CN114834102A - Heat-shrinkable packaging film for inhibiting fresh meat spoilage bacteria and preparation method thereof - Google Patents

Heat-shrinkable packaging film for inhibiting fresh meat spoilage bacteria and preparation method thereof Download PDF

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Publication number
CN114834102A
CN114834102A CN202210364407.7A CN202210364407A CN114834102A CN 114834102 A CN114834102 A CN 114834102A CN 202210364407 A CN202210364407 A CN 202210364407A CN 114834102 A CN114834102 A CN 114834102A
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China
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layer
antibacterial
packaging film
borneol
film
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CN202210364407.7A
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Chinese (zh)
Inventor
张德权
杨伟
侯成立
李欣
范文春
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Shenghui New Material Co ltd
Institute of Food Science and Technology of CAAS
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Shenghui New Material Co ltd
Institute of Food Science and Technology of CAAS
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Priority to CN202210364407.7A priority Critical patent/CN114834102A/en
Publication of CN114834102A publication Critical patent/CN114834102A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • 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
    • 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
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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 discloses a heat-shrinkable packaging film for inhibiting fresh meat spoilage bacteria, which comprises a first blocking layer, a first bonding layer, a middle film layer, a second bonding layer and an inner slow-release antibacterial layer which are sequentially arranged, wherein the first blocking layer and the middle film layer are respectively a polyethylene layer and a polyvinylidene chloride layer, the inner slow-release antibacterial layer comprises 84-92% of polyethylene master batches and 8-16% of antibacterial master batches in percentage by mass, and the antibacterial master batches comprise 50-65% of polyethylene resin and 50-65% of nano TiO 2 12-20% of borneol-based antibacterial material, 15-25% of antioxidant, 0.5-3% of dispersant and 0.5-5% of dispersant. The invention also discloses a preparation method of the heat-shrinkable packaging film for inhibiting the fresh meat putrefying bacteria. The bacteria adhesion type borneol-based antibacterial material and the sterilization type nano TiO are mixed 2 The antibacterial material with double antibacterial effects is prepared, and is used for manufacturing a packaging film, so that the antibacterial material can kill and inhibit microorganisms polluted by fresh meat in the processes of packaging, storage, transportation and circulation, can prevent the microorganisms from adhering to the antibacterial material, and further increases the antibacterial effect.

Description

Heat-shrinkable packaging film for inhibiting fresh meat spoilage bacteria and preparation method thereof
Technical Field
The invention relates to the technical field of packaging films, in particular to a heat-shrinkable packaging film for inhibiting spoilage bacteria of raw fresh meat and a preparation method thereof.
Background
China is a big country for meat production and consumption, meat products have great price difference in every part of China, in order to reduce the price difference, people often transport meat products in areas with lower price to areas with higher price in a long-distance transportation mode, and because the meat products are easy to go bad in the long-distance transportation process, the meat products are usually frozen firstly in the transportation process, and then the frozen meat is packed and transported. Along with the improvement of living standard of people, the acceptance of people to frozen meat is reduced, raw and fresh meat is more and more popular, and according to statistics, the raw and fresh meat becomes the most main meat consumption type in China at present and accounts for more than 80 percent of the total meat consumption amount in China.
In order to ensure that the fresh meat is not easy to deteriorate in the transportation process and guarantee the storage life and shelf life of the fresh meat, the heat-shrinkable packaging film which has high barrier property, puncture resistance, environmental protection and no pollution and meets the international hygienic standard gradually enters the market. Most of the heat shrinkable films on the market at present are of a multilayer structure, and comprise a surface layer, a core layer and a heat sealing layer, wherein the core layer can be made of a gas barrier material, such as PVDC (polyvinyl dichloride) or EVOH (ethylene vinyl alcohol), or an adhesive material, and the heat sealing layer is made of a polyolefin heat sealing material, such as LDPE (low-density polyethylene), LLDPE (linear low-density polyethylene), VLDPE (very low-density polyethylene), ULDE (ultra low-density polyethylene), SURLYN (SURLYN), and the like; the surface layer is made of a material with good wear resistance, smoothness and processability, and metallocene PE is usually adopted as the surface layer. Although these packaging films having a heat-shrinkable function have a function of preventing contamination and can prevent the entry of air, water vapor and the like into the packaging films to prevent the spoilage of meat, they do not have a special antibacterial function, and therefore, it is important to develop a heat-shrinkable packaging film having an antibacterial function in order to reduce the contamination of food during transportation, processing, distribution and the like and to extend the shelf life of the food.
