CN112743943B - Controlled release type degradable active packaging film and preparation method and application thereof - Google Patents
Controlled release type degradable active packaging film and preparation method and application thereof Download PDFInfo
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- CN112743943B CN112743943B CN202011618379.4A CN202011618379A CN112743943B CN 112743943 B CN112743943 B CN 112743943B CN 202011618379 A CN202011618379 A CN 202011618379A CN 112743943 B CN112743943 B CN 112743943B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
Abstract
The invention provides a controlled release type degradable active packaging film and a preparation method and application thereof, wherein the inner layer of the film in a multilayer composite structure is a cellulose acetate film containing glycerol, the middle layer is a starch/polyvinyl alcohol film composed of active substances, the outer layer is a polylactic acid film or a poly adipic acid/butylene terephthalate film, and the active substances comprise an antibacterial agent and an antioxidant; the glycerol and the cellulose acetate in the inner layer film interact to form a plasticizing area in the cellulose acetate film, the film with nano pores can be formed under the action of water flow with certain pressure, and the porosity is increased along with the increase of the glycerol content, so that the permeability of the film is increased, and the release of active substances in the middle layer is accelerated; meanwhile, the size and porosity of the gaps formed in the cellulose acetate film are increased along with the increase of the water flow pressure, so that the permeability of the film is increased, and the release of active substances is accelerated.
Description
Technical Field
The invention belongs to the technical field of composite films, and particularly relates to a controlled-release type degradable active packaging film and a preparation method and application thereof, in particular to a multilayer composite controlled-release type degradable active packaging film based on regulation and control of a cellulose acetate film with glycerol in an inner layer, and a preparation method and application thereof.
Background
Compared with the traditional food packaging technology, the active packaging technology has incomparable advantages, can improve the food quality and prolong the food shelf life, and becomes a hot spot for domestic and foreign research, and the research of the active packaging film material is one of the active packaging film materials. The active packaging film has the functions of resisting bacteria, resisting oxidation and the like by mainly adding active substances into the polymer, can effectively inhibit the spoilage of foods and achieves the effect of prolonging the shelf life of the foods. In addition, due to the exhaustion of petroleum resources and the increasing problem of environmental pollution, the degradable packaging film material becomes a focus of research and development at home and abroad. Starch and PVA are degradable high polymer materials, and researches show that the starch/PVA film has better mechanical property, transparency, gas barrier property and the like, is widely applied to the fields of food packaging, agriculture, biomedicine and the like, and is a green and sustainable production material capable of replacing petroleum-based packaging. The controlled release active packaging film is one type of active packaging, which is prepared by taking a film material as a base material, adding active substances such as an antibacterial agent, an antioxidant and the like into the film base material, and preparing the active film with antibacterial, antioxidant and the like by a film forming technology. The effective acting time of the active substances is regulated by regulating the release rate of the active substances to ensure that the active substances are released slowly and continuously, so that the shelf life of the food is prolonged. Patent CN 107379703B discloses a controlled release type active packaging film and a preparation method thereof, the film is a multilayer composite structure, and is composed of an inner layer, an intermediate layer and an outer layer, the permeability of the inner layer film is regulated by an inner layer laser drilling process, thereby realizing the control of the release rate of active substances in the intermediate active layer and achieving the purpose of controlled release.
Disclosure of Invention
In view of the shortcomings in the prior art, the primary purpose of the invention is to provide a controlled release type degradable active packaging film.
A second object of the present invention is to provide a method for preparing the above-mentioned controlled release type degradable active packaging film.
It is another object of the present invention to provide the use of the controlled release type degradable active packaging film.
To achieve the above primary object, the solution of the present invention is:
the controlled release degradable active packaging film is a multilayer composite structure, and is specifically prepared by compositing an inner layer, an intermediate layer and an outer layer; the inner layer is a cellulose acetate film containing glycerol, the middle layer is a starch/polyvinyl alcohol film composed of active substances, the outer layer is a degradable film, and the degradable film is selected from more than one of polylactic acid film and poly adipic acid/butylene terephthalate film.
The active substance is selected from more than one of antibacterial agent and antioxidant.
