CN110421944A - The antibacterial preserving fruit and vegetable utilizing material and preparation method of a kind of decomposing ethylene and slow-release function - Google Patents

The antibacterial preserving fruit and vegetable utilizing material and preparation method of a kind of decomposing ethylene and slow-release function Download PDF

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CN110421944A
CN110421944A CN201910751091.5A CN201910751091A CN110421944A CN 110421944 A CN110421944 A CN 110421944A CN 201910751091 A CN201910751091 A CN 201910751091A CN 110421944 A CN110421944 A CN 110421944A
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ethylene
lldpe
layer
antibacterial
slow
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郑文冉
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The antibacterial preserving fruit and vegetable utilizing material of the antibacterial preserving fruit and vegetable utilizing material and preparation method of a kind of decomposing ethylene and slow-release function, a kind of described decomposing ethylene and slow-release function is made of five layer materials；By different proportion using nano zine oxide as catalyst in the LLDPE+MLLDPE of first layer A, same auxiliary agent, diatomite material, polyvinyl resin or polypropylene fusion are blended, pass through sustained release, it allows ethylene and oxygen to aoxidize under the action of nano zine oxide is as catalyst, ethylene is finally decomposed and generates carbon dioxide and water；Third layer C, as catalyst, realizes barrier, antibacterial, antibacterial action using LLDPE or polypropylene+nano zine oxide.The invention is with strong points, safety and environmental protection, absorb and remove decomposing ethylene, formaldehyde, sulfide, pesticide and a variety of carbonic acid gas, fruits and vegetables zero ethylene in transporting procedures can greatly be kept, improve the storage fresh-keeping phase of fruits and vegetables, ethylene absorbent materials are convenient, and cost of material is low, are applied in postharvest technology of fruits and vegetables field.

Description

The antibacterial preserving fruit and vegetable utilizing material and preparation method of a kind of decomposing ethylene and slow-release function
Technical field
The present invention relates to one of postharvest technology of fruits and vegetables field decomposing ethylene and the antibacterial preserving fruit and vegetable utilizing materials of slow-release function Material and preparation method.
Background technique
With the development of economy, improvement of living standard, the dietetic life of people is by past unification mistake simply having adequate food and clothing Cross diversified auxotype till now.The demand of fruit is increasing, and the requirement to its freshness is also higher and higher.Due to Fresh fruit picking after continue to breathe, and breathe simultaneously with metabolism, moisture evaporation and ethylene synthesis, promote fruits and vegetables into One step is mature；This storage condition is easy to breed bacterium, and breeds rapidly, and fruit is caused to rot.Ethylene gas is that plant is raw Long hormone.Although ethylene can promote plant growth and fruit maturation, it is to cause fruits and vegetables perishable Main cause.Ethylene induces the aging of fruits and vegetables, reduces its shelf-life, is greatly lowered its vision and organoleptic quality.
The method for eliminating ethylene at present, which has, to be added potassium permanganate class oxidant pack, molecular sieve or activated carbon adsorbent is added Etc. means.The ethylene absorbents such as potassium permanganate can accumulate in packaging bag to avoid ethylene, but potassium permanganate is easily dissolved ring Moisture in border and cause fruit to be colored, and potassium permanganate is a kind of chemicals, must not contact food.Also there is report in the country Road is clipped in corrugated case or paper pulp molding package box using molecular sieve or activated carbon as ethene adsorbent, influences whether corrugation The intensity of carton, ethylene absorption efficiency are relatively low.
Ethylene can be discharged after fruit tree harvesting in transporting procedures, ethylene can generate the influence of some unfavorable fruit storings, packet It includes and promotes aging, promotes mature and softening, so that fruit is easy by pathogenic bacterial infection and is caused physiologic derangement, reduce the storage of banana It transports the time, therefore the ethylene that must be discharged to ethylene in environment and banana itself when banana storing be purged and absorb.
The evaporation and nutriment of fresh fruit and vegetables after picking, due to stronger respiration, along with moisture Consumption and gradually atrophy even rot.So antistaling agent is often used to inhibit the growth of fruit and vegetable surfaces mushroom, to extend storage Hide freshness date.In addition, fresh fruit of vegetables is sealed in packaging material, dehydration can be not only prevented, can also be reduced in packaging bag The content of oxygen reduces fruits and vegetables respiratory rate, to delay the consumption of nutriment.
The patent No. 200510041240.7 discloses a kind of granular concave rod alcohol antistaling agent, by porous particle concave convex rod, Edible alcohol, citric acid, sodium Diacetate and water composition, but alcohol burst size is not easily controlled.
