CN113211924B - Thermal insulation packaging bag for cooling and preventing dewing of quick-frozen food - Google Patents

Thermal insulation packaging bag for cooling and preventing dewing of quick-frozen food Download PDF

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Publication number
CN113211924B
CN113211924B CN202011353606.5A CN202011353606A CN113211924B CN 113211924 B CN113211924 B CN 113211924B CN 202011353606 A CN202011353606 A CN 202011353606A CN 113211924 B CN113211924 B CN 113211924B
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China
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layer
cooling
water
film
solution
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CN113211924A (en
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刘霞
刘宇昊
汪轩羽
王春雨
张敬燕
郑家轩
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Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
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Abstract

The invention relates to a heat-insulating packaging bag for cooling and preventing dewing of quick-frozen foods, which comprises a chromogenic cooling layer, a water-absorbing and gas-absorbing layer, a bacteriostasis bionic layer and a high-efficiency heat-insulating layer, wherein the chromogenic cooling layer, the water-absorbing and gas-absorbing layer and the bacteriostasis bionic layer are closely adhered together from outside to inside; the color development cooling layer comprises a unidirectional water-permeable and breathable fiber film and a cooling and color development coating coated on the film, wherein the cooling and color development coating is arranged on the inner side; the water and gas absorption layer is a three-dimensional multi-metal ion skeleton adsorption crystal loaded on the semi-dewatering-activating-bacterial cellulose membrane. The inner layer of the packaging heat-insulating bag adopts a unidirectional permeable and breathable fiber film, has the function of developing color and cooling when meeting water, and is coated with cooling particles on the bottom layer of the color-developing film, so that when dissolved water meets the cooling particles, the environment temperature is reduced, the dissolving speed is delayed, and meanwhile, the growth of bacterial colonies is inhibited at low temperature.

Description

Thermal insulation packaging bag for cooling and preventing dewing of quick-frozen food
Technical Field
The invention relates to the technical field of fresh-keeping packaging, in particular to a heat-preserving packaging bag for cooling and preventing condensation of quick-frozen foods.
Background
The existing quick-frozen package has the following problems: (1) is easily influenced by environmental changes, and has poor heat preservation performance; (2) Temperature fluctuation often occurs, and food thawing-refreezing is not easy to detect; (3) The transportation process is prone to the formation of water droplets or frost in the package due to thawing.
According to the investigation, it was found that the main cause of this problem is: (1) The whole process of freezing the food needs to be stored at low temperature, and if temperature fluctuation is encountered, the whole temperature of the food is greatly influenced; (2) The existing packaging bag is mainly made of PE and PP materials, and has poor heat preservation effect; (3) The frozen food and the surrounding environment are not completely separated, and the relative vacuum environment with extremely small heat transfer coefficient is not provided.
The prior art has the following defects when solving the problems:
(1) Aiming at the problem of poor heat preservation performance of the package, the plastic thickness is mainly increased or the material is modified, but the plastic thickness and the material are not combined or blocked from heat exchange by gas.
(2) During transportation or storage, thawing-refreezing phenomena may occur, but are not perceived, and microorganisms are easily caused to grow.
Aiming at the problems of poor heat preservation performance, poor antibacterial effect and the like of the packaging bag, the prior art only aims at researches on improvement of a film structure, material mixing and the like, and has no relevant report on the packaging bag with the effects of heat preservation, temperature reduction, antibacterial and the like of specific quick-frozen foods. At present, many studies are mainly conducted on the hydrophobicity, degradability and the like of films, for example, as follows:
(1) Patent number CN201810129907, hydrophobic bubble film and its preparation process, and hydrophobic coating with nanometer silica, methyltrimethoxysilane, ethyl orthosilicate, organic montmorillonite and tetrahydrofuran as material. However, the method has the advantages of multiple times, multiple types and large dosage of the used reagents, is extremely easy to cause degradation difficulty and causes burden to the environment.