Preferably, the cellulose acetate film in the inner layer is 67-95wt% and the glycerol is 5-33wt%.
Preferably, the content of active substance in the intermediate layer is 1-15wt%. The antibacterial agent is sodium lactate, and the antioxidant is anthocyanin.
To achieve the second object, the solution of the present invention is:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of glycerol-containing cellulose acetate film: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing 10+/-0.1 g of cellulose acetate, glycerol and the acetone aqueous solution, stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution, spreading the first mixed solution on a glass plate, drying at 25+/-1 ℃ for 15+/-1 min, removing the cellulose acetate film containing glycerol from the glass plate, then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.3-0.8MPa, and finally placing the film into an oven for drying to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing active substances: mixing 4+/-0.1 g of corn starch with water, stirring in a water bath at 95+/-1 ℃ until the corn starch is completely dissolved to obtain a starch solution, mixing 4+/-0.1 g of polyvinyl alcohol (PVA) resin with water, and stirring in the water bath at 95+/-1 ℃ until the polyvinyl alcohol resin is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2+/-0.01 g of glycerol and 1.2+/-0.01 g of citric acid, mixing, and stirring in a water bath at 95+/-1 ℃ until the mixture is uniform to obtain a second mixed solution; then cooling the second mixed solution to 45 ℃, adding 1.2+/-0.01 g of active substance, stirring in a water bath at 45 ℃ until the active substance and the active substance are uniformly mixed, and performing ultrasonic defoaming for later use.
(3) Preparing a three-layer composite film:
spreading the cellulose acetate film containing glycerol prepared in the step (1) on a glass plate, clamping two ends of the cellulose acetate film by using clamps, spreading the starch/polyvinyl alcohol film liquid containing active substances in the step (2) on the cellulose acetate film, and drying for 1+/-0.1 h at 45+/-1 ℃ to obtain a composite film;
and (3) carrying out a dry compounding process on the polylactic acid film or the poly (adipic acid)/butylene terephthalate film and the composite film on the outer layer to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
In the step (2), the active substance is selected from more than one of an antibacterial agent and an antioxidant, wherein the antibacterial agent is sodium lactate, and the antioxidant is anthocyanin.
To achieve the other object, the solution of the present invention is:
the controlled release type degradable active packaging film can be applied to food packaging.
By adopting the scheme, the invention has the beneficial effects that:
the glycerol and the cellulose acetate in the inner layer film interact to form a plasticizing area in the cellulose acetate film, and the film with nano pores can be formed under the action of water flow with certain pressure, so that the porosity is increased along with the increase of the glycerol content, the permeability of the film is increased, and the release of active substances in the middle layer is accelerated; meanwhile, the size and the porosity of the gaps formed in the cellulose acetate film are increased along with the increase of the water flow pressure, so that the permeability of the film is increased, and the release of active substances is accelerated.
The second, the degradable active packaging film of the invention takes degradable material as film base material, the film is a multi-layer composite structure, comprising an inner layer, an intermediate layer and an outer layer, the film is based on the multi-layer composite controlled release principle, the starch/PVA active film layer is taken as the intermediate layer, the cellulose acetate film containing glycerin is taken as the inner layer material, the outer layer is a degradable film such as polylactic acid film or poly adipic acid/butylene terephthalate film, etc., the multi-layer composite film is prepared, the release of active substances such as antibiosis, antioxidation, etc. can be regulated and controlled by regulating the permeability of the inner layer cellulose acetate film, the controlled release effect is achieved, thereby being applied to food packaging, being more beneficial to protecting food, prolonging the shelf life of food, and simultaneously the material is green and environment-friendly.
Drawings
FIG. 1 is a graph showing the release amount of sodium lactate from a film into a food simulant (water) in the films of examples and comparative examples according to the present invention.
FIG. 2 is a graph showing the release amount of anthocyanin in the films from the films into the food simulant (water) in the examples and comparative examples of the present invention with time.
Detailed Description
The invention provides a controlled release type degradable active packaging film, and a preparation method and application thereof.
The present invention is further illustrated by the following examples and comparative examples.
