A two-dimensional composite material and a method for preparing the same, a barrier coating and applications thereof

Abstract

The application belongs to the technical field of packaging materials, and particularly relates to a two-dimensional composite material and a preparation method thereof, a barrier coating material and application thereof. The two-dimensional composite material provided by the application comprises a two-dimensional sheet material and a nanomaterial attached to the surface of the two-dimensional sheet material; the nanomaterial comprises a metal oxide nanomaterial or a nanometal. In the application, the two-dimensional sheet material has a high width-to-height ratio and a high specific surface area, and has excellent ability to block the penetration of moisture; the metal oxide and the nanometal particle have reactivity, can react with the penetrated water molecules to convert them into other substances to achieve a moisture blocking effect, and in addition, can be dispersed in different directions on the surface of the two-dimensional material to block the penetration of water molecules in different directions. The two-dimensional composite material provided by the application can be used as a moisture blocking functional filler to obtain a high-performance moisture blocking coating.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of packaging materials, and particularly relates to a two-dimensional composite material and a preparation method thereof, a barrier coating material and application thereof. BACKGROUND

[0002] The storage life or service life of fresh food, medicine, electronic equipment and polyurethane material is directly related to the moisture in the environment; for example, the active ingredients in medicine are highly sensitive to oxygen, moisture and microorganisms, and the performance of medicine will be affected by the external environment. Effective packaging of food and medicine can play a role as a passivation layer to ensure that food and medicine are not affected by the external environment; at the same time, when electronic devices are packaged, their stability and reliability can be improved, and the influence of the external environment can be weakened; in addition, polyurethane foam is widely used as a damping and packaging material, but it has strong hygroscopicity, which causes the foam to plasticize, swell and deform, affecting the size accuracy of precision parts. Therefore, effective and reasonable moisture resistance is a necessary prerequisite for protecting materials from the external environment, maintaining their quality and safety, and realizing their functions and values during storage, transportation, post-processing and sales.

[0003] At present, the main way to make it barrier is to coat a barrier coating on the surface of the packaging material, but the barrier performance of the component coating formed by the existing coating is still low and needs to be improved. SUMMARY

[0004] Therefore, the present application provides a two-dimensional composite material and a preparation method thereof, a barrier coating material and application thereof. The two-dimensional composite material provided by the present application can greatly improve the moisture-proof performance of the coating as a coating filler.

[0005] To solve the above technical problems, the present application provides a two-dimensional composite material, which comprises a two-dimensional sheet material and a nano material attached to the surface of the two-dimensional sheet material; the nano material comprises a metal oxide nano material or a nano metal.

[0006] Preferably, the metal oxide nano material comprises magnesium oxide, calcium oxide, aluminum oxide or zinc oxide; the shape of the metal oxide nano material is sheet-shaped, and the sheet diameter of the metal oxide nano material is 100-1000 nm.

[0007] The nano metal comprises iron, copper, magnesium, cobalt or zinc; the shape of the nano metal is sheet-shaped or particulate, and the sheet diameter or particle diameter of the nano metal is 50-500 nm.

[0008] Preferably, the mass ratio of the two-dimensional sheet material and the nano material is 1:10-25.

[0009] Preferably, the two-dimensional sheet material comprises one or more of graphene oxide, molybdenum disulfide, hexagonal boron nitride, mica sheet, MXene material and clay;

[0010] The sheet diameter of the two-dimensional sheet material is 1000-10000 nm.

[0011] The application also provides a preparation method of the two-dimensional composite material, comprising the following steps:

[0012] Mixing the two-dimensional sheet material, the nanomaterial precursor solution and the solvent to obtain a dispersion liquid;

[0013] When the nanomaterial is a metal oxide, the nanomaterial precursor solution is a first soluble metal salt solution; mixing the dispersion liquid and an alkaline solution to perform first in-situ growth, and then calcining under nitrogen protection to obtain the two-dimensional composite material;

[0014] When the nanomaterial is a nanometal, the nanomaterial precursor solution is a second soluble metal salt solution; mixing the dispersion liquid, the solvent, a dispersant and a surfactant to perform second in-situ growth, and then calcining under nitrogen protection to obtain the two-dimensional composite material.

[0015] Preferably, the soluble metal salt in the first soluble metal salt solution is magnesium sulfate, magnesium nitrate hexahydrate, aluminum nitrate, calcium methoxide, zinc nitrate hexahydrate or zinc acetate dihydrate; the alkaline solution comprises sodium hydroxide solution, potassium hydroxide solution or ammonia water;

[0016] The temperature of the first in-situ growth is 80-250℃, and the time is 2-20 h;

[0017] The temperature of the calcining is 400-500℃, the holding time is 3-5 h, and the heating rate to the temperature required for the calcining is 1-10℃ / min.

[0018] Preferably, the soluble metal salt in the second soluble metal salt solution is magnesium chloride, zinc chloride, copper chloride dihydrate, iron chloride hexahydrate or cobalt chloride hexahydrate;

[0019] The solvent is ethylene glycol, the surfactant is polyethylene glycol, and the dispersant is sodium acetate;

[0020] The temperature of the second in-situ growth is 100-300℃, and the time is 1-48 h.

