A high-barrier composite packaging material and preparation method thereof

Abstract

The present invention belongs to the technical field of iodine barrier material preparation, and specifically discloses a high-barrier composite packaging material and a preparation method thereof. The high-barrier composite packaging material is composed of an aluminum foil layer, a vinyl resin heat-seal coating, a composite coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom; wherein the composite coating is obtained by coating a coating liquid, and the preparation of the coating liquid comprises the following steps: (1) adding PVA resin to deionized water, stirring, and then adding a first portion of functional particles, heating and stirring to obtain solution I, which is set aside; (2) adding polylactic acid to the mixed solution, stirring, and then adding a second portion of functional particles, heating and stirring to obtain solution II; (3) adding the obtained solution I to the obtained solution II, stirring evenly, and the result is that the iodine barrier packaging material prepared by the present invention has good iodine barrier, oxygen barrier, and water vapor barrier properties, good tensile strength, and excellent comprehensive properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of iodine barrier material preparation, and in particular relates to a high-barrier composite packaging material and a preparation method thereof. Background Art

[0002] Blister packaging, also known as press-through packaging (PTP), is a major form of pharmaceutical packaging, suitable for the mechanized packaging of solid dosage forms such as tablets, capsules, suppositories, and pills. However, for currently available pharmaceuticals containing a certain amount of iodine, the use of conventional PTP aluminum foil for packaging not only significantly increases iodine loss but also easily damages the aluminum foil layer, rendering the packaging completely ineffective and failing to meet iodine-blocking requirements. Therefore, the development of barrier packaging materials with high iodine-blocking properties is of vital importance.

[0003] In the prior art, the applicant's earlier patent CN220841724U discloses an iodine-barrier aluminum foil blister packaging structure, which discloses the specific composition of the packaging structure, but does not provide detailed descriptions of the materials used in each layer, especially the barrier layer; the patent document CN117183483A provides an iodine-barrier packaging material, including a cover film and a base film, the cover film including a paper layer, a first aluminum foil layer and a first PET layer stacked in sequence from top to bottom, the base film including a glue layer, a second PET layer, a second aluminum foil layer and a polyamide layer arranged in sequence from top to bottom, in the preparation process of the polyamide layer, graphite carbon nitride and other materials are used, the cost is relatively high, and the performance of the obtained packaging material, except for iodine barrier, needs to be further improved in other aspects.

[0004] After further research into relevant literature, the applicant found few reports on iodine-barrier packaging materials, with most studies focusing on water and gas barriers. However, imparting iodine-barrier properties to packaging materials is a practical challenge facing the packaging industry. Therefore, the present invention was proposed. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a high-barrier composite packaging material and a preparation method thereof, which has good iodine barrier function, good mechanical properties and excellent comprehensive performance.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a high-barrier composite packaging material, which is composed of an aluminum foil layer, a vinyl resin heat-seal coating, a composite coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0008] The composite coating is obtained by coating with a coating liquid, and the preparation of the coating liquid includes the following steps:

[0009] (1) PVA resin is added to deionized water, stirred, and then the first part of functional particles is added. After heating and stirring, solution I is obtained and set aside.

[0010] (2) Adding polylactic acid to the mixed solution, stirring, and then adding the second part of functional particles, heating and stirring, to obtain solution II;

[0011] (3) Add the obtained solution I to the obtained solution II and stir evenly.

[0012] Preferably, in step (1), the mass ratio of PVA resin, deionized water, and the first part of functional particles is 60-80:10-15:4-8; the stirring treatment temperature is 50-65°C, and the treatment time is 2-6 hours;

[0013] In step (2), the mass ratio of polylactic acid, the mixed solution, and the second part of functional particles is 20-40:6-12:4-8; the mass ratio of the first part of functional particles to the second part of functional particles is 1:1; the mixed solution is obtained by mixing dimethyl sulfoxide and deionized water in a volume ratio of 1:4; the stirring treatment temperature is 50-65°C, and the treatment time is 2-6 hours.

[0014] Preferably, the preparation of functional particles comprises the following steps:

[0015] S1. Modification of titanium dioxide: treating titanium dioxide in concentrated acid, filtering, washing, and drying to obtain modified titanium dioxide;

[0016] S2. Immobilization of titanium dioxide: chitosan was added to deionized water, followed by the modified titanium dioxide obtained in step S1. After stirring, acetic acid was added to adjust the pH value of the system. The system was heated and stirred. After the treatment, the system was centrifuged, washed, and dried to obtain the modified chitosan.

[0017] S3. Pre-modification of montmorillonite: adding montmorillonite to deionized water, adding CTAB under heating and stirring conditions, then maintaining the heating and stirring temperature for reaction. After the reaction is completed, filtering and drying to obtain pre-modified montmorillonite;

[0018] S4, modification of montmorillonite: adding the pre-modified montmorillonite obtained in step S3 to deionized water, stirring, adding a dopamine aqueous solution, stirring again, adding Tris-HCl buffer to adjust the pH value, heating for reaction, centrifuging, washing, and drying to obtain modified montmorillonite;

[0019] S5. Compounding: adding the modified chitosan obtained in step S2 and the modified montmorillonite obtained in step S4 into deionized water respectively, heating and stirring, and then filtering, drying, and sieving to obtain functional particles.

