CN112831070B - Preparation method of functional composite fruit and vegetable preservative film - Google Patents

Preparation method of functional composite fruit and vegetable preservative film Download PDF

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CN112831070B
CN112831070B CN202011642591.4A CN202011642591A CN112831070B CN 112831070 B CN112831070 B CN 112831070B CN 202011642591 A CN202011642591 A CN 202011642591A CN 112831070 B CN112831070 B CN 112831070B
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ethyl cellulose
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film
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邵平
吴唯娜
刘黎明
陈杭君
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Zhejiang University of Technology ZJUT
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Abstract

A preparation method of a functional composite fruit and vegetable preservative film comprises the following steps: preparing a carboxymethyl chitosan hydrogel film; (2) Adding 0.02-0.1 part of 1-methylcyclopropene generating agent and 0.02-0.1 part of palladium-carbon into 20mL of adhesive to obtain preservative solution; uniformly pouring the preservative solution on the hydrogel film obtained in the step (1), and drying at room temperature to obtain a preservative layer; (3) Weighing 1-2 parts of ethyl cellulose, dissolving the ethyl cellulose in 50 parts of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding glycerol to enable the concentration of the glycerol to be 0.5-1wt%, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and removing to obtain the composite fruit and vegetable preservative film. The preservative can induce the preservative layer to play a role according to water vapor generated by respiration of fruits and vegetables, has good internal moisturizing and humidifying performance and external waterproof and air permeability, and can effectively prolong the quality guarantee period of the fruits and vegetables.

Description

Preparation method of functional composite fruit and vegetable preservative film
(I) the technical field
The invention belongs to the field of packaging materials, and particularly relates to a preparation method of a functional composite fruit and vegetable preservative film.
(II) technical background
Fruits and vegetables play an important role in the daily dietary structure of people, but most fruits and vegetables are easy to decay, so that serious economic loss is caused. Fruit and vegetable rot caused by postharvest diseases in developed countries is generally lower than 5%, and the average loss rate of postharvest fruits in China is higher than 30%, so that the development of a safe and effective preservative and fresh-keeping technology for prolonging or maintaining the quality of fruits and vegetables becomes an important food research subject.
Because the fresh fruits and vegetables have the characteristic of generating ethylene in the growth and maturation process, the existence of the ethylene in the picked fruit and vegetable packages can directly influence the picked color, nutrient and freshness of the fruits and vegetables, so that the fruits and vegetables lose water and are wilted, the nutrient is lost, the fruits and vegetables are rotted and become stale, and the shelf life is shortened. The fruit and vegetable package has the function of improving the internal environment of the fruit and vegetable package while keeping the unique external sensory quality of the product. 1-methylcyclopropene (1-MCP) is a fruit and vegetable preservative which is used more at present, but the fumigation treatment condition of 1-MCP is complex, the space needs to be sealed, the preservative is released instantly, the concentration is difficult to control, professional personnel are generally required to operate, and otherwise the expected effect is difficult to achieve. Since ethylene in the storage and transportation environment is not only derived from endogenous ethylene, but also in part from exogenous ethylene, it is also important to remove and absorb ethylene in the storage and transportation environment. The common ethylene adsorbent potassium permanganate has potential safety hazard of polluting fruits and vegetables, and the physical adsorption type also has the possibility of desorption, so the application is limited to a certain extent.
Patent CN 201710689522.0 discloses a high-efficiency ethylene absorbent for fruit and vegetable preservation and a preparation method thereof, wherein the high-efficiency ethylene absorbent comprises a high-efficiency adsorption carrier loaded with saturated potassium permanganate and active calcium oxide, but potassium permanganate used in the method has the hidden danger of polluting fruits and vegetables. Patent CN201920045188.X discloses a manufacturing method of a fruit, vegetable and flower fresh-keeping bag, wherein a fresh-keeping laminate is adhered to the inner layer of the packaging bag, and the laminate comprises a high-breathability layer and a fresh-keeping agent layer, but the fresh-keeping agent in the fresh-keeping bag only adopts 1-MCP, ethylene cannot be removed from multiple aspects, and the high-breathability layer of the inner layer cannot inhibit a small amount of release of the fresh-keeping agent in the storage process of the fresh-keeping bag.
