Water vapor barrier coating liquid, preparation method thereof, and water vapor barrier coating

Abstract

The present invention provides a water vapor barrier coating liquid and a preparation method thereof and a water vapor barrier coating. The raw materials for preparing the water vapor barrier coating liquid of the present invention include inorganic nanopowder, which is composed of inorganic oxide nanoparticles; the structural formula of the inorganic oxide nanoparticles is M a O b H c , 0<a≤3; 0<b≤5; 0≤c≤2; wherein M is one of magnesium, aluminum, silicon, calcium, scandium, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, and zirconium; when c=0, the hydrogen atoms on the surface of the inorganic nanopowder exist in non-covalently bonded water molecules; when c>0, the hydrogen atoms on the surface of the inorganic nanopowder exist in the form of covalent bonds. The water vapor barrier coating liquid prepared by the present invention has good water vapor barrier performance and good stability, does not produce organic solvents released into the atmosphere, does not require high-temperature heating during preparation, has simple steps, low energy consumption, and can be prepared in batches.

Description

Technical Field

[0001] The invention belongs to the technical field of barrier coatings and relates to a water vapor barrier coating liquid and a preparation method thereof and a water vapor barrier coating. Background Art

[0002] Water-blocking coatings have application value in many fields, such as photovoltaic module backplanes, frontplanes and packaging films, quantum dot display barrier films, organic light-emitting diodes (OLED), electronic paper, pharmaceuticals and food packaging industries. It can protect the protected objects from erosion by water vapor, thereby increasing service life and reducing costs. Therefore, the research and development of water vapor barrier coatings is of great value.

[0003] Regarding water-blocking coatings, several related patents have been reported.

[0004] CN103958185B discloses a composite structure, a packaging material and a molded product using the same, and a method for manufacturing the same and a coating liquid, wherein the coating liquid uses aluminum isopropoxide as the main raw material, and a water vapor barrier coating is prepared by means of high-temperature hydrolysis, condensation, and the like. However, in the preparation method of the coating liquid, the aluminum isopropoxide needs to be hydrolyzed first, and the isopropanol produced in this step will evaporate into the atmosphere in large quantities, causing pollution to the environment. In addition, the hydrolysis temperature is relatively high, reaching 95°C, which greatly increases the energy consumption of the coating liquid preparation, and the preparation involves multi-step chemical reactions, the steps are cumbersome, and the time and labor costs are increased. In addition, the water-blocking coating obtained by this method has a short storage period, is prone to failure in a short period of time, and has a short operating window.

[0005] CN103958078B discloses a composite structure and a manufacturing method thereof, a packaging material and a molded product using the same, and a coating liquid, which uses aluminum hydroxide as a main raw material and prepares a water vapor barrier coating through alkali dissolution, precipitation, high-speed dispersion, condensation and other means.

[0006] CN112063241A discloses a coating liquid, a preparation method and a barrier film thereof, which uses aluminum isopropoxide as a main raw material, and prepares a water vapor barrier coating through high-temperature hydrolysis, condensation and the assistance of other chemical substances.

[0007] However, in the above patented technology, the preparation of the coating liquid requires multiple chemical reactions, which are cumbersome and energy-intensive, and the byproduct organic solvents produced therein will cause serious harm to the environment. In addition, the preparation method uses silicon precursors, aluminum oxide precursors, etc. as film-forming materials, assisted by vapor deposition methods (such as plasma vapor deposition, magnetron sputtering vapor deposition, etc.) to prepare the water-blocking coating, but the equipment cost, operation, and maintenance costs are very high, and its production capacity is greatly limited by the volume and size of the equipment. Summary of the invention

[0008] In view of the deficiencies in the prior art, the object of the present invention is to provide a water vapor barrier coating liquid, a preparation method thereof, and a water vapor barrier coating. The prepared water vapor barrier coating liquid has good water vapor barrier performance and good stability, does not produce organic solvents released into the atmosphere, does not require high-temperature heating during preparation, has simple steps, low energy consumption, and can be prepared in batches.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] One of the purposes of the present invention is to provide a water vapor barrier coating liquid, wherein the raw material for preparing the water vapor barrier coating liquid comprises an inorganic nanopowder, wherein the inorganic nanopowder is composed of inorganic oxide nanoparticles; the structural formula of the inorganic oxide nanoparticles is M a O b H c , 0<a≤3; 0<b≤5; 0≤c≤2; wherein M is one of magnesium, aluminum, silicon, calcium, scandium, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, and zirconium; when c=0, the hydrogen atoms on the surface of the inorganic nanopowder exist in non-covalently bonded water molecules; when c>0, the hydrogen atoms on the surface of the inorganic nanopowder exist in the form of covalent bonds.

