Preparation method of composite packaging film for capsules

Abstract

The invention relates to the technical field of packaging films, in particular to a preparation method of a composite packaging film for capsules, which comprises the following steps: (1) preparing an antibacterial starch layer; (2) preparing a PVA layer; (3) preparing a modified starch solution; and (4) preparing the antibacterial starch / PVA / modified starch film. Starch is adopted as a base material inside and outside, the defect that the function is overcome by compounding multiple traditional different materials is changed, the raw materials are cheap and easy to obtain, and the production cost of an enterprise is greatly reduced; and meanwhile, the composite packaging film is biodegradable, so that the environmental pressure is reduced. The prepared composite film is an antibacterial starch / PVA / modified starch multilayer film, overcomes the defect of poor water resistance of a single-layer antibacterial film, has hydrophobicity and a long-acting antibacterial function, and also has good water vapor barrier property.

Description

Technical Field

[0001] The invention relates to the technical field of packaging films, and in particular to a method for preparing a composite packaging film for capsules. Background Art

[0002] As the pharmaceutical industry market continues to grow, the country has put forward stricter requirements on materials and containers that directly contact drugs while promoting the innovation and upgrading of pharmaceutical research and development. At present, there are three main forms of drug packaging: bottled, bagged and aluminum-plastic packaging. Among them, aluminum-plastic blister packaging is convenient and hygienic for taking medicines, easy for storage and transportation, and is widely used in capsule packaging. Aluminum-plastic blister packaging is a plastic material extruded into a blister shape, and then the drug is placed in the blister, and then heat-sealed with aluminum foil to form a blister package. However, aluminum-plastic blister drugs are prone to problems such as blister dents and damage, powder leakage, and wrinkled and dirty drug plates.

[0003] The plastic materials of aluminum-plastic blister packaging mainly use traditional petroleum-based plastics such as polypropylene (PP), polyethylene (PE) and polyvinyl chloride (PVC), etc. These materials have the disadvantages of being difficult to degrade and non-reusable. Improperly handled plastic waste not only causes serious pollution to the soil, but also seriously restricts the sustainable development of the ocean. Therefore, finding a packaging material that is degradable, has excellent mechanical properties, high transparency, stable chemical properties, non-toxic, and has excellent film-forming properties is still an urgent issue to be solved. Summary of the invention

[0004] In view of the problems existing in the background technology, the present invention provides a method for preparing a composite packaging film for capsules, which can replace the traditional aluminum-plastic blister, has good gas barrier properties and moisture resistance, and can ensure the quality and stability of the drug, and is achieved by the following technical solutions: A method for preparing a composite packaging film for capsules comprises the following steps: a. Preparation of antibacterial starch layer: adding antibacterial microcapsules into starch solution; b. Preparation of PVA layer: Dry PVA and heat to melt; c. Preparation of modified starch solution; d. The antibacterial starch and modified starch solution prepared in the above steps a and c are coated on the upper and lower surfaces of the PVA layer respectively in a certain proportion to obtain a composite packaging film for the capsule.

[0005] Preferably, the preparation method of the antibacterial starch layer in step a is: weigh corn starch, dissolve it in deionized water, prepare a starch solution of a certain concentration, heat and stir until gelatinization, slowly add formamide plasticizer while stirring, then add enhancer, cool to 50°C after full fusion, add antibacterial microcapsules, stir and mix, place in a vacuum drying oven for degassing, and seal for standby use.

[0006] More preferably, the concentration of the starch solution is 2%, the heating gelatinization temperature is 95° C., and the reinforcing agent is cellulose nanofibrils.

[0007] Further preferably, the preparation steps of the antibacterial microcapsules are: adding the antibacterial agent to the gelatin solution and crushing and emulsifying it with a cell crusher to obtain an emulsion of gelatin and the antibacterial agent; dropping the gum arabic solution into the obtained emulsion, stirring for 30 minutes, and adjusting the pH value to perform a complex coagulation reaction; after the reaction is completed, cooling to room temperature, cooling in an ice bath to 5-10°C, then adjusting the pH to 8-9, and adding 2 mL of 0.3% CaCl2 curing agent; after the reaction is complete, washing with distilled water three times, centrifuging with a centrifuge and freeze-drying for 24 hours to obtain a finished antibacterial microcapsule.

