CN112009859A - Special mould-proof, dust-proof and fresh-keeping net bag for sugar-cored apples and preparation method thereof - Google Patents

Special mould-proof, dust-proof and fresh-keeping net bag for sugar-cored apples and preparation method thereof Download PDF

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CN112009859A
CN112009859A CN202010854962.9A CN202010854962A CN112009859A CN 112009859 A CN112009859 A CN 112009859A CN 202010854962 A CN202010854962 A CN 202010854962A CN 112009859 A CN112009859 A CN 112009859A
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proof
fresh
keeping
net
parts
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CN112009859B (en
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王露茵
李喜宏
杜美军
韩双胜
邵重晓
朱艺
王猛
郭根林
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Aksu Yuneng Agricultural Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D29/00Sacks or like containers made of fabrics; Flexible containers of open-work, e.g. net-like construction
    • B65D29/04Net-like containers made of plastics material
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154Organic compounds; Microorganisms; Enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00Methods preventing fouling
    • B08B17/02Preventing deposition of fouling or of dust
    • B08B17/06Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D28/00Producing nets or the like, e.g. meshes, lattices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D29/00Sacks or like containers made of fabrics; Flexible containers of open-work, e.g. net-like construction
    • B65D29/02Sacks with laminated or multiple walls
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/30Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure
    • B65D85/34Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure for fruit, e.g. apples, oranges or tomatoes
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Engineering & Computer Science (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention relates to a mould-proof, dust-proof and fresh-keeping special net bag for sugar-cored apples and a preparation method thereof, wherein the method comprises the following process flows of: mixing ingredients, heating to melt, introducing foaming agent to foam, double-layer extrusion by a net sleeve extrusion unit, cooling to form, spraying sodiumRice mildew-proof and fresh-keeping material and mesh structure part spraying CO2Gas sensitive material, cooling solid type. The original low-density polyethylene is used as a main raw material and modified, the extrusion process is improved, the limited expansion enables the sizes of the pores in the net to be staggered and orderly arranged, and the recovery is improved by 20%. The modified material has the characteristics of static resistance and strong hydrophobicity, and effectively repels dust falling adsorption. In addition, CO is innovated2The gas-sensitive material is sprayed on the mesh structure part of the net cover, the gas-sensitive material consists of a wall material and a wall core, and the wall material consists of La1Ca2FeO3Is prepared by crosslinking nano material and alcohol soluble protein, and has inner side of CO2Concentration of gas sensitive material>When the content of the active ingredients is 2%, the wall-breaking slow-release antioxidant fresh-keeping substances are broken, the material net cover also has the effects of preventing mildew and inhibiting microorganisms in a broad spectrum, and the substances act on the surfaces of fruits to effectively delay the ageing and softening of the fruits.

Description

Special mould-proof, dust-proof and fresh-keeping net bag for sugar-cored apples and preparation method thereof
Technical Field
The invention belongs to the field of fruit and vegetable fresh-keeping processing, relates to a fresh-keeping bag preparation technology, and particularly relates to a mould-proof, dust-proof and fresh-keeping special net cover bag for a sugar core apple and a preparation method thereof.
Background
The sugar core apples are mainly produced in areas such as Aksu in Xinjiang, have fine and smooth pulp and transparent kernels, have strong fruit aroma, thick sweet taste and rich nutritional value compared with common apples, and are transported to markets all over the country after being matured every year. However, the sugar core apples are not storage-resistant, and the mechanical damage and dust pollution in the storage and transportation process can aggravate the fruit mildew and rot, reduce the appearance quality and cause great economic loss.
Aiming at the problems, at present, picked sugar-cored apples are subjected to fresh-keeping packaging by using a pearl cotton net bag, and the pearl cotton net bag is a high-foam polyethylene product which is produced by extruding low-density polyethylene (LDPE) serving as a main raw material and has the advantages of moisture resistance, shock resistance and the like. The use of the pearl cotton net bag reduces the collision damage of the sugar core apple fruits to a certain extent, and the common use of the disease bag aiming at the disease prevention and control of the fruit storage and transportation can realize the sensing detection of gases such as ethylene, and the like, discover the diseases as early as possible and prevent and control the diseases in time, but the application and popularization are not good due to the difficult specific implementation, high cost and difficult maintenance.
