CN113002099A - Composite antibacterial film and preparation method thereof - Google Patents
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- CN113002099A CN113002099A CN202110217481.1A CN202110217481A CN113002099A CN 113002099 A CN113002099 A CN 113002099A CN 202110217481 A CN202110217481 A CN 202110217481A CN 113002099 A CN113002099 A CN 113002099A
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- 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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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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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
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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Abstract
The invention belongs to the field of antibacterial materials, and particularly relates to a composite antibacterial film and a preparation method thereof. The invention provides a brand new composite antibacterial film which is composed of at least three layers, wherein the upper layer and the lower layer both contain enough PLA capable of realizing slow release of tea polyphenol, and the main antibacterial component of the middle layer is tea polyphenol. Under normal use state, tea polyphenol in the middle layer is slowly released through the upper layer and the lower layer, and partial and relatively weak sterilization effect is provided. When the bacteriostatic ability needs to be improved, at least one of the upper layer and the lower layer can expose the middle layer partially or completely, so that the middle layer can be directly contacted with the outside, the release capacity of tea polyphenol is effectively improved, and the sterilization effect is improved.
Description
Technical Field
The invention belongs to the field of antibacterial materials, and particularly relates to a composite antibacterial film and a preparation method thereof.
Background
Including food packaging, infant and baby products, etc., require the antibacterial ability of the material. The tea polyphenol is an active ingredient extracted from tea leaves, has good antibacterial performance and oxidation resistance, is a food-grade safe product, and can be widely used for material antibiosis.
In the prior art, tea polyphenol is generally directly added into various materials to directly play a role in bacteriostasis, so that slow release and controlled release are difficult to realize. PLA is a degradable material and has certain antibacterial performance. But the antibacterial performance of PLA is relatively limited, and the PLA is not easy to grow pathogenic bacteria but difficult to inhibit and kill pathogenic bacteria in the environment. If the tea polyphenol is filled into the PLA, the PLA coats the tea polyphenol, so that the release speed of the tea polyphenol is greatly hindered, the slow release is realized, and the PLA has certain capability of killing pathogenic bacteria in the environment.
However, in this way, the release rate of tea polyphenols is very slow, and often the tea polyphenols are not completely released until the end of the service life of the material. In some application scenarios, higher antibacterial effect is needed, and controllable improvement of the antibacterial effect cannot be realized by simply wrapping tea polyphenol with PLA.
Disclosure of Invention
The invention aims to provide a composite antibacterial film and a preparation method thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a composite bacteriostatic film at least comprises three layers, namely a bottom layer, a middle layer and a surface layer; the middle layer is an antibacterial layer, and the bottom layer and the surface layer contain components capable of preventing the antibacterial components in the middle layer from releasing; at least one of the bottom layer and the surface layer can be completely or partially exposed to the outside during the gradual use process or when needed.
Preferably, the bacteriostatic agent of the bacteriostatic layer comprises tea polyphenol, and the component for hindering the release of the bacteriostatic component is PLA.
Preferably, the method for exposing all or part of the bacteriostatic layer to the outside is as follows: at least one of the bottom layer or the face layer disintegrates or partially disintegrates or is torn in whole or in part.
Preferably, the bacteriostatic layer is fully or partially exposed to contact with the outside in a manner that: tearing the bottom layer and separating the bottom layer from the bacteriostatic layer;
the composite bacteriostatic film at least comprises 4 layers of structures, and the structures are as follows from top to bottom: bottom layer, gluing layer, bacteriostasis layer, surface layer.
Preferably, the bacteriostatic layer is fully or partially exposed to contact with the outside in a manner that: the bottom layer disintegrates in the illumination environment;
the bottom layer comprises the following components in parts by weight: 0.03-0.05 part of ferric stearate, 0.1-0.15 part of titanium dioxide, 85-90 parts of LDPE and 85-90 parts of PLA.
Preferably, the preparation method of the bottom layer comprises the following steps: heating LDPE to 150 ℃ to melt, adding ferric stearate and modified titanium dioxide, and uniformly stirring to obtain LDPE slurry;
simultaneously melting PLA at 180 ℃;
and slowly cooling the PLA in the molten state under the stirring state, and uniformly mixing the PLA with the LDPE slurry when the temperature is reduced to 150 ℃.
Preferably, the formula of the antibacterial layer comprises the following components in parts by weight: 30-50 parts of gelatin, 10-20 parts of glycerol, 1-2 parts of tea polyphenol, 10-20 parts of chitosan, 5-10 parts of calcium chloride solution, and 1% w/v.
