A ptp aluminum foil composite film and a method for manufacturing the same

Abstract

The application belongs to the field of medicine packaging film, and specifically provides a PTP aluminum foil composite film and a preparation method thereof. The PTP aluminum foil composite film comprises, in sequence, a heat-sealing adhesive layer, an inner printing layer, an aluminum foil, an outer printing layer, an inner protective layer and an outer protective layer. The inner protective layer is formed by coating a protective agent comprising OP varnish and a barrier agent on the outer printing layer and then curing. The PTP aluminum foil composite film prepared by the application has good water vapor barrier effect and high breaking strength.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of medicine packaging film, and particularly relates to a PTP aluminum foil composite film and a preparation method thereof. BACKGROUND

[0002] The PTP aluminum foil is a key material for packaging in the fields of medicines, foods and the like. The high-purity aluminum foil substrate endows the PTP aluminum foil with excellent ductility and formability, can adapt to the stamping process of blister packaging, and accurately fits the form of the packaged product. Meanwhile, the PTP aluminum foil has excellent light shielding property, can block light from damaging the sensitive contents, avoids degradation and oxidation of the contents due to light, and guarantees stable product quality. The bonding layer ensures firm combination between the layers, the printing layer realizes the function of identification and information transmission, and the protective layer improves the surface wear resistance and anti-pollution ability, thereby providing comprehensive protection for packaging processing and use.

[0003] Relying on these performance advantages, the PTP aluminum foil is widely applied in the medical industry and is a core material for blister packaging of solid oral preparations such as tablets and capsules. In the application of packaging, the PTP aluminum foil can realize sealed packaging through a specific process, form an independent protection space, can realize single-dose packaging of medicines, facilitate accurate use of medicines by patients, can isolate oxygen, moisture and the like in the external environment from affecting the medicines, prolong the shelf life of the medicines, and can also avoid damage to the medicines due to collision and friction during transportation and storage, thereby guaranteeing the quality and safety of the medicines.

[0004] In actual application, the water vapor barrier property and the rupture strength of the PTP aluminum foil directly affect the protection effect and use reliability of the packaging. In terms of the water vapor barrier property, although the PTP aluminum foil as a whole has certain barrier ability, the weak links for water vapor penetration may be formed at the combined parts between the layers or in the process of processing. Under long-term storage or in harsh environmental conditions, external water vapor is easy to penetrate into the packaging through these weak links, thereby causing the contents to be damp and deteriorated. In terms of the rupture strength, the overall thickness of the PTP aluminum foil is relatively thin due to the demand for lightweight packaging, and the impact resistance and rupture resistance are relatively limited. During processing, transportation and use, the PTP aluminum foil is easy to be broken due to extrusion, collision or improper operation, thereby damaging the sealing property of the packaging and further causing contamination or damage of the contents. Therefore, improving the water vapor barrier property and the rupture strength of the PTP aluminum foil has become a key direction in the current research and application of this type of packaging material. SUMMARY

[0005] In order to further improve the barrier property and mechanical property of the PTP aluminum foil, the application provides a PTP aluminum foil composite film and a preparation method thereof.

[0006] The application first provides a PTP aluminum foil composite film, which comprises, in sequence, a heat-sealing adhesive layer, an inner printing layer, an aluminum foil, an outer printing layer, an inner protective layer and an outer protective layer.

[0007] The inner protective layer is formed by applying a protective agent onto the outer printed layer and then curing it.

[0008] The protective agent includes OP varnish and a barrier agent;

[0009] The barrier agent is prepared by loading magnesium oxide onto pretreated montmorillonite and then grafting it with polyether molecules.

[0010] Furthermore, the preparation method of the barrier agent includes the following steps:

[0011] S1: After mixing the pretreated montmorillonite and solvent, add magnesium chloride, stir for a period of time, concentrate, dry, pulverize, and calcine to obtain modified montmorillonite.

[0012] S2: Mix modified montmorillonite and xylene, then add epoxy silane and react. Next, add alkyl alcohol and polymerize under the action of a catalyst. After the reaction is complete, centrifuge, wash, and dry to obtain the barrier agent.

