CN113442540B - Biodegradable film material and preparation method and application thereof - Google Patents

Biodegradable film material and preparation method and application thereof Download PDF

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Publication number
CN113442540B
CN113442540B CN202110709406.7A CN202110709406A CN113442540B CN 113442540 B CN113442540 B CN 113442540B CN 202110709406 A CN202110709406 A CN 202110709406A CN 113442540 B CN113442540 B CN 113442540B
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parts
surface layer
biodegradable
film material
polylactic acid
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CN113442540A (en
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罗珊珊
秦舒浩
庞会霞
李娟�
王彦文
张黎
高成涛
胡继粗
黄绍文
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GUIZHOU MATERIAL TECHNOLOGY INNOVATION BASE
Guizhou Material Industrial Technology Research Institute
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GUIZHOU MATERIAL TECHNOLOGY INNOVATION BASE
Guizhou Material Industrial Technology Research Institute
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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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B7/152—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154—Organic compounds; Microorganisms; Enzymes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/157—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • 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
    • 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
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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
    • C08J2367/04—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
    • 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
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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

Abstract

The invention relates to the technical field of fruit and vegetable fresh-keeping, in particular to a biodegradable film material and a preparation method and application thereof. The biodegradable film material comprises a first surface layer, a second surface layer and an intermediate layer; the interfaces of the first surface layer and the middle layer, and the interfaces of the second surface layer and the middle layer are all provided with transverse crystal structures perpendicular to the gas permeation direction; the first skin layer includes: 73.7 to 94.7 parts of polylactic acid, 5 to 20 parts of biodegradable polyester, 0.1 to 5 parts of catalytic oxidizer, 0.1 to 1 part of antibacterial agent and 0.1 to 0.3 part of opening agent; the intermediate layer comprises: 75 to 94.9 parts of polylactic acid, 5 to 20 parts of biodegradable polyester and 0.1 to 5 parts of nucleating agent; the second surface layer includes: 80-95 parts of polylactic acid and 5-20 parts of biodegradable polyester. The biodegradable film material has proper transmission rates of oxygen, carbon dioxide and water vapor, and can better prolong the storage time of fresh fruits and vegetables by cooperating with an ethylene elimination function and an antibacterial function, thereby having great economic value.

Description

Biodegradable film material and preparation method and application thereof
Technical Field
The invention relates to the technical field of fruit and vegetable fresh-keeping, in particular to a biodegradable film material and a preparation method and application thereof.
Background
At present, with the improvement of living standard, people have greatly changed the diet concept after solving the problem of temperature saturation, and the demand for fresh and nutrient fruits and vegetables is higher and higher. The fruits and vegetables are used as food with life activities, and continue breathing and metabolism after picking, and are accompanied by moisture evaporation, ethylene gas generation and bacterial growth. Under the normal temperature environment, the stronger the respiration rate of the fruits and vegetables is, the easier the fruits and vegetables are aged. When the content of ethylene gas is more than 0.01 mu L/L, the respiration of fruits and vegetables is obviously promoted, the ripening of the fruits and vegetables is accelerated, meanwhile, the fruits and vegetables are decomposed and deteriorated due to bacteria, and the loss of the fruits and vegetables in the circulation and sales process after picking is huge. The loss rate of fruits and vegetables in China is as high as 25-30% each year, and huge resource waste, economic loss and environmental pollution are caused.
Theoretically, the key point of prolonging the shelf life of fruits and vegetables is as follows: proper oxygen and carbon dioxide concentration can inhibit respiration of fruits and vegetables, eliminate ethylene and inhibit bacterial growth. Therefore, the fruit and vegetable preservative film with the functions of air conditioning, ethylene elimination and antibacterial is a hot spot for research in the current preservative film. For the air conditioning function, the micro-structure of the composite material is mainly used for regulation and control, and the ethylene elimination is started from the directions of inhibiting ethylene generation, adsorbing ethylene and catalyzing ethylene oxide, and the antibacterial agent is mainly used for inhibiting bacterial generation. CN110421944a discloses an antibacterial fruit and vegetable fresh-keeping material with ethylene decomposition and slow release functions and a preparation method thereof, and the polyethylene-based fresh-keeping film material with ethylene decomposition and antibacterial functions is prepared through catalytic oxidation and antibacterial effects of nano zinc oxide. CN103965539B discloses an intelligent breathing fruit and vegetable fresh-keeping functional film and a preparation method thereof, ethylene is eliminated by using an ethylene adsorption material and a porous structure, and meanwhile, bacteria breeding is inhibited by using N-acetamido-4-vinylpyridine, so that the fresh-keeping time of fruit and vegetable foods is prolonged. Literature studies show that the existing fruit and vegetable fresh-keeping technology is mainly combined with an antibacterial technology through an ethylene elimination technology. However, the prior art has the defects of poor ethylene elimination and antibacterial effect, complex process and the like, so that the commercial fruit and vegetable preservative film is difficult to prolong the fruit and vegetable preservative time.