A composite film for packing the cold fresh meat is disclosed by CN111169124A, which features that basic magnesium hypochlorite as antibacterial agent is added to PVA and then mixed with CO in the package 2 The reaction generates nascent oxygen to kill or inhibit the microorganisms polluted by the cold fresh meat in the processes of packaging, storage, transportation and circulation, and the color of the cold fresh meat is kept; the water loss of the chilled meat is controlled by the high-barrier outer layer film. Chinese patent publication No. CN110356090A discloses a shrink packaging film with antibacterial function and a method for producing the same, which is characterized in that a stepped antibacterial protective layer is formed inside the shrink packaging film, so that the shrink packaging film has a good antibacterial effect, and the antibacterial effect of the shrink packaging film is not reduced by high-temperature heat sealing. Although both patents disclose techniques that kill or inhibit the formation of chillHowever, the technologies disclosed in the two patents adopt a single antibacterial mode, which cannot completely prevent the adhesion of bacteria, and killed bacteria may adhere to the surface of the film to form a biological film, thereby weakening the antibacterial effect of the packaging film. Therefore, the development of a heat-shrinkable packaging film having high-efficiency and durable antibacterial properties has been the focus of research.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and the borneol-based antibacterial material is grafted on the nano TiO 2 And mixing the antibacterial master batch with polyethylene to prepare an antibacterial master batch, mixing the antibacterial master batch with the polyethylene master batch to obtain an inner layer slow-release antibacterial layer, and preparing the thermal contraction packaging film with the structure of the first barrier layer/the first bonding layer/the middle film layer/the second bonding layer/the inner layer slow-release antibacterial layer by a co-extrusion blow molding method together with the materials of the barrier layer, the bonding layer and the middle film layer. The borneol-based antibacterial material belongs to an adhesive antibacterial material, and the nano TiO 2 The heat-shrinkable packaging film provided by the invention is prepared by combining the two antibacterial materials, and has excellent antibacterial performance.
In order to achieve the purpose, the technical scheme of the invention is to provide a heat-shrinkable packaging film for inhibiting fresh meat spoilage bacteria, which is characterized by comprising a first blocking layer, a first bonding layer, a middle film layer, a second bonding layer and an inner layer slow-release antibacterial layer which are sequentially arranged, wherein the first blocking layer and the middle film layer are respectively a polyethylene layer and a polyvinylidene chloride layer, the inner layer slow-release antibacterial layer comprises 84-92% of polyethylene master batches and 8-16% of antibacterial master batches by mass percentage, and the antibacterial master batches comprise 50-65% of polyethylene resin and 50-65% of nano TiO 2 12-20% of borneol-based antibacterial material, 15-25% of antioxidant, 0.5-3% of dispersant and 0.5-5% of antioxidant.
The further preferable technical scheme is that the materials of the first bonding layer and the second bonding layer are ethylene-vinyl acetate copolymer.
According to a further preferable technical scheme, all layers of the packaging film are connected in a co-extrusion compounding mode, and the total thickness of the packaging film is 40-50 microns.
The further preferred technical scheme is that the borneol-based antibacterial material comprises any one or more of a borneol-chitosan composite material, a borneol acrylate and a borneol-polylactic acid composite material.