[0013] Furthermore, the pretreated montmorillonite is obtained by sequentially treating montmorillonite with acid, hydrogen peroxide solution, and arginine aqueous solution.

[0014] Furthermore, the mass ratio of the OP varnish to the barrier agent is (50-60):1.

[0015] Furthermore, in step S1, the solvent is a mixture of deionized water and ethanol in a mass ratio of (4-5.8):1.

[0016] Furthermore, in step S1, the calcination process parameters are: temperature 500-600℃, heating rate 4-6℃ / min.

[0017] Furthermore, in step S2, the polymerization reaction is carried out at a temperature of 50-60°C for 2-3 hours.

[0018] Furthermore, the mass percentage concentration of the arginine aqueous solution is 20%-22%.

[0019] This application also provides a method for preparing a PTP aluminum foil composite film, comprising the following steps:

[0020] 1) Remove the aluminum foil and print the ink on the bright and dark sides of the aluminum foil to form an inner printing layer and an outer printing layer. Dry the printed aluminum foil to obtain a first-processed aluminum foil.

[0021] 2) Apply the protective agent evenly to the outer printed layer of the primary-treated aluminum foil, dry it to form an inner protective layer, and obtain the secondary-treated aluminum foil;

[0022] 3) Apply OP varnish evenly to the inner protective layer of the secondary-treated aluminum foil, dry it to form the outer protective layer, and obtain the tertiary-treated aluminum foil;

[0023] 4) Apply the adhesive evenly to the inner printed layer of the three-stage aluminum foil, dry, roll up, and cut to obtain the PTP aluminum foil composite film.

[0024] Furthermore, in step 2), the dry weight of the protective agent coating is 1.2-1.4 g / m². 2 ;

[0025] And / or, in step 4), the dry coating weight of the adhesive is 2.8-3.2 g / m³. 2 .

[0026] Compared with the prior art, this application has the following beneficial effects:

[0027] 1. The layered structure of montmorillonite creates a highly efficient barrier with a "maze effect" in the membrane layer, extending the penetration distance and time of small molecules and blocking their contact with the aluminum foil substrate. At the same time, the magnesium oxide attached to the montmorillonite can effectively adsorb water molecules that have entered the membrane layer, reducing the further movement of water molecules to the aluminum foil layer and improving the stability of the composite membrane.

[0028] 2. The amino group in arginine has a good chelating effect on magnesium ions. Using arginine to intercalate montmorillonite increases the interlayer spacing of montmorillonite and enhances the amount of magnesium ions attached to montmorillonite, thereby improving the water vapor barrier performance of the barrier agent.

[0029] 3. Grafting polyether molecules onto the surface of montmorillonite enhances the compatibility and bonding strength between montmorillonite and the OP varnish matrix, allowing the montmorillonite to be uniformly dispersed in the inner protective layer. Within the inner protective layer, the montmorillonite acts as a micro-support framework, bridging microcracks and dispersing stress under external forces, thereby improving the mechanical properties of the composite membrane. Furthermore, the long-chain alkyl groups at the ends of the polyether molecules possess excellent hydrophobic properties, reducing the penetration of water vapor into the interior of the composite membrane, thus improving the water resistance and stability of the composite membrane. Attached Figure Description

[0030] Figure 1 The results show the water vapor barrier performance of the PTP aluminum foil composite films in Examples 1-3 and Control Groups 1-2 of this application.

[0031] Figure 2 The results are the burst strength test results of the PTP aluminum foil composite films in Examples 1-3 and Control Groups 1-2 of this application. Detailed Implementation

[0032] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0034] When using “including,” “having,” and “contains” as described herein, the intention is to cover non-exclusive inclusion, unless an explicit qualifying term such as “only,” “consisting of,” etc., is used, in which case another component may be added.

[0035] The terms "preferred," "more preferably," "better," and "even better" used in this application refer to embodiments of this application that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this application. That is, in this application, "preferred," "more preferably," "better," and "even better" are merely descriptions of implementations or embodiments with better effects, but do not constitute a limitation on the scope of protection of this application.