Patent No. 200810025653.X discloses a kind of alcohol antistaling agent wrapper paper and preparation method thereof, by a variety of works The microporous barrier of skill production or the making hole film of mechanical means production discharge to control ethyl alcohol, and not only production process is complex, and And it is difficult for fruits and vegetables and high humility, suitable oxygen and carbon dioxide controlled atmospheric packing storage atmosphere is provided.
The patent No. 201010522442.4 disclose fruit-preserving green packing material with ethylene adsorption function and its Preparation method, the patent the problem is that, by preparing al silicate molecular sieve and polyethylene blend blown film, play ethylene adsorption Effect, but the fruit-vegetable food big for respiratory capacity, can exist absorption it is full after influence fresh-keeping effect or adsorption saturation after discharge again The problem of ethylene, it is unobvious to will lead to fresh-keeping effect.
Patent No. 201310071444.X discloses the production of the fruit and vegetable fresh-keeping agent pack and packaging film of a kind of controlled release Method, the patent the problem is that, be unfavorable for scale use, program is cumbersome, increase use cost；It not only increases poly- The process that vermiculite pack is placed in olefin material, causes the weight of vegetable and fruit packaging object to increase, and is weighing balance heave hand to perplex, simultaneously There is the requirement of controlled atmosphere to polyolefin packing material, is unfavorable for being widely popularized, it cannot the marketization.
The patent No. 201710072764.5 discloses a kind of ethylene absorbent and preparation method thereof and in banana storage fresh-keeping In application, the patent the problem is that, need to be immersed in banana in potassium permanganate fresh-keeping solution and handle, and dry in the air naturally It is dry, it is contemplated that potassium permanganate is chemicals, can bring food safety hazards because of the absorption of banana itself in soaking process, So also not recommending.
Therefore, the antibacterial preserving fruit and vegetable utilizing material and preparation method for developing a kind of decomposing ethylene and slow-release function be always New issue anxious to be resolved.
Summary of the invention
The purpose of the present invention is to provide the antibacterial preserving fruit and vegetable utilizing materials and preparation side of a kind of decomposing ethylene and slow-release function Method, the invention be to overcome the disadvantage in original technology technique, and the antibacterial for providing a kind of elimination decomposing ethylene and slow-release function is gone out The comprehensive solution of bacterium preserving fruit and vegetable utilizing material and preparation method, it is fresh-keeping to vegetables and fruits to play antibacterial by multi-layer co-extruded new process, Bacteriostasis, while by catalyst slow-release function, oxygenolysis ethylene ultimately generates carbon dioxide and water, to reach guarantor Fresh effect prepares nano zine oxide etc. (catalyst) and polyethylene or acrylic resin melt blending through curtain coating or blown film At can be with the Fresh-Keeping Packaging Materials of decomposing ethylene gas.
The object of the present invention is achieved like this: the antibacterial preserving fruit and vegetable utilizing material of a kind of decomposing ethylene and slow-release function, institute The antibacterial preserving fruit and vegetable utilizing material of a kind of decomposing ethylene and slow-release function stated is made of five layer materials；
First layer A presses different proportion for nano zine oxide using LLDPE+MLLDPE in the LLDPE+MLLDPE of first layer A As catalyst, same to auxiliary agent, diatomite material, polyvinyl resin or polypropylene fusion are blended, and by sustained release, allow ethylene and oxygen It is aoxidized under the action of nano zine oxide is as catalyst, ethylene is finally decomposed and generates carbon dioxide and water；
Second layer B, using LDPE+LLDPE；
Third layer C realizes barrier, antibacterial, antibacterial action using LLDPE or polypropylene+nano zine oxide as catalyst；
4th layer of D, using LDPE+LLDPE；
Layer 5 E, using LLDPE+MLLDPE；
The LLDPE is linear low density polyethylene resin；The MLLDPE is metallocene PE；
The LDPE is low-density high-pressure polyethylene；
The nano zine oxide same auxiliary agent, diatomite material, polyvinyl resin or polypropene blended is made as catalyst Bulk material；
The first layer A of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function includes following components: 70- 90 mass fraction polyvinyl resins or polypropylene, 0.5-2 mass fraction auxiliary agent, 800 mesh diatomite material of 0.5-3 mass fraction, 5-29 mass fraction nano zine oxide；Third layer C includes following components: the LLDPE or polypropylene of 97-99.5 mass fraction, The nano zine oxide of 0.5-3 mass fraction；
The preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function is that specific steps are such as Under:
(1) preparation of the antibacterial preserving fruit and vegetable utilizing layer of material A of decomposing ethylene and slow-release function:
By 70-90 mass fraction polyvinyl resin or polypropylene, 0.5-2 mass fraction auxiliary agent, 0.5-3 mass fraction diatomite, The blending of 5-29 mass fraction nano zine oxide, tie rod, extrusion, pelletizing are spare；
(2) preparation of the antibacterial preserving fruit and vegetable utilizing material C layer of decomposing ethylene and slow-release function:
By the blending of the nano zine oxide of the LLDPE of 97-99.5 mass fraction or polypropylene and 0.05-3 mass fraction, tie rod, squeeze Out, pelletizing is spare；
(3) B, D, E layers of the antibacterial preserving fruit and vegetable utilizing material of decomposing ethylene and slow-release function is respectively as follows:
Second layer B respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
4th layer of D, respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
Layer 5 E, using LLDPE+MLLDPE, LLDPE and MLLDPE；Respectively account for 50%；
LDPE+LLDPE, LDPE+LLDPE, LLDPE+MLLDPE are blended spare respectively；
(4) preparation of film:
Five layer material of A-E is salivated equipment by five-layer co-squeezing to melt, then salivates into film；
(5) bag making is cut:
By above-mentioned salivation five-layer co-squeezing film dividing, banding keeps bag at the freshness of the 300*250mm of one side opening；
(6) test of the mechanical property of freshness protection package and elimination decomposing ethylene performance:
Under normal circumstances, due to joined nano zine oxide as catalyst and auxiliary agent, diatomite material, consideration can give film power It learns performance to cause to change, be adversely affected to storage and transportation, it is therefore desirable to which the mechanical property of antistaling film is tested；
In a freshness protection package of a packaged invention preparation, it is full of air, the second of 1ml is then squeezed into syringe Alkene gas measures the numerical value that ethylene gas concentration reduces in fresh-keeping packaging bag, that is, indicates that the freshness packaging bag is decomposed and eliminate second The ability of alkene gas, also includes the ability of film transmission ethylene gas, and antistaling film prepared by the present invention has ethylene adsorption Decomposition, decomposition rate reaches 0.35-0.85ml/day ㎡ ethylene；OTR oxygen transmission rate 1300-4600ml/day ㎡；
The technical principle that the preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function is realized is, The ethylene of the inside attachment of freshness protection package, will be reacted with oxygen by nano zine oxide, and resolve into water and carbon dioxide, be sustained in addition Effect can be such that the ethylene for causing corruption to be acidified and oxygen reduces, play preservation；It is held by the circulation of absorption, decomposition, exclusion Continuous processing ethylene gas, and continue to eliminate the mould and bacterium for causing corruption, reach long acting fresh-keeping effect, non-rhizome can be extended 7-20 days freshness dates of class fruit-vegetable food；Nano zine oxide is good antibacterial agent and catalysis material, have it is nontoxic, it is tasteless, It is nonirritant, it does not decompose, never degenerates, the features such as thermal stability is good；And large specific surface area, Active sites are more, surface Effect and bulk effect make it have high catalytic activity and selectivity；Can to the organic matter in pesticide, ethylene and atmosphere into Row photocatalysis Decomposition, makes it be ultimately oxidized as CO2And H2O etc. is pollution-free substance；Meanwhile nano zine oxide is to large intestine bar function, golden yellow The pathogenic bacteria such as color grape ball function, Salmonella have strong inhibition or killing effect, are more suitable for the anti-of fresh fruit-vegetable food Bacterium sterilizing；
The antibacterial mechanisms of nano zine oxide are complex, antibacterial action may be several different mechanisms it is coefficient as a result, It can sum up are as follows:
(1) nanoparticle aggregation causes thallus to damage on mycoderm surface；
(2) nanoparticle release free zinc ion destroys thallus inner ion stable state, then causes thallus dead；
(3) nanoparticle generates ROS and aoxidizes the intracorporal organic matter of mattress, reaches antibacterial action.
Antibacterial preserving fruit and vegetable utilizing material, preparation method and the skill of the decomposing ethylene for being characterized by it and slow-release function of the invention Art principle.
The antibacterial preserving fruit and vegetable utilizing material and preparation method of a kind of decomposing ethylene and slow-release function compared with prior art, have With strong points, safety and environmental protection has to absorb and remove decomposing ethylene, formaldehyde, sulfide, pesticide and a variety of carbonic acid gas etc. and make With can greatly keep fruits and vegetables zero ethylene in transporting procedures, improve the storage fresh-keeping phase of fruits and vegetables；The ethylene absorbent takes simultaneously Material is convenient, and cost of material is low, simple process, has the advantages that wide popularization and application meaning and market prospects, will widely apply In postharvest technology of fruits and vegetables field.