The existing fruit and vegetable preservative film mainly uses PE and PVC as raw materials, is difficult to degrade after being used once, is one of the main culprits for causing white pollution, and causes serious injury to the nature.
In view of this, the present invention has been made.
Disclosure of Invention
A first object of the present invention is to provide a biodegradable film material having a layered structure and a transverse crystal structure, having a spontaneous air conditioning function, a synergistic catalytic oxidation agent and an antibacterial agent, and having both an ethylene elimination function and an antibacterial function.
The second object of the present invention is to provide a method for preparing the biodegradable film material, which is simple to operate and can prepare the biodegradable film material with self-air-conditioning function, ethylene elimination function and antibacterial function.
The third object of the present invention is to provide an application of the biodegradable film material, wherein the biodegradable film material can be used for fresh-keeping of fresh fruits and vegetables, and can prolong the storage time of fruits and vegetables.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a biodegradable film material, which comprises a first surface layer, a second surface layer and an intermediate layer arranged between the first surface layer and the second surface layer; the interface between the first surface layer and the middle layer and the interface between the second surface layer and the middle layer are provided with transverse crystal structures perpendicular to the gas permeation direction;
the first surface layer is mainly prepared from the following raw materials in parts by weight: 73.7 to 94.7 parts of polylactic acid, 5 to 20 parts of biodegradable polyester, 0.1 to 5 parts of catalytic oxidizer, 0.1 to 1 part of antibacterial agent and 0.1 to 0.3 part of opening agent;
the intermediate layer is mainly prepared from the following raw materials in parts by mass: 75 to 94.9 parts of polylactic acid, 5 to 20 parts of biodegradable polyester and 0.1 to 5 parts of nucleating agent;
the second surface layer is mainly prepared from the following raw materials in parts by mass: 80-95 parts of polylactic acid and 5-20 parts of biodegradable polyester.
On the other hand, the invention also provides a preparation method of the biodegradable film material, which comprises the following steps:
(A) Respectively and uniformly mixing the raw materials of the first surface layer, the middle layer and the second surface layer, and then extruding and granulating to obtain first surface layer master batch, middle layer master batch and second surface layer master batch;
(B) And putting the first surface layer master batch, the middle layer master batch and the second surface layer master batch into a film blowing machine for blow molding to form a film, thus obtaining the biodegradable film material.
In a further aspect, the invention further provides application of the degradable film material in fruit and vegetable fresh-keeping.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a biodegradable film material, which realizes the self-gas regulating function of the biodegradable film material by constructing a three-layer microstructure and self-assembling a nucleating agent at a layer interface to induce polylactic acid to form a transverse crystal structure with platelet perpendicular to the gas permeation direction to cooperatively regulate the permeation rate of oxygen, carbon dioxide and water vapor molecules; the catalytic oxidant and the antibacterial agent of the first surface layer endow the biodegradable film material with the functions of eliminating ethylene and resisting bacteria; the biodegradable film material of the invention has proper transmittance of oxygen, carbon dioxide and water vapor, ethylene elimination function and antibacterial function.
(2) The preparation method of the biodegradable film material provided by the invention can be used for preparing the biodegradable film material with the spontaneous air conditioning function, the ethylene elimination function and the antibacterial function, is simple to operate, has high efficiency, has low requirements on equipment, and can realize large-scale industrial production.
