CN113912894A - Transparent high-barrier polyester aluminum oxide-plated film and preparation method thereof - Google Patents
Transparent high-barrier polyester aluminum oxide-plated film and preparation method thereof Download PDFInfo
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- CN113912894A CN113912894A CN202111091721.4A CN202111091721A CN113912894A CN 113912894 A CN113912894 A CN 113912894A CN 202111091721 A CN202111091721 A CN 202111091721A CN 113912894 A CN113912894 A CN 113912894A
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C23C14/0021—Reactive sputtering or evaporation
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The application relates to the field of aluminized films, and particularly discloses a transparent high-barrier polyester aluminized aluminum film and a preparation method thereof. The transparent high-barrier polyester aluminum oxide-plated film comprises a base material, a polyurethane bottom coating, an aluminum oxide layer and a polyurethane top coating, wherein the base material, the polyurethane bottom coating, the aluminum oxide layer and the polyurethane top coating are sequentially arranged, the thickness of the polyurethane bottom coating and the thickness of the polyurethane top coating are both 8-15 micrometers, the thickness of the aluminum oxide layer is 80-140 angstroms, the polyurethane bottom coating is formed by drying a polyurethane coating liquid, and the polyurethane top coating is formed by drying the polyurethane coating liquid. The preparation method comprises the following steps: s1, obtaining a primer film on a polyurethane primer layer of a substrate; s2, forming an aluminum oxide layer on the polyurethane bottom coating to obtain a primary plating film; and S3, forming a polyurethane surface coating on the alumina layer, and curing to obtain the transparent high-barrier polyester alumina-plated film. The alumina-plated film of the present application has the advantages of good retort resistance and barrier properties.
Description
Technical Field
The application relates to the field of aluminized films, in particular to a transparent high-barrier polyester aluminized aluminum film and a preparation method thereof.
Background
With the improvement of living standard of people, people pay more attention to quality problems during shopping, particularly in the field of food, so that sold food is generally wrapped by an outer package. The outer package of food is mainly used for slowing down the food spoilage speed, and is generally formed by compounding multiple layers of films, wherein the films are roughly divided into a heat sealing layer, a barrier layer and a printing layer, and the barrier layer is used for blocking outside water and oxygen so as to delay the spoilage of the water and the oxygen on the food.
Barrier layers on the market are various at present, aluminum-plated films and nylon films are common, and because the aluminum-plated films are opaque, customers cannot observe the state of food conveniently if the aluminum-plated films are used for packaging the food; the nylon film is transparent, has high strength and good barrier property, is easily influenced by ultraviolet rays, and has limited application scenes, so that a new material is required to be used as the barrier layer.
The alumina-plated film is a transparent film, which is a film obtained by evaporating high-purity aluminum wires into a gaseous state at a high temperature, introducing oxygen to obtain alumina, and depositing the alumina on a film substrate, and has good oxygen barrier property and water vapor barrier property, so that the alumina-plated film has excellent barrier property.
Disclosure of Invention
In order to obtain an alumina-plated film with good boiling resistance, the application provides a transparent high-barrier polyester alumina-plated film and a preparation method thereof.
In a first aspect, the application provides a transparent high-barrier polyester aluminum oxide-plated film, which adopts the following technical scheme: the transparent high-barrier polyester aluminum oxide-plated film comprises a base material, a polyurethane bottom coating, an aluminum oxide layer and a polyurethane top coating which are sequentially arranged, wherein the thickness of the polyurethane bottom coating and the thickness of the polyurethane top coating are both 8-15 micrometers, the thickness of the aluminum oxide layer is 80-140 angstroms, and the polyurethane bottom coating and the polyurethane top coating are both formed by drying polyurethane coating liquid.
By adopting the technical scheme, the polyurethane bottom coating improves the surface smoothness of the base material, is beneficial to alumina deposition and forms an alumina layer stably connected with the base material; the polyurethane surface coating covers and protects the alumina layer, thereby effectively preventing the alumina layer from being scratched or damaged by the outside world and improving the strength of the film.
In addition, through the order setting of polyurethane priming coat, aluminium oxide layer and polyurethane top-coat layer, and the polyurethane top-coat layer, aluminium oxide layer and the thickness cooperation of polyurethane priming coat in specific range, make the polyurethane top-coat layer stabilize the aluminium oxide layer laminating in the polyurethane priming coat, improve the stability of aluminium oxide layer, make aluminium oxide layer also can keep stable state in the film under high temperature, and polyurethane priming coat and polyurethane top-coat layer make the both sides of aluminium oxide layer receive the extrusion, aluminium oxide improves the compactness of aluminium oxide layer, thereby not only the barrier property improves, still improve the structural stability of film under high temperature state, make the film be applicable to the packing of the food that needs high temperature heating more.
