Iodine-blocking packaging material and preparation method thereof

Abstract

The present invention belongs to the technical field of iodine barrier material preparation, and specifically discloses an iodine barrier packaging material and a preparation method thereof. The iodine barrier packaging material is composed of an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom; wherein the modified PVA coating is obtained by coating with a PVA coating liquid, and the preparation of the PVA coating liquid comprises the following steps: adding PVA resin to deionized water, stirring at 80-90°C for 0.5-4h, then cooling to 25-35°C, then adding a modified composite filler and stirring for 0.5-3h; after the treatment is completed, cooling to room temperature. The iodine barrier packaging material provided by the present invention has good barrier properties such as iodine and oxygen, and good mechanical properties and excellent comprehensive indicators.

Description

Technical Field

[0001] The invention belongs to the technical field of iodine barrier material preparation, and particularly relates to an iodine barrier packaging material and a preparation method thereof. Background Art

[0002] Packaging materials are widely used in real-world applications, such as food and pharmaceuticals. Blister packaging has been the fastest-growing flexible packaging material in recent years and is a key packaging format for pharmaceuticals, health supplements, food, and other sectors. Blister packaging, also known as blister packaging, uses industrial pure aluminum foil as a base material. Using a pharmaceutical PTP (Press Through Packing) aluminum foil coating machine, text and patterns are printed on the foil surface using gravure printing and roller coating, followed by a protective layer and an adhesive layer on the other side. However, for pharmaceuticals currently packaged in the market, using ordinary PTP aluminum foil for packaging contains a certain amount of iodine. This results in iodine loss far exceeding the required level and the aluminum foil layer is easily damaged by the iodine, completely failing to provide the packaging's protective properties. Since pharmaceutical aluminum foil packaging lacks anti-counterfeiting markings, it is easily counterfeited, hindering the storage and identification of the drug. Furthermore, the control of the pharmaceutical PTP aluminum foil coating process can result in low heat seal strength and barrier properties for blister packaging, making it difficult to guarantee the safety and effectiveness of the drug. Therefore, it is imperative to carry out research on pharmaceutical packaging materials with high barrier properties, strong corrosion resistance and chemical stability, especially packaging materials that can effectively protect drugs from the influence of the external environment.

[0003] In the prior art, patent document CN220841724U provides an iodine-barrier aluminum foil blister packaging structure, which discloses the corresponding iodine-barrier structure, but does not disclose how the iodine-barrier structure is prepared. This patent is also an earlier patent technology of the applicant; patent document CN117183483A provides an iodine-barrier packaging material, including a cover film and a base film, the cover film includes a paper layer, a first aluminum foil layer and a first PET layer stacked in sequence from top to bottom, and the base film includes 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, materials such as graphite carbon nitride are used, and the cost is relatively high. In addition, the performance of the obtained packaging material, except for iodine barrier, needs to be further improved in other aspects. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide an iodine-barrier packaging material and a preparation method thereof, which has good barrier properties such as iodine and oxygen barrier, good mechanical properties and excellent comprehensive indicators.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides an iodine-blocking packaging material, which is composed, from top to bottom, of an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet;

[0007] The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps:

[0008] Add PVA resin to deionized water, stir at 80-90°C for 0.5-4h, then cool to 25-35°C, then add modified composite filler and stir for 0.5-3h; after the treatment, cool to room temperature to obtain the product.

[0009] The structure of the packaging material in the above-mentioned technical solution can be further understood by referring to prior art, such as patent document CN220841724U. The technical solution provided by the present invention is a further development based on this prior art. It should be emphasized that, as a practical requirement, the aluminum foil layer is also printed with gravure aluminum foil ink and provided with a corresponding protective coating.

[0010] Preferably, the mass ratio of PVA resin, deionized water, and modified composite filler is 100:20-35:8-15.

[0011] Preferably, the preparation of the modified composite filler comprises the following steps:

[0012] S1. Modification of attapulgite: first, attapulgite is mixed with sodium hydroxide and then subjected to high-temperature treatment. After the treatment, it is added to a hydrochloric acid solution and shaken. After the treatment, it is centrifuged, washed, dried, and finally sieved to obtain modified attapulgite;

[0013] S2. Modification of wood fiber: adding wood fiber and sodium chloroacetate to water for heating reaction, adding sodium hydroxide after the reaction is completed, and reacting at room temperature. After the reaction is completed, washing to neutrality and drying are performed to obtain modified wood fiber;

[0014] S3. Modification of silicon dioxide: adding silicon dioxide to the mixed solution, and then treating it under heating and stirring conditions. After the treatment is completed, centrifugation, washing, and drying are performed to obtain modified silicon dioxide;

[0015] S4. Compounding of tea polyphenols: adding the modified attapulgite obtained in step S1, the modified wood fiber obtained in step S2 and the modified silicon dioxide obtained in step S3 to water, stirring and then adding tea polyphenols, stirring under heating conditions, centrifuging and drying after the treatment to obtain a modified composite filler.