[0020] Preferably, in step S1, the concentrated acid is 98% concentrated sulfuric acid, the treatment temperature is 70-85° C., and the treatment time is 1-4 h; and the dosage ratio of titanium dioxide to concentrated acid is 1 g: 3-6 mL.

[0021] Preferably, in step S2, the pH value of the system is 4.5-6.5; the usage ratio of chitosan, deionized water, and modified titanium dioxide is 1 g: 5-10 mL: 0.45-0.65;

[0022] The heating and stirring treatment temperature is 30~35℃, and the treatment time is 2~6h.

[0023] Preferably, in step S3, the usage ratio of montmorillonite, deionized water, and CTAB is 1 g: 5-12 mL: 0.4-0.65 g;

[0024] The heating and stirring temperature is 70~85℃, and the reaction time is 2~6h.

[0025] Preferably, in step S4, the pH value of the system is adjusted to 8-9; the usage ratio of pre-modified montmorillonite, deionized water, and dopamine aqueous solution is 1 g: 30-60 mL: 0.8-1.2 g;

[0026] The concentration of dopamine aqueous solution is 0.45~0.85 g / mL;

[0027] The heating reaction temperature is 35~45℃ and the reaction time is 6~18h.

[0028] Preferably, in step S5, the usage ratio of modified chitosan, modified montmorillonite, and deionized water is 2 g: 0.5-0.8 g: 6-12 mL;

[0029] The heating and stirring temperature is 30~35℃, and the heating and stirring treatment time is 2~6h;

[0030] The sieving mesh number is 80~150 mesh.

[0031] In a second aspect, the present invention further provides a method for preparing the above-mentioned high-barrier composite packaging material, comprising the following steps:

[0032] (1) applying vinyl resin heat seal adhesive on the surface of the aluminum foil layer and drying to form a vinyl resin heat seal coating;

[0033] (2) applying a coating liquid on the surface of the vinyl resin heat seal coating and drying it to form a composite coating;

[0034] (3) Applying VC glue on the surface of the composite coating and drying it to form a VC glue coating;

[0035] (4) Applying polyurethane heat-sealing adhesive on the surface of the VC glue coating, and drying to form a polyurethane heat-sealing coating to obtain a semi-finished product;

[0036] (5) The semi-finished product obtained in step (4) is compounded with a polyvinyl chloride sheet and cut into pieces to obtain an iodine-blocking packaging material.

[0037] Preferably, the coating amount of the vinyl resin heat sealant is 5 to 8 g / m 2 ;

[0038] The coating amount of the coating liquid is 3~5 g / m 2 ;

[0039] The coating amount of VC glue is 4~6 g / m 2 ;

[0040] The coating amount of polyurethane heat sealant is 5~8 g / m 2 .

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] The iodine-barrier packaging material provided by the present invention is composed of a multi-layer structure, has good iodine-barrier function, good mechanical properties, and excellent comprehensive performance.

[0043] In the iodine-barrier packaging material provided by the present invention, the composite coating plays a key iodine-barrier effect. Specifically, the coating liquid used in the composite coating uses PVA and polylactic acid as the main film-forming substances. The main reason is that a single PVA resin as a film-forming substance has insufficient moldability and poor flexibility, heat sealing and mechanical strength. Therefore, polylactic acid with good oxygen barrier and heat sealing properties is introduced. However, there is a compatibility problem when the two are directly mixed. Therefore, functional particles are introduced in the present invention to modify the two separately. The functional particles are composed of a compound of organic and inorganic substances. Through specific treatment, their own dispersibility is guaranteed. Based on the rich functional groups introduced, the "lubrication" effect between PVA and polylactic acid is played, thereby improving the compatibility of PVA and polylactic acid, thereby greatly improving the barrier performance of the composite coating.

[0044] In the present invention, the functional particles are mainly composed of titanium dioxide, montmorillonite and chitosan. Titanium dioxide is introduced into PVA and polylactic acid as an inorganic filler. While improving the wear resistance of the coating, it can also effectively improve the density of the coating matrix and reduce the permeability of gas and water vapor. In order to improve its dispersibility and compatibility, the present invention performs a simple acid treatment on it to introduce groups (such as hydroxyl groups) to facilitate the improvement of its immobilization effect with chitosan. The introduction of chitosan plays a very important role in the present invention. It has very rich groups and compatibility. As a medium material, it can form a composite system with PVA resin and polylactic acid on the one hand, and on the other hand, it can form a compound with modified montmorillonite to improve the dispersibility of montmorillonite. Montmorillonite is another inorganic filler used, which can The mechanical properties, thermal stability and barrier properties of the coating are further improved by working together with titanium dioxide. During specific use, CTAB intercalation modification is first performed on it to preliminarily improve the compatibility of montmorillonite, and the twisted migration channel formed by the increase in the interlayer spacing preliminarily improves its barrier properties. In order to further improve its compatibility, dopamine is then introduced into the montmorillonite for modification in the present invention. The amino, hydroxyl and other groups contained in dopamine itself not only improve the composite properties of the modified montmorillonite and chitosan, but also form a hydrogen bond system between the amino and hydroxyl groups possessed by the functional particles and the PVA resin and polylactic acid, thereby improving the compatibility between the PVA resin and polylactic acid, as well as between the PVA resin, polylactic acid and the functional particles, thereby ensuring the barrier and mechanical properties of the coating.