Disclosure of the invention
Aiming at the problems, the invention aims to provide a preparation method of a composite fruit and vegetable preservative film.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a composite fruit and vegetable preservative film, which consists of a hydrogel film layer, a preservative layer and a barrier layer; the preparation method comprises the following steps:
(1) Preparing a carboxymethyl chitosan hydrogel film;
(2) Adding 0.02-0.1 part of 1-methylcyclopropene generating agent and 0.02-0.1 part of palladium-carbon into 20mL of adhesive to obtain preservative solution; uniformly pouring the preservative solution on the hydrogel film obtained in the step (1), and drying at room temperature to obtain a preservative layer; said adhesive is 2-4% w/v ethyl cellulose ethanol solution;
(3) Weighing 1-2 parts of ethyl cellulose, dissolving the ethyl cellulose in 50 parts of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding glycerol to enable the concentration of the glycerol to be 0.5-1wt%, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and tearing off to obtain the composite fruit and vegetable preservative film.
Preferably, the carboxymethyl chitosan hydrogel film is prepared by the following steps:
weighing 2-5 parts of carboxymethyl chitosan, dissolving in 200 parts of pure water, and stirring to completely dissolve the carboxymethyl chitosan to obtain a carboxymethyl chitosan solution; weighing 0.03-0.1 part of genipin, dissolving in 10 parts of pure water in advance, dropwise adding into carboxymethyl chitosan solution, performing ultrasonic treatment to uniformly disperse the genipin in the solution, and standing for 4-12h to complete crosslinking to obtain hydrogel solution; pouring the hydrogel solution onto a glass plate, and drying to obtain the hydrogel film.
Further preferably, in the step (1), the drying temperature is 30 to 60 ℃.
In the invention, the parts are all parts by mass.
The hydrogel film layer in the functional composite fruit and vegetable preservative film prepared by the invention is in contact with the internal environment of the film, and the ethyl cellulose layer is in contact with the external environment, so that the preservative film can play a role according to the water vapor generated by the respiration of fruits and vegetables, has good internal moisture retention and humidity regulation and external waterproof and air permeability, and can effectively prolong the shelf life of the fruits and vegetables.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the preservative particles are loaded between the moisture absorption inner layer and the moisture blocking outer layer of the film as the middle layer, the inner layer film absorbs moisture under high relative humidity to promote the preservative to generate effect, and can be used as a barrier layer of the preservative particles together with the moisture blocking layer under low relative humidity, so that the loss of effective components caused by the advanced effect of the preservative when not applied is avoided, and the moisture blocking outer layer can prolong the effect life of the preservative particles and the moisture absorption inner layer.
Specifically, the humidity-adjusting inner layer can adjust the humidity in the fruit and vegetable package, absorb water vapor in the package when the relative humidity in the package is high, avoid overhigh humidity and condensed water in the package, release the absorbed water into the package when the humidity is low, and avoid the fruit and vegetable from losing water and losing freshness; after the moisture-adjusting inner layer absorbs water vapor, the swelling behavior of hydrophilic polymer molecules enables the polymer meshes to be enlarged, the gas permeability to be correspondingly increased, and the separation barrier between the preservative particles and the fruits and vegetables is weakened, so that the preservative is more likely to act on the fruits and vegetables, and ethylene gas generated by the fruits and vegetables is more likely to enter the middle layer and be removed; after the moisture absorption of the inner layer is regulated, the acting force between water molecules and cyclodextrin of the shell layer of the 1-MCP preservative in the adjacent middle layer is higher than the acting force between the 1-MCP and the cyclodextrin, when the moisture content is high, the cyclodextrin shell layer is directly dissolved in water, and the 1-MCP gas is actively released to act on fruits and vegetables; when the moisture-adjusting agent is not applied to fruits and vegetables, the relative humidity is low, and the moisture-adjusting inner layer and the moisture-blocking outer layer are compact in structure and can be used as a barrier layer to inhibit the release of the preservative. Therefore, the film can only play a role in actual application, and the problem of inconvenient application and storage is solved. The film has humidity response controlled release effect on preservative particles, and the release rates of the preservative are different under different relative humidity.