(2) Patent number CN201910731020, entitled a degradable high-strength composite bubble film and a processing method thereof, discloses a bubble film comprising a bubble film layer, a reinforcing layer, a wear-resistant layer and a flame-retardant layer, wherein the bubble film takes polyethylene as a base material, and the degradation speed is improved by adding a biodegradation additive. But no intensive studies have been made on heat preservation and insulation.
(3) Patent number CN201820494377, name a novel biodegradable bubble bag discloses novel biodegradable bubble bag, including bubble bag, banding and sealing extension strip, the fixed bonding of bubble bag outer loop has from paper, kraft paper, inner chamber through connection has the copper wire, the modern design is difficult for deformation. However, the heat insulation performance of the packaging bag is not deeply studied.
Disclosure of Invention
The invention solves the problems in the prior art by analyzing the prior art, and provides the heat preservation bag which is particularly suitable for reducing the temperature of frozen foods in the transportation or storage process, additionally provides a cold source, increases the heat preservation performance of the packaging bag, and isolates the requirements on the air exchange between the surrounding environment and the foods and the like by defining the freezing state of the contents through the color change of the packaging bag.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the heat-insulating packaging bag comprises a chromogenic cooling layer, a water-absorbing and gas-absorbing layer, a bacteriostasis bionic layer and a high-efficiency heat-insulating layer, wherein the chromogenic cooling layer, the water-absorbing and gas-absorbing layer and the bacteriostasis bionic layer are tightly adhered together from outside to inside, and the bacteriostasis bionic layer is arranged inside and extruded on the high-efficiency heat-insulating layer at intervals to form a packaging space so as to form a heat-insulating bag;
the color development cooling layer comprises a unidirectional water-permeable and breathable fiber film and a cooling and color development coating coated on the film, wherein the cooling and color development coating is arranged on the inner side;
the water and gas absorption layer is a three-dimensional multi-metal ion skeleton adsorption crystal loaded on a semi-dewatering-activating-bacterial cellulose membrane;
the antibacterial bionic layer comprises a hydrophobic bionic film and a coating antibacterial substance, so as to form the hydrophobic antibacterial film;
the glass wool core material double-layer heat-insulating material is coated by the high-efficiency heat-insulating layer epoxy resin-based foaming material.
Moreover, the preparation method of the color development cooling layer comprises the following steps:
(1) unidirectional water-permeable and breathable fiber film
SiO is made of 2 Adding the nano particles into dimethylformamide solution, performing ultrasonic dispersion, adding 10-15% polyvinylidene fluoride into the solution after the nano particles form a uniform phase, standing for 10-20 min, and putting the flask into an oil bath pot for heating and dissolving; carrying out dimethylformamide air spinning; obtaining nascent SiO 2 PVDF nanofiber membrane.
Winding the treated polyester non-woven fabric strip on a metal roller receiver, and fixing; filling the prepared spinning solution into a syringe, fixing the syringe into a notch of a syringe pump, adjusting proper spinning parameters, and spinning to obtain a unidirectional water-permeable and breathable fiber film;
(2) cooling and color-developing coating
4-5 g of modified starch and 15-20 mL of distilled water are added into a four-mouth bottle provided with a condensing reflux pipe, a nitrogen guide pipe and a stirring paddle, and stirred into uniform solution at 50-60 ℃. At N 2 Adding an initiator ammonium persulfate solution under protection, and stirring for 25-30 min; adding mixed solution containing 6-8 g of glycerin (mass concentration is 25%), and 20-30 g of potassium nitrate (absorbing heat when meeting water and reducing temperature); after 20-30 min, adding cross-linking agent N, N' -methylene bisacrylamide, raising the temperature, stirring and reacting for 150-200 min, wherein the whole reaction process is carried out under N 2 Under protection, centrifuging for 25-30 min at 5000r/min, and collecting supernatant for later use;
vacuum drying the obtained product, and finally crushing and sieving the dried and cooled microspheres for standby;
anthocyanin is extracted from purple cabbage and is combined with cooling microspheres and a fiber film in a coating mode, and the surface density of the coating is 15-20 mg/dm 2 The temperature is 55-60 ℃, and the unidirectional water-permeable and breathable fiber membrane with color development and temperature reduction is obtained.
