CN115302934A - Full-biodegradable double-layer antibacterial composite film and preparation method thereof - Google Patents

Full-biodegradable double-layer antibacterial composite film and preparation method thereof Download PDF

Info

Publication number
CN115302934A
CN115302934A CN202210978897.XA CN202210978897A CN115302934A CN 115302934 A CN115302934 A CN 115302934A CN 202210978897 A CN202210978897 A CN 202210978897A CN 115302934 A CN115302934 A CN 115302934A
Authority
CN
China
Prior art keywords
film
pla
pbat
solution
sodium alginate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210978897.XA
Other languages
Chinese (zh)
Inventor
李亚娜
任纪州
张永林
刘晓鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Polytechnic University
Original Assignee
Wuhan Polytechnic University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Polytechnic University filed Critical Wuhan Polytechnic University
Priority to CN202210978897.XA priority Critical patent/CN115302934A/en
Publication of CN115302934A publication Critical patent/CN115302934A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • 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
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/04—Alginic acid; Derivatives thereof
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • 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
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a full-biodegradable double-layer bacteriostatic composite film and a preparation method thereof, wherein the full-biodegradable double-layer bacteriostatic composite film comprises an inner film layer, an outer film layer and a bonding layer arranged between the inner film layer and the outer film layer, the inner film layer is made of sodium alginate, glycerol and a bacteriostatic agent, the outer film layer is made of PLA and PBAT, and the bonding layer is formed by starch adhesive. The fully biodegradable double-layer antibacterial composite film provided by the invention has good barrier property and mechanical property, good toughness and good antibacterial property, and has obvious antibacterial effect on escherichia coli and staphylococcus aureus, so that the PLA/PBAT composite film can be applied to the field of food packaging, for example, as a food preservative film.

Description

Full-biodegradable double-layer antibacterial composite film and preparation method thereof
Technical Field
The invention relates to the technical field of PLA composite membranes, in particular to a full-biodegradable double-layer antibacterial composite membrane and a preparation method thereof.
Background
The biodegradable materials comprise biodegradable high polymer materials of biological sources and artificially synthesized degradable high polymer materials, the most common biodegradable high polymer materials of biological sources at present comprise starch, protein, chitosan, polyhydroxyalkanoate (PHA) and Polyhydroxybutyrate (PHB), and the high polymer materials prepared by using the materials as raw materials have poor mechanical strength and toughness, such as starch-based degradable plastics which are high in brittleness and easy to break and can be damaged in the food packaging process. The artificially synthesized degradable high polymer material mainly comprises polylactic acid (PLA), polybutylene succinate (PBS), polyvinyl alcohol (PVA), polypropylene carbonate (PPC) and Polycaprolactone (PCL). The polylactic acid (PLA) is a completely biodegradable polymer material obtained by polymerizing lactic acid serving as a main raw material, has sufficient raw material source, is renewable, has little pollution in the production process, and is an ideal green high polymer material. PLA as a packaging material has good transparency and mechanical properties, no toxicity, no irritation, easy processing and forming, good biocompatibility and the like, and is a most successful biodegradable packaging material developed in markets at home and abroad so far. The completely biodegradable film prepared from polylactic acid (PLA) has good transparency, mechanical properties, no toxicity, no irritation, easy processing and good biocompatibility, but has poor PLA barrier property, low elongation at break and no antibacterial activity when being used as a food preservative material, such as a food preservative film.
Disclosure of Invention
The invention mainly aims to provide a full-biodegradable double-layer antibacterial composite film and a preparation method thereof, and aims to provide a PLA composite film with good barrier property, good toughness and antibacterial property.
In order to achieve the above purpose, the present invention provides a full biodegradable dual-layer bacteriostatic composite film, which includes an inner film layer, an outer film layer, and a bonding layer disposed between the inner film layer and the outer film layer, wherein the inner film layer is made of sodium alginate, glycerol, and a bacteriostatic agent, the outer film layer is made of PLA and PBAT, and the bonding layer is formed of a starch adhesive.
Optionally, the starch adhesive is prepared by the following steps:
mixing starch with water, then adding a sodium hydroxide aqueous solution, stirring for 20-40 min at 65-75 ℃ for gelatinization, mixing the gelatinized substance with cold water, and uniformly stirring to obtain a first solution;
dissolving potassium pyroantimonate in water, and then mixing the potassium pyroantimonate with borax and starch in water at the temperature of 33-37 ℃ to form a second solution;
and adding the first solution into the second solution under the stirring action, and mixing and stirring to obtain the starch adhesive.
Optionally, the step of mixing starch with water, adding an aqueous solution of sodium hydroxide, stirring at 65-75 ℃ for 20-40 min for gelatinization, mixing the gelatinized product with cold water, and stirring uniformly to obtain a first solution comprises:
mixing 25g of starch with 70mL of water, adding a sodium hydroxide aqueous solution, wherein the sodium hydroxide aqueous solution is obtained by dissolving 9g of sodium hydroxide in 15g of water, and then stirring at 65-75 ℃ for 20-40 min for gelatinization to obtain a gelatinized substance;
and mixing the gelatinate with 150mL of cold water, and uniformly stirring to obtain a first solution.
Optionally, the step of dissolving potassium pyroantimonate in water and then mixing with borax and starch in water at 33-37 ℃ to form a second solution comprises:
0.5g of potassium pyroantimonate is dissolved in 25g of water, the obtained solution is added into 500mL of water with the temperature of 33-37 ℃, 3g of borax and 250g of starch are simultaneously added, and a second solution is obtained by mixing and stirring.
Optionally, the starch is corn starch.
Optionally, in the outer film layer, the mass ratio of the PLA to the PBAT is 7; and/or the presence of a gas in the atmosphere,
in the inner film layer, the mass of the bacteriostatic agent is 1-5% of the mass of the sodium alginate; and/or the presence of a gas in the gas,
the bacteriostatic agent comprises at least one of chitosan, nano silver and nano zinc oxide.
In order to achieve the above object, the present invention further provides a preparation method of the above fully biodegradable double-layer antibacterial composite membrane, comprising the following steps:
preparing PLA/PBAT mixed master batches from PLA and PBAT in a melt blending mode, and preparing the PLA/PBAT mixed master batches into a PLA/PBAT film by a tape casting method;
preparing a starch adhesive;
dissolving sodium alginate in water to prepare a sodium alginate aqueous solution, adding a bacteriostatic agent into the sodium alginate aqueous solution, stirring the solution to dissolve the bacteriostatic agent, adding glycerol into the solution, stirring the solution to obtain a composite solution, and preparing the composite solution into a sodium alginate film containing the bacteriostatic agent by a tape casting method;
and compounding the PLA/PBAT film and the sodium alginate film by using the starch adhesive to prepare the full-biodegradable double-layer bacteriostatic composite film.
Optionally, dissolving sodium alginate in water to prepare a sodium alginate aqueous solution, adding a bacteriostatic agent into the sodium alginate aqueous solution, stirring to dissolve the bacteriostatic agent, adding glycerol, stirring to obtain a composite solution, and preparing the composite solution into a sodium alginate film containing the bacteriostatic agent by a tape casting method, wherein the step of preparing the composite solution into the sodium alginate film containing the bacteriostatic agent comprises the following steps:
300-500 mL of water and 3-5 mL of glycerol are added for every 8g of sodium alginate.
Optionally, the step of compounding the PLA/PBAT film with the sodium alginate film by using the starch adhesive to prepare a fully biodegradable double-layer bacteriostatic composite film includes:
coating the starch adhesive on the surface of the PLA/PBAT film by using a bar coater, then flatly paving the sodium alginate film on the PLA/PBAT film to be bonded with the PLA/PBAT film, and standing for 3-5 hours under a dark condition to obtain the full-biodegradable double-layer bacteriostatic composite film.
Optionally, the wire bar specification of the wire bar coater is 6-10 μm, and the coating speed is set to 1-4 m/min.
