CN104974490A - Preservative film, preparation and application - Google Patents
Preservative film, preparation and application Download PDFInfo
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- CN104974490A CN104974490A CN201510398785.7A CN201510398785A CN104974490A CN 104974490 A CN104974490 A CN 104974490A CN 201510398785 A CN201510398785 A CN 201510398785A CN 104974490 A CN104974490 A CN 104974490A
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- film
- aluminium silicate
- pure aluminium
- powder
- preservative film
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
A preservative film, preparation and application, belonging to the technical field of packaging materials. The polylactic acid film modified by aluminum silicate, wherein the content of aluminum silicate porous powder is 5-15 wt%, the silicon-aluminum ratio of the aluminum silicate porous powder is 25-28, and the average grain diameter of the powder is 1-5 microns. The preservative film has high water vapor permeability, moderate oxygen transmission rate and carbon dioxide permeability, and also has ethylene removal (ethylene adsorption) performance, when the preservative bag with four active functions is filled with cherries, a self-modified atmosphere environment with low carbon dioxide concentration and low oxygen (relative to air) is formed in the preservative bag, and the preservative film is particularly suitable for the preservation of the cherries and can preserve the cherries for 4-6 days at normal temperature.
Description
Technical field
The present invention relates to a kind of preservative film, for cherry normal-temperature fresh-keeping, belong to field of packaging material.
Background technology
Still continue respiration after fresh fruit picking, nutritive ingredient is oxidized, and releases heat, produces the meta-bolitess such as moisture, carbonic acid gas, ethene; Under normal temperature environment, fruits and vegetables respiratory rate is stronger, easier old and feeble, the dehydration of fruits and vegetables and lose commercial value; In the closed environment that common freshness protection package is formed, breathe the ethene, carbonic acid gas and the moisture that produce and can not be rejected to the external world in time, in freshness protection package, enrichment can occur.The ethene of enrichment can accelerate fruits and vegetables respiratory rate, accelerates fruits and vegetables maturation; The high humidity environment that the moisture that respiration produces is formed in freshness protection package, makes fruits and vegetables more easily grow pathogenic bacteria, causes fruits and vegetables to rot; The carbonic acid gas of higher concentration also can impel some fruit that old and feeble, rotten or brown stain occur.Therefore reduce the respiratory rate of fruits and vegetables, keep low humidity storage condition, prevent growing pathogenic bacteria, set up a suitable hypoxemia, low carbon dioxide atmosphere is the key solving preserving fruit and vegetable utilizing problem, people develop many fruit and vegetable preserving methods and technology for this reason, such as low temperature, controlled atmosphere, dipping, pharmacy fumigation etc.
Poly(lactic acid) is a kind of renewable, degradable macromolecular material, has higher water vapor transmission rate (WVTR) and OTR oxygen transmission rate, compares and be suitable as Fresh-Keeping Packaging Materials, but is that raw material prepares the research report of fruit fresh-keeping bag specially seldom with poly(lactic acid).Patent CN103252964A discloses a kind of polylactic acid film and preparation method thereof, and this film comprises poly(lactic acid) sandwich layer and is attached to the smooth upper layer of at least one side surface of described poly(lactic acid) sandwich layer; CN104312121A then discloses a kind of method improving polylactic resin toughness; CN104387732A toughner, lubricant, opening agent etc. increase toughness, the transparency of polylactic acid film; CN103232689A utilizes the toughness of softening agent, polynite, antioxidant raising poly(lactic acid); CN104479315A is then by adding modified montmorillonoid, modified kaolin or modified white carbon black as toughener, and epoxies acrylic copolymer is as compatilizer, and polydactyl acid, increases the toughness of polylactic acid film; CN103724957A utilize layered nano silicate, xylogen, compatilizer and superfine titanic oxide to improve poly(lactic acid) mechanical property, increase the transparency and flexibility; The technique that CN103232691A then discloses and a kind ofly utilizes modified superfine calcium carbonate, static inhibitor improves polylactic acid film antistatic property; CN102702702A utilizes polylactic resin and more carboxyl polymer to prepare polylactic acid modified film, and its elongation at break and intensity all have obvious raising; CN101250295 discloses a kind of PE modified polylactic acid degradable film utilizing 50% ~ 80% weight part; CN101328307 utilizes poly(lactic acid) and other resin alloy to prepare the film of low water vapor transmission rate (WVTR) (15 ~ 25g/m224h); CN102241876A utilizes modified Nano grade silicon dioxide, softening agent, oxidation inhibitor, lubricant modified poly(lactic acid), improves tensile strength and the elongation at break of polylactic acid film; CN104048958A is that base material is prepared one and can be indicated CO in freshness protection package with polylactic acid film
2the food freshness indicating card of concentration.