Preferably, the preparation method of the antibacterial layer comprises the following steps: dissolving gelatin and glycerol in water, stirring and heating to 50-60 ℃, keeping stirring and adding tea polyphenol and chitosan, then dropwise adding a calcium chloride solution while stirring, and stirring and reacting for 1 h.
Preferably, the surface layer is a PLA layer.
Correspondingly, the preparation method of the composite antibacterial membrane comprises the following steps:
(1) preparing a bottom layer: heating LDPE to 150 ℃ to melt, adding ferric stearate and modified titanium dioxide, and uniformly stirring to obtain LDPE slurry; simultaneously melting PLA at 180 ℃; slowly cooling the molten PLA under stirring, cooling to 150 ℃, uniformly mixing with the LDPE slurry to obtain a bottom layer slurry, and keeping the temperature of 150 ℃ under stirring for later use;
(2) preparing an antibacterial layer: dissolving gelatin and glycerol in water, stirring and heating to 50-60 ℃, keeping stirring, adding tea polyphenol and chitosan, then dropwise adding a calcium chloride solution while stirring, stirring and reacting for 1h, keeping 60 ℃, and stirring for later use;
(3) preparing a surface layer: melting PLA for later use;
(4) respectively placing the materials of the bottom layer, the antibacterial layer and the surface layer in different charging barrels of a co-extruder, controlling the temperature in the charging barrels of the bottom layer and the surface layer to be 150 ℃, controlling the temperature in the charging barrels of the antibacterial layer to be 100 ℃, and continuously stirring in the charging barrels; and co-extruding the materials of each layer through a die head according to the sequence of the bottom layer, the antibacterial layer and the surface layer, controlling the temperature of the die head to be 110-120 ℃, and then gradually and slowly cooling, solidifying and coiling.
The invention has the following beneficial effects: the invention provides a brand new composite antibacterial film which is composed of at least three layers, wherein the upper layer and the lower layer both contain enough PLA capable of realizing slow release of tea polyphenol, and the main antibacterial component of the middle layer is tea polyphenol. Under normal use state, tea polyphenol in the middle layer is slowly released through the upper layer and the lower layer, and partial and relatively weak sterilization effect is provided. When the bacteriostatic ability needs to be improved, at least one of the upper layer and the lower layer can expose the middle layer partially or completely, so that the middle layer can be directly contacted with the outside, the release capacity of tea polyphenol is effectively improved, and the sterilization effect is improved.
When the surface layer is set to be a photodegradable material layer, the composite bacteriostatic film can also gradually receive light in use, and the bacteriostatic ability is gradually enhanced. Meanwhile, when the antibacterial film is used for materials needing strict disinfection, such as infant products, medical supplies and the like, a user needs to disinfect the products by using certain ultraviolet light before using the antibacterial film, so that the antibacterial capacity of the composite film is activated. In one embodiment, titanium dioxide is added into the photodegradable material layer, and the photodegradable material layer can play a certain bacteriostatic effect under the activation of light, so that the bacteriostatic ability is further improved.
When the photodegradable material layer is gradually used or is disintegrated under the activation of strong light, the material disintegrated on the surface layer is directly brushed off, and then the normal use can be continued. The material of the layer is degradable and can be directly discharged into the environment.
Detailed Description
The invention provides a composite antibacterial film. The composite bacteriostatic film at least comprises three layers, namely a bottom layer, a middle layer and a surface layer. Wherein the middle layer is antibacterial layer, and the main antibacterial agent is tea polyphenols. The upper layer and the lower layer (the bottom layer and the surface layer) both contain PLA (polylactic acid), which can slowly release tea polyphenol and slowly and gradually exert partial bacteriostatic effect. At least one of the upper layer and the lower layer can be gradually used, or can be disintegrated or partially disintegrated when needed, or can be torn completely or partially, so that the bacteriostatic layer is directly contacted with the outside, and the bacteriostatic effect is improved.
