Aluminum-plated high-barrier composite laser packaging film and its preparation process

Abstract

The present invention relates to the field of laser packaging films, and specifically discloses an aluminum-plated high-barrier composite laser packaging film and its preparation process; the specific operation steps are as follows: take a BOPP layer, apply a laser layer coating on one side thereof, and the dry coating amount is 0.9-1.1g / m 2 , laser holographic molding is performed on a laser molding machine at a temperature of 155-165°C and a molding speed of 45-50m / min to obtain a BOPP laser film; a vacuum aluminum coating machine is used to heat the aluminum wire to 1300-1400°C under vacuum conditions of 0.003-0.004Pa to vaporize it, and then it is attached to the BOPP laser film to form an aluminum coating layer with a thickness of 90-120nm to obtain a BOPP aluminum-coated laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum-coated surface of the BOPP aluminum-coated laser film to form a protective layer of 3-5μm, and an aluminum-coated high-barrier composite laser packaging film is obtained.

Description

Technical Field

[0001] The invention relates to the field of laser packaging films, and specifically discloses an aluminum-plated high-barrier composite laser packaging film and a preparation process thereof. Background Art

[0002] With the development of printing technology, the post-press processing technology of printed products has also been rapidly improved. Based on ordinary electrochemical aluminum hot stamping foil, electrochemical aluminum hot stamping foil manufacturers have combined laser holographic technology to develop laser electrochemical aluminum hot stamping foil. Its advantages are exquisite hot stamping patterns and high-tech anti-counterfeiting functions. It is suitable for product packaging and has broad application prospects.

[0003] Packaging films need to have excellent barrier properties against moisture and aroma, offering moisture-proof and aroma-retaining properties. The barrier properties of commonly used aluminized laser packaging films still need to be improved. Furthermore, insufficient adhesion between layers of aluminized laser composite packaging films, leading to separation, can also reduce the barrier properties of the product, impacting practical performance. Therefore, developing aluminized high-barrier composite laser packaging films with excellent water and gas barrier properties is of great significance. Summary of the Invention

[0004] The object of the present invention is to provide an aluminum-plated high-barrier composite laser packaging film and a preparation process thereof to solve the problems raised in the above background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A preparation process of an aluminum-plated high-barrier composite laser packaging film comprises the following steps: S1: taking a double bond monomer, a dispersant, modified silica, a high-barrier glue, and ethanol, and stirring to obtain a laser layer coating;

[0007] S2: Take the BOPP layer, apply a laser layer coating on one side thereof, and perform laser holographic molding on a laser molding machine to obtain a BOPP laser film; heat and vaporize the aluminum wire under vacuum conditions, and attach it to the BOPP laser film to form an aluminum-plated layer to obtain a BOPP aluminum-plated laser film; melt the PE plastic particles and apply them on the aluminum-plated surface of the BOPP aluminum-plated laser film to form a protective layer to obtain an aluminum-plated high-barrier composite laser packaging film.

[0008] Preferably, the double bond monomer includes at least one of methyl acrylate, butyl acrylate, methyl methacrylate, acrylic acid, acrylamide, 2-hydroxyethyl methacrylate phosphate, and styrene.

[0009] Preferably, the specific steps of S2 are: take the BOPP layer and apply the laser coating on one side thereof, with the dry coating amount being 0.9-1.1 g / m 2, laser holographic molding is performed on a laser molding machine at a temperature of 155-165°C and a molding speed of 45-50m / min to obtain a BOPP laser film; a vacuum aluminizing machine heats the aluminum wire to 1300-1400°C under vacuum conditions of 0.003-0.004Pa to vaporize it, and then adheres it to the BOPP laser film to form an aluminum layer with a thickness of 90-120nm to obtain a BOPP aluminized laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum surface of the BOPP aluminized laser film to form a protective layer of 3-5μm, and an aluminized high-barrier composite laser packaging film is obtained.

[0010] Preferably, the laser layer coating comprises the following raw materials, calculated by mass: 15 to 40 parts of double bond monomer, 1 to 2 parts of dispersant, 3 to 6 parts of modified silica, 3 to 6 parts of high barrier glue, and 60 to 80 parts of ethanol.

[0011] Preferably, the double bond monomers in the laser layer coating include, by mass, 5 to 10 parts of methyl acrylate, 5 to 10 parts of butyl acrylate, 1 to 5 parts of methyl methacrylate, and 5 to 10 parts of acrylic acid.

[0012] Preferably, the preparation of the high barrier glue comprises the following steps: taking EVOH, treating it with alkali, adding a chloroether resin solution, and soaking it at 30-40°C for 2-3 hours to obtain a modifier; taking a double bond monomer, a modifier, and benzoyl peroxide, heating it to 80-100°C under nitrogen protection and reacting it for 4-6 hours to obtain a high barrier glue.