Through a search of the existing published patent documents, the following several related published patent documents are found:
1. a fruit mesh bag (publication number: CN209536000U) comprises a woven bag body formed by weaving warps and wefts, wherein a bag inlet is formed in the upper end of the woven bag body, a lifting opening is formed in the side portion, close to the bag inlet, of the woven bag body, protective blocks made of latex are sleeved on the wefts below the lifting opening and the wefts at the bottom of the woven bag body, the protective blocks are oval, wrapping rings in oval opening shapes are respectively arranged on the end faces of the two sides of each protective block in a protruding mode, and a plurality of separation grooves are formed in each wrapping ring. Thus, the technical effect of good protection performance is realized.
2. A disease sensing sleeve bag (publication number: CN110012763A) is provided, which is used for protecting an object in the disease sensing sleeve bag and comprises a first surface and a second surface, wherein the second surface is opposite to the first surface and is positioned on the same side of the object, and the material of the disease sensing sleeve bag comprises Polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP) or a combination thereof. The disease sensing sleeve bag can be used for sensing ethylene released by objects in the sleeve bag due to external factors so as to early discover infected objects in the disease sensing sleeve bag.
3. A packaging method for preventing grape from being collision and fresh-keeping in transportation (publication number: CN201610069622.9) discloses a packaging method for preventing grape from being collision and fresh-keeping in transportation, which comprises an inner package, wherein the inner package method comprises the following steps: pretreating grapes, and tightly wrapping the pretreated grapes with a flexible material; the pretreatment method comprises the following steps: and (3) cutting and removing the protruded grape stalks to ensure that cut surfaces of the cut grape stalks do not contact with the grape fruit grains. The packing method provided by the invention greatly improves the completeness of the grapes in the long-distance transportation process, and prevents the grapes from being cracked and rotten due to the falling of fruit grains and the falling of the grapes caused by collision and extrusion generated by transportation bumping; the grape preservative can also play a role in keeping the grape fresh without additionally using a preservative and a preservative.
Compared with the present invention, the above-mentioned patent publications have similar technical problems, but have different technical features, and the technical features and the technical effects caused by the different technical features are not described in the above-mentioned patent publications.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the special mould-proof, dust-proof and fresh-keeping net bag for the sugar core apples, which is prepared from the modified low-density polyethylene as the main raw material by improving the pressurizing process, has the characteristics of static resistance and strong hydrophobicity, effectively avoids dust adsorption and has the mould-proof and fresh-keeping effects, and the preparation method thereof.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a sugar core apple mould-proof dust-proof fresh-keeping special-purpose net bag and a preparation method thereof, the method comprises the following process flows: mixing ingredients → heating and melting → foaming by introducing foaming agent → double-layer extrusion of net sleeve extrusion unit → cooling and forming → spraying nano mildew-proof and fresh-keeping material → spraying CO on the mesh structure part2Gas sensitive material → cooling solid type.
And the ingredients comprise mesh inner layer ingredients and mesh outer layer ingredients, wherein the mesh inner layer ingredients comprise the following components in parts by mass: 80-95 parts of high-pressure low-density polyethylene and 7-10 parts of polyurethane, wherein the mesh outer layer comprises the following ingredients in parts by mass: 70-75 parts of polyurethane, 4-5 parts of modified nano silicon dioxide, 10-12 parts of polymethyl methacrylate, 7-8 parts of acrylic resin and 2-3 parts of talcum powder.
Moreover, the preparation method of the modified nano silicon dioxide comprises the following steps:
dissolving 2.0g of hexadecyl trimethyl ammonium bromide and 2.0g of gelatin in 100mL of deionized water, then adding 100mL of anhydrous ethanol and 15mL of 26.5% and 0.20mol/L ammonia water, stirring for 20min, and then adding 1.7g of tetraethoxysilane;
continuously stirring the mixed solution obtained in the step for 4 hours at room temperature, centrifugally washing the mixed solution with deionized water, drying the mixed solution in vacuum at 45 ℃, roasting the dried mixed solution for 5 hours at 680 ℃, and obtaining white nano SiO, wherein the heating rate is 15 ℃/min2
Obtaining 2g of the ground material, and obtaining the white SiO2Activating at 110 ℃ for 5h, dispersing in 100mL of absolute ethanol after activation, transferring to a three-neck flask with magnetic stirring and condensation reflux, and starting heating and stirring;
fourthly, when the mixture is stirred uniformly and the temperature rises to 75 ℃, adding 2-3mL of hexamethyldisilazane and 4-5 drops of dibutyltin dilaurate, and continuously heating and refluxing for 5 hours;
after the reaction is finished, cooling to room temperature, performing centrifugal separation, washing for 3 times with anhydrous ethanol, and performing vacuum drying at 40 ℃ for 36 hours.