In one embodiment, at least one of the upper and lower layers is made of a photodegradable material. The formula comprises the following components in parts by weight: ferric stearate (FeSt)3) 0.03-0.05 part of modified titanium dioxide, 0.1-0.15 part of LDPE, 85-90 parts of LDPE and 85-90 parts of PLA. The preparation method of the ferric stearate comprises the following steps: preparing a stearic acid aqueous solution, weighing ferric chloride hexahydrate to prepare a ferric chloride aqueous solution, dropwise adding the ferric chloride aqueous solution into the stearic acid aqueous solution, and obtaining a precipitate through reaction, namely the ferric stearate. The method is mature in the prior art and is not described in detail. The modified titanium dioxide is as follows: grafting hydrophilic polypropylene onto the surface of the nano titanium dioxide through a silane coupling agent to obtain the modified titanium dioxide. Modification ofThe method is mature prior art and is not described in detail. The titanium dioxide can also be not modified, the stirring speed and the stirring time are increased, and the agglomeration of the titanium dioxide is avoided.
The preparation method of the photodegradable material comprises the following steps: and heating the LDPE to 150 ℃ for melting, adding ferric stearate and modified titanium dioxide, and uniformly stirring to obtain the LDPE slurry. While melting the PLA at 180 ℃. Slowly cooling PLA in a molten state under a stirring state, and mixing the PLA with LDPE slurry when the temperature is reduced to 150 ℃; keeping the temperature at 150 deg.C under stirring, and making into layer 1 or layers 1 and 3 for use.
An optional formulation for the antibacterial layer is: according to the mass parts, 30-50 parts of gelatin, 10-20 parts of glycerol, 1-2 parts of tea polyphenol, 10-20 parts of chitosan and 5-10 parts of calcium chloride solution (1%, w/v). The preparation method of the antibacterial layer comprises the following steps: dissolving gelatin and glycerol in water, stirring and heating to 50-60 ℃, keeping stirring and adding tea polyphenol and chitosan, then dropwise adding a calcium chloride solution while stirring, and stirring and reacting for 1 h; the mixture was stirred at 60 ℃ and kept as layer 2.
The antibacterial layer is positioned in the middle (layer 2), and the upper layer and the lower layer (layers 1 and 3) can both use light degradable materials. Preferably, the layer 1 is made of a photodegradable material and the layer 3 is made of a pure PLA material.
The preparation method of the composite antibacterial film comprises the following steps: the materials (in a dissolved or molten state) of the layers 1, 2 and 3 are respectively placed in different charging barrels of a co-extruder, the temperature in the charging barrels of the layers 1 and 3 is controlled to be 150 ℃, the temperature in the charging barrel of the layer 2 is controlled to be 100 ℃, and the materials are continuously stirred in the charging barrels. And co-extruding the three layers of materials through a die head according to the sequence of the layers 1, 2 and 3, controlling the temperature of the die head to be 110-120 ℃, and then gradually and slowly cooling, solidifying and coiling.
In another embodiment, the composite antibacterial film at least comprises 4 layers of structures, which are sequentially from top to bottom: layer 1 is the bottom, and layer 2 is the gluing layer, and layer 3 is the antibacterial layer, and layer 4 is the surface course. PLA is contained in the bottom layer and the surface layer, and the slow release of the tea polyphenol in the antibacterial layer can be realized by using the PLA. The bottom layer can be torn off from the adhesive layer, so that the composite bacteriostatic film is attached to a required position. The preparation of the antibacterial layer can be carried out with reference to the above embodiment, and the materials of the bottom layer, the adhesive layer and the top layer and the preparation method are carried out with reference to the adhesive sticker, except that a sufficient amount of PLA is added to the corresponding materials. Under the implementation mode, the bottom layer can be torn off under a specific situation, the composite bacteriostatic film is pasted on a required object, and the double functions of the self-adhesive and sterilization are realized.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Examples
1. 9 groups of photodegradable bacteriostatic composite films were prepared, the method was performed as stated above, and the specific formulation, preparation method and film composition of each group are shown in table 1. The data in Table 1 are in parts by weight. And a single layer of pure PLA was set as a control group (group 10).
Table 1 table showing preparation method of each composite film group
2. The bacteriostatic effect of each group is tested, and the test method comprises the following steps: respectively cutting each group of prepared composite films into materials with the diameter of 2cm, continuously placing the materials in a light environment for 0, 30 and 60 hours at room temperature, and observing the surface morphology characteristics of each group under an electron microscope; the illumination environment refers to ultraviolet intensity of 20mW/cm2. And placing the materials subjected to different light treatments in a culture dish filled with golden yellow grape balls, and measuring the diameter of a transparent ring formed around the composite film after 48 hours (the distance from one end edge of the transparent ring to the opposite side edge, if the transparent ring is not formed and bacteria do not grow on the composite film, the diameter of the transparent ring is 2cm, namely the diameter of the composite film). The results are shown in Table 2.