2. According to the invention, 1-MCP and palladium-loaded active carbon act on fruits and vegetables together, so that on one hand, ethylene generated by the fruits and vegetables is inhibited and catalyzed after adsorption, on the other hand, the ethylene is inhibited from being combined with a receptor, and the storage time of the fruits and vegetables can be obviously prolonged.
Specifically, 1-MCP is widely used as an ethylene inhibitor in the postharvest treatment process of respiratory transition fruits and vegetables, and can block the action of ethylene at a receptor level and inhibit the synthesis of ethylene. In addition, exogenous ethylene also affects the quality of fruits and vegetables, and the problem cannot be solved by using 1-MCP alone. Therefore, the invention adopts the combination of the 1-MCP and the activated carbon loaded with metal palladium to coat the intermediate layer of the film, the 1-MCP blocks the combination of ethylene and a receptor, and simultaneously, the activated carbon loaded with metal palladium firstly adsorbs ethylene onto palladium/carbon and then carries out catalytic reaction on the surface to remove the ethylene. And with the humidity control function complex of film itself, use at the commodity circulation in-process, control the influence of fruit vegetables from a plurality of aspects, the function is complete, and is various, has restrained the commodity circulation, stores and sells the fruit vegetables loss that probably takes place in-process.
Description of the drawings
FIGS. 1-a, 1-b and 1-c show the release performance of 1-MCP of the composite fruit and vegetable preservative films prepared in the examples and the comparative examples at 50%, 75% and 100 humidity respectively;
FIGS. 2-a, 2-b and 2-c show the ethylene clearance rate of the composite fruit and vegetable preservative films prepared in the examples and the comparative examples at 50%, 75% and 100 humidity respectively.
FIGS. 3-a and 3-b show the change of ACO and ACS enzyme activities of the composite fruit and vegetable preservative films prepared in the examples and comparative examples during storage, respectively.
(V) detailed description of the preferred embodiments
The following examples are set forth in order to provide a thorough understanding of the invention and to provide a further understanding of the invention. However, the present invention is not limited by the following examples.
The various sources of raw materials used in the examples:
ethyl cellulose: 90-110mPa Shanghai Mecang Biotech, inc.;
carboxymethyl chitosan: the degree of substitution is more than or equal to 80 percent, shanghai Maxlin Biochemical technology Co., ltd;
genipin: 98%, shanghai Michelin Biochemical technology, inc.;
glycerol: 99%, west longa science, inc;
ethanol: 99.7%, shanghai Michelin Biotechnology, inc.;
palladium on carbon: 5%, shanghai Aladdin Biotechnology, inc.;
1-methylcyclopropene generator: 3.5% of 1-MCP, shanghai-derived leaf Biotechnology Co., ltd.
Example 1
(1) Weighing 2g of carboxymethyl chitosan, dissolving in 200mL of pure water, and stirring to completely dissolve the carboxymethyl chitosan to obtain a carboxymethyl chitosan solution; weighing 0.03g of genipin, dissolving the genipin in 10mL of pure water in advance, dropwise adding the pure water into a carboxymethyl chitosan solution, performing ultrasonic treatment to uniformly disperse the genipin in the solution, and standing for 4 hours to complete crosslinking to obtain a hydrogel solution; pouring the hydrogel solution onto a 20-0 cm glass plate, and drying in an air drying oven at 50 ℃ to obtain a hydrogel film;
(2) Adding 0.1g of 1-methylcyclopropene generator (3.5% of 1-MCP content) and 0.1g of palladium carbon into 20mL of adhesive (2.4% w/v ethyl cellulose ethanol solution) to obtain an antistaling agent solvent; and (2) uniformly pouring the preservative solution onto the hydrogel film obtained in the step (1), and drying at room temperature to form a preservative layer.