[0016] Preferably, in step S1, the mass ratio of attapulgite to sodium hydroxide is 1:0.4-0.8, the high temperature treatment temperature is 790-805° C., and the treatment time is 0.5-4 h.

[0017] Preferably, in step S1, the concentration of the hydrochloric acid solution is 0.5-2.5 mol / L; the mass ratio of attapulgite to hydrochloric acid solution is 1 g:8-12 mL; the shaking treatment rate is 150-200 rpm, and the shaking treatment time is 0.5-2 h; and the sieve mesh size is 100-200 mesh.

[0018] Preferably, in step S2, the mass ratio of wood fiber, sodium chloroacetate, water and sodium hydroxide is 1:1.2~2:20~30:1~1.5; the heating reaction temperature is 55~70°C, the heating reaction time is 2~8h; and the reaction time at room temperature is 12~36h.

[0019] Preferably, in step S3, the mixed solution is obtained by mixing concentrated sulfuric acid and hydrogen peroxide, the concentration of concentrated sulfuric acid is 11-18 mol / L, the concentration of hydrogen peroxide is 8-12 mol / L, and the volume ratio of concentrated sulfuric acid to hydrogen peroxide is 1:2-4; the amount ratio of silicon dioxide to the mixed solution is 1 g:5-8 mL; the heating and stirring treatment temperature is 35-50 ° C, the treatment time is 0.5-4 h, and the stirring rate of the heating and stirring is 80-150 rpm.

[0020] Preferably, in step S4, the mass ratio of modified attapulgite, modified wood fiber, modified silica, tea polyphenols and water is 1:2~3:0.5~1:0.1~0.3:8~12; the heating temperature is 30~35°C, the stirring treatment time is 1~4h, and the stirring rate is 60~120rpm.

[0021] In a second aspect, the present invention provides a method for preparing the above-mentioned iodine-blocking packaging material, comprising the following steps:

[0022] (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;

[0023] (2) applying a PVA coating liquid on the surface of the vinyl resin heat seal coating and drying the coating to form a modified PVA coating;

[0024] (3) Applying VC glue on the surface of the modified PVA coating and drying it to form a VC glue coating;

[0025] (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;

[0026] (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.

[0027] Preferably, the coating amount of the vinyl resin heat sealant is 5 to 8 g / m 2 ;

[0028] The coating amount of PVA coating liquid is 4~6 g / m 2 ;

[0029] The coating amount of VC glue is 4~6 g / m 2 ;

[0030] The coating amount of polyurethane heat sealant is 5~8 g / m 2 .

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The iodine-barrier packaging material provided by the present invention is composed of a multi-layer structure, has good adhesion, good mechanical strength, has the functions of blocking iodine and blocking water and oxygen, and has excellent comprehensive performance.