Detailed description of the invention
The following describes the present invention in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is preserving fruit and vegetable utilizing material structural schematic diagram of the invention.
Fig. 2 is the antimicrobial technology schematic diagram of nano zine oxide of the invention.
Fig. 3 is the reduction effect picture for the ethylene that the freshness of the invention containing 1% master batch keeps bag.
Fig. 4 is the generation spirogram that freshness of the invention keeps bag carbon dioxide.
Fig. 5 is the ethylene concentration variation diagram of the invention for keeping being discharged in bag from the freshness of 1% content of master batch.
Fig. 6 is the ethylene ratio example diagram of the invention for keeping being discharged in bag from the freshness of 1% content of master batch.
Specific embodiment
Referring to attached drawing, the antibacterial preserving fruit and vegetable utilizing material of a kind of decomposing ethylene and slow-release function, a kind of decomposing ethylene And the antibacterial preserving fruit and vegetable utilizing material of slow-release function is made of five layer materials；
First layer A presses different proportion for nano zine oxide using LLDPE+MLLDPE in the LLDPE+MLLDPE of first layer A As catalyst, same to auxiliary agent, diatomite material, polyvinyl resin or polypropylene fusion are blended, and by sustained release, allow ethylene and oxygen It is aoxidized under the action of nano zine oxide is as catalyst, ethylene is finally decomposed and generates carbon dioxide and water；
Second layer B, using LDPE+LLDPE；
Third layer C realizes barrier, antibacterial, antibacterial action using LLDPE or polypropylene+nano zine oxide as catalyst；
4th layer of D, using LDPE+LLDPE；
Layer 5 E, using LLDPE+MLLDPE；
The LLDPE is linear low density polyethylene resin；The MLLDPE is metallocene PE；
The LDPE is low-density high-pressure polyethylene.
The nano zine oxide is as catalyst, same to auxiliary agent, diatomite material, polyvinyl resin or polypropene blended system At granular material.
The first layer A of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function includes following components: 70-90 mass fraction polyvinyl resin or polypropylene, 0.5-2 mass fraction auxiliary agent, 800 mesh diatomite material of 0.5-3 mass fraction Material, 5-29 mass fraction nano zine oxide；Third layer C includes following components: the LLDPE or polypropylene of 97-99.5 mass fraction, The nano zine oxide of 0.5-3 mass fraction.
The preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function is specific steps It is as follows:
(1) preparation of the antibacterial preserving fruit and vegetable utilizing layer of material A of decomposing ethylene and slow-release function:
By 70-90 mass fraction polyvinyl resin or polypropylene, 0.5-2 mass fraction auxiliary agent, 0.5-3 mass fraction diatomite, The blending of 5-29 mass fraction nano zine oxide, tie rod, extrusion, pelletizing are spare；
(2) preparation of the antibacterial preserving fruit and vegetable utilizing material C layer of decomposing ethylene and slow-release function:
By the blending of the nano zine oxide of the LLDPE of 97-99.5 mass fraction or polypropylene and 0.05-3 mass fraction, tie rod, squeeze Out, pelletizing is spare；
(3) B, D, E layers of the antibacterial preserving fruit and vegetable utilizing material of decomposing ethylene and slow-release function is respectively as follows:
Second layer B respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
4th layer of D, respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
Layer 5 E, using LLDPE+MLLDPE, LLDPE and MLLDPE；Respectively account for 50%；
LDPE+LLDPE, LDPE+LLDPE, LLDPE+MLLDPE are blended spare respectively；
(4) preparation of film:
Five layer material of A-E is salivated equipment by five-layer co-squeezing to melt, then salivates into film；
(5) bag making is cut:
By above-mentioned salivation five-layer co-squeezing film dividing, banding keeps bag (can basis at the freshness of the 300*250mm of one side opening Demand prepares the sack of various specifications)；
(6) test of the mechanical property of freshness protection package and elimination decomposing ethylene performance:
Under normal circumstances, due to joined nano zine oxide as catalyst and auxiliary agent, diatomite material, consideration can give film power It learns performance to cause to change, be adversely affected to storage and transportation, it is therefore desirable to which the mechanical property of antistaling film is tested；
In a freshness protection package of a packaged invention preparation, it is full of air, the second of 1ml is then squeezed into syringe Alkene gas measures the numerical value that ethylene gas concentration reduces in fresh-keeping packaging bag, that is, indicates that the freshness packaging bag is decomposed and eliminate second The ability of alkene gas, also includes the ability of film transmission ethylene gas, and antistaling film prepared by the present invention has ethylene adsorption Decomposition, decomposition rate reaches 0.35-0.85ml/day ㎡ ethylene；OTR oxygen transmission rate 1300-4600ml/day ㎡.