(3) The invention provides application of the biodegradable film material, which can be applied to fruit and vegetable fresh-keeping, and has the functions of eliminating ethylene, inhibiting bacterial growth and inhibiting the respiration intensity of fresh fruits and vegetables, thereby achieving the purpose of prolonging the storage time of the fruits and vegetables.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a biodegradable film material prepared in example 2 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The biodegradable film material, the preparation method and the application of the biodegradable film material according to the embodiment of the invention are specifically described below.
Some embodiments of the present invention provide a biodegradable film material comprising a first skin layer and a second skin layer, and an intermediate layer disposed between the first skin layer and the second skin layer; the interface between the first surface layer and the middle layer and the interface between the second surface layer and the middle layer are provided with transverse crystal structures perpendicular to the gas permeation direction;
the first surface layer is mainly prepared from the following raw materials in parts by weight: 73.7 to 94.7 parts of polylactic acid, 5 to 20 parts of biodegradable polyester, 0.1 to 5 parts of catalytic oxidizer, 0.1 to 1 part of antibacterial agent and 0.1 to 0.3 part of opening agent;
the intermediate layer is mainly prepared from the following raw materials in parts by mass: 75 to 94.9 parts of polylactic acid, 5 to 20 parts of biodegradable polyester and 0.1 to 5 parts of nucleating agent;
the second surface layer is mainly prepared from the following raw materials in parts by mass: 80-95 parts of polylactic acid and 5-20 parts of biodegradable polyester.
The biodegradable film material has good air permeability by constructing three layers of microstructures and self-assembling a transverse crystal structure of a nucleating agent at a layer interface, which induces a platelet formed by polylactic acid to be perpendicular to the air permeation direction, so that the biodegradable film material has good air permeability, gas composition and concentration are regulated, and an air self-regulating function is given to the biodegradable film material; and the catalytic oxidizer, antimicrobial agent in the first skin layer can impart ethylene-eliminating and antimicrobial functions to the biodegradable film material.
Typical but non-limiting parts by mass of raw polylactic acid in the first skin layer are, for example, 73.7 parts, 75 parts, 78 parts, 80 parts, 83 parts, 85 parts, 87 parts, 90 parts, 92 parts and 94.7 parts; typical but non-limiting parts by mass of biodegradable polyesters are for example 5 parts, 7 parts, 10 parts, 12 parts, 15 parts, 17 parts and 20 parts; typical but non-limiting parts by mass of catalytic oxidants are for example 0.1 parts, 1 part, 2 parts, 3 parts, 4 parts and 5 parts; typical but non-limiting parts by weight of antimicrobial agents are for example 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts and 1 part; typical but non-limiting parts by weight of the opening agent are for example 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts and 0.3 parts.
Typical but non-limiting parts by mass of raw polylactic acid in the middle layer are, for example, 75 parts, 78 parts, 80 parts, 83 parts, 85 parts, 87 parts, 90 parts, 92 parts and 94.9 parts; typical but non-limiting parts by mass of biodegradable polyesters are for example 5 parts, 7 parts, 10 parts, 12 parts, 15 parts, 17 parts and 20 parts; exemplary, but non-limiting, parts by weight of nucleating agents are, for example, 0.1 parts, 1 part, 2 parts, 3 parts, 4 parts, and 5 parts.
Typical but non-limiting parts by mass of the raw polylactic acid in the second skin layer are, for example, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 92 parts and 95 parts; typical but non-limiting parts by mass of biodegradable polyesters are for example 5 parts, 7 parts, 10 parts, 12 parts, 15 parts, 17 parts and 20 parts.
By adding the raw materials and limiting the content of the raw materials, the biodegradable film material has the functions of eliminating ethylene and inhibiting bacterial growth while having a spontaneous air conditioning function.
Polylactic acid (PLA) is a biodegradable material, is a polymer obtained by polymerizing lactic acid serving as a main raw material, and can be prepared from agricultural and sideline products with high starch content; the composite material has good biodegradability, can be completely decomposed under the action of microorganisms, water, acid, alkali and the like, and the final product is carbon dioxide and water, so that the composite material does not pollute the environment, and is very beneficial to protecting the environment; besides biodegradability, the polylactic acid has good oxygen and carbon dioxide permeability.
