CN104803078B - Multifunctional unit freshness protection package and preparation method - Google Patents
Multifunctional unit freshness protection package and preparation method Download PDFInfo
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- CN104803078B CN104803078B CN201510015357.1A CN201510015357A CN104803078B CN 104803078 B CN104803078 B CN 104803078B CN 201510015357 A CN201510015357 A CN 201510015357A CN 104803078 B CN104803078 B CN 104803078B
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Abstract
Multifunctional unit freshness protection package and preparation method, belong to packaging material field.So that ethylene absorption, ethene suppression, antibacterial, high carbon dioxide selection are passed through, high water vapor passes through function film as material film, 25 kinds of the selection as needed from above-mentioned functions film, it is prepared into multifunctional unit freshness protection package, the multifunctional unit freshness protection package is suitable for the fresh-keeping of high respiratory intensity fruits and vegetables, is particularly suitable for climacteric type fruit at normal temperatures fresh-keeping.
Description
Technical field
Inhaled the present invention relates to fruit fresh-keeping packaging material, more particularly to high oxygen flow, permeable, saturating carbon dioxide, ethene
The design of multifunctional unit freshness protection package and the preparation methods such as attached, ethene suppression, belong to packaging material field.
Background technology
Continue to carry out respiration after fresh fruit and vegetable harvesting, heat is released in the oxidation for occurring nutritional ingredient, is produced
The metabolites such as moisture, carbon dioxide, ethene；Normal temperature, it is naked put in the environment of, fruits and vegetables respiratory rate is strong, the easy aging of fruits and vegetables,
Dry out and lose commercial value；In the closed environment of common fresh-keeping bag formation, ethene, carbon dioxide and moisture can not fill
Divide and exclude in time, ethene can accelerate fruits and vegetables respiratory intensity, promote the further ripening and senscence of fruits and vegetables；The moisture shape that respiration is produced
Into high humidity environment be easier grow pathogen, cause fruits and vegetables rot；It is rotten that high carbon dioxide environment will also result in some fruits and vegetables
Rotten aggravation.Therefore reduction fruits and vegetables respiratory rate, keep moisture, prevent grow pathogen, set up an appropriate hypoxemia, it is low
Carbon dioxide atmosphere environment is the key for solving the problems, such as preserving fruit and vegetable utilizing, is that this people develops many fruit and vegetable preserving methods and skill
Art, such as temperature, controlled atmosphere, dipping, pharmacy fumigation.The species for the feature antistaling film (freshness protection package) succeeded in developing is very
It is many.
Patent ZL 03113758.X introduce a kind of freshness protection package being made up of non-woven fabrics, high with gas permeability, do not bear water mist
Feature；In order to improve gas permeability, ZL 201210466049.7 and ZL201310071920.8 are provided with some apertures on bag,
ZL200910034625.9 designs a silicon window increase gas permeability on bag；ZL200710061409.4 is then introduced in polyethylene
Air-permeable masterbatch is added in material film is made, then handled with light face twin rollers, the small of diameter 1mm-1.5mm is formed on film
Hole, pore density 50~1,000,000/square meter is to increase freshness protection package gas permeability；Patent 200810059439.6 is then using blending tree
Fat method of modifying improves freshness protection package gas permeability, and the compositions such as silica, rubber are added in polyvinyl resin.
ZL201210275448.5 then introduces a kind of complex freshness protection package design, and the freshness protection package includes bag film and pre-
Box out, there is upper strata labeling on preformed hole, the Push And Release for controlling preformed hole；ZL200720037273.9 freshness protection package design
It is similar to above-identified patent, this freshness protection package include controlled atmosphere film, base material, adhesive and the polybag for having air-vent, in controlled atmosphere film with
Base material is combined, and is had by adhesive bonding in polybag on the position of air-vent, using controlled atmosphere film to the oxygen in packaging bag and two
The content of the gases such as carbonoxide is adjusted, so as to inhibit the respiratory intensity of fruits and vegetables.In order to increase bacteriostasis property,
ZL201110334707.2 has invented a kind of electret preservative film, is moulded using polytetrafluoroethylene (PTFE) or ethylene-tetrafluoroethylene copolymer
Thin-film material is made in the processed refinement of material, and electret technical finesse is carried out using electret corona method or Breakdown Method；
Enteromorpha fiber is added in paper pulp fiber by ZL201210588963.9 by a certain percentage, and the freshness protection package containing enteromorpha fiber is made,
5% half chitosan solution is finally smeared in freshness protection package increases the bacteriostasis of freshness protection package；
ZL200710158884.3 is introduced and is added cinnamic acid in PE films, cinnamic acid to by fruit and vegetable preservation without blanching effect.
Freshness protection package above has single layer structure, and many freshness protection packages have double-decker in addition.
The freshness protection package that ZL201110368214.0 is introduced is made up of ventilative protective layer and fresh-keeping layer, provided with a sight on ventilative protective layer
Window is examined, and fresh-keeping layer is then made up of polyvinyl resin, sodium alginate, chitosan；What ZL201220487692.3 was introduced does not like
It is made up of outer bag and inner bag, inner bag is provided with outer bag body, the bottom of outer bag and inner bag is bonding, outer bag and interior
Heat-insulation layer is provided between bag.