[0013] Preferably, the alkali treatment process comprises the following steps: taking EVOH and soaking it in a 3 mol / L NaOH ethanol solution at 30-40° C. for 30-40 minutes.

[0014] Preferably, the chloroether resin solution comprises chloroether resin MP-25 and 1 to 2 times the mass of ethylene glycol butyl ether.

[0015] Preferably, in the modifier, the molar ratio of the chloroether resin to the EVOH is (1-2):1; the high barrier glue comprises the following raw materials, calculated by mass: 80-150 parts of double bond monomer, 40-50 parts of modifier, and 1-3 parts of benzoyl peroxide.

[0016] Preferably, the double bond monomers in the high barrier glue include 20 to 30 parts of methyl methacrylate, 10 to 20 parts of acrylic acid, 10 to 20 parts of styrene, and 50 to 60 parts of butyl acrylate, calculated by mass.

[0017] Preferably, the preparation of the dispersant comprises the following steps: taking a double bond monomer, ethanol, and benzoyl peroxide, heating to 70-80° C., keeping warm for 1-2 hours, adjusting the pH to 7-8 after cooling, and drying to obtain the dispersant.

[0018] Preferably, the dispersant comprises the following raw materials, calculated by mass: 60 to 120 parts of double bond monomer, 80 to 100 parts of ethanol, and 1 to 2 parts of benzoyl peroxide.

[0019] Preferably, the double bond monomers in the dispersant include, by mass, 20 to 30 parts of acrylamide, 20 to 30 parts of acrylic acid, 20 to 30 parts of butyl acrylate, and 5 to 10 parts of 2-hydroxyethyl methacrylate phosphate.

[0020] Preferably, the preparation of the modified silica comprises the following steps: taking a PVA aqueous solution and tetraethyl orthosilicate,

[0021] Stir, adjust the hydrogen ion concentration to 0.05-0.25 mol / L, heat to 60-70°C and hydrolyze for 2-3 days to obtain PVA / SiO2 sol, add soybean oil, stir for 1-2 hours, add glutaraldehyde, stir for 2-3 hours, centrifuge, wash and dry to obtain PVA-modified SiO2; take PVA-modified SiO2, water, ethanol and silane coupling agent, heat to 40-60°C, stir for 4-6 hours, filter and dry to obtain modified silica.

[0022] Preferably, the mass of PVA in the PVA aqueous solution is 5-8%; the PVA-modified SiO2 includes the following raw materials, calculated in parts by mass: 100 parts of PVA aqueous solution, 20-30 parts of tetraethyl orthosilicate; the amount of soybean oil added is 10-15 times the mass of the PVA / SiO2 sol; the amount of glutaraldehyde added is 0.1-0.4g / g PVA; the modified silica includes the following raw materials, calculated in parts by mass: 20-30 parts of PVA-modified SiO2, 60-80 parts of water, 60-80 parts of ethanol, and 1-3 parts of silane coupling agent.

[0023] Compared with the existing technology, the beneficial effects achieved by the present invention are as follows: the aluminum-plated high-barrier composite laser packaging film includes a BOPP layer, a laser layer coating, an aluminum-plated layer, and a protective layer, and has good moisture-proof and fragrance-preserving capabilities; the laser layer coating includes modified silica, a double-bond monomer, a dispersant, and a high-barrier glue. The modified silica is modified with PVA and a silane coupling agent with a double bond. The addition of silica to the laser layer coating is beneficial to improving the molding continuity and barrier properties. The introduced PVA is low in price and has good film-forming properties and gas resistance. It has good bulk barrier properties and is also compatible with acrylic acid to a certain extent. The introduced silane coupling agent further improves the dispersibility of silica. The high-barrier glue is polymerized from a variety of double-bond monomers to improve adhesion, making it difficult for the layers of the packaging film to fall off, ensuring high barrier properties. It has good compatibility with the double-bond monomers and dispersants in the coating, and there will be no decrease in barrier properties due to compatibility issues. The high-barrier glue includes a modifier, which is EVOH modified with a chloroether resin. EVOH has high barrier properties to gases, but due to its hydrophilicity, it has poor barrier properties to water vapor. Therefore, it is modified with a chloroether resin. The chloroether resin has good water resistance, and the presence of a large number of ether bonds in the molecular structure can improve adhesion. The dispersant is also polymerized from a variety of double-bond monomers and has good dispersibility. The raw materials of the dispersant and high-barrier glue include double-bond monomers, and the modified silica also contains double bonds. Therefore, the raw materials of the laser layer coating have good affinity with each other, and the raw materials are simple and easy to prepare. The laser layer coating includes 3 to 6 parts of modified silica and 3 to 6 parts of high-barrier glue. The introduction of modified silica can improve the molding continuity and barrier properties, but too much addition will lead to a decrease in film-forming properties, or even precipitation that destroys the integrity of the film, which in turn leads to a decrease in barrier properties. Adding high-barrier glue improves adhesion, making it difficult for the layers of the packaging film to fall off. Adding too much will cause the viscosity of the laser layer coating to be too high, which will cause anti-sticking during molding, affecting the molding effect and also affecting the barrier properties. Therefore, it is important to control the addition amount. DETAILED DESCRIPTION