[0011] The water vapor barrier coating liquid of the present invention uses inorganic nano powder as the main raw material, and connects the inorganic nano powder by adding a coupling agent to form a dense nano coating, thereby achieving an excellent water vapor barrier effect. The water vapor barrier coating liquid does not produce an organic solvent released into the atmosphere, does not require high-temperature heating during preparation, has simple steps, low energy consumption, and can be prepared in batches. The prepared water vapor barrier coating liquid has good stability and has a storage stability of up to 2 months.

[0012] In the present invention, the particle size of the inorganic nano powder is 1-500nm, for example, 1nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm. nm, etc.; preferably 1-50nm, for example 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm, etc., more preferably 1-20nm, for example 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm or 20nm, etc.

[0013] Preferably, the inorganic oxide nanoparticles are any one of aluminum oxide nanoparticles, silicon oxide nanoparticles, calcium oxide nanoparticles, scandium oxide nanoparticles, zinc oxide nanoparticles, titanium oxide nanoparticles, germanium oxide nanoparticles, and zirconium oxide nanoparticles, or a mixture of at least two of them, preferably any one of aluminum oxide nanoparticles, silicon oxide nanoparticles, zinc oxide nanoparticles, and titanium oxide nanoparticles, or a mixture of at least two of them.

[0014] In the present invention, the raw materials for preparing the water vapor barrier coating liquid further include a solvent and a coupling agent.

[0015] In the present invention, the mass ratio of the inorganic nanopowder to the solvent is 1:(4-140), for example, 1:4, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130 or 1:140, etc., preferably 1:(10-70), for example, 1:10, 1:12, 1:14, 1:16, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, etc.; the molar ratio N of the coupling agent to the inorganic nanopowder is Z / N M is (0.1-1.85):1, for example, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.85:1, etc., NZ Represents the total number of boron, nitrogen, silicon, phosphorus, sulfur, fluorine, chlorine, bromine and iodine atoms contained in the coupling agent; N M Represents the total number of atoms of other elements in the inorganic nanopowder except hydrogen and oxygen atoms.

[0016] In the present invention, the solvent is water or a mixture of water and a small molecule alcohol.

[0017] Preferably, the small molecule alcohol is any one of methanol, ethanol, isopropanol, or a mixture of at least two of them.

[0018] In the present invention, the structural formula of the coupling agent is Z k O l R 1 m R 2 n .

[0019] Among them, 0<k≤3, k is an integer; 0≤l≤4, l is an integer; 0≤m≤4, m is an integer; 0≤n≤4, n is an integer.

[0020] Z is one of boron, nitrogen, silicon, phosphorus, sulfur, fluorine, chlorine, bromine and iodine.

[0021] R 1 , R 2 Each of the following is independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an olefin group, a phenyl group, an aralkyl group, an alkoxy group, and an acyloxy group.

[0022] Preferably, the halogen atom is one of fluorine, chlorine, bromine and iodine.

[0023] Preferably, the alkyl group is one of methyl, ethyl, propyl, butyl and derivatives thereof.

[0024] Preferably, the olefin group is one of vinyl and allyl.

[0025] Preferably, the alkoxy group is one of methoxy, ethoxy, propoxy and butoxy.

[0026] In the present invention, the coupling agent is any one of boron-containing inorganic acids, nitrogen-containing inorganic acids, silicon-containing alkoxy compounds, silicon-containing halogen compounds, phosphorus-containing inorganic acids, sulfur-containing inorganic acids and halogen-containing inorganic acids, or a mixture of at least two thereof.

[0027] Preferably, the boron-containing inorganic acid is one or a mixture of at least two of boric acid and its derivatives.