[0045] The preparation method of the iodine-barrier packaging material provided by the present invention mainly uses a four-layer coating process, is simple, and is easy to implement. DETAILED DESCRIPTION

[0046] The embodiments of the present invention are described in detail below. All embodiments are exemplary and intended to be used to explain the present invention, but are not to be construed as limiting the present invention.

[0047] In the present invention, titanium dioxide was purchased from Guangzhou Leisheng Technology Co., Ltd.; montmorillonite was purchased from Guangzhou Yifeng Chemical Technology Co., Ltd.

[0048] In the present invention, VC glue was purchased from Xi'an Tianyi Adhesive Materials Co., Ltd.; vinyl resin heat sealant was purchased from Shanghai Weikai Optoelectronic New Materials Co., Ltd. with the brand name VC-1100; PVA resin was purchased from Jining Fangyu Chemical Co., Ltd. with the brand name 1799; polyurethane heat sealant was purchased from Michelman (Shanghai) Chemical Trading Co., Ltd.; polylactic acid was purchased from Nature Works, USA with the model name 3001D; and chitosan was purchased from Qingdao Yunzhou Biotechnology Co., Ltd.

[0049] In the present invention, other matters not described are conventional means known to those skilled in the art (such as coating method, drying and compounding, etc.); materials without source description are all commercially available.

[0050] It should be noted that the structure of each layer in the present invention can be adjusted according to actual needs. For example, the thickness can be selected as follows: the thickness of the aluminum foil layer is 0.032 mm, the thickness of the polyvinyl chloride sheet is 0.03 mm; the thickness of the vinyl resin heat-seal coating, the composite coating, the VC glue coating, and the polyurethane heat-seal coating are all 0.015 mm.

[0051] In the present invention, the concentration of concentrated sulfuric acid is 98%.

[0052] The coating speed and drying temperature of vinyl resin heat sealant, coating liquid, VC glue, and polyurethane heat sealant can be selected according to the actual characteristics of the product. For example, the coating speed of VC glue can be 50m / min, the drying temperature is about 160~175℃, and the composite pressure of semi-finished product and PVC sheet is 2.5kg / cm 2 The selection of the above process parameters can be actually selected by those skilled in the art as needed. The above parameters of the present invention are only examples and do not constitute a limitation on the scope of protection of the present invention. The specific implementation is subject to the ability of those skilled in the art.

[0053] Example 1

[0054] A high-barrier composite packaging material, consisting of an aluminum foil layer, a vinyl resin heat-seal coating, a composite coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0055] The composite coating is obtained by coating with a coating liquid, and the preparation of the coating liquid includes the following steps:

[0056] (1) PVA resin was added to deionized water in a mass ratio of 65:13:6 among PVA resin, deionized water and functional particles. After stirring, functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3h), solution I was obtained and set aside.

[0057] (2) According to the mass ratio of polylactic acid, mixed solution and functional particles being 35:9:6, polylactic acid was added to the mixed solution (prepared by mixing dimethyl sulfoxide and deionized water in a volume ratio of 1:4), stirred, and then the functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3h), solution II was obtained;

[0058] (3) Add the obtained solution I to the obtained solution II and stir evenly.

[0059] The preparation of functional particles includes the following steps:

[0060] S1. Modification of titanium dioxide: titanium dioxide was treated in 98% concentrated sulfuric acid (70°C, 1 h) at a ratio of 1 g titanium dioxide to concentrated acid of 5.5 mL. After the treatment, the titanium dioxide was filtered, washed, and dried to obtain modified titanium dioxide.

[0061] S2. Immobilization of titanium dioxide: Chitosan was added to deionized water, followed by the modified titanium dioxide obtained in step S1. After stirring, acetic acid was added to adjust the pH of the system to 5.5. The mixture was heated and stirred at 35°C for 3.5 hours. After the treatment, the mixture was centrifuged, washed, and dried to obtain modified chitosan. The ratio of chitosan, deionized water, and modified titanium dioxide was 1 g: 10 mL: 0.5.

[0062] S3. Pre-modification of montmorillonite: Montmorillonite was added to deionized water, and CTAB was added under heating and stirring conditions. The reaction was then carried out at a temperature of 75°C for 4 hours. After the reaction was completed, the pre-modified montmorillonite was filtered and dried. The ratio of montmorillonite, deionized water, and CTAB was 1 g:10 mL:0.5 g.