Polylactic acid is a crystalline polymer, but since polylactic acid has a low crystallization rate and a low crystallinity, polylactic acid hardly crystallizes in the actual molding process; to overcome this drawback, the crystallization speed and crystallinity thereof can be increased by adding a nucleating agent; the nucleating agent is used as crystal nucleus for crystal growth, can promote the growth of polymer crystal, quicken the crystallization rate and refine the crystal size, can be used for the nucleating agent of polylactic acid and comprises an inorganic nucleating agent and an organic nucleating agent, has little use amount, has no influence on the performance of the material and can well keep the inherent characteristics of the polylactic acid.
The addition of the catalytic oxidant can oxidize and decompose ethylene to finally generate carbon dioxide and water, so that the biodegradable film material has the function of eliminating ethylene; the antibacterial agent has the effect of killing or inhibiting the growth of pathogenic microorganisms, and the addition of the antibacterial agent enables the biodegradable film material to have the function of inhibiting the growth of microorganisms.
In order to obtain the biodegradable film material with more excellent performance, the proportion relation of the raw materials is optimized, and in some embodiments, the first surface layer is mainly prepared from the following raw materials in parts by weight: 73.7-80 parts of polylactic acid, 10-20 parts of biodegradable polyester, 1-5 parts of catalytic oxidizer, 0.1-1 part of antibacterial agent and 0.1-0.3 part of opening agent;
the intermediate layer is mainly prepared from the following raw materials in parts by mass: 75-85 parts of polylactic acid, 10-20 parts of biodegradable polyester and 1-5 parts of nucleating agent;
the second surface layer is mainly prepared from the following raw materials in parts by mass: 80-90 parts of polylactic acid and 10-20 parts of biodegradable polyester.
Specifically, in some embodiments, the first surface layer is mainly prepared from the following raw materials in parts by weight: 73.7 parts of polylactic acid, 20 parts of polybutylene succinate (PBS), 5 parts of nano titanium dioxide, 1 part of cassia oil and 0.3 part of oleamide;
the intermediate layer is mainly prepared from the following raw materials in parts by mass: 75 parts of polylactic acid, 20 parts of polybutylene succinate (PBS) and 5 parts of adipic acid diphenyl dihydrazide;
the second surface layer is mainly prepared from the following raw materials in parts by mass: 80 parts of polylactic acid and 20 parts of polybutylene succinate (PBS).
In other embodiments, the first surface layer is mainly prepared from the following raw materials in parts by weight: 73.7 parts of polylactic acid, 15 parts of Polycaprolactone (PCL), 2 parts of nano zinc oxide, 0.5 part of eucalyptus oil and 0.2 part of diatomite;
the intermediate layer is mainly prepared from the following raw materials in parts by mass: 83 parts of polylactic acid, 15 parts of Polycaprolactone (PCL) and 2 parts of adipic acid diphenyl dihydrazide;
the second surface layer is mainly prepared from the following raw materials in parts by mass: 85 parts of polylactic acid and 15 parts of Polycaprolactone (PCL).
In some embodiments, the nucleating agent comprises at least one of N, N', N "-tricyclohexyl-1, 3, 5-benzenetricarboxamide, zinc phenylphosphonate, sebacic acid diphenyl dihydrazide, and adipic acid diphenyl dihydrazide. For example, the nucleating agent may be N, N' -tricyclohexyl-1, 3, 5-benzenetricarboxamide, or may be zinc phenylphosphonate, or sebacic acid diphenyl dihydrazide or adipic acid diphenyl dihydrazide.
Inorganic nucleating agents include montmorillonite, talcum powder, hydrotalcite and the like, but the nucleating agents are applied to polylactic acid, have poor compatibility with the polylactic acid and are easy to agglomerate; the organic nucleating agent has good compatibility with the polylactic acid, can be uniformly dispersed into the polylactic acid, fully plays the nucleation function, can induce the crystallization of the polylactic acid after self-assembly at a layer interface, and can induce the crystallization of the polylactic acid to form a highly oriented crystallization structure while accelerating the crystallization of the polylactic acid, thereby forming a transverse crystal structure with platelets perpendicular to the gas permeation direction.
In some embodiments, the catalytic oxidizer comprises at least one of nano zinc oxide, nano titanium dioxide, potassium permanganate, and ferric oxide. For example, the catalytic oxidizer may be nano zinc oxide, nano titanium dioxide, or potassium permanganate or ferric oxide. Preferably, the catalytic oxidizer is nano titanium dioxide or nano zinc oxide.