There is the freshness protection package of many 3-tier architectures in addition, ZL200710119153.8 develops a kind of air-adjustable fresh-keeping bag, is designed to
Three-decker from inside to outside, wherein bag are by outer layers towards inner layers successively by air-conditioning preservative film, ventilative hydrophilic materials, ventilative
Hydrophobic material layer composition, bag sets sealing area at each default paragraph；The bag of ZL201320479168.6 freshness protection package
Body top is built with sealing strip, and the bag is divided into fresh-keeping layer, moisturizing adsorption layer and fresh-keeping air-permeable layer from outside to inside, wherein
Moisturizing adsorption layer is provided with ethene adsorbent, and fresh-keeping ventilative layer surface is provided with small ventilating holes.
Oxygen and steam breathability can not be accurately controlled with the design that micropore is beaten on non-woven fabrics making bag or bag, to two
Carbon oxide gas pass through non-selectivity；Inorganic particulate or rubber constituent are added in polyethylene or acrylic resin, can be increased
OTR oxygen transmission rate, but it is not notable to the permeability increase of steam；Because silicon window area is smaller, therefore it is difficult fully to be appeared by it
Vapor and carbon dioxide, and the design of silicon window causes the increase of freshness protection package processing cost；For the bag that those designs are complicated, increase
Production cost, is hardly formed mass mechanized production；The freshness protection package of double-decker and three-decker design, their gas permeability
It can reduce, often result in oxygen supply deficiency in freshness protection package, steam can not be excluded in time；Inhaled to increase bacteria resistance function, ethene
Attached function and pack is added in freshness protection package is also common packaged form, but pack it is damaged after can pollute fruits and vegetables, or pack
Bactericide-release excessive concentration causes fruits and vegetables to be contaminated, and loses local flavor.Existing vegetable and fruit packaging is often attended to one thing and lose sight of another, single film
Design is difficult to realize the work(that high oxygen flow, high permeable, high carbon dioxide selective penetrated property, antibacterial, ethylene absorption, ethene suppress simultaneously
Can, the design of double-deck or MULTILAYER COMPOSITE can increase antibacterial, ethylene absorption, the function of ethene suppression, but lose high oxygen flow,
High permeable, high carbon dioxide passes through property；The present invention then successfully solves these contradictions using the design of multifunctional unit freshness protection package, makes
Freshness protection package has the function that antibacterial, ethylene absorption, ethene suppress simultaneously, while having high oxygen flow, high permeable, high carbon dioxide choosing
Select by function.
The content of the invention
It is an object of the present invention to provide multifunctional unit freshness protection package design and preparation method thereof.Using a variety of function films, if
Multifunctional unit freshness protection package is produced in family planning.Using them as raw material film, multifunctional unit film coil is prepared into, many work(are then prepared into
Can integrated freshness protection package, make freshness protection package while all fresh-keeping functions that there is our material films to have, and various fresh-keeping functions
It will not influence each other, will not mutually weaken.
The described integrated freshness protection package of a variety of functions is spliced at least two in following 5 kinds of materials：
Function film 1 (ANTI-MICROBIALS, AM films)：MULTILAYER COMPOSITE with intelligent slow-release bactericide function
How much film, can grow pathogen, film can discharge the gas phase bactericide of various concentrations automatically according to by fruit and vegetable preservation, should
Bactericide will not produce any residual on fruits and vegetables, and the type of bactericide meets international EC and FDA standards.
Function film 2 (ETHYLENE ABSORBERS, EA films)：Fruit freshness preserving packaging with ethylene adsorption function
Film, discloses a kind of fruit freshness preserving packaging with ethylene adsorption function thin present invention preferably employs ZL201010522442.4
Film, the film is that by a certain proportion of alumina silicate powder and polyvinyl resin melt blending, then blown film is obtained, and it has ethene
Adsorption capacity is high, the characteristics of ethylene absorption is not influenceed by steam.
Function film 3 (1-MCP releasing, MR films)：Laminated film with 1-MCP release functions.1- first
Cyclopropene (1-MCP) gas can suppress fruits and vegetables and produce ethene, and the 1-MCP preparations of in the market are in ring paste by 1-MCP absorption
On smart carrier, the cyclodextrin is dispersed in water, certain density 1-MCP gases can be discharged, fruits and vegetables are carried out stifling fresh-keeping；
Due to being difficult to release concentration and deenergized period accurate control, therefore application is restricted；Present invention preferably employs
A kind of laminated film with 1-MCP release functions disclosed in CN102862361A, the film runs into the water that fruits and vegetables breathing is produced
Automatic sustained release gas phase 1-MCP after vapour, when fruits and vegetables respiratory intensity is big, relative humidity is high in freshness protection package, and the 1-MCP of film release is dense
Degree is bigger, and the inhibition to fruits and vegetables respiration is higher, realizes that what fruits and vegetables were metabolized slows down regulation automatically.
(the High CO of function film 42TR and OTR film,HCO films)：One kind has high oxygen permeability and height
Carbon dioxide selects the film of gas permeability, it is preferred to use disclosed in ZL201210363822.7 it is a kind of have high oxygen permeability and
High carbon dioxide selects the film of gas permeability, and the OTR oxygen transmission rate (OTR) of film is 105ml/m2.day.atm more than, and preferably
Transmitance (the CO of carbon dioxide2TR) it is 6 times of OTR, the carbon dioxide of fruits and vegetables respiration generation can be excluded in time, is prevented
It is carbon dioxide enriched to cause fruits and vegetables aging.
