[0085] The concentration of the etching solution is 0.5 mol / L to 2.0 mol / L;

[0086] When the metal substrate of the composite body is removed by electrochemical bubbling, platinum or graphite is used as the anode and the metal substrate is used as the cathode for electrochemical reaction; wherein,

[0087] The electrolyte is one of sodium hydroxide solution, potassium hydroxide solution, sodium nitrate solution, potassium nitrate solution, and ammonium nitrate solution, or at least two of them mixed in any proportion;

[0088] The concentration of the electrolyte is 0.5mol / L~2.0mol / L.

[0089] Specifically, the metal substrate is removed to obtain a composite structure membrane, which includes a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic glue layer and a flexible substrate from bottom to top. The metal substrate can be removed by etching or bubbling. When the metal substrate is removed by etching, the etching solution is a solution of one or more of copper chloride, ferric chloride, potassium ferrocyanide, hydrochloric acid or nitric acid, and the concentration of the etching solution is preferably but not limited to 0.5 mol / L to 2.0 mol / L. When the metal substrate is removed by bubbling, platinum or graphite can be used as the anode, the metal substrate can be used as the cathode, and the electrolyte can be a solution of one or more of sodium hydroxide, potassium hydroxide, sodium nitrate, potassium nitrate, and ammonium nitrate, and the concentration of the electrolyte is preferably but not limited to 0.5 mol / L to 2.0 mol / L. After the metal substrate is completely etched or separated by bubbling, the composite membrane is placed in deionized water for cleaning, the residual etching solution or electrolyte is removed, and the composite structure membrane is obtained after drying.

[0090] Step S4, coating a two-dimensional material layer on the material connection surface of one composite structure membrane to fit it with the material connection surface of another composite structure membrane to obtain a water and oxygen barrier membrane.

[0091] As a preferred embodiment of the present invention, a water and oxygen barrier film is obtained by coating a two-dimensional material layer on the material connection surface of a composite structure film to fit with the material connection surface of another composite structure film, including:

[0092] Spin coating a two-dimensional material on a material connection surface of a composite structure film to form a two-dimensional material layer on the material connection surface;

[0093] Laying the material connection surface of another composite structure film on the surface of the two-dimensional material layer, and rolling the two composite structures together by rolling to obtain a primary water and oxygen barrier film; wherein the rolling temperature is 40°C to 100°C;

[0094] The primary water-oxygen barrier film is subjected to hot pressing treatment to obtain the water-oxygen barrier film; wherein the hot pressing treatment temperature is 40° C. to 100° C., the pressure is 300 Pa to 500 Pa, and the treatment time is 60 min to 240 min.

[0095] As a preferred embodiment of the present invention, the thickness of the two-dimensional material layer is 0.5 nm to 5 μm;

[0096] The two-dimensional material layer is made of any one of the two-dimensional materials of hexagonal boron nitride, hydroxyboron nitride, and molybdenum disulfide, or is made by mixing at least two of the above two-dimensional materials in any proportion, or is made by stacking at least two of the above two-dimensional materials in any order.

[0097] Specifically, the two-dimensional material is dispersed in an organic solvent to form a dispersion, and then the two-dimensional material dispersion is applied to the material connection surface of a composite structure membrane. After the solvent is volatilized by heating on a hot plate, a two-dimensional material layer is formed on the material connection surface of the composite structure membrane. The coating method can also be any appropriate method, such as scraping, spin coating, spraying, etc. The two-dimensional material layer is selected from one or more of hexagonal boron nitride, hydroxy boron nitride, molybdenum disulfide, etc. According to the selected two-dimensional material and coating method, an appropriate solvent and solution concentration are selected. The specific parameters are not limited here. Those skilled in the art can understand that the purpose of preparing the two-dimensional material dispersion is to form a two-dimensional material layer, as long as the two-dimensional material dispersion can achieve the above purpose. The two-dimensional material layer in the composite structure membrane with the two-dimensional material layer is attached to the material connection surface of another composite structure membrane, and the two composite structures are pressed together by a pressure roller and subjected to hot pressing to obtain a water and oxygen barrier film.

[0098] The water-oxygen barrier film provided by the present invention is characterized in that it is prepared by the preparation method of the water-oxygen barrier film of the present invention as described above.

[0099] In order to better explain the preparation method of the water-oxygen barrier film provided by the present invention and the technical effects achieved, the following examples are given:

[0100] Four copper substrates of 10 cm×10 cm were prepared and numbered as copper substrate No. 1, copper substrate No. 2, copper substrate No. 3 and copper substrate No. 4 respectively.