[0028] Preferably, the nitrogen-containing inorganic acid is one or both of nitric acid and nitrous acid.

[0029] Preferably, the silicon-containing alkoxy compound is tetramethoxysilane, tetraethoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-(2,3-epoxypropyloxy)propyltrimethoxysilane, 3-(2,3-epoxypropyloxy)propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane. , 3-iodopropyltrimethoxysilane, 3-iodopropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, trimethoxychlorosilane, triethoxychlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltriacetoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, any one or a mixture of at least two thereof.

[0030] Preferably, the silicon-containing halogen compound is one of silicon tetrachloride, methyltrichlorosilane, trichloroethylsilane, propyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-bromopropyltrichlorosilane, phenyltrichlorosilane, (3-phenylpropyl)trichlorosilane, dimethyldichlorosilane, or a mixture of at least two thereof.

[0031] Preferably, the phosphorus-containing inorganic acid is any one of hypophosphorous acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, and polyphosphoric acid, or a mixture of at least two of them.

[0032] Preferably, the sulfur-containing inorganic acid is any one of sulfuric acid, sulfurous acid, and pyrosulfuric acid, or a mixture of at least two of them.

[0033] Preferably, the fluorine-containing inorganic acid is hydrofluoric acid.

[0034] Preferably, the chlorine-containing inorganic acid is any one of hydrochloric acid, hypochlorous acid, and perchloric acid, or a mixture of at least two of them.

[0035] Preferably, the bromine-containing inorganic acid is any one of bromic acid, hypobromous acid, and perbromic acid, or a mixture of at least two of them.

[0036] Preferably, the iodine-containing inorganic acid is any one of hydroiodic acid, hypoiodous acid, and periodic acid, or a mixture of at least two of them.

[0037] A second object of the present invention is to provide a method for preparing the water vapor barrier coating liquid as described in the first object, comprising the following steps:

[0038] 1) dispersing the inorganic nano powder in a solvent according to a ratio to obtain a nano dispersion;

[0039] 2) Under stirring conditions, adding a coupling agent to the nano-dispersion liquid, and continuing stirring to obtain the water vapor barrier coating liquid.

[0040] The third object of the present invention is to provide a water vapor barrier coating, which is obtained by coating with the water vapor barrier coating liquid described in the first object.

[0041] The fourth object of the present invention is to provide a method for preparing the water vapor barrier coating described in the third object, wherein the water vapor barrier coating liquid described in the first object is coated on the surface of a substrate, and the water vapor barrier coating is obtained by drying and aging.

[0042] The coating method is any one of spraying, scraping, roller coating, brushing, shower coating and extrusion coating.

[0043] Preferably, the substrate is a sheet-type or film-type polymer substrate, and the substrate may be corona-treated or directly coated without corona treatment; preferably, the substrate is corona-treated.

[0044] Preferably, the substrate is any one of a polyester film, a polyolefin film, a polyamide film, a poly(meth)acrylate film, a polyvinyl alcohol film, a polyvinyl alcohol-ethylene copolymer film, a polystyrene film, a polycarbonate film, a polyurethane film, a polyurea film, a polyimide film, a polyethersulfone film, and a polyetheretherketone film; specifically, according to the composition classification, it includes polyester films, such as polyethylene terephthalate, polybutylene terephthalate, polyhexane terephthalate and copolymers formed by any combination of the above; it also includes polyolefin films, such as polyethylene, polypropylene, etc.; it also includes polyamide films. Amine films, such as nylon-6, nylon 66, nylon 12, etc.; also include poly (meth) acrylate films, such as poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) n-butyl acrylate, poly (meth) isobutyl acrylate, poly (meth) tert-butyl acrylate, poly (meth) 2-ethylhexyl acrylate, poly (meth) cyclohexyl acrylate, poly (meth) isobornyl methacrylate and copolymers formed by any combination thereof; also include polyvinyl alcohol, polyvinyl alcohol-ethylene copolymer, polystyrene, polycarbonate, polyurethane, polyurea, polyimide, polyether sulfone, polyether ether ketone, etc. The above polymers and polymer sheets or films formed by any combination thereof can be used as the substrate of the coating liquid.

[0045] Preferably, the drying temperature is 0-120°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C, etc., preferably 45-100°C, for example, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C or 100°C, etc.