From upper surface analysis, be that raw material prepares the correlative study of wrapping material mainly with the raising strength of materials with poly(lactic acid), improve barrier, improve for the purpose of toughness, properties-correcting agent used mostly is nano silicon, softening agent, oxidation inhibitor, lubricant, titanium dioxide, polynite, kaolin or modified white carbon black etc., and although preservative film involved in the present invention also adopts poly(lactic acid) to be raw material preparation, but this polylactic acid film has significantly different from above-mentioned poly(lactic acid) relevant report, polylactic acid film of the present invention has higher water vapor transmission, moderate OTR oxygen transmission rate and carbon dioxide transmission rate, and ethylene absorption totally four kinds of active functions.
Summary of the invention
The object of this invention is to provide a kind of preservative film with higher water vapor transmission, moderate OTR oxygen transmission rate and carbon dioxide transmission rate and ethylene absorption totally four kinds of active functions, for the preparation of freshness protection package, preserve fruit, especially cherry.
Preservative film of the present invention is the polylactic acid film of pure aluminium silicate modification, preservative film thickness is 10-20 micron, wherein dispersed in preservative film have pure aluminium silicate voluminous powder, pure aluminium silicate voluminous powder content is 5-15wt%, the silica alumina ratio of this pure aluminium silicate voluminous powder is 25-28, and the median size of powder is 1-5 micron.
The preparation of preservative film:
(1) the pure aluminium silicate voluminous powder that silica alumina ratio is 25-28 is first prepared;
Aluminum nitrate is neutralized into Alkaline Sodium Aluminate Solution by sodium hydroxide, then mix with certain mol ratio (Si:Al=25-28) with water glass (water glass), this mixed solution sulfuric acid is neutralized to PH=6.5-5.5, generate gel, be heated to 80-95 DEG C with vigorous stirring and generate porous silica gel, then sedimentation, immersion, washing, filtration, drying are (as 120-150 DEG C, 5 hours), calcination (as 550-600 DEG C, 2 hours), pulverize obtain the pure aluminium silicate powder that particle diameter is 1-5 micron.
(2) production modified polylactic resin; Be after the pure aluminium silicate voluminous powder of 25-28 and polylactic resin mechanical blending by silica alumina ratio, granulation after melt blending at 160-190 DEG C on the twin screw extruder.
(3) prepare on film casting production line, the thickness of film is 10-20 micron.As adopted the technique of production four active function normal-temperature fresh-keeping bag.
Preservative film of the present invention for the preparation of Fruit fresh-preservation bag, and is exclusively used in the preservation of cherry.