Moreover, the preparation method of the water and gas absorbing layer comprises the following steps:
(1) preparing three-dimensional multi-metal ion skeleton adsorption crystal
(2) Preparation of semi-dehydrated-activated-bacterial cellulose membranes
Placing the bacterial cellulose membrane into a container filled with 100mL of sodium hydroxide solution with the mass concentration of 20g/L, stirring at 75-80 ℃ for 0.5-1 h, and carrying out mercerization treatment to obtain an activated bacterial cellulose membrane; washing the activated-bacterial cellulose membrane with ultrapure water to a pH of 7; then placing the obtained activated-bacterial cellulose membrane into an ethanol water solution containing 100mL, controlling the stirring speed to be 160-200 r/min, and continuously stirring for 1-2 h; taking out the membrane, sucking the membrane by filter paper, adding the membrane into ethanol again, continuously stirring and extracting for 1-2 hours, and sucking the membrane by filter paper again to obtain the semi-dewatering-activating-bacterial cellulose membrane.
(3) Preparation of high-elasticity strong-adsorption cellulose membrane
At N 2 In which 15 to 20g of adsorption crystals and a semi-dehydrated-activated-bacterial cellulose membrane are mixed in a four-necked flask and vigorously stirred under mechanical stirring for 12h; after pouring out the residual solution from the four-necked flask, 100mL of NaBH was added dropwise 4 The white film turns black rapidly, and after the solution is added dropwise within 30-45 min, the reaction is kept for 1-2 h; the method comprises the steps of carrying out a first treatment on the surface of the A highly elastic, strongly adsorbed cellulose film is subsequently obtained.
Moreover, the preparation method of the antibacterial bionic layer comprises the following steps:
preparing a polyvinyl alcohol film, and then loading polydimethylsiloxane to obtain a PDMS bionic film with a plant surface microstructure; and (5) coating antibacterial substances.
Moreover, the bacteriostatic substance is prepared as follows:
accurately weighing 0.2-0.5 g of zirconium tetrachloride, dissolving 0.15-0.25 g of 2-amino terephthalic acid into 30-50 mLN, adding 5-6 mL of acetic acid and 0.05-0.06 mL of hydrochloric acid, stirring uniformly, transferring into a 100mL hydrothermal reaction kettle, carrying out microwave for 15-20 min, and then reacting at 120 ℃ for 10-12 h. After the reaction is finished, pouring the solution into a centrifuge tube, centrifuging for 15-20 min at the rotating speed of 9000r/min, washing for 3 times by using DMF, soaking for 20-24 h by using acetone, centrifuging, and vacuum drying the product at 60 ℃ for 12h;
350-400 mg of the product is weighed and soaked in 50mg/mL of thymol methanol solution, and the mixture is stirred for one night in a sealing way, so that the MOF fully adsorbs the thymol. Centrifuging at 9000r/min, pouring out the solution, standing and drying the rest solid in a fume hood, and removing the rest small amount of solution to obtain the antibacterial substance.
Moreover, the preparation method of the efficient heat-insulating layer comprises the following steps:
(1) preparation of membrane material
Preparing mixed solution of epoxy resin, curing agent, auxiliary agent and nano inorganic particles according to the proportion of 8.5-10:2.5-3:0.85-1:3.5-4, foaming for 3-4 hours at 110-150 ℃, free cooling to room temperature after post-curing, and demoulding to obtain the epoxy resin-based foaming material serving as a film material;
(2) preparation of core material
Preparing a thin glass cotton felt by using an ultrafine glass cotton core material;
(3) double-layer heat-insulating layer
Firstly, preparing the film material into a packaging bag with a specified size, cutting the core material into the required size, then drying the film material and the core material, and packaging the core material by the film material after the film material and the core material are dried.