Optionally, the polyurethane coating liquid comprises the following raw materials in parts by weight: 90-100 parts of aqueous polyurethane dispersion liquid, 45-60 parts of diluent and 2-8 parts of cross-linking agent.
By adopting the technical scheme, the polyurethane is flexible and wear-resistant, the adhesive force of the waterborne polyurethane is high, the polyurethane is more environment-friendly compared with solvent-based polyurethane, the residual harmful solvent is less, the waterborne polyurethane is more suitable for food packaging, and the waterborne polyurethane dispersion liquid is matched with the diluent to help the waterborne polyurethane to be uniformly dispersed, so that the uniformity of a polyurethane bottom coating and a polyurethane top coating is improved.
Optionally, the diluent is a composition consisting of isopropanol and water, wherein the weight ratio of the isopropanol to the water is 1: 4-6, and preferably, the weight ratio of the isopropanol to the water is 1: 5.
Optionally, the crosslinker is an aziridine crosslinker.
Optionally, the raw materials of the polyurethane coating liquid also comprise 20-25 parts by weight of modified silica sol, wherein the modified silica sol is prepared from raw materials comprising the silica sol, 2 '-diphenylmethane diisocyanate, span 80, a catalyst and a solvent, and the weight ratio of the silica sol, the 2,2' -diphenylmethane diisocyanate, the span 80, the catalyst and the solvent is 10: 0.12-0.22: 1-1.5: 0.0008-0.002: 10-20.
By adopting the technical scheme, the doping of the silicon dioxide sol in the polyurethane coating liquid is beneficial to improving the mechanical property of the polyurethane coating, the isocyanate groups in the silicon dioxide sol are arranged in a staggered manner after the silicon dioxide sol is modified by 2,2' -diphenylmethane diisocyanate, and the silicon dioxide sol has good compatibility with the waterborne polyurethane, so that the uniformity of the silicon dioxide component in the waterborne polyurethane is improved, the internal tightness of the waterborne polyurethane is improved, the compactness of the polyurethane coating is improved, and the boiling resistance and the barrier property are further improved.
Optionally, the solvent is isopropanol, and the catalyst is dibutyltin diacetate.
Optionally, the substrate is selected from one of CPP, BOPP, PET, PA, PLA and PE.
In a second aspect, the application provides a preparation method of a transparent high-barrier polyester aluminum oxide-plated film, which adopts the following technical scheme:
a preparation method of a transparent high-barrier polyester aluminum oxide-plated film comprises the following steps:
s1, coating a polyurethane coating liquid on a substrate, drying, and forming a polyurethane bottom coating on the substrate to obtain a bottom coating film;
s2, feeding the primary coating film into a vacuum aluminizing device, vacuumizing, heating an aluminum wire, introducing oxygen, and forming an aluminum oxide layer on the polyurethane primary coating to obtain a primary coating film;
and S3, coating the polyurethane coating liquid on the aluminum oxide layer, drying, forming a polyurethane surface coating on the aluminum oxide layer, and curing to obtain the transparent high-barrier polyester aluminum oxide-plated film.
By adopting the technical scheme, the polyurethane bottom coating is formed on the substrate, the aluminum oxide layer is plated on the polyurethane bottom coating, the stability of the aluminum oxide layer is improved, the polyurethane top coating is formed on the aluminum oxide layer, the stability of the aluminum oxide layer is further improved while the aluminum oxide layer is protected, and the boiling resistance of the film is improved.
Optionally, in the step S1, the drying temperature of the undercoat film is 90 to 100 ℃, and the drying time is 6 to 10 seconds; s3, drying the surface coating film at 100-110 ℃ for 6-10S; the curing temperature in the step S3 is 50-60 ℃, and the curing time is 36-60 h.
Through adopting above-mentioned technical scheme, just curing after the polyurethane top coat forms, just plate the aluminium oxide layer after the preliminary shaping of polyurethane priming coat to in the curing process, further shaping of polyurethane priming coat and polyurethane top coat, the further increase of degree of connection with the aluminium oxide layer, thereby improve the bonding strength of polyurethane coating and aluminium oxide, improve the structural stability of film.