In some embodiments, the antimicrobial agent comprises at least one of star anise oil, cassia oil, cinnamon essential oil, and eucalyptus oil. For example, any one or a combination of two or three of star anise oil, cassia oil, cinnamon essential oil and eucalyptus oil. The antibacterial agent is processed from natural substances, and the biodegradable film material can be directly used for preserving fruits and vegetables, and is safe and nontoxic.
In some embodiments, the biodegradable polyester comprises at least one of polybutylene terephthalate, polybutylene succinate, polycaprolactone, and polypropylene carbonate. For example, any one or a combination of two or three of polybutylene terephthalate, polybutylene succinate, polycaprolactone, and polypropylene carbonate. The polylactic acid is subjected to blending modification by adopting the biodegradable polyester, and the performance of the polylactic acid can be effectively improved by selecting proper biodegradable polyester components and adjusting the proportion among the components.
In some embodiments, the opening agent comprises at least one of silica, diatomaceous earth, erucamide, oleamide, and talc. For example, any one of silica, diatomaceous earth, erucamide, oleamide, and talc, or a combination of two or three thereof.
The invention also provides a preparation method of the biodegradable film material, which comprises the following steps:
(A) Respectively and uniformly mixing the raw materials of the first surface layer, the middle layer and the second surface layer, and then extruding and granulating to obtain first surface layer master batch, middle layer master batch and second surface layer master batch;
(B) Putting the first surface layer master batch, the middle layer master batch and the second surface layer master batch into a film blowing machine for blow molding to form a film, thus obtaining a biodegradable film material;
optionally, the granulating is performed by a twin screw extruder;
alternatively, the process of pelletization by a twin-screw extruder is divided into: a feeding section, a conveying section, a melting section and a homogenizing section;
optionally, the temperature of the feeding section is 130-160 ℃, the temperature of the conveying section is 180-200 ℃, the temperature of the melting section is 190-210 ℃, and the temperature of the homogenizing section is 180-200 ℃; in some embodiments, the temperature of the feed section is 150 ℃, the temperature of the delivery section is 190 ℃, the temperature of the melting section is 200 ℃, and the temperature of the homogenization section is 190 ℃;
optionally, the film blowing machine is a three-layer film blowing machine.
Some embodiments also provide the application of the biodegradable film material in fruit and vegetable fresh-keeping.
Because fresh fruits and vegetables still continue to breathe after being picked, and the respiration is accompanied with metabolism and ethylene generation, the fruits and vegetables are promoted to age and rot, and the storage time of the fruits and vegetables is reduced; the biodegradable film material disclosed by the invention has the advantages that through the construction of a three-layer microstructure and the self-assembly of the nucleating agent at a layer interface, the transverse crystal structure of the polylactic acid forming lamellar crystals perpendicular to the gas permeation direction is used for synergistically adjusting the permeation rate of oxygen, carbon dioxide and water vapor when the film is permeated, the gas is adjusted, the ventilation effect of the biodegradable film material is improved, the adjusting gas different from the normal atmospheric component is obtained, and fruits and vegetables are in a proper gas environment, so that the respiration of the fruits and vegetables is delayed; suitable water vapor permeability can timely remove redundant moisture in the preservative film, reduce the humidity in the preservative film, and further reduce the breeding of bacteria.
The ethylene gas released by the fruits and vegetables is further oxidized and decomposed into carbon dioxide and water by adding a catalytic oxidant into the first surface layer which is in direct contact with the fruits and vegetables, so that the effect of removing ethylene is achieved; the antibacterial agent is added on the basis, so that the growth of microorganisms can be inhibited, an antibacterial effect is achieved, and excellent inhibition effects on staphylococcus aureus, escherichia coli and the like are achieved; the biodegradable film material provided by the invention has the functions of eliminating ethylene, inhibiting bacterial growth and inhibiting the respiration intensity of fresh fruits and vegetables, and can effectively prolong the storage time of fruits and vegetables.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a biodegradable film material and a preparation method thereof, wherein the biodegradable film material comprises the following raw materials:
a first surface layer: 94.7 parts of polylactic acid, 5 parts of polybutylene terephthalate adipate (PBAT), 0.1 part of potassium permanganate, 0.1 part of cinnamon essential oil and 0.1 part of erucamide;
an intermediate layer: 94.9 parts of polylactic acid, 5 parts of polybutylene terephthalate adipate (PBAT) and 0.1 part of N, N' -tricyclohexyl-1, 3, 5-benzenetricarboxamide;
a second surface layer: 95 parts of polylactic acid and 5 parts of polybutylene terephthalate adipate (PBAT).