The beneficial effects of the invention are as follows:
1. the inner layer of the packaging heat-insulating bag adopts a unidirectional permeable and breathable fiber film, and has the functions of developing color and reducing temperature when meeting water: (1) electro-spinning is adopted to deposit electro-spinning fiber on the surface of hydrophilic material to prepare film material with humidity gradient in vertical direction, and inorganic oxide (SiO) is introduced 2 ) The unidirectional water-permeable and air-permeable film is prepared by combining fibers by an ultrasonic dispersion method. (2) The pH chromogenic film is prepared, namely, when food is thawed, water drops are accumulated on the surface of the food, and the food drops onto the chromogenic film. By the color change, whether the food is thawed during storage can be judged. (3) The bottom layer of the color developing film is coated with cooling particles, when dissolved water encounters the cooling particles to reduce the environmental temperature (potassium nitrate is dissolved in water to absorb heat), the melting speed is delayed, and meanwhile, the growth of bacterial colonies is inhibited at low temperature.
2. The bacterial cellulose membrane of the packaging heat-preserving bag is loaded with a multi-metal oxygen cluster ion skeleton, and has high water absorption and gas absorption capacity: (1) the bacterial cellulose membrane is composed of an ultrafine nanofiber network and has a three-dimensional structure, so that heavy metals can be adsorbed, generated particles are prevented from agglomerating, and the network structure has high elasticity and strong water absorption capacity. (2) Constructing an ion framework based on the covalent modification of a tri-hydroxyl ligand and a poly-metal oxygen cluster. When the counter ion is ammonium, the multi-metal oxygen clusters which are modified by the double sides of the trihydroxy ligand and take cobalt as hetero atoms can form a porous structure. The structure has open pore canal and high adsorption capacity to gas.
3. The bionic film with the wrapping heat preservation bag and the antibacterial succulent plant structured super-hydrophobic surface has the hydrophobic antibacterial effect: (1) the plant surface has superhydrophobicity and self-cleaning property, i.e. water drops on the surface of the material easily slide down. The surface of succulent plant leaves is used as a template, and a secondary transfer method is utilized to construct a bionic polymer film, so that moisture generated by temperature fluctuation of food cannot be accumulated on the bag. (2) Mainly aims at staphylococcus aureus, salmonella and listeria monocytogenes, adopts a zirconium-based metal organic framework of an organic ligand as a thymol carrier, and adsorbs thymol essential oil to ensure that the thymol essential oil has antibacterial effect.
4. The packaging heat-insulating bag of the invention uses glass wool as a core material and an epoxy resin-based microporous foaming material as a membrane material to prepare a high-efficiency heat-insulating layer: (1) the glass wool core material has the advantages of small fiber diameter, small lap joint area between fibers, complex heat conduction path along solid state heat, prolonged heat transmission channel, low heat conduction and good heat preservation effect. (2) The proportion of the nano inorganic particles and the matrix resin regulates and controls the gel network structure of the epoxy prepolymer, and the epoxy resin-based microporous foaming material is prepared by combining free foaming, so that the high-performance high-heat-insulation film material is prepared. (3) The smaller the heat conductivity coefficient is, the higher the heat insulation performance is, and researches show that the heat conductivity coefficient is solid > liquid > gas, so that an air layer is covered on the heat insulation layer, and the heat insulation performance is improved.
Drawings
FIG. 1 shows the inhibition of E.coli by the biomimetic membrane of the present invention (24 h, (1) experimental group and (2) blank control).
Fig. 2 is a photograph of a thermal insulation bag.
Fig. 3 is a cross-sectional view of a thermal insulation bag.
Wherein 1 is a chromogenic cooling layer, 2 is a water and gas absorption layer, 3 is a bacteriostasis bionic layer, 4 is a packaging space, and 5 is a high-efficiency heat preservation layer.