[0021] The application also provides a barrier coating, comprising the following components by mass:

[0022]

[0023]

[0024] The moisture barrier functional filler is the two-dimensional composite material in the above technical solution or the two-dimensional composite material prepared by the preparation method in the above technical solution.

[0025] The application also provides application of the moisture barrier functional filler in moisture barrier protection of electronic devices, food packaging and engineering materials.

[0026] Preferably, the method for preparing the barrier coating layer by using the barrier coating material comprises the following steps:

[0027] After the barrier coating material is coated on the surface of the substrate material, directional arrangement is performed to obtain the barrier coating layer.

[0028] The coating method includes leveling, spraying, pouring, spin coating or dipping.

[0029] The directional arrangement method includes external field induction, melting pouring or hot pressing solvent volatilization.

[0030] The thickness of the barrier coating layer is 10-100 microns.

[0031] The application provides a two-dimensional composite material, which comprises a two-dimensional sheet material and a nanomaterial attached to the surface of the two-dimensional sheet material; the nanomaterial comprises a metal oxide nanomaterial or a nanometal. In the application, the two-dimensional sheet material has a high aspect ratio and a high specific surface area, and has excellent moisture barrier permeability; the metal oxide and the nanometal have reactivity and can react with water molecules to convert the water molecules into other substances to achieve the moisture barrier effect; in addition, the nanometal can be dispersed in different directions on the surface of the two-dimensional material to achieve the barrier effect on water molecules penetrating in different directions. The two-dimensional composite material provided by the application can be used as a moisture barrier functional filler to obtain a high-performance moisture barrier coating. DETAILED DESCRIPTION

[0032] The application provides a two-dimensional composite material, which comprises a two-dimensional sheet material and a nanomaterial attached to the surface of the two-dimensional sheet material; the nanomaterial comprises a metal oxide nanomaterial or a nanometal.

[0033] The two-dimensional composite material provided by the application comprises two-dimensional sheet materials. In the application, the two-dimensional sheet materials preferably comprise one or more of graphene oxide, molybdenum disulfide, hexagonal boron nitride, mica sheet, MXene material and clay, more preferably one of graphene oxide, molybdenum disulfide, hexagonal boron nitride, mica sheet and clay, and further more preferably graphene oxide. In the application, when the two-dimensional sheet materials comprise two or more of the above specific substances, the application does not have special requirements for the ratio of the specific substances. In the application, the sheet diameter of the two-dimensional sheet materials is preferably 1000-10000 nm, more preferably 1000-8000 nm, and further more preferably 2000-5000 nm.

[0034] The two-dimensional composite material provided by the application further comprises nanomaterials attached to the surface of the two-dimensional sheet materials; the nanomaterials comprise metal oxide nanomaterials or nanometals, preferably metal oxide nanomaterials. In the application, the metal oxide nanomaterials preferably comprise magnesium oxide, calcium oxide, aluminum oxide or zinc oxide, and more preferably magnesium oxide; the shape of the metal oxide nanomaterials is preferably sheet-shaped, and the sheet diameter of the metal oxide nanomaterials is preferably 100-1000 nm, and more preferably 200-800 nm.

[0035] In the application, the nanometals preferably comprise iron, copper, magnesium, aluminum, cobalt or zinc, and more preferably magnesium, cobalt or zinc; the shape of the nanometals is preferably sheet-shaped or particulate, and more preferably sheet-shaped; the sheet diameter or particle diameter of the nanometals is preferably 50-500 nm, and more preferably 100-300 nm.

[0036] In the application, the mass ratio of the two-dimensional sheet materials and the nanomaterials is preferably 1:10-25, and more preferably 1:15-20.

[0037] In the application, after the two-dimensional sheet materials and the nanomaterials are compounded, there is a good synergistic effect, which plays a role in physical blocking in horizontal, vertical and other directions and chemical reaction blocking of active reaction substances. The highly horizontally arranged two-dimensional sheet materials can greatly improve the physical barrier effect of the coating and prolong the penetration path of water molecules; the sheet-shaped nanomaterials can grow at any angle on the surface of the two-dimensional materials and react with trace water molecules diffused into the layer to convert water into other substances, thereby preventing the diffusion of water into the interior; when the nanomaterials are micro-nano particles, they can also be uniformly dispersed in the coating to fill small pores, making the coating more dense and further improving the barrier performance.

[0038] The application further provides a preparation method of the two-dimensional composite material described in the above technical solution, comprising the following steps:

[0039] The two-dimensional sheet materials, the nanomaterial precursor solution and the solvent are mixed to obtain a dispersion liquid.

[0040] When the nanomaterial is a metal oxide, the nanomaterial precursor solution is a first soluble metal salt; the dispersion liquid and the alkaline solution are mixed for first in-situ growth, and then calcined under nitrogen protection to obtain the two-dimensional composite material;

[0041] When the nanomaterial is a nanometal, the nanomaterial precursor is a second soluble metal salt; the dispersion liquid, the solvent, the dispersant and the surfactant are mixed for second in-situ growth, and then calcined under nitrogen protection to obtain the two-dimensional composite material.