Example 1:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 5wt% glycerol: preparing an aqueous acetone solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 0.53g of glycerol and 90g of the aqueous acetone solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.8MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing sodium lactate: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then the second mixed solution is cooled to 45 ℃, then 1.2g of sodium lactate (serving as an antibacterial agent) is added, and the mixture is stirred in a water bath at 45 ℃ until the mixture is uniformly mixed, and then ultrasonic defoaming is carried out for later use.
(3) Preparing a three-layer composite film:
spreading the glycerin-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the film by using clamps, spreading the sodium lactate-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying the film for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry type compounding process on the polylactic acid film and the composite film on the outer layer to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Example 2:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 33wt% glycerol: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 5g of glycerol and 90g of acetone aqueous solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.8MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing sodium lactate: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then the second mixed solution is cooled to 45 ℃, then 1.2g of sodium lactate (serving as an antibacterial agent) is added, and the mixture is stirred in a water bath at 45 ℃ until the mixture is uniformly mixed, and then ultrasonic defoaming is carried out for later use.
(3) Preparing a three-layer composite film:
spreading the glycerin-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the film by using clamps, spreading the sodium lactate-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying the film for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry type compounding process on the polylactic acid film and the composite film on the outer layer to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Example 3:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 33wt% glycerol: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 5g of glycerol and 90g of acetone aqueous solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.3MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing sodium lactate: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then the second mixed solution is cooled to 45 ℃, then 1.2g of sodium lactate (serving as an antibacterial agent) is added, and the mixture is stirred in a water bath at 45 ℃ until the mixture is uniformly mixed, and then ultrasonic defoaming is carried out for later use.
(3) Preparing a three-layer composite film:
spreading the glycerin-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the film by using clamps, spreading the sodium lactate-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying the film for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry type compounding process on the polylactic acid film and the composite film on the outer layer to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Example 4:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 33wt% glycerol: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 5g of glycerol and 90g of acetone aqueous solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.5MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing sodium lactate: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then the second mixed solution is cooled to 45 ℃, then 1.2g of sodium lactate (serving as an antibacterial agent) is added, and the mixture is stirred in a water bath at 45 ℃ until the mixture is uniformly mixed, and then ultrasonic defoaming is carried out for later use.
(3) Preparing a three-layer composite film:
spreading the glycerin-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the film by using clamps, spreading the sodium lactate-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying the film for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry type compounding process on the polylactic acid film and the composite film on the outer layer to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Example 5:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 5wt% glycerol: preparing an aqueous acetone solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 0.53g of glycerol and 90g of the aqueous acetone solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.8MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of anthocyanin-containing starch/polyvinyl alcohol film liquid: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then cooling the second mixed solution to 45 ℃, adding 1.2g of anthocyanin (serving as an antioxidant) into the second mixed solution, stirring the mixture in a water bath at 45 ℃ until the mixture is uniformly mixed, and performing ultrasonic defoaming for later use.
(3) Preparing a three-layer composite film:
spreading the glycerol-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the glycerol-containing cellulose acetate film by using clamps, spreading the anthocyanin-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry compounding process on the outer-layer poly (adipic acid)/butylene terephthalate film and the composite film to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Example 6:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 33wt% glycerol: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 5g of glycerol and 90g of acetone aqueous solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.8MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of anthocyanin-containing starch/polyvinyl alcohol film liquid: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then cooling the second mixed solution to 45 ℃, adding 1.2g of anthocyanin (serving as an antioxidant) into the second mixed solution, stirring the mixture in a water bath at 45 ℃ until the mixture is uniformly mixed, and performing ultrasonic defoaming for later use.
(3) Preparing a three-layer composite film:
spreading the glycerol-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the glycerol-containing cellulose acetate film by using clamps, spreading the anthocyanin-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry compounding process on the outer-layer poly (adipic acid)/butylene terephthalate film and the composite film to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Example 7:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 33wt% glycerol: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 5g of glycerol and 90g of acetone aqueous solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.3MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of anthocyanin-containing starch/polyvinyl alcohol film liquid: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then cooling the second mixed solution to 45 ℃, adding 1.2g of anthocyanin (serving as an antioxidant) into the second mixed solution, stirring the mixture in a water bath at 45 ℃ until the mixture is uniformly mixed, and performing ultrasonic defoaming for later use.