Detailed Description
The invention will now be further illustrated by the following examples, which are intended to be illustrative only and not limiting in any way.
The utility model provides a quick-frozen food cooling anti-dewfall's heat preservation wrapping bag, includes chromogenic cooling layer 1, absorbs water and absorbs gas layer 2, antibacterial bionic layer 3 and high-efficient heat preservation 5, by chromogenic cooling layer, absorb water and absorb gas layer, antibacterial bionic layer from outside to inside closely attach together, and the back is crowded altogether to the three-layer, and antibacterial bionic layer is inside, and the interval extrudes on high-efficient heat preservation, forms packing space 4, forms the heat preservation bag. The following describes the manufacturing process and the effect of each layer:
the color development cooling layer comprises a unidirectional water-permeable and breathable fiber film and a cooling and color development coating coated on the film, wherein the cooling and color development coating is arranged on the inner side.
1. Color development cooling layer
(1) Unidirectional water-permeable and air-permeable fiber film (the weight of liquid is calculated by weight).
SiO is made of 2 Adding nano particles into Dimethylformamide (DMF) solution, performing ultrasonic dispersion for 50min, adding 15% polyvinylidene fluoride (PVDF) into the solution after the nano particles form a uniform phase, wherein the addition amounts are 8 parts of silicon dioxide particles, 25 parts of 10% DMF solution and 20 parts of PVDF solution respectively, standing for 20min, putting the flask into an oil bath kettle, heating at 60 ℃, and mechanically stirring for 6h until the nano particles are completely dissolved; the prepared DMF solution was then poured into a 50mL disposable syringe and clamped to the spinning apparatus to begin air spinning.
The advancing speed is 10mL/h, the air flow pressure is 0.5MPa, the temperature is 60 ℃, the relative humidity is 50%, and the primary SiO can be obtained after spinning is completed 2 PVDF nanofiber membrane.
Winding the treated polyester non-woven fabric strip on a metal roller receiver, and fixing the polyester non-woven fabric strip by using an adhesive tape; and loading the prepared spinning solution into a syringe, fixing the syringe into a notch of a syringe pump, and adjusting proper spinning parameters to spin. The spinning voltage is 30kV, the spinning speed is 1.5ml/h, the receiving distance is 20cm, the rotating speed of the roller is 800rpm, and the unidirectional water-permeable and air-permeable fiber film with uniform diameter distribution and clear appearance is obtained.
(2) Cooling and color-developing coating
5g of modified tapioca starch (which is a commercially available tapioca modified starch) and 20mL of distilled water were added to a four-necked flask equipped with a condensate return pipe, a nitrogen gas pipe and a stirring paddle, and stirred at 60℃to obtain a uniform solution. At N 2 Adding an initiator ammonium persulfate solution under protection, and stirring for 30min; adding a mixed solution containing 8g of glycerin (mass concentration 25%) and 30g of potassium nitrate (absorbing heat when meeting water and reducing temperature). After 30min, adding cross-linking agent N, N' -methylene bisacrylamide, raising the temperature, stirring and reacting for 180min, wherein the whole reaction process is carried out under N 2 Under protection ofCentrifuging at 5000r/min for 30min, and collecting supernatant.
And (3) vacuum drying the obtained product at 50 ℃, and finally crushing and sieving the dried and cooled microspheres for standby. Anthocyanin is extracted from purple cabbage, and is combined with cooling microsphere and fiber film in the form of coating with surface density of 20mg/dm 2 The temperature is 60 ℃, and the unidirectional water-permeable and breathable fiber membrane with color development and temperature reduction is obtained.