In the technical scheme provided by the invention, the full-biodegradable double-layer bacteriostatic composite film comprises an inner film layer, an outer film layer and an adhesive layer, wherein the inner film layer is made of sodium alginate, glycerol and a bacteriostatic agent, namely the inner film layer is made of a sodium alginate film containing the bacteriostatic agent, the outer film layer is made of PLA and PBAT, namely the outer film layer is made of a PLA/PBAT composite film, and the adhesive layer is made of starch adhesive; so, full biodegradable double-deck antibacterial composite film has good barrier properties and mechanical properties, and toughness is good, and has good antibacterial activity, all has obvious antibacterial effect to escherichia coli and staphylococcus aureus, thereby makes full biodegradable double-deck antibacterial composite film can be used in the food packaging field, for example as food preservative film.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of an embodiment of a preparation method of a fully biodegradable double-layer bacteriostatic composite membrane provided by the invention;
FIG. 2 is an apparent photograph of a fully biodegradable double-layer bacteriostatic composite membrane prepared according to an embodiment of the invention;
FIG. 3 shows the mechanical performance test results of the fully biodegradable double-layered bacteriostatic composite membrane prepared according to the embodiment of the invention;
FIG. 4 shows the results of the barrier performance test of the fully biodegradable double-layered bacteriostatic composite membrane prepared according to the embodiment of the present invention;
FIG. 5 shows the results of the bacteriostatic performance test of the fully biodegradable double-layer bacteriostatic composite film on Escherichia coli according to the embodiment of the present invention;
fig. 6 shows the result of the bacteriostatic performance test of the fully biodegradable double-layer bacteriostatic composite film on staphylococcus aureus, which is prepared by the embodiment of the invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
PLA as a packaging material has good transparency and mechanical properties, no toxicity, no irritation, easy processing and forming, good biocompatibility and the like, and is a most successful biodegradable packaging material developed in markets at home and abroad so far. The completely biodegradable film prepared from polylactic acid (PLA) has good transparency, mechanical properties, no toxicity, no irritation, easy processing and good biocompatibility, but has poor PLA barrier property, low elongation at break and no antibacterial activity when being used as a food preservative material, such as a food preservative film.
In view of the above, the present invention provides a full-biodegradable dual-layer bacteriostatic composite film, which includes an inner film layer, an outer film layer, and a bonding layer disposed between the inner film layer and the outer film layer, wherein the inner film layer includes sodium alginate, glycerol, and a bacteriostatic agent, the outer film layer includes PLA and PBAT, and the bonding layer is formed by a starch adhesive.
Polylactic acid (PLA) is a completely biodegradable polymer material obtained by polymerizing lactic acid serving as a main raw material, has sufficient raw material source, is renewable, has little pollution in the production process, and is an ideal green high polymer material. PLA as a packaging material has good transparency and mechanical properties, no toxicity, no irritation, easy processing and forming, good biocompatibility and the like, and is a most successful biodegradable packaging material developed in markets at home and abroad so far. The poly (butylene adipate terephthalate) (PBAT) is aliphatic-aromatic copolyester, the PBAT has low elastic modulus, high elongation at break and good ductility, the PBAT has the comprehensive properties of aliphatic polyester and aromatic polyester due to the main chain structure characteristics of the PBAT, and the polyester material has relatively high flexibility because the crystal structure is damaged after copolymerization.
Sodium Alginate (SA) has good biological properties as natural polysaccharide, and SA can be compounded with bacteriostatic agent, antioxidant, etc., to solve the problems in food industry, thereby maintaining good food quality. At present, sodium alginate is relatively more researched as a base material, and good transparency and tensile strength are the most outstanding advantages of a sodium alginate film, but the sodium alginate film does not have hydrophobicity and limits the application of the sodium alginate film.
In the technical scheme provided by the invention, the full-biodegradable double-layer bacteriostatic composite film comprises an inner film layer, an outer film layer and an adhesive layer, wherein the inner film layer is made of sodium alginate, glycerol and a bacteriostatic agent, namely the inner film layer is made of a sodium alginate film containing the bacteriostatic agent, the outer film layer is made of PLA and PBAT, namely the outer film layer is made of a PLA/PBAT composite film, and the adhesive layer is made of starch adhesive; so, full biodegradable double-deck antibacterial composite film has good barrier properties and mechanical properties, and toughness is good, and has better peel strength, good intermembrane bonding interface and good bacteriostasis, all has obvious antibacterial effect to escherichia coli and staphylococcus aureus, thereby makes full biodegradable double-deck antibacterial composite film can be used in the food package field, for example as food preservative film. When the full-biodegradable double-layer antibacterial composite film is used as a food packaging film, the inner film layer is a food contact layer and contacts food materials inwards.
The adhesive layer is formed by the starch adhesive, so that the adhesive strength between the outer film layer and the inner film layer can be improved well. Specifically, in an embodiment of the present invention, the starch adhesive is a self-made starch adhesive, and is prepared through the following steps:
step S10, mixing starch and water, then adding a sodium hydroxide aqueous solution, stirring for 20-40 min at 65-75 ℃ for gelatinization, mixing the gelatinized substance with cold water, and stirring uniformly to obtain a first solution;
s20, dissolving potassium pyroantimonate in water, and then mixing the potassium pyroantimonate with borax and starch in the water with the temperature of 33-37 ℃ to form a second solution;
and S30, adding the first solution into the second solution under the stirring action, and mixing and stirring to obtain the starch adhesive.
More specifically, in a specific embodiment of the present invention, the step of self-preparing the starch adhesive is as follows:
firstly, mixing 25g of starch and 70mL of pure water, wherein the starch is preferably corn starch, then adding an aqueous sodium hydroxide solution into the mixture of the starch and the pure water, wherein the aqueous sodium hydroxide solution is obtained by dissolving 9g of sodium hydroxide in 15g of water, and then stirring at 65-75 ℃ for 20-40 min for gelatinization, preferably at 70 ℃ for 30min to obtain a gelatinized product; and mixing the gelatinate with 150mL of cold water, and uniformly stirring to obtain a first solution. Then, 0.5g of potassium pyroantimonate is dissolved in 25g of water to form a potassium pyroantimonate solution, then the potassium pyroantimonate solution is added into 500mL of pure water with the temperature of 33-37 ℃, preferably 35 ℃, and 3g of borax and 250g of starch are added at the same time, and the mixture is mixed and stirred to obtain a second solution. And finally, slowly pouring the first solution into the second solution under the stirring action, and mixing and stirring for 0.5 hour after the addition is finished to obtain the starch adhesive.
It should be noted that, in the present embodiment, the addition amount of each raw material does not represent the actual addition amount in the production process, but represents only the addition ratio relationship between the raw materials. In addition, the sequence between step S10 and step S20 is not limited, and step S10 may be before step S20, step S20 may be after step S, step S20 may be before step S1, or step S10 and step S20 may be performed synchronously, which all belong to the protection scope of the present invention.
The outer film layer is composed of a PLA and PBAT composite film, wherein the mass ratio of the PLA to the PBAT is 7-100, so that the PBAT can play a relatively ideal toughening role on the PLA, and the finally prepared PLA/PBAT composite film has relatively good mechanical properties.
The inner membrane layer is formed by a sodium alginate film added with bacteriostatic agent and glycerol, wherein the mass of the bacteriostatic agent is 1-5% of the mass of the sodium alginate, the glycerol is used as a thickening agent, and the addition amount of the glycerol is 2-5 mL, preferably 4mL, correspondingly added in each 8g of the sodium alginate.
Further, the bacteriostatic agent includes at least one of chitosan, nano silver and nano zinc oxide, that is, the bacteriostatic agent may only include chitosan, nano silver or nano zinc oxide, and may also be a combination of any two or three of chitosan, nano silver and nano zinc oxide. In some embodiments of the present invention, the bacteriostatic agent is chitosan, specifically, the chitosan is analytically pure, and the deacetylation degree is 80-95%. Furthermore, the addition amount of the chitosan is 1-5% of the mass of the sodium alginate. In other embodiments of the present invention, the bacteriostatic agent is nano silver, specifically, the nano silver has a particle size of 10 to 80nm and a purity of greater than 99.9%. Furthermore, the addition amount of the nano silver is 1-2% of the mass of the sodium alginate. In still other embodiments of the present invention, the bacteriostatic agent is nano zinc oxide, specifically, the nano zinc oxide has a particle size of 10-80 nm and a purity of more than 90%. Furthermore, the addition amount of the nano zinc oxide is 1-2% of the mass of the sodium alginate.