[0024] The following describes preferred implementations of the present invention. Obviously, the described embodiments are only a portion of the embodiments of the present invention, not all of them. It will be apparent to those skilled in the art that all other implementations derived without inventive effort, without departing from the principles of the present invention, are within the scope of protection of the present invention.

[0025] Example 1: S1: Take PVA and water to prepare a 6% PVA aqueous solution; take 100 parts of PVA aqueous solution, 25 parts of tetraethyl orthosilicate, add 1 mol / L hydrochloric acid to adjust the hydrogen ion concentration to 0.2 mol / L, stir, heat to 60°C and hydrolyze for 2 days to obtain PVA / SiO2 sol, add soybean oil 10 times the mass of PVA / SiO2 sol, stir for 1 hour, add glutaraldehyde in an amount of 0.3 g / g PVA, stir for 3 hours, centrifuge, wash, and dry to obtain PVA-modified SiO2; take 25 parts of PVA-modified SiO2, 80 parts of water, 60 parts of ethanol, and 3 parts of silane coupling agent KH-171, heat to 50°C, stir for 5 hours, filter, and dry to obtain modified silica;

[0026] S2: Take chloroether resin and 1 times its mass of ethylene glycol butyl ether, heat to 100°C under nitrogen protection, stir until the chloroether resin is dissolved to obtain a chloroether resin solution; take EVOH, soak it in a 3 mol / L NaOH ethanol solution at 30°C for 40 minutes, then add the chloroether resin solution and soak it at 40°C for 3 hours to obtain a modifier, with a molar ratio of chloroether resin to EVOH of 1.5:1; take 30 parts of methyl methacrylate, 10 parts of acrylic acid, 10 parts of styrene, 60 parts of butyl acrylate, 45 parts of modifier, and 2 parts of benzoyl peroxide, heat to 100°C under nitrogen protection and react for 5 hours to obtain a high barrier glue;

[0027] S3: Take 25 parts of acrylamide, 20 parts of acrylic acid, 30 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate phosphate, 100 parts of ethanol, and 1 part of benzoyl peroxide, heat to 70°C, keep warm for 2 hours, cool, adjust the pH to 7, and dry to obtain a dispersant;

[0028] S4: Take 6 parts of methyl acrylate, 8 parts of butyl acrylate, 4 parts of methyl methacrylate, 10 parts of acrylic acid, 1.5 parts of dispersant, 5 parts of modified silica, 5 parts of high barrier glue, and 80 parts of ethanol, and stir at a speed of 1200 m / min for 4 hours to obtain a laser layer coating;

[0029] S5: Take the BOPP layer and apply laser coating on one side. The dry coating amount is 1g / m 2 , laser holographic molding is performed on a laser molding machine at a temperature of 160°C and a molding speed of 50m / min to obtain a BOPP laser film; a vacuum aluminizing machine heats the aluminum wire to 1300°C under a vacuum condition of 0.004Pa to vaporize it, and then adheres it to the BOPP laser film to form an aluminum-plated layer with a thickness of 100nm to obtain a BOPP aluminized laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum-plated surface of the BOPP aluminized laser film to form a 4μm protective layer, and an aluminized high-barrier composite laser packaging film is obtained.

[0030] Example 2: S1: Take PVA and water to prepare a 5% PVA aqueous solution; take 100 parts of PVA aqueous solution, 20 parts of tetraethyl orthosilicate, add 1 mol / L hydrochloric acid to adjust the hydrogen ion concentration to 0.2 mol / L, stir, heat to 60°C and hydrolyze for 2 days to obtain PVA / SiO2 sol, add soybean oil 10 times the mass of PVA / SiO2 sol, stir for 1 hour, add glutaraldehyde in an amount of 0.3 g / g PVA, stir for 3 hours, centrifuge, wash, and dry to obtain PVA-modified SiO2; take 20 parts of PVA-modified SiO2, 80 parts of water, 60 parts of ethanol, and 1 part of silane coupling agent KH-171, heat to 50°C, stir for 5 hours, filter, and dry to obtain modified silica;