Function film 5 (High MVTR film, HM films)：ZL 201010532453.0 discloses a kind of diatom land reform
Property polyethylene film, porous and hydrophilic diatomite has higher permeability to vapor, and the vapor of modified film is passed through
Rate (WVTR) reaches 100-200g/m2.day, the steam produced in packaging bag (freshness protection package) can be excluded in time, reduce freshness protection package
Interior relative humidity, suppresses bacteria breed.
Wherein OTR, CO of function film 1 (AM films)2TR numerical value is in 2000-5000ml/m2.day.atm between, relatively
Contributions of HCO films, the AM films to oxygen flow and saturating carbon dioxide can be ignored；AM films WVTR is less than 10g/
m2.day, relative to HM films, contributions of the AM films to steam breathability can also be ignored；I.e. in Integrated design, AM
Films only contributes bactericidal property, and the contribution to Gas permeability can be ignored.
Function film 1 of the present invention is preferred to use any disclosed in application number 200910086775.4 and 201210365158.X
A kind of film.
Wherein 200910086775.4 include：(a) internal layer, is controlled release layer, has with a certain proportion of polyethylene vinegar
Vinyl acetate copolymer-low density polyethylene (LDPE) blending resin is constituted；(b) middle level, is the generation layer of bactericide, there is binding agent and institute
State bactericide precursor composition；(c) outer layer, is the barrier layer and/or printing layer of sulfur dioxide, by the material in consisting of
Expect the nonpolar film constituted：Low density polyethylene (LDPE) or low density polyethylene (LDPE) and LLDPE, high-density polyethylene
The blending and modifying resin film of alkene, medium density polyethylene, or Biaxially oriented polypropylene；Alternatively, (d) the first extra play,
First extra play is located between the outside that layer middle level is produced as the inside of the outer layer of printing layer and as bactericide, and first
Extra play is selected from nylon film, pet film.
201210365158.X includes three layers, and outer layer is high-obstruction；Intermediate layer is adhesive layer, is a dry glue film；It is interior
Layer is food contact layer；Outer layer is with KBOPP, VMCPP, VMPET, SiOx/PET, Al of high oxygen barrier2O3One kind in/PET
Or the Obstruct membrane of several compositions；Intermediate layer is that one or more of mixing in organic acid or organic acid sodium salt are used as active antibacterial
Composition, is added them in polyurethane or acrylate adhesives, and the quality percentage of active antibacterial composition in the intermediate layer contains
Measure as 2-15%, the consumption of binding agent dry glue is 3-7 grams per square meters；Internal layer is the LDPE modified resins that EVA is modified, and EVA accounts for internal layer
The 5-50% of gross mass；Organic acid is one or more of mixed in citric acid, sorbic acid, malic acid, tartaric acid, benzoic acid
Close.
OTR, CO of function film 2 (EA films)2TR numerical value is also in 2000-5000ml/m2.day.atm between, and WVTR
Less than 10g/m2.day, in Integrated design, EA films only contribute ethylene absorption performance, and to the contribution of Gas permeability
It can ignore.
The disclosed water with ethylene adsorption function of function film 2 (EA films) of the present invention preferably ZL201010522442.4
Really fresh-keeping environmentally friendly packing material, including following components：100-90 mass fractions polyethylene or acrylic resin and 0.5-10 mass
Number al silicate molecular sieve, al silicate molecular sieve granularity is 5~100 microns, and silica alumina ratio is 5~100；Its preparation method, including
Following steps：At room temperature, boehmite is added in water, be uniformly mixed；Then template and Ludox are added, directly
To formation gel；Gel is fitted into stainless steel autoclave, airtight heating carries out constant temperature to 200~250 DEG C under pressure itself
Crystallization 48 hours；After crystallization is complete, it is washed with deionized and dries；Most 4~6 hours are calcined with complete after 500~700 DEG C
Template is removed, 5~100 microns of grain warp is crushed to, that is, it is 5- to obtain the Si/Al mol ratios in molecular screen primary powder, molecular sieve
100；After 100~90 parts of polyethylene or acrylic resin resin are uniformly mixed with 0.5~10 part of molecular sieve, in twin-screw
Melt blending on extruder, is then blow molded into film.
The situation of function film 3 (MR films) is also similar to EA films, AM films, in Integrated design, MR
Films only discharges 1-MCP, and contribution ethene suppresses function, and the contribution to Gas permeability can be ignored.
A kind of function film 3 (MR films) of the present invention releasable 1- methyl cyclopropenes preferably disclosed in CN102862361A
Fresh-Keeping Packaging Materials, the packaging material is multi-layer compound film, including outermost layer be to the barrier layers of 1-MCP gases, in
Between layer binder or 1-MCP releasing layers, innermost layer be food contact layer or 1-MCP control release layer；Outer layer obstructs for 1-MCP
Layer, is with one kind in low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), high density polyethylene (HDPE) (HDPE)
Or several is main body, or based on polypropylene film BOPP (bidirectional stretching polypropylene film), CPP (prolonging polypropylene film)
Body, or based on above-mentioned polyethylene and acrylic resin, EVA (ethylene-vinyl acetate copolymer) is added in main body
Film for modifying agent etc. is used as outer layer；Internal layer is used as using EVA modified PEs-rubber blend；Made with 1- methyl cyclopropenes (1-MCP)
For active component, 1-MCP/ cyclodextrin is added to the drying adhesive layer that is obtained in conventional polyurethane or acrylate adhesives as
Intermediate layer, 1-MCP/ cyclodextrin is that 1-MCP is adsorbed on cyclodextrin carrier and 1-MCP mass content 3-5%, and the polarity of outer layer is high
It is higher than the barrier of internal layer in the barrier of the polarity of internal layer, and outer layer.