The synthetic aluminium silicate voluminous powder institute modification that described poly(lactic acid) is 25-28 by a kind of silica alumina ratio, this aluminium silicate powder foot couple ethene has Selective absorber, absorb the ability of ethene not by the impact of steam, 1 gram of this powder can absorb 3 liters of ethylene gas, this powder with specific silicon aluminum ratio is blended into after in polylactic acid film, this polylactic acid film has just possessed ethylene absorption active function, diameter is that the pure aluminium silicate powder particle dispersion of 1-5 micron is in the polylactic acid film of 10-20 micron thickness, the wetting ability of pure aluminium silicate adds the perviousness of film to water vapour, make the water vapor transmission rate (WVTR) of film up to 60-200g/m
2.day.atm, the pure aluminium silicate of porous adds the transmitance of film to oxygen and carbonic acid gas, makes the transmitance of film to oxygen and carbonic acid gas reach 10
4-10
5ml/m
2.day.atm.The higher water vapor transmission rate (WVTR) that this pure aluminium silicate polydactyl acid film has, ensures the humidity environment that in freshness protection package, formation one is lower, prevents moisture from condensing inside film, also avoids high humidity environment to induce breed bacteria; For the fruit of this kind of not storage endurances such as cherry, the OTR oxygen transmission rate of general packaging film and carbon dioxide transmission rate are difficult to meet the fresh-keeping requirement under its normal temperature, because too low usually initiation of ventilation property is crossed presenility by fresh-keeping fruit because of anoxic and carbon dioxide enrichment, shelf-life shortens on the contrary.The special four active function normal-temperature fresh-keeping bags of cherry of the present invention solve these problems.With fruit such as the fresh-keeping cherries of this freshness protection package, the controlled atmosphere environment of a hypoxemia (relative to air), low carbon dioxide, low humidity just can be formed in this freshness protection package, and film can absorb the ethylene gas that cherry respiration produces, eliminate ethene to the dematuration of cherry, 4-6 days can be reached for fresh-keeping cherry under normal temperature, fruit infection rate, lower than 10%, is still kept vivid green by fresh-keeping cherry, and mouthfeel does not have difference compared with when just plucking.
Embodiment
Utilize bag production line that the polydactyl acid film obtained is sealed into the freshness protection package that physical dimension is the three side sealing of 22 × 25 centimetres.This freshness protection package has water vapor transmission, moderate OTR oxygen transmission rate and carbon dioxide transmission rate and ethylene absorption totally four kinds of active functions, is particularly suitable for large cherry at normal temperatures fresh-keeping.
Performance test
The ethylene absorption performance test of pure aluminium silicate powder: take powder after 1 gram of calcination, be placed in ethylene gas, measures powder weightening finish, is then converted into the standard volume of ethene.
The ventilation property test of pure aluminium silicate polydactyl acid film: the test of water vapor transmission rate (WVTR) is according to " GB/T 1037-88 plastics film and sheet material water vapor permeability test method ", and it is 50cm that film is cut into area
2circle, adopts the model of Mocon company of the U.S. to be the test of Model 3/33 water vapor permeation rate tester; According to the OTR oxygen transmission rate of " GB/T 1038-2000 plastics film and thin slice gas-premeable test method pressure differential method " testing film, testing tool to be Mocon company of U.S. model be 8001 OTR oxygen transmission rate tester.
Each fresh-keeping packed 500 grams of large cherry, test the gas concentration lwevel in freshness protection package and oxygen concentration every day.
Below in conjunction with embodiment the present invention done and illustrate furtherly, but the present invention is not limited to following examples.
Embodiment 1
Take 613 grams of ANN aluminium nitrate nonahydrate (Al (NO
3)
39H
2o), be dissolved in the distilled water of 10000 milliliters, under the condition stirred, be neutralized to PH=10 with the sodium hydroxide solution of 5mol/L; Then the sodium silicate water glass being 40 ° of Be with 10000 grams of degree Beaume mixes, and is neutralized to PH=5.5 while stirring, is then warming up to 95 DEG C with the sulphuric acid soln of 5mol/L, vigorous stirring 1 hour; Stop stirring, sedimentation, be separated, filter, filter cake is washed with distilled water to sulfate radical-free ion, dries 5 hours for 140 DEG C, then 600 DEG C of roastings 2 hours, then utilizing Jet Mill to be crushed to median size is 1 micron, obtains the pure aluminium silicate powder that silica alumina ratio is 28.