[0036] In this application, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0037] In this application, "at least one" means one or more, such as one, two, or more. "Multiple" or "several" means at least two, such as two, three, etc., and "multi-layered" means at least two layers, such as two layers, three layers, etc., unless otherwise explicitly specified. In the description of this application, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0038] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0039] Unless otherwise specified, all steps in this application may be performed sequentially or randomly. For example, the method comprising steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order; for example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc. Unless otherwise stated, singular terms may include plural forms and should not be construed as having a quantity of one.

[0040] In this application, "above" or "below" includes the number itself. For example, "below 1" includes 1.

[0041] In this application, room temperature refers to 0-40°C, including but not limited to 10-40°C, or further to 20-30°C.

[0042] Based on extensive experimental research, this application provides a PTP aluminum foil composite film, which sequentially includes a heat-sealing adhesive layer, an inner printing layer, an aluminum foil, an outer printing layer, an inner protective layer, and an outer protective layer.

[0043] The inner protective layer is formed by applying a protective agent onto the outer printed layer and then curing it.

[0044] The protective agent includes OP varnish and a barrier agent;

[0045] The barrier agent is prepared by loading magnesium oxide onto pretreated montmorillonite and then grafting it with polyether molecules.

[0046] In some embodiments of this application, the method for preparing the barrier agent includes the following steps:

[0047] S1: After mixing the pretreated montmorillonite and solvent, add magnesium chloride, stir at 300-500 rpm for 30-60 min, then sonicate at 25-40 kHz for 15-20 min, concentrate at 50-60℃, dry, pulverize, and calcine to obtain modified montmorillonite.

[0048] S2: Mix modified montmorillonite and xylene, then add epoxy silane and react at a temperature of 70-75℃ for 3-4 hours. Then add alkyl alcohol and polymerize under the action of a catalyst. After the reaction is complete, centrifuge, wash, and dry to obtain the barrier agent.

[0049] In some embodiments of this application, the preparation method of the pretreated montmorillonite includes the following steps: montmorillonite and acid solution are mixed and stirred for 40-60 min, then allowed to stand for 20-30 min, followed by the addition of a hydrogen peroxide solution with a mass percentage concentration of 25%-30%, and stirring is continued for 30-40 min. After centrifugation, washing, and drying, the mixture is mixed evenly with deionized water, and then an arginine aqueous solution is added at a rate of 3-4 mL / min. After the addition is completed, the mixture is allowed to stand, sonicated, centrifuged, washed, and dried to obtain the pretreated montmorillonite.

[0050] In some embodiments of this application, the mass ratio of the OP varnish to the barrier agent is (50-60):1.

[0051] In some specific embodiments of this application, the mass ratio of the OP varnish to the barrier agent can be (50-52):1, (52-54):1, (54-56):1, (56-58):1, or (58-60):1; typically, but not limitingly, it can be 50:1, 54:1, or 56:1.

[0052] In some embodiments of this application, in step S1, the solvent is a mixture of deionized water and ethanol in a mass ratio of (4-5.8):1.

[0053] In some specific embodiments of this application, the mass ratio of deionized water to ethanol can be (4-4.3):1, (4.3-4.6):1, (4.6-4.9):1, (4.9-5.2):1, (5.2-5.5):1, or (5.5-5.8):1; typically, but not limitingly, it can be 4.5:1 or 5.6:1.

[0054] In some embodiments of this application, the calcination process parameters in step S1 are: temperature 500-600℃, heating rate 4-6℃ / min.

[0055] In some specific embodiments of this application, the calcination temperature can be 500-550℃ or 550-600℃; typically, but not limitingly, it can be 520℃, 550℃, or 580℃.

[0056] In some specific embodiments of this application, in step S2, the polymerization reaction temperature is 50-60°C and the time is 2-3 hours.

[0057] In some embodiments of this application, the mass percentage concentration of the arginine aqueous solution is 20%-22%.

[0058] In some specific embodiments of this application, the mass percentage concentration of the arginine aqueous solution can be 20%-20.5%, 20.5%-21%, 21%-21.5%, or 21.5%-22%; typically, but not limitingly, it can be 20% or 21%.