Based on the above-mentioned fully biodegradable double-layer bacteriostatic composite film provided by the invention, the invention further provides a preparation method of the fully biodegradable double-layer bacteriostatic composite film, which comprises the steps of preparing a PLA/PBAT film by adopting a melt blending and tape casting method, preparing a sodium alginate film from a mixed solution of sodium alginate, a bacteriostatic agent and a thickening agent by adopting a tape casting method, preparing a starch adhesive, and compounding the PLA/PBAT film and the sodium alginate film by utilizing the starch adhesive, wherein fig. 1 shows an embodiment of the preparation method of the fully biodegradable double-layer bacteriostatic composite film provided by the invention.
Referring to fig. 1, in this embodiment, the preparation method of the fully biodegradable two-layer bacteriostatic composite membrane includes the following steps:
s100, preparing PLA/PBAT mixed master batches from PLA and PBAT in a melt blending mode, and preparing the PLA/PBAT mixed master batches into a PLA/PBAT film by a tape casting method;
s200, preparing a starch adhesive;
step S300, dissolving sodium alginate in water to prepare a sodium alginate aqueous solution, adding a bacteriostatic agent into the sodium alginate aqueous solution, stirring to dissolve the sodium alginate aqueous solution, adding glycerol into the dissolved sodium alginate aqueous solution, stirring to obtain a composite solution, and preparing the composite solution into a sodium alginate film containing the bacteriostatic agent by a tape casting method;
and S400, compounding the PLA/PBAT film and the sodium alginate film by using the starch adhesive to prepare the fully biodegradable double-layer antibacterial composite film.
It should be noted that the sequence among step S100, step S200, and step S300 is not limited in the present invention, and it is only necessary to separately prepare the PLA/PBAT film, the starch adhesive, and the sodium alginate film before step S400. In the embodiment of the invention, the preparation method of the PLA/PBAT composite film is described in detail by taking the steps S100, S200, S300, and S400 as examples in sequence.
Firstly, PLA and PBAT are made into PLA/PBAT mixed master batches in a melt blending mode, and before melt blending, the PLA and the PBAT are preferably dried, in particular, the PLA and the PBAT are dried in a blast drying oven for 3 hours at 40 ℃. The preparation of the PLA/PBAT mixed master batch can be realized by melting, extruding and granulating by using a double-screw extruder, and specifically, the parameters of the double-screw extruder are as follows: the temperature of the screw zone is 180 ℃, 185 ℃, 180 ℃, the die temperature is 165 ℃ and the screw rotating speed is 70r/min along the material conveying direction. The preparation of the PLA/PBAT film by the casting method can be realized by a casting film testing machine, specifically, the parameters of the casting film testing machine are set as follows: the temperature of the screw zone (along the conveying direction of the materials) is 180 ℃, 185 ℃ and 180 ℃ in sequence, the temperature of the die orifice is 165 ℃, and the rotating speed of the screw is 30r/min. Similarly, before the PLA/PBAT master batch is put into the cast film tester, the PLA/PBAT master batch may be dried, specifically, the PLA/PBAT mixed master batch is dried in a blast drying oven at 40 ℃ for 3 hours.
Then, according to the method for self-making the starch adhesive provided by the invention, the starch adhesive is prepared according to the steps of S10, S20 and S30.
Then, dissolving sodium alginate in ultrapure water to prepare a sodium alginate aqueous solution, wherein the adding ratio of the sodium alginate to the ultrapure water can be that each 8g of the sodium alginate is correspondingly dissolved in 300-500 mL of the ultrapure water, preferably 400mL, and the dissolving process can be that the sodium alginate is completely dissolved by stirring at the temperature of 30 ℃ for 0.5 h. Next, adding a bacteriostatic agent into the sodium alginate solution, stirring for dissolving, specifically placing the sodium alginate solution on a magnetic stirrer, stirring for 4 hours at the temperature of 40 ℃ until the bacteriostatic agent is completely dissolved, adding glycerol serving as a thickening agent into the sodium alginate solution, and continuously stirring for 0.5 hour to obtain a composite solution; wherein, the addition amount of the glycerol can be as follows: 2 to 5mL of glycerin, preferably 4mL, is added per 8g of sodium alginate. Then, preparing the composite solution into a sodium alginate film containing a bacteriostatic agent by a tape casting method, which specifically comprises the following steps: pouring the composite solution onto an acrylic glass plate, uniformly scraping the composite solution by using a scraper, putting the composite solution into an oven, drying the composite solution at 40 ℃, cooling and uncovering the membrane to obtain the sodium alginate membrane.
Finally, the PLA/PBAT film is compounded with the sodium alginate film by utilizing the starch adhesive, so that the PLA/PBAT composite film can be obtained, the PLA/PBAT composite film can be realized by an automatic coating machine, the PLA/PBAT film is firstly paved on the automatic coating machine and clamped, then the starch adhesive is uniformly coated on the surface of the PLA/PBAT film by adopting a wire bar coating machine, then the sodium alginate film is paved on the PLA/PBAT film and is bonded with the PLA/PBAT film, then the sodium alginate film is transferred into a dark room, and the PLA/PBAT film is kept stand and balanced for 3 to 5 hours, preferably 4 hours, under the light-tight condition, so that the full-biodegradable double-layer antibacterial composite film is obtained. Wherein the specification of the wire bar coater is 6-10 mu m, and the coating speed is set to be 1-4 m/min.
According to the preparation method of the full-biodegradable double-layer antibacterial composite film, the PLA/PBAT film is used as the outer film layer, the sodium alginate film is used as the inner film layer, and the PLA/PBAT film and the sodium alginate film are compounded by using the starch adhesive, so that the prepared full-biodegradable double-layer antibacterial composite film has good barrier property and mechanical property, good toughness, good peeling strength, good inter-film bonding interface and good antibacterial property, and has an obvious antibacterial effect on escherichia coli and staphylococcus aureus, and the full-biodegradable double-layer antibacterial composite film can be applied to the field of food packaging, such as being used as a food preservative film. Meanwhile, the preparation process is simple, and the prepared product has stable performance and is easy to realize large-scale industrial production.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
The PLA adopted in the following examples is purchased from Shandong grass plastic raw material Ming-Hu, dongguan, PBAT is purchased from Chengyi plastic Co., ltd, dongguan, and chitosan is purchased from chemical reagents Co., ltd, a national medicine group.
Example 1
The PLA/PBAT composite film comprises:
(1) The outer film layer is a PLA/PBAT film, wherein the mass ratio of PLA to PBAT is 7;
(2) The inner membrane layer is a sodium alginate film added with chitosan and glycerol, wherein the chitosan is analytically pure, the deacetylation degree is 80-95%, the mass of the chitosan is 1% of the mass of the sodium alginate, and 4mL of glycerol is added into each 8g of the sodium alginate;
(3) The adhesive layer is formed by a starch adhesive, wherein the starch adhesive is prepared by the following steps:
mixing 25g of corn starch with 70mL of pure water, adding a sodium hydroxide aqueous solution (9 g of sodium hydroxide +15g of water), and stirring at 70 ℃ for 30min to gelatinize to obtain a gelatinized product; then mixing the gelatinate with 150mL of cold water, and uniformly stirring to obtain a first solution;
dissolving 0.5g of potassium pyroantimonate in 25g of water to form a potassium pyroantimonate solution, then adding the potassium pyroantimonate solution into 500mL of pure water at the temperature of 35 ℃, simultaneously adding 3g of borax and 250g of starch, and mixing and stirring to obtain a second solution;
slowly pouring the prepared first solution into the prepared second solution under the stirring action, and mixing and stirring for 0.5h after the addition is finished to obtain the starch adhesive.