[0046] Preferably, the drying time is 1-120 min, for example, 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min or 120 min, etc., preferably 5-20 min, for example, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, etc.

[0047] Preferably, the aging temperature is 0-180°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C, etc.; preferably 45-150°C, for example, 45°C, 50°C, 55°C, 60°C , 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃ or 150℃, etc.; more preferably 120-150℃, for example 120℃, 125℃, 130℃, 135℃, 140℃, 145℃ or 150℃, etc.

[0048] Preferably, the aging time is 1-1440 min, for example, 1 min, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 200 min, 300 min, 400 min, 500 min, 600 min, 700 min, 800 min, 900 min, 1000 min, 1100 min, 1200 min, 1300 min, 1400 min, 1410 min, 1420 min, 1430 min, 1440 min, etc.; preferably, 20-60 min, for example, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min or 60 min, etc.

[0049] The fifth object of the present invention is to provide an application of the water vapor barrier coating described in the third object, and the water vapor barrier coating is used for the preparation of photovoltaic backplanes, front panels and packaging films, electronic paper, quantum dot display water vapor barrier films, OLEDs, medicines and food packaging.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] The water vapor barrier coating liquid of the present invention has low raw material cost, abundant sources, low equipment cost, environmental friendliness, wide process window, good stability, and a storage stability of up to 0.5-2 months. During the storage period, the water vapor barrier coating prepared by the water vapor barrier coating has a water vapor barrier effect equivalent to that of the water vapor barrier coating prepared by the initial coating liquid; it has a good water vapor barrier effect. Specifically, when the water barrier coating is coated on one side of the substrate, the water vapor transmission value is between 0.1-1.0 g / day·m 2 When the water-blocking coating is applied on both sides of the substrate, the water vapor transmission value is between 0.001-0.1g / day·m 2When the substrate coated with water-blocking coating is used in combination with other barrier films, the water vapor transmission value is between 0.0001-0.01g / day·m 2 . BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is a schematic structural diagram of the first water vapor barrier material of the present invention;

[0053] Figure 2 is a schematic structural diagram of a second water vapor barrier material of the present invention;

[0054] Figure 3 is a schematic structural diagram of a third water vapor barrier material of the present invention;

[0055] Figure 4 This is a schematic diagram of infrared characterization of the water vapor barrier coating of Example 1;

[0056] The reference numerals are as follows:

[0057] 1-substrate; 2-water vapor barrier coating; 3-primer coating; 4-protective coating. DETAILED DESCRIPTION

[0058] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0059] Unless otherwise specified, various raw materials of the present invention can be purchased from the market or prepared according to conventional methods in the art.

[0060] The raw materials for preparing the water vapor barrier coating liquid of the present invention include inorganic nanopowder, solvent and coupling agent, wherein the inorganic nanopowder is composed of inorganic oxide nanoparticles; the structural formula of the inorganic oxide nanoparticles is M a O b H c , 0<a≤3; 0<b≤5; 0≤c≤2; wherein M is one of magnesium, aluminum, silicon, calcium, scandium, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, and zirconium; when c=0, the hydrogen atoms on the surface of the inorganic nanopowder exist in non-covalently bonded water molecules; when c>0, the hydrogen atoms on the surface of the inorganic nanopowder exist in the form of covalent bonds.

[0061] The coating process of the water vapor barrier coating liquid of the present invention can be to directly coat the water vapor barrier coating liquid on the surface of the substrate 1 to form a water vapor barrier coating 2, such as Figure 1 The first water vapor barrier material shown in FIG. 1 ; a base coating 3 may be pre-coated on the surface of the substrate, and then a water vapor barrier coating 2 is coated on the base coating 3 to form a second water vapor barrier material having a structure as shown in FIG. Figure 2The composition of the primer layer can be any polymer coating that can increase the adhesion of the water-blocking coating, including polyacrylate coatings, polyurethane coatings, polyurea coatings, epoxy resin coatings, amino resin coatings, fluorocarbon resin coatings, etc.