[0059] A second aspect of this application is to provide a method for preparing a PTP aluminum foil composite film, comprising the following steps:

[0060] 1) Remove the aluminum foil and print the ink on the bright and dark sides of the aluminum foil to form an inner printing layer and an outer printing layer. Dry the printed aluminum foil to obtain a first-processed aluminum foil.

[0061] 2) Apply the protective agent evenly to the outer printed layer of the primary-treated aluminum foil, dry it to form an inner protective layer, and obtain the secondary-treated aluminum foil;

[0062] 3) Apply OP varnish evenly to the inner protective layer of the secondary-treated aluminum foil, dry it to form the outer protective layer, and obtain the tertiary-treated aluminum foil;

[0063] 4) Apply the adhesive evenly to the inner printed layer of the three-stage aluminum foil, dry, roll up, and cut to obtain the PTP aluminum foil composite film.

[0064] In some embodiments of this application, in step 2), the dry weight of the protective agent coating is 1.2-1.4 g / m². 2 ;

[0065] And / or, in step 4), the dry coating weight of the adhesive is 2.8-3.2 g / m³. 2 .

[0066] The present application will be further illustrated by the following examples, but these examples do not limit the scope of the present application.

[0067] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in this application, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. All reagents or instruments whose manufacturers are not specified are conventional products that can be purchased commercially. In addition to the specific methods, equipment, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description in this application, any prior art methods, equipment, and materials similar to or equivalent to those described, used, or made by the methods, equipment, and materials in the embodiments of this application may be used to implement this application.

[0068] The OP-001 varnish used in the embodiments and control group of this application is from Chengdu Tuozhan New Material Co., Ltd.; the VC-1100A adhesive used in the embodiments and control group of this application is from Zhejiang Chengying New Material Co., Ltd.; the black ink used in the embodiments and control group of this application is from Shengweike Ink Co., Ltd.; and the nano-montmorillonite used in the embodiments and control group of this application is from Hubei Weideli Chemical Technology Co., Ltd., model HBWS-M66.

[0069] Example 1

[0070] The preparation method of the barrier agent in this embodiment is as follows:

[0071] S1: Weigh 50g of nano-montmorillonite into a 500mL beaker, add 100mL of 10% hydrochloric acid aqueous solution, stir for 60min, let stand for 30min, then add 4.2mL of 30% hydrogen peroxide solution, continue stirring for 30min, then centrifuge, wash, dry, and mix evenly with 600g of deionized water. Then add 100g of 21% L-arginine aqueous solution at a rate of 3mL / min. After the addition is completed, let stand for 30min, sonicate at 35kHz for 50min, let stand for 3h, centrifuge, wash, and dry at 60℃ for 8h to obtain pretreated montmorillonite.

[0072] S2: Weigh 55g of pretreated montmorillonite into a 1000mL beaker, add 450g of deionized water and 100g of ethanol, stir at 300rpm for 30min, then sonicate at 25kHz for 20min, add 2.2g of magnesium chloride while stirring continuously, continue stirring for 1.5h, evaporate and concentrate to a paste at 50℃, dry at 70℃ for 10h, pulverize, heat to 520℃ at a heating rate of 4℃ / min, calcine for 3h to obtain modified montmorillonite;

[0073] S3: Weigh 15g of modified montmorillonite into a 500mL three-necked flask, add 300mL of xylene, stir and mix evenly, then add 4.5g of KH-560 under a nitrogen atmosphere, heat to 70℃, and react at a constant temperature for 4h. Then adjust the temperature to 50℃, add 3.8g of n-dodecyl alcohol, stir evenly, then add 1g of sodium hydroxide and 0.25g of benzyltriethylammonium chloride, and react for 3h. After the reaction is completed, centrifuge, wash, and dry to obtain the barrier agent.

[0074] The preparation method of the PTP aluminum foil composite film in this embodiment is as follows:

[0075] 1) Take out an aluminum foil with a thickness of 20μm, mix black ink and isopropanol at a mass ratio of 3:1, and print them on the bright and dark sides of the aluminum foil to form an inner printing layer and an outer printing layer. Dry the printed aluminum foil at a temperature of 80℃ to obtain a first-processed aluminum foil.