Example 2
The PLA/PBAT composite film comprises:
(1) The outer film layer is a PLA/PBAT film, wherein the mass ratio of the PLA to the PBAT is 7;
(2) The inner membrane layer is a sodium alginate film added with chitosan and glycerol, wherein the chitosan is analytically pure, the deacetylation degree is 80-95%, the mass of the chitosan is 3% of the mass of the sodium alginate, and 2mL of glycerol is added into each 8g of the sodium alginate;
(3) The adhesive layer is formed by starch adhesive, wherein the starch adhesive is prepared by the following steps:
mixing 25g of corn starch with 70mL of pure water, adding a sodium hydroxide aqueous solution (9 g of sodium hydroxide +15g of water), and stirring at 65 ℃ for 40min to gelatinize to obtain a gelatinized product; mixing the gelatinated substance with 150mL of cold water, and uniformly stirring to obtain a first solution;
dissolving 0.5g of potassium pyroantimonate in 25g of water to form a potassium pyroantimonate solution, then adding the potassium pyroantimonate solution into 500mL of pure water at the temperature of 33 ℃, simultaneously adding 3g of borax and 250g of starch, and mixing and stirring to obtain a second solution;
slowly pouring the prepared first solution into the prepared second solution under the stirring action, and mixing and stirring for 0.5h after the addition is finished to obtain the starch adhesive.
Example 3
The PLA/PBAT composite film comprises:
(1) The outer film layer is a PLA/PBAT film, wherein the mass ratio of the PLA to the PBAT is 7;
(2) The inner membrane layer is a sodium alginate film added with chitosan and glycerol, wherein the chitosan is analytically pure, the deacetylation degree is 80-95%, the mass of the chitosan is 5% of the mass of the sodium alginate, and 5mL of glycerol is added into every 8g of the sodium alginate;
(3) The adhesive layer is formed by starch adhesive, wherein the starch adhesive is prepared by the following steps:
mixing 25g of corn starch with 70mL of pure water, adding a sodium hydroxide aqueous solution (9 g of sodium hydroxide +15g of water), and stirring at 75 ℃ for 20min to gelatinize to obtain a gelatinized product; mixing the gelatinated substance with 150mL of cold water, and uniformly stirring to obtain a first solution;
dissolving 0.5g of potassium pyroantimonate in 25g of water to form a potassium pyroantimonate solution, then adding the potassium pyroantimonate solution into 500mL of pure water at 37 ℃, simultaneously adding 3g of borax and 250g of starch, and mixing and stirring to obtain a second solution;
slowly pouring the prepared first solution into the prepared second solution under the stirring action, and mixing and stirring for 0.5h after the addition is finished to obtain the starch adhesive.
Example 4
The PLA/PBAT composite film comprises:
(1) The outer film layer is a PLA/PBAT film, wherein the mass ratio of PLA to PBAT is 7;
(2) The inner membrane layer is a sodium alginate film added with nano zinc oxide and glycerol, wherein the particle size of nano zinc oxide particles is 20nm, the purity is more than 90%, the mass of the nano zinc oxide is 1% of that of the sodium alginate, and 4mL of glycerol is added into each 8g of the sodium alginate;
(3) The adhesive layer is formed by starch adhesive, wherein the starch adhesive is prepared by the following steps:
mixing 25g of corn starch with 70mL of pure water, adding a sodium hydroxide aqueous solution (9 g of sodium hydroxide +15g of water), and stirring at 70 ℃ for 30min to gelatinize to obtain a gelatinized product; then mixing the gelatinate with 150mL of cold water, and uniformly stirring to obtain a first solution;
dissolving 0.5g of potassium pyroantimonate in 25g of water to form a potassium pyroantimonate solution, then adding the potassium pyroantimonate solution into 500mL of pure water at the temperature of 35 ℃, simultaneously adding 3g of borax and 250g of starch, and mixing and stirring to obtain a second solution;
slowly pouring the prepared first solution into the prepared second solution under the stirring action, and mixing and stirring for 0.5h after the addition is finished to obtain the starch adhesive.
Example 5
The PLA/PBAT composite film comprises:
(1) The outer film layer is a PLA/PBAT film, wherein the mass ratio of the PLA to the PBAT is 7;
(2) The inner membrane layer is a sodium alginate film added with nano zinc oxide and glycerol, wherein the particle size of nano zinc oxide particles is 20nm, the purity is more than 90%, the mass of the nano zinc oxide is 2% of that of the sodium alginate, and 4mL of glycerol is added into each 8g of the sodium alginate;
(3) The adhesive layer is formed by a starch adhesive, wherein the starch adhesive is prepared by the following steps:
mixing 25g of corn starch with 70mL of pure water, adding a sodium hydroxide aqueous solution (9 g of sodium hydroxide +15g of water), and stirring at 70 ℃ for 30min to gelatinize to obtain a gelatinized product; then mixing the gelatinate with 150mL of cold water, and uniformly stirring to obtain a first solution;
dissolving 0.5g of potassium pyroantimonate in 25g of water to form a potassium pyroantimonate solution, then adding the potassium pyroantimonate solution into 500mL of pure water at the temperature of 35 ℃, simultaneously adding 3g of borax and 250g of starch, and mixing and stirring to obtain a second solution;
slowly pouring the prepared first solution into the prepared second solution under the stirring action, and mixing and stirring for 0.5h after the addition is finished to obtain the starch adhesive.
Example 6
The PLA/PBAT composite film comprises:
(1) The outer film layer is a PLA/PBAT film, wherein the mass ratio of PLA to PBAT is 7;
(2) The inner membrane layer is a sodium alginate film added with nano silver and glycerol, wherein the particle size of nano silver particles is 20nm, the purity is more than 99.9%, the mass of the nano silver is 1% of the mass of the sodium alginate, and 4mL of glycerol is added into each 8g of the sodium alginate;
(3) The adhesive layer is formed by starch adhesive, wherein the starch adhesive is prepared by the following steps:
mixing 25g of corn starch with 70mL of pure water, adding a sodium hydroxide aqueous solution (9 g of sodium hydroxide +15g of water), and stirring at 70 ℃ for 30min to gelatinize to obtain a gelatinized product; then mixing the gelatinate with 150mL of cold water, and uniformly stirring to obtain a first solution;
dissolving 0.5g of potassium pyroantimonate in 25g of water to form a potassium pyroantimonate solution, then adding the potassium pyroantimonate solution into 500mL of pure water at the temperature of 35 ℃, simultaneously adding 3g of borax and 250g of starch, and mixing and stirring to obtain a second solution;
slowly pouring the prepared first solution into the prepared second solution under the stirring action, and mixing and stirring for 0.5h after the addition is finished to obtain the starch adhesive.
Example 7
The PLA/PBAT composite film comprises:
(1) The outer film layer is a PLA/PBAT film, wherein the mass ratio of PLA to PBAT is 7;
(2) The inner membrane layer is a sodium alginate film added with nano silver and glycerol, wherein the particle size of nano silver particles is 20nm, the purity is more than 99.9%, the mass of the nano silver is 2% of the mass of the sodium alginate, and 4mL of glycerol is added into each 8g of the sodium alginate;
(3) The adhesive layer is formed by starch adhesive, wherein the starch adhesive is prepared by the following steps:
mixing 25g of corn starch with 70mL of pure water, adding a sodium hydroxide aqueous solution (9 g of sodium hydroxide +15g of water), and stirring at 70 ℃ for 30min to gelatinize to obtain a gelatinized product; mixing the gelatinated substance with 150mL of cold water, and uniformly stirring to obtain a first solution;
dissolving 0.5g of potassium pyroantimonate in 25g of water to form a potassium pyroantimonate solution, then adding the potassium pyroantimonate solution into 500mL of pure water at the temperature of 35 ℃, simultaneously adding 3g of borax and 250g of starch, and mixing and stirring to obtain a second solution;
slowly pouring the prepared first solution into the prepared second solution under the stirring action, and mixing and stirring for 0.5h after the addition is finished to obtain the starch adhesive.