Be pure aluminium silicate powder and the granulation of 4500 grams of polylactic resin melt blendings of 28 by 500 grams of silica alumina ratios above, then pellet curtain coating become the film of 10 microns.The OTR oxygen transmission rate (OTR) of testing film and water vapor transmission rate (WVTR) (CO
2tR), utilize bag production line that this polylactic acid film is prepared into the freshness protection package that physical dimension is the three side sealing of 22 × 25 centimetres, load 500 grams of large cherry post heat-seal, deposit in the environment of 25 ± 5 DEG C, to test in freshness protection package headspace gas composition every day, and the decayed fruit rate (courses of infection rate) of cherry in freshness protection package.
Embodiment 2
Take 686 grams of ANN aluminium nitrate nonahydrate (Al (NO
3)
39H
2o), be dissolved in the distilled water of 10000 milliliters, under the condition stirred, be neutralized to PH=10 with the sodium hydroxide solution of 5mol/L; Then the sodium silicate water glass being 40 ° of Be with 10000 grams of degree Beaume mixes, and is neutralized to PH=6.5 while stirring, is then warming up to 80 DEG C with the sulphuric acid soln of 5mol/L, vigorous stirring 1 hour; Stop stirring, sedimentation, be separated, filter, filter cake is washed with distilled water to sulfate radical-free ion, and dry 5 hours for 150 DEG C, then 550 DEG C of roastings 2 hours, then utilizing Jet Mill to be crushed to particle diameter is 5 microns, obtains the pure aluminium silicate powder that silica alumina ratio is 25.
Be pure aluminium silicate powder and the granulation of 4500 grams of polylactic resin melt blendings of 25 by 500 grams of silica alumina ratios, then pellet curtain coating become the film of 10 microns.The OTR oxygen transmission rate (OTR) of testing film and water vapor transmission rate (WVTR) (CO
2tR), utilize bag production line that this polylactic acid film is prepared into the freshness protection package that physical dimension is the three side sealing of 22 × 25 centimetres, load 500 grams of large cherry post heat-seal, deposit in the environment of 25 ± 5 DEG C, to test in freshness protection package headspace gas composition every day, and the decayed fruit rate (courses of infection rate) of cherry in freshness protection package.
Embodiment 3
Take 636 grams of ANN aluminium nitrate nonahydrate (Al (NO
3)
39H
2o), be dissolved in the distilled water of 10000 milliliters, under the condition stirred, be neutralized to PH=10 with the sodium hydroxide solution of 5mol/L; Then the sodium silicate water glass being 40 ° of Be with 10000 grams of degree Beaume mixes, and is neutralized to PH=6.0 while stirring, is then warming up to 85 DEG C with the sulphuric acid soln of 5mol/L, vigorous stirring 1 hour; Stop stirring, sedimentation, be separated, filter, filter cake is washed with distilled water to sulfate radical-free ion, and dry 5 hours for 140 DEG C, then 570 DEG C of roastings 2 hours, then utilizing Jet Mill to be crushed to particle diameter is 3 microns, obtains the pure aluminium silicate powder that silica alumina ratio is 27.
Be pure aluminium silicate powder and the granulation of 4500 grams of polylactic resin melt blendings of 27 by 500 grams of silica alumina ratios, then pellet curtain coating become the film of 15 microns.The OTR oxygen transmission rate (OTR) of testing film and water vapor transmission rate (WVTR) (CO
2tR), utilize bag production line that this polylactic acid film is prepared into the freshness protection package that physical dimension is the three side sealing of 22 × 25 centimetres, after loading 500 grams of large cherry, tighten sack, deposit in the environment of 25 ± 5 DEG C, to test in freshness protection package headspace gas composition every day, and the decayed fruit rate (courses of infection rate) of cherry in freshness protection package.