[0008] Preferably, the preparation method of the PVA layer in step b is: weigh a certain amount of dry PVA, slowly inject it into 100 mL of deionized water, heat and stir for 2 hours to obtain a 10% PVA solution, cool it to room temperature and seal it for later use.

[0009] Preferably, the preparation method of the modified starch solution in step c is as follows: (1) weighing a certain amount of corn starch and adding it to deionized water, stirring evenly, heating for 5 minutes to gelatinize the starch solution, then adding a certain amount of water to adjust the starch emulsion concentration to 4%, stirring at 90° C. for 15 minutes, then adding stearic acid and hydrochloric acid to the emulsion and heating to 95° C. and stirring for 40 minutes; cooling to room temperature, washing with ethanol three times, then centrifuging to remove unreacted substances, and then placing it in a freeze dryer and drying it for 24 hours to obtain stearic acid starch ester; (2) Weigh a certain amount of stearic acid starch ester and place it in a beaker. Add deionized water solution to form a starch emulsion. Stir the starch emulsion at 95°C until gelatinization. Add a certain amount of plasticizer and enhancer. Lower the temperature to 65°C and keep warm for 20 minutes. Then vacuum dry the film-forming liquid for 5 to 10 minutes to remove bubbles for later use.

[0010] More preferably, the solution concentration of the starch emulsion reaches about 3% (w / w), and the plasticizer is composed of glycerol and azodicarbonamide in a ratio of 1:1.

[0011] Preferably, the preparation method of the antibacterial starch / PVA / modified starch film in step d is: the antibacterial starch and modified starch solution prepared above are respectively coated on the upper and lower surfaces of the PVA layer in a certain proportion to obtain a composite packaging film for capsules, and dried in an oven at 50° C. for 6 to 8 hours to obtain a composite packaging film for capsules.

[0012] The beneficial effects of the present invention are: The present invention changes the traditional method of combining multiple different materials to solve the functional defects. The present invention uses starch as the base material both inside and outside. The raw materials are cheap and easy to obtain, which greatly reduces the production cost of the enterprise. At the same time, the composite packaging film is biodegradable, which reduces environmental pressure. The film uses starch as the base material, cellulose nanofibers as the reinforcing agent, glycerol / azodicarbonamide as the plasticizer, PVA as the isolation layer, and stearic acid is hydrophobically modified to make starch film as the outermost layer to prepare a composite packaging film for capsules. The film is an antibacterial starch / PVA / modified starch multilayer film, which solves the defect of poor water resistance of single-layer antibacterial film, has hydrophobicity and long-lasting antibacterial function, and has good water vapor barrier properties, which can reach 1.3×10 - 10 g cm / cm 2 .s.Pa. DETAILED DESCRIPTION

[0013] The following embodiments of the technical solution of the present invention are described in detail in conjunction with the embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and are therefore only used as examples, and cannot be used to limit the protection scope of the present invention.

[0014] It should be noted that the experimental methods used in the implementation examples are all conventional methods unless otherwise specified; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.

[0015] In the present invention, unless otherwise specified, all "parts" and percentages (%) refer to percentages by weight.

[0016] In the present invention, unless otherwise specified, the sum of all percentages in all compositions is 100%.

[0017] In the present invention, unless otherwise specified, the numerical range "a-b" represents an abbreviation of any real number combination between a-b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.

[0018] In the present invention, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0019] In the present invention, unless otherwise specified, all the steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially; for example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially; for example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0020] In the present invention, unless otherwise specified, the specific numerical values ​​and specific substances in the embodiments of the present invention may be combined with other features of the description part of the present invention; for example, if the specification mentions that the reaction temperature is 10~100°C, and the embodiment mentions that the reaction temperature is 20°C, then it can be considered that the present invention has specifically disclosed the range of 10~20°C, or the range of 20~100°C, and this range can be combined with other features of the description part to form a new technical solution. Example

[0021] The antibacterial agent was added to the gelatin solution and crushed and emulsified with a cell crusher to obtain an emulsion of gelatin and antibacterial agent; the gum arabic solution was added dropwise to the obtained emulsion, stirred for 30 minutes, and the pH value was adjusted to perform a complex coagulation reaction; after the reaction was completed, it was cooled to room temperature and then cooled to 7°C in an ice bath, and then the pH was adjusted to 8-9, and 2 mL of 0.3% CaCl2 curing agent was added; after the reaction was complete, it was washed three times with distilled water, centrifuged in a centrifuge, and freeze-dried for 24 hours to obtain the finished antibacterial microcapsules.