[0076] 2) Mix OP-001 varnish, barrier agent, and ethyl acetate at a mass ratio of 50:1:10 until homogeneous, then evenly coat the mixture onto the outer printing layer of the primary-treated aluminum foil. The dry coating weight is 1.2 g / m². 2 The aluminum foil is then placed in an oven for drying. The temperatures in each zone of the oven are: 180℃ in zone 1, 180℃ in zone 2, and 190℃ in zone 3, forming an inner protective layer and resulting in a secondary-treated aluminum foil.

[0077] 3) Mix OP-001 varnish and ethyl acetate at a mass ratio of 1:0.15 until homogeneous, then evenly coat the mixture onto the inner protective layer of the secondary-treated aluminum foil. The dry coating weight is 0.8 g / m². 2 The aluminum foil is then placed in an oven for drying. The temperatures in each zone of the oven are: 180℃ in zone 1, 190℃ in zone 2, and 200℃ in zone 3, forming an outer protective layer and resulting in a three-stage processed aluminum foil.

[0078] 4) Mix VC-1100A and ethyl acetate at a mass ratio of 1:0.2 until homogeneous, then evenly coat the mixture onto the inner printing layer of the triple-treated aluminum foil. The dry coating weight is 3.2 g / m². 2 The film is then placed in an oven for drying. The temperatures in each zone of the oven are: 150℃ in zone 1, 170℃ in zone 2, 190℃ in zone 3, and 200℃ in zone 4. After drying, the film is rolled up and cut to obtain a PTP aluminum foil composite film.

[0079] Example 2

[0080] The preparation method of the barrier agent in this embodiment is as follows:

[0081] S1: Weigh 50g of nano-montmorillonite into a 500mL beaker, add 100mL of 10% hydrochloric acid aqueous solution, stir for 40min, let stand for 20min, then add 4.5mL of 25% hydrogen peroxide solution, continue stirring for 40min, then centrifuge, wash, dry, and mix evenly with 600g of deionized water. Then add 100g of 21% L-arginine aqueous solution at a rate of 4mL / min. After the addition is completed, let stand for 30min, sonicate at 45kHz for 50min, let stand for 3h after sonication, centrifuge, wash, and dry at 60℃ for 8h to obtain pretreated montmorillonite.

[0082] S2: Weigh 57g of pretreated montmorillonite into a 1000mL beaker, add 560g of deionized water and 100g of ethanol, stir at 500rpm for 60min, then sonicate at 40kHz for 15min, add 2.5g of magnesium chloride while stirring continuously, continue stirring for 2h, evaporate and concentrate to a paste at 60℃, dry at 70℃ for 10h, pulverize, heat to 580℃ at a heating rate of 5℃ / min, calcine for 3h to obtain modified montmorillonite;

[0083] S3: Weigh 15g of modified montmorillonite into a 500mL three-necked flask, add 300mL of xylene, stir and mix evenly, then add 4.3g of KH-560 under a nitrogen atmosphere, heat to 75℃, and react at a constant temperature for 3h. Then adjust the temperature to 50℃, add 3.8g of n-dodecyl alcohol, stir evenly, then add 1g of sodium hydroxide and 0.25g of benzyltriethylammonium chloride, and react for 3h. After the reaction is completed, centrifuge, wash, and dry to obtain the barrier agent.

[0084] The preparation method of the PTP aluminum foil composite film in this embodiment is as follows:

[0085] 1) Take out an aluminum foil with a thickness of 20μm, mix black ink and isopropanol at a mass ratio of 3:1, and print them on the bright and dark sides of the aluminum foil to form an inner printing layer and an outer printing layer. Dry the printed aluminum foil at a temperature of 90℃ to obtain a first-processed aluminum foil.

[0086] 2) Mix OP-001 varnish, barrier agent, and ethyl acetate at a mass ratio of 54:1:10.5 until homogeneous, then evenly coat the mixture onto the outer printing layer of the primary-treated aluminum foil. The dry coating weight is 1.3 g / m². 2 The aluminum foil is then placed in an oven for drying. The temperatures in each zone of the oven are: 180℃ in zone 1, 190℃ in zone 2, and 190℃ in zone 3, forming an inner protective layer and resulting in a secondary-treated aluminum foil.