[0063] S4. Modification of montmorillonite: The pre-modified montmorillonite obtained in step S3 was added to deionized water, stirred, and then a dopamine aqueous solution (0.55 g / mL) was added. After stirring again, Tris-HCl buffer was added to adjust the pH value to 8.8. The mixture was heated for reaction (40°C, 10 h), centrifuged, washed, and dried to obtain modified montmorillonite. The ratio of the pre-modified montmorillonite, deionized water, and dopamine aqueous solution was 1 g:45 mL:0.95 g.

[0064] S5. Compounding: According to the usage ratio of modified chitosan, modified montmorillonite and deionized water of 2 g:0.65 g:10 mL, the modified chitosan obtained in step S2 and the modified montmorillonite obtained in step S4 were added to deionized water respectively, and heated and stirred (35°C, 3.5 h), and then filtered, dried and sieved through 100 mesh to obtain functional particles.

[0065] This embodiment also provides a method for preparing a high-barrier composite packaging material, comprising the following steps:

[0066] (1) On the surface of the aluminum foil layer, the pressure should be 5.5 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0067] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the coating liquid in a coating amount of , and form a composite coating after drying;

[0068] (3) On the composite coating surface according to 3.8 g / m 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0069] (4) Apply 5 g / m2 of VC glue coating on the surface. 2 Applying polyurethane heat sealing adhesive in a coating amount of , forming a polyurethane heat sealing coating after drying to obtain a semi-finished product;

[0070] (5) The semi-finished product obtained in step (4) is compounded with a polyvinyl chloride sheet, and after cutting, a high-barrier composite packaging material is obtained.

[0071] Example 2

[0072] A high-barrier composite packaging material, consisting of an aluminum foil layer, a vinyl resin heat-seal coating, a composite coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0073] The composite coating is obtained by coating with a coating liquid, and the preparation of the coating liquid includes the following steps:

[0074] (1) PVA resin was added to deionized water in a mass ratio of 65:12:6 to deionized water, and functional particles were added after stirring (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3h), solution I was obtained and set aside.

[0075] (2) According to the mass ratio of polylactic acid, mixed solution and functional particles being 35:10:6, polylactic acid was added to the mixed solution (prepared by mixing dimethyl sulfoxide and deionized water in a volume ratio of 1:4), stirred, and then the functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3.5h), solution II was obtained;

[0076] (3) Add the obtained solution I to the obtained solution II and stir evenly.

[0077] The preparation of functional particles includes the following steps:

[0078] S1. Modification of titanium dioxide: titanium dioxide was treated in 98% concentrated sulfuric acid (75°C, 0.5 h) at a ratio of 1 g titanium dioxide to concentrated acid (6 mL). After the treatment, the titanium dioxide was filtered, washed, and dried to obtain modified titanium dioxide.

[0079] S2. Immobilization of titanium dioxide: Chitosan was added to deionized water, followed by the modified titanium dioxide obtained in step S1. After stirring, acetic acid was added to adjust the pH of the system to 5.5. The mixture was heated and stirred at 35°C for 4 hours. After the treatment, the mixture was centrifuged, washed, and dried to obtain modified chitosan. The ratio of chitosan, deionized water, and modified titanium dioxide was 1 g: 10 mL: 0.5.

[0080] S3. Pre-modification of montmorillonite: Montmorillonite was added to deionized water, and CTAB was added under heating and stirring conditions. The reaction was then carried out at a temperature of 75°C for 4 hours. After the reaction was completed, the pre-modified montmorillonite was filtered and dried. The ratio of montmorillonite, deionized water, and CTAB was 1 g:10 mL:0.5 g.

[0081] S4. Modification of montmorillonite: The pre-modified montmorillonite obtained in step S3 was added to deionized water, stirred, and then a dopamine aqueous solution (0.55 g / mL) was added. After stirring again, Tris-HCl buffer was added to adjust the pH value to 9. The mixture was heated for reaction (40°C, 10 h), centrifuged, washed, and dried to obtain modified montmorillonite. The ratio of the pre-modified montmorillonite, deionized water, and dopamine aqueous solution was 1 g:45 mL:1 g.

[0082] S5. Compounding: According to the usage ratio of modified chitosan, modified montmorillonite and deionized water of 2 g:0.6 g:10 mL, the modified chitosan obtained in step S2 and the modified montmorillonite obtained in step S4 were added to deionized water respectively, and heated and stirred (35°C, 3.5 h), and then filtered, dried and sieved through 100 mesh to obtain functional particles.

[0083] This embodiment also provides a method for preparing a high-barrier composite packaging material, comprising the following steps:

[0084] (1) On the surface of the aluminum foil layer, the pressure should be 5.5 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0085] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the coating liquid in a coating amount of , and form a composite coating after drying;

[0086] (3) On the composite coating surface according to 3.8 g / m 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0087] (4) Apply 5 g / m2 of VC glue coating on the surface. 2Applying polyurethane heat sealing adhesive in a coating amount of , forming a polyurethane heat sealing coating after drying to obtain a semi-finished product;

[0088] (5) The semi-finished product obtained in step (4) is compounded with a polyvinyl chloride sheet, and after cutting, a high-barrier composite packaging material is obtained.