(3) Preparing a three-layer composite film:
spreading the glycerol-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the glycerol-containing cellulose acetate film by using clamps, spreading the anthocyanin-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry compounding process on the outer-layer poly (adipic acid)/butylene terephthalate film and the composite film to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Example 8:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 33wt% glycerol: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 5g of glycerol and 90g of acetone aqueous solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.5MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of anthocyanin-containing starch/polyvinyl alcohol film liquid: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then cooling the second mixed solution to 45 ℃, adding 1.2g of anthocyanin (serving as an antioxidant) into the second mixed solution, stirring the mixture in a water bath at 45 ℃ until the mixture is uniformly mixed, and performing ultrasonic defoaming for later use.
(3) Preparing a three-layer composite film:
spreading the glycerol-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the glycerol-containing cellulose acetate film by using clamps, spreading the anthocyanin-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry compounding process on the outer-layer poly (adipic acid)/butylene terephthalate film and the composite film to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Example 9:
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film containing 33wt% glycerol: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing 10g of cellulose acetate, 5g of glycerol and 90g of acetone aqueous solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and removing the first mixed solution from the glass plate to obtain a cellulose acetate film containing glycerol; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.8MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing anthocyanin and sodium lactate: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then the second mixed solution is cooled to 45 ℃, then 0.6g of sodium lactate (used as an antibacterial agent) and 0.6g of anthocyanin (used as an antioxidant) are added, and the mixture is stirred in a water bath at 45 ℃ until the mixture is uniformly mixed, and then ultrasonic defoaming is carried out for later use.
(3) Preparing a three-layer composite film:
spreading the glycerol-containing cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the glycerol-containing cellulose acetate film by using clamps, spreading the anthocyanin-and sodium lactate-containing starch/polyvinyl alcohol film liquid prepared in the step (2) on the cellulose acetate film, and drying for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry compounding process on the outer-layer poly (adipic acid)/butylene terephthalate film and the composite film to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Comparative example 1:
the preparation method of the controlled release type degradable active packaging film of the comparative example comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film (no glycerol): preparing an aqueous acetone solution with the mass ratio of 9:1, mixing 10g of cellulose acetate and 90g of the aqueous acetone solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and then removing the first mixed solution from the glass plate to obtain a cellulose acetate film; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.8MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing sodium lactate: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then the second mixed solution is cooled to 45 ℃, then 1.2g of sodium lactate (serving as an antibacterial agent) is added, and the mixture is stirred in a water bath at 45 ℃ until the mixture is uniformly mixed, and then ultrasonic defoaming is carried out for later use.
(3) Preparing a three-layer composite film:
spreading the cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the cellulose acetate film by using clamps, spreading the starch/polyvinyl alcohol film liquid containing sodium lactate in the step (2) on the cellulose acetate film, and drying for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry type compounding process on the polylactic acid film and the composite film on the outer layer to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
Comparative example 2:
the preparation method of the controlled release type degradable active packaging film of the comparative example comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of cellulose acetate film (no glycerol): preparing an aqueous acetone solution with the mass ratio of 9:1, mixing 10g of cellulose acetate and 90g of the aqueous acetone solution, and stirring at normal temperature until the mixture is dissolved to obtain a first mixed solution; spreading the first mixed solution on a glass plate, drying at 25 ℃ for 15min, and then removing the first mixed solution from the glass plate to obtain a cellulose acetate film; and then placing the cellulose acetate film into a high-pressure water device runner to enable water flow to pass through the film for 1h, wherein the pressure of the water is 0.8MPa, and finally placing the film into an oven to be dried to obtain the dried film.
(2) And (3) preparing an intermediate layer:
preparation of anthocyanin-containing starch/polyvinyl alcohol film liquid: weighing 4g of corn starch and mixing with 50g of water, stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a starch solution, weighing 4g of polyvinyl alcohol (PVA) resin and mixing with 50g of water, and stirring in a water bath at 95 ℃ until the corn starch is completely dissolved to obtain a polyvinyl alcohol glue solution; adding polyvinyl alcohol glue solution into starch solution, adding 1.2g of glycerol and 1.2g of citric acid, mixing, and stirring in a water bath at 95 ℃ until the mixture is uniform to obtain a second mixed solution; then cooling the second mixed solution to 45 ℃, adding 1.2g of anthocyanin (serving as an antioxidant) into the second mixed solution, stirring the mixture in a water bath at 45 ℃ until the mixture is uniformly mixed, and performing ultrasonic defoaming for later use.