[0031] S2: Take chloroether resin and 1 times its mass of ethylene glycol butyl ether, heat to 100°C under nitrogen protection, stir until the chloroether resin is dissolved to obtain a chloroether resin solution; take EVOH, soak it in a 3 mol / L NaOH ethanol solution at 30°C for 40 minutes, then add the chloroether resin solution and soak it at 40°C for 3 hours to obtain a modifier, with a molar ratio of chloroether resin to EVOH of 1:1; take 20 parts of methyl methacrylate, 10 parts of acrylic acid, 10 parts of styrene, 60 parts of butyl acrylate, 40 parts of modifier, and 2 parts of benzoyl peroxide, heat to 100°C under nitrogen protection and react for 6 hours to obtain a high barrier glue;

[0032] S3: Take 20 parts of acrylamide, 20 parts of acrylic acid, 30 parts of butyl acrylate, 10 parts of 2-hydroxyethyl methacrylate phosphate, 100 parts of ethanol, and 1 part of benzoyl peroxide, heat to 70°C, keep warm for 1 hour, cool, adjust the pH to 7, and dry to obtain a dispersant;

[0033] S4: Take 10 parts of methyl acrylate, 10 parts of butyl acrylate, 1 part of methyl methacrylate, 5 parts of acrylic acid, 1 part of dispersant, 3 parts of modified silica, 3 parts of high barrier glue, and 80 parts of ethanol, and stir at a speed of 1200 m / min for 4 hours to obtain a laser layer coating;

[0034] S5: Take the BOPP layer and apply laser coating on one side. The dry coating amount is 0.9g / m 2 , laser holographic molding is performed on a laser molding machine at a temperature of 160°C and a molding speed of 50m / min to obtain a BOPP laser film; a vacuum aluminizing machine heats the aluminum wire to 1300°C under a vacuum condition of 0.004Pa to vaporize it, and then adheres it to the BOPP laser film to form an aluminum layer with a thickness of 90nm to obtain a BOPP aluminized laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum surface of the BOPP aluminized laser film to form a 3μm protective layer, and an aluminized high-barrier composite laser packaging film is obtained.

[0035] Example 3: S1: Take PVA and water to prepare 8% PVA aqueous solution; take 100 parts of PVA aqueous solution, 30 parts of tetraethyl orthosilicate, add 1 mol / L hydrochloric acid to adjust the hydrogen ion concentration to 0.2 mol / L, stir, heat to 60°C and hydrolyze for 2 days to obtain PVA / SiO2 sol, add soybean oil 10 times the mass of PVA / SiO2 sol, stir for 1 hour, add glutaraldehyde in an amount of 0.3 g / g PVA, stir for 3 hours, centrifuge, wash, and dry to obtain PVA-modified SiO2; take 30 parts of PVA-modified SiO2, 80 parts of water, 60 parts of ethanol, 3 parts of silane coupling agent KH-171, heat to 50°C, stir for 5 hours, filter, and dry to obtain modified silica;

[0036] S2: Take chloroether resin and 1 times its mass of ethylene glycol butyl ether, heat to 100°C under nitrogen protection, stir until the chloroether resin is dissolved to obtain a chloroether resin solution; take EVOH, soak it in a 3 mol / L NaOH ethanol solution at 30°C for 40 minutes, then add the chloroether resin solution and soak it at 40°C for 3 hours to obtain a modifier, with a molar ratio of chloroether resin to EVOH of 2:1; take 20 parts of methyl methacrylate, 20 parts of acrylic acid, 20 parts of styrene, 50 parts of butyl acrylate, 40 parts of modifier, and 2 parts of benzoyl peroxide, heat to 100°C under nitrogen protection and react for 4 hours to obtain a high barrier glue;

[0037] S3: Take 30 parts of acrylamide, 20 parts of acrylic acid, 30 parts of butyl acrylate, 10 parts of 2-hydroxyethyl methacrylate phosphate, 100 parts of ethanol, and 1 part of benzoyl peroxide, heat to 70°C, keep warm for 2 hours, cool, adjust the pH to 7, and dry to obtain a dispersant;

[0038] S4: Take 10 parts of methyl acrylate, 10 parts of butyl acrylate, 5 parts of methyl methacrylate, 5 parts of acrylic acid, 2 parts of dispersant, 6 parts of modified silica, 6 parts of high barrier glue, and 80 parts of ethanol, and stir at a speed of 1200 m / min for 4 hours to obtain a laser layer coating;

[0039] S5: Take the BOPP layer and apply laser coating on one side. The dry coating amount is 1.1g / m 2 , laser holographic molding is performed on a laser molding machine at a temperature of 160°C and a molding speed of 50m / min to obtain a BOPP laser film; a vacuum aluminizing machine heats the aluminum wire to 1300°C under a vacuum condition of 0.004Pa to vaporize it, and then adheres it to the BOPP laser film to form an aluminum-plated layer with a thickness of 120nm to obtain a BOPP aluminized laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum-plated surface of the BOPP aluminized laser film to form a 5μm protective layer, and an aluminized high-barrier composite laser packaging film is obtained.