[0042] In the present application, the mixing preferably comprises the following steps:

[0043] The two-dimensional sheet material is dispersed in a solvent to obtain a first dispersion liquid;

[0044] The first dispersion liquid and the nanomaterial precursor solution are first mixed.

[0045] In the present application, the solvent is preferably water; the water is preferably deionized water. The present application does not have special requirements for the amount of the solvent, as long as the two-dimensional sheet material can be uniformly dispersed.

[0046] In the present application, the dispersion is preferably carried out under ultrasonic conditions. The present application does not have special requirements for the power and time of the ultrasonic, as long as the dispersion is uniform.

[0047] After obtaining the first dispersion liquid, the first dispersion liquid and the nanomaterial precursor solution are first mixed in the present application. In the present application, when the nanomaterial is a metal oxide, the nanomaterial precursor solution is a first soluble metal salt; the soluble metal salt in the first soluble metal salt is preferably magnesium sulfate, magnesium nitrate hexahydrate, aluminum nitrate, calcium methoxide, zinc nitrate hexahydrate or zinc acetate dihydrate, and more preferably magnesium nitrate hexahydrate. In the present application, when the nanomaterial is a nanometal, the nanomaterial precursor solution is a second soluble metal salt solution; the soluble metal salt in the second soluble metal salt solution is preferably magnesium chloride, zinc chloride, copper chloride dihydrate, iron chloride hexahydrate or cobalt chloride hexahydrate, and more preferably magnesium chloride or zinc chloride. In the present application, the soluble metal salt is preferably a powder. In the present application, the first mixing is preferably carried out under stirring. The present application does not have special requirements for the speed and time of the stirring, as long as the mixing is uniform.

[0048] After obtaining the dispersion, when the nanomaterial is a metal oxide, the dispersion is mixed with a basic solution for first in-situ growth and then calcination under nitrogen protection to obtain the two-dimensional composite material. In the present application, the basic solution preferably comprises a sodium hydroxide solution, a potassium hydroxide solution or ammonia water, and more preferably is a sodium hydroxide solution. In the present application, the molar concentration of the basic solution is preferably 1-20 mol / L, and more preferably 1-10 mol / L. In the present application, the molar ratio of the nanomaterial precursor to the hydroxyl ion in the basic solution is preferably 1:10-25, and more preferably 1:10-15. In the present application, the temperature of the first in-situ growth is preferably 80-250℃, and more preferably 80-180℃; and the time of the first in-situ growth is preferably 2-20 h, and more preferably 5-15 h. The present application controls the type of precursor, the type of solvent, the temperature and the time of the first in-situ growth to regulate the morphology of the metal oxide.

[0049] In the present application, after the first in-situ growth, the system is preferably cooled to room temperature and then sequentially washed and dried. In the present application, the temperature of the room temperature is preferably 20-35℃, and more preferably 25-30℃. In the present application, the cooling is preferably natural cooling. In the present application, the washing preferably comprises sequentially water washing and ethanol washing; the water used for the water washing is preferably deionized water, and the number of times of the water washing is preferably 6-8 times; the ethanol used for the ethanol washing is preferably anhydrous ethanol, and the number of times of the ethanol washing is preferably 4-8 times, and more preferably 5-7 times. In the present application, the drying is preferably freeze-drying.

[0050] In the present application, the temperature of the calcination is preferably 400-500℃, and more preferably 450℃; the heating rate for heating to the temperature required for the calcination is preferably 1-10℃ / min, and more preferably 5-8℃ / min; and the holding time of the calcination is preferably 3-5 h, and more preferably 4 h. In the present application, the metal ion in the metal oxide precursor in the dispersion and the hydroxyl ion in the basic solution react to generate metal hydroxide attached to the surface of the two-dimensional sheet material during the first in-situ growth; and the metal hydroxide is converted into metal oxide through calcination. The present application limits the heating rate of the calcination to avoid sudden collapse of the oxide structure during the calcination.

[0051] After obtaining the dispersion, when the nanomaterial is a nanometal, the dispersion, a solvent, a dispersant and a surfactant are mixed for a second in-situ growth, and then calcined under nitrogen protection to obtain the two-dimensional composite material. In the present application, the solvent is preferably ethylene glycol, the dispersant is preferably sodium acetate (NaAc), and the surfactant is preferably polyethylene glycol. In the present application, the volume ratio of the dispersion and the solvent is preferably 1:1-5:1, and more preferably 2:1-4:1. The mass ratio of the dispersant and the solvent is preferably 1:1-1:5, and more preferably 1:2-1:3. The volume ratio of the surfactant and the solvent is preferably 1:1-5:1, and more preferably 2:1-4:1.