(3) Preparing a three-layer composite film:
spreading the cellulose acetate film prepared in the step (1) on a glass plate, clamping two ends of the cellulose acetate film by using clamps, spreading the anthocyanin-containing starch/polyvinyl alcohol film liquid in the step (2) on the cellulose acetate film, and drying the cellulose acetate film for 1h at 45 ℃ to obtain a composite film;
and (3) carrying out a dry compounding process on the outer-layer poly (adipic acid)/butylene terephthalate film and the composite film to obtain a three-layer composite film material, namely the controlled release type degradable active packaging film.
< experiment >
The following release performance experiments were performed using the controlled release type degradable active packaging films prepared in the above examples and comparative examples as products:
the active substances (sodium lactate and anthocyanin) released from the film into the food simulation liquid are measured periodically by a release (migration) experiment by taking distilled water as the food simulation liquid (simulated water-based food), and fig. 1 is a change condition of the release amount of sodium lactate from the film into the food simulation liquid with time, and the ordinate is the ratio of the amount (Mt) of sodium lactate released from the film into the food simulation liquid to the original sodium lactate content (Mp) in the film. FIG. 2 shows the release amount of anthocyanin in the film from the film into the food simulant over time, and the ordinate shows the ratio of the amount of anthocyanin in the film released into the food simulant (Mt) to the original anthocyanin content in the film (Mp). The experimental results were as follows:
as can be seen from fig. 1 and 2, the release amounts of sodium lactate and anthocyanin in the film respectively gradually increase with time. Comparing the four films of comparative example 1, example 2 and example 9, the rate of release to reach equilibrium is: example 2. Apprxeq. Example 9. More than example 1. More than comparative example 1. Comparing the four films of comparative example 2, example 5, example 6 and example 9, the rate of release to reach equilibrium is: example 6. Apprxeq. Example 9. More than example 5. More than comparative example 2. From this, it can be seen that the release rates of sodium lactate and anthocyanin in the film both increased with the increase in glycerol content in the inner cellulose acetate film. The reason is that glycerol and cellulose acetate interact to form a plasticizing area inside the cellulose acetate film, the film with nano pores can be formed under the action of water flow with certain pressure, and the porosity is increased along with the increase of the glycerol content, so that the permeability of the film is increased, and the release of active substances is accelerated. Comparing the four films of example 2, example 3, example 4 and example 9, the rate of release to reach equilibrium is: example 2. Apprxeq. Example 9. More than example 4. More than example 3. Comparing the four films of example 6, example 7, example 8 and example 9, the rate of release to reach equilibrium is: example 6. Apprxeq. Example 9. More than example 8. More than example 7. From this, it can be seen that as the process water pressure increases during the preparation of the cellulose acetate film, the release rates of sodium lactate and anthocyanin in the film increase. The reason for this is that the size and porosity of the voids formed in the cellulose acetate film increase with increasing water flow pressure, thereby increasing the permeability of the film and accelerating the release of the active substance. Thus, the following conclusion can be drawn: the multilayer composite film can control the release of active substances (sodium lactate and anthocyanin) in the film by adjusting the permeability of the inner cellulose acetate film.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art will appreciate that, in light of the principles of the present invention, improvements and modifications can be made without departing from the scope of the invention.