The invention also provides a preparation method of the heat-shrinkable packaging film for inhibiting the spoilage bacteria of the fresh meat, which is characterized by comprising the following steps:
(1) borneol-based antibacterial material grafted nano TiO 2 : modifying the nano TiO by a silane coupling agent 2 Dissolving in absolute ethyl alcohol, performing ultrasonic dispersion for 25-40 min, adding a borneol-based antibacterial material, introducing nitrogen for reaction for 2-3 h at the temperature of 60-80 ℃, performing centrifugal washing for 2-3 times by using the absolute ethyl alcohol, and drying for later use;
(2) preparing the antibacterial master batch: fully mixing the materials in a high-speed mixer for 40-50 min at the rotating speed of 300-400 r/min, and kneading the materials on an extrusion granulator to prepare master batches;
(3) Preparation of the heat-shrinkable packaging film: the antibacterial master batch and the polyethylene master batch are uniformly mixed and then are placed into a hopper corresponding to an extruder, the film materials of the outer layer, the first bonding layer, the middle film layer and the second bonding layer are sequentially and respectively placed into an extruded charging barrel, and the steps of co-extrusion, blow molding and sizing are adopted to prepare the heat-shrinkable packaging film.
The further preferable technical proposal is that nano TiO is grafted on the borneol-based antibacterial material 2 In the step (2), for nano TiO 2 When the modification is carried out, the silane coupling agent is firstly dissolved in the ethanol-water mixed solution, and the nano TiO is 2 Dispersing and mixing with the mixed solution in a high-speed dispersion machine, dissolving the dispersed solution in absolute ethyl alcohol, centrifuging by adopting a high-speed centrifuge, and taking a precipitate.
The further preferable technical scheme is that in the preparation step of the antibacterial master batch, the kneading time is 30-40 minutes, the screw temperature is 140-160 ℃, and the screw rotating speed is 250-300 r/min.
The further preferred technical scheme is that in the preparation step of the thermal contraction packaging film, materials of all layers are co-extruded to prepare a blank tube, the blank tube is cooled, hot steam is adopted to preheat the cooled blank tube, after the temperature reaches 40-90 ℃, the blank tube is transversely stretched, compressed air is used for secondary blowing, the blown film is drawn to a setting machine for setting treatment, and the setting temperature is 50-80 ℃.
In the prior art, in order to keep fruits, vegetables and meat fresh and reduce the attachment and growth of spoilage bacteria, some packaging film manufacturing enterprises generally add antibacterial materials into film materials, determine optimal parameters by researching the influence of the antibacterial materials on the spoilage bacteria, and finally manufacture packaging films with better antibacterial effects. At present, antibacterial materials widely applied to packaging film materials mainly comprise two major types, namely inorganic antibacterial materials and organic antibacterial materials, the inorganic antibacterial materials mainly comprise two types, namely metal ions and metal oxide nanoparticles, and commonly used metal antibacterial agents comprise silver (Ag), copper (Cu), zinc (Zn) and the like, wherein the most typical antibacterial materials are metal silver and metal ions thereof. The metal type antibacterial agent mainly utilizes the ionization characteristic of metals such as silver, copper, zinc and the like, namely, metal ions are released from the surface, thereby achieving the antibacterial effect. The most deeply studied of the metal oxide nanoparticles is titanium dioxide (TiO) 2 ) And zinc oxide (ZnO), whose antibacterial mechanism is mainly due to Reactive Oxygen Species (ROS) produced, and which are capable of killing a wide variety of organisms, such as gram-negative and gram-positive bacteria, endospores, algal protozoa and viruses. The organic antibacterial material mainly comprises three types of low-molecular, high-molecular and natural antibacterial materials, and the most common materials are quaternary ammonium salt, chitosan and phenolic compounds. In contrast, inorganic antibacterial materials are widely used because of their advantages such as good spectrum antibacterial property, excellent antibacterial effect, and low cost. However, when the antibacterial property of a packaging film containing an inorganic antibacterial material is studied, it has been found that the inorganic antibacterial material is mainly a bactericidal antibacterial material which, although effective in killing bacteria, does not completely prevent adhesion of bacteria, and at the same time, killed bacteria may still adhere to the packaging film Attached on the surface of the film to form a biological film, thereby weakening the antibacterial effect of the packaging film.