[0052] In the present application, the temperature of the second in-situ growth is preferably 100-300℃, and more preferably 150-250℃; the time of the second in-situ growth is preferably 1-48h, and more preferably 1-16h. The present application controls the morphology of the nanometal by controlling the type of precursor, the type of solvent, the temperature and time of the second in-situ growth.

[0053] In the present application, after the second in-situ growth, the system is preferably cooled to room temperature, and then sequentially filtered, washed and dried. In the present application, the temperature of the room temperature is preferably 20-35℃, and more preferably 25-30℃. In the present application, the cooling is preferably natural cooling. The present application does not have special requirements for the filtering, and a conventional manner in the art can be used. In the present application, the washing preferably includes sequentially water washing and ethanol washing; the water used for the water washing is preferably deionized water, and the number of times of the water washing is preferably 6-8 times; the ethanol used for the ethanol washing is preferably anhydrous ethanol, and the number of times of the ethanol washing is preferably 4-8 times, and more preferably 5-7 times. In the present application, the drying is preferably nitrogen protection drying, the temperature of the drying is preferably 55-65℃, and more preferably 60℃; and the time of the drying is preferably 3-5h, and more preferably 4h.

[0054] The present application also provides a barrier coating, which comprises the following components by mass:

[0055]

[0056] The moisture-proof functional filler is the two-dimensional composite material described in the above technical solution or the two-dimensional composite material prepared by the preparation method described in the above technical solution.

[0057] In the present application, all components are commercially available products well known to those skilled in the art, unless otherwise specified.

[0058] The barrier coating provided by the present application comprises 10-20 parts of adhesive, preferably 12-18 parts, and more preferably 14-16 parts by mass. In the present application, the adhesive preferably comprises an organic adhesive or an inorganic adhesive; the organic adhesive preferably comprises one or more of acrylic resin, silicone-modified phenolic resin, alkyd resin, silicone resin, polysulfone resin, and soluble special engineering resin, more preferably one or more of acrylic resin, silicone-modified phenolic resin, alkyd resin, silicone resin, and polysulfone resin, and more preferably one of acrylic resin, silicone-modified phenolic resin, alkyd resin, silicone resin, and polysulfone resin. In the present application, the inorganic adhesive preferably comprises one or more of sodium silicate, potassium silicate, aluminum silicate, and aluminum phosphate, and more preferably one of sodium silicate, potassium silicate, aluminum silicate, and aluminum phosphate. In the present application, when the adhesive is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the above specific substances, and any ratio can be mixed.

[0059] The barrier coating provided by the present application comprises 5-10 parts of diluent, preferably 6-8 parts by mass of the adhesive. In the present application, the diluent preferably comprises xylene, acrylic diluent, epoxy resin diluent, ethyl acetate, butyl acetate, n-butanol, methanol, pyrrolidone, or acetone.

[0060] The barrier coating provided by the present application comprises 2-4 parts of curing agent, preferably 3 parts by mass of the adhesive. In the present application, the curing agent preferably comprises acrylic curing agent, N75 curing agent, and polyamide curing agent.

[0061] The barrier coating provided by the present application comprises 0.05-4.5 parts of moisture-proof functional filler, preferably 0.5-4.0 parts, and more preferably 1.5-3.0 parts by mass of the adhesive. In the present application, the moisture-proof functional filler is the two-dimensional composite material described in the above technical solution or the two-dimensional composite material prepared by the preparation method described in the above technical solution.

[0062] The barrier coating provided by the present application comprises 10-20 parts of solvent based on the mass parts of the binder. In the present application, the solvent preferably comprises an organic solvent or an inorganic solvent. The present application selects different solvents according to the type of the binder. When the binder is an organic binder, an organic solvent is selected; when the binder is an inorganic binder, an inorganic solvent is selected. In the present application, the organic solvent preferably comprises xylene, propylene glycol methyl ether acetate, butyl acetate, n-hexane, ethyl acetate, dimethylacetamide or pyrrolidone, and more preferably xylene, propylene glycol methyl ether acetate or pyrrolidone. In the present application, the inorganic binder is preferably water. In the present application, the solvent serves to disperse the filler and other components. In the present application, when the solvent is xylene, the mass parts of the solvent are preferably 10-15 parts, more preferably 11-14 parts, and more preferably 12-13 parts. In the present application, when the solvent is propylene glycol methyl ether acetate, the mass parts of the solvent are preferably 10-20 parts, more preferably 12-18 parts, and more preferably 14-15 parts.

[0063] The barrier coating provided by the present application comprises 0.1-0.5 parts of an auxiliary agent based on the mass parts of the binder, preferably 0.2-0.4 parts, and more preferably 0.25-0.35 parts. In the present application, the auxiliary agent preferably comprises a dispersing agent, a leveling agent, an antifoaming agent and an anti-settling agent. In the present application, the dispersing agent preferably comprises one or more of MIEL P1041, MIEL HY-257, ENZE 2513 and RUTA LD-64200, and more preferably one of MIEL P1041, MIEL HY-257, ENZE 2513 and RUTA LD-64200. In the present application, when the dispersing agent is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the specific substances, and the mixing can be performed in any ratio. In the present application, the dispersing agent can improve the dispersibility of the filler in the system.