Example 8
The structure and the composition of the PLA/PBAT composite film are the same as those of the embodiment 1, and the preparation steps comprise:
(1) Drying PLA and PBAT in a blast drying oven at 40 ℃ for 3h, then putting the dried PLA and PBAT into a double-screw extruder for melt extrusion and granulation to obtain PLA/PBAT mixed master batch, wherein the parameters of the double-screw extruder are as follows: the temperature of the screw zone is 180 ℃, 185 ℃, 180 ℃, the die temperature is 165 ℃ and the screw rotating speed is 70r/min along the material conveying direction in sequence; then, drying the PLA/PBAT mixed master batch for 3h at 40 ℃ in a blast drying oven, and then putting the dried master batch into a casting film testing machine to prepare a PLA/PBAT film by a casting method, wherein the parameters of the casting film testing machine are as follows: the temperature of the screw zone (along the conveying direction of the material) is 180 ℃, 185 ℃ and 180 ℃ in sequence, the temperature of the die orifice is 165 ℃, and the rotating speed of the screw is 30r/min.
(2) The starch adhesive is prepared according to the method for preparing the self-made starch adhesive provided in the embodiment 1.
(3) Dissolving 8g of sodium alginate in 400mL of ultrapure water, stirring for 0.5h at the temperature of 30 ℃ to prepare a sodium alginate aqueous solution, then adding chitosan into the sodium alginate solution, placing the sodium alginate solution on a magnetic stirrer, stirring for 4h at the temperature of 40 ℃ until the chitosan is completely dissolved, adding glycerol serving as a thickening agent into the solution, and continuously stirring for 0.5h to obtain a composite solution; and then, pouring the obtained composite solution on an acrylic glass plate, uniformly scraping the solution by using a scraper plate, putting the solution into an oven, drying the solution at 40 ℃, cooling the solution, and uncovering the film to obtain the sodium alginate film.
(4) Firstly, a PLA/PBAT film is paved on an automatic coating machine and clamped, then a wire bar coater is adopted to uniformly coat the starch adhesive on the surface of the PLA/PBAT film, then a sodium alginate film is paved on the PLA/PBAT film to be bonded with the PLA/PBAT film, then the PLA/PBAT film is transferred to a dark room, and the PLA/PBAT film is kept stand and balanced for 4 hours under the condition of light shielding, so that the full-biodegradable double-layer bacteriostatic composite film is obtained; wherein, the specification of a wire bar of the wire bar coater is 8 μm, and the coating speed is set to be 2m/min.
Example 9
The structure and the components of the PLA/PBAT composite membrane are the same as those of the example 2, and the preparation steps comprise:
(1) Drying PLA and PBAT in a blast drying oven at 40 ℃ for 3h, then putting the dried PLA and PBAT into a double-screw extruder for melting, extruding and granulating to obtain PLA/PBAT mixed master batch, wherein the parameters of the double-screw extruder are as follows: the temperature of the screw zone is 180 ℃, 185 ℃, 180 ℃, the die temperature is 165 ℃ and the screw rotating speed is 70r/min in sequence along the material conveying direction; then, drying the PLA/PBAT mixed master batch for 3h at 40 ℃ in a blast drying oven, and then putting the dried master batch into a casting film testing machine to prepare a PLA/PBAT film by a casting method, wherein the parameters of the casting film testing machine are as follows: the temperature of the screw zone (along the conveying direction of the material) is 180 ℃, 185 ℃ and 180 ℃ in sequence, the temperature of the die orifice is 165 ℃, and the rotating speed of the screw is 30r/min.
(2) The starch adhesive is prepared according to the method for preparing the self-made starch adhesive provided in the embodiment 2.
(3) Dissolving 8g of sodium alginate in 300mL of ultrapure water, stirring for 0.5h at the temperature of 30 ℃ to prepare a sodium alginate aqueous solution, then adding chitosan into the sodium alginate solution, placing the sodium alginate solution on a magnetic stirrer, stirring for 4h at the temperature of 40 ℃ until the chitosan is completely dissolved, adding glycerol serving as a thickening agent into the solution, and continuously stirring for 0.5h to obtain a composite solution; and then, pouring the obtained composite solution on an acrylic glass plate, uniformly scraping the solution by using a scraper plate, putting the solution into an oven, drying the solution at 40 ℃, cooling the solution, and uncovering the film to obtain the sodium alginate film.
(4) Firstly, a PLA/PBAT film is paved on an automatic coating machine and clamped, then a wire bar coater is adopted to uniformly coat the starch adhesive on the surface of the PLA/PBAT film, then a sodium alginate film is paved on the PLA/PBAT film to be bonded with the PLA/PBAT film, then the PLA/PBAT film is transferred to a dark room, and the PLA/PBAT film is kept stand and balanced for 3 hours under the condition of light shielding, so that the full-biodegradable double-layer bacteriostatic composite film is obtained; wherein, the specification of the wire bar coater is 6 μm, and the coating speed is set to 1m/min.
Example 10
The structure and composition of the PLA/PBAT composite film are the same as those of example 3, and the preparation steps comprise:
(1) Drying PLA and PBAT in a blast drying oven at 40 ℃ for 3h, then putting the dried PLA and PBAT into a double-screw extruder for melting, extruding and granulating to obtain PLA/PBAT mixed master batch, wherein the parameters of the double-screw extruder are as follows: the temperature of the screw zone is 180 ℃, 185 ℃, 180 ℃, the die temperature is 165 ℃ and the screw rotating speed is 70r/min along the material conveying direction in sequence; then, drying the PLA/PBAT mixed master batch in a blast drying oven at 40 ℃ for 3h, and then putting the dried master batch into a casting film testing machine to prepare a PLA/PBAT film by a casting method, wherein the parameters of the casting film testing machine are set as follows: the temperature of the screw zone (along the conveying direction of the materials) is 180 ℃, 185 ℃ and 180 ℃ in sequence, the temperature of the die orifice is 165 ℃, and the rotating speed of the screw is 30r/min.
(2) And preparing the starch adhesive according to the method for preparing the self-made starch adhesive provided by the embodiment 3.
(3) Dissolving 8g of sodium alginate in 500mL of ultrapure water, stirring for 0.5h at the temperature of 30 ℃ to prepare a sodium alginate aqueous solution, then adding chitosan into the sodium alginate solution, placing the sodium alginate solution on a magnetic stirrer, stirring for 4h at the temperature of 40 ℃ until the chitosan is completely dissolved, adding glycerol serving as a thickening agent into the solution, and continuously stirring for 0.5h to obtain a composite solution; and then, pouring the obtained composite solution on an acrylic glass plate, uniformly scraping the solution by using a scraper plate, putting the solution into an oven, drying the solution at 40 ℃, cooling the solution, and uncovering the film to obtain the sodium alginate film.
(4) Firstly, a PLA/PBAT film is paved on an automatic coating machine and clamped, then a wire bar coater is adopted to uniformly coat the starch adhesive on the surface of the PLA/PBAT film, then a sodium alginate film is paved on the PLA/PBAT film to be bonded with the PLA/PBAT film, then the PLA/PBAT film is transferred to a dark room, and the PLA/PBAT film is kept stand and balanced for 5 hours under the condition of light shielding, so that the full-biodegradable double-layer bacteriostatic composite film is obtained; wherein, the specification of a wire bar of the wire bar coater is 10 μm, and the coating speed is set to be 4m/min.
Example 11
The structure and the components of the PLA/PBAT composite film are the same as those of the embodiment 4, and the preparation steps comprise:
(1) Drying PLA and PBAT in a blast drying oven at 40 ℃ for 3h, then putting the dried PLA and PBAT into a double-screw extruder for melting, extruding and granulating to obtain PLA/PBAT mixed master batch, wherein the parameters of the double-screw extruder are as follows: the temperature of the screw zone is 180 ℃, 185 ℃, 180 ℃, the die temperature is 165 ℃ and the screw rotating speed is 70r/min along the material conveying direction in sequence; then, drying the PLA/PBAT mixed master batch for 3h at 40 ℃ in a blast drying oven, and then putting the dried master batch into a casting film testing machine to prepare a PLA/PBAT film by a casting method, wherein the parameters of the casting film testing machine are as follows: the temperature of the screw zone (along the conveying direction of the materials) is 180 ℃, 185 ℃ and 180 ℃ in sequence, the temperature of the die orifice is 165 ℃, and the rotating speed of the screw is 30r/min.