Borneol is a safe Chinese medicinal material, has great application value in medicine and biological materials, can be extracted from valerian, chamomile and other plants, and is often applied to the preparation of antibacterial agents and antibacterial medicaments due to the unique chiral characteristic and good antibacterial adhesion property. In recent years, with the successive synthesis of borneol-based composite materials, some of the borneol-based composite materials, such as isobornyl acrylate, borneol-chitosan and the like, are widely used in the fields of textiles, medicines, packaging and the like due to excellent antibacterial adhesion. The heat-shrinkable packaging film provided by the invention is a packaging film which sequentially comprises a first barrier layer, a first bonding layer, a middle film layer, a second bonding layer and an inner-layer slow-release antibacterial layer from outside to inside, wherein the inner-layer slow-release antibacterial layer is an inner-layer film which is prepared by combining a borneol-based antibacterial material and an inorganic antibacterial material to prepare antibacterial master batches and then mixing the antibacterial master batches with polyethylene master batches to prepare the antibacterial master batches with double antibacterial effects. The borneol-based composite material belongs to an antibacterial adhesion type material, and an antibacterial material prepared by combining the borneol-based composite material with a sterilization type inorganic antibacterial material has double antibacterial effects of adhesion and bacteria killing.
The packaging film takes polyethylene as the barrier layer and is arranged on the outermost layer of the film, so that water vapor and oxygen can be effectively prevented from entering, polyvinylidene chloride (PVDC) is taken as the intermediate film, the shrinkage performance of the heat shrinkable film is mainly ensured, the water and oxygen blocking performance of the composite film can be enhanced, EVA is selected as the binding material, and the layers are connected together in a co-extrusion compounding manner, so that the packaging film is safe and sanitary, the co-extrusion compounding production process is short, the consumption of energy and manpower is reduced, and the production cost can be greatly reduced.
The invention also provides a heat shrinkage method for inhibiting the putrefying bacteria of fresh meatThe preparation method of the packaging film mainly comprises the steps of grafting the borneol-based antibacterial material with the nano TiO 2 The preparation of antibacterial master batch and the preparation of the heat-shrinkable packaging film, wherein borneol-based antibacterial material is grafted on the nano TiO 2 Before the above, it is necessary to first align the nano TiO 2 Surface treatment is carried out to enlarge nano TiO 2 Activity of the surface. Use of silane coupling agent to nano TiO 2 When the surface treatment is carried out, the nano TiO is firstly treated 2 Dissolving in mixed solution of ethanol and water, adding silane coupling agent for dispersing and mixing, and facilitating hydrolysis of the silane coupling agent and mixing with nanometer TiO 2 The hydroxyl groups on the surface are bonded. The grafting of the borneol-based antibacterial material is mainly compounded with amino on a silane coupling agent, the compounded antibacterial material with double antibacterial effects is mixed with polyethylene resin and granulated to form antibacterial master batches, then the antibacterial master batches are mixed with the polyethylene master batches, and the mixture is co-extruded and blown by an extruder together with outer-layer polyethylene, a bonding layer EVA material and an intermediate-layer polyvinylidene chloride material to prepare the heat-shrinkable composite film. The grafted antibacterial material is prepared into master batches and mixed with polyethylene, so that the antibacterial material is uniformly dispersed in the polyethylene, and the phenomena of agglomeration and nonuniform mixing of the antibacterial material can be effectively reduced. The interaction between the grafted antibacterial material and the macromolecular chains of the polyethylene also has a positive influence on the mechanical property of the packaging film.
The invention has the advantages and beneficial effects that:
1. the antibacterial material with double antibacterial effects is prepared by combining a bacteria adhesion type borneol-based antibacterial material and a sterilization type inorganic antibacterial material, and is used for manufacturing a heat-shrinkable packaging film, so that not only can microorganisms polluted in the packaging, storage, transportation and circulation processes of fresh meat be killed and inhibited, but also the adhesion of the microorganisms on the fresh meat can be prevented, the antibacterial effect is further improved, the efficient and long-term sterilization effect is achieved, and the quality guarantee period and the shelf life of the fresh meat are prolonged.
2. Polyvinylidene chloride is used as an intermediate film, EVA is used as a bonding material, and all layers are connected together in a co-extrusion compounding mode, so that the contractibility and the recyclability of the packaging film are guaranteed, the production process is safe and sanitary, the production process is shortened, the consumption of energy and manpower is reduced, and the production cost is greatly reduced.