And the heating and melting process comprises the steps of heating the mixture of the ingredients at the inner layer of the mesh to 165 ℃, heating the mixture at the outer layer of the mesh to 180 ℃, respectively forming softened mixtures, increasing the temperature of the softened mixtures to 210 ℃, introducing a foaming agent with the mass part of 10-15% of the softened mixture, respectively foaming and expanding the two softened mixtures to form compact micro-aerated molecules in the softened matters, cooling the two foamed softened mixtures to 100 ℃, sending the foamed mixtures into a mesh sleeve extrusion unit, carrying out frequency conversion extrusion to expand the materials again to generate larger aerated molecules, cooling and forming an extruded product into a mesh material to obtain a foam mesh, spraying a layer of nano mildew-proof and freshness-keeping material on the inner side of the cooled and formed foam mesh, namely the side directly contacting with the fruits, and spraying CO on the mesh structure part2Gas sensitive material, and then cooling the solid form.
Moreover, the foaming agent is N, N '-dimethyl-N, N' -dinitrosoterephthalamide with 70 percent of effective components, wherein the foaming agent comprises the following components in parts by mass:
60-70 parts of N, N '-dimethyl-N, N' -dinitrosoterephthalamide;
25-35 parts of resin;
the gas evolution is 126 mL/g.
Moreover, the conversion frequency of the net extruder is 55-80 Hz, the frequency is changed alternately, the retention time is 5s, the frequency conversion period is 10s, and the length-diameter ratio of a screw of the net extruder is as follows: 1: 50, die head motor power: 3KW, main motor power: 11KW, cutting machine motor power: 1.5KW, total power of heating ring: 18KW, power of the motor of the heat pump: 0.55KW, nitrogen pump motor power: 1.1KW, fan power: 480W, total power consumption: 220KW/24h, yield: 500-900kg/24h, the external dimension (mm) of the host machine: 5000 × 700 × 1350, unit weight: 2900kg, footprint (mm): 3000X 9000.
Moreover, the processing method of the nanometer mildew-proof fresh-keeping material comprises the following steps: mixing foamed polyurethane with nano TiO2Fully stirring and crosslinking under the negative pressure condition of 80-85 ℃, wherein the foaming aerated molecules are absolute ethyl alcohol steam, and fresh-keeping slow-release components are mixed and dissolved in the steam, and the fresh-keeping slow-release components comprise the following components in parts by mass:
Figure BDA0002646101630000031
furthermore, the sol-gel method is adopted to prepare CO2The specific process flow of the gas sensitive material is as follows:
⑴La1Ca2FeO3preparing nanocrystalline powder:
weighing 2.5g of lanthanum nitrate, 3g of calcium nitrate and 2g of ferric nitrate according to a stoichiometric ratio, mixing, dissolving in 100mL of deionized water, mixing, and adding 2g of citric acid to prepare a solution;
secondly, the solution is placed in a water bath kettle to be heated and stirred, 10mL of polyethylene glycol is added, and the mixture is stirred until gel is formed;
taking out the gel, drying, sintering and forming to obtain pure La1Ca2FeO3A nanocrystalline powder material;
⑵CO2preparing a gas-sensitive capsule wall material: 5-6 parts of soybean protein isolate and 6-8 parts of corn starch → 10-12 parts of distilled water → 0.5-1 part of glycerol and 0.1-0.3 part of La1Ca2FeO3Nanoparticle → 7.6 value of p h → magnetic stirring for 40min → water bath stirring → cooling to room temperature → adding 0.2-0.3 part of MTGase enzyme with 2-6U/g activity → 4000r/min homogenizing for 30s → gelatinizing at room temperature to obtain CO2A gas-sensitive capsule wall material;
⑶CO2preparing a gas-sensitive capsule core material: compounding with absolute ethyl alcoholC,VEAnd procyanidin as core material, and chitosan, VC,VEAnd procyanidins according to 3: 1: 1: mixing at a ratio of 1, stirring at high speed under shaking to obtain sustained-release fresh-keeping antioxidant nanopowder, gradually adding antioxidant nanopowder into 100mL of 99% anhydrous ethanol, stirring at 25-30 deg.C and stirring speed of 450r/min for 1h, ultrafiltering the obtained emulsion at 4 deg.C and 10000r/m, centrifuging for 30min to obtain precipitate which is CO as sustained-release fresh-keeping antioxidant component2A gas-sensitive capsule core material;
fourthly, stirring for 60 minutes at 350 rpm by taking the wall-core ratio of 4:1 and the homogeneous emulsifier Tween-80 as 0.1%, standing for 24 hours at 4 ℃ to prepare a white sticky substance, adding the white sticky substance into a 3% zein solution, stirring uniformly, and filtering to obtain a mixed solution;
and fifthly, mixing and stirring the mixed solution uniformly, spraying the mixed solution to the inner side of the formed net sleeve, and curing at normal temperature for 24 hours.