[0022] Weigh 4 g corn starch, dissolve it in deionized water to prepare a 2% starch solution, heat to 95 ° C and stir until gelatinized, slowly add formamide plasticizer while stirring, then add reinforcing agent cellulose nanofibrils, cool to 50 ° C after full fusion, add antibacterial microcapsules, stir and mix, place in a vacuum drying oven for degassing, and seal for later use.

[0023] Weigh 20 g of dry PVA and slowly inject it into 100 mL of deionized water. Heat and stir for 2 hours to obtain a 10% PVA solution. After cooling to room temperature, seal it for later use.

[0024] Weigh 8g corn starch into a 200mL beaker, add 50mL deionized water, stir evenly, heat for 5 minutes to gelatinize the starch solution, then add 150mL water to adjust the starch emulsion concentration to 4%, stir at 90℃ for 15 minutes, then add 2mol / L stearic acid and 0.1mL hydrochloric acid to the emulsion and heat to 95℃, stir for 40 minutes. Cool to room temperature, wash three times with 50% ethanol, then centrifuge to remove unreacted substances, then put it into a freeze dryer and dry it for 24 hours to obtain stearic acid starch ester.

[0025] Weigh 3 g of the above-mentioned stearic acid starch ester and put it in a 150 mL beaker, add 100 mL of deionized water solution to form a starch emulsion of about 3%, stir the starch emulsion at 95°C until gelatinization, add a certain amount of plasticizer and enhancer, reduce the temperature to 65°C, keep warm for 20 minutes, and then vacuum dry the film-forming liquid for 6 minutes to remove bubbles for later use.

[0026] The antibacterial starch / polyvinyl alcohol / modified starch prepared above were coated on the upper and lower surfaces of the PVA layer in a mass ratio of 80 / 20 / 0 to obtain a composite packaging film for capsules, and the composite packaging film for capsules was obtained by drying in an oven at 50°C for 6 hours. Example

[0027] The antibacterial agent was added to the gelatin solution and crushed and emulsified with a cell crusher to obtain an emulsion of gelatin and antibacterial agent; the gum arabic solution was added dropwise to the obtained emulsion, stirred for 30 minutes, and the pH value was adjusted to perform a complex coagulation reaction; after the reaction was completed, it was cooled to room temperature and then cooled to 10°C in an ice bath, and then the pH was adjusted to 9, and 2 mL of 0.3% CaCl2 curing agent was added; after the reaction was complete, it was washed three times with distilled water, centrifuged with a centrifuge, and freeze-dried for 24 hours to obtain the finished antibacterial microcapsules.

[0028] Weigh 4 g corn starch, dissolve it in deionized water to prepare a 2% starch solution, heat to 95 ° C and stir until gelatinized, slowly add formamide plasticizer while stirring, then add reinforcing agent cellulose nanofibrils, cool to 50 ° C after full fusion, add antibacterial microcapsules, stir and mix, place in a vacuum drying oven for degassing, and seal for later use.

[0029] Weigh 20 g of dry PVA and slowly inject it into 100 mL of deionized water. Heat and stir for 2 hours to obtain a 10% PVA solution. After cooling to room temperature, seal it for later use.

[0030] Weigh 8g corn starch into a 200mL beaker, add 50mL deionized water, stir evenly, heat for 5 minutes to gelatinize the starch solution, then add 150mL water to adjust the starch emulsion concentration to 4%, stir at 90℃ for 15 minutes, then add 2mol / L stearic acid and 0.1mL hydrochloric acid to the emulsion and heat to 95℃, stir for 40 minutes. Cool to room temperature, wash three times with 50% ethanol, then centrifuge to remove unreacted substances, then put it into a freeze dryer and dry it for 24 hours to obtain stearic acid starch ester.