3. Grafting borneol-based antibacterial material to nano TiO 2 In the above, the grafted antibacterial material and the polyethylene resin are made into the antibacterial master batch, then the antibacterial master batch and the polyethylene master batch are mixed, and the thermal contraction packaging film is prepared by a co-extrusion blow molding method, so that the uniform dispersion of the antibacterial material in the polyethylene is facilitated, and the phenomena of agglomeration and uneven mixing of the antibacterial material can be effectively reduced.
Detailed Description
The following examples are provided to further illustrate embodiments of the present invention. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A heat-shrinkable packaging film for inhibiting fresh meat spoilage bacteria comprises a polyethylene layer, an EVA layer, a polyvinylidene chloride layer, an EVA layer and an inner slow-release antibacterial layer which are sequentially arranged, all layers of the packaging film are connected in a co-extrusion compounding manner, and the total thickness of the film layers is 40 micrometers. The inner layer slow-release antibacterial layer comprises 84 percent of polyethylene master batch and 16 percent of antibacterial master batch by mass percentage, and the components of the antibacterial master batch comprise 60 percent of polyethylene resin and nano TiO 2 14 percent of borneol-chitosan composite material, 25 percent of antioxidant and 0.5 percent of dispersant.
A preparation method of a heat-shrinkable packaging film for inhibiting fresh meat putrefying bacteria comprises the following steps:
(1) borneol-based antibacterial material grafted nano TiO 2 : dissolving silane coupling agent in ethanol-water mixed solution, and dissolving nano TiO 2 Dispersing and mixing the mixed solution in a high-speed dispersion machine, dissolving the dispersed solution in absolute ethyl alcohol, centrifuging by adopting a high-speed centrifuge, dissolving the precipitate in absolute ethyl alcohol, ultrasonically dispersing for 25min, adding a borneol-based antibacterial material, introducing nitrogen to react for 2h at the temperature of 80 ℃, centrifuging and washing for 2-3 times by using absolute ethyl alcohol, and drying for later use;
(2) preparing the antibacterial master batch: putting the materials into a high-speed mixer for fully mixing, wherein the mixing time is 40min, the rotating speed is 400r/min, and then kneading the materials on an extrusion granulator to prepare master batches, wherein the kneading time is 30 min, the screw temperature is 160 ℃, and the screw rotating speed is 250 r/min;
(3) preparation of heat-shrinkable packaging film: the method comprises the steps of uniformly mixing antibacterial master batches and polyethylene master batches, then putting the mixture into hoppers corresponding to an extruder, sequentially putting film materials of an outer layer, a first bonding layer, a middle film layer and a second bonding layer into extruded material cylinders, co-extruding the materials of the layers to obtain blank pipes, cooling the blank pipes, preheating the cooled blank pipes by using hot steam, transversely stretching the blank pipes after the temperature reaches 40 ℃, performing secondary blowing by using compressed air, drawing blown films to a setting machine for setting, wherein the setting temperature is 80 ℃.
Example 2
A heat-shrinkable packaging film for inhibiting fresh meat spoilage bacteria comprises a polyethylene layer, an EVA layer, a polyvinylidene chloride layer, an EVA layer and an inner slow-release antibacterial layer which are sequentially arranged, all layers of the packaging film are connected in a co-extrusion compounding manner, and the total thickness of the film layers is 45 microns. The inner layer slow-release antibacterial layer comprises 88 percent of polyethylene master batch and 12 percent of antibacterial master batch by mass percentage, and the components of the antibacterial master batch comprise 50 percent of polyethylene resin and nano TiO 2 20 percent of borneol-chitosan composite material, 24 percent of antioxidant and 4 percent of dispersant.