Claims (9)
1. A controlled release type degradable active packaging film, which is characterized in that: the composite material is prepared by compounding an inner layer, an intermediate layer and an outer layer; the inner layer is a cellulose acetate film containing glycerol, the middle layer is a starch/polyvinyl alcohol film composed of active substances, and the outer layer is a degradable film;
the degradable film is selected from more than one of polylactic acid film and poly (adipic acid)/butylene terephthalate film;
the active substance is selected from more than one of antibacterial agent and antioxidant;
the content of active substances in the intermediate layer is 1-15wt%, the antibacterial agent is sodium lactate, and the antioxidant is anthocyanin;
the content of the cellulose acetate film in the inner layer is 67-95wt% and the content of glycerol is 5-33wt%;
the cellulose acetate film in the inner layer is a cellulose acetate film with nano pores;
the preparation method of the controlled release type degradable active packaging film comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of glycerol-containing cellulose acetate film: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing and dissolving cellulose acetate, glycerol and the acetone aqueous solution to obtain a first mixed solution, spreading the first mixed solution on a glass plate, drying to obtain a glycerol-containing cellulose acetate film, enabling water flow to pass through the cellulose acetate film, and drying after the water pressure is 0.3-0.8 MPa;
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing active substances: weighing starch and water, mixing and dissolving to obtain a starch solution, weighing polyvinyl alcohol resin and water, mixing and dissolving to obtain a polyvinyl alcohol glue solution; adding the polyvinyl alcohol glue solution into the starch solution, and then adding glycerol and citric acid for mixing to obtain a second mixed solution; then cooling the second mixed solution to 45 ℃, adding active substances, mixing in a water bath at 45 ℃, and carrying out ultrasonic treatment for later use;
(3) Preparing a three-layer composite film:
spreading the glycerol-containing cellulose acetate film prepared in the step (1) on a glass plate, spreading the active substance-containing starch/polyvinyl alcohol film liquid in the step (2) on the cellulose acetate film, and drying to obtain a composite film;
and (3) carrying out a dry type compounding process on the outer degradable film and the composite film to obtain the controlled release type degradable active packaging film.
2. A method of preparing a controlled release type degradable active packaging film according to claim 1, characterized in that: the method comprises the following steps:
(1) And (3) preparation of an inner layer:
preparation of glycerol-containing cellulose acetate film: preparing an acetone aqueous solution with the mass ratio of 9:1, mixing and dissolving cellulose acetate, glycerol and the acetone aqueous solution to obtain a first mixed solution, spreading the first mixed solution on a glass plate, drying to obtain a glycerol-containing cellulose acetate film, enabling water flow to pass through the cellulose acetate film, and drying after the water pressure is 0.3-0.8 MPa;
(2) And (3) preparing an intermediate layer:
preparation of starch/polyvinyl alcohol film liquid containing active substances: weighing starch and water, mixing and dissolving to obtain a starch solution, weighing polyvinyl alcohol resin and water, mixing and dissolving to obtain a polyvinyl alcohol glue solution; adding the polyvinyl alcohol glue solution into the starch solution, and then adding glycerol and citric acid for mixing to obtain a second mixed solution; then cooling the second mixed solution to 45 ℃, adding active substances, mixing in a water bath at 45 ℃, and carrying out ultrasonic treatment for later use;
(3) Preparing a three-layer composite film:
spreading the glycerol-containing cellulose acetate film prepared in the step (1) on a glass plate, spreading the active substance-containing starch/polyvinyl alcohol film liquid in the step (2) on the cellulose acetate film, and drying to obtain a composite film;
and (3) carrying out a dry type compounding process on the outer degradable film and the composite film to obtain the controlled release type degradable active packaging film.
3. The preparation method according to claim 2, characterized in that: in the step (1), the drying temperature is 25+/-1 ℃, and the drying time is 15+/-1 min.
4. The preparation method according to claim 2, characterized in that: in the step (2), the temperature of the mixed dissolution is 95+/-1 ℃.
5. The preparation method according to claim 2, characterized in that: in the step (2), the active substance is selected from at least one of an antibacterial agent and an antioxidant.
6. The method of manufacturing according to claim 5, wherein: the antibacterial agent is sodium lactate, and the antioxidant is anthocyanin.
7. The preparation method according to claim 2, characterized in that: in the step (3), the drying temperature is 45+/-1 ℃, and the drying time is 1+/-0.1 h.
8. The preparation method according to claim 2, characterized in that: in the step (3), the degradable film is selected from more than one of polylactic acid film and poly (adipic acid)/butylene terephthalate film.
9. Use of a controlled release type degradable active packaging film according to claim 1 in food packaging.
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