[0089] Example 3

[0090] A high-barrier composite packaging material, consisting of an aluminum foil layer, a vinyl resin heat-seal coating, a composite coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0091] The composite coating is obtained by coating with a coating liquid, and the preparation of the coating liquid includes the following steps:

[0092] (1) PVA resin was added to deionized water in a mass ratio of 65:12:5.5 among PVA resin, deionized water and functional particles. After stirring, functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3h), solution I was obtained and set aside.

[0093] (2) According to the mass ratio of polylactic acid, mixed solution and functional particles being 35:10:5, polylactic acid was added to the mixed solution (prepared by mixing dimethyl sulfoxide and deionized water in a volume ratio of 1:4), stirred, and then the functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (50°C, 4.5h), solution II was obtained;

[0094] (3) Add the obtained solution I to the obtained solution II and stir evenly.

[0095] The preparation of functional particles includes the following steps:

[0096] S1. Modification of titanium dioxide: titanium dioxide was treated in 98% concentrated sulfuric acid (70°C, 1 h) at a ratio of 1 g titanium dioxide to concentrated acid of 5.5 mL. After the treatment, the titanium dioxide was filtered, washed, and dried to obtain modified titanium dioxide.

[0097] S2. Immobilization of titanium dioxide: Chitosan was added to deionized water, followed by the modified titanium dioxide obtained in step S1. After stirring, acetic acid was added to adjust the pH of the system to 5.5. The mixture was heated and stirred at 35°C for 4 hours. After the treatment, the mixture was centrifuged, washed, and dried to obtain modified chitosan. The ratio of chitosan, deionized water, and modified titanium dioxide was 1 g: 10 mL: 0.48.

[0098] S3. Pre-modification of montmorillonite: Montmorillonite was added to deionized water, and CTAB was added under heating and stirring conditions. The reaction was then carried out at a temperature of 75°C for 4 hours. After the reaction was completed, the pre-modified montmorillonite was filtered and dried. The ratio of montmorillonite, deionized water, and CTAB was 1 g:10 mL:0.5 g.

[0099] S4. Modification of montmorillonite: The pre-modified montmorillonite obtained in step S3 was added to deionized water, stirred, and then a dopamine aqueous solution (0.58 g / mL) was added. After stirring again, Tris-HCl buffer was added to adjust the pH value to 9. The mixture was heated for reaction (40°C, 10 h), and then centrifuged, washed, and dried to obtain modified montmorillonite. The ratio of the pre-modified montmorillonite, deionized water, and dopamine aqueous solution was 1 g:45 mL:1 g.

[0100] S5. Compounding: According to the usage ratio of modified chitosan, modified montmorillonite and deionized water of 2 g:0.55 g:10 mL, the modified chitosan obtained in step S2 and the modified montmorillonite obtained in step S4 were added to deionized water respectively, and heated and stirred (35°C, 3.5 h), and then filtered, dried and sieved through 100 mesh to obtain functional particles.

[0101] This embodiment also provides a method for preparing a high-barrier composite packaging material, comprising the following steps:

[0102] (1) On the surface of the aluminum foil layer, the pressure should be 5.5 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0103] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the coating liquid in a coating amount of , and form a composite coating after drying;

[0104] (3) On the composite coating surface according to 3.8 g / m 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0105] (4) Apply 5 g / m2 of VC glue coating on the surface. 2 Applying polyurethane heat sealing adhesive in a coating amount of , forming a polyurethane heat sealing coating after drying to obtain a semi-finished product;

[0106] (5) The semi-finished product obtained in step (4) is compounded with a polyvinyl chloride sheet, and after cutting, a high-barrier composite packaging material is obtained.

[0107] Comparative Example 1

[0108] Compared with Example 1, Comparative Example 1 does not use functional particles to treat PVA resin and polylactic acid respectively. Specifically, the comparative example provides a high-barrier composite packaging material, which is composed of an aluminum foil layer, a vinyl resin heat-seal coating, a composite coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0109] The composite coating is obtained by coating with a coating liquid, and the preparation of the coating liquid includes the following steps:

[0110] PVA resin, polylactic acid, dimethyl sulfoxide and functional particles were added to deionized water and heated and stirred (55°C, 3h). The amount of each substance used was the same as in Example 1.

[0111] The preparation of functional particles includes the following steps:

[0112] S1. Modification of titanium dioxide: titanium dioxide was treated in 98% concentrated sulfuric acid (70°C, 1 h) at a ratio of 1 g titanium dioxide to concentrated acid of 5.5 mL. After the treatment, the titanium dioxide was filtered, washed, and dried to obtain modified titanium dioxide.

[0113] S2. Immobilization of titanium dioxide: Chitosan was added to deionized water, followed by the modified titanium dioxide obtained in step S1. After stirring, acetic acid was added to adjust the pH of the system to 5.5. The mixture was heated and stirred at 35°C for 3.5 hours. After the treatment, the mixture was centrifuged, washed, and dried to obtain modified chitosan. The ratio of chitosan, deionized water, and modified titanium dioxide was 1 g: 10 mL: 0.5.