A preparation method of a heat-shrinkable packaging film for inhibiting fresh meat putrefying bacteria comprises the following steps:
(1) borneol-based antibacterial material grafted nano TiO 2 : dissolving silane coupling agent in ethanol-water mixed solution, and dissolving nano TiO 2 Dispersing and mixing the mixed solution in a high-speed dispersion machine, dissolving the dispersed solution in absolute ethyl alcohol, centrifuging by adopting a high-speed centrifuge, dissolving the precipitate in absolute ethyl alcohol, ultrasonically dispersing for 30min, adding a borneol-based antibacterial material, introducing nitrogen to react for 3h at the temperature of 80 ℃, centrifuging and washing for 2-3 times by using absolute ethyl alcohol, and drying for later use;
(2) preparing the antibacterial master batch: putting the materials into a high-speed mixer for fully mixing, wherein the mixing time is 50min, the rotating speed is 300r/min, and then kneading the materials on an extrusion granulator to prepare master batches, wherein the kneading time is 40 min, the screw temperature is 140 ℃, and the screw rotating speed is 300 r/min;
(3) Preparation of heat-shrinkable packaging film: the method comprises the steps of uniformly mixing antibacterial master batches and polyethylene master batches, then putting the mixture into hoppers corresponding to an extruder, sequentially putting film materials of an outer layer, a first bonding layer, a middle film layer and a second bonding layer into extruded material cylinders, co-extruding the materials of the layers to obtain blank pipes, cooling the blank pipes, preheating the cooled blank pipes by using hot steam, transversely stretching the blank pipes after the temperature reaches 60 ℃, performing secondary blowing by using compressed air, drawing blown films to a setting machine for setting, wherein the setting temperature is 60 ℃.
Example 3
A heat-shrinkable packaging film for inhibiting fresh meat spoilage bacteria comprises a polyethylene layer, an EVA layer, a polyvinylidene chloride layer, an EVA layer and an inner slow-release antibacterial layer which are sequentially arranged, all layers of the packaging film are connected in a co-extrusion compounding manner, and the total thickness of the film layers is 50 microns. The inner layer slow-release antibacterial layer comprises 92 percent of polyethylene master batch and 8 percent of antibacterial master batch by mass percentage, and the components of the antibacterial master batch comprise 65 percent of polyethylene resin and nano TiO 2 12 percent of borneol-chitosan composite material, 15 percent of antioxidant and 5 percent of dispersant.
A preparation method of a heat-shrinkable packaging film for inhibiting fresh meat putrefying bacteria comprises the following steps:
(1) Borneol-based antibacterial material grafted nano TiO 2 : dissolving silane coupling agent in ethanol-water mixed solution, and dissolving nano TiO 2 Dispersing and mixing the mixed solution in a high-speed dispersion machine, dissolving the dispersed solution in absolute ethyl alcohol, centrifuging by adopting a high-speed centrifuge, dissolving the precipitate in absolute ethyl alcohol, ultrasonically dispersing for 40min, adding a borneol-based antibacterial material, introducing nitrogen to react for 3h at the temperature of 60 ℃, centrifuging and washing for 2-3 times by using absolute ethyl alcohol, and drying for later use;
(2) preparing the antibacterial master batch: putting the materials into a high-speed mixer for fully mixing, wherein the mixing time is 50min, the rotating speed is 300r/min, and then kneading the materials on an extrusion granulator to prepare master batches, wherein the kneading time is 30 min, the screw temperature is 150 ℃, and the screw rotating speed is 300 r/min;
(3) preparation of heat-shrinkable packaging film: the method comprises the steps of uniformly mixing antibacterial master batches and polyethylene master batches, then putting the mixture into hoppers corresponding to an extruder, sequentially putting film materials of an outer layer, a first bonding layer, a middle film layer and a second bonding layer into extruded material cylinders, co-extruding the materials of the layers to obtain blank pipes, cooling the blank pipes, preheating the cooled blank pipes by using hot steam, transversely stretching the blank pipes after the temperature reaches 90 ℃, performing secondary blowing by using compressed air, drawing blown films to a setting machine for setting, wherein the setting temperature is 80 ℃.
Comparative example 1
The difference between the comparative example 1 and the example 2 is that the heat-shrinkable packaging film for inhibiting the spoilage bacteria of the fresh meat comprises a polyethylene layer, an EVA layer, a polyvinylidene chloride layer, an EVA layer and an inner polyethylene layer which are sequentially arranged, the layers of the packaging film are connected in a co-extrusion compounding mode, and the total thickness of the layers is 45 microns.