Comparative example 1
Commercially available thickness is utilized to be the food-grade polyethylene preservative film of 10 microns, be prepared into the freshness protection package that physical dimension is the three side sealing of 22 × 25 centimetres, load 500 grams of large cherry post heat-seal, deposit in the environment of 25 ± 5 DEG C, to test in freshness protection package headspace gas composition every day, and the decayed fruit rate (courses of infection rate) of cherry in freshness protection package.
Comparative example 2
Commercially available thickness is utilized to be the food polyethylene film of 20 microns, be prepared into the freshness protection package that physical dimension is the three side sealing of 22 × 25 centimetres, load 500 grams of large cherry post heat-seal, deposit in the environment of 25 ± 5 DEG C, to test in freshness protection package headspace gas composition every day, and the decayed fruit rate (courses of infection rate) of cherry in freshness protection package.
Comparative example 3
Large cherry is naked to be placed in the air ambient of 25 ± 5 DEG C, observes decayed fruit situation
Table 1 and table 2 list utilize the present invention to prepare four active function freshness protection packages to the fresh-keeping effect of large cherry.Very easily dehydration is softening for the naked large cherry (comparative example 3) put in atmosphere, grow pathogenic bacteria, nakedly put the 3rd day fruit 50% and occur softening, 20% there is mildew, and lose commercial value, the naked cherry shelf-lives put is short, only have about 2 days, major cause is the cherry after adopting, and metabolic rate is vigorous in atmosphere, ripe rapidly, softening; The cherry that (comparative example 1) preserves in common preservative film, because the air concentration in polyethylene preservative film is lower than the oxygen concentration of extraneous 20%, the respiratory rate of cherry can be reduced to a certain extent, but because this film is very low to the transmitance of water vapour, the moisture enrichment in preservative film produced breathed by cherry, relative humidity in bag (RH) is caused to increase, therefore store under normal temperature and put the easier generation of group rot than naked, preserve after 3 days, in bag, RH enrichment makes cherry rot rapidly; Cherry in 20 microns of PE films (comparative example 2), because sack ventilation property is poorer, causes cherry to breathe the steam produced and is difficult to get rid of, only had 1 day by fresh-keeping cherry shelf-lives.Four active function antistaling films of the present invention, bag internal oxygen gas concentration is lower than extraneous 2-5%, inhibit the breathing of cherry, slow down the generation of climacteric, the freshness protection package of this type has cross-country traveling ability to water vapour, cherry can be got rid of in time and breathe the moisture generated, keep RH lower in bag, suppress to grow pathogenic bacteria, in freshness protection package gas concentration lwevel comparatively control group 1 and control group 2 low, be beneficial to the fresh-keeping of cherry, prevent cherry old and feeble, the cherry outward appearance fresh-keeping by four active function freshness protection packages described in this patent is as before vivid, mouthfeel is without any change, cherry when fresh-keeping 6 days also has commercial value, decayed fruit is lower than 10%.Four active function freshness protection packages described in this patent are fresh-keeping, and to be particularly suitable under the fruit normal temperature such as cherry fresh-keeping.
The performance index of table 1 pure aluminium silicate polydactyl acid film and the fresh-keeping fresh fruit to large cherry
Table 2 pure aluminium silicate polydactyl acid film is to the fresh-keeping effect of large cherry
Claims (6)
1. a fruit freshness preserving film, is characterized in that, is the polylactic acid film of pure aluminium silicate modification, wherein dispersed in preservative film have pure aluminium silicate voluminous powder, pure aluminium silicate voluminous powder content is 5-15wt%, and the silica alumina ratio of this pure aluminium silicate voluminous powder is 25-28, and the median size of powder is 1-5 micron.
2. a kind of fruit freshness preserving film of claim 1, is characterized in that, preservative film thickness is 10-20 micron.