(2) The starch adhesive is prepared according to the method for self-making the starch adhesive provided in example 4.
(3) Dissolving 8g of sodium alginate in 400mL of ultrapure water, stirring for 0.5h at the temperature of 30 ℃ to prepare a sodium alginate aqueous solution, then adding chitosan into the sodium alginate solution, placing the sodium alginate solution on a magnetic stirrer, stirring for 4h at the temperature of 40 ℃ until the chitosan is completely dissolved, adding glycerol serving as a thickening agent into the solution, and continuously stirring for 0.5h to obtain a composite solution; and then pouring the obtained composite solution onto an acrylic glass plate, uniformly scraping the composite solution by using a scraper, putting the composite solution into an oven, drying the composite solution at 40 ℃, and then cooling and uncovering the film to obtain the sodium alginate film.
(4) Firstly, a PLA/PBAT film is paved on an automatic coating machine and clamped, then a wire bar coater is adopted to uniformly coat the starch adhesive on the surface of the PLA/PBAT film, then a sodium alginate film is paved on the PLA/PBAT film to be bonded with the PLA/PBAT film, then the PLA/PBAT film is transferred to a dark room, and the PLA/PBAT film is kept stand and balanced for 4 hours under the condition of light shielding, so that the full-biodegradable double-layer bacteriostatic composite film is obtained; wherein, the specification of a wire bar of the wire bar coater is 8 μm, and the coating speed is set to be 2m/min.
Example 12
The structure and the composition of the PLA/PBAT composite film are the same as those of example 5, and the preparation steps comprise:
(1) Drying PLA and PBAT in a blast drying oven at 40 ℃ for 3h, then putting the dried PLA and PBAT into a double-screw extruder for melting, extruding and granulating to obtain PLA/PBAT mixed master batch, wherein the parameters of the double-screw extruder are as follows: the temperature of the screw zone is 180 ℃, 185 ℃, 180 ℃, the die temperature is 165 ℃ and the screw rotating speed is 70r/min in sequence along the material conveying direction; then, drying the PLA/PBAT mixed master batch in a blast drying oven at 40 ℃ for 3h, and then putting the dried master batch into a casting film testing machine to prepare a PLA/PBAT film by a casting method, wherein the parameters of the casting film testing machine are set as follows: the temperature of the screw zone (along the conveying direction of the materials) is 180 ℃, 185 ℃ and 180 ℃ in sequence, the temperature of the die orifice is 165 ℃, and the rotating speed of the screw is 30r/min.
(2) The starch adhesive was prepared according to the method of self-making starch adhesive provided in example 5.
(3) Dissolving 8g of sodium alginate in 400mL of ultrapure water, stirring for 0.5h at the temperature of 30 ℃ to prepare a sodium alginate aqueous solution, then adding chitosan into the sodium alginate solution, placing the sodium alginate solution on a magnetic stirrer, stirring for 4h at the temperature of 40 ℃ until the chitosan is completely dissolved, adding glycerol serving as a thickening agent into the solution, and continuously stirring for 0.5h to obtain a composite solution; and then, pouring the obtained composite solution on an acrylic glass plate, uniformly scraping the solution by using a scraper plate, putting the solution into an oven, drying the solution at 40 ℃, cooling the solution, and uncovering the film to obtain the sodium alginate film.
(4) Firstly, a PLA/PBAT film is paved on an automatic coating machine and clamped, then a bar coater is adopted to uniformly coat the starch adhesive on the surface of the PLA/PBAT film, then a sodium alginate film is paved on the PLA/PBAT film to be bonded with the PLA/PBAT film, then the PLA/PBAT film is transferred to a dark room, and the PLA/PBAT film is kept stand and balanced for 4 hours under the light-tight condition, so that the full-biodegradable double-layer bacteriostatic composite film is obtained; wherein, the specification of a wire bar of the wire bar coater is 8 μm, and the coating speed is set to be 2m/min.
Example 13
The structure and the components of the PLA/PBAT composite film are the same as those of the example 6, and the preparation steps comprise:
(1) Drying PLA and PBAT in a blast drying oven at 40 ℃ for 3h, then putting the dried PLA and PBAT into a double-screw extruder for melting, extruding and granulating to obtain PLA/PBAT mixed master batch, wherein the parameters of the double-screw extruder are as follows: the temperature of the screw zone is 180 ℃, 185 ℃, 180 ℃, the die temperature is 165 ℃ and the screw rotating speed is 70r/min along the material conveying direction in sequence; then, drying the PLA/PBAT mixed master batch for 3h at 40 ℃ in a blast drying oven, and then putting the dried master batch into a casting film testing machine to prepare a PLA/PBAT film by a casting method, wherein the parameters of the casting film testing machine are as follows: the temperature of the screw zone (along the conveying direction of the materials) is 180 ℃, 185 ℃ and 180 ℃ in sequence, the temperature of the die orifice is 165 ℃, and the rotating speed of the screw is 30r/min.
(2) The starch adhesive is prepared according to the method for preparing the self-made starch adhesive provided in the embodiment 6.
(3) Dissolving 8g of sodium alginate in 400mL of ultrapure water, stirring for 0.5h at the temperature of 30 ℃ to prepare a sodium alginate aqueous solution, then adding chitosan into the sodium alginate solution, placing the sodium alginate solution on a magnetic stirrer, stirring for 4h at the temperature of 40 ℃ until the chitosan is completely dissolved, adding glycerol serving as a thickening agent into the solution, and continuously stirring for 0.5h to obtain a composite solution; and then, pouring the obtained composite solution on an acrylic glass plate, uniformly scraping the solution by using a scraper plate, putting the solution into an oven, drying the solution at 40 ℃, cooling the solution, and uncovering the film to obtain the sodium alginate film.
(4) Firstly, a PLA/PBAT film is paved on an automatic coating machine and clamped, then a wire bar coater is adopted to uniformly coat the starch adhesive on the surface of the PLA/PBAT film, then a sodium alginate film is paved on the PLA/PBAT film to be bonded with the PLA/PBAT film, then the PLA/PBAT film is transferred to a dark room, and the PLA/PBAT film is kept stand and balanced for 4 hours under the condition of light shielding, so that the full-biodegradable double-layer bacteriostatic composite film is obtained; wherein, the specification of a wire bar of the wire bar coater is 8 μm, and the coating speed is set to be 2m/min.
Example 14
The structure and composition of the PLA/PBAT composite film are the same as in example 7, and the preparation method comprises the steps of:
(1) Drying PLA and PBAT in a blast drying oven at 40 ℃ for 3h, then putting the dried PLA and PBAT into a double-screw extruder for melting, extruding and granulating to obtain PLA/PBAT mixed master batch, wherein the parameters of the double-screw extruder are as follows: the temperature of the screw zone is 180 ℃, 185 ℃, 180 ℃, the die temperature is 165 ℃ and the screw rotating speed is 70r/min along the material conveying direction in sequence; then, drying the PLA/PBAT mixed master batch for 3h at 40 ℃ in a blast drying oven, and then putting the dried master batch into a casting film testing machine to prepare a PLA/PBAT film by a casting method, wherein the parameters of the casting film testing machine are as follows: the temperature of the screw zone (along the conveying direction of the material) is 180 ℃, 185 ℃ and 180 ℃ in sequence, the temperature of the die orifice is 165 ℃, and the rotating speed of the screw is 30r/min.
(2) The starch adhesive was prepared according to the method of self-making starch adhesive provided in example 7.
(3) Dissolving 8g of sodium alginate in 400mL of ultrapure water, stirring for 0.5h at the temperature of 30 ℃ to prepare a sodium alginate aqueous solution, then adding chitosan into the sodium alginate solution, placing the sodium alginate solution on a magnetic stirrer, stirring for 4h at the temperature of 40 ℃ until the chitosan is completely dissolved, adding glycerol serving as a thickening agent into the solution, and continuously stirring for 0.5h to obtain a composite solution; and then, pouring the obtained composite solution on an acrylic glass plate, uniformly scraping the solution by using a scraper plate, putting the solution into an oven, drying the solution at 40 ℃, cooling the solution, and uncovering the film to obtain the sodium alginate film.