[0033] In the iodine-blocking packaging material provided by the present invention, the modified PVA coating plays a key iodine-blocking function. The modified PVA coating is prepared by modifying common attapulgite, wood fiber and silica. Specifically, attapulgite is an inorganic filler, and wood fiber is an organic filler. The combination of organic and inorganic fillers ensures the filling density and the use effect. However, the use of the two will reduce the mechanical properties of the packaging material to a certain extent. Therefore, a small amount of silica is also used in the present invention. The combined use of the three ensures the mechanical properties and comprehensive performance of the packaging material. The film-forming density of the PVA resin will greatly affect the iodine-blocking effect. Therefore, the present invention carries out targeted modification of the above three substances, wherein the attapulgite is first subjected to a high-temperature alkali melting treatment, which is beneficial to enriching its pores and improving the subsequent adsorption of tea polyphenols. The invention further improves the pores and subsequently undergoes acid treatment, which not only enriches the active sites of attapulgite, but also facilitates subsequent composite with silica and wood fiber and the adsorption of tea polyphenols. Wood fiber itself has a very rich group, but its activity is not high and its mechanical properties are poor. After being modified with carboxymethyl, its activity is increased, facilitating composite with silica and attapulgite, and also facilitating the adsorption of tea polyphenols. Silica itself can significantly improve the mechanical properties of the resin, but its compatibility with the resin is poor. Therefore, in the present invention, it is treated with mixed acid to introduce hydroxyl groups, etc., which helps improve its dispersibility in the PVA resin and facilitates the formation of hydrogen bonding systems with attapulgite and silica, ensuring the dispersion and stability of the composite filler in the PVA resin. Tea polyphenols contain abundant phenolic hydroxyl groups. The addition of tea polyphenols not only further improves the barrier effect of the packaging material (blocking iodine and oxygen, etc.), but also gives the packaging material prepared by the present invention corresponding properties due to its inherent antibacterial and antioxidant properties. In summary, the present invention selects attapulgite, silica and wood fiber, all of which contain rich hydroxyl groups and the like, and can efficiently composite-graft with each other in the form of hydrogen bonds and the like, while also being able to react with tea polyphenols, so that tea polyphenols can be combined with the filler system in the form of hydrogen bonds, adsorption and the like, thereby ensuring the dispersibility and stability of the filler system; the raw materials of each substance are relatively common and the cost is controllable.

[0034] 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

[0035] 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.

[0036] In the present invention, the particle size of silicon dioxide is about 20 nm.

[0037] 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 VC-1100; PVA resin was purchased from Jining Fangyu Chemical Co., Ltd. with the brand 1799; and polyurethane heat sealant was purchased from Michelman (Shanghai) Chemical Trading Co., Ltd.

[0038] 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.

[0039] 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, modified PVA coating, VC glue coating, and polyurethane heat-seal coating are all 0.015 mm.

[0040] In the present invention, the concentration of hydrogen peroxide is 9 mol / L, and the concentration of concentrated sulfuric acid is 18 mol / L.

[0041] The coating speed and drying temperature of vinyl resin heat sealant, PVA 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 polyvinyl chloride 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.

[0042] Example 1

[0043] An iodine-resistant packaging material, consisting of an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0044] The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps:

[0045] According to the mass ratio of PVA resin, deionized water and modified composite filler being 100:30:9.5, PVA resin is added to deionized water and stirred at 85°C for 2.5 hours. Then the temperature is lowered to 30°C and the modified composite filler is added and stirred for 2 hours. After the treatment, the temperature is lowered to room temperature to obtain the product.

[0046] The preparation of the modified composite filler comprises the following steps:

[0047] S1. Modification of attapulgite: attapulgite and sodium hydroxide were mixed in a mass ratio of 1:0.5 and then subjected to high temperature treatment (795°C, 1.5 h). After the treatment, the mixture was added to a 1.6 mol / L hydrochloric acid solution and shaken (180 rpm, 1.5 h). After the treatment, the mixture was centrifuged, washed, dried, and finally sieved through 150 mesh to obtain modified attapulgite. The mass ratio of attapulgite to hydrochloric acid solution was 1 g:10 mL.

[0048] S2. Modification of wood fiber: adding wood fiber and sodium chloroacetate to water in a mass ratio of wood fiber, sodium chloroacetate, water, and sodium hydroxide of 1:1.5:23:1.2 to carry out heating reaction (65°C, 4 hours). After the reaction is completed, sodium hydroxide is added and the reaction is continued at room temperature for 18 hours. After the reaction is completed, the modified wood fiber is washed to neutrality and dried.

[0049] S3. Modification of silica: Silica was added to a mixed solution (concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 1:3), followed by heating and stirring (40°C, 2h, 100rpm). After the treatment, the modified silica was obtained by centrifugation, washing, and drying. The amount ratio of silica to the mixed solution was 1g:6mL.

[0050] S4. Compounding of tea polyphenols: according to the mass ratio of modified attapulgite, modified wood fiber, modified silica, tea polyphenols and water being 1:2.5:0.7:0.2:10, the modified attapulgite obtained in step S1, the modified wood fiber obtained in step S2 and the modified silica obtained in step S3 are added to water, stirred and then tea polyphenols are added, and stirred under heating conditions (35°C, 2h, 80rpm). After the treatment, the mixture is centrifuged and dried to obtain a modified composite filler.