2. The preparation method of the water-absorbing and gas-absorbing layer comprises the following steps:
(1) three-dimensional multi-metal ion skeleton adsorption crystal (IF-Co-Me)
Weigh 0.5g CoSO 4 ·7H 2 O、2.5g(NH 4 ) 6 Mo 7 O 24 ·4H 2 O and 0.48g CH 3 C(CH 2 OH) 3 Dissolved in 20mL CH 3 COONa/CH 3 COOH (p H =4.7) buffer solution was stirred continuously. The temperature was gradually increased to 80℃and after 30min the heating was stopped. The solution was filtered while hot to give a pink solution which was slowly evaporated over a day at room temperature to precipitate pink crystals.
(2) Bacterial cellulose membrane activation
Placing a bacterial cellulose membrane in a container filled with 100mL of sodium hydroxide solution with the mass concentration of 20g/L, stirring for 1h at 80 ℃, and treating the bacterial cellulose membrane with 5mol/L sodium hydroxide solution to increase the surface gloss of the bacterial cellulose membrane to obtain an activated-bacterial cellulose membrane; washing the activated-bacterial cellulose membrane with ultrapure water to a pH of 7; then placing the obtained activated-bacterial cellulose membrane into an ethanol water solution containing 100mL (the volume of ethanol and water is 7:3), controlling the stirring speed to be 180r/min, and continuously stirring for 1.5h; taking out the membrane, sucking the membrane with filter paper, adding the membrane into ethanol again, continuously stirring and extracting for 1-2h, and sucking the membrane with filter paper again to obtain the semi-dewatering-activating-bacterial cellulose membrane.
(3) Preparation of high-elasticity strong-adsorption cellulose membrane
At N 2 In this, 20g of the adsorption crystals and the semi-dehydrated-activated-bacterial cellulose membrane were mixed in a four-necked flask and vigorously stirred under mechanical stirring for 1.5 hours. After pouring out the residual solution from the four-necked flask, 100mL of NaBH was added dropwise 4 Solution (30 g/L concentration). The white film turns black rapidly, and the solution is kept to react for 1.5h after the dripping is completed within 45 min. Finally, the film was washed three times with oxygen-free water. The obtained highly elastic, strongly adsorbed cellulose film is then used.
3. The antibacterial bionic layer comprises a bionic film and a coating antibacterial substance, and forms a hydrophobic antibacterial film.
Mixing water and polyvinyl alcohol (PVA) according to the ratio of 9:1, adding the mixture into a beaker, standing the mixture for 45min, putting the mixture into a constant-temperature water bath (the temperature is 90 ℃) and stirring the mixture for a plurality of times until no gap exists between PVA particles. Adding a rotor into a beaker, placing the beaker on a magnetic stirrer, heating and stirring the beaker at 90 ℃ at a rotating speed of 80r/min, stirring the beaker for 45min, and standing the beaker at normal temperature until no bubbles exist. Uniformly smearing PVA glue solution on the prepared sample by using a clean glass rod, and placing the sample at a cool and ventilated place for drying in the shade. After waiting for a period of time, the PVA film solution is completely coagulated, the coagulated PVA film is peeled off, and the PVA film is fixed on a glass slide by using double-sided adhesive tape.
30mL of Polydimethylsiloxane (PDMS) and 3mL of phenolsulfonic acid (curing agent) were mixed in a 10:1 ratio in a beaker. Adding a magnetic rotor, placing the beaker on a magnetic stirrer for stirring, stirring at the rotating speed of 50r/min for about 3 hours at room temperature so as to completely mix the curing agent and the main agent, and standing at the room temperature until no bubbles exist. The polydimethylsiloxane in the beaker was picked up with a clean glass rod and uniformly applied to the PVA film that had solidified. Placing in an electrothermal blowing drying oven, heating for solidification, adjusting to 120deg.C for 1.5 hr. And (3) tearing off the cured PDMS film from the PVA film when the temperature is reduced to normal temperature, so that the PDMS bionic film with the plant surface microstructure can be obtained.