(4) Firstly, a PLA/PBAT film is paved on an automatic coating machine and clamped, then a wire bar coater is adopted to uniformly coat the starch adhesive on the surface of the PLA/PBAT film, then a sodium alginate film is paved on the PLA/PBAT film to be bonded with the PLA/PBAT film, then the PLA/PBAT film is transferred to a dark room, and the PLA/PBAT film is kept stand and balanced for 4 hours under the condition of light shielding, so that the full-biodegradable double-layer bacteriostatic composite film is obtained; wherein, the specification of a wire bar of the wire bar coater is 8 μm, and the coating speed is set to be 2m/min.
The performance tests of the fully biodegradable double-layer bacteriostatic composite films of the embodiments 8 to 14 include an apparent performance test, a mechanical performance test, a barrier performance test and a bacteriostatic performance test, and the specific test method can refer to related test standards, wherein the bacteriostatic performance test is performed by selecting escherichia coli and staphylococcus aureus, and the absorbance with the wavelength of 600nm is tested.
For convenience of description, the fully biodegradable two-layer bacteriostatic composite films prepared in examples 8 to 14 are referred to as PLA/PBAT/C1, PLA/PBAT/C3, PLA/PBAT/C5, PLA/PBAT/Z1, PLA/PBAT/Z2, PLA/PBAT/A1, and PLA/PBAT/A2 in sequence.
Test results and analysis:
(1) Apparent Properties
Fig. 2 is a photograph showing a sample of the fully biodegradable two-layer bacteriostatic composite film prepared in examples 8 to 14 of the present invention, and it can be seen from fig. 2 that the prepared film is gray yellow and the color becomes lighter or darker depending on the formulation.
(2) Mechanical Property test
Fig. 3 shows the mechanical performance test results (using PLA/PBAT films as comparison) of the fully biodegradable two-layer bacteriostatic composite films prepared in examples 8 to 14 of the present invention.
As can be seen from FIG. 3, the fully biodegradable double-layered antibacterial composite membrane prepared by the embodiment of the invention has excellent mechanical properties. Compared with a PLA/PBAT film, the tensile strength and the elongation at break of the full-biodegradable double-layer antibacterial composite film are increased to a certain extent, and the tensile strength result shows that after the PLA/PBAT film is compounded with a sodium alginate film, the tensile strength is only slightly increased, which is possibly related to insufficient mechanical property of the sodium alginate. The increase of the elongation at break can be related to the addition of the adhesive, the addition of the adhesive can effectively prevent the crack propagation of the PLA/PBAT film and the sodium alginate film, so that the elongation at break is increased, but the significant analysis finds that the adhesive and sodium alginate composite layer has no significant influence (P is more than 0.05) on the elongation at break of the composite film, which indicates that the PLA/PBAT plays a leading role.
(3) Test for Barrier Properties
Fig. 4 shows the test results of oxygen barrier performance and water vapor barrier performance (using PLA/PBAT film as comparison) of the fully biodegradable two-layer bacteriostatic composite films prepared in examples 8 to 14 of the present invention.
As can be seen from fig. 4, the oxygen barrier capacity of the fully biodegradable double-layer antibacterial composite film obtained by compounding the starch adhesive with the sodium alginate film is greatly improved, the addition of the adhesive and the sodium alginate film is mainly benefited, no obvious change is observed after the antibacterial agent is added, the result error of the oxygen barrier capacity of the composite film added with the antibacterial agent is small, and the change of the oxygen barrier capacity caused by adding a certain amount of the antibacterial agent can not play a key role.
It can be seen from fig. 4 that the water vapor barrier ability of the fully biodegradable double-layer antibacterial composite film after the sodium alginate film is added is improved, which accords with the expected effect, the structure of the composite film can determine the water-blocking effect, usually, the multilayer composite film can play a good barrier effect, and water molecules must pass through the PLA/PBAT thin film layer, the adhesive layer and the sodium alginate thin film layer, so that the barrier ability is played by prolonging the path of the water molecules, but the composite layer substrate is sodium alginate, and the hydrophilicity is stronger, so that the effect is limited. Although a small amount of bacteriostatic agent cannot play a dominant role in the result of water vapor barrier property, a certain change can be found in the figure, the barrier property is slightly enhanced after the nano silver particles are added, the hydrophilic chitosan does not achieve the effect, the water vapor barrier property of the chitosan-containing composite membrane depends on the molecular weight of the chitosan, the higher the molecular weight is, the water vapor permeability of the composite membrane is increased, and the deacetylation degree of the chitosan is less influenced.
(4) Test of bacteriostatic Property
Fig. 5 and 6 show the bacteriostatic test results of the fully biodegradable two-layer bacteriostatic composite films prepared in examples 8 to 14 of the present invention on escherichia coli and staphylococcus aureus, respectively.
From fig. 5 and fig. 6, it can be clearly observed that the fully biodegradable double-layer antibacterial composite membrane containing nano silver particles has good antibacterial effects on two representative gram bacteria, while the antibacterial effect of chitosan is relatively weak, which may be related to the content of chitosan and the hydrophilicity of sodium alginate, and because sodium alginate has strong hydrophilicity, it is easier to load chitosan with hydrophilicity, and the load rate on zinc oxide nano particles and silver nano particles is relatively low. The low water resistance of sodium alginate in the NB culture medium causes the metal nanoparticles to be easy to burst, which is not beneficial to playing the effect of slow release, durability and bacteriostasis. In addition, as shown in fig. 5 and 6, the nano zinc oxide particles have better inhibition capability on staphylococcus aureus than escherichia coli, and the difference between the 72 th result and the 24 th result is observed, so that the metal nanoparticles have certain bacteriostasis durability.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.

Claims (10)

1. The utility model provides a full biodegradable double-deck antibacterial composite membrane, its characterized in that, full biodegradable double-deck antibacterial composite membrane includes interior rete and adventitia and locates interior rete with bond line between the adventitia, the component material of interior rete includes sodium alginate, glycerine and bacteriostatic agent, the component material of adventitia includes PLA and PBAT, the bond line is formed by starch adhesive.
2. The fully biodegradable two-layer bacteriostatic composite membrane according to claim 1, wherein said starch adhesive is prepared by the following steps:
mixing starch and water, then adding a sodium hydroxide aqueous solution, stirring for 20-40 min at 65-75 ℃ for gelatinization, mixing the gelatinized substance with cold water, and uniformly stirring to obtain a first solution;
dissolving potassium pyroantimonate in water, and then mixing the potassium pyroantimonate with borax and starch in water at the temperature of 33-37 ℃ to form a second solution;
and adding the first solution into the second solution under the stirring action, and mixing and stirring to obtain the starch adhesive.
3. The fully biodegradable double-layered antibacterial composite membrane according to claim 2, wherein the step of mixing starch with water, adding an aqueous solution of sodium hydroxide and stirring at 65-75 ℃ for 20-40 min to gelatinize, mixing the gelatinized product with cold water, and stirring uniformly to obtain a first solution comprises:
mixing 25g of starch with 70mL of water, adding a sodium hydroxide aqueous solution, wherein the sodium hydroxide aqueous solution is obtained by dissolving 9g of sodium hydroxide in 15g of water, and then stirring at 65-75 ℃ for 20-40 min for gelatinization to obtain a gelatinized substance;
and mixing the gelatinate with 150mL of cold water, and uniformly stirring to obtain a first solution.
4. The fully biodegradable bi-layer bacteriostatic composite membrane according to claim 2, wherein the step of dissolving potassium pyroantimonate in water and then mixing borax and starch in water at 33-37 ℃ to form a second solution comprises:
dissolving 0.5g of potassium pyroantimonate in 25g of water, adding the obtained solution into 500mL of water with the temperature of 33-37 ℃, simultaneously adding 3g of borax and 250g of starch, and mixing and stirring to obtain a second solution.