[0040] Comparative Example 1 (PVA is not introduced into the modified silica, and the remaining steps are the same as those in Example 1): S1: 25 parts of SiO2, 80 parts of water, 60 parts of ethanol, and 3 parts of silane coupling agent KH-171 are taken, heated to 50°C, stirred for 5 hours, filtered, and dried to obtain modified silica;

[0041] S2: Take chloroether resin and 1 times its mass of ethylene glycol butyl ether, heat to 100°C under nitrogen protection, stir until the chloroether resin is dissolved to obtain a chloroether resin solution; take EVOH, soak it in a 3 mol / L NaOH ethanol solution at 30°C for 40 minutes, then add the chloroether resin solution and soak it at 40°C for 3 hours to obtain a modifier, with a molar ratio of chloroether resin to EVOH of 1.5:1; take 30 parts of methyl methacrylate, 10 parts of acrylic acid, 10 parts of styrene, 60 parts of butyl acrylate, 45 parts of modifier, and 2 parts of benzoyl peroxide, heat to 100°C under nitrogen protection and react for 5 hours to obtain a high barrier glue;

[0042] S3: Take 25 parts of acrylamide, 20 parts of acrylic acid, 30 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate phosphate, 100 parts of ethanol, and 1 part of benzoyl peroxide, heat to 70°C, keep warm for 2 hours, cool and adjust the pH to 7.

[0043] Drying to obtain a dispersant;

[0044] S4: Take 6 parts of methyl acrylate, 8 parts of butyl acrylate, 4 parts of methyl methacrylate, 10 parts of acrylic acid, 1.5 parts of dispersant, 5 parts of modified silica, 5 parts of high barrier glue, and 80 parts of ethanol, and stir at a speed of 1200 m / min for 4 hours to obtain a laser layer coating;

[0045] S5: Take the BOPP layer and apply laser coating on one side. The dry coating amount is 1g / m 2 , laser holographic molding is performed on a laser molding machine at a temperature of 160°C and a molding speed of 50m / min to obtain a BOPP laser film; a vacuum aluminizing machine heats the aluminum wire to 1300°C under a vacuum condition of 0.004Pa to vaporize it, and then adheres it to the BOPP laser film to form an aluminum-plated layer with a thickness of 100nm to obtain a BOPP aluminized laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum-plated surface of the BOPP aluminized laser film to form a 4μm protective layer, and an aluminized high-barrier composite laser packaging film is obtained.

[0046] Comparative Example 2 (changing the amount of modifier added, the remaining method steps are the same as Example 1): S1: Take PVA and water to prepare a 6% PVA aqueous solution; take 100 parts of PVA aqueous solution, 25 parts of tetraethyl orthosilicate, add 1 mol / L hydrochloric acid to adjust the hydrogen ion concentration to 0.2 mol / L, stir, heat to 60°C and hydrolyze for 2 days to obtain PVA / SiO2 sol, add soybean oil 10 times the mass of PVA / SiO2 sol, stir for 1 hour, add glutaraldehyde in an amount of 0.3 g / g PVA, stir for 3 hours, centrifuge, wash, and dry to obtain PVA-modified SiO2; take 25 parts of PVA-modified SiO2, 80 parts of water, 60 parts of ethanol, 3 parts of silane coupling agent KH-171, heat to 50°C, stir for 5 hours, filter, and dry to obtain modified silica;

[0047] S2: Take chloroether resin and 1 times its mass of ethylene glycol butyl ether, heat to 100°C under nitrogen protection, stir until the chloroether resin is dissolved to obtain a chloroether resin solution; take EVOH, soak it in a 3 mol / L NaOH ethanol solution at 30°C for 40 minutes, then add the chloroether resin solution and soak it at 40°C for 3 hours to obtain a modifier, with a molar ratio of chloroether resin to EVOH of 1.5:1; take 30 parts of methyl methacrylate, 10 parts of acrylic acid, 10 parts of styrene, 60 parts of butyl acrylate, 30 parts of modifier, and 2 parts of benzoyl peroxide, heat to 100°C under nitrogen protection and react for 5 hours to obtain a high barrier glue;

[0048] S3: Take 25 parts of acrylamide, 20 parts of acrylic acid, 30 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate phosphate, 100 parts of ethanol, and 1 part of benzoyl peroxide, heat to 70°C, keep warm for 2 hours, cool, adjust the pH to 7, and dry to obtain a dispersant;