[0051] In this embodiment, a method for preparing the above-mentioned iodine-blocking packaging material is also provided, comprising the following steps:

[0052] (1) On the surface of the aluminum foil layer, the pressure should be 6 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0053] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the PVA coating liquid in a coating amount of , and form a modified PVA coating after drying;

[0054] (3) On the surface of the modified PVA coating, the 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0055] (4) Apply 5.2 g / m2 of VC glue coating on the surface. 2 Applying a polyurethane heat seal adhesive in a coating amount of , and forming a polyurethane heat seal coating after drying to obtain a semi-finished product;

[0056] (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.

[0057] Example 2

[0058] An iodine-resistant packaging material, consisting of an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0059] The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps:

[0060] According to the mass ratio of PVA resin, deionized water and modified composite filler being 100:28:10, PVA resin is added to deionized water and stirred at 86°C for 2 hours, then cooled to 30°C and then the modified composite filler is added and stirred for 2.5 hours; after the treatment, the temperature is cooled to room temperature to obtain the product.

[0061] The preparation of the modified composite filler comprises the following steps:

[0062] S1. Modification of attapulgite: attapulgite and sodium hydroxide were mixed in a mass ratio of 1:0.45 and then subjected to high temperature treatment (800°C, 1 h). After the treatment, the mixture was added to a 1.5 mol / L hydrochloric acid solution and shaken (180 rpm, 1.5 h). After the treatment, the mixture was centrifuged, washed, dried, and finally sieved through 150 mesh to obtain modified attapulgite. The mass ratio of attapulgite to hydrochloric acid solution was 1 g:9 mL.

[0063] S2. Modification of wood fiber: adding wood fiber and sodium chloroacetate to water in a mass ratio of wood fiber, sodium chloroacetate, water, and sodium hydroxide of 1:1.5:23:1.2 to carry out heating reaction (60°C, 4.5 hours). After the reaction is completed, sodium hydroxide is added and the reaction is continued at room temperature for 18 hours. After the reaction is completed, the modified wood fiber is washed to neutrality and dried.

[0064] S3. Modification of silica: Silica was added to a mixed solution (concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 1:3), followed by heating and stirring (40°C, 2.5 hours, 120 rpm). After the treatment, the modified silica was obtained by centrifugation, washing, and drying. The amount ratio of silica to the mixed solution was 1 g: 6 mL.

[0065] S4. Compounding of tea polyphenols: according to the mass ratio of modified attapulgite, modified wood fiber, modified silica, tea polyphenols and water being 1:2.6:0.6:0.22:10, the modified attapulgite obtained in step S1, the modified wood fiber obtained in step S2 and the modified silica obtained in step S3 are added to water, stirred and then tea polyphenols are added, and stirred under heating conditions (35°C, 2h, 80rpm). After the treatment, the mixture is centrifuged and dried to obtain a modified composite filler.

[0066] In this embodiment, a method for preparing the above-mentioned iodine-blocking packaging material is also provided, comprising the following steps:

[0067] (1) On the surface of the aluminum foil layer, the pressure should be 6 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0068] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the PVA coating liquid in a coating amount of , and form a modified PVA coating after drying;

[0069] (3) On the surface of the modified PVA coating, the 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0070] (4) Apply 5.2 g / m2 of VC glue coating on the surface. 2 Applying a polyurethane heat seal adhesive in a coating amount of , and forming a polyurethane heat seal coating after drying to obtain a semi-finished product;

[0071] (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.

[0072] Example 3

[0073] An iodine-resistant packaging material, consisting of an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0074] The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps:

[0075] According to the mass ratio of PVA resin, deionized water and modified composite filler being 100:33:10.5, PVA resin is added to deionized water and stirred at 85°C for 2.5 hours. Then the temperature is lowered to 30°C and the modified composite filler is added and stirred for 2 hours. After the treatment, the temperature is lowered to room temperature to obtain the product.

[0076] The preparation of the modified composite filler comprises the following steps:

[0077] S1. Modification of attapulgite: attapulgite and sodium hydroxide were mixed in a mass ratio of 1:0.5 and then subjected to high temperature treatment (805°C, 1 h). After the treatment, the mixture was added to a 1.7 mol / L hydrochloric acid solution and shaken (180 rpm, 1.5 h). After the treatment, the mixture was centrifuged, washed, dried, and finally sieved through 150 mesh to obtain modified attapulgite. The mass ratio of attapulgite to hydrochloric acid solution was 1 g:11 mL.