OTR, CO of function film 4 (HCO films)2TR numerical value is 105-106ml/m2.day.atm between, main function is
The carbon dioxide in oxygen, discharge freshness protection package is provided for freshness protection package；HCO films WVTR is less than 20g/m2.day, integrated
During design, HCO films to water vapo(u)r transmission can contribution can ignore, only consider to oxygen and COZ permeability
Contribution.
Function film 4 (HCO films) is preferred to use thin-film material disclosed in 201210363822.7, with single layer structure,
It is with one kind or several in low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), high density polyethylene (HDPE) (HDPE)
The film to be blow molded after matrix resin, with amorphous polymer melt blending is planted, amorphous polymer is styrene-fourth two
Alkene block copolymer (SBS), ethylene propylene diene rubber (EPDM), ethylene-octene copolymer (POE), polybutadiene (PB), natural rubber
One or more in glue (NR), ethylene-vinyl acetate (EVA), toatl proportion of the amorphous polymer in system is 25-
30%.
OTR, CO of function film 5 (HM films)2TR numerical value is 104ml/m2.day.atm or so, relative to HCO
Films, the contribution to oxygen and COZ permeability is smaller, can also generally ignore；HM films WVTR exists
100-200g/m2.day between, in Integrated design, HM films only consider the contribution to water vapo(u)r transmission, and to dioxy
Changing the contribution of carbon and permeability can ignore.
Function film 5 (HM films), which is preferred to use the 201010532453.0 disclosed fruit with high air permeability, to be protected
Fresh packaging material, the raw material of the material includes modified diatomite and LDPE, and modified diatomite superscribes a strata for surface
The diatomite of vinyl acetate, polyacrylic resin or their copolymer；The method of diatomite modified：Diatomite is dispersed in water
In, vinyl acetate or/and acrylic monomer are then added, 40-60 DEG C is warming up to, the hydrogen peroxide that concentration is 30% is added, connects
The ferrous chloride aqueous solution for adding mass concentration 10%, is reacted 4~10 hours, is then dried, crushing obtains modification infusorial earth；
Wherein above-mentioned 100 grams of diatomite correspondence is dispersed in 500ml water, is then corresponded to and is added 5~200ml monomers, hydrogen peroxide is added
Amount 0.5~5ml of correspondence, ferrous chloride aqueous solution correspondence adds 0.2~2ml；Aforesaid propylene acrylic monomer is methyl acrylate list
Body or methyl methacrylate monomer.
According to by the kind of fruit and vegetable preservation, selection needs integrated function quantity, species；According to the weight of fruits and vegetables, fresh-keeping temperature
Respiratory rate under degree, calculates the area of each function film.
Generally, the HCO films of function film 4 and the HM films of function film 5 are that the every kind of freshness protection package of design must
Standby, HCO films provide suitable oxygen concentration and gas concentration lwevel for freshness protection package, and HM films then exclude freshness protection package in time
Interior moisture, prevents condensation on the inside of freshness protection package, and the probability of pathogen is grown in reduction；If climacteric type fruit, then EA films
Or MR films are to be necessary the function film of addition, the ethene that fruit breathing is produced can be sponged in time, delays and delay to exhale
Inhale transition；Such as fruit and vegetable easily grows fungi or other pathogens, then adds bacteria resistance function AM films in freshness protection package design.
If W kilograms of fruit needs, the freshness protection package that a profile is a height of H meters, width is D meters is fresh-keeping, and preservation temperature is T,
At such a temperature, the respiratory rate of fruit is production R ml CO2/ (kg.hr) or consumption R ml O2/ (kg.hr), fruit
Respiratory rate is existing or knowable at a temperature of certain；Gas concentration is reached after balance in freshness protection package, the balanced body of each component
Product percent concentration is respectively CO2、CCO2, relative humidity be RH, the concentration of volume percent of oxygen is 20%, two in outside air
It is zero to aoxidize concentration of carbon, and outside air relative humidity is RH0, then there is following relationship：
The oxidation reaction of glucose：
C6H12O6+6O2=6CO2+6H2O+ heats (1)
According to formula (1), it can derive, if it is R mlCO to load W kg, respiratory rate in freshness protection package2/(kg·hr)
(or R mlO2/ (kghr)) fruits and vegetables, because the steam quality (g) that respiration is produced per hour is：
H2O (g/hr)=W × R × 18/ (22.4 × 1000) (2)
Gas has lower column balancing with gas in external environment in freshness protection package：
Oxygen equilibrium：W × R=OTRHCO×H×diHCO× (20%-CO2)×24hr (3)
Carbon dioxide balance：W × R=CO2TRHCO×H×diHCO×(CCO2-0)×24hr(4)
The balance of vapor：
W × R × 18/ (22.4 × 1000) × 24hr=WVTR × H × diHM×(RH-RH0)(5)
Above-mentioned W- fruit weight, kg；The respiratory rate of R- fruit, ml/ (kghr)；OTRHCO(HCO is thin for-function film 4
Film) OTR oxygen transmission rate, ml/m2·24hr.atm；CO2TRHCOThe carbon dioxide of-function film 4 (HCO films) is passed through
Rate, ml/m2·day·atm；CO2- gas reached after balance, the volumn concentration of oxygen, % in freshness protection package；CCO2- gas reaches
To after balance, the volumn concentration of carbon dioxide, % in freshness protection package；H- bags of high, m；diHCOThe width of function film 4 in-sack
Degree, according to formula (3) and (4), takes the higher value in both, m；diHMThe width of function film 5, m in-sack；WVTR- functions
The moisture-vapor transmission of film 5, g/m224hr100%RH；RH- gases reach after balance that relative humidity in freshness protection package is single
Position is %；RH0The relative humidity of-outside air, unit %；CCO2、CO2The general atmosphere composition for taking fruit and vegetable preservation optimal, can be with
Obtained, or oneself measured according to fresh-keeping experiment according to Literature Consult.WVTR is HM moisture-vapor transmission.