3. prepare the method for a kind of fruit freshness preserving film of claim 1 or 2, it is characterized in that, comprise the following steps:
(1) the pure aluminium silicate voluminous powder that silica alumina ratio is 25-28 is first prepared;
(2) production modified polylactic resin; Be after the pure aluminium silicate voluminous powder of 25-28 and polylactic resin mechanical blending by silica alumina ratio, granulation after melt blending at 160-190 DEG C on the twin screw extruder;
(3) prepare on film casting production line.
4. according to the method for claim 3, it is characterized in that, silica alumina ratio is the preparation of the pure aluminium silicate voluminous powder of 25-28: aluminum nitrate is neutralized into Alkaline Sodium Aluminate Solution by sodium hydroxide, then with water glass with certain mixed in molar ratio, this mixed solution sulfuric acid is neutralized to PH=6.5-5.5, generates gel, is heated to 80-95 DEG C with vigorous stirring and generates porous silica gel, then sedimentation, immersion, washing, filtration, drying, calcination, pulverize and obtain the pure aluminium silicate powder that particle diameter is 1-5 micron.
5. the preservative film of claim 1 or 2 is for the preparation of Fruit fresh-preservation bag.
6. the preservative film of claim 1 or 2 is for the preparation of cherry freshness protection package.
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|---|---|---|---|
| CN201510398785.7A CN104974490B (en) | 2015-07-08 | 2015-07-08 | Preservative film, preparation and application |
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| CN104974490B CN104974490B (en) | 2016-09-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385126A (en) * | 2015-12-17 | 2016-03-09 | 梅庆波 | Polylactic acid / porous geopolymer composite material preparation method |
| CN106987106A (en) * | 2017-04-21 | 2017-07-28 | 戴琪 | A kind of preparation method for removing ethene antibacterial and mouldproof fruit-vegetable plastic wrap |
| CN107641300A (en) * | 2017-10-09 | 2018-01-30 | 常州美帛纺织品有限公司 | A kind of preparation method of vapor-permeable type polyethylene terephthalate thin film |
| CN114956107A (en) * | 2022-07-15 | 2022-08-30 | 大家智合(北京)网络科技股份有限公司 | Modified aluminum silicate powder and preparation method thereof, degradable composite membrane and preparation method and application thereof |
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| CN101967245A (en) * | 2010-10-22 | 2011-02-09 | 北京印刷学院 | Fruit-preserving green packing material with ethylene adsorption function and preparation method thereof |
| CN102827464A (en) * | 2012-09-04 | 2012-12-19 | 天津盛天利材料科技有限公司 | Environment friendly biological preservative film and preparation method thereof |
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| CN101235156A (en) * | 2007-11-16 | 2008-08-06 | 江苏科技大学 | Polylactic acid/thermoplastic starch extrusion blow molding film and its producing method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105385126A (en) * | 2015-12-17 | 2016-03-09 | 梅庆波 | Polylactic acid / porous geopolymer composite material preparation method |
| CN106987106A (en) * | 2017-04-21 | 2017-07-28 | 戴琪 | A kind of preparation method for removing ethene antibacterial and mouldproof fruit-vegetable plastic wrap |
| CN107641300A (en) * | 2017-10-09 | 2018-01-30 | 常州美帛纺织品有限公司 | A kind of preparation method of vapor-permeable type polyethylene terephthalate thin film |
| CN114956107A (en) * | 2022-07-15 | 2022-08-30 | 大家智合(北京)网络科技股份有限公司 | Modified aluminum silicate powder and preparation method thereof, degradable composite membrane and preparation method and application thereof |
| CN114956107B (en) * | 2022-07-15 | 2023-11-07 | 大家智合(北京)网络科技股份有限公司 | Modified aluminum silicate powder and preparation method thereof, degradable composite film and preparation method and application thereof |
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| CN104974490B (en) | 2016-09-28 |
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