[0062] exist Figure 2 Based on the structure shown in FIG. 1 , a protective coating 4 may be coated on the surface of the water vapor barrier coating 2 to form a third water vapor barrier material having a structure as shown in FIG. Figure 3 The protective coating may be composed of any polymer coating that can enhance the high temperature and high humidity resistance of the barrier coating, including polyacrylate coatings, polyurethane coatings, polyurea coatings, epoxy resin coatings, amino resin coatings, fluorocarbon resin coatings, and the like.

[0063] Example 1

[0064] The water vapor barrier coating liquid of this embodiment is prepared by the following method:

[0065] 10 g of nano-silicon dioxide (molecular formula SiO2, particle size 20-50 nm) powder was weighed, 140 g of water and 35 g of anhydrous ethanol were added, and the mixture was mechanically stirred and dispersed for 20 minutes to obtain dispersion A. Then, 12 g of 85% mass concentration phosphoric acid and 3 g of methyltriethoxysilane were added to the dispersion A under stirring conditions, and stirring was continued for 30 minutes to obtain a water vapor barrier coating liquid S.

[0066] The water vapor barrier coating liquid S obtained by the above method is coated on a corona treated polyethylene terephthalate (PET) film, and dried at 80°C for 5 minutes; then the PET film coated with the water vapor barrier coating is aged at 150°C for 30 minutes. After the above method is completed, a PET film laminated with a water vapor barrier coating is obtained.

[0067] Example 2

[0068] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 1 except that 10g of nano silicon dioxide powder is replaced by 13.3g of nano titanium dioxide (molecular formula TiO2, particle size 3-5nm) powder. The other raw materials and operation steps are the same as those of Embodiment 1.

[0069] Example 3

[0070] The water vapor barrier coating liquid of this embodiment is the same as that of Example 1 except that 10g of nano silicon dioxide powder is replaced by 8.5g of nano aluminum oxide (molecular formula: Al2O3, particle size: 5-30nm) powder. The other raw materials and operation steps are the same as those of Example 1.

[0071] Example 4

[0072] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 1 except that 10g of nano silicon dioxide powder is replaced by 20.5g of nano zirconium dioxide (molecular formula: ZrO2, particle size: 20-30nm) powder. The other raw materials and operation steps are the same as those of Embodiment 1.

[0073] Example 5

[0074] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 1 except that 10 g of nano-silicon dioxide powder is replaced by 10 g of nano-pseudo-boehmite (molecular formula: AlOOH, particle size: 3-20 nm) powder. The other raw materials and operation steps are the same as those of Embodiment 1.

[0075] Example 6

[0076] The water vapor barrier coating liquid of this embodiment is prepared by the following method:

[0077] 13.3 g of nano titanium dioxide (molecular formula TiO2, particle size 5-10 nm) powder was weighed, 280 g of water and 70 g of anhydrous methanol were added, and mechanical stirring and dispersion were performed for 20 minutes to obtain dispersion A. Then, 16 g of 85% mass concentration phosphoric acid and 3 g of tetraethoxysilane were added to the dispersion A under stirring conditions, and stirring was continued for 30 minutes to obtain a water vapor barrier coating liquid S.

[0078] The water vapor barrier coating liquid S obtained by the above method is coated on a corona treated polyethylene terephthalate (PET) film, and dried at 80°C for 5 minutes; then the PET film coated with the water vapor barrier coating is aged at 150°C for 30 minutes. After the above method is completed, a PET film laminated with a water vapor barrier coating is obtained.

[0079] Example 7

[0080] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 6 except that the amount of tetraethoxysilane is increased from 3 g to 9 g. The other raw materials and steps are the same as those of Embodiment 6.

[0081] Example 8

[0082] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 6 except that 3g of tetraethoxysilane is replaced by 3g of mercaptopropyltrimethoxysilane. The other raw materials and steps are the same as those of Embodiment 6.

[0083] Example 9

[0084] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 6 except that 16 g of 85% mass concentration phosphoric acid is replaced by 17 g of phosphorous acid. The other raw materials and steps are the same as those of Embodiment 6.

[0085] Example 10

[0086] The water vapor barrier coating liquid of this embodiment is the same as that of Example 6 except that 2 g of concentrated nitric acid is additionally added to the dispersion. The remaining materials and steps are the same as those of Example 6.