A preparation method of a heat shrinkable packaging film for inhibiting fresh meat spoilage bacteria comprises the following steps of respectively putting film materials of an outer layer, a first bonding layer, an intermediate film layer, a second bonding layer and an inner layer into an extruded charging barrel in sequence, and co-extruding the materials of the layers to prepare a blank pipe; cooling the blank pipe, preheating the cooled blank pipe by hot steam, transversely stretching the blank pipe after the temperature reaches 60 ℃, and performing secondary blowing by using compressed air; and drawing the blown film to a setting machine for setting treatment, wherein the setting temperature is 60 ℃.
Comparative example 2
The difference between the comparative example 2 and the comparative example 1 is that the heat-shrinkable packaging film for inhibiting the spoilage bacteria of the raw fresh meat comprises a polyethylene layer, an EVA layer, a polyvinylidene chloride layer, an EVA layer and an inner slow-release antibacterial layer which are sequentially arranged, all layers of the packaging film are connected in a co-extrusion compounding mode, and the total thickness of the film layers is 45 microns. The inner slow-release antibacterial layer comprises 92 percent of polymer by mass percentage Ethylene master batch and 8 percent of antibacterial master batch, wherein the components of the antibacterial master batch comprise 65 percent of polyethylene resin and nano TiO 2 30 percent of antioxidant, 2 percent of antioxidant and 3 percent of dispersant.
A preparation method of a heat-shrinkable packaging film for inhibiting fresh meat putrefying bacteria comprises the following steps:
(1) preparing the antibacterial master batch: putting the materials into a high-speed mixer for fully mixing, wherein the mixing time is 50min, the rotating speed is 300r/min, and then kneading the materials on an extrusion granulator to prepare master batches, wherein the kneading time is 40 min, the screw temperature is 140 ℃, and the screw rotating speed is 300 r/min;
(3) preparation of heat-shrinkable packaging film: the method comprises the steps of uniformly mixing antibacterial master batches and polyethylene master batches, then putting the mixture into hoppers corresponding to an extruder, sequentially putting film materials of an outer layer, a first bonding layer, a middle film layer and a second bonding layer into extruded material cylinders, co-extruding the materials of the layers to obtain blank pipes, cooling the blank pipes, preheating the cooled blank pipes by using hot steam, transversely stretching the blank pipes after the temperature reaches 60 ℃, performing secondary blowing by using compressed air, drawing blown films to a setting machine for setting, wherein the setting temperature is 60 ℃.
Comparative example 3
The difference between the comparative example 3 and the comparative example 2 is that the heat-shrinkable packaging film for inhibiting the spoilage bacteria of the raw fresh meat comprises a polyethylene layer, an EVA layer, a polyvinylidene chloride layer, an EVA layer and an inner slow-release antibacterial layer which are sequentially arranged, all layers of the packaging film are connected in a co-extrusion compounding mode, and the total thickness of the film layers is 45 microns. The inner layer slow-release antibacterial layer comprises 84 percent of polyethylene master batch and 16 percent of antibacterial master batch by mass percentage, and the components of the antibacterial master batch comprise 60 percent of polyethylene resin and nano TiO 2 44%, antioxidant 2% and dispersant 4%.
The packaging films prepared in the embodiments 1-3 and the comparative examples 1-3 are taken, the antibacterial effect test is carried out on the dominant putrefying bacteria (pseudomonas MN10, lactobacillus VMR17, carnobacterium VE51 and lactococcus VE58) of the fresh meat according to the antibacterial performance test method in the national standard GB/T31402-2015, and the viable count is determined according to the method in the national standard GB/T4789.2. The bacteriostatic effects of pseudomonas MN10, VMR17, carnobacterium VE51 and lactococcus VE58 are shown in Table 1.
TABLE 1 antibacterial rate of antibacterial heat-shrinkable packaging film to various bacteria
Figure BDA0003586433380000101
The mechanical properties and physical properties of the packaging films prepared in examples 1-3 and comparative examples 1-3 were measured according to national standards GB/T1040.3, GB/T26253-2010 and GB/T1038, and the results are shown in tables 2 and 3.