[0064] In the present application, the leveling agent preferably comprises one or more of MIEL HY-5030, RUTA LD-91083 and RUTA LD-9604, and more preferably one of MIEL HY-5030, RUTA LD-91083 and RUTA LD-9604. In the present application, when the leveling agent is two or more of the above specific choices, the present application does not have any special limitation on the ratio of the specific substances, and the mixing can be performed in any ratio. In the present application, the leveling agent can reduce the surface tension between the coating and the substrate, so that the coating has good wettability with the substrate and the flowability of the coating is improved.

[0065] In the present application, the defoaming agent preferably comprises one or more of MIEL HY-037, MIEL HY-62S, ENZE B-100 and RILDEBE LD-220, and more preferably one of MIEL HY-037, MIEL HY-62S, ENZE B-100 and RILDEBE LD-220. In the present application, when the defoaming agent is two or more of the above specific choices, the present application does not have any special limitation on the specific substance ratio, and mixing in any ratio can be used. In the present application, the defoaming agent can effectively eliminate the bubbles in the coating, and increase the compactness of the coating.

[0066] In the present application, the anti-settling agent preferably comprises one or more of RILDEBE LD-1291S, YUANYU YB-201A and YUANYU YB-401A, and more preferably one of RILDEBE LD-1291S, YUANYU YB-201A and YUANYU YB-401A. In the present application, when the anti-settling agent is two or more of the above specific choices, the present application does not have any special limitation on the specific substance ratio, and mixing in any ratio can be used. In the present application, the anti-settling agent can prevent the precipitation of fillers in the coating system, and improve the stability of the coating.

[0067] In the present application, the mass ratio of the dispersing agent, the leveling agent, the defoaming agent and the anti-settling agent is preferably 1:0.3-1.0:0.5-1.2:0.8-1.5, and more preferably 1:0.4-0.8:0.8-1:1-1.2; specifically 1:0.8:1, 1:1:0.8 or 1:1:1.

[0068] The present application uses a low-surface-energy binder to impart the adhesion of the coating to the substrate, moisture resistance, and low moisture permeation rate and low permeation rate; a two-dimensional sheet material is used as a substrate, and a nano material with adjustable morphology and size is grown in situ on the surface of the two-dimensional material; the two-dimensional material has a high width-height ratio and a high specific surface area, and has outstanding ability to block the penetration of moisture; the two-dimensional material is directly grown in situ on the surface of the two-dimensional material by a hydrothermal method, and has adjustable morphology; by controlling the growth conditions, the two-dimensional material can grow in various directions on the surface of the two-dimensional material, and can block moisture molecules in various directions; the metal oxide and metal nano material can react with the moisture molecules entering the coating, thereby protecting the substrate; the directional horizontal arrangement of the two-dimensional material can improve the barrier performance of the coating by more than half, and the barrier properties of the two-dimensional material are optimized. The additives can ensure that the coating does not easily settle, and the fillers are uniformly dispersed in the system and have good wetting and leveling properties on the surface of the substrate. The moisture barrier coating prepared from the coating has the advantages of compactness, no bubbles, no nodules and the like, and good adhesion and moisture resistance.

[0069] The present application also provides a preparation method of the barrier coating described in the above technical solution, which comprises the following steps:

[0070] Mixing the adhesive, diluent, curing agent, moisture-proof functional filler, solvent and auxiliary agent to obtain the barrier coating.

[0071] In the present application, the mixing preferably comprises the following steps:

[0072] Dispersing the moisture-proof functional filler in the solvent to obtain a filler dispersion;

[0073] First mixing the filler dispersion, adhesive, diluent and curing agent to obtain a first mixed solution;

[0074] Second mixing the first mixed solution and auxiliary agent.

[0075] In the present application, before the dispersing, the moisture-proof functional filler is preferably vacuum dried. In the present application, the time of the vacuum drying is preferably 70-75h, more preferably 72-73h. In the present application, the temperature of the vacuum drying is preferably 60-100℃, more preferably 70-90℃.

[0076] In the present application, the dispersing is preferably carried out under ultrasonic condition. In the present application, the time of the ultrasonic is preferably 30-90min, more preferably 40-60min, most preferably 40-50min. In the present application, the power of the ultrasonic is not particularly limited as long as it can disperse uniformly.

[0077] In the present application, the first mixing is preferably carried out under stirring condition. In the present application, the temperature of the stirring is preferably 20-30℃, more preferably 23-25℃; the time of the stirring is preferably 0.1-0.3h, more preferably 0.15h. In the present application, the rotating speed of the stirring is not particularly limited as long as it can mix uniformly without precipitation.

[0078] In the present application, the second mixing is preferably carried out under stirring condition. In the present application, the stirring is not particularly limited as long as it can mix uniformly.

[0079] In the present application, after the mixing, the system is preferably allowed to stand. In the present application, the standing can remove the bubbles in the coating. In the present application, the standing time is not particularly limited as long as it can remove the bubbles.