[0078] S2. Modification of wood fiber: adding wood fiber and sodium chloroacetate to water in a mass ratio of wood fiber, sodium chloroacetate, water, and sodium hydroxide of 1:1.6:22:1.3 to carry out heating reaction (65°C, 4 hours). After the reaction is completed, sodium hydroxide is added and the reaction is continued at room temperature for another 24 hours. After the reaction is completed, the modified wood fiber is washed to neutrality and dried.

[0079] S3. Modification of silica: Silica was added to a mixed solution (concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 1:3), followed by heating and stirring (45°C, 1.5 hours, 100 rpm). After the treatment, the modified silica was obtained by centrifugation, washing, and drying. The amount ratio of silica to the mixed solution was 1 g:5.5 mL.

[0080] S4. Compounding of tea polyphenols: according to the mass ratio of modified attapulgite, modified wood fiber, modified silica, tea polyphenols and water being 1:2.6:0.72:0.2:11, the modified attapulgite obtained in step S1, the modified wood fiber obtained in step S2 and the modified silica obtained in step S3 are added to water, stirred and then tea polyphenols are added, and stirred under heating conditions (35°C, 2h, 80rpm). After the treatment, the mixture is centrifuged and dried to obtain a modified composite filler.

[0081] In this embodiment, a method for preparing the above-mentioned iodine-blocking packaging material is also provided, comprising the following steps:

[0082] (1) On the surface of the aluminum foil layer, the pressure should be 6 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0083] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the PVA coating liquid in a coating amount of , and form a modified PVA coating after drying;

[0084] (3) On the surface of the modified PVA coating, the 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0085] (4) Apply 5.2 g / m2 of VC glue coating on the surface. 2 Applying a polyurethane heat seal adhesive in a coating amount of , and forming a polyurethane heat seal coating after drying to obtain a semi-finished product;

[0086] (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.

[0087] Comparative Example 1

[0088] Compared with Example 1, the attapulgite in Comparative Example 1 was not modified, i.e., step S1 was omitted. Specifically, an iodine-blocking packaging material is composed, from top to bottom, of an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet;

[0089] The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps:

[0090] According to the mass ratio of PVA resin, deionized water and modified composite filler being 100:30:9.5, PVA resin is added to deionized water and stirred at 85°C for 2.5 hours. Then the temperature is lowered to 30°C and the modified composite filler is added and stirred for 2 hours. After the treatment, the temperature is lowered to room temperature to obtain the product.

[0091] The preparation of the modified composite filler comprises the following steps:

[0092] S1. Take attapulgite soil and set aside;

[0093] S2. Modification of wood fiber: adding wood fiber and sodium chloroacetate to water in a mass ratio of wood fiber, sodium chloroacetate, water, and sodium hydroxide of 1:1.5:23:1.2 to carry out heating reaction (65°C, 4 hours). After the reaction is completed, sodium hydroxide is added and the reaction is continued at room temperature for 18 hours. After the reaction is completed, the modified wood fiber is washed to neutrality and dried.

[0094] S3. Modification of silica: Silica was added to a mixed solution (concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 1:3), followed by heating and stirring (40°C, 2h, 100rpm). After the treatment, the modified silica was obtained by centrifugation, washing, and drying. The amount ratio of silica to the mixed solution was 1g:6mL.

[0095] S4. Compounding of tea polyphenols: according to the mass ratio of attapulgite, modified wood fiber, modified silica, tea polyphenols and water being 1:2.5:0.7:0.2:10, the attapulgite obtained in step S1, the modified wood fiber obtained in step S2 and the modified silica obtained in step S3 are added to water, stirred and then tea polyphenols are added, and stirred under heating conditions (35°C, 2h, 80rpm). After the treatment, the mixture is centrifuged and dried to obtain a modified composite filler.

[0096] In this comparative example, a method for preparing the above-mentioned iodine-blocking packaging material is also provided, comprising the following steps:

[0097] (1) On the surface of the aluminum foil layer, the pressure should be 6 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0098] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the PVA coating liquid in a coating amount of , and form a modified PVA coating after drying;

[0099] (3) On the surface of the modified PVA coating, the 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0100] (4) Apply 5.2 g / m2 of VC glue coating on the surface. 2 Applying a polyurethane heat seal adhesive in a coating amount of , and forming a polyurethane heat seal coating after drying to obtain a semi-finished product;

[0101] (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.