The technology that the preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function is realized is former Reason is that the ethylene of the inside attachment of freshness protection package will be reacted with oxygen by nano zine oxide, and resolve into water and carbon dioxide, add Slow releasing function, the ethylene and oxygen that can make to cause corruption to be acidified reduces, and plays preservation；Pass through absorption, decomposition, exclusion Circulation continuous handles ethylene gas, and continues to eliminate the mould and bacterium for causing corruption, reaches long acting fresh-keeping effect, can extend Non- tubers fruit-vegetable food 7-20 days freshness dates；Nano zine oxide is good antibacterial agent and catalysis material, have it is nontoxic, It is tasteless, it is nonirritant, it does not decompose, never degenerates, the features such as thermal stability is good；And large specific surface area, Active sites are more, Skin effect and bulk effect make it have high catalytic activity and selectivity；It can be to organic in pesticide, ethylene and atmosphere Object carries out photocatalysis Decomposition, it is made to be ultimately oxidized as CO2And H2O etc. is pollution-free substance；Meanwhile nano zine oxide to large intestine bar function, The pathogenic bacteria such as Staphylococcus aureus function, Salmonella have strong inhibition or killing effect, are more suitable for fresh fruit-vegetable food Antibacterial sterilizing；
The antibacterial mechanisms of nano zine oxide are complex, antibacterial action may be several different mechanisms it is coefficient as a result, It can be attributed to and (be detailed in Fig. 2):
(1) nanoparticle aggregation causes thallus to damage on mycoderm surface；
(2) nanoparticle release free zinc ion destroys thallus inner ion stable state, then causes thallus dead；
(3) nanoparticle generates ROS and aoxidizes the intracorporal organic matter of mattress, reaches antibacterial action.
Embodiment one
The preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function is that specific steps are such as Under:
(1) preparation of the antibacterial preserving fruit and vegetable utilizing layer of material A of decomposing ethylene and slow-release function:
By 70 mass fraction polyvinyl resins or polypropylene, 0.5 mass fraction auxiliary agent, 0.5 mass fraction diatomite, 29 mass The blending of number nano zine oxide, tie rod, extrusion, pelletizing are spare；
(2) preparation of the antibacterial preserving fruit and vegetable utilizing material C layer of decomposing ethylene and slow-release function:
The blending of the nano zine oxide of the LLDPE of 97 mass fractions or polypropylene and 3 mass fractions, tie rod, extrusion, pelletizing is standby With；
(3) B, D, E layers of the antibacterial preserving fruit and vegetable utilizing material of decomposing ethylene and slow-release function is respectively as follows:
Second layer B respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
4th layer of D, respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
Layer 5 E, using LLDPE+MLLDPE, LLDPE and MLLDPE；Respectively account for 50%；
LDPE+LLDPE, LDPE+LLDPE, LLDPE+MLLDPE are blended spare respectively；
(4) preparation of film:
Five layer material of A-E is salivated equipment by five-layer co-squeezing to melt, then salivates into film；
(5) bag making is cut:
By above-mentioned salivation five-layer co-squeezing film dividing, banding keeps bag (can basis at the freshness of the 300*250mm of one side opening Demand prepares the sack of various specifications)；
(6) test of the mechanical property of freshness protection package and elimination decomposing ethylene performance:
Under normal circumstances, due to joined nano zine oxide as catalyst and auxiliary agent, diatomite material, consideration can give film power It learns performance to cause to change, be adversely affected to storage and transportation, it is therefore desirable to which the mechanical property of antistaling film is tested；
In a freshness protection package of a packaged invention preparation, it is full of air, the second of 1ml is then squeezed into syringe Alkene gas measures the numerical value that ethylene gas concentration reduces in fresh-keeping packaging bag, that is, indicates that the freshness packaging bag is decomposed and eliminate second The ability of alkene gas, also includes the ability of film transmission ethylene gas, and antistaling film prepared by the present invention has ethylene adsorption Decomposition, decomposition rate reaches 0.35-0.85ml/day ㎡ ethylene；OTR oxygen transmission rate 1300-4600ml/day ㎡.