[0114] S3. Pre-modification of montmorillonite: Montmorillonite was added to deionized water, and CTAB was added under heating and stirring conditions. The reaction was then carried out at a temperature of 75°C for 4 hours. After the reaction was completed, the pre-modified montmorillonite was filtered and dried. The ratio of montmorillonite, deionized water, and CTAB was 1 g:10 mL:0.5 g.

[0115] S4. Modification of montmorillonite: The pre-modified montmorillonite obtained in step S3 was added to deionized water, stirred, and then a dopamine aqueous solution (0.55 g / mL) was added. After stirring again, Tris-HCl buffer was added to adjust the pH value to 8.8. The mixture was heated for reaction (40°C, 10 h), centrifuged, washed, and dried to obtain modified montmorillonite. The ratio of the pre-modified montmorillonite, deionized water, and dopamine aqueous solution was 1 g:45 mL:0.95 g.

[0116] S5. Compounding: According to the usage ratio of modified chitosan, modified montmorillonite and deionized water of 2 g:0.65 g:10 mL, the modified chitosan obtained in step S2 and the modified montmorillonite obtained in step S4 were added to deionized water respectively, and heated and stirred (35°C, 3.5 h), and then filtered, dried and sieved through 100 mesh to obtain functional particles.

[0117] In this comparative example, a method for preparing a high-barrier composite packaging material is also provided, comprising the following steps:

[0118] (1) On the surface of the aluminum foil layer, the pressure should be 5.5 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0119] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the coating liquid in a coating amount of , and form a composite coating after drying;

[0120] (3) On the composite coating surface according to 3.8 g / m 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0121] (4) Apply 5 g / m2 of VC glue coating on the surface. 2 Applying polyurethane heat sealing adhesive in a coating amount of , forming a polyurethane heat sealing coating after drying to obtain a semi-finished product;

[0122] (5) The semi-finished product obtained in step (4) is compounded with a polyvinyl chloride sheet, and after cutting, a high-barrier composite packaging material is obtained.

[0123] Comparative Example 2

[0124] Compared with Example 1, S2 is omitted in the preparation process of the functional particles in Comparative Example 2. Specifically, in Comparative Example 2, a high-barrier composite packaging material is provided, which is composed of an aluminum foil layer, a vinyl resin heat-seal coating, a composite coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0125] The composite coating is obtained by coating with a coating liquid, and the preparation of the coating liquid includes the following steps:

[0126] (1) PVA resin was added to deionized water in a mass ratio of 65:13:6 among PVA resin, deionized water and functional particles. After stirring, functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3h), solution I was obtained and set aside.

[0127] (2) According to the mass ratio of polylactic acid, mixed solution and functional particles being 35:9:6, polylactic acid was added to the mixed solution (prepared by mixing dimethyl sulfoxide and deionized water in a volume ratio of 1:4), stirred, and then the functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3h), solution II was obtained;

[0128] (3) Add the obtained solution I to the obtained solution II and stir evenly.

[0129] The preparation of functional particles includes the following steps:

[0130] S1. Modification of titanium dioxide: titanium dioxide was treated in 98% concentrated sulfuric acid (70°C, 1 h) at a ratio of 1 g titanium dioxide to concentrated acid of 5.5 mL. After the treatment, the titanium dioxide was filtered, washed, and dried to obtain modified titanium dioxide.

[0131] S2, take chitosan and set aside;

[0132] S3. Pre-modification of montmorillonite: Montmorillonite was added to deionized water, and CTAB was added under heating and stirring conditions. The reaction was then carried out at a temperature of 75°C for 4 hours. After the reaction was completed, the pre-modified montmorillonite was filtered and dried. The ratio of montmorillonite, deionized water, and CTAB was 1 g:10 mL:0.5 g.

[0133] S4. Modification of montmorillonite: The pre-modified montmorillonite obtained in step S3 was added to deionized water, stirred, and then a dopamine aqueous solution (0.55 g / mL) was added. After stirring again, Tris-HCl buffer was added to adjust the pH value to 8.8. The mixture was heated for reaction (40°C, 10 h), centrifuged, washed, and dried to obtain modified montmorillonite. The ratio of the pre-modified montmorillonite, deionized water, and dopamine aqueous solution was 1 g:45 mL:0.95 g.

[0134] S5. Compounding: The modified titanium dioxide obtained in step S1, the chitosan obtained in step S2, and the modified montmorillonite obtained in step S4 were added to deionized water, respectively, and heated and stirred (35°C, 3.5h), followed by filtration, drying, and sieving through 100 mesh to obtain functional particles; the amount of each substance used was the same as in Example 1.