[0102] Comparative Example 2

[0103] Compared with Example 1, the wood fiber in Comparative Example 2 was not modified, i.e., step S2 was omitted. Specifically, an iodine-blocking packaging material is composed, from top to bottom, of an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet;

[0104] The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps:

[0105] According to the mass ratio of PVA resin, deionized water and modified composite filler being 100:30:9.5, PVA resin is added to deionized water and stirred at 85°C for 2.5 hours. Then the temperature is lowered to 30°C and the modified composite filler is added and stirred for 2 hours. After the treatment, the temperature is lowered to room temperature to obtain the product.

[0106] The preparation of the modified composite filler comprises the following steps:

[0107] S1. Modification of attapulgite: attapulgite and sodium hydroxide were mixed in a mass ratio of 1:0.5 and then subjected to high temperature treatment (795°C, 1.5 h). After the treatment, the mixture was added to a 1.6 mol / L hydrochloric acid solution and shaken (180 rpm, 1.5 h). After the treatment, the mixture was centrifuged, washed, dried, and finally sieved through 150 mesh to obtain modified attapulgite. The mass ratio of attapulgite to hydrochloric acid solution was 1 g:10 mL.

[0108] S2, take wood fiber and set aside;

[0109] S3. Modification of silica: Silica was added to a mixed solution (concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 1:3), followed by heating and stirring (40°C, 2h, 100rpm). After the treatment, the modified silica was obtained by centrifugation, washing, and drying. The amount ratio of silica to the mixed solution was 1g:6mL.

[0110] S4. Compounding of tea polyphenols: according to the mass ratio of modified attapulgite, wood fiber, modified silica, tea polyphenols and water being 1:2.5:0.7:0.2:10, the modified attapulgite obtained in step S1, the wood fiber in step S2 and the modified silica obtained in step S3 are added to water, stirred and then tea polyphenols are added, and stirred under heating conditions (35°C, 2h, 80rpm). After the treatment, the mixture is centrifuged and dried to obtain a modified composite filler.

[0111] In this comparative example, a method for preparing the above-mentioned iodine-blocking packaging material is also provided, comprising the following steps:

[0112] (1) On the surface of the aluminum foil layer, the pressure should be 6 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0113] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the PVA coating liquid in a coating amount of , and form a modified PVA coating after drying;

[0114] (3) On the surface of the modified PVA coating, the 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0115] (4) Apply 5.2 g / m2 of VC glue coating on the surface. 2 Applying a polyurethane heat seal adhesive in a coating amount of , and forming a polyurethane heat seal coating after drying to obtain a semi-finished product;

[0116] (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.

[0117] Comparative Example 3

[0118] Compared with Example 1, the silicon dioxide in Comparative Example 3 is not modified, that is, step S3 is omitted. Specifically, an iodine-blocking packaging material is composed of, from top to bottom, an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet;

[0119] The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps:

[0120] According to the mass ratio of PVA resin, deionized water and modified composite filler being 100:30:9.5, PVA resin is added to deionized water and stirred at 85°C for 2.5 hours. Then the temperature is lowered to 30°C and the modified composite filler is added and stirred for 2 hours. After the treatment, the temperature is lowered to room temperature to obtain the product.

[0121] The preparation of the modified composite filler comprises the following steps:

[0122] S1. Modification of attapulgite: attapulgite and sodium hydroxide were mixed in a mass ratio of 1:0.5 and then subjected to high temperature treatment (795°C, 1.5 h). After the treatment, the mixture was added to a 1.6 mol / L hydrochloric acid solution and shaken (180 rpm, 1.5 h). After the treatment, the mixture was centrifuged, washed, dried, and finally sieved through 150 mesh to obtain modified attapulgite. The mass ratio of attapulgite to hydrochloric acid solution was 1 g:10 mL.

[0123] S2. Modification of wood fiber: adding wood fiber and sodium chloroacetate to water in a mass ratio of wood fiber, sodium chloroacetate, water, and sodium hydroxide of 1:1.5:23:1.2 to carry out heating reaction (65°C, 4 hours). After the reaction is completed, sodium hydroxide is added and the reaction is continued at room temperature for 18 hours. After the reaction is completed, the modified wood fiber is washed to neutrality and dried.

[0124] S3, take silicon dioxide and set aside;

[0125] S4. Compounding of tea polyphenols: according to the mass ratio of modified attapulgite, modified wood fiber, silicon dioxide, tea polyphenols and water being 1:2.5:0.7:0.2:10, the modified attapulgite obtained in step S1, the modified wood fiber obtained in step S2 and the silicon dioxide obtained in step S3 are added to water, stirred and then tea polyphenols are added, and stirred under heating conditions (35°C, 2h, 80rpm). After the treatment, the mixture is centrifuged and dried to obtain a modified composite filler.