The invention has the advantages and positive effects that:
1. aiming at the problem of poor dustproof effect of the existing apple mesh bag, the invention sprays a layer of compact material with strong antistatic and hydrophobic properties on the surface layer of the foamed pearl wool, and the material is prepared from Thermoplastic Polyurethane (TPU) with strong waterproof and air-permeable capabilities and hydrophobically modified nano silicon dioxide (SiO)2) The material is formed by cross-linking and polymerizing with polymethyl methacrylate (PMMA) with an antistatic function, the cross-linking adhesive is acrylic resin, and the material is sprayed on the peripheral part which is not in direct contact with the apples, so that the long-term dustproof effect of the fruits is realized.
2. Aiming at the mildew-proof function of the existing apple mesh bagThe problem is solved by spraying a layer of slow-release long-acting nano mildew-proof material on the part of the mesh bag, which is close to the fruit, wherein the material is prepared from foamed polyurethane and nano TiO2The slow-release mildew inhibitor is formed by cross-linking, has a microporous structure, is prepared from a slow-release carrier which is absolute ethyl alcohol, and is prepared from sodium nitroprusside, gibberellin, polylysine and chitosan, and can realize long-acting bacteriostasis and mildew prevention of apples.
3. The invention converts CO into2The gas-sensitive material is sprayed on the mesh structure part of the net cover, the gas-sensitive material consists of a wall material and a wall core, and the wall material consists of La1Ca2FeO3Nanometer materials and prolamin. La1Ca2FeO3Nanocrystal pair CO2Gas is very sensitive, and the La prepared by the method of the invention1Ca2FeO3CO in the environment of the nanocrystal powder2Active target recognition above 2% and CO2Combine to result in La1Ca2FeO3The chelating sites of the protein are broken, the wall materials form pores, so that the content in the wall core can slowly volatilize, the content in the wall core is a volatile antioxidant mixture, and the substance acts on the fruits to realize the effects of scavenging free radicals and delaying the aging of the fruits.
4. The invention takes the original low-density polyethylene as the main raw material and modifies the low-density polyethylene, improves the extrusion process, and realizes the staggered and ordered arrangement of the sizes of the pores in the net silk by the restrictive expansion, thereby improving the recovery by 20 percent. The modified material has the characteristics of static resistance and strong hydrophobicity, and effectively repels dust falling adsorption. In addition, the material net cover also has the effects of mildew prevention and broad-spectrum microorganism inhibition, and the inner side of the net cover is CO2Concentration of gas sensitive material>When the content of the antioxidant preservative is 2 percent, the wall-breaking slow-release antioxidant preservative substance acts on the surface of the fruit, so that the ageing and softening of the fruit are effectively delayed.
Drawings
FIG. 1 shows the medium CO of the present invention2Schematic diagram of gas-sensitive wall-breaking antioxidant principle;
FIG. 2 is a comparison chart of the results of epidermal colonies of 8 months storage of experimental sugar core apples, wherein 2a is a non-net-cover control group, and 2b is a common net-cover control group; 3a is the net cover using group of the invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
A sugar core apple mould-proof dust-proof fresh-keeping special-purpose net bag and a preparation method thereof, the method comprises the following process flows:
mixing ingredients → heating and melting → foaming by introducing foaming agent → double-layer extrusion of net sleeve extrusion unit → cooling and forming → spraying nano mildew-proof and fresh-keeping material → spraying CO on the mesh structure part2Gas sensitive material → cooling solid type. Specifically, the method comprises the following steps:
1. mixing ingredients:
the mesh inner layer comprises the following ingredients in parts by mass: 80-95 parts of high-pressure low-density polyethylene (LDPE) and 7-10 parts of polyurethane (TPU);
the mesh outer layer comprises the following ingredients in parts by mass: 70-75 parts of polyurethane (TPU) and modified nano silicon dioxide (SiO)2)4-5 parts of polymethyl methacrylate (PMMA), 10-12 parts of acrylic resin, 7-8 parts of acrylic resin and 2-3 parts of talcum powder (the talcum powder plays a role in resisting adhesion and flowing).