[0087] Embodiment 11

[0088] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 6 except that the aging temperature is lowered from 150° C. to 45° C. The other raw materials and steps are the same as those of Embodiment 6.

[0089] Example 12

[0090] The water vapor barrier coating liquid of this embodiment is prepared by the following method:

[0091] 15 g of nano zinc oxide (molecular formula: ZnO, particle size: 10-30 nm) powder was weighed, 140 g of water and 35 g of anhydrous ethanol were added, and the mixture was mechanically stirred and dispersed for 20 minutes to obtain dispersion A. Then, 10 g of 85% mass concentration phosphoric acid and 6 g of tetramethoxysilane were added to the dispersion A under stirring conditions, and stirring was continued for 30 minutes to obtain a water vapor barrier coating liquid S.

[0092] The water vapor barrier coating liquid S obtained by the above method is coated on a corona treated polyethylene terephthalate (PET) film, and dried at 80°C for 5 minutes; then the PET film coated with the water vapor barrier coating is aged at 150°C for 30 minutes. After the above method is completed, a PET film laminated with a water vapor barrier coating is obtained.

[0093] Example 13

[0094] The water vapor barrier coating liquid of this embodiment is the same as that of Example 12 except that tetramethoxysilane is not added. The other raw materials and steps are the same as those of Example 12.

[0095] Embodiment 14

[0096] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 12 except that 10 g of 85% mass concentration phosphoric acid is replaced by 12.8 g of 90% mass concentration pyrophosphoric acid. The other raw materials and steps are the same as those of Embodiment 12.

[0097] Embodiment 15

[0098] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 12 except that the single-sided coating is changed to double-sided coating. The other raw materials and steps are the same as those of Embodiment 12.

[0099] Example 16

[0100] This example is based on the water vapor barrier sheet obtained in Example 15, and then compared with a commercially available water vapor barrier sheet (produced by Mitsubishi Chemical of Japan with a water permeability of 0.3 g / day·m 2, LS water vapor barrier film with a thickness of 12 microns) are glued together to obtain a composite sheet.

[0101] Embodiment 17

[0102] The water vapor barrier coating liquid of this embodiment is the same as that of Example 12 except that an acrylic coating layer is coated on the outer surface of the water barrier coating layer stacked on the polyethylene terephthalate film. The remaining materials and steps are the same as those of Example 12.

[0103] Embodiment 18

[0104] The water vapor barrier coating liquid of this embodiment is the same as that of the first embodiment except that methyltriethoxysilane is replaced by dimethyldiethoxysilane. The other raw materials and steps are the same as those of the first embodiment.

[0105] Embodiment 19

[0106] The water vapor barrier coating liquid of this embodiment is the same as that of Example 1 except that phosphoric acid is replaced by polyphosphoric acid. The other raw materials and steps are the same as those of Example 1.

[0107] Embodiment 20

[0108] The water vapor barrier coating liquid of this embodiment is the same as that of Example 6 except that phosphoric acid is replaced by hypophosphorous acid. The other raw materials and steps are the same as those of Example 6.

[0109] Embodiment 21

[0110] The water vapor barrier coating liquid of this embodiment is the same as that of Example 12 except that phosphoric acid is replaced by hydrochloric acid. The other raw materials and steps are the same as those of Example 12.

[0111] Embodiment 22

[0112] In the water vapor barrier coating liquid of this embodiment, the particle size of pseudo-boehmite is 500 nm, and the other raw materials and steps are the same as those in Example 5.

[0113] Embodiment 23

[0114] The water vapor barrier coating liquid of this embodiment has the same raw materials and steps as those of Embodiment 6 except that the mass of phosphoric acid is reduced to 0.24 g.

[0115] Embodiment 24

[0116] The water vapor barrier coating liquid of this embodiment has the same raw materials and steps as those of Embodiment 6 except that the mass of phosphoric acid is increased to 34 g.

[0117] Embodiment 25

[0118] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 6 except that the total mass of the solvent is reduced to 26.6 g. The other raw materials and steps are the same as those of Embodiment 6.

[0119] Embodiment 26

[0120] The water vapor barrier coating liquid of this embodiment is the same as that of Embodiment 6 except that the amount of nano titanium dioxide is reduced from 13.3 g to 2.4 g. The other raw materials and steps are the same as those of Embodiment 6.