[0135] In this comparative example, a method for preparing a high-barrier composite packaging material is also provided, comprising the following steps:

[0136] (1) On the surface of the aluminum foil layer, the pressure should be 5.5 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0137] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the coating liquid in a coating amount of , and form a composite coating after drying;

[0138] (3) On the composite coating surface according to 3.8 g / m 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0139] (4) Apply 5 g / m2 of VC glue coating on the surface. 2 Applying polyurethane heat sealing adhesive in a coating amount of , forming a polyurethane heat sealing coating after drying to obtain a semi-finished product;

[0140] (5) The semi-finished product obtained in step (4) is compounded with a polyvinyl chloride sheet, and after cutting, a high-barrier composite packaging material is obtained.

[0141] Comparative Example 3

[0142] Compared with Example 1, step S4 is omitted in the preparation process of the functional particles in Comparative Example 3. Specifically, in Comparative Example 3, a high-barrier composite packaging material is composed of an aluminum foil layer, a vinyl resin heat-seal coating, a composite coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0143] The composite coating is obtained by coating with a coating liquid, and the preparation of the coating liquid includes the following steps:

[0144] (1) PVA resin was added to deionized water in a mass ratio of 65:13:6 among PVA resin, deionized water and functional particles. After stirring, functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3h), solution I was obtained and set aside.

[0145] (2) According to the mass ratio of polylactic acid, mixed solution and functional particles being 35:9:6, polylactic acid was added to the mixed solution (prepared by mixing dimethyl sulfoxide and deionized water in a volume ratio of 1:4), stirred, and then the functional particles were added (the amount added was half of the mass of all functional particles). After heating and stirring (55°C, 3h), solution II was obtained;

[0146] (3) Add the obtained solution I to the obtained solution II and stir evenly.

[0147] The preparation of functional particles includes the following steps:

[0148] S1. Modification of titanium dioxide: titanium dioxide was treated in 98% concentrated sulfuric acid (70°C, 1 h) at a ratio of 1 g titanium dioxide to concentrated acid of 5.5 mL. After the treatment, the titanium dioxide was filtered, washed, and dried to obtain modified titanium dioxide.

[0149] S2. Immobilization of titanium dioxide: Chitosan was added to deionized water, followed by the modified titanium dioxide obtained in step S1. After stirring, acetic acid was added to adjust the pH of the system to 5.5. The mixture was heated and stirred at 35°C for 3.5 hours. After the treatment, the mixture was centrifuged, washed, and dried to obtain modified chitosan. The ratio of chitosan, deionized water, and modified titanium dioxide was 1 g: 10 mL: 0.5.

[0150] S3. Pre-modification of montmorillonite: Montmorillonite was added to deionized water, and CTAB was added under heating and stirring conditions. The reaction was then carried out at a temperature of 75°C for 4 hours. After the reaction was completed, the pre-modified montmorillonite was filtered and dried. The ratio of montmorillonite, deionized water, and CTAB was 1 g:10 mL:0.5 g.

[0151] S4. Compounding: According to the usage ratio of modified chitosan, pre-modified montmorillonite and deionized water of 2 g:0.65 g:10 mL, the modified chitosan obtained in step S2 and the pre-modified montmorillonite obtained in step S3 were added to deionized water respectively, and heated and stirred (35°C, 3.5 h), and then filtered, dried, and sieved through 100 mesh to obtain functional particles.

[0152] In this comparative example, a method for preparing a high-barrier composite packaging material is also provided, comprising the following steps:

[0153] (1) On the surface of the aluminum foil layer, the pressure should be 5.5 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0154] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the coating liquid in a coating amount of , and form a composite coating after drying;

[0155] (3) On the composite coating surface according to 3.8 g / m 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0156] (4) Apply 5 g / m2 of VC glue coating on the surface. 2 Applying polyurethane heat sealing adhesive in a coating amount of , forming a polyurethane heat sealing coating after drying to obtain a semi-finished product;

[0157] (5) The semi-finished product obtained in step (4) is compounded with a polyvinyl chloride sheet, and after cutting, a high-barrier composite packaging material is obtained.

[0158] The iodine-blocking packaging materials prepared in Example 1 and Comparative Examples 1 to 4 were tested as follows:

[0159] Iodine barrier performance test: The above-mentioned iodine barrier packaging material is made into an iodine cap, and an iodine-containing molecular drug is placed in it. After standing for 2 months, the iodine content is analyzed using potentiometric analysis.

[0160] Oxygen permeability test: The test is carried out in accordance with GB / T1038.1-2022.

[0161] Water vapor barrier test: The test is carried out in accordance with GB / T1037-2021.

[0162] Tensile strength test: carried out in accordance with GB / T 1040.3-2006.

[0163] The specific test results are shown in Table 1.

[0164] Table 1 Performance test results

[0165]

[0166] As can be seen from Table 1, the iodine-barrier packaging material prepared in the present invention has good iodine barrier, oxygen barrier and water vapor barrier properties, as well as good tensile strength and excellent comprehensive properties.