[0101] Example 1

[0102] The following treatments are performed on copper substrate No. 1 and copper substrate No. 2 at the same time:

[0103] Step S1, growing a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on a copper substrate.

[0104] Step S2, dissolving EVA (ethylene-vinyl acetate copolymer) in toluene, the mass fraction of EVA is 4%, and spin coating the EVA solution on the surface of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride at a speed of 2000 rpm by spin coating, and curing at 80°C for 15 minutes, wherein the thickness of the EVA layer is 10 μm; rolling and bonding the composite structure of EVA-hexagonal boron nitride and amorphous hexagonal boron nitride-copper substrate to the composite of PET (polyethylene terephthalate) and polyacrylic acid layer to obtain a composite combination; wherein the composite combination includes a metal substrate, a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic adhesive layer and a flexible substrate (a composite of PET and polyacrylic acid layer) from bottom to top.

[0105] Step S3, immersing the composite combination in a ferric chloride etching solution, and after the metal foil is completely etched, washing it in 1M dilute hydrochloric acid and deionized water respectively, removing the residual etching solution, and obtaining a composite structure membrane, wherein the composite structure membrane includes a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic glue layer and a flexible substrate from bottom to top, and the composite structure membranes obtained by copper substrate No. 1 and copper substrate No. 2 are placed in a vacuum drying oven at 60°C and dried for 8 hours to obtain composite structure membrane No. 1 and composite structure membrane No. 2, respectively.

[0106] Step S4, spin-coating hydroxyl boron nitride on the composite structure surface of hexagonal boron nitride and amorphous hexagonal boron nitride of composite structure film No. 1, drying on a hot plate at 80°C for 30 minutes, bonding the composite structure surface of hexagonal boron nitride and amorphous hexagonal boron nitride of composite structure film No. 2 to the surface of hydroxyl boron nitride, passing through a roller press to tightly fit the two composite structure films with the middle hydroxyl boron nitride layer, and then hot pressing at 80°C for 4 hours to obtain a water and oxygen barrier film.

[0107] Comparative Example 1

[0108] The following treatments are performed on the No. 3 copper substrate and the No. 4 copper substrate simultaneously:

[0109] Step S1, growing a single layer of hexagonal boron nitride on a copper substrate;

[0110] Step S2, dissolving the same EVA as in Example 1 in toluene, with a mass fraction of EVA of 4%, and spin coating the EVA solution on the surface of the single-layer hexagonal boron nitride layer at a rotation speed of 2000 rpm by spin coating, and rolling and bonding the EVA-hexagonal boron nitride-copper substrate composite to the same PET and polyacrylic acid layer composite as in Example 1 to obtain a composite composite; wherein the composite composite includes a metal substrate, a hexagonal boron nitride layer, an organic adhesive layer and a flexible substrate (a composite of PET and polyacrylic acid layer) from bottom to top.

[0111] Step S3, immersing the composite combination in a ferric chloride etching solution, and after the metal foil is completely etched, washing it in 1M dilute hydrochloric acid and deionized water respectively to remove the residual etching solution to obtain a composite structure membrane, wherein the composite structure membrane includes a hexagonal boron nitride layer, an organic glue layer and a flexible substrate from bottom to top, and the composite structure membranes obtained from the No. 3 copper substrate and the No. 4 copper substrate are placed in a vacuum drying oven at 60°C and dried for 8 hours to obtain a No. 3 composite structure membrane and a No. 4 composite structure membrane, respectively.

[0112] Step S4, spin-coat hydroxyl boron nitride on the hexagonal boron nitride surface of composite structure membrane No. 3, dry on a hot plate at 80°C for 30 minutes, adhere the hexagonal boron nitride surface of composite structure membrane No. 4 to the hydroxyl boron nitride surface, pass through a roller press to make the two composite structure membranes fit tightly with the middle hydroxyl boron nitride layer, and then, hot press at 80°C for 4 hours to obtain a comparative water and oxygen barrier film.

[0113] After the water-oxygen barrier film prepared in Example 1 was transferred to a SiO2 substrate, optical microscopy and Raman spectroscopy tests were performed. Figure 3 and Figure 4 As shown, it can be seen that the hexagonal boron nitride-amorphous boron nitride film prepared in Example 1 of the present invention has a compact structure.