(3) Weighing 1g of ethyl cellulose, dissolving the ethyl cellulose in 50mL of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding glycerol to enable the concentration of the glycerol to be 0.5wt%, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and tearing off to obtain the composite fruit and vegetable preservative film.
Example 2
(1) Weighing 5g of carboxymethyl chitosan, dissolving in 200mL of pure water, and stirring to completely dissolve the carboxymethyl chitosan to obtain a carboxymethyl chitosan solution; weighing 0.05g of genipin, dissolving in 10mL of pure water in advance, dropwise adding the obtained solution into a carboxymethyl chitosan solution, carrying out ultrasonic treatment to uniformly disperse the genipin in the solution, standing for 12 hours to complete crosslinking, and fully dispersing to obtain a hydrogel solution; pouring the hydrogel solution into a 20-inch (0 cm) glass plate, and drying in a forced air drying oven at 50 ℃ to obtain a hydrogel film;
(2) Adding 0.02g of 1-methylcyclopropene generator (3.5% of 1-MCP content) and 0.06g of palladium carbon into 20mL of adhesive (2.4% w/v ethyl cellulose) to obtain an antistaling agent solvent; and (2) uniformly pouring the preservative solution onto the hydrogel film obtained in the step (1), and drying at room temperature to form a preservative layer.
(3) Weighing 1.5g of ethyl cellulose, dissolving the ethyl cellulose in 50mL of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding glycerol to enable the concentration of the glycerol to be 1wt%, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and removing to obtain the composite fruit and vegetable preservative film.
Example 3
(1) Weighing 3g of carboxymethyl chitosan, dissolving in 200mL of pure water, and stirring to completely dissolve the carboxymethyl chitosan to obtain a carboxymethyl chitosan solution; weighing 0.1g of genipin, dissolving in 10 parts of pure water in advance, dropwise adding the obtained solution into a carboxymethyl chitosan solution, carrying out ultrasonic treatment to uniformly disperse the genipin in the solution, standing for 8 hours to complete crosslinking, and fully dispersing to obtain a hydrogel solution; pouring the hydrogel solution into a 20-0 cm glass plate, and drying in an air drying oven at 30 ℃ to obtain a hydrogel film;
(2) Adding 0.06g of 1-methylcyclopropene generator (3.5% of 1-MCP content) and 0.02g of palladium on carbon to 20mL of an adhesive (2.4% w/v ethyl cellulose) to obtain an antistaling agent solvent; and (2) uniformly pouring the preservative solution onto the hydrogel film obtained in the step (1), and drying at room temperature to form a preservative layer.
(3) Weighing 2g of ethyl cellulose, dissolving the ethyl cellulose in 50mL of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding 0.7% of glycerol, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and removing to obtain the composite fruit and vegetable preservative film.
Comparative example 1
(1) Weighing 2g of carboxymethyl chitosan, dissolving in 200mL of pure water, and stirring to completely dissolve the carboxymethyl chitosan to obtain a carboxymethyl chitosan solution; weighing 0.03g of genipin, dissolving the genipin in 10mL of pure water in advance, dropwise adding the pure water into a carboxymethyl chitosan solution, performing ultrasonic treatment to uniformly disperse the genipin in the solution, and standing for 4 hours to complete crosslinking to obtain a hydrogel solution; pouring the hydrogel solution into a 20-inch (0 cm) glass plate, and drying in a forced air drying oven at 50 ℃ to obtain a hydrogel film;
(2) Adding 0.1g of 1-methylcyclopropene generator (1-MCP content 3.5%) to 20mL of an adhesive (2.4% w/v ethyl cellulose ethanol solution) to obtain a preservative solvent; and (3) uniformly pouring the preservative solution onto the hydrogel film obtained in the step (1), and drying at room temperature to form a preservative layer.