TABLE 2 mechanical Property test results of heat-shrinkable packaging films
Figure BDA0003586433380000111
TABLE 3 test results of physical Properties of heat-shrinkable packaging film
Figure BDA0003586433380000112
As can be seen from the data in the table, the nano TiO was added compared with the packaging film without any antibacterial component 2 Then, the packaging film can inhibit the bacteria inhibition rate of the dominant putrefying bacteria such as pseudomonas, lactobacillus, carnobacterium and lactococcus in the fresh meat along with the nano TiO 2 The addition amount is increased, and in comparison, the nano TiO modified borneol antibacterial material contains borneol-based antibacterial material and nano TiO 2 The packaging film of the two antibacterial materials has the best antibacterial effect. Moreover, the borneol-based antibacterial material is grafted with nano TiO 2 The addition of (2) does not have great influence on the mechanical property and the physical property of the packaging film.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. The utility model provides an restrain heat shrink packaging film of living fresh meat spoilage bacteria, its characterized in that, including first barrier layer, first tie coat, intermediate film layer, second tie coat, the antibiotic layer of inlayer slowly-releasing that sets gradually, first barrier layer with intermediate film layer is polyethylene layer and polyvinylidene chloride layer respectively, contains the volume according to the mass percent, the antibiotic layer of inlayer slowly-releasing includes 84 ~ 92% polyethylene master batch and 8 ~ 16% antibiotic master batch, the component of antibiotic master batch includes 50 ~ 65% of polyethylene resin, nanometer TiO 50 ~ 65%, nanometer 2 12-20% of borneol-based antibacterial material, 15-25% of antioxidant, 0.5-3% of dispersant and 0.5-5% of dispersant.
2. The packaging film of claim 1, wherein the first and second adhesive layers are made of ethylene-vinyl acetate copolymer.
3. The packaging film according to claim 2, wherein the packaging film is connected with each other through co-extrusion compounding, and the total thickness of the packaging film is 40-50 μm.
4. The packaging film of claim 3, wherein the borneol-based antibacterial material comprises any one or more of a borneol-chitosan composite material, a borneol-acrylate and a borneol-polylactic acid composite material.
5. A method for producing the packaging film according to claim 4, comprising the steps of:
(1) borneol-based antibacterial material grafted nano TiO 2 : modifying the nano TiO by a silane coupling agent 2 Dissolving in absolute ethyl alcohol, performing ultrasonic dispersion for 25-40 min, adding a borneol-based antibacterial material, introducing nitrogen for reaction for 2-3 h at the temperature of 60-80 ℃, performing centrifugal washing for 2-3 times by using the absolute ethyl alcohol, and drying for later use;
(2) preparing the antibacterial master batch: fully mixing the materials in a high-speed mixer for 40-50 min at the rotating speed of 300-400 r/min, and kneading the materials on an extrusion granulator to prepare master batches;
(3) preparation of heat-shrinkable packaging film: the antibacterial master batch and the polyethylene master batch are uniformly mixed and then are placed into a hopper corresponding to an extruder, the film materials of the outer layer, the first bonding layer, the middle film layer and the second bonding layer are sequentially and respectively placed into an extruded charging barrel, and the steps of co-extrusion, blow molding and sizing are adopted to prepare the heat-shrinkable packaging film.
6. The method according to claim 5, wherein the nano TiO is grafted on the borneol-based antibacterial material 2 In the step (2), for nano TiO 2 When the modification is carried out, the silane coupling agent is firstly dissolved in the ethanol-water mixed solution, and the nano TiO is 2 Dispersing and mixing with the mixed solution in a high-speed dispersion machine, dissolving the dispersed solution in absolute ethyl alcohol, centrifuging by adopting a high-speed centrifuge, and taking a precipitate.
7. The preparation method according to claim 5, wherein in the step of preparing the antibacterial masterbatch, the kneading time is 30-40 min, the screw temperature is 140-160 ℃, and the screw rotation speed is 250-300 r/min.
8. The method according to claim 5, wherein in the step of preparing the heat shrinkable packaging film, the layers are co-extruded to prepare a parison, the parison is cooled, the cooled parison is preheated by hot steam at a temperature of 40 to 90 ℃, the parison is transversely stretched and secondarily blown by compressed air, and the blown film is drawn to a setting machine for setting at a temperature of 50 to 80 ℃.
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