Embodiment two
The preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function is that specific steps are such as Under:
(1) preparation of the antibacterial preserving fruit and vegetable utilizing layer of material A of decomposing ethylene and slow-release function:
By 80 mass fraction polyvinyl resins or polypropylene, 1 mass fraction auxiliary agent, 2 mass fraction diatomite, 17 mass fractions Nano zine oxide blending, tie rod, extrusion, pelletizing are spare；
(2) preparation of the antibacterial preserving fruit and vegetable utilizing material C layer of decomposing ethylene and slow-release function:
The blending of the nano zine oxide of the LLDPE of 98 mass fractions or polypropylene and 2 mass fractions, tie rod, extrusion, pelletizing is standby With；
(3) B, D, E layers of the antibacterial preserving fruit and vegetable utilizing material of decomposing ethylene and slow-release function is respectively as follows:
Second layer B respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
4th layer of D, respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
Layer 5 E, using LLDPE+MLLDPE, LLDPE and MLLDPE；Respectively account for 50%；
LDPE+LLDPE, LDPE+LLDPE, LLDPE+MLLDPE are blended spare respectively；
(4) preparation of film:
Five layer material of A-E is salivated equipment by five-layer co-squeezing to melt, then salivates into film；
(5) bag making is cut:
By above-mentioned salivation five-layer co-squeezing film dividing, banding keeps bag (can basis at the freshness of the 300*250mm of one side opening Demand prepares the sack of various specifications)；
(6) test of the mechanical property of freshness protection package and elimination decomposing ethylene performance:
Under normal circumstances, due to joined nano zine oxide as catalyst and auxiliary agent, diatomite material, consideration can give film power It learns performance to cause to change, be adversely affected to storage and transportation, it is therefore desirable to which the mechanical property of antistaling film is tested；
In a freshness protection package of a packaged invention preparation, it is full of air, the second of 1ml is then squeezed into syringe Alkene gas measures the numerical value that ethylene gas concentration reduces in fresh-keeping packaging bag, that is, indicates that the freshness packaging bag is decomposed and eliminate second The ability of alkene gas, also includes the ability of film transmission ethylene gas, and antistaling film prepared by the present invention has ethylene adsorption Decomposition, decomposition rate reaches 0.35-0.85ml/day ㎡ ethylene；OTR oxygen transmission rate 1300-4600ml/day ㎡.
Embodiment three
The preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function is that specific steps are such as Under:
(1) preparation of the antibacterial preserving fruit and vegetable utilizing layer of material A of decomposing ethylene and slow-release function:
90 mass fraction polyvinyl resins or polypropylene, 2 mass fraction auxiliary agents, 3 mass fraction diatomite, 5 mass fractions are received The blending of rice zinc oxide, tie rod, extrusion, pelletizing are spare；
(2) preparation of the antibacterial preserving fruit and vegetable utilizing material C layer of decomposing ethylene and slow-release function:
By the blending of the nano zine oxide of the LLDPE of 99.5 mass fractions or polypropylene and 0.5 mass fraction, tie rod, extrusion, pelletizing It is spare；
(3) B, D, E layers of the antibacterial preserving fruit and vegetable utilizing material of decomposing ethylene and slow-release function is respectively as follows:
Second layer B respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
4th layer of D, respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
Layer 5 E, using LLDPE+MLLDPE, LLDPE and MLLDPE；Respectively account for 50%；
LDPE+LLDPE, LDPE+LLDPE, LLDPE+MLLDPE are blended spare respectively；
(4) preparation of film:
Five layer material of A-E is salivated equipment by five-layer co-squeezing to melt, then salivates into film；
(5) bag making is cut:
By above-mentioned salivation five-layer co-squeezing film dividing, banding keeps bag (can basis at the freshness of the 300*250mm of one side opening Demand prepares the sack of various specifications)；
(6) test of the mechanical property of freshness protection package and elimination decomposing ethylene performance:
Under normal circumstances, due to joined nano zine oxide as catalyst and auxiliary agent, diatomite material, consideration can give film power It learns performance to cause to change, be adversely affected to storage and transportation, it is therefore desirable to which the mechanical property of antistaling film is tested；
In a freshness protection package of a packaged invention preparation, it is full of air, the second of 1ml is then squeezed into syringe Alkene gas measures the numerical value that ethylene gas concentration reduces in fresh-keeping packaging bag, that is, indicates that the freshness packaging bag is decomposed and eliminate second The ability of alkene gas, also includes the ability of film transmission ethylene gas, and antistaling film prepared by the present invention has ethylene adsorption Decomposition, decomposition rate reaches 0.35-0.85ml/day ㎡ ethylene；OTR oxygen transmission rate 1300-4600ml/day ㎡.
1 indicates that nanoparticle aggregation in phage surface, causes phage surface to damage in Fig. 2；2 expression particles enter in bacterium；3 Indicate the leakage of bacterium content；4 indicate that mycoderm is caused to rupture；5 indicate hydroxy radical；6 indicate to generate active oxygen；7 indicate peroxidating Hydrogen etc.；8 indicate that particle and active oxygen generate interference to substance in bacterium (protein)；9 indicate DNA damage.