[0087] 3) Mix OP-001 varnish and ethyl acetate at a mass ratio of 1:0.15 until homogeneous, then evenly coat the mixture onto the inner protective layer of the secondary-treated aluminum foil. The dry coating weight is 0.8 g / m². 2 The aluminum foil is then placed in an oven for drying. The temperatures in each zone of the oven are: 180℃ in zone 1, 190℃ in zone 2, and 190℃ in zone 3, forming an outer protective layer and resulting in a three-stage processed aluminum foil.

[0088] 4) Mix VC-1100A and ethyl acetate at a mass ratio of 1:0.2 until homogeneous, then evenly coat the mixture onto the inner printing layer of the three-stage treated aluminum foil. The dry coating weight is 2.8 g / m². 2 The film is then placed in an oven for drying. The temperatures in each zone of the oven are: Zone 1 160℃, Zone 2 180℃, Zone 3 190℃, and Zone 4 200℃. After drying, the film is rolled up and cut to obtain a PTP aluminum foil composite film.

[0089] Example 3

[0090] The preparation method of the barrier agent in this embodiment is as follows:

[0091] S1: Weigh 50g of nano-montmorillonite into a 500mL beaker, add 100mL of 10% hydrochloric acid aqueous solution, stir for 50min, let stand for 25min, then add 4mL of 27% hydrogen peroxide solution, continue stirring for 35min, then centrifuge, wash, dry, and mix evenly with 600g of deionized water. Then add 100g of 20% L-arginine aqueous solution at a rate of 3.2mL / min. After the addition is completed, let stand for 30min, sonicate at 35kHz for 50min, let stand for 3h after sonication, centrifuge, wash, and dry at 60℃ for 8h to obtain pretreated montmorillonite.

[0092] S2: Weigh 55g of pretreated montmorillonite into a 1000mL beaker, add 500g of deionized water and 100g of ethanol, stir at 350rpm for 50min, then sonicate at 30kHz for 18min, add 2.2g of magnesium chloride while stirring continuously, continue stirring for 2h, evaporate and concentrate to a paste at 55℃, dry at 70℃ for 10h, pulverize, heat to 550℃ at a heating rate of 6℃ / min, calcine for 3h to obtain modified montmorillonite;

[0093] S3: Weigh 15g of modified montmorillonite into a 500mL three-necked flask, add 300mL of xylene, stir and mix evenly, add 5g of KH-560 under a nitrogen atmosphere, heat to 73℃, and react at a constant temperature for 3.5h. Then adjust the temperature to 50℃, add 4.2g of n-dodecyl alcohol, stir evenly, then add 1g of sodium hydroxide and 0.26g of benzyltriethylammonium chloride, and react for 3h. After the reaction is completed, centrifuge, wash and dry to obtain the barrier agent.

[0094] The preparation method of the PTP aluminum foil composite film in this embodiment is as follows:

[0095] 1) Take out an aluminum foil with a thickness of 20μm, mix black ink and isopropanol at a mass ratio of 3:1, and print them on the bright and dark sides of the aluminum foil to form an inner printing layer and an outer printing layer. Dry the printed aluminum foil at a temperature of 90℃ to obtain a first-processed aluminum foil.

[0096] 2) Mix OP-001 varnish, barrier agent, and ethyl acetate at a mass ratio of 56:1:10.5 until homogeneous, then evenly coat the mixture onto the outer printing layer of the primary-treated aluminum foil. The dry coating weight is 1.4 g / m². 2 The aluminum foil is then placed in an oven for drying. The temperatures in each zone of the oven are: 180℃ in zone 1, 180℃ in zone 2, and 200℃ in zone 3, forming an inner protective layer and resulting in a secondary-treated aluminum foil.

[0097] 3) Mix OP-001 varnish and ethyl acetate at a mass ratio of 1:0.15 until homogeneous, then evenly coat the mixture onto the inner protective layer of the secondary-treated aluminum foil. The dry coating weight is 0.8 g / m². 2 The aluminum foil is then placed in an oven for drying. The temperatures in each zone of the oven are: 190℃ in zone 1, 190℃ in zone 2, and 200℃ in zone 3, forming an outer protective layer and resulting in a three-stage processed aluminum foil.