Optionally, in the step S2, the flow rate of the introduced oxygen is 14700 to 16800 sccm.
By adopting the technical scheme, the speed of forming the aluminum oxide is controlled in a proper range, and the aluminum oxide is favorably deposited on the polyurethane bottom coating, so that the tightly arranged aluminum oxide layer is formed, and the barrier property of the film is improved.
Optionally, in the step S2, the temperature of the heated aluminum wire is 1280 to 1360 ℃, the diameter of the aluminum wire is 1.5 to 1.9mm, and the wire feeding speed of the aluminum wire is 240 to 265 mm/min.
By adopting the technical scheme, the evaporation rate of the aluminum is controlled in a proper range, and the barrier property of the film is further improved.
Optionally, in the step S2, the temperature of the heated aluminum wire is 1320 to 1340 ℃, the flow rate of the introduced oxygen is 15200 to 16300sccm, the diameter of the aluminum wire is 1.7 to 1.8mm, and the wire feeding speed of the aluminum wire is 245 to 250 mm/min.
Through adopting above-mentioned technical scheme, the evaporation rate of control aluminium and the formation rate of aluminium oxide simultaneously for the compactness of aluminium oxide layer improves and the degree of consistency is better, is applicable to the aluminium oxide layer that thickness is littleer, thereby improves the luminousness of film.
Optionally, the preparation method of the polyurethane coating liquid comprises the following steps: and mixing and stirring the aqueous polyurethane dispersion liquid, the diluent and the cross-linking agent to obtain the polyurethane coating liquid.
Optionally, the preparation method of the polyurethane coating liquid comprises the following steps: mixing and stirring the aqueous polyurethane dispersion liquid, the modified silica sol, the diluent and the cross-linking agent to obtain a polyurethane coating liquid; the preparation method of the modified silica sol comprises the following steps: mixing the silica sol, span 80, a catalyst and a solvent, dropwise adding 2,2' -diphenylmethane diisocyanate while stirring at 70-76 ℃, continuously stirring after dropwise adding, drying to 65-70% of the original volume of the silica sol, and filtering to obtain the modified silica sol.
By adopting the technical scheme, the modification of the silica sol is realized, partial moisture and solvent of the modified silica sol are removed by drying the reaction solution, and the stability of isocyanate groups in the modified silica sol is improved, so that the compatibility of the modified silica sol and the waterborne polyurethane dispersion solution is improved.
In summary, the present application has the following beneficial effects:
1. according to the method, the polyurethane bottom coating, the alumina layer and the polyurethane top coating are combined in sequence, the polyurethane bottom coating improves the surface smoothness of the substrate and is beneficial to alumina deposition, and the polyurethane top coating can cover and protect the alumina layer and improve the strength of the film; cooperate the polyurethane top-coat layer, the thickness cooperation of aluminium oxide layer and polyurethane under-coat in specific range, make the polyurethane top-coat layer stabilize the aluminium oxide layer in the polyurethane under-coat, improve the stability of aluminium oxide layer, make the aluminium oxide layer also can keep stable state in the film under high temperature, and polyurethane under-coat and polyurethane top-coat layer make the both sides of aluminium oxide layer receive the extrusion, aluminium oxide improves the compactness of aluminium oxide layer, thereby not only the separation nature improves, still improve the structural stability of film under the high temperature state, make the film be applicable to the packing that needs the food of high temperature heating more.
2. In the application, the combination of the aqueous polyurethane and the modified silica sol is preferably adopted, so that the mechanical property of the polyurethane coating is improved, and the barrier property and the structural stability of the film are improved.
3. According to the method, the evaporation rate of aluminum and the formation rate of aluminum oxide are controlled simultaneously in a mode of limiting the oxygen flow, the temperature of heating the aluminum wire, the diameter of the aluminum wire and the wire feeding speed of the aluminum wire, so that good barrier property and high-temperature stability effects are obtained.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
The waterborne polyurethane is selected from new materials of great Huatai, Anhui, model AH-1704-1.
Silica sol was purchased from Nicoti Henxin chemical technology, Inc., model THI S-S30.
The above mentioned manufacturer's models are used to support the solution of the present application for completeness of disclosure and are not limited to the listed manufacturer's models.