[0080] The present application further provides the use of the barrier coating as described in the above technical solutions in the moisture-proof protection of electronic devices, food packaging and engineering materials.

[0081] In the present application, the method for preparing a barrier coating layer using the barrier coating preferably comprises the following steps:

[0082] After the barrier coating is coated on the surface of the base material, the barrier coating layer is obtained by directional arrangement.

[0083] In the present application, the base material preferably comprises a polyurethane foam, a hydrophilic polymer film or a solar panel, and more preferably is a polyurethane foam. In the present application, the polyurethane foam is preferably a rigid closed-cell polyurethane foam.

[0084] In the present application, the coating method preferably comprises flow coating, spray coating, casting, spin coating or dipping, and more preferably is spray coating or casting.

[0085] In the present application, the directional arrangement method preferably comprises field induction, melt casting or hot-pressing solvent evaporation, and more preferably is hot-pressing solvent evaporation. The present application does not have any special requirements for field induction, melt casting or hot-pressing solvent evaporation, which can be performed according to the conventional methods in the art. In the present application, the temperature for directional arrangement is preferably 40-80℃, more preferably 45-70℃, and most preferably 50-60℃; and the time for directional arrangement is preferably 10-24h, more preferably 15-20h. In the present application, when the two-dimensional material is graphene oxide and the directional arrangement is performed by hot-pressing solvent evaporation, hydrazine hydrate needs to be added to the coating. The present application preferably adds hydrazine hydrate to the filler dispersion.

[0086] In the present application, the thickness of the barrier coating is preferably 10-100μm, and more preferably 20-80μm.

[0087] In the present application, the adhesion of the barrier coating is preferably 0-1 grade; and the moisture permeability is reduced by more than 50% compared with that before the base is coated with the barrier coating.

[0088] The moisture barrier coating provided by the present application has good flexibility, adhesion, mechanical properties, long-term performance and excellent moisture resistance. The barrier coating provided by the present application can effectively avoid the negative effects such as material failure, food spoilage and equipment wear caused by moisture, oxygen and microorganisms.

[0089] In order to further illustrate the present application, the technical solutions provided by the present application are described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0090] Example 1

[0091] 0.1g of two-dimensional sheet-like material graphene oxide was dispersed in 100mL of deionized water under ultrasonic conditions to obtain a first dispersion;

[0092] The first dispersion and 2.5g of nano-metal precursor (zinc chloride) were first mixed under stirring to obtain a dispersion;

[0093] The dispersion liquid, ethylene glycol (50 mL), sodium acetate (1.8 g) and polyethylene glycol (50 mL) were mixed, and after second in-situ growth at 200°C for 2 h, the mixture was cooled to 25°C, filtered, and the obtained solid was washed with deionized water for 7 times and with anhydrous ethanol for 5 times. The washed solid was dried under nitrogen protection at 150°C for 4 h to obtain a two-dimensional composite material (the two-dimensional sheet material is graphene oxide, and the nanomaterial is granular zinc nanoparticles with an average particle size of 60 nm);

[0094] The two-dimensional composite material was vacuum dried at 60°C for 72 h to obtain a dried two-dimensional composite material. 0.05 g of the dried two-dimensional composite material was dispersed in 10 g of solvent xylene under ultrasonic conditions (power 1000 W, time 40 min) to obtain a filler dispersion liquid;

[0095] The filler dispersion liquid, 10 g of a binder (acrylic resin), 5 g of a diluent (acrylic diluent) and 2 g of a curing agent (acrylic curing agent) were stirred at 80°C for 6 h to obtain a first mixed solution;

[0096] The first mixed solution, 0.1 g of Mael P1041, 0.05 g of Mael HY-5030, 0.07 g of Enze B-100 and 0.1 g of Ruida LD-1291S were continuously stirred until uniform and free of precipitates, and then allowed to stand without air bubbles to obtain a barrier coating.

[0097] Ethylene vinyl acetate copolymer (EVA) was used as a substrate, the barrier coating was sprayed on the surface of the substrate, and a parallelly aligned barrier coating layer was obtained by applying an external electric field at a temperature of 45°C for 10 h.

[0098] Example 2

[0099] 0.1 g of the two-dimensional sheet material graphene oxide was dispersed in 100 mL of deionized water under ultrasonic conditions to obtain a first dispersion liquid;

[0100] The first dispersion liquid and 2.5 g of the nanomaterial precursor Mg(NO3)2·6H2O were first mixed under stirring to obtain a dispersion liquid;

[0101] The dispersion liquid and a sodium hydroxide solution with a molar concentration of 10 mol / L were mixed, and after first in-situ growth at 80°C for 2 h, the mixture was cooled to 25°C. The obtained solid was washed with deionized water for 6 times and then with anhydrous ethanol for 4 times. After washing, the solid was freeze-dried, and then calcined at 450°C for 4 h under nitrogen protection to obtain a two-dimensional composite material (the two-dimensional sheet material is graphene oxide, and the nanomaterial is magnesium oxide sheet with an average sheet size of 200-300 nm);