Table 2 bacteriostatic effect display table for each composite film group
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various changes, modifications, alterations, and substitutions which may be made by those skilled in the art without departing from the spirit of the present invention shall fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. A composite antibacterial film is characterized in that: the composite bacteriostatic film at least comprises three layers, namely a bottom layer, a middle layer and a surface layer; the middle layer is an antibacterial layer, and the bottom layer and the surface layer contain components capable of preventing the antibacterial components in the middle layer from releasing; at least one of the bottom layer and the surface layer can be completely or partially exposed to the outside during the gradual use process or when needed.
2. The composite antibacterial film according to claim 1, characterized in that: the bacteriostatic agent of the bacteriostatic layer comprises tea polyphenol, and the component for hindering the release of the bacteriostatic component is PLA.
3. The composite antibacterial film according to claim 1, characterized in that: the mode of exposing the bacteriostatic layer to the outside or contacting the bacteriostatic layer with the outside is as follows: at least one of the bottom layer or the face layer disintegrates or partially disintegrates or is torn in whole or in part.
4. The composite antibacterial film according to claim 1, characterized in that: the mode of exposing the bacteriostatic layer to the outside in whole or in part is as follows: tearing the bottom layer and separating the bottom layer from the bacteriostatic layer;
the composite bacteriostatic film at least comprises 4 layers of structures, and the structures are as follows from top to bottom: bottom layer, gluing layer, bacteriostasis layer, surface layer.
5. The composite antibacterial film according to claim 1, characterized in that: the mode of exposing the bacteriostatic layer to the outside in whole or in part is as follows: the bottom layer disintegrates in the illumination environment;
the bottom layer comprises the following components in parts by weight: 0.03-0.05 part of ferric stearate, 0.1-0.15 part of titanium dioxide, 85-90 parts of LDPE and 85-90 parts of PLA.
6. The composite antibacterial film according to claim 5, characterized in that: the preparation method of the bottom layer comprises the following steps: heating LDPE to 150 ℃ to melt, adding ferric stearate and titanium dioxide, and uniformly stirring to obtain LDPE slurry;
simultaneously melting PLA at 180 ℃;
and slowly cooling the PLA in the molten state under the stirring state, and uniformly mixing the PLA with the LDPE slurry when the temperature is reduced to 150 ℃.
7. The composite antibacterial film according to claim 1, characterized in that: the formula of the antibacterial layer comprises the following components in parts by weight: 30-50 parts of gelatin, 10-20 parts of glycerol, 1-2 parts of tea polyphenol, 10-20 parts of chitosan, 5-10 parts of calcium chloride solution, and 1% w/v.
8. The composite antibacterial film according to claim 7, characterized in that: the preparation method of the antibacterial layer comprises the following steps: dissolving gelatin and glycerol in water, stirring and heating to 50-60 ℃, keeping stirring and adding tea polyphenol and chitosan, then dropwise adding a calcium chloride solution while stirring, and stirring and reacting for 1 h.
9. The composite antibacterial film according to claim 1, characterized in that: the surface layer is a PLA layer.
10. A method for preparing the composite antibacterial film according to any one of claims 5 to 9, characterized in that: the method comprises the following steps:
(1) preparing a bottom layer: heating LDPE to 150 ℃ to melt, adding ferric stearate and titanium dioxide, and uniformly stirring to obtain LDPE slurry; simultaneously melting PLA at 180 ℃; slowly cooling the molten PLA under stirring, cooling to 150 ℃, uniformly mixing with the LDPE slurry to obtain a bottom layer slurry, and keeping the temperature of 150 ℃ under stirring for later use;
(2) preparing an antibacterial layer: dissolving gelatin and glycerol in water, stirring and heating to 50-60 ℃, keeping stirring, adding tea polyphenol and chitosan, then dropwise adding a calcium chloride solution while stirring, stirring and reacting for 1h, keeping 60 ℃, and stirring for later use;
(3) preparing a surface layer: melting PLA for later use;
(4) respectively placing the materials of the bottom layer, the antibacterial layer and the surface layer in different charging barrels of a co-extruder, controlling the temperature in the charging barrels of the bottom layer and the surface layer to be 150 ℃, controlling the temperature in the charging barrels of the antibacterial layer to be 100 ℃, and continuously stirring in the charging barrels; and co-extruding the materials of each layer through a die head according to the sequence of the bottom layer, the antibacterial layer and the surface layer, controlling the temperature of the die head to be 110-120 ℃, and then gradually and slowly cooling, solidifying and coiling.
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