Preparation example
Preparation example 1
The polyurethane coating liquid comprises the following raw materials:
9kg of aqueous polyurethane dispersion, 0.75kg of isopropanol, 3.75kg of water, 0.2kg of aziridine crosslinking agent.
The preparation method of the polyurethane masking liquid comprises the following steps:
stirring the aqueous polyurethane dispersion liquid, isopropanol, water and an aziridine crosslinking agent, and fully mixing to obtain the polyurethane coating liquid.
Preparation example 2
The polyurethane coating liquid comprises the following raw materials:
9.5kg of an aqueous polyurethane dispersion, 1kg of isopropanol, 5kg of water and 0.8kg of an aziridine crosslinking agent.
The preparation method of the polyurethane masking liquid comprises the following steps:
stirring the aqueous polyurethane dispersion liquid, isopropanol, water and an aziridine crosslinking agent, and fully mixing to obtain the polyurethane coating liquid.
Preparation example 3
The polyurethane coating liquid comprises the following raw materials:
10kg of an aqueous polyurethane dispersion, 0.9kg of isopropanol, 4.5kg of water and 0.5kg of an aziridine crosslinking agent.
The preparation method of the polyurethane masking liquid comprises the following steps:
stirring the aqueous polyurethane dispersion liquid, isopropanol, water and an aziridine crosslinking agent, and fully mixing to obtain the polyurethane coating liquid.
Preparation example 4
The polyurethane coating liquid comprises the following raw materials:
10kg of an aqueous polyurethane dispersion, 2kg of a silica sol, 0.9kg of isopropanol, 4.5kg of water and 0.5kg of an aziridine crosslinking agent.
The preparation method of the polyurethane masking liquid comprises the following steps:
stirring the aqueous polyurethane dispersion liquid, the silicon dioxide sol, the isopropanol, the water and the aziridine crosslinking agent, and fully mixing to obtain the polyurethane coating liquid.
Preparation example 5
The modified silica sol comprises the following raw materials:
10kg of silica sol, 0.12kg of 2,2' -diphenylmethane diisocyanate, 1kg of span 80, 0.8g of dibutyltin diacetate and 10kg of isopropanol.
The preparation method of the modified silica sol comprises the following steps:
mixing the silica sol, span 80 and isopropanol, dropwise adding 2,2' -diphenylmethane diisocyanate while stirring at 70 ℃, continuing stirring for 2h after 30min of dropwise addition, putting the obtained reaction solution into a 60 ℃ oven, drying until the volume of the reaction solution is 65% of that of the original silica sol, and filtering to obtain the modified silica sol.
The polyurethane coating liquid comprises the following raw materials:
10kg of an aqueous polyurethane dispersion, 2kg of a modified silica sol, 0.9kg of isopropanol, 4.5kg of water and 0.5kg of an aziridine crosslinking agent.
The preparation method of the polyurethane masking liquid comprises the following steps:
stirring the aqueous polyurethane dispersion liquid, the modified silica sol, the isopropanol, the water and the aziridine crosslinking agent, and fully mixing to obtain the polyurethane coating liquid.
Preparation example 6
The modified silica sol comprises the following raw materials:
10kg of silica sol, 0.22kg of 2,2' -diphenylmethane diisocyanate, 1.5kg of span 80, 2g of dibutyltin diacetate and 20kg of isopropanol.
The preparation method of the modified silica sol comprises the following steps:
mixing the silica sol, span 80 and isopropanol, dropwise adding 2,2' -diphenylmethane diisocyanate while stirring at 76 ℃, continuing stirring for 2h after finishing dropwise adding for 40min, putting the obtained reaction solution into a 60 ℃ oven, drying until the volume of the reaction solution is 70% of the volume of the original silica sol, and filtering to obtain the modified silica sol.
The polyurethane coating liquid comprises the following raw materials: 10kg of an aqueous polyurethane dispersion, 2.5kg of a modified silica sol, 0.9kg of isopropanol, 4.5kg of water and 0.5kg of an aziridine crosslinking agent.
The preparation method of the polyurethane masking liquid comprises the following steps:
stirring the aqueous polyurethane dispersion liquid, the modified silica sol, the isopropanol, the water and the aziridine crosslinking agent, and fully mixing to obtain the polyurethane coating liquid.
Examples
Example 1
A transparent high-barrier polyester aluminum oxide-plated film comprises the following layer structures which are arranged in sequence:
PET film, polyurethane bottom coat, aluminium oxide layer and polyurethane top coat.