[0121] Comparative Example 1

[0122] In the water vapor barrier coating liquid of this comparative example, the inorganic nanopowder is replaced by silver oxide nanoparticles (particle size is 5-20 nm), and the other raw materials and steps are the same as those of Example 6.

[0123] The water vapor barrier coating prepared in Example 1 was subjected to infrared characterization, as shown in FIG. Figure 4 As shown, the bond shown by MOZ is between 1150 and 1230 cm -1 The band has a strong infrared absorption peak.

[0124] The performance of the water vapor barrier coatings prepared in Examples 1-26 and Comparative Example 1 was tested, and the test results are shown in Table 1.

[0125] The transmittance test in the wavelength range of 400 to 1100 nm is carried out in accordance with the GB / T 2410-2008 standard, and the water vapor transmission value test is carried out in accordance with the GB / T26253-2010 standard.

[0126] Table 1

[0127]

[0128]

[0129]

[0130] It can be seen from Table 1 that the water vapor transmission values ​​of the water-blocking coatings obtained in Examples 1-22 are all less than 1.0 g / day·m 2 Except for some examples, the water vapor transmission value of most examples is lower than 0.6g / day·m 2 , can be further reduced to 0.1g / day·m by double-sided coating 2 The following describes that the coating prepared by the present invention has a high water vapor barrier function.

[0131] Example 16 When the substrate coated with the water-blocking coating is used in combination with other barrier films, the water vapor transmission value is further reduced to 0.005 g / day·m 2 .

[0132] Example 23, the amount of coupling agent used was greatly reduced, making the Nz / Nm value lower than 0.1, and the water vapor barrier function of the coating was seriously reduced, and the water vapor transmission value exceeded 7.0g / day·m 2 .

[0133] Example 24, the amount of coupling agent used was greatly increased, making the Nz / Nm value higher than 1.85, and the water vapor barrier function of the coating was seriously reduced, and the water vapor transmission value exceeded 7.0g / day·m 2 .

[0134] The above two embodiments illustrate that a better water vapor barrier effect can be achieved only when the usage of the coupling agent and the inorganic nanoparticles is within a certain range.

[0135] Example 25: After greatly increasing the mass concentration of the inorganic nanopowder, the obtained coating does not have a water vapor barrier function, and the water vapor transmission value exceeds 7.0 g / day·m 2 .

[0136] Example 26: After the mass concentration of the inorganic nanopowder is greatly reduced, the obtained coating does not have a water vapor barrier function, and the water vapor transmission value exceeds 7.0 g / day·m 2 .

[0137] Example 25 and Example 26 illustrate that when the mass concentration of the inorganic nanopowder is within a certain range, the obtained coating has a better water vapor barrier effect.

[0138] Comparative Example 1: After the nanoparticles were replaced with silver oxide nanoparticles, the water vapor barrier function of the coating was seriously reduced, and the water vapor transmission value exceeded 7.0 g / day·m 2 This indicates that the silver oxide nanoparticles did not interact with the coupling agent molecules and did not form a dense coating.

[0139] The present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0140] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0141] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0142] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A water vapor barrier coating liquid, characterized in that: The raw materials for preparing the water vapor barrier coating liquid are composed of inorganic nano powder, solvent and coupling agent, and the inorganic nano powder is composed of inorganic oxide nano particles; The mass ratio of the inorganic nanopowder to the solvent is 1:(4-140), and the molar ratio of the coupling agent to the inorganic nanopowder is (0.1-1.85):1; The inorganic oxide nanoparticles have the structural formula M a O b H c , 0<a≤3; 0<b≤5; 0≤c≤2; Wherein, M is one of magnesium, aluminum, silicon, scandium, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, and zirconium; When c=0, the hydrogen atoms on the surface of the inorganic nanopowder exist in water molecules bonded by non-covalent bonds; When c>0, the hydrogen atoms on the surface of the inorganic nanopowder exist in the form of covalent bonds; The solvent is water or a mixture of water and small molecule alcohol.

2. The water vapor barrier coating liquid according to claim 1, characterized in that: The inorganic nano powder is composed of spherical or irregular nano particles with a particle size of 1-500nm.