The modified nano silicon dioxide (SiO)2) The preparation method comprises the following steps:
dissolving 2.0g of hexadecyl trimethyl ammonium bromide (CTAB) and 2.0g of gelatin in 100mL of deionized water, adding 100mL of anhydrous ethanol and 15mL of ammonia water (26.5%, 0.20mol/L), stirring for 20min, and adding 1.7g of Tetraethoxysilane (TEOS);
continuously stirring the mixed solution obtained in the step for 4 hours at room temperature, centrifugally washing the mixed solution with deionized water, drying the mixed solution in vacuum at 45 ℃, and finally roasting the dried mixed solution at 680 ℃ for 5 hours (the heating rate is 15 ℃/min) to obtain white nano SiO2
Obtaining 2g of the ground material, and obtaining the white SiO2Activating at 110 ℃ for 5h, dispersing in 100mL of absolute ethanol after activation, transferring to a three-neck flask with magnetic stirring and condensation reflux, and starting heating and stirring;
fourthly, when the mixture is stirred uniformly and the temperature is raised to 75 ℃, adding 2-3mL of Hexamethyldisilazane (HMDS) and 4-5 drops of dibutyltin dilaurate, and continuously heating and refluxing for 5 hours;
after the reaction is finished, cooling to room temperature, performing centrifugal separation, washing for 3 times with anhydrous ethanol, and performing vacuum drying at 40 ℃ for 36 hours.
2. Heating for melting: the inner layer furnish mixture was heated to 165 c and the outer layer furnish mixture was heated to 180 c to form a softening mixture, respectively, and then the temperature of the softening mixture was increased to 210 c.
3. Introducing a foaming agent for foaming: and (3) introducing a foaming agent with the mass fraction of 10-15% of the softened mixture, and respectively foaming and expanding the two softened mixtures so as to form compact micro-aerated molecules in the softened mixture. The foaming agent is N, N '-dimethyl-N, N' -dinitrosoterephthalamide with 70 percent of effective components, and a large amount of nitrogen gas-filled molecules are released by thermal decomposition. The foaming agent is continuously and rapidly stirred after being introduced, so that the aerated molecules are uniformly distributed. The technological parameters of the foaming agent are as follows: 60-70 parts of N, N '-dimethyl-N, N' -dinitrosoterephthalamide and 25-35 parts of resin, wherein the gas forming amount is 126 mL/g.
4. Double-layer extrusion of a net sleeve extruder set: and (3) cooling the two foamed softened mixtures to 100 ℃, feeding the two foamed softened mixtures into a net sleeve extruder set, carrying out variable frequency extrusion to ensure that the materials are expanded again to generate larger inflated molecules, wherein the conversion frequency is 55-80 Hz, the double frequencies are alternated, the retention time is 5s, and the variable frequency period is 10s, and then the materials enter a free expansion area, and the inflated molecules naturally expand but cannot explosively expand at room temperature and normal pressure.
The parameters of the net extruder are as follows: length-diameter ratio of screw: 1: 50, die head motor power: 3KW, main motor power: 11KW, cutting machine motor power: 1.5KW, total power of heating ring: 18KW, power of the motor of the heat pump: 0.55KW, nitrogen pump motor power: 1.1KW, fan power: 480W, total power consumption: 220KW/24h, yield: 500-900kg/24h, the external dimension (mm) of the host machine: 5000 × 700 × 1350, unit weight: 2900kg, footprint (mm): 3000X 9000.
5. And (3) cooling and forming: cooling and molding the extrudate into a net-shaped material to obtain the foam net.
6. Spraying a nano mildew-proof material: and spraying a layer of nano mildew-proof fresh-keeping material on the inner side (the side directly contacted with the fruits) of the cooled and formed foaming net.
The processing method of the nanometer mildew-proof fresh-keeping material comprises the following steps: mixing foamed polyurethane with nano TiO2Fully stirring and crosslinking under the condition of negative pressure at the temperature of 80-85 ℃, wherein the foaming aerated molecules are absolute ethyl alcohol steam, and fresh-keeping slow-release components, namely 1-2 parts of sodium nitroprusside, 0.5-1 part of gibberellin, 1-2 parts of polylysine and 3-5 parts of chitosan, are mixed and dissolved in the steam.