According to formula (3) and (4), it can be deduced that after gas component is balanced in freshness protection package, reach optimum oxygen or titanium dioxide
During concentration of carbon, it is di to prepare multifunctional unit freshness protection package to need the HCO thin-film widths that height is HHCO, typically take larger one
Why value (is not to determine value)；It can show that (RH is less than when realizing that freshness protection package inner side does not condense according to formula (5)
100%, relative humidity takes 95%-100% in general freshness protection package), outside air relative humidity is a changing value, typically takes and works as
Season, the same day average relative humidity RH, it is necessary to HM thin-film widths diHM。
Freshness protection package total surface area is D × H formulas (3) square meter, and di is obtained according to formula (3) and (4)HCO(the i.e. face of HCO films
Product), the area of HM films is obtained according to formula (5), after both film usable floor areas are determined, the remaining area (D of freshness protection package
×H-H(diHCO+diHM)) concentration level of ethene can be discharged according to fruits and vegetables and easily grows the degree of pathogen and determines second
Alkene suppression, ethylene absorption, the area of bacteriostatic film.
Such as fruit and vegetable non-respiratory transition type, or respiration does not generate ethene substantially, then can be used that three functions are integrated to be set
Meter, without using ethylene absorption function, only uses the function of HCO, HM and AM tri-；As fruit and vegetable respiration produces ethylene concentration very
Height, then using the integrated freshness protection package design of five-function, i.e., in above-mentioned four function fresh-keeping bag design basis, increase uses MR films
(ethene suppression) function film.
The unsuitable breed bacteria of such as fruit and vegetable, and respiration does not produce ethene, then using two function Integrated designs, only with
HCO and HM films；In this case, if the size of freshness protection package is larger, and find that the HCO films and HM that need are thin after calculating
The area summation of film is less than H × D, then can increase HM film sizes.
If multi-function membrane area summation is more than H × D needed for being found after calculating, need preparation gas permeability higher
HCO films, HM films, also need to increase the gas permeability of AM and EA films if necessary.
Bag-making method
Required several function film coiled materials are cut into required width (di), it is then viscous with heat-sealing or adhesive
Corresponding coiled material (shown in Fig. 2) is made in the mode of conjunction, then seals or be bonded into the guarantor of Lilezhen form on automatic bag-mfg. machine
Fresh bag, the height of sack is H.
Fresh-keeping application
Multifunctional unit freshness protection package is particularly suitable for the preserving fruit and vegetable utilizing that respiratory intensity is high, breathing generation ethene is more, especially
It is suitable for the fresh-keeping of climacteric type fruits and vegetables, is particularly suitable for the fresh-keeping of fruits and vegetables under normal temperature.Select and have no mechanical damage, do not infect
The fruits and vegetables of pathogen, are directly placed into multifunctional unit freshness protection package, tighten sack, and freshness protection package is preferably placed at bottom and breathed freely
Dividing plate on, allow the film at each position of freshness protection package all to play permeation functions, film is being just on the downside of the freshness protection package of transference pallet contact
Often play a role.
Matrimony vine has the pulp of pulpous state, thin skin, and easily damaged, its commodity is usually dry wolfberry form；That has just plucked is fresh
Matrimony vine, decayed fruit rate can be to more than 10% within second day, and the 3rd day decayed fruit rate reaches 30%, reaches 50% or so within the 4th day.Due to
The fresh-keeping problem of fresh fructus lycii, which never has, to be resolved, and causes fresh fructus lycii at source to sell.Utilize multifunctional unit freshness protection package
Successfully solve the fresh-keeping problem of fresh matrimony vine.
Brief description of the drawings
The integrated freshness protection package design diagram of Fig. 1 five-functions.
Fig. 2 multifunctional unit preservative film coiled material schematic diagrames.
Embodiment
The present invention is done with reference to embodiment and furtherly illustrated, but the present invention is not limited to following examples.