Those skilled in the art it should be appreciated that above content only of the invention is illustrated, do not constitute to this The limitation of invention, can carry out a variety of improvement, combination, sub-combination and transformation to it as needed, all improvement, combination, Sub-combination, transformation and equivalence replacement etc. are both fallen within the scope of the appended claims.

Claims (5)

1. the antibacterial preserving fruit and vegetable utilizing material of a kind of decomposing ethylene and slow-release function, it is characterised in that: a kind of decomposing ethylene And the antibacterial preserving fruit and vegetable utilizing material of slow-release function is made of five layer materials；
First layer A presses different proportion for nano zine oxide using LLDPE+MLLDPE in the LLDPE+MLLDPE of first layer A As catalyst, same to auxiliary agent, diatomite material, polyvinyl resin or polypropylene fusion are blended, and by sustained release, allow ethylene and oxygen It is aoxidized under the action of nano zine oxide is as catalyst, ethylene is finally decomposed and generates carbon dioxide and water；
Second layer B, using LDPE+LLDPE；
Third layer C realizes barrier, antibacterial, antibacterial action using LLDPE or polypropylene+nano zine oxide as catalyst；
4th layer of D, using LDPE+LLDPE；
Layer 5 E, using LLDPE+MLLDPE；
The LLDPE is linear low density polyethylene resin；The MLLDPE is metallocene PE；
The LDPE is low-density high-pressure polyethylene.
2. the antibacterial preserving fruit and vegetable utilizing material of a kind of decomposing ethylene according to claim 1 and slow-release function, it is characterised in that: Same auxiliary agent, diatomite material, polyvinyl resin or polypropene blended graininess is made as catalyst in the nano zine oxide Material.
3. the antibacterial preserving fruit and vegetable utilizing material of a kind of decomposing ethylene according to claim 1 and slow-release function, it is characterised in that: The first layer A of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function includes following components: 70-90 matter Measure number polyvinyl resin or polypropylene, 0.5-2 mass fraction auxiliary agent, 800 mesh diatomite material of 0.5-3 mass fraction, 5-29 Mass fraction nano zine oxide；Third layer C includes following components: the LLDPE or polypropylene of 97-99.5 mass fraction, 0.5-3 matter Measure the nano zine oxide of number.
4. the preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of decomposing ethylene according to claim 1 and slow-release function, It is characterized by: the preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function is, it is specific Steps are as follows:
(1) preparation of the antibacterial preserving fruit and vegetable utilizing layer of material A of decomposing ethylene and slow-release function:
By 70-90 mass fraction polyvinyl resin or polypropylene, 0.5-2 mass fraction auxiliary agent, 0.5-3 mass fraction diatomite, The blending of 5-29 mass fraction nano zine oxide, tie rod, extrusion, pelletizing are spare；
(2) preparation of the antibacterial preserving fruit and vegetable utilizing material C layer of decomposing ethylene and slow-release function:
By the blending of the nano zine oxide of the LLDPE of 97-99.5 mass fraction or polypropylene and 0.05-3 mass fraction, tie rod, squeeze Out, pelletizing is spare；
(3) B, D, E layers of the antibacterial preserving fruit and vegetable utilizing material of decomposing ethylene and slow-release function is respectively as follows:
Second layer B respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
4th layer of D, respectively accounts for 50% using LDPE+LLDPE, LDPE and LLDPE；
Layer 5 E, using LLDPE+MLLDPE, LLDPE and MLLDPE；Respectively account for 50%；
LDPE+LLDPE, LDPE+LLDPE, LLDPE+MLLDPE are blended spare respectively；
(4) preparation of film:
Five layer material of A-E is salivated equipment by five-layer co-squeezing to melt, then salivates into film；
(5) bag making is cut:
By above-mentioned salivation five-layer co-squeezing film dividing, banding keeps bag at the freshness of the 300*250mm of one side opening；
(6) test of the mechanical property of freshness protection package and elimination decomposing ethylene performance:
Under normal circumstances, due to joined nano zine oxide as catalyst and auxiliary agent, diatomite material, consideration can give film power It learns performance to cause to change, be adversely affected to storage and transportation, it is therefore desirable to which the mechanical property of antistaling film is tested；
In a freshness protection package of a packaged invention preparation, it is full of air, the second of 1ml is then squeezed into syringe Alkene gas measures the numerical value that ethylene gas concentration reduces in fresh-keeping packaging bag, that is, indicates that the freshness packaging bag is decomposed and eliminate second The ability of alkene gas, also includes the ability of film transmission ethylene gas, and antistaling film prepared by the present invention has ethylene adsorption Decomposition, decomposition rate reaches 0.35-0.85ml/day ㎡ ethylene；OTR oxygen transmission rate 1300-4600ml/day ㎡.