[0114] like Figure 5 and Figure 6 As shown in the figure, the water barrier performance of the water-oxygen barrier film prepared in Example 1 of the present invention is better than that of the comparative barrier performance prepared in Comparative Example 1. This is mainly because the amorphous hexagonal boron nitride grown on the surface of hexagonal boron nitride further reduces the channels for water molecules to penetrate, and the polarity of amorphous hexagonal boron nitride further affects the slip length of water molecules and prolongs the water permeation path, making it more difficult for water molecules to penetrate. The large amount of hydroxyl groups contained in the two-dimensional material can form hydrogen bonds with water molecules, significantly reducing the permeability of water molecules.

[0115] It should be noted that the above specific embodiments are only for the purpose of verifying the effect of the method for preparing the water and oxygen barrier film provided by the present invention in the actual experimental process, and are not intended to limit the technical solution provided by the present invention.

[0116] It can be seen from the above specific embodiments that the preparation method of the water-oxygen barrier film and the water-oxygen barrier film provided by the present invention achieve surface modification of the hexagonal boron nitride by preparing a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate. Compared with the artificially bonded hexagonal boron nitride composite film, the directly prepared composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is more tightly bonded, free of bubbles, wrinkles, impurities and damage, thereby greatly improving the water-oxygen barrier performance of the barrier film; the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is isolated by an organic adhesive layer so as to be in direct contact with the flexible substrate, so that the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride is perfectly bonded to the organic adhesive layer, and it is not easy to produce gaps, thereby ensuring that the hexagonal boron nitride and amorphous hexagonal boron nitride are bonded to the organic adhesive layer. The integrity of the composite structure of boron nitride; the strong friction of water molecules on the surface of hexagonal boron nitride and other characteristics slow down the slip of water molecules on the surface of boron nitride; the organic adhesive layer is retained as a functional layer to avoid the damage of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride caused by stress when the organic adhesive layer is removed. The support strength of the organic adhesive layer can be improved by a flexible substrate, and the operating requirements for workers during the transfer of the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride are reduced, thereby improving the transfer efficiency, making the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride complete after transfer, and bonding the two composite structure films together through a two-dimensional material layer. The hydrogen bonding between the two-dimensional material and water molecules is used to further improve the barrier properties of water molecules, thereby making the barrier properties of the water-oxygen barrier film even better.

[0117] As described above, the method for preparing the water-oxygen barrier film and the water-oxygen barrier film proposed in the present invention are described by way of example with reference to the accompanying drawings. However, those skilled in the art should understand that various improvements can be made to the method for preparing the water-oxygen barrier film and the water-oxygen barrier film proposed in the present invention without departing from the content of the present invention. Therefore, the protection scope of the present invention should be determined by the content of the attached claims.

Claims

1. A method for preparing a water and oxygen barrier film, characterized in that: The steps include: Preparing a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate; wherein the hexagonal boron nitride layer in the composite structure is located on the surface of the metal substrate; The organic glue layer is coated on the surface of the amorphous hexagonal boron nitride layer of the composite structure to adhere the surface of the amorphous hexagonal boron nitride layer of the composite structure to the flexible substrate to obtain a composite body; wherein the composite body comprises a metal substrate, a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic glue layer and a flexible substrate in order from bottom to top; The metal substrate of the composite body is removed, and the exposed surface of the hexagonal boron nitride layer is used as a material connection surface to obtain a composite structure membrane; wherein the composite structure membrane includes a hexagonal boron nitride layer, an amorphous hexagonal boron nitride layer, an organic glue layer and a flexible substrate in order from bottom to top; A water and oxygen barrier film is obtained by coating a two-dimensional material layer on the material connection surface of a composite structure film so as to fit it with the material connection surface of another composite structure film.

2. The method for preparing a water and oxygen barrier film according to claim 1, characterized in that: The method of preparing a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on a metal substrate comprises: By chemical vapor deposition technology, in a tube furnace, using a boron-ammine complex as a precursor, hexagonal boron nitride and amorphous hexagonal boron nitride are grown on the metal substrate to prepare a composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride on the metal substrate; wherein, During the growth of hexagonal boron nitride and amorphous hexagonal boron nitride on the metal substrate, argon is used as a carrier gas for transporting the precursor, and hydrogen is used as a protective gas for the deposition and growth of the precursor on the metal substrate.

3. The method for preparing a water and oxygen barrier film according to claim 1, characterized in that: The metal substrate is any one of copper, iron and nickel or an alloy substrate prepared by mixing at least two of the metals in any proportion.

4. The method for preparing a water and oxygen barrier film according to claim 1, characterized in that: In the composite structure of hexagonal boron nitride and amorphous hexagonal boron nitride, the thickness of the amorphous hexagonal boron nitride is 0.5 nm to 500 nm.