Embodiment 1
A piece of 0.3m × 0.25m HM films and the AM films of same size, as two panels up and down, are prepared into two function collection
Into freshness protection package, load 80 (about 40 grams) fresh grain matrimony vines, the integrated freshness protection package of two functions is placed on ventilative dividing plate by sealing,
Observed at room temperature in 25 DEG C.
Comparative example 1：
80 fresh matrimony vines of same quality are placed in polypropylene (PP) plastic casing, plastic casing appearance and size be 10cm ×
10cm × 8cm, lid, side, downside are punched, aperture 5mm, altogether 20 holes, observe Decay.Two work(are detected after four days
Head space atmosphere and decayed fruit rate can be counted in integrated freshness protection package.
The integrated freshness protection package of two functions is observed, water smoke does not occur on the inside of freshness protection package in 1-4 days, decayed fruit rate is only after 4 days
15%, find that oxygen concentration is stable 12.5% in freshness protection package by analysis, gas concentration lwevel 5.8% illustrates the work(of HM/AM bis-
The integrated freshness protection package of energy can substantially reduce fresh fructus lycii breathing, delay matrimony vine maturation, aging, rot, with control group decayed fruit rate 45%
Compare, decayed fruit rate is reduced to 1/3.
Embodiment 2
The HCO film sealings of 0.1m × 0.25m AM films and 0.2m × 0.25m are spliced into the big of 0.3m × 0.25m
It is small, AM/HCO integrated thin-films are made, the HM films with other a piece of 0.3m × 0.25m are prepared into three functions as two panels up and down
Integrated freshness protection package AM/HCO/HM, loads 200 (about 100 grams) fresh grain matrimony vines, and the integrated freshness protection package of three functions is placed in by sealing
On the ventilative dividing plate in lower end, observed at room temperature in 25 degree；
Comparative example 2
200 fresh matrimony vines of same quality are placed in polypropylene (PP) plastic casing, plastic casing appearance and size and punching feelings
Condition observes matrimony vine Decay with comparative example 1.Head space atmosphere is detected in the integrated freshness protection package of three functions after four days and decayed fruit is counted
Rate.
The integrated freshness protection package of the functions of AM/HCO/HM tri- is observed, water smoke did not occur on the inside of freshness protection package in 1-4 days, it is rotten after 4 days
Fruit rate only 10%, finds that oxygen concentration is stable 15.5% in freshness protection package, gas concentration lwevel 0.4% illustrates AM/ through analysis
The function fresh-keepings of HCO/HM tri- bag can substantially reduce fresh fructus lycii breathing, delay matrimony vine maturation, aging, and matrimony vine breathing is appeared in time
The carbon dioxide of generation, prevents that carbon dioxide is too high and matrimony vine is damaged；Compared with control group decayed fruit rate 50%, three function collection
Decayed fruit rate into freshness protection package is reduced to the 1/5 of control group.
Embodiment 3
By 1 0.15m × 0.25m AM films and 1 0.15m × 0.25m HCO film sealings into 0.3m × 0.25m
Size one sheet of film (AM/HCO films)；The MR of 1 0.15m × 0.25m HM films and 1 0.15m × 0.25m is thin
The one sheet of film (MR/HM films) of film sealing 0.3m × 0.25m size；By 1 good AM/HCO film prepared above and 1
MR/HM films are prepared into the integrated freshness protection package AM/HCO/HM/MR of four functions as two panels up and down, load 200 fresh matrimony vines, envelope
Mouthful, the integrated freshness protection package of four functions is placed on the ventilative dividing plate in lower end, observed at room temperature in 25 degree；
Comparative example 3
200 fresh matrimony vines of same quality are placed in polypropylene (PP) plastic casing, plastic casing appearance and size and punching feelings
Condition observes matrimony vine Decay with comparative example 1.Head space atmosphere is detected in the integrated freshness protection package of three functions after four days and decayed fruit is counted
Rate.
The integrated freshness protection package of the functions of AM/HCO/HM/MR tetra- is observed, water smoke, 4 days did not occur on the inside of freshness protection package in 1-4 days
Decayed fruit rate only 5%, finds that oxygen concentration is stable in 13.5%, gas concentration lwevel 1.4%, explanation in freshness protection package through analysis afterwards
The integrated freshness protection package of the functions of AM/HCO/HM/MR tetra- is that can substantially reduce fresh fructus lycii breathing, delays that matrimony vine is ripe, aging, and having can be with
The carbon dioxide that matrimony vine breathing is produced is appeared in time, can also substantially be suppressed matrimony vine in addition and be produced ethene, along with antibacterial work(
Can, this four function and into freshness protection package compared with control group decayed fruit rate 50%, decayed fruit rate is reduced to 1/10.
This multifunctional unit freshness protection package is ingenious to solve multi-functional integration problem, it is to avoid existing freshness protection package designed
, as needed can be with integrated more functions the problems such as influence of the complicated, MULTILAYER COMPOSITE to gas permeability, but need gas permeability more
Big function film is used as material film.Those skilled in the art is it will be clearly understood that above preferred embodiment is simply to the present invention
Illustrate, be not construed as limiting the invention.It can be carried out as needed it is a variety of improve, combination, sub-combination with
And conversion, all improvement, combination, sub-combination, conversion and equivalence replacements are both fallen within the scope of the appended claims.