A preparation method of a transparent high-barrier polyester aluminum oxide-plated film comprises the following steps:
s1. coating the polyurethane coating liquid of preparation example 1 on a PET film with a coating weight of 5g/m2Then, the PET film is sent into a drying oven for drying at the drying temperature of 90 ℃, the path of the PET film passing through the drying oven is 10m, the drying time is 6s, a polyurethane base coat is formed on the PET film, and the thickness of the polyurethane base coat is 8 mu m, so that the base coat film is obtained;
s2, feeding the aluminum wire and the base coat film into a vacuum aluminum plating machine, wherein the diameter of the aluminum wire is 1.2mm, the wire feeding speed of the aluminum wire is 210mm/min, and vacuumizing until the evaporation vacuum degree is 4 multiplied by 10-4mbar, then heating an evaporation boat of a vacuum aluminum plating machine, wherein the heating temperature is 1180 ℃, introducing oxygen, the flow of the introduced oxygen is 13000sccm, forming an aluminum oxide layer on the polyurethane bottom coating, and the thickness of the aluminum oxide layer is 80 angstroms to obtain a primary plating film;
s3, coating polyurethane coating liquid on the aluminum oxide layer, wherein the coating weight is 5g/m2And then, drying the film in an oven at the drying temperature of 100 ℃, wherein the path of the primary plated film in the oven is 10m, the drying time is 6s, a polyurethane surface coating is formed on the alumina layer, the thickness of the polyurethane surface coating is 8 mu m, and then, the film is placed in the oven at the temperature of 50 ℃ for curing for 36h to obtain the transparent high-barrier polyester plated alumina film.
Examples 2 to 3
The differences between examples 2 to 3 and example 1 are shown in table 1, and the polyurethane coating liquid used in example 2 is the polyurethane coating liquid prepared in preparation example 2, and the polyurethane coating liquid used in example 3 is the polyurethane coating liquid prepared in preparation example 3.
TABLE 1
Example 4
The difference between this embodiment and embodiment 3 lies in the difference of step S2, and in step S2 of this embodiment, the flow rate of the introduced oxygen is 14700 sccm.
Example 5
The difference between this embodiment and embodiment 3 lies in the difference of step S2, and in step S2 of this embodiment, the flow rate of the introduced oxygen is 16800 sccm.
Example 6
The difference between this embodiment and embodiment 3 lies in the difference of the step S2, in the step S2 of this embodiment, the temperature of the heated aluminum wire is 1280 ℃, the diameter of the aluminum wire is 1.5mm, and the wire feeding speed of the aluminum wire is 240 mm/min.
Example 7
The difference between this example and example 3 lies in the difference of the step S2, in the step S2 of this example, the temperature of the heated aluminum wire is 1360 ℃, the diameter of the aluminum wire is 1.9mm, and the wire feeding speed of the aluminum wire is 265 mm/min.
Example 8
The difference between this embodiment and embodiment 3 lies in the difference of the step S2, in the step S2 of this embodiment, the diameter of the aluminum wire is 1.7mm, the wire feeding speed of the aluminum wire is 245mm/min, the temperature of the heated aluminum wire is 1320 ℃, and the flow rate of the introduced oxygen is 15200 sccm.
Example 9
The difference between this embodiment and embodiment 3 lies in the difference of the step S2, in the step S2 of this embodiment, the diameter of the aluminum wire is 1.8mm, the wire feeding speed of the aluminum wire is 250mm/min, the temperature of the heated aluminum wire is 1340 ℃, and the flow rate of the introduced oxygen is 16300 sccm.
Example 10
This example is different from example 9 in the polyurethane coating liquid, and the polyurethane coating liquids used in the steps S2 and S3 of this example are the polyurethane coating liquids prepared in preparation example 4.
Example 11
This example is different from example 9 in the polyurethane coating liquid, and the polyurethane coating liquids used in the steps S2 and S3 of this example are the polyurethane coating liquid prepared in preparation example 5.
Example 12
This example is different from example 9 in the polyurethane coating liquid, and the polyurethane coating liquids used in the steps S2 and S3 of this example are the polyurethane coating liquid prepared in preparation example 6.
Comparative example
Comparative example 1
This comparative example differs from example 3 in that it is not provided with a polyurethane topcoat.
Comparative example 2
This comparative example differs from example 3 in that the thickness of the polyurethane basecoat and the thickness of the polyurethane topcoat of this comparative example are both 25 μm, and the thickness of the alumina layer is 60 angstroms.