[0126] In this comparative example, a method for preparing the above-mentioned iodine-blocking packaging material is also provided, comprising the following steps:

[0127] (1) On the surface of the aluminum foil layer, the pressure should be 6 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0128] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the PVA coating liquid in a coating amount of , and form a modified PVA coating after drying;

[0129] (3) On the surface of the modified PVA coating, the 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0130] (4) Apply 5.2 g / m2 of VC glue coating on the surface. 2 Applying a polyurethane heat seal adhesive in a coating amount of , and forming a polyurethane heat seal coating after drying to obtain a semi-finished product;

[0131] (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.

[0132] Comparative Example 4

[0133] Compared with Example 1, tea polyphenols were not added in Comparative Example 4. Specifically, an iodine-blocking packaging material is composed of an aluminum foil layer, a vinyl resin heat-seal coating, a modified PVA coating, a VC glue coating, a polyurethane heat-seal coating, and a polyvinyl chloride sheet from top to bottom;

[0134] The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps:

[0135] According to the mass ratio of PVA resin, deionized water and modified composite filler being 100:30:9.5, PVA resin is added to deionized water and stirred at 85°C for 2.5 hours. Then the temperature is lowered to 30°C and the modified composite filler is added and stirred for 2 hours. After the treatment, the temperature is lowered to room temperature to obtain the product.

[0136] The preparation of the modified composite filler comprises the following steps:

[0137] S1. Modification of attapulgite: attapulgite and sodium hydroxide were mixed in a mass ratio of 1:0.5 and then subjected to high temperature treatment (795°C, 1.5 h). After the treatment, the mixture was added to a 1.6 mol / L hydrochloric acid solution and shaken (180 rpm, 1.5 h). After the treatment, the mixture was centrifuged, washed, dried, and finally sieved through 150 mesh to obtain modified attapulgite. The mass ratio of attapulgite to hydrochloric acid solution was 1 g:10 mL.

[0138] S2. Modification of wood fiber: adding wood fiber and sodium chloroacetate to water in a mass ratio of wood fiber, sodium chloroacetate, water, and sodium hydroxide of 1:1.5:23:1.2 to carry out heating reaction (65°C, 4 hours). After the reaction is completed, sodium hydroxide is added and the reaction is continued at room temperature for 18 hours. After the reaction is completed, the modified wood fiber is washed to neutrality and dried.

[0139] S3. Modification of silica: Silica was added to a mixed solution (concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 1:3), followed by heating and stirring (40°C, 2h, 100rpm). After the treatment, the modified silica was obtained by centrifugation, washing, and drying. The amount ratio of silica to the mixed solution was 1g:6mL.

[0140] S4. Compounding: The modified attapulgite obtained in step S1, the modified wood fiber obtained in step S2, and the modified silica obtained in step S3 are added to water in a mass ratio of modified attapulgite, modified wood fiber, modified silica, and water of 1:2.5:0.7:10. The mixture is stirred under heating conditions (35°C, 2h, 80rpm). After the treatment, the mixture is centrifuged and dried to obtain a modified composite filler.

[0141] In this comparative example, a method for preparing the above-mentioned iodine-blocking packaging material is also provided, comprising the following steps:

[0142] (1) On the surface of the aluminum foil layer, the pressure should be 6 g / m 2 Applying vinyl resin heat seal adhesive in a coating amount of , and forming a vinyl resin heat seal coating after drying;

[0143] (2) On the surface of vinyl resin heat seal coating, the 2 Apply the PVA coating liquid in a coating amount of , and form a modified PVA coating after drying;

[0144] (3) On the surface of the modified PVA coating, the 2 Apply VC glue in a coating amount of 100% and form a VC glue coating after drying;

[0145] (4) Apply 5.2 g / m2 of VC glue coating on the surface. 2 Applying a polyurethane heat seal adhesive in a coating amount of , and forming a polyurethane heat seal coating after drying to obtain a semi-finished product;

[0146] (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.

[0147] The iodine-blocking packaging materials prepared in Example 1 and Comparative Examples 1 to 4 were tested as follows:

[0148] 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.

[0149] Oxygen permeability test: The test is carried out in accordance with GB / T1038.1-2022.

[0150] Tensile strength test: carried out in accordance with GB / T 1040.3-2006.

[0151] The specific test results are shown in Table 1.