5. The method for preparing a water and oxygen barrier film according to claim 1, characterized in that: The method comprises coating an organic glue layer on the surface of the amorphous hexagonal boron nitride layer of the composite structure to adhere the surface of the amorphous hexagonal boron nitride layer of the composite structure to a flexible substrate to obtain a composite body, comprising: Spin coating an organic glue material on the surface of the amorphous hexagonal boron nitride layer of the composite structure to form an organic glue layer on the surface of the amorphous hexagonal boron nitride layer; The flexible substrate is adhered to the surface of the organic adhesive layer, and the flexible substrate and the surface of the amorphous hexagonal boron nitride layer are rolled and laminated by rolling to obtain a primary composite body; wherein the flexible substrate is a composite film structure composed of a polymer layer and a polyacrylic acid layer; the polyacrylic acid layer is in contact with the organic adhesive layer; the temperature of the pressing roller is 40°C to 100°C; The primary composite body is subjected to a hot pressing treatment to obtain a composite body; wherein the hot pressing treatment temperature is 40°C to 100°C, the pressure is 300Pa to 500Pa, and the treatment time is 60min to 240min.

6. The method for preparing a water and oxygen barrier film according to claim 5, characterized in that: The polymer layer is made of any one of polyethylene naphthalate, polyethylene terephthalate, polyimide, polytetrafluoroethylene, biaxially oriented polypropylene, polyethylene, and polyolefin elastomer, or is made by mixing at least two of the above polymers in any proportion, or is made by stacking at least two of the above polymers in any order; and / or, The thickness of the polymer layer is 50 μm to 150 μm; and / or, The acrylic acid modified part of the polyacrylic acid material used in the polyacrylic acid layer contains any one or at least two of the elements C, H, O, N, S, P, Si, F, and Cl; and / or, The thickness of the polyacrylic acid layer is 1 μm to 30 μm, and the peel strength of the polyacrylic acid layer is 1 to 200 g / 25 mm; and / or, The thickness of the organic glue layer is 500nm to 10μm; and / or, The organic adhesive layer is made of any one of ethylene vinyl acetate, polyvinylidene fluoride, polystyrene, and polyolefin elastomer, or is made by mixing at least two of the above materials in any proportion, or is made by stacking at least two of the above materials in any order.

7. The method for preparing a water and oxygen barrier film according to claim 1, characterized in that: The metal substrate of the composite body is removed by etching or electrochemical bubbling; wherein, When the metal substrate of the composite body is removed by etching; The etching solution is any one of cupric chloride solution, ferric chloride solution, potassium ferrocyanide solution, hydrochloric acid solution or nitric acid solution, or at least two of them mixed in any proportion; The concentration of the etching solution is 0.5 mol / L to 2.0 mol / L; When the metal substrate of the composite body is removed by electrochemical bubbling, platinum or graphite is used as an anode and the metal substrate is used as a cathode to carry out an electrochemical reaction; wherein, The electrolyte is one of sodium hydroxide solution, potassium hydroxide solution, sodium nitrate solution, potassium nitrate solution, and ammonium nitrate solution, or at least two of them mixed in any proportion; The concentration of the electrolyte is 0.5 mol / L to 2.0 mol / L.

8. The method for preparing a water and oxygen barrier film according to claim 1, characterized in that: The method comprises coating a two-dimensional material layer on the material connection surface of a composite structure film to fit the material connection surface of another composite structure film to obtain a water and oxygen barrier film, comprising: Spin coating a two-dimensional material on a material connection surface of a composite structure film to form a two-dimensional material layer on the material connection surface; Laying the material connection surface of another composite structure film on the surface of the two-dimensional material layer, and laminating the two composite structures by rolling, to obtain a primary water and oxygen barrier film; wherein the rolling temperature is 40° C. to 100° C.; The primary water-oxygen barrier film is subjected to a hot pressing treatment to obtain a water-oxygen barrier film; wherein the hot pressing treatment temperature is 40° C. to 100° C., the pressure is 300 Pa to 500 Pa, and the treatment time is 60 min to 240 min.

9. The method for preparing a water and oxygen barrier film according to claim 1, characterized in that: The thickness of the two-dimensional material layer is 0.5 nm to 5 μm; The two-dimensional material layer is made of any one of the two-dimensional materials of hexagonal boron nitride, hydroxyboron nitride, and molybdenum disulfide, or is made by mixing at least two of the above two-dimensional materials in any proportion, or is made by stacking at least two of the above two-dimensional materials in any order.

10. A water and oxygen barrier film, characterized in that: The water-oxygen barrier film is prepared by the preparation method of the water-oxygen barrier film according to any one of claims 1 to 9.

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