[0102] The two-dimensional composite material is vacuum dried at 60°C for 72h to obtain a dried two-dimensional composite material; 0.05g of the dried two-dimensional composite material is dispersed in 10g of solvent dimethylbenzene under ultrasonic condition (power 1000W, time 50min), and then 0.5g of hydrazine hydrate is added, and stirring is carried out at 80°C for 6h to reduce the graphene oxide, to obtain a filler dispersion liquid;

[0103] The filler dispersion liquid, 10g of a binder (silicone resin), 5g of a diluent (ethyl acetate) and 2g of a curing agent (N75 curing agent) are stirred at 25°C for 10min to obtain a first mixed solution;

[0104] The first mixed solution, 0.1g of Mier P1041, 0.05g of Mier HY-5030, 0.07g of Enze B-100 and 0.1g of Lida LD-1291S are continuously stirred until uniform and no precipitate, and are left to stand without air bubbles, to obtain a barrier coating.

[0105] With rigid closed-cell polyurethane foam as a substrate, the barrier coating is sprayed on the surface of the substrate, and then heat pressing is carried out at a temperature of 50°C for 15h to volatilize the solvent and self-align to obtain a directional arrangement of the barrier coating.

[0106] Example 3

[0107] 0.1g of two-dimensional sheet material graphene oxide is dispersed in 100mL of deionized water under ultrasonic condition to obtain a first dispersion liquid;

[0108] The first dispersion liquid and 2.5g of nano material precursor Zn(CH3COO)2·2H2O are first mixed under stirring condition to obtain a dispersion liquid;

[0109] The dispersion liquid and NH3·H2O solution are mixed, and in-situ growth is first carried out at 180°C for 24h, and then the temperature is lowered to 25°C; the obtained mixed liquid is washed with deionized water for 6 times and with anhydrous ethanol for 4 times, the washed mixed liquid is freeze-dried, and then calcination is carried out at 450°C for 4h to obtain a two-dimensional composite material (the two-dimensional sheet material is graphene oxide, and the nano material is zinc oxide with an average flake diameter of 600-800nm;

[0110] The two-dimensional composite material is vacuum dried at 60°C for 72h to obtain a dried two-dimensional composite material; 0.05g of the dried two-dimensional composite material is dispersed in 10g of solvent dimethylbenzene under ultrasonic condition (power 1000W, time 30min), and then stirring is carried out for 20min to obtain a filler dispersion liquid;

[0111] The filler dispersion liquid, 10g of a binder (silicone resin), 5g of a diluent (butyl acetate) and 2g of a curing agent (N75 curing agent) are stirred at 25°C for 10min to obtain a first mixed solution;

[0112] The first mixed solution, 0.1 g of Mill P1041, 0.05 g of Mill HY-5030, 0.07 g of Enze B-100, and 0.1 g of Ruida LD-1291S, are continuously stirred until uniform and no precipitate, and left to stand without air bubbles, to obtain a barrier coating.

[0113] The thermoplastic polyurethane elastomer (TPU) is used as a substrate, the barrier coating is sprayed on the surface of the substrate, and the barrier coating is oriented and arranged by an external electric field under the condition of a temperature of 45 ℃ and a time of 20 h.

[0114] Example 4

[0115] 0.1 g of two-dimensional sheet material Mxene is dispersed in 100 mL of deionized water under ultrasonic conditions to obtain a first dispersion;

[0116] The first dispersion and 2.5 g of nano material precursor Mg(NO3)2·6H2O are first mixed under stirring conditions to obtain a dispersion;

[0117] The dispersion and a sodium hydroxide solution with a molar concentration of 10 mol / L are mixed, and after in-situ growth at 80 ℃ for 2 h, the temperature is lowered to 25 ℃. The obtained mixture is washed with deionized water for 6 times and then washed with anhydrous ethanol for 4 times. After washing, freeze-drying is performed, and then calcination is performed at 450 ℃ under nitrogen protection for 4 h to obtain a two-dimensional composite material (the two-dimensional sheet material is Mxene, and the nano material is magnesium oxide with an average sheet diameter of 200-300 nm).

[0118] The two-dimensional composite material is vacuum dried for 72 h to obtain a dried two-dimensional composite material; 0.05 g of the dried two-dimensional composite material is dispersed in 10 g of solvent dimethylbenzene under ultrasonic conditions (power 1000 W, time 40 min) to obtain a filler dispersion;

[0119] The filler dispersion, 10 g of a binder (acrylic resin), 5 g of a diluent (dimethylbenzene), and 2 g of a curing agent (N75 curing agent) are stirred at 25 ℃ for 10 min to obtain a first mixed solution;

[0120] The first mixed solution, 0.1 g of Mill P1041, 0.05 g of Mill HY-5030, 0.07 g of Enze B-100, and 0.1 g of Ruida LD-1291S, are continuously stirred until uniform and no precipitate, and left to stand without air bubbles, to obtain a barrier coating.