[0152] Table 1 Performance test results

[0153]

[0154] As can be seen from Table 1, the iodine-barrier packaging material prepared in the present invention has good iodine and oxygen barrier properties, good tensile strength, and excellent comprehensive performance.

[0155] 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. An iodine-barrier packaging material, characterized in that: From top to bottom, it is composed of aluminum foil layer, vinyl resin heat seal coating, modified PVA coating, VC glue coating, polyurethane heat seal coating and polyvinyl chloride sheet; The modified PVA coating is obtained by coating with a PVA coating solution, and the preparation of the PVA coating solution comprises the following steps: PVA resin is added to deionized water, stirred at 80-90°C for 0.5-4h, then cooled to 25-35°C, and then the modified composite filler is added and stirred for 0.5-3h. After the treatment, the mixture is cooled to room temperature to obtain the product. The preparation of the modified composite filler comprises the following steps: S1. Modification of attapulgite: first, attapulgite is mixed with sodium hydroxide and then subjected to high-temperature treatment. After the treatment, it is added to a hydrochloric acid solution and shaken. After the treatment, it is centrifuged, washed, dried, and finally sieved to obtain modified attapulgite; S2. Modification of wood fiber: adding wood fiber and sodium chloroacetate to water for heating reaction, adding sodium hydroxide after the reaction is completed, and reacting at room temperature. After the reaction is completed, washing to neutrality and drying are performed to obtain modified wood fiber; S3. Modification of silicon dioxide: adding silicon dioxide to the mixed solution, and then treating it under heating and stirring conditions. After the treatment is completed, centrifugation, washing, and drying are performed to obtain modified silicon dioxide; S4. Compounding of tea polyphenols: adding the modified attapulgite obtained in step S1, the modified wood fiber obtained in step S2 and the modified silicon dioxide obtained in step S3 to water, stirring and then adding tea polyphenols, stirring under heating conditions, centrifuging and drying after the treatment to obtain a modified composite filler.

2. The iodine-barrier packaging material according to claim 1, characterized in that: The mass ratio of PVA resin, deionized water and modified composite filler is 100:20~35:8~15.

3. The iodine-barrier packaging material according to claim 1, characterized in that: In step S1, the mass ratio of attapulgite to sodium hydroxide is 1:0.4-0.8, the high temperature treatment temperature is 790-805° C., and the treatment time is 0.5-4 h.

4. The iodine-barrier packaging material according to claim 1, characterized in that: In step S1, the concentration of the hydrochloric acid solution is 0.5-2.5 mol / L; the mass ratio of attapulgite to the hydrochloric acid solution is 1 g:8-12 mL; the shaking treatment rate is 150-200 rpm, and the shaking treatment time is 0.5-2 h; and the sieve mesh size is 100-200 mesh.

5. The iodine-barrier packaging material according to claim 1, characterized in that: In step S2, the mass ratio of wood fiber, sodium chloroacetate, water and sodium hydroxide is 1:1.2-2:20-30:1-1.5; the heating reaction temperature is 55-70°C, the heating reaction time is 2-8 hours; and the reaction time at room temperature is 12-36 hours.

6. The iodine-barrier packaging material according to claim 1, characterized in that: In step S3, the mixed solution is obtained by mixing concentrated sulfuric acid and hydrogen peroxide, the concentration of the concentrated sulfuric acid is 11-18 mol / L, the concentration of the hydrogen peroxide is 8-12 mol / L, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 1:2-4; the amount ratio of silicon dioxide to the mixed solution is 1 g:5-8 mL; the heating and stirring treatment temperature is 35-50 ° C, the treatment time is 0.5-4 h, and the stirring rate of the heating and stirring is 80-150 rpm.

7. The iodine-barrier packaging material according to claim 1, characterized in that: In step S4, the mass ratio of modified attapulgite, modified wood fiber, modified silica, tea polyphenols and water is 1:2~3:0.5~1:0.1~0.3:8~12; the heating temperature is 30~35°C, the stirring treatment time is 1~4h, and the stirring rate is 60~120rpm.

8. A method for preparing the iodine-barrier 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 PVA coating liquid on the surface of the vinyl resin heat seal coating and drying the coating to form a modified PVA coating; (3) Applying VC glue on the surface of the modified PVA 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 5~8g / m 2 ; The coating amount of PVA coating liquid is 4~6g / m 2 ; The coating amount of VC glue is 4~6g / m 2 ; The coating amount of polyurethane heat sealant is 5~8g / m 2 .

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