[0049] S4: Take 6 parts of methyl acrylate, 8 parts of butyl acrylate, 4 parts of methyl methacrylate, 10 parts of acrylic acid, 1.5 parts of dispersant, 5 parts of modified silica, 5 parts of high barrier glue, and 80 parts of ethanol, and stir at a speed of 1200 m / min for 4 hours to obtain a laser layer coating;

[0050] S5: Take the BOPP layer and apply laser coating on one side. The dry coating amount is 1g / m 2 , laser holographic molding is performed on a laser molding machine at a temperature of 160°C and a molding speed of 50m / min to obtain a BOPP laser film; a vacuum aluminizing machine heats the aluminum wire to 1300°C under a vacuum condition of 0.004Pa to vaporize it, and then adheres it to the BOPP laser film to form an aluminum-plated layer with a thickness of 100nm to obtain a BOPP aluminized laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum-plated surface of the BOPP aluminized laser film to form a 4μm protective layer, and an aluminized high-barrier composite laser packaging film is obtained.

[0051] Comparative Example 3 (using EVOH instead of the modifier, and the remaining method steps are the same as Example 1): S1: Take PVA and water to prepare a 6% PVA aqueous solution; take 100 parts of PVA aqueous solution, 25 parts of tetraethyl orthosilicate, add 1 mol / L hydrochloric acid to adjust the hydrogen ion concentration to 0.2 mol / L, stir, heat to 60°C and hydrolyze for 2 days to obtain PVA / SiO2 sol, add soybean oil 10 times the mass of PVA / SiO2 sol, stir for 1 hour, add glutaraldehyde in an amount of 0.3 g / g PVA, stir for 3 hours, centrifuge, wash, and dry to obtain PVA-modified SiO2; take 25 parts of PVA-modified SiO2, 80 parts of water, 60 parts of ethanol, and 3 parts of silane coupling agent KH-171, heat to 50°C, stir for 5 hours, filter, and dry to obtain modified silica;

[0052] S2: Take 30 parts of methyl methacrylate, 10 parts of acrylic acid, 10 parts of styrene, 60 parts of butyl acrylate, 45 parts of EVOH, and 2 parts of benzoyl peroxide, heat to 100°C under nitrogen protection and react for 5 hours to obtain a high barrier adhesive;

[0053] S3: Take 25 parts of acrylamide, 20 parts of acrylic acid, 30 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate phosphate, 100 parts of ethanol, and 1 part of benzoyl peroxide, heat to 70°C, keep warm for 2 hours, cool, adjust the pH to 7, and dry to obtain a dispersant;

[0054] S4: Take 6 parts of methyl acrylate, 8 parts of butyl acrylate, 4 parts of methyl methacrylate, 10 parts of acrylic acid, 1.5 parts of dispersant, 5 parts of modified silica, 5 parts of high barrier glue, and 80 parts of ethanol, and stir at a speed of 1200 m / min for 4 hours to obtain a laser layer coating;

[0055] S5: Take the BOPP layer and apply laser coating on one side. The dry coating amount is 1g / m 2 , laser holographic molding is performed on a laser molding machine at a temperature of 160°C and a molding speed of 50m / min to obtain a BOPP laser film; a vacuum aluminizing machine heats the aluminum wire to 1300°C under a vacuum condition of 0.004Pa to vaporize it, and then adheres it to the BOPP laser film to form an aluminum-plated layer with a thickness of 100nm to obtain a BOPP aluminized laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum-plated surface of the BOPP aluminized laser film to form a 4μm protective layer, and an aluminized high-barrier composite laser packaging film is obtained.

[0056] Comparative Example 4 (changing the amount of dispersant, modified silica, high barrier glue, and double bond monomer added to the laser layer coating, and the remaining method steps are the same as Example 1): S1: Take PVA and water to prepare a 6% PVA aqueous solution; take 100 parts of PVA aqueous solution, 25 parts of tetraethyl orthosilicate, add 1 mol / L hydrochloric acid to adjust the hydrogen ion concentration to 0.2 mol / L, stir, heat to 60°C and hydrolyze for 2 days to obtain PVA / SiO2 sol, add soybean oil 10 times the mass of PVA / SiO2 sol, stir for 1 hour, add glutaraldehyde in an amount of 0.3 g / g PVA, stir for 3 hours, centrifuge, wash, and dry to obtain PVA-modified SiO2; take 25 parts of PVA-modified SiO2, 80 parts of water, 60 parts of ethanol, and 3 parts of silane coupling agent KH-171, heat to 50°C, stir for 5 hours, filter, and dry to obtain modified silica;