7. Preparation of CO by sol-gel method2Gas sensitive material:
⑴La1Ca2FeO3preparing nanocrystalline powder:
weighing 2.5g of lanthanum nitrate, 3g of calcium nitrate and 2g of ferric nitrate (analytically pure) according to a stoichiometric ratio, dissolving the lanthanum nitrate, the calcium nitrate and the ferric nitrate into 100mL of deionized water, mixing the components, and adding 2g of citric acid to prepare a solution;
heating and stirring the solution in a water bath kettle, adding 10mL of polyethylene glycol (PEG, the molecular weight is more than 20000) later, and continuing stirring until gel is formed;
taking out the gel, drying, sintering and forming to obtain pure La1Ca2FeO3A nanocrystalline powder material;
⑵CO2preparing a gas-sensitive capsule wall material: 5-6 parts of soybean protein isolate and 6-8 parts of corn starch → 10-12 parts of distilled water → 0.5-1 part of glycerol and 0.1-0.3 part of La1Ca2FeO3Nanoparticle → 7.6 value of p h → magnetic stirring for 40min → water bath stirring → cooling to room temperature → adding 0.2-0.3 part of MTGase enzyme with 2-6U/g activity → 4000r/min homogenizing for 30s → gelatinizing at room temperature to obtain CO2A gas-sensitive capsule wall material;
⑶CO2preparing a gas-sensitive capsule core material: compounding with absolute ethyl alcoholC,VEAnd procyanidin as core material, and chitosan, VC,VEAnd procyanidins according to 3: 1: 1: 1 proportion, stirring at high speed to obtain slow-release fresh-keeping antioxidant nano powder, gradually adding the antioxidant nano powder into 100mL of 99% absolute ethyl alcohol,stirring at 25-30 deg.C and stirring speed of 450r/min for 1 hr, ultrafiltering the obtained emulsion at 4 deg.C and 10000r/m, centrifuging for 30min, and collecting precipitate as slow-release fresh-keeping antioxidant Component (CO)2A gas-sensitive capsule core material;
fourthly, stirring for 60 minutes at 350 rpm by taking the wall-core ratio of 4:1 and the homogeneous phase emulsifier Tween-80 as 0.1%, standing for 24 hours at 4 ℃ to prepare white sticky matter, adding the white sticky matter into 3% zein solution, stirring uniformly, and filtering to obtain a mixed solution.
Fifthly, mixing and stirring the mixed solution uniformly, spraying the mixed solution to the inner side of the formed net sleeve, curing at normal temperature for 24 hours, and using the mixed solution in a microenvironment of the net sleeve with CO2At a concentration of > 2%, La1Ca2FeO3With CO2The combination leads the chelating sites of the core material and the protein to be broken, the wall material forms pores, and the gaseous antioxidant in the core material is slowly released, thereby playing the roles of eliminating surface free radicals and delaying senescence for the fruits.
8. Cooling and solidifying: the prepared net cover is solidified at normal temperature for 12 hours and can be used.
Aiming at the problem of the lack of the function of fruit aging prevention of the existing apple mesh bag, the invention sprays CO around the mesh structure of the mesh bag2Gas-sensitive freshness-retaining material, consisting of a wall material and a wall core, as shown in FIG. 1, CO2The concentration is 'automatic fresh-keeping switch', when the fruit is aged and diseased, the microenvironment CO around the fruit2Will accumulate continuously, and when the safety threshold value (2%) is exceeded, La in the wall material1Ca2FeO3The nanocrystal will react with CO2Targeting active recognition and binding, resulting in native association with La1Ca2FeO3The chelated protein sites are broken, the wall materials are cracked, the wall core is exposed, and the content in the wall core slowly volatilizes, is a volatile fresh-keeping antioxidant component, mainly comprises VC, VE and procyanidine nano atomized steam, so that the free radicals on the surface of the fruits are eliminated, and the aging of the fruits is delayed.
The technical scheme of the patent is applied to the sugar core apples, and the quality change after 8 months of storage is shown in the following table 1
TABLE 1 comparison of the quality of sugar-cored apples after 8 months storage
Apple without net cover Common net cover apple The invention relates to a net cover apple
Rate of mechanical damage 27% 8% 5%
Brightness L of pericarp 43 55 61
Weight loss ratio 9.7% 8.3% 5.2%
Rate of decay 5.5% 5.3% 2.1%
Soluble Solids (SSC) 12.8% 13.1% 14.3%
Titratable Acid (TA) 0.53% 0.55% 0.62%
Table 1 compares the difference in fruit quality between apples with sugar cores stored for 8 months in the absence of a sleeve, with a common net sleeve and with the net sleeve of the present invention. Obviously, the net cover can effectively reduce the mechanical damage of the fruits, and the net cover has better effect; in the aspect of maintaining the brightness of the fruit peel, the net cover effectively realizes the effect of maintaining the brightness of the fruit, and shows that the fruit has less dust fall and the after-ripening and aging of the fruit are inhibited; in addition, the net cover of the invention effectively delays the fruit weight loss and reduces the rotting problem caused by microorganism infection. However, the conventional net fails to exert a significant effect in maintaining the fruit SSC and TA, but the net of the present invention shows a positive effect. The net cover of the invention can effectively keep the storage quality of the sugar core apples.