[0098] 4) Mix VC-1100A and ethyl acetate at a mass ratio of 1:0.2 until homogeneous, then evenly coat the mixture onto the inner printing layer of the triple-treated aluminum foil. The dry coating weight is 3 g / m². 2 The film is then placed in an oven for drying. The temperatures in each zone of the oven are: Zone 1 140℃, Zone 2 170℃, Zone 3 200℃, and Zone 4 200℃. The film is then wound up and cut to obtain a PTP aluminum foil composite film.

[0099] Control group 1

[0100] The preparation method of the barrier agent in this control group is as follows:

[0101] S1: Weigh 50g of nano-montmorillonite into a 500mL beaker, add 100mL of 10% hydrochloric acid aqueous solution, stir for 60min, let stand for 30min, then add 4.2mL of 30% hydrogen peroxide solution, continue stirring for 30min, then centrifuge, wash, dry, and calcine at a heating rate of 4℃ / min to 520℃ for 3h to obtain modified montmorillonite;

[0102] S2: Weigh 15g of modified montmorillonite into a 500mL three-necked flask, add 300mL of xylene, stir and mix evenly, then add 4.5g of KH-560 under a nitrogen atmosphere, heat to 70℃, and react at a constant temperature for 4h. Then adjust the temperature to 50℃, add 3.8g of n-dodecyl alcohol, stir evenly, then add 1g of sodium hydroxide and 0.25g of benzyltriethylammonium chloride, and react for 3h. After the reaction is completed, centrifuge, wash, and dry to obtain the barrier agent.

[0103] The preparation method of the PTP aluminum foil composite film in this control group is the same as that in Example 1.

[0104] Control group 2

[0105] The preparation method of the barrier agent in this control group is as follows:

[0106] S1: Weigh 50g of nano-montmorillonite into a 500mL beaker, add 100mL of 10% hydrochloric acid aqueous solution, stir for 60min, let stand for 30min, then add 4.2mL of 30% hydrogen peroxide solution, continue stirring for 30min, then centrifuge, wash, dry, and mix evenly with 600g of deionized water. Then add 100g of 21% L-arginine aqueous solution at a rate of 3mL / min. After the addition is completed, let stand for 30min, sonicate at 35kHz for 50min, let stand for 3h, centrifuge, wash, and dry at 60℃ for 8h to obtain pretreated montmorillonite.

[0107] S2: Weigh 55g of pretreated montmorillonite into a 1000mL beaker, add 450g of deionized water and 100g of ethanol, stir at 300rpm for 30min, then sonicate at 25kHz for 20min, add 2.2g of magnesium chloride while stirring continuously, continue stirring for 1.5h, evaporate and concentrate to a paste at 50℃, dry at 70℃ for 10h, pulverize, heat to 520℃ at a heating rate of 4℃ / min, calcine for 3h to obtain the barrier agent.

[0108] The preparation method of the PTP aluminum foil composite film in this control group is the same as that in Example 1.

[0109] Performance testing

[0110] 1. Water vapor transmission rate: The water vapor barrier performance of PTP aluminum foil composite film was tested according to standard GB / T 1037-2021. The sample size was a circle with a diameter of 7cm, the diameter of the wet penetration cup was 6cm, the desiccant was anhydrous calcium chloride, and the temperature and relative humidity of the constant temperature and humidity chamber were 38℃ and 90%. The test results are as follows. Figure 1 As shown.

[0111] 2. Bursting Strength: Referring to Clause 6.4.6 of GB 12255-90 standard, the bursting strength of the PTP aluminum foil composite film was tested. The sample size was 40mm × 40mm. The test results are as follows: Figure 2 As shown.

[0112] 3. The appearance, pinholes, heat-sealing strength of the adhesive layer, heat resistance of the protective layer, unwinding performance, and adhesive coating amount of the PTP aluminum foil composite film were tested. The test results are shown in Table 1 below.