[0057] S2: Take chloroether resin and 1 times its mass of ethylene glycol butyl ether, heat to 100°C under nitrogen protection, stir until the chloroether resin is dissolved to obtain a chloroether resin solution; take EVOH, soak it in a 3 mol / L NaOH ethanol solution at 30°C for 40 minutes, then add the chloroether resin solution and soak it at 40°C for 3 hours to obtain a modifier, with a molar ratio of chloroether resin to EVOH of 1.5:1; take 30 parts of methyl methacrylate, 10 parts of acrylic acid, 10 parts of styrene, 60 parts of butyl acrylate, 45 parts of modifier, and 2 parts of benzoyl peroxide, heat to 100°C under nitrogen protection and react for 5 hours to obtain a high barrier glue;

[0058] S3: Take 25 parts of acrylamide, 20 parts of acrylic acid, 30 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate phosphate, 100 parts of ethanol, and 1 part of benzoyl peroxide, heat to 70°C, keep warm for 2 hours, cool, adjust the pH to 7, and dry to obtain a dispersant;

[0059] S4: Take 6 parts of methyl acrylate, 8 parts of butyl acrylate, 4 parts of methyl methacrylate, 10 parts of acrylic acid, 3 parts of dispersant, 8 parts of modified silica, 8 parts of high barrier glue, and 80 parts of ethanol, and stir at a speed of 1200 m / min for 4 hours to obtain a laser layer coating;

[0060] S5: Take the BOPP layer and apply laser coating on one side. The dry coating amount is 1g / m 2, laser holographic molding is performed on a laser molding machine at a temperature of 160°C and a molding speed of 50m / min to obtain a BOPP laser film; a vacuum aluminizing machine heats the aluminum wire to 1300°C under a vacuum condition of 0.004Pa to vaporize it, and then adheres it to the BOPP laser film to form an aluminum-plated layer with a thickness of 100nm to obtain a BOPP aluminized laser film; a laminating machine is used to continue to melt the PE plastic particles and then coat them on the aluminum-plated surface of the BOPP aluminized laser film to form a 4μm protective layer, and an aluminized high-barrier composite laser packaging film is obtained.

[0061] In the above examples, all raw materials are from the following sources: PVA (PVA1788, Kramar); tetraethyl orthosilicate (CAS: 562-90-3); soybean oil (Article No.: S24362, Shanghai Yuanye); glutaraldehyde (CAS: 111-30-8); ethanol (CAS: 64-17-5); silane coupling agent (KH-171, Huaian Heyuan Chemical Co., Ltd.); chloroether resin (MP-25, Jiangsu Liside New Materials Co., Ltd.); ethylene glycol butyl ether (diethylene glycol butyl ether, CAS: 112-34-5); EVOH (G156B, Ningbo Qihuida Materials Technology Co., Ltd.); methyl methacrylate (CAS: 80-62-6 ); acrylic acid (CAS: 79-10-7); styrene (CAS: 100-42-5); butyl acrylate (CAS: 141-32-2); benzoyl peroxide (CAS: 94-36-0); acrylamide (CAS: 79-06-1); 2-hydroxyethyl methacrylate phosphate (CAS: 52628-03-2); methyl acrylate (CAS: 96-33-3); BOPP layer (HP2622, Dongguan Langfeng Plastic Raw Materials Co., Ltd.); aluminum wire (purity >99.9%, Huainan Kedi Chemical Technology Co., Ltd.); PE plastic particles (LJA-322, Dongguan Jinshixiang Plastic Raw Materials Co., Ltd.).

[0062] Experiment: Take the aluminum-plated high-barrier composite laser packaging films prepared in Examples 1 to 3 and Comparative Examples 1 to 4; (1) refer to ASTM F1249-2020 to test the water vapor transmission rate; (2) refer to DIN 53360-3 to test the oxygen transmission rate; specific data are shown in the table below;

[0063]

[0064] Conclusion: From the table above, in Comparative Example 1, PVA is not introduced into the modified silica, resulting in poor gas barrier performance; in Comparative Example 2, the amount of modifier added is changed, and the barrier properties to water and gas are not as good as those in the embodiment; in Comparative Example 3, EVOH is used instead of the modifier, and the water vapor permeability increases. This is because EVOH contains hydrophilic vinyl alcohol, and not using chloroether resin modification will lead to a decrease in its barrier properties to water; in Comparative Example 4, the amount of dispersant, modified silica, high-barrier glue, and double-bond monomer added to the laser layer coating is changed, and the barrier performance decreases significantly. Increasing the amount of modified silica leads to a decrease in film forming properties, and even precipitation destroys the integrity of the film. Excessive glue addition will also lead to excessive viscosity, which will cause back-sticking during molding and affect the molding effect. In summary, the aluminum-plated high-barrier composite laser packaging film prepared by the present invention has good water and gas barrier effects and is very practical.