Meanwhile, different control groups culture epidermal colonies of the sugar-cored apples stored for 8 months, as shown in fig. 2, 2a is a non-net-cover control group, 2b is a common net-cover control group, and 3a is a net-cover using group of the invention.
Obviously, the varieties and the number of the bacterial colonies on the surface of the fruit without the net cover are very large, the number of the bacterial colonies on the surface of the fruit using the common net cover is also large, and the varieties and the number of the bacterial colonies on the surface of the fruit using the net cover are very small, so that the net cover has obvious inhibiting and killing effects on harmful bacteria on the surface of the fruit.
Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the embodiments disclosed.

Claims (8)

1. A sugar core apple mould-proof dust-proof fresh-keeping special net bag and a preparation method thereof are characterized in that: the method comprises the following process flows: mixing ingredients, heating and melting, introducing foaming agent for foaming, double-layer extrusion by a net cover extrusion unit, cooling and forming, spraying nanometer mildew-proof and fresh-keeping material, and spraying CO on mesh structure parts2Gas sensitive material, cooling solid type.
2. The special mould-proof, dust-proof and fresh-keeping net bag for the sugar-cored apples and the preparation method thereof according to claim 1 are characterized in that: the batching includes net silk inlayer batching and net silk skin batching, and net silk inlayer batching includes by the mass fraction: 80-95 parts of high-pressure low-density polyethylene and 7-10 parts of polyurethane, wherein the mesh outer layer comprises the following ingredients in parts by mass: 70-75 parts of polyurethane, 4-5 parts of modified nano silicon dioxide, 10-12 parts of polymethyl methacrylate, 7-8 parts of acrylic resin and 2-3 parts of talcum powder.
3. The special mould-proof, dust-proof and fresh-keeping net bag for the sugar-cored apples and the preparation method thereof according to claim 1 are characterized in that: the preparation method of the modified nano silicon dioxide comprises the following steps:
dissolving 2.0g of hexadecyl trimethyl ammonium bromide and 2.0g of gelatin in 100mL of deionized water, then adding 100mL of anhydrous ethanol and 15mL of 26.5% and 0.20mol/L ammonia water, stirring for 20min, and then adding 1.7g of tetraethoxysilane;
continuously stirring the mixed solution obtained in the step for 4 hours at room temperature, centrifugally washing the mixed solution with deionized water, drying the mixed solution in vacuum at 45 ℃, roasting the dried mixed solution for 5 hours at 680 ℃, and obtaining white nano SiO, wherein the heating rate is 15 ℃/min2
Obtaining 2g of the ground material, and obtaining the white SiO2Activating at 110 ℃ for 5h, dispersing in 100mL of absolute ethanol after activation, transferring to a three-neck flask with magnetic stirring and condensation reflux, and starting heating and stirring;
fourthly, when the mixture is stirred uniformly and the temperature rises to 75 ℃, adding 2-3mL of hexamethyldisilazane and 4-5 drops of dibutyltin dilaurate, and continuously heating and refluxing for 5 hours;
after the reaction is finished, cooling to room temperature, performing centrifugal separation, washing for 3 times with anhydrous ethanol, and performing vacuum drying at 40 ℃ for 36 hours.
4. The special mould-proof, dust-proof and fresh-keeping net bag for the sugar-cored apples and the preparation method thereof according to claim 1 are characterized in that: heating to melt, namely heating the mixture of ingredients in the inner layer of the mesh to 165 ℃, heating the mixture of ingredients in the outer layer of the mesh to 180 ℃, respectively forming softened mixtures, then increasing the temperature of the softened mixtures to 210 ℃, introducing a foaming agent accounting for 10-15% of the mass of the softened mixtures, respectively foaming and expanding the two softened mixtures to form compact micro-aerated molecules in a softened object, cooling the two foamed softened mixtures to 100 ℃, sending the foamed mixtures into a mesh sleeve extruder set, carrying out variable-frequency extrusion to expand the materials again to generate larger aerated molecules, then cooling and forming an extruded product into a mesh material to obtain a foam net, spraying a layer of nano mildew-proof fresh-keeping material on the inner side of the foam net which is formed by cooling, namely the side which is directly contacted with fruits, and spraying CO on the mesh structure part2Gas sensitive material, and then cooling the solid form.