Comparative example 3
This comparative example differs from example 3 in that the thickness of the polyurethane basecoat and the thickness of the polyurethane topcoat of this comparative example are both 6 μm and the thickness of the alumina layer is 220 angstroms.
Comparative example 4
The present comparative example is different from example 3 in that in step S1 of the present comparative example, after the polyurethane coating liquid was dried, it was put into an oven at 55 ℃ to be cured for 48 hours to form a polyurethane base coat.
Performance test
And (3) testing the cooking property: the films of examples 1 to 12 and comparative examples 1 to 4 were heat-sealed into small bags of 200mm × 120mm, two thirds of the bag volume was filled with water, the bags were sealed by evacuation, the bags were placed in an autoclave, the water boiling was carried out for 15min, the autoclave was cooled to room temperature after 15min, the bags were taken out by reduced pressure cooling, and the presence of abnormal phenomena such as significant deformation and interlayer peeling was checked, and the results were recorded in table 2.
Oxygen barrier property test: the oxygen transmission rates of the films of examples 1-12 and comparative examples 1-4 were tested according to ASTM D3985, and the test results are shown in Table 2.
Water vapor barrier property: the moisture vapor transmission rates of the films of examples 1-12 and comparative examples 1-4 were tested according to ASTM F1249, and the test results are shown in Table 2.
And (3) testing light transmittance: the films of examples 1-12 and comparative examples 1-4 were tested for light transmission according to GB/T2410-.
TABLE 2
Wherein the standard value of the oxygen permeability is less than or equal to 0.5cc/m2Day, standard value of moisture permeability of not more than 1.0cc/m2Day, the standard value of the light transmittance is not less than 88%.
According to table 2, it can be seen by combining example 3 with comparative example 1 that the polyurethane top coat is disposed on the alumina layer, so that the protection degree of the alumina layer can be improved, the stability of the whole film is further maintained, the film can still maintain good structural stability under the high-temperature cooking of 121 ℃, and the oxygen permeability and moisture permeability of the film are both significantly reduced and meet the requirements of standard values.
Combining example 3 with comparative examples 2-3, it can be seen that when the polyurethane topcoat, alumina layer and polyurethane basecoat meet a specific thickness combination, the film has good structural stability at a high temperature of 121 ℃ due to the improved stability of the alumina layer, and also has good oxygen barrier properties and water vapor barrier properties.
Combining example 3 with comparative example 4, it can be seen that if the polyurethane primer is coated with an aluminum oxide layer after being preliminarily formed on the substrate, the film has higher stability at high temperature steaming at 121 ℃.
When the oxygen flow is limited to 14700-16800 sccm, the oxygen barrier property and the water vapor barrier property are improved to a certain extent, which shows that controlling the formation rate of alumina helps to improve the compactness of the alumina layer, thereby improving the oxygen barrier property and the water vapor barrier property, as can be seen from combining examples 3 and 4-5.
Combining the example 3 with the examples 6-7, it can be seen that when the temperature of the heating aluminum wire is limited to 1280-1360 ℃, the diameter of the aluminum wire is 1.5-1.9 mm, and the wire feeding speed of the aluminum wire is 240-265 mm/min, the oxygen barrier property and the water vapor barrier property are both improved to a certain extent, which shows that the oxygen barrier property and the water vapor barrier property can be improved by controlling the evaporation rate of aluminum.
When the oxygen flow rate, the temperature of heating the aluminum wire, the diameter of the aluminum wire, and the wire feeding speed of the aluminum wire are further defined at the same time, that is, when the evaporation rate of aluminum and the formation rate of aluminum oxide are controlled within specific ranges at the same time, it can be seen that not only the oxygen barrier property and the water vapor barrier property of the film are improved, but also the uniformity of the aluminum oxide layer may be further improved, so that the light transmittance of the film is improved.
When the unmodified silica sol is added to the polyurethane coating solution, the oxygen barrier property and the water vapor barrier property of the film are not improved, and the light transmittance is reduced; it can be seen from the combination of examples 9 and 11-12 that when the modified silica sol was added to the polyurethane coating solution, not only the oxygen barrier property and the water vapor barrier property were improved and the light transmittance was higher than that of example 10, but also the film could maintain good structural stability at 135 ℃ high temperature cooking.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The transparent high-barrier polyester aluminum oxide-plated film is characterized by comprising a base material, a polyurethane bottom coating, an aluminum oxide layer and a polyurethane top coating which are sequentially arranged, wherein the thickness of the polyurethane bottom coating and the thickness of the polyurethane top coating are both 8-15 micrometers, the thickness of the aluminum oxide layer is 80-140 angstroms, and the polyurethane bottom coating and the polyurethane top coating are both formed by drying polyurethane coating liquid.