The preparation method of the biodegradable film material comprises the following steps:
(A) Respectively and uniformly mixing the raw materials of the first surface layer, the middle layer and the second surface layer, and then extruding and granulating by adopting a double-screw extruder to obtain a first surface layer master batch, a middle layer master batch and a second surface layer master batch;
the granulating process of the double-screw extruder is divided into: a feeding section, a conveying section, a melting section and a homogenizing section;
the temperature of the feeding section is 150 ℃, the temperature of the conveying section is 190 ℃, the temperature of the melting section is 200 ℃, and the temperature of the homogenizing section is 190 ℃;
(B) And putting the first surface layer master batch, the middle layer master batch and the second surface layer master batch into three extruders of a three-layer film blowing machine for blow molding to form a film, thus obtaining the biodegradable film material.
Example 2
The embodiment provides a biodegradable film material and a preparation method thereof, wherein the biodegradable film material comprises the following raw materials:
a first surface layer: 73.7 parts of polylactic acid, 20 parts of polybutylene succinate (PBS), 5 parts of nano titanium dioxide, 1 part of cassia oil and 0.3 part of oleamide;
an intermediate layer: 75 parts of polylactic acid, 20 parts of polybutylene succinate (PBS) and 5 parts of adipic acid diphenyl dihydrazide;
a second surface layer: 80 parts of polylactic acid and 20 parts of polybutylene succinate (PBS).
The preparation method of the biodegradable film material of this example is the same as that of example 1.
Fig. 1 is a schematic structural diagram of a biodegradable film material prepared in example 2 of the present invention.
Example 3
The embodiment provides a biodegradable film material and a preparation method thereof, wherein the biodegradable film material comprises the following raw materials:
a first surface layer: 73.7 parts of polylactic acid, 15 parts of Polycaprolactone (PCL), 2 parts of nano zinc oxide, 0.5 part of eucalyptus oil and 0.2 part of diatomite;
an intermediate layer: 83 parts of polylactic acid, 15 parts of Polycaprolactone (PCL) and 2 parts of adipic acid diphenyl dihydrazide;
a second surface layer: 85 parts of polylactic acid and 15 parts of Polycaprolactone (PCL).
The preparation method of the biodegradable film material of this example is the same as that of example 1.
Comparative example 1
The embodiment provides a biodegradable film material and a preparation method thereof, wherein the biodegradable film material comprises the following raw materials:
a first surface layer: 94.7 parts of polylactic acid, 5 parts of polybutylene terephthalate adipate (PBAT), 0.1 part of potassium permanganate, 0.1 part of cinnamon essential oil and 0.1 part of erucamide;
an intermediate layer: 95 parts of polylactic acid and 5 parts of polybutylene terephthalate adipate (PBAT);
a second surface layer: 95 parts of polylactic acid and 5 parts of polybutylene terephthalate adipate (PBAT).
The preparation method of the biodegradable film material of this example is the same as that of example 1.
Comparative example 2
The embodiment provides a biodegradable film material and a preparation method thereof, wherein the biodegradable film material comprises the following raw materials:
a first surface layer: 94.9 parts of polylactic acid, 5 parts of polybutylene terephthalate adipate (PBAT) and 0.1 part of erucamide;
an intermediate layer: 94.9 parts of polylactic acid, 5 parts of polybutylene terephthalate adipate (PBAT) and 0.1 part of N, N' -tricyclohexyl-1, 3, 5-benzenetricarboxamide;
a second surface layer: 95 parts of polylactic acid and 5 parts of polybutylene terephthalate adipate (PBAT).
The preparation method of the biodegradable film material of this example is the same as that of example 1.
Experimental example 1
The biodegradable film materials provided in examples 1 to 3 and comparative examples 1 to 2 were selected in this experimental example, and the oxygen permeability, the carbon dioxide permeability and the water vapor permeability of the biodegradable film materials of examples 1 to 3 and comparative examples 1 to 2 were tested with reference to ASTM 1434-1982 and ASTM E96-2005; the biodegradable film materials of examples 1 to 3 and comparative examples 1 to 2 were tested for antibacterial properties with reference to GB/T31402-2015 standards. Test data are recorded in table 1.