[0121] The rigid closed-cell polyurethane foam is used as a substrate, and the barrier coating is oriented and arranged by a melting pouring method under the condition of a temperature of 60 ℃ and a time of 10 h.

[0122] The performance of the barrier coating prepared in Examples 1-4 was tested according to the following methods, and the results are listed in Table 1.

[0123] Moisture barrier performance test: The moisture barrier test was performed according to the test method of GB / T17146-2015, and the test conditions were 25℃, humidity 80%, and test time 120h;

[0124] Adhesion performance test: The adhesion test was performed according to the grid method test method of GB / T 9286-1998;

[0125] Thickness test: The coating thickness was tested according to the method of GB1764-79(89) using a thickness gauge;

[0126] Mechanical property test: The coating mechanical property test was performed according to the method of GB / T33541 using a tensile machine.

[0127] Table 1 Performance parameters of the moisture barrier coating of Examples 1-4

[0128]

[0129]

[0130] As can be seen from Table 1, the coating prepared from the moisture barrier coating provided by the present application has excellent moisture barrier performance, long-term performance, and high mechanical properties.

[0131] Although the above examples have made a detailed description of the present application, it is only a part of the embodiments of the present application, not all the embodiments, and other embodiments can be obtained according to the present embodiments without creativity, which all belong to the protection scope of the present application.

Claims

1. A barrier coating, characterized in that, consists of the following components by mass parts: The moisture-proof functional filler is a two-dimensional composite material; the two-dimensional composite material comprises a two-dimensional sheet material and a nanomaterial attached to the surface of the two-dimensional sheet material; the nanomaterial comprises a metal oxide nanomaterial or a nanometal; the mass ratio of the two-dimensional sheet material and the nanomaterial is 1:10-25; the metal oxide nanomaterial is in the shape of a sheet, and the sheet diameter of the metal oxide nanomaterial is 100-1000 nm; the nanometal is in the shape of a sheet or a particle, and the sheet diameter or particle diameter of the nanometal is 50-500 nm; the sheet diameter of the two-dimensional sheet material is 1000-10000 nm.

2. The barrier coating of claim 1, wherein, The metal oxide nanomaterial comprises magnesium oxide, calcium oxide, aluminum oxide, or zinc oxide; The nanometal comprises iron, copper, magnesium, cobalt, or zinc.

3. The barrier coating of claim 1, wherein, The two-dimensional sheet material comprises one or more of graphene oxide, molybdenum disulfide, hexagonal boron nitride, mica sheet, MXene material, and clay.

4. The barrier coating according to claim 1 or 3, characterized in that The preparation method of the two-dimensional composite material comprises the following steps: Mixing the two-dimensional sheet material, a nanomaterial precursor solution, and a solvent to obtain a dispersion liquid; When the nanomaterial is a metal oxide, the nanomaterial precursor solution is a first soluble metal salt solution; mixing the dispersion liquid and an alkaline solution to perform first in-situ growth, and then calcining under nitrogen protection to obtain the two-dimensional composite material; When the nanomaterial is a nanometal, the nanomaterial precursor solution is a second soluble metal salt solution; mixing the dispersion liquid, ethylene glycol, a dispersant, and a surfactant to perform second in-situ growth, and then calcining under nitrogen protection to obtain the two-dimensional composite material.

5. The barrier coating of claim 4, wherein the coating is applied to the surface of the substrate by a process selected from the group consisting of spraying, brushing, dipping, and combinations thereof. The soluble metal salt in the first soluble metal salt solution is magnesium sulfate, magnesium nitrate hexahydrate, aluminum nitrate, calcium methoxide, zinc nitrate hexahydrate, or zinc acetate dihydrate; the alkaline solution comprises a sodium hydroxide solution, a potassium hydroxide solution, or ammonia water; The temperature of the first in-situ growth is 80-250°C, and the time is 2-20 h; The calcination temperature is 400-500°C, the holding time is 3-5 h, and the heating rate to the required temperature for calcination is 1-10°C / min.

6. The barrier coating of claim 4, wherein the coating is applied to the surface of the substrate by a process selected from the group consisting of spraying, brushing, dipping, and combinations thereof. The soluble metal salt in the second soluble metal salt solution is magnesium chloride, zinc chloride, copper chloride dihydrate, iron chloride hexahydrate, or cobalt chloride hexahydrate; The surfactant is polyethylene glycol, and the dispersant is sodium acetate; The temperature of the second in-situ growth is 100-300°C, and the time is 1-48 h.

7. Use of the barrier coating material in claims 1-6 in the moisture-proof protection of electronic devices, food packaging, and engineering materials.

8. Use according to claim 7, characterized in that, A method for preparing a barrier coating layer using the barrier coating material, comprising the following steps: After coating the barrier coating material on the surface of a base material, performing directional arrangement to obtain a barrier coating layer; The coating method comprises leveling, spraying, casting, spin coating, or immersion; The directional arrangement method comprises field induction, melt casting, or hot pressing solvent evaporation; The thickness of the barrier coating layer is 10-100 μm.

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