Claims (11)
1. multifunctional unit freshness protection package, it is characterised in that a variety of integrated freshness protection packages of function are at least two in following 5 kinds of materials
It is spliced：
Function film 1, is AM films：Multi-layer compound film with intelligent slow-release bactericide function；
Function film 2, is EA films：Fruit freshness preserving packing film with ethylene adsorption function；
Function film 3, is MR films：Laminated film with 1-MCP release functions；
Function film 4, is HCO films：A kind of film with high oxygen permeability and high carbon dioxide selection gas permeability；
Function film 5, is HM films, and a kind of diatomite modified polyethylene film, the moisture-vapor transmission WVTR of modified film reaches
To 100-200g/m2.day。
2. according to the multifunctional unit freshness protection package described in claim 1, it is characterised in that wherein OTR, CO of AM films2TR numerical value
In 2000-5000ml/m2.day.atm between, with respect to HCO films, contribution of the AM films to oxygen flow and saturating carbon dioxide is ignored；
The WVTR of AM films is less than 10g/m2.day, relative to HM films, contribution of the AM films to steam breathability is also ignored；I.e. in collection
Into during design, AM films only contribute bactericidal property, and the contribution to Gas permeability is ignored.
3. according to the multifunctional unit freshness protection package described in claim 1, it is characterised in that the film of function film 1 uses following
A kind of one film；
A kind of film, including：(a) internal layer, is controlled release layer, has with a certain proportion of plastic of poly vinyl acetate copolymerization
Thing-low density polyethylene (LDPE) blending resin is constituted；(b) middle level, is the generation layer of bactericide, there is binding agent and the bactericide precursor
Constitute；(c) outer layer, is the barrier layer and/or printing layer of sulfur dioxide, and what is be made up of the material in consisting of is nonpolar
Film：Low density polyethylene (LDPE) or low density polyethylene (LDPE) and LLDPE, high density polyethylene (HDPE), the poly- second of Midst density
The blending and modifying resin film of alkene, or Biaxially oriented polypropylene；(d) the first extra play, first extra play, which is located at, to be made
Between inside for the outer layer of printing layer and the outside that layer middle level is produced as bactericide, the first extra play be selected from nylon film,
Pet film；
Or a kind of film：Including three layers, outer layer is high-obstruction；Intermediate layer is adhesive layer, is a dry glue film；Internal layer is food
Contact layer；Outer layer is with KBOPP, VMCPP, VMPET, SiOx/PET, Al of high oxygen barrier2O3One or more of groups in/PET
Into Obstruct membrane；Intermediate layer is used as active antibacterial composition, general for one or more of mixing in organic acid or organic acid sodium salt
They are added in polyurethane or acrylate adhesives, and the weight/mass percentage composition of active antibacterial composition in the intermediate layer is 2-
15%, the consumption of binding agent dry glue is 3-7 grams per square meters；Internal layer is the LDPE modified resins that EVA is modified, and EVA accounts for internal layer gross mass
5-50%；Organic acid is one or more of mixing in citric acid, sorbic acid, malic acid, tartaric acid, benzoic acid.
4. according to the multifunctional unit freshness protection package described in claim 1, it is characterised in that OTR, CO of function film 22TR numerical value
In 2000-5000ml/m2.day.atm between, and WVTR is less than 10g/m2.day, in Integrated design, EA films are only contributed
Ethylene absorption performance, and the contribution to Gas permeability can be ignored.
5. according to the multifunctional unit freshness protection package described in claim 1, it is characterised in that function film 3 is a kind of releasable 1-
The Fresh-Keeping Packaging Materials of methyl cyclopropene, the packaging material is multi-layer compound film, including outermost layer is to 1-MCP gases
Barrier layer, interlayer bond or 1-MCP releasing layers, innermost layer be food contact layer or 1-MCP control release layer；Outer layer
For 1-MCP barrier layers, be based on the one or more in low density polyethylene (LDPE) (LDPE), high density polyethylene (HDPE) (HDPE),
Either based on polypropylene film BOPP (bidirectional stretching polypropylene film), CPP (prolonging polypropylene film) or with above-mentioned poly-
Ethene and acrylic resin are main body, and the film conduct that EVA (ethylene-vinyl acetate copolymer) is modifying agent is added in main body
Outer layer；Internal layer is used as using EVA modified PEs-rubber blend；Using 1- methyl cyclopropenes (1-MCP) as active component, by 1-
MCP/ cyclodextrin is added to the drying adhesive layer obtained in conventional polyurethane or acrylate adhesives as intermediate layer, 1-MCP/ rings
Dextrin is that 1-MCP is adsorbed on cyclodextrin carrier and 1-MCP mass content 3-5%, and the polarity of outer layer is higher than the polarity of internal layer, and
The barrier of outer layer is higher than the barrier of internal layer.
6. according to the multifunctional unit freshness protection package described in claim 1, it is characterised in that the OTR of described function film 4,
CO2TR numerical value is 105-106ml/m2.day.atm between, the WVTR of HCO AM films is less than 20g/m2.day。
7. according to the multifunctional unit freshness protection package described in claim 1, it is characterised in that described function film 4 has individual layer
Structure, is with one in low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), high density polyethylene (HDPE) (HDPE)
Plant or several films to be blow molded after matrix resin, with amorphous polymer melt blending, amorphous polymer is benzene second
Alkene-butadiene block copolymer (SBS), ethylene propylene diene rubber (EPDM), ethylene-octene copolymer (POE), polybutadiene
(PB), the one or more in natural rubber (NR), ethylene-vinyl acetate (EVA), amorphous polymer is total in system
Ratio is 25-30%.