5. the preparation side of the antibacterial preserving fruit and vegetable utilizing material of a kind of decomposing ethylene and slow-release function according to claim 1 or 5 Method, it is characterised in that: what the preparation method of the antibacterial preserving fruit and vegetable utilizing material of a kind of described decomposing ethylene and slow-release function was realized Technical principle is that the ethylene of the inside attachment of freshness protection package will be reacted with oxygen by nano zine oxide, and resolve into water and titanium dioxide Carbon, slow releasing function, can be such that the ethylene for causing corruption to be acidified and oxygen reduces, play preservation in addition；By absorption, decomposition, The circulation continuous of exclusion handles ethylene gas, and continues to eliminate the mould and bacterium for causing corruption, reaches long acting fresh-keeping effect, can To extend non-tubers fruit-vegetable food 7-20 days freshness dates；Nano zine oxide is good antibacterial agent and catalysis material, tool Have it is nontoxic, it is tasteless, it is nonirritant, do not decompose, never degenerate, the features such as thermal stability is good；And large specific surface area, in surface-active The heart is more, and skin effect and bulk effect make it have high catalytic activity and selectivity；It can be in pesticide, ethylene and atmosphere Organic matter carry out photocatalysis Decomposition, so that it is ultimately oxidized as CO2And H2O etc. is pollution-free substance；Meanwhile nano zine oxide is to big The pathogenic bacteria such as intestines bar function, Staphylococcus aureus function, Salmonella have strong inhibition or killing effect, are more suitable for fresh fruit The antibacterial of cooked food product sterilizes；
The antibacterial mechanisms of nano zine oxide are complex, antibacterial action may be several different mechanisms it is coefficient as a result, It can sum up are as follows:
(1) nanoparticle aggregation causes thallus to damage on mycoderm surface；
(2) nanoparticle release free zinc ion destroys thallus inner ion stable state, then causes thallus dead；
(3) nanoparticle generates ROS and aoxidizes the intracorporal organic matter of mattress, reaches antibacterial action.
CN201910751091.5A 2019-08-15 2019-08-15 The antibacterial preserving fruit and vegetable utilizing material and preparation method of a kind of decomposing ethylene and slow-release function Pending CN110421944A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111657347A (en) * 2020-06-19 2020-09-15 福建省凡通科技发展有限公司 Fruit and vegetable antibacterial material capable of actively removing ethylene and preparation process thereof
CN112373926A (en) * 2020-10-29 2021-02-19 鲸果科技(杭州)有限公司 Photocatalytic self-air-adjusting fruit and vegetable fresh-keeping bag

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CN104803078A (en) * 2015-01-12 2015-07-29 北京印刷学院 Multifunctional integrated freshness protection package and preparation method thereof
CN106146990A (en) * 2016-08-18 2016-11-23 安徽颍美彩印包装有限公司 A kind of antibacterial food packaging material with sustained release performance and preparation method thereof
CN107903471A (en) * 2017-11-28 2018-04-13 厦门艾美森新材料科技股份有限公司 A kind of raw material, bag product, packing film for being used to prepare film and preparation method thereof
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CN104803078A (en) * 2015-01-12 2015-07-29 北京印刷学院 Multifunctional integrated freshness protection package and preparation method thereof
CN108602969A (en) * 2016-02-04 2018-09-28 株式会社日省化学 Functional membrane, function container and preservation method
CN106146990A (en) * 2016-08-18 2016-11-23 安徽颍美彩印包装有限公司 A kind of antibacterial food packaging material with sustained release performance and preparation method thereof
CN107903471A (en) * 2017-11-28 2018-04-13 厦门艾美森新材料科技股份有限公司 A kind of raw material, bag product, packing film for being used to prepare film and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN111657347A (en) * 2020-06-19 2020-09-15 福建省凡通科技发展有限公司 Fruit and vegetable antibacterial material capable of actively removing ethylene and preparation process thereof
CN112373926A (en) * 2020-10-29 2021-02-19 鲸果科技(杭州)有限公司 Photocatalytic self-air-adjusting fruit and vegetable fresh-keeping bag
CN112373926B (en) * 2020-10-29 2023-10-27 鲸果科技(杭州)有限公司 Photocatalysis self-air-conditioning fruit and vegetable fresh-keeping bag

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