The antibacterial substance is prepared as follows:
0.5g of zirconium tetrachloride (ZrCl) was accurately weighed 4 ) 0.25g of 2-amino terephthalic acid is dissolved in 50mLN, N-Dimethylformamide (DMF), 6mL of acetic acid is added, 0.06mL of hydrochloric acid is added, the mixture is stirred uniformly, the mixture is transferred to a 100mL hydrothermal reaction kettle, microwaves are carried out for 20min, and then the mixture is reacted for 12h at 120 ℃. After the reaction, the solution was poured into a centrifuge tube, centrifuged at 9000r/min for 20min, washed 3 times with DMF, soaked in acetone for 24h and centrifuged, and the product was subjected to centrifugation at 6Vacuum drying at 0deg.C for 12h.
400mg of the product was weighed and soaked in 50mg/mL of Thymol (Thymol) in methanol, and stirred in a sealed condition overnight to allow the MOF to fully adsorb Thymol. Centrifuging at 9000r/min, pouring out the solution, standing and drying the rest solid in a fume hood, and removing the rest small amount of solution to obtain the antibacterial adsorbate.
4. High-efficiency heat-insulating layer
(1) Preparation of membrane material
Epoxy resin, curing agent (methyltetrahydrophthalic anhydride), auxiliary agent (DMP-30) and nano inorganic particles (30 nm SiO) 2 ) Preparing a mixed solution according to the ratio of 10:3:1:4, and placing the mixed solution into an ultrasonic dispersing machine for ultrasonic dispersion for 30min at 50 ℃ so as to uniformly disperse the nano inorganic particles. Placing the epoxy mixture into an oil bath pot at 85 ℃, heating, stirring and pre-solidifying to a proper reaction degree (torque is tested by a rheometer), taking out and cooling; the cooled epoxy mixture and blowing agent (dinitroso pentamethylene tetramine) were ground to a powder at a ratio of 5:2. The powder is put into a die, pressed into sheets by a tablet press under the pressure of 10MPa, then put into a preheated stainless steel die with fixed cavity volume (diameter 25.4mm multiplied by thickness 4 mm), foamed for 3 hours at 150 ℃, and after post-solidified, cooled to room temperature freely, and then demoulded to obtain the epoxy resin-based foaming material.
(2) Preparation of core material
The superfine glass wool core material is selected and wet forming technology is adopted. The wet forming core material is to prepare thin glass cotton felt from glass cotton raw cotton by steps of chopping, pulping, papermaking and the like, and finally prepare the glass cotton core material by steps of cotton spreading, cutting and the like, and the wet forming can change three-dimensional distributed glass fibers into two-dimensional stacked glass fibers, so that the heat conductivity coefficient is further reduced
(3) Double-layer heat-insulating layer
Firstly, preparing a film material into a packaging bag with a specified size, cutting a core material into a required size, and then putting the film material and the core material into an infrared drying channel for drying, wherein the drying condition of the core material is 150 ℃ for 5min; the drying condition of the film material is 100 ℃ for 3min. After the film material and the core material are dried, the core material and a getter (calcium oxide) are filled in 30 secondsPackaging in a vacuum packaging machine under the following packaging conditions: vacuum degree 1.0X10 -3 Pa, dwell time 70s, heat temperature 200 ℃, heat seal time 8s, heat seal pressure 70N.
5. Blow-molded coating film
And (3) carrying out low-temperature multilayer adhesion compounding on the chromogenic cooling layer, the water-absorbing and air-absorbing layer and the antibacterial bionic layer according to the proportion of 1:1:2, maintaining the bioavailability of the bionic layer, and preparing a semi-finished product after slitting, film cutting and bag making. And meanwhile, the obtained mixed layer is coated in a high-efficiency heat-insulating layer to prepare a bubble bag containing an air layer. In order to increase the strength during multi-layer adhesion, acrylic structural adhesive can be coated between layers, and the adhesive consumption is very small.