8. according to the multifunctional unit freshness protection package described in claim 1, it is characterised in that described function film 5 is with height
The fruit fresh-keeping packaging material of air permeability, the raw material of the material includes modified diatomite and LDPE, modified diatomite
The diatomite of a strata vinyl acetate, polyacrylic resin or their copolymer is superscribed for surface；The side of diatomite modified
Method：Diatomite is dispersed in water, vinyl acetate or/and acrylic monomer is then added, 40-60 DEG C is warming up to, added dense
The hydrogen peroxide for 30% is spent, the ferrous chloride aqueous solution of mass concentration 10% is subsequently added into, reacted 4~10 hours, then dry,
Crushing obtains modification infusorial earth；Wherein above-mentioned 100 grams of diatomite correspondence is dispersed in 500ml water, then correspond to and add 5~
200ml monomers, hydrogen peroxide addition 0.5~5ml of correspondence, ferrous chloride aqueous solution correspondence adds 0.2~2ml；Aforesaid propylene acid
Class monomer is methacrylate monomer or methyl methacrylate monomer.
9. according to the multifunctional unit freshness protection package described in claim 1, it is characterised in that the HCO at least including function film 4 is thin
The HM films of film and function film 5.
10. according to the multifunctional unit freshness protection package described in claim 8, it is characterised in that if W kilograms of fruit needs one
Profile is a height of H meters, width is fresh-keeping for D meters of freshness protection package, and preservation temperature is T, at such a temperature, and the respiratory rate of fruit is production
R ml CO2/ (kg.hr) or consumption R ml O2/ (kg.hr), the respiratory rate of fruit is existing at a temperature of certain or understood
's；Gas concentration is reached after balance in freshness protection package, and the equilibrium volume percent concentration of each component is respectively CO2、CCO2, relative humidity
For RH, the concentration of volume percent of oxygen is 20% in outside air, and gas concentration lwevel is zero, and outside air relative humidity is
RH0, then there is following relationship：
The oxidation reaction of glucose：
C6H12O6+6O2=6CO2+6H2O+ heats (1)
According to formula (1), it can derive, if it is R mlCO to load W kg, respiratory rate in freshness protection package2/ (kghr) or R
mlO2/ (kghr) fruits and vegetables, because the steam quality g that respiration is produced per hour is：
H2O (g/hr)=W × R × 18/ (22.4 × 1000) (2)
Gas has lower column balancing with gas in external environment in freshness protection package：
Oxygen equilibrium：W × R=OTRHCO×H×diHCO× (20%-CO2)×24hr (3)
Carbon dioxide balance：W × R=CO2TRHCO×H×diHCO×(CCO2-0)×24hr (4)
The balance of vapor：
W × R × 18/ (22.4 × 1000) × 24hr=WVTR × H × diHM×(RH-RH0) (5)
Above-mentioned W- fruit weight, kg；The respiratory rate of R- fruit, ml/ (kghr)；OTRHCO- function film 4 (HCO films)
OTR oxygen transmission rate, ml/m2·24hr.atm；CO2TRHCOThe carbon dioxide transmitance of-function film 4 (HCO films), ml/
m2·day·atm；CO2- gas reached after balance, the volumn concentration of oxygen, % in freshness protection package；CCO2- gas reaches balance
Afterwards, in freshness protection package carbon dioxide volumn concentration, %；H- bags of high, m；diHCOThe width of function film 4 in-sack, according to
Formula (3) and (4), take the higher value in both, m；diHMThe width of function film 5, m in-sack；WVTR- function films 5
Moisture-vapor transmission, g/m224hr100%RH；RH- gases reach after balance that relative humidity in freshness protection package, unit is %；
RH0The relative humidity of-outside air, unit %；CCO2、CO2Take the atmosphere composition that fruit and vegetable preservation is optimal；WVTR is HM vapor
Transmitance.
11. the preparation method of the multifunctional unit freshness protection package according to claim 1, it is characterised in that be prepared into first multi-functional
Integrated thin-film coiled material, is then prepared into multifunctional unit freshness protection package.
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| CN110421944A (en) * | 2019-08-15 | 2019-11-08 | 郑文冉 | The antibacterial preserving fruit and vegetable utilizing material and preparation method of a kind of decomposing ethylene and slow-release function |
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Correction item: Claims|Description Correct: Claims 1-10 submitted on December 8, 2020|Paragraphs 1-68 of the specification submitted on November 26, 2020 False: Claims 1-11 submitted on May 10, 2017|Paragraphs 1-68 of the specification submitted on May 25, 2015 Number: 28-02 Page: ?? Volume: 33 |
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Effective date of registration: 20210202 Address after: 100089 1005, 1st floor, area A8, block D, Xisanqi culture and Technology Park, 27 xixiaokou Road, Qinghe Xiaoying, Haidian District, Beijing Patentee after: Beijing Jianzhen fresh keeping Technology Co.,Ltd. Address before: 102600 Daxing District Xinghua street, Beijing (two paragraph) 1 Patentee before: BEIJING INSTITUTE OF GRAPHIC COMMUNICATION |