5. The fully biodegradable bi-layer bacteriostatic composite membrane according to claim 2, wherein said starch is corn starch.
6. The fully biodegradable two-layer bacteriostatic composite film according to claim 1, wherein in the outer film layer, the mass ratio of the PLA to the PBAT is 7; and/or the presence of a gas in the gas,
in the inner film layer, the mass of the bacteriostatic agent is 1-5% of the mass of the sodium alginate; and/or the presence of a gas in the atmosphere,
the bacteriostatic agent comprises at least one of chitosan, nano silver and nano zinc oxide.
7. A preparation method of the full biodegradable double-layer bacteriostatic composite membrane according to any one of claims 1 to 6, characterized by comprising the following steps:
preparing PLA/PBAT mixed master batches from PLA and PBAT in a melt blending mode, and preparing the PLA/PBAT mixed master batches into a PLA/PBAT film by a tape casting method;
preparing a starch adhesive;
dissolving sodium alginate in water to prepare a sodium alginate aqueous solution, adding a bacteriostatic agent into the sodium alginate aqueous solution, stirring to dissolve, adding glycerol, stirring to obtain a composite solution, and preparing the composite solution into a sodium alginate film containing the bacteriostatic agent by a tape casting method;
and compounding the PLA/PBAT film and the sodium alginate film by using the starch adhesive to prepare the full-biodegradable double-layer antibacterial composite film.
8. The method for preparing the fully biodegradable double-layer antibacterial composite membrane according to claim 7, wherein the step of dissolving sodium alginate in water to prepare a sodium alginate aqueous solution, adding the antibacterial agent into the sodium alginate aqueous solution, stirring to dissolve the sodium alginate aqueous solution, adding glycerol into the dissolved sodium alginate aqueous solution, stirring to obtain a composite solution, and preparing the composite solution into the sodium alginate film containing the antibacterial agent by a tape casting method comprises the following steps:
300-500 mL of water and 3-5 mL of glycerol are added for every 8g of sodium alginate.
9. The method for preparing the fully biodegradable bi-layer bacteriostatic composite film according to claim 7, wherein the step of compounding the PLA/PBAT film and the sodium alginate film by using the starch adhesive to prepare the fully biodegradable bi-layer bacteriostatic composite film comprises the following steps:
coating the starch adhesive on the surface of the PLA/PBAT film by using a wire bar coater, then flatly paving the sodium alginate film on the PLA/PBAT film to be bonded with the PLA/PBAT film, and standing for 3-5 h under a dark condition to obtain the full-biodegradable double-layer antibacterial composite film.
10. The method for preparing the full biodegradable double-layer bacteriostatic composite membrane according to claim 9, wherein the wire rod specification of the wire rod coater is 6-10 μm, and the coating speed is set to 1-4 m/min.
CN202210978897.XA 2022-08-12 2022-08-12 Full-biodegradable double-layer antibacterial composite film and preparation method thereof Pending CN115302934A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210978897.XA CN115302934A (en) 2022-08-12 2022-08-12 Full-biodegradable double-layer antibacterial composite film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210978897.XA CN115302934A (en) 2022-08-12 2022-08-12 Full-biodegradable double-layer antibacterial composite film and preparation method thereof

Publications (1)

Publication Number Publication Date
CN115302934A true CN115302934A (en) 2022-11-08

Family

ID=83863674

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210978897.XA Pending CN115302934A (en) 2022-08-12 2022-08-12 Full-biodegradable double-layer antibacterial composite film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115302934A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115612182A (en) * 2022-11-07 2023-01-17 广西民族大学 CMC/starch/ZnO/anthocyanin intelligent active packaging film and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103053670A (en) * 2012-12-19 2013-04-24 东北农业大学 Composited sodium alga acid antibacterial film and application thereof in preservation of livestock meat carcass
CN105802541A (en) * 2016-05-12 2016-07-27 陈志冲 Corn starch glue and preparing method thereof
CN107840981A (en) * 2017-11-08 2018-03-27 海南师范大学 A kind of sodium alginate chitosan bilayer edible film, its preparation method and its application
CN108384068A (en) * 2018-04-16 2018-08-10 合肥聪亨新型建材科技有限公司 A kind of fruit and vegetable preservative film special and preparation method thereof
CN109294003A (en) * 2018-09-03 2019-02-01 太原理工大学 A kind of chitosan containing ZnO/sodium alginate antimicrobial preservative film and preparation method thereof
CN111098574A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Full-biodegradable high-water-resistance film and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103053670A (en) * 2012-12-19 2013-04-24 东北农业大学 Composited sodium alga acid antibacterial film and application thereof in preservation of livestock meat carcass
CN105802541A (en) * 2016-05-12 2016-07-27 陈志冲 Corn starch glue and preparing method thereof
CN107840981A (en) * 2017-11-08 2018-03-27 海南师范大学 A kind of sodium alginate chitosan bilayer edible film, its preparation method and its application
CN108384068A (en) * 2018-04-16 2018-08-10 合肥聪亨新型建材科技有限公司 A kind of fruit and vegetable preservative film special and preparation method thereof
CN109294003A (en) * 2018-09-03 2019-02-01 太原理工大学 A kind of chitosan containing ZnO/sodium alginate antimicrobial preservative film and preparation method thereof
CN111098574A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Full-biodegradable high-water-resistance film and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115612182A (en) * 2022-11-07 2023-01-17 广西民族大学 CMC/starch/ZnO/anthocyanin intelligent active packaging film and preparation method thereof

Similar Documents

Publication Publication Date Title
EP0474705B1 (en) Starch derived shaped articles
ITTO980735A1 (en) BIODEGRADABLE COMPOSITIONS INCLUDING STARCH AND CELLULOSE ESTERS.
CN110091564A (en) A kind of complete biological 100% degradable composite membrane and its processing technology and application
Yu et al. Preparation, characterization, and antibacterial properties of biofilms comprising chitosan and ε-polylysine
CN112940474B (en) Antibacterial puncture-resistant biodegradable packaging bag and preparation method thereof
Yun et al. Preparation of chitosan/polyvinyl alcohol blended films containing sulfosuccinic acid as the crosslinking agent using UV curing process
TW201307461A (en) Blends of a polylactic acid and a water soluble polymer
KR20210144743A (en) Multilayer Articles Containing Enzymes
CN115302934A (en) Full-biodegradable double-layer antibacterial composite film and preparation method thereof
KR20160072652A (en) Protein-polymer-graphene oxide nanocomposites and nanocomposite films comprising them
CN115593061A (en) High-barrier biodegradable composite membrane and preparation process thereof
CN116218173A (en) New packaging bag material with strong antibacterial property and preparation method thereof
Zhang et al. Physicochemical properties and antibacterial activity of polylactic acid/starch acetate films incorporated with chitosan and tea polyphenols
WO2021148665A1 (en) Method for preparing an enzyme masterbatch
CN112500600B (en) Self-cleaning antibacterial degradable daily chemical bottle and preparation method thereof
CN112898612B (en) Method for preparing biodegradable hydrophobic film from alcohol soluble protein and fatty acid
WO2021028918A1 (en) Composites and uses thereof
CN113801448B (en) Biodegradable color master batch and preparation method thereof
JPH06218878A (en) Biodegradable film or sheet having heat sealing property
WO2024142049A1 (en) Biodegradable and barrier pvoh-based materials and products made therefrom
CN115710409A (en) Bio-based antibacterial packaging film and preparation method thereof
Thakkar et al. A comparative study of the effects of graphite, wollastonite, and titanium dioxide fillers on the properties of starch-based biodegradable plastic film
Horvat et al. Simple, One-Pot Method for Preparing Transparent Ethyl Cellulose Films with Good Mechanical Properties. Polymers 2022, 14, 2399
WO2023001872A1 (en) Method for preparing an enzyme masterbatch
CN117844032A (en) Method for preparing high oxygen barrier biodegradable film by layer-by-layer assembly method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20221108