3. The water vapor barrier coating liquid according to claim 2, characterized in that: The particle size of the nanoparticles is 1-50 nm.

4. The water vapor barrier coating liquid according to claim 3, characterized in that: The particle size of the nanoparticles is 1-20 nm.

5. The water vapor barrier coating liquid according to claim 1, characterized in that: The inorganic oxide nanoparticles are any one of aluminum oxide nanoparticles, silicon oxide nanoparticles, scandium oxide nanoparticles, zinc oxide nanoparticles, titanium oxide nanoparticles, germanium oxide nanoparticles, and zirconium oxide nanoparticles, or a mixture of at least two of them.

6. The water vapor barrier coating liquid according to claim 1, characterized in that: The inorganic oxide nanoparticles are any one of aluminum oxide nanoparticles, silicon oxide nanoparticles, zinc oxide nanoparticles, and titanium oxide nanoparticles, or a mixture of at least two of them.

7. The water vapor barrier coating liquid according to claim 1, characterized in that: The small molecule alcohol is any one of methanol, ethanol and isopropanol or a mixture of at least two of them.

8. The water vapor barrier coating liquid according to claim 1, characterized in that: The coupling agent is any one of a silicon-containing alkoxy compound, a silicon-containing halogen compound or a phosphorus-containing inorganic acid or a mixture of at least two thereof.

9. The water vapor barrier coating liquid according to claim 8, characterized in that: The silicon-containing alkoxy compound is at least one compound selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and derivatives thereof.

10. The water vapor barrier coating liquid according to claim 8, characterized in that: The silicon-containing halogen compound is at least one compound selected from silicon tetrachloride and its derivatives.

11. The water vapor barrier coating liquid according to claim 8, characterized in that: The phosphorus-containing inorganic acid is any one of hypophosphorous acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, and polyphosphoric acid, or a mixture of at least two of them.

12. A method for preparing a water vapor barrier coating liquid according to any one of claims 1 to 11, characterized in that: The steps include: 1) Dispersing the inorganic nanopowder in a solvent according to a ratio to obtain a nano-dispersion liquid; 2) Under stirring conditions, adding a coupling agent to the nano-dispersion liquid, and continuing to stir, to obtain the water vapor barrier coating liquid.

13. A water vapor barrier coating, characterized in that: The coating is obtained by coating with the water vapor barrier coating liquid as claimed in any one of claims 1 to 11.

14. A method for preparing a water vapor barrier coating according to claim 13, characterized in that: The water vapor barrier coating liquid according to any one of claims 1 to 11 is coated on the surface of a substrate, and then dried and aged to obtain the water vapor barrier coating.

15. The preparation method according to claim 14, characterized in that: The coating method is any one of spraying, scraping, roller coating, brushing, shower coating and extrusion coating.

16. The preparation method according to claim 14, characterized in that: The substrate is a sheet type.

17. The preparation method according to claim 14, characterized in that: The substrate is any one of polyester film, polyolefin film, polyamide film, poly(meth)acrylate film, polyvinyl alcohol film, polyvinyl alcohol-ethylene copolymer film, polystyrene film, polyurethane film, polyurea film, polyimide film, polyether sulfone film and polyether ether ketone film.

18. The preparation method according to claim 14, characterized in that: The drying temperature is 40-120°C.

19. The preparation method according to claim 18, characterized in that: The drying temperature is 45-100°C.

20. The preparation method according to claim 14, characterized in that: The drying time is 1-120 min.

21. The preparation method according to claim 20, characterized in that: The drying time is 5-20 minutes.

22. The preparation method according to claim 14, characterized in that: The aging temperature is 0-180°C.

23. The preparation method according to claim 22, characterized in that: The aging temperature is 45-150°C.

24. The preparation method according to claim 23, characterized in that: The aging temperature is 120-150°C.

25. The preparation method according to claim 14, characterized in that: The aging time is 1-1440 min.

26. The preparation method according to claim 25, characterized in that: The aging time is 20-60 minutes.

27. A use of the water vapor barrier coating according to claim 13, characterized in that: The water vapor barrier coating is used for the preparation of photovoltaic module back panels, electronic paper, quantum dot display water vapor barrier films, and medicine and food packaging.

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