(3) Weighing 1g of ethyl cellulose, dissolving the ethyl cellulose in 50mL of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding 0.5% of glycerol, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and removing to obtain the 1-MCP-independently-loaded functional fruit and vegetable preservative film (1-MCP-loaded).
Comparative example 2
(1) Weighing 2g of carboxymethyl chitosan, dissolving in 200mL of pure water, and stirring to completely dissolve the carboxymethyl chitosan to obtain a carboxymethyl chitosan solution; weighing 0.03g of genipin, dissolving the genipin in 10mL of pure water in advance, dropwise adding the solution into a carboxymethyl chitosan solution, performing ultrasonic treatment to uniformly disperse the genipin in the solution, and standing for 4 hours to complete crosslinking to obtain a hydrogel solution; pouring the hydrogel solution into a 20-0 cm glass plate, and drying in an air drying oven at 50 ℃ to obtain a hydrogel film;
(2) Adding 0.1g of palladium-carbon into 20mL of adhesive (2.4% w/v ethyl cellulose ethanol solution) to obtain a preservative solvent; and (3) uniformly pouring the preservative solution onto the hydrogel film obtained in the step (1), and drying at room temperature to form a preservative layer.
(3) Weighing 1g of ethyl cellulose, dissolving the ethyl cellulose in 50mL of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding 0.5% of glycerol, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and removing to obtain the functional fruit and vegetable preservative film (Pd/C loaded) independently loaded with palladium and carbon.
Comparative example 3
(1) Weighing 2g of carboxymethyl chitosan, dissolving in 200mL of pure water, and stirring to completely dissolve the carboxymethyl chitosan to obtain a carboxymethyl chitosan solution; weighing 0.03g of genipin, dissolving the genipin in 10mL of pure water in advance, dropwise adding the pure water into a carboxymethyl chitosan solution, performing ultrasonic treatment to uniformly disperse the genipin in the solution, and standing for 4 hours to complete crosslinking to obtain a hydrogel solution; pouring the hydrogel solution into a 20-inch (0 cm) glass plate, and drying in a forced air drying oven at 50 ℃ to obtain a hydrogel film;
(2) Weighing 1g of ethyl cellulose, dissolving the ethyl cellulose in 50mL of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding 0.5% of glycerol, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and removing to obtain the functional fruit and vegetable preservative film (unloaded) without preservative particles.
The testing method of the membrane obtained in the embodiment of the invention is as follows:
(1) Ethylene clearance and 1-MCP release rate determination methods:
gas chromatography (Agilent, USA) was used to analyze the ability of the film to remove ethylene and release 1-MCP. Film samples were cut to 100cm 2 The portion of (2) was put into a 50mL glass tube and then sealed with a cap fitted with a spacer. An ethylene standard was injected into the prepared glass tube so that the ethylene concentration in the tube reached 5. Mu.L -1 . The glass tubes were incubated at 25 ℃. Next, 2mL of headspace gas was collected from the glass tube and injected into the gas chromatograph. The ability of the film to degrade ethylene gas and release 1-MCP gas was investigated by measuring the ethylene concentration and 1-MCP concentration in the vessel after 8, 12, 16, 24 and 48 hours. The ethylene degradation and 1-MCP release rate (%) were calculated using the equation.
Figure BDA0002881159930000091
Figure BDA0002881159930000092
Wherein C is t=0 And C t=t Are the initial time and the ethylene concentration at time t, respectively. D S Is the concentration of 1-MCP in a glass tube after 0.1g1-MCP powder is directly dissolved in water and completely released, D t=t Is the concentration of 1-MCP at time t.