[0031] Weigh 3g of stearic acid starch ester and place it in a 150mL beaker, add 100mL of deionized water solution to form a starch emulsion of about 3%, stir the starch emulsion at 95℃ until gelatinization, add a certain amount of plasticizer and enhancer, reduce the temperature to 65℃, keep warm for 20 minutes, and then vacuum dry the film-forming liquid for 10 minutes to remove bubbles for later use.

[0032] The antibacterial starch / polyvinyl alcohol / modified starch prepared above are coated on the upper and lower surfaces of the PVA layer according to a mass ratio of 68 / 17 / 15 to obtain a composite packaging film for capsules, and the composite packaging film for capsules is obtained by drying in an oven at 50° C. for 6 to 8 hours. Example

[0033] The preparation method refers to Example 1. In this example, in the preparation stage of the antibacterial starch / PVA / modified starch film, the antibacterial starch / polyvinyl alcohol / modified starch are coated on the upper and lower surfaces of the PVA layer in a mass ratio of 60 / 15 / 25 to obtain a composite packaging film for capsules, which is then dried in an oven at 50°C for 6 hours to obtain a composite packaging film for capsules. Example

[0034] The preparation method refers to Example 1. In this example, in the preparation stage of the antibacterial starch / PVA / modified starch film, the antibacterial starch / polyvinyl alcohol / modified starch are coated on the upper and lower surfaces of the PVA layer in a mass ratio of 52 / 13 / 35 to obtain a composite packaging film for capsules, which is then dried in an oven at 50°C for 6 hours to obtain a composite packaging film for capsules. Example

[0035] The preparation method refers to Example 1. In this example, in the preparation stage of the antibacterial starch / PVA / modified starch film, the antibacterial starch / polyvinyl alcohol / modified starch are coated on the upper and lower surfaces of the PVA layer in a mass ratio of 40 / 10 / 50 to obtain a composite packaging film for capsules, which is then dried in an oven at 50°C for 6 hours to obtain a composite packaging film for capsules. Example

[0036] The preparation method refers to Example 1. In this example, in the preparation stage of the antibacterial starch / PVA / modified starch film, the antibacterial starch / polyvinyl alcohol / modified starch prepared above are coated on the upper and lower surfaces of the PVA layer in a mass ratio of 0 / 25 / 75 to obtain a composite packaging film for capsules, which is then dried in an oven at 50°C for 6 hours to obtain a composite packaging film for capsules.

[0037] Performance Testing The above-mentioned embodiments 1 to 6 were used as experimental examples, and commercially available PVA films were used as comparative examples for the experiments.

[0038] Water vapor transmission rate test Add 15mL of deionized water to the permeable cup, put in a black sealing ring to prevent the sample from contacting the water at the bottom of the cup, then put in the sample film, then put in another black sealing rubber ring, and finally put in a white sealing ring, and tighten the cup cover. Then put the equipped permeable cup into the corresponding cavity in the water vapor transmission rate tester, and check the water vapor transmission value after 12 hours. Calculate the water vapor transmission coefficient according to formula 1, and take the average value of three tests. Formula 1: WVP=WVTR×( d / ∆P ) WVP: Water Vapor Passage Coefficient; WVTR: Water Vapor Passage Value measured by the instrument; d : Paper thickness; ∆P： Test pressure 0.2MPa.

[0039] Table 1 <![CDATA[Water vapor transmission rate / (g·cm / cm 2 .s·Pa)]]> Example 1 <![CDATA[4.8×10 -10 ]]> Example 2 <![CDATA[1.3×10 -10 ]]> Example 3 <![CDATA[2.5×10 -10 ]]> Example 4 <![CDATA[3.4×10 -10 ]]> Example 5 <![CDATA[2.2×10 -10 ]]> Example 6 <![CDATA[5.6×10 -10 ]]> Comparative Example <![CDATA[1.3×10 -8 ]]> Mechanical properties test The tensile strength of the composite packaging film was measured using a servo high and low temperature controlled tensile testing machine. The tensile speed was 50 mm and 1 mm / s. Each sample should be tested five times and the calculated results were averaged.

[0040] Table 2 Elongation at break / % Tensile strength / MPa Example 1 5.7 17.9 Example 2 12.3 23.2 Example 3 8.2 29.6 Example 4 12.7 18.4 Example 5 14.0 10.4 Example 6 11.5 21.4 Comparative Example 2.4 1.2 The addition of modified starch layer improves the water vapor barrier performance and mechanical properties of the multilayer composite film. Its water vapor transmission coefficient can reach as low as 1.3×10 -10 g cm / cm 2 .s.Pa, meeting the packaging needs of capsules.