5. The special mould-proof, dust-proof and fresh-keeping net bag for the sugar-cored apples and the preparation method thereof according to claim 4 are characterized in that: the foaming agent is N, N '-dimethyl-N, N' -dinitrosoterephthalamide with 70% of effective components, wherein the foaming agent comprises the following components in parts by mass:
60-70 parts of N, N '-dimethyl-N, N' -dinitrosoterephthalamide;
25-35 parts of resin;
the gas evolution is 126 mL/g.
6. The special mould-proof, dust-proof and fresh-keeping net bag for the sugar-cored apples and the preparation method thereof according to claim 4 are characterized in that: the conversion frequency of the net extruder is 55-80 Hz, the frequency is changed alternately, the retention time is 5s, the frequency conversion period is 10s, and the length-diameter ratio of a screw of the net extruder is as follows: 1: 50, die head motor power: 3KW, main motor power: 11KW, cutting machine motor power: 1.5KW, total power of heating ring: 18KW, power of the motor of the heat pump: 0.55KW, nitrogen pump motor power: 1.1KW, fan power: 480W, total power consumption: 220KW/24h, yield: 500-900kg/24h, the external dimension (mm) of the host machine: 5000 × 700 × 1350, unit weight: 2900kg, footprint (mm): 3000X 9000.
7. The special mould-proof, dust-proof and fresh-keeping net bag for the sugar-cored apples and the preparation method thereof according to claim 4 are characterized in that: the processing method of the nanometer mildew-proof fresh-keeping material comprises the following steps: mixing foamed polyurethane with nano TiO2Fully stirring and crosslinking under the negative pressure condition of 80-85 ℃, wherein the foaming aerated molecules are absolute ethyl alcohol steam, and fresh-keeping slow-release components are mixed and dissolved in the steam, and the fresh-keeping slow-release components comprise the following components in parts by mass:
Figure FDA0002646101620000021
8. the special mould-proof, dust-proof and fresh-keeping net bag for the sugar-cored apples and the preparation method thereof according to claim 4 are characterized in that: preparation of CO by sol-gel method2The specific process flow of the gas sensitive material is as follows:
⑴La1Ca2FeO3preparing nanocrystalline powder:
weighing 2.5g of lanthanum nitrate, 3g of calcium nitrate and 2g of ferric nitrate according to a stoichiometric ratio, mixing, dissolving in 100mL of deionized water, mixing, and adding 2g of citric acid to prepare a solution;
secondly, the solution is placed in a water bath kettle to be heated and stirred, 10mL of polyethylene glycol is added, and the mixture is stirred until gel is formed;
taking out the gel, drying, sintering and forming to obtain pure La1Ca2FeO3A nanocrystalline powder material;
⑵CO2preparing a gas-sensitive capsule wall material: 5-6 parts of soybean protein isolate and 6-8 parts of corn starch, adding 10-12 parts of distilled water, adding 0.5-1 part of glycerol0.1-0.3 part of La1Ca2FeO3Regulating pH to 7.6, magnetically stirring for 40min, stirring in water bath, cooling to room temperature, adding 0.2-0.3 part of MTGase enzyme with activity of 2-6U/g, homogenizing at 4000r/min for 30s, standing at room temperature to gelatinize to obtain CO2A gas-sensitive capsule wall material;
⑶CO2preparing a gas-sensitive capsule core material: compounding with absolute ethyl alcoholC,VEAnd procyanidin as core material, and chitosan, VC,VEAnd procyanidins according to 3: 1: 1: mixing at a ratio of 1, stirring at high speed under shaking to obtain sustained-release fresh-keeping antioxidant nanopowder, gradually adding antioxidant nanopowder into 100mL of 99% anhydrous ethanol, stirring at 25-30 deg.C and stirring speed of 450r/min for 1h, ultrafiltering the obtained emulsion at 4 deg.C and 10000r/m, centrifuging for 30min to obtain precipitate which is CO as sustained-release fresh-keeping antioxidant component2A gas-sensitive capsule core material;
fourthly, stirring for 60 minutes at 350 rpm by taking the wall-core ratio of 4:1 and the homogeneous emulsifier Tween-80 as 0.1%, standing for 24 hours at 4 ℃ to prepare a white sticky substance, adding the white sticky substance into a 3% zein solution, stirring uniformly, and filtering to obtain a mixed solution;
and fifthly, mixing and stirring the mixed solution uniformly, spraying the mixed solution to the inner side of the formed net sleeve, and curing at normal temperature for 24 hours.
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