[0113] Table 1 Performance test results of PTP aluminum foil composite film

[0114]

[0115] Analysis of Examples 1-3 and Control Group 1, combined with Table 1, Figure 1 and Figure 2 It can be seen that, compared with control group 1, in the preparation process of the barrier agent, magnesium oxide was loaded onto the montmorillonite layer in Examples 1-3, which stabilized the interlayer structure of the montmorillonite and improved its mechanical properties. Furthermore, the hygroscopic properties of magnesium oxide enabled the barrier agent to have good water vapor barrier properties. Therefore, the PTP aluminum foil composite films of Examples 1-3 have good water vapor barrier properties. Analysis of Examples 1-3 and control group 2, combined with Table 1, shows... Figure 1 and Figure 2 As can be seen, in Examples 1-3 compared to Control Group 2, hydrophobic polyethers were grafted onto the surface of pretreated montmorillonite during the preparation of the barrier agent. This enhanced the compatibility between the barrier agent and OP varnish, allowed the barrier agent to be uniformly dispersed in the inner protective layer, and enabled rapid stress dispersion, effectively improving the barrier performance and tear strength of the PTP aluminum foil composite film.

[0116] Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A PTP aluminum foil composite film, characterized in that: It consists of, in sequence, a heat-sealing adhesive layer, an inner printed layer, an aluminum foil, an outer printed layer, an inner protective layer, and an outer protective layer; The inner protective layer is formed by applying a protective agent onto the outer printed layer and then curing it. The protective agent includes OP varnish and a barrier agent; The barrier agent is prepared by loading magnesium oxide onto pretreated montmorillonite and then grafting it with polyether molecules. The pretreated montmorillonite is obtained by sequentially treating montmorillonite with acid, hydrogen peroxide solution, and arginine aqueous solution. The preparation method of the barrier agent includes the following steps: S1: After mixing the pretreated montmorillonite and solvent, add magnesium chloride, stir for a period of time, concentrate, dry, pulverize, and calcine to obtain modified montmorillonite. S2: Mix modified montmorillonite and xylene, then add epoxy silane and react. Next, add alkyl alcohol and polymerize under the action of a catalyst. After the reaction is complete, centrifuge, wash, and dry to obtain the barrier agent.

2. The PTP aluminum foil composite film according to claim 1, characterized in that: The mass ratio of the OP varnish to the barrier agent is (50-60):

1.

3. The PTP aluminum foil composite film according to claim 1, characterized in that: In step S1, the solvent is a mixture of deionized water and ethanol in a mass ratio of (4-5.8):

1.

4. The PTP aluminum foil composite film according to claim 1, characterized in that: In step S1, the calcination process parameters are: temperature 500-600℃, heating rate 4-6℃ / min.

5. The PTP aluminum foil composite film according to claim 1, characterized in that: In step S2, the polymerization reaction is carried out at a temperature of 50-60℃ for 2-3 hours.

6. The PTP aluminum foil composite film according to claim 1, characterized in that: The mass percentage concentration of the arginine aqueous solution is 20%-22%.

7. A method for preparing a PTP aluminum foil composite film, characterized in that: Includes the following steps: 1) Remove the aluminum foil and print the ink on the bright and dark sides of the aluminum foil to form an inner printing layer and an outer printing layer. Dry the printed aluminum foil to obtain a first-processed aluminum foil. 2) Apply the protective agent evenly to the outer printed layer of the primary-treated aluminum foil, dry it to form an inner protective layer, and obtain the secondary-treated aluminum foil; 3) Apply OP varnish evenly to the inner protective layer of the secondary-treated aluminum foil, dry it to form the outer protective layer, and obtain the tertiary-treated aluminum foil; 4) Apply the adhesive evenly to the inner printed layer of the three-stage aluminum foil, dry, roll up, and cut to obtain the PTP aluminum foil composite film.

8. The method for preparing a PTP aluminum foil composite film according to claim 7, characterized in that: In step 2), the dry weight of the protective agent coating is 1.2-1.4 g / m². 2 ; And / or, in step 4), the dry coating weight of the adhesive is 2.8-3.2 g / m³. 2 .

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