Ethylene elimination performance test: after the film is made into a sealed fresh-keeping bag, 1ml of ethylene gas is injected into the fresh-keeping bag by a syringe, and after 24 hours, the value of the reduction of the ethylene gas concentration in the fresh-keeping bag is measured by a gas chromatograph. Test data are recorded in table 1.
TABLE 1
Figure BDA0003132857860000131
As can be seen from the results in table 1, the biodegradable film materials provided in examples 1 to 3 have moderate oxygen, carbon dioxide and water vapor transmission rates, and ethylene elimination and bacteriostasis properties; comparing examples 1-3 with comparative examples 1-2 shows that the transverse crystal structure, the catalytic oxidizer and the antibacterial agent in the biodegradable film material act synergistically, and simultaneously have the self-air conditioning function, the ethylene eliminating function and the antibacterial function, so that the performance of the biodegradable film material can be comprehensively improved, and the fresh-keeping effect of fruits and vegetables is improved.
Experimental example 2
In the experimental example, the biodegradable film materials provided in examples 1-3 and comparative examples 1-2 are selected for packaging the now-picked mango, and the actual fresh-keeping effect of the mango is examined. Test data are recorded in table 2.
TABLE 2
Figure BDA0003132857860000132
From the results in table 2, it can be seen that the mango preservation time of the package using the biodegradable film materials provided in examples 1 to 3 is relatively excellent, wherein examples 2 and 3 have moderate oxygen, carbon dioxide and water vapor transmission rates and relatively excellent ethylene elimination and bacteriostasis properties, so that fresh fruits and vegetables are in a good fresh-keeping environment, and the mango preservation time is relatively long, and the mango preservation effect is relatively excellent.
In summary, the path of oxygen, carbon dioxide and water vapor passing through the membrane is changed, so that the biodegradable membrane material has good air permeability, and excess water is discharged, so that fresh fruits and vegetables are in a proper gas environment, and the respiration intensity of the fruits and vegetables is inhibited; and through the action of the catalytic oxidant and the antibacterial agent in the first surface layer which is in direct contact with the fresh fruits and vegetables, ethylene can be decomposed, and the growth of microorganisms can be inhibited, so that the preserved fruits and vegetables are in a good preservation environment, and the storage time of the fresh fruits and vegetables is effectively prolonged.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The biodegradable modified atmosphere film material for fruit and vegetable fresh-keeping is characterized by comprising a first surface layer, a second surface layer and an intermediate layer arranged between the first surface layer and the second surface layer; the interface between the first surface layer and the middle layer and the interface between the second surface layer and the middle layer are provided with transverse crystal structures perpendicular to the gas permeation direction;
the first surface layer is mainly prepared from the following raw materials in parts by weight: 73.7-78 parts of polylactic acid, 12-20 parts of biodegradable polyester, 1-5 parts of catalytic oxidizer, 0.1-1 part of antibacterial agent and 0.1-0.3 part of opening agent;
the intermediate layer is mainly prepared from the following raw materials in parts by mass: 75-85 parts of polylactic acid, 10-20 parts of biodegradable polyester and 1-5 parts of nucleating agent;
the second surface layer is mainly prepared from the following raw materials in parts by weight: 80-90 parts of polylactic acid and 10-20 parts of biodegradable polyester;
the nucleating agent comprises at least one of N, N' -tricyclohexyl-1, 3, 5-benzene tricarboxamide, zinc phenylphosphonate, sebacic acid diphenyl dihydrazide and adipic acid diphenyl dihydrazide;
the catalytic oxidant comprises at least one of nano zinc oxide, nano titanium dioxide, potassium permanganate and ferric oxide;
the antibacterial agent comprises at least one of star anise oil, cassia oil, cinnamon essential oil and eucalyptus oil;
the biodegradable polyester comprises at least one of polybutylene terephthalate, polybutylene succinate, polycaprolactone, and polypropylene carbonate.
2. The biodegradable modified atmosphere packaging material for preserving fruits and vegetables according to claim 1, wherein said opening agent comprises at least one of silica, diatomaceous earth, erucamide, oleamide and talc.