[0041] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.

Claims

1. A method for preparing a composite packaging film for capsules, comprising the following steps: Step a, preparation of antibacterial starch layer: adding antibacterial microcapsules into starch solution; Step b, preparation of PVA layer: drying PVA and heating and melting; Step c, preparing a modified starch solution; Step d: coating the antibacterial starch and modified starch solution prepared in the above steps a and c on the upper and lower surfaces of the PVA layer in a certain proportion, respectively, to obtain a composite packaging film for the capsule.

2. The method for preparing a composite packaging film for capsules according to claim 1, characterized in that: The preparation method of the antibacterial starch layer in step a is as follows: weigh corn starch, dissolve it in deionized water, prepare a starch solution of a certain concentration, heat and stir until gelatinization, slowly add formamide plasticizer while stirring, then add enhancer, cool to 50°C after full fusion, add antibacterial microcapsules, stir and mix well, place in a vacuum drying oven for degassing, and seal for standby use.

3. The method for preparing a composite packaging film for capsules according to claim 2, characterized in that: The concentration of the starch solution is 2%, the heating gelatinization temperature is 95°C, and the reinforcing agent is cellulose nanofibrils.

4. The method for preparing a composite packaging film for capsules according to claim 2, characterized in that: The preparation steps of the antibacterial microcapsules are as follows: adding the antibacterial agent to the gelatin solution and crushing and emulsifying it with a cell crusher to obtain an emulsion of gelatin and the antibacterial agent; dropping the gum arabic solution into the obtained emulsion, stirring for 30 minutes, and adjusting the pH value to perform a complex coagulation reaction; after the reaction is completed, cooling to room temperature, cooling in an ice bath to 5-10°C, then adjusting the pH to 8-9, and adding 2 mL of a 0.3% CaCl2 curing agent; after the reaction is complete, washing with distilled water three times, centrifuging with a centrifuge and freeze-drying for 24 hours to obtain a finished antibacterial microcapsule.

5. The method for preparing a composite packaging film for capsules according to claim 1, characterized in that: The preparation method of the PVA layer in step b is: weigh a certain amount of dry PVA, slowly inject it into 100 mL of deionized water, heat and stir for 2 hours to obtain a 10% PVA solution, cool it to room temperature and seal it for later use.

6. The method for preparing a composite packaging film for capsules according to claim 1, characterized in that: The preparation method of the modified starch solution in step c is: (1) Weigh a certain amount of corn starch and add it to deionized water, stir it evenly, heat it for 5 minutes to gelatinize the starch solution, then add a certain amount of water to adjust the starch emulsion concentration to 4%, stir it at 90°C for 15 minutes, then add stearic acid and hydrochloric acid to the emulsion and heat it to 95°C, stir it for 40 minutes, cool it to room temperature, wash it with ethanol three times, then centrifuge it to remove unreacted substances, and then put it into a freeze dryer to dry it for 24 hours to obtain stearic acid starch ester; (2) Weigh a certain amount of stearic acid starch ester and place it in a beaker. Add deionized water solution to form a starch emulsion. Stir the starch emulsion at 95°C until gelatinization. Add a certain amount of plasticizer and enhancer and then lower the temperature to 65°C. Keep the temperature for 20 minutes. Then vacuum dry the film-forming liquid for 5 to 10 minutes to remove bubbles for later use.

7. The method for preparing a composite packaging film for capsules according to claim 6, characterized in that: The solution concentration of the starch emulsion reaches about 3% (w / w), and the plasticizer is composed of glycerol and azodicarbonamide in a ratio of 1:

1.

8. The method for preparing a composite packaging film for capsules according to claim 1, characterized in that: The preparation method of the antibacterial starch / PVA / modified starch film in step d is: the antibacterial starch and modified starch solution prepared above are respectively coated on the upper and lower surfaces of the PVA layer in a certain proportion to obtain a composite packaging film for capsules, and the composite packaging film for capsules is obtained by drying in an oven at 50° C. for 6 to 8 hours.