[0167] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A high barrier composite packaging material, characterized in that: From top to bottom, it is composed of aluminum foil layer, vinyl resin heat seal coating, composite coating, VC glue coating, polyurethane heat seal coating and polyvinyl chloride sheet; The composite coating is obtained by coating with a coating liquid, and the preparation of the coating liquid includes the following steps: (1) PVA resin is added to deionized water, stirred, and then the first part of functional particles is added. After heating and stirring, solution I is obtained and set aside. (2) Adding polylactic acid to the mixed solution, stirring, and then adding the second part of functional particles, heating and stirring, to obtain solution II; (3) Add the obtained solution I to the obtained solution II and stir evenly; The preparation of functional particles includes the following steps: S1. Modification of titanium dioxide: treating titanium dioxide in concentrated acid, filtering, washing, and drying to obtain modified titanium dioxide; S2. Immobilization of titanium dioxide: chitosan was added to deionized water, followed by the modified titanium dioxide obtained in step S1. After stirring, acetic acid was added to adjust the pH value of the system. The system was heated and stirred. After the treatment, the system was centrifuged, washed, and dried to obtain the modified chitosan. S3. Pre-modification of montmorillonite: adding montmorillonite to deionized water, adding CTAB under heating and stirring conditions, then maintaining the heating and stirring temperature for reaction. After the reaction is completed, filtering and drying to obtain pre-modified montmorillonite; S4, modification of montmorillonite: adding the pre-modified montmorillonite obtained in step S3 to deionized water, stirring, adding a dopamine aqueous solution, stirring again, adding Tris-HCl buffer to adjust the pH value, heating for reaction, centrifuging, washing, and drying to obtain modified montmorillonite; S5. Compounding: adding the modified chitosan obtained in step S2 and the modified montmorillonite obtained in step S4 to deionized water respectively, heating and stirring, and then filtering, drying, and sieving to obtain functional particles; The mass ratio of the first part of functional particles to the second part of functional particles is 1:1; the mixed solution is obtained by mixing dimethyl sulfoxide and deionized water in a volume ratio of 1:

4.

2. The high barrier composite packaging material according to claim 1, characterized in that: In step (1), the mass ratio of PVA resin, deionized water, and the first part of functional particles is 60-80:10-15:4-8; the stirring treatment temperature is 50-65°C, and the treatment time is 2-6 hours; In step (2), the mass ratio of polylactic acid, mixed solution, and the second part of functional particles is 20-40:6-12:4-8; the stirring treatment temperature is 50-65°C, and the treatment time is 2-6 hours.

3. The high barrier composite packaging material according to claim 1, characterized in that: In step S1, the concentrated acid is 98% concentrated sulfuric acid, the treatment temperature is 70-85° C., and the treatment time is 1-4 hours; the usage ratio of titanium dioxide and concentrated acid is 1 g: 3-6 mL.

4. The high barrier composite packaging material according to claim 1, characterized in that: In step S2, the pH value of the system is 4.5-6.5; the dosage ratio of chitosan, deionized water, and modified titanium dioxide is 1 g: 5-10 mL: 0.45-0.65; The heating and stirring treatment temperature is 30~35℃, and the treatment time is 2~6h.

5. The high barrier composite packaging material according to claim 1, characterized in that: In step S3, the ratio of montmorillonite, deionized water, and CTAB is 1 g: 5-12 mL: 0.4-0.65 g; The heating and stirring temperature is 70~85℃, and the reaction time is 2~6h.

6. The high barrier composite packaging material according to claim 1, characterized in that: In step S4, the pH value of the system is adjusted to 8-9; the usage ratio of pre-modified montmorillonite, deionized water, and dopamine aqueous solution is 1 g: 30-60 mL: 0.8-1.2 g; The concentration of dopamine aqueous solution is 0.45~0.85 g / mL; The heating reaction temperature is 35~45℃ and the reaction time is 6~18h.

7. The high barrier composite packaging material according to claim 1, characterized in that: In step S5, the ratio of modified chitosan, modified montmorillonite, and deionized water is 2 g: 0.5-0.8 g: 6-12 mL; The heating and stirring temperature is 30~35℃, and the heating and stirring treatment time is 2~6h; The sieving mesh number is 80~150 mesh.

8. A method for preparing the high barrier composite packaging material according to any one of claims 1 to 7, characterized in that: The steps include: (1) applying vinyl resin heat seal adhesive on the surface of the aluminum foil layer and drying to form a vinyl resin heat seal coating; (2) applying a coating liquid on the surface of the vinyl resin heat seal coating and drying it to form a composite coating; (3) Applying VC glue on the surface of the composite coating and drying it to form a VC glue coating; (4) Applying polyurethane heat-sealing adhesive on the surface of the VC glue coating, and drying to form a polyurethane heat-sealing coating to obtain a semi-finished product; (5) The semi-finished product obtained in step (4) is compounded with a polyvinyl chloride sheet and cut into pieces to obtain an iodine-blocking packaging material.

9. The preparation method according to claim 8, characterized in that The coating amount of vinyl resin heat sealant is 5~8 g / m 2 ; The coating amount of the coating liquid is 3~5 g / m 2 ; The coating amount of VC glue is 4~6 g / m 2 ; The coating amount of polyurethane heat sealant is 5~8 g / m 2 .

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