3. The method for preparing the biodegradable modified atmosphere film material for fruit and vegetable fresh-keeping according to claim 1 or 2, comprising the following steps:
(A) Respectively and uniformly mixing the raw materials of the first surface layer, the middle layer and the second surface layer, and then extruding and granulating to obtain a first surface layer master batch, a middle layer master batch and a second surface layer master batch;
(B) And putting the first surface layer master batch, the middle layer master batch and the second surface layer master batch into a film blowing machine for blow molding to form a film, thereby obtaining the biodegradable film material.
4. The method for preparing biodegradable modified atmosphere film material for fresh-keeping of fruits and vegetables according to claim 3, wherein said granulating adopts a twin screw extruder.
5. The method for preparing the biodegradable modified atmosphere film material for fruit and vegetable fresh-keeping according to claim 4, wherein the granulating process of the twin-screw extruder is divided into: a feeding section, a conveying section, a melting section and a homogenizing section.
6. The method for preparing biodegradable film material for fresh-keeping of fruits and vegetables according to claim 5, wherein the temperature of the feeding section is 130-160 ℃, the temperature of the conveying section is 180-200 ℃, the temperature of the melting section is 190-210 ℃, and the temperature of the homogenizing section is 180-200 ℃.
7. The method for preparing biodegradable film-conditioning material for fresh-keeping of fruits and vegetables according to claim 3, wherein the film blowing machine comprises a three-layer film blowing machine.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012236867A (en) * 2011-05-09 2012-12-06 Nissan Chem Ind Ltd Method for producing crystal nucleating agent for resin
CN103554856A (en) * 2013-10-22 2014-02-05 山西省化工研究所（有限公司） Polylactic acid nucleating agent composition and application thereof
CN105200552A (en) * 2015-10-23 2015-12-30 四川大学 High heat-resistant and high-strength polylactic acid fiber and preparation method thereof
CN106220889A (en) * 2016-08-24 2016-12-14 合肥学院 A kind of phenyl-phosphonic acid zinc nucleator, preparation method, morphological control method and application
CN110128806A (en) * 2019-06-10 2019-08-16 中山市正合色彩资源有限公司 A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle
CN110922729A (en) * 2019-12-12 2020-03-27 安徽丰原乳酸聚酯材料有限公司 Heat-resistant polylactic acid material and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008037939A (en) * 2006-08-03 2008-02-21 Mitsui Chemicals Inc Lactic acid resin composition
CN106751629A (en) * 2017-01-24 2017-05-31 威海共达塑胶化工制品有限公司 Complete biodegradable preservative film and preparation method thereof
CN110760169B (en) * 2019-10-25 2022-11-15 深圳市鸿翔包装有限公司 Barrier material and preparation method thereof
CN110774713B (en) * 2019-10-31 2021-06-04 厦门长塑实业有限公司 Coating type high-barrier bidirectional-stretching polylactic acid film and preparation method thereof
CN111333888A (en) * 2020-03-26 2020-06-26 江阴市德惠热收缩包装材料有限公司 Degradable polylactic acid antibacterial film and preparation method thereof
CN112063133B (en) * 2020-08-21 2022-06-14 深圳市绿自然生物降解科技有限公司 Biodegradable breathable film and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012236867A (en) * 2011-05-09 2012-12-06 Nissan Chem Ind Ltd Method for producing crystal nucleating agent for resin
CN103554856A (en) * 2013-10-22 2014-02-05 山西省化工研究所（有限公司） Polylactic acid nucleating agent composition and application thereof
CN105200552A (en) * 2015-10-23 2015-12-30 四川大学 High heat-resistant and high-strength polylactic acid fiber and preparation method thereof
CN106220889A (en) * 2016-08-24 2016-12-14 合肥学院 A kind of phenyl-phosphonic acid zinc nucleator, preparation method, morphological control method and application
CN110128806A (en) * 2019-06-10 2019-08-16 中山市正合色彩资源有限公司 A kind of heat-resistance polylactic acid composite material and preparation method thereof of short degradation cycle
CN110922729A (en) * 2019-12-12 2020-03-27 安徽丰原乳酸聚酯材料有限公司 Heat-resistant polylactic acid material and preparation method thereof

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