[0065] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention, but the scope of protection of this application is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the spirit and principles of the present invention and within the technical scope disclosed in this application should be included in the scope of protection of this application. The embodiments and features of the embodiments of this application can be combined with each other unless there is a conflict. Therefore, the scope of protection of this application should be based on the scope of protection of the claims.

Claims

1. A process for preparing an aluminum-plated high-barrier composite laser packaging film, characterized by: The following steps are involved: S1: Take double bond monomer, dispersant, modified silica, high barrier glue, and ethanol, stir, and obtain laser layer coating; S2: Take the BOPP layer, apply a laser layer coating on one side thereof, and perform laser holographic molding on a laser molding machine to obtain a BOPP laser film; heat and vaporize the aluminum wire under vacuum conditions, and adhere it to the BOPP laser film to form an aluminum-plated layer to obtain a BOPP aluminum-plated laser film; melt PE plastic particles and apply them on the aluminum-plated surface of the BOPP aluminum-plated laser film to form a protective layer to obtain an aluminum-plated high-barrier composite laser packaging film; The double bond monomer includes at least one of methyl acrylate, butyl acrylate, methyl methacrylate, acrylic acid, acrylamide, 2-hydroxyethyl methacrylate phosphate, and styrene; The laser layer coating comprises the following raw materials, calculated by weight: 15-40 parts of double bond monomer, 1-2 parts of dispersant, 3-6 parts of modified silica, 3-6 parts of high barrier glue, and 60-80 parts of ethanol; the double bond monomer in the laser layer coating comprises 5-10 parts of methyl acrylate, 5-10 parts of butyl acrylate, 1-5 parts of methyl methacrylate, and 5-10 parts of acrylic acid; The preparation of the high-barrier glue comprises the following steps: taking EVOH, treating it with alkali, adding a chloroether resin solution, and soaking it at 30-40°C for 2-3 hours to obtain a modifier; taking a double bond monomer, the modifier, and benzoyl peroxide, heating it to 80-100°C under nitrogen protection, and reacting it for 4-6 hours to obtain the high-barrier glue; In the modifier, the molar ratio of the chloroether resin to the EVOH is (1-2):1; the high-barrier glue comprises the following raw materials, calculated by mass: 80-150 parts of a double bond monomer, 40-50 parts of a modifier, and 1-3 parts of benzoyl peroxide; the double bond monomer in the high-barrier glue comprises 20-30 parts of methyl methacrylate, 10-20 parts of acrylic acid, 10-20 parts of styrene, and 50-60 parts of butyl acrylate; The preparation of the dispersant comprises the following steps: taking a double bond monomer, ethanol, and benzoyl peroxide, heating to 70-80° C., keeping the temperature for 1-2 hours, adjusting the pH to 7-8 after cooling, and drying to obtain the dispersant; The dispersant comprises the following raw materials, calculated by mass: 60-120 parts of double bond monomer, 80-100 parts of ethanol, and 1-2 parts of benzoyl peroxide; the double bond monomer in the dispersant comprises 20-30 parts of acrylamide, 20-30 parts of acrylic acid, 20-30 parts of butyl acrylate, and 5-10 parts of 2-hydroxyethyl methacrylate phosphate; The preparation of the modified silica comprises the following steps: taking a PVA aqueous solution and tetraethyl orthosilicate, stirring, adjusting the hydrogen ion concentration to 0.05-0.25 mol / L, heating to 60-70° C. and hydrolyzing for 2-3 days to obtain a PVA / SiO2 sol, adding soybean oil, stirring for 1-2 hours, adding glutaraldehyde, stirring for 2-3 hours, centrifuging, washing, and drying to obtain PVA-modified SiO2; taking the PVA-modified SiO2, water, ethanol, and a silane coupling agent, heating to 40-60° C., stirring for 4-6 hours, filtering, and drying to obtain the modified silica; The mass of PVA in the PVA aqueous solution is 5~8%; the PVA-modified SiO2 includes the following raw materials, calculated by mass: 100 parts of PVA aqueous solution, 20~30 parts of tetraethyl orthosilicate; the amount of soybean oil added is 10~15 times the mass of PVA / SiO2 sol; the amount of glutaraldehyde added is 0.1~0.4g / g PVA; the modified silica includes the following raw materials, calculated by mass: 20~30 parts of PVA-modified SiO2, 60~80 parts of water, 60~80 parts of ethanol, and 1~3 parts of silane coupling agent.

2. The aluminized high-barrier composite laser packaging film prepared according to the preparation process of the aluminized high-barrier composite laser packaging film according to claim 1.

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