2. The transparent high-barrier polyester aluminum oxide-plated film according to claim 1, wherein: the polyurethane coating liquid comprises the following raw materials in parts by weight: 90-100 parts of aqueous polyurethane dispersion liquid, 45-60 parts of diluent and 2-8 parts of cross-linking agent.
3. The transparent high-barrier polyester aluminum oxide-plated film according to claim 2, wherein: the polyurethane coating liquid comprises the following raw materials, by weight, 20-25 parts of modified silica sol, wherein the modified silica sol is prepared from raw materials including the silica sol, 2 '-diphenylmethane diisocyanate, span 80, a catalyst and a solvent, and the weight ratio of the silica sol, the 2,2' -diphenylmethane diisocyanate, the span 80, the catalyst and the solvent is 10 (0.12-0.22): (1-1.5): 0.0008-0.002): 10-20.
4. A preparation method of a transparent high-barrier polyester aluminum oxide-plated film is characterized by comprising the following steps: a process for preparing a transparent high-barrier polyester alumina-coated film according to any one of claims 1 to 3, comprising the steps of:
s1, coating a polyurethane coating liquid on a substrate, drying, and forming a polyurethane bottom coating on the substrate to obtain a bottom coating film;
s2, feeding the primary coating film into a vacuum aluminizing device, vacuumizing, heating an aluminum wire, introducing oxygen, and forming an aluminum oxide layer on the polyurethane primary coating to obtain a primary coating film;
and S3, coating the polyurethane coating liquid on the aluminum oxide layer, drying, forming a polyurethane surface coating on the aluminum oxide layer, and curing to obtain the transparent high-barrier polyester aluminum oxide-plated film.
5. The method for preparing the transparent high-barrier polyester aluminum oxide-plated film according to claim 4, wherein the method comprises the following steps: s1, drying the bottom coating film at 90-100 ℃ for 6-10S; s3, drying the surface coating film at 100-110 ℃ for 6-10S; the curing temperature in the step S3 is 50-60 ℃, and the curing time is 36-60 h.
6. The method for preparing the transparent high-barrier polyester aluminum oxide-plated film according to claim 4, wherein the method comprises the following steps: in the step S2, the flow rate of the introduced oxygen is 14700-16800 sccm.
7. The method for preparing the transparent high-barrier polyester aluminum oxide-plated film according to claim 4, wherein the method comprises the following steps: in the step S2, the temperature of the heating aluminum wire is 1280-1360 ℃, the diameter of the aluminum wire is 1.5-1.9 mm, and the wire feeding speed of the aluminum wire is 240-265 mm/min.
8. The method for preparing the transparent high-barrier polyester aluminum oxide-plated film according to claim 4, wherein the method comprises the following steps: in the step S2, the temperature of the heated aluminum wire is 1320-1340 ℃, the flow rate of the introduced oxygen is 15200-16300 sccm, the diameter of the aluminum wire is 1.7-1.8 mm, and the wire feeding speed of the aluminum wire is 245-250 mm/min.
9. The method for preparing the transparent high-barrier polyester aluminum oxide-plated film according to claim 4, wherein the method comprises the following steps: the preparation method of the polyurethane coating liquid comprises the following steps: and mixing and stirring the aqueous polyurethane dispersion liquid, the diluent and the cross-linking agent to obtain the polyurethane coating liquid.
10. The method for preparing the transparent high-barrier polyester aluminum oxide-plated film according to claim 4, wherein the method comprises the following steps: the preparation method of the polyurethane coating liquid comprises the following steps: mixing and stirring the aqueous polyurethane dispersion liquid, the modified silica sol, the diluent and the cross-linking agent to obtain a polyurethane coating liquid; the preparation method of the modified silica sol comprises the following steps: mixing the silica sol, span 80, a catalyst and a solvent, dropwise adding 2,2' -diphenylmethane diisocyanate while stirring at 70-76 ℃, continuously stirring after dropwise adding, drying to 65-70% of the original volume of the silica sol, and filtering to obtain the modified silica sol.
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