The results are shown in FIGS. 1-a, 1-b, 1-c, 2-a, 2-b, 2-c:
the results showed that only a very small amount of 1-MCP release was observed at 50% relative humidity, whereas at 100% relative humidity, the amount of 1-MCP released was close to the total amount released at that time by 1-MCP powder directly dissolved in water. There is also a significant difference in the ethylene removal capacity of the films at different relative humidities. At 50% relative humidity, ethylene removal was lowest, while at 100% relative humidity, most of the ethylene was removed. The film has the function of controlling the function of the antistaling agent by humidity response.
(2) A fresh-keeping effect measuring method (taking agaricus bisporus as an example):
every 500 g of mushrooms are put into a 1L preservation box and sealed by a film. All mushrooms were stored in an incubator (RXZ-280A, ningbo Jiangnan Instrument works) at 20 + -0.5 deg.C to simulate a room temperature environment. The characteristics of the mushrooms were measured every two days.
1-aminocyclopropane-1-carboxylic Acid (ACC) synthetase (ACS) and ACC oxidase (ACO) enzyme activities assay: 5mL of extraction buffer was added to 5g of mushroom tissue, and the homogenate was ground in an ice bath and then centrifuged at 12000 Xg at 4 ℃ for 30 minutes, and the collected supernatant was an enzyme extract. And detecting the ACS and ACO enzyme activities by using a Jiangsu Jingmei kit.
The results are shown in FIGS. 3-a and 3-b. The results show that ACS, ACO enzyme activity increases during storage. On the sixth day, the activity of the mushroom related enzyme preserved by the composite preservative film is lowest, the enzyme activities of ACS and ACO related to ethylene are inhibited, and the synthesis of ethylene is delayed. And the composite preservative film has more excellent effect of inhibiting the agaricus bisporus ethylene than the effect of singly using a 1-MCP preservative film and a Pd/C preservative film.

Claims (3)

1. A preparation method of a composite fruit and vegetable preservative film comprises a hydrogel film layer, a preservative layer and a barrier layer; the preparation method comprises the following steps:
(1) Preparing a carboxymethyl chitosan hydrogel film;
(2) Adding 0.02-0.1 part of 1-methylcyclopropene generator and 0.02-0.1 part of palladium-carbon into 20mL of adhesive to obtain preservative solution; uniformly pouring the preservative solution on the hydrogel film obtained in the step (1), and drying at room temperature to obtain a preservative layer; the adhesive is ethyl cellulose ethanol solution with the content of w/v being 2-4 percent;
(3) Weighing 1-2 parts of ethyl cellulose, dissolving the ethyl cellulose in 50 parts of ethanol, heating and stirring to completely dissolve the ethyl cellulose, adding glycerol to enable the concentration of the glycerol to be 0.5-1wt%, and continuously stirring uniformly to obtain an ethyl cellulose solution; and (3) pouring the ethyl cellulose solution onto the preservative layer obtained in the step (2), drying at room temperature to form a barrier layer, and tearing off to obtain the composite fruit and vegetable preservative film.
2. The method of claim 1, wherein: the carboxymethyl chitosan hydrogel film is prepared by the following steps:
weighing 2-5 parts of carboxymethyl chitosan, dissolving in 200 parts of pure water, and stirring to completely dissolve the carboxymethyl chitosan to obtain a carboxymethyl chitosan solution; weighing 0.03-0.1 part of genipin, dissolving in 10 parts of pure water in advance, dropwise adding the obtained solution into a carboxymethyl chitosan solution, performing ultrasonic treatment to uniformly disperse the genipin in the solution, and standing for 4-12h to complete crosslinking to obtain a hydrogel solution; pouring the hydrogel solution onto a glass plate, and drying to obtain the hydrogel film.
3. The method of claim 2, wherein: in the step (1), the drying temperature is 30-60 ℃.
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