The quick-frozen food packed by the packaging bag has good heat preservation effect and can delay the time of food temperature rise due to the good heat preservation layer and air layer on the outer layer of the packaging bag.
However, as the time increases and the external temperature increases, the temperature of the quick-frozen food increases, thawing occurs, and water is separated out. When the water drops fall into the color-developing cooling layer of the inner layer, the color of the packaging bag changes, and whether the food is thawed or unfrozen or not can be seen from the bag (the more the water is, the darker the color is). Meanwhile, when water meets the cooling particles, the potassium nitrate absorbs heat when meeting the water, so that the ambient temperature is reduced, and the continuous rising of the temperature of food is delayed.
The excessive moisture can be completely absorbed by the water absorption layer, so that the outer layer structure of the bag is not influenced, a dry environment is formed, and the growth of microorganisms is inhibited; the metal clusters contained in the absorption layer can absorb gas, so that the gas around the quick-frozen food is led into the packaging layer to cause a partial vacuum environment, on one hand, the heat preservation performance is enhanced, and on the other hand, the microorganism breeding caused by thawing is prevented; meanwhile, as the inner layer is a unidirectional permeable and breathable film, moisture and gas can only move from the inner side to the outer layer, and pollution caused by bidirectional flow can not be caused.
The bionic film with hydrophobic and antibacterial effects utilizing the surface characteristics of succulent plants is arranged in the middle of the packaging bag, so that a compact isolation mechanism is formed between quick-frozen foods and the external environment, and the exchange of internal and external gases, microorganisms and the like is prevented, so that a relatively sterile environment is formed.
(III) Effect analysis
1. Temperature effect
The product and the common thermal insulation bag are placed in the same thermal insulation box under the state of constant temperature and constant humidity, and are kept stand for 15 hours, and the data are shown in table 1. The data shows that the scheme greatly reduces the lowest temperature, effectively prolongs the low-temperature environment and maintains the low-temperature environment.
TABLE 1 temperature parameter Table
Figure GDA0003940246540000081
2. Antibacterial effect
The preservative film in the item is compared with the common preservative film, and the bacteriostatic action of the preservative film on escherichia coli is compared. The inhibition zone phenomenon of the experimental group is obvious, while the control group does not form an obvious inhibition zone, and the effect is shown in figure 1.

Claims (2)

1. A quick-frozen food cooling anti-dewing heat preservation packaging bag is characterized in that: the device comprises a color development cooling layer, a water absorption and gas absorption layer, a bacteriostasis bionic layer and a heat preservation layer, wherein the color development cooling layer, the water absorption and gas absorption layer and the bacteriostasis bionic layer are tightly adhered together from outside to inside, and the bacteriostasis bionic layer is arranged inside and is extruded on the heat preservation layer at intervals to form a heat preservation, moisture preservation and bacteriostasis heat preservation bag;
the color development cooling layer comprises a unidirectional water-permeable and breathable fiber film and a cooling and color development coating coated on the film, wherein the cooling and color development coating is arranged on the inner side;
the water and gas absorption layer is a three-dimensional multi-metal ion skeleton adsorption crystal loaded on a semi-dewatering-activating-bacterial cellulose membrane;
the antibacterial bionic layer comprises a hydrophobic bionic film and a coating antibacterial substance, so as to form the hydrophobic antibacterial film;
the heat preservation layer is made of a glass wool core material double-layer heat preservation material wrapped by an epoxy resin-based foaming material;
the preparation method of the water and gas absorption layer comprises the following steps:
(1) preparing three-dimensional multi-metal ion skeleton adsorption crystal
Weigh 0.5g CoSO 4 ·7H 2 O、2.5g(NH4) 6 Mo 7 O 2 4·4H 2 O and 0.48. 0.48gCH 3 C(CH 2 OH) 3 Dissolved in 20mLCH 3 COONa/CH 3 Continuously stirring the solution in COOH (pH=4.7), gradually increasing the temperature to 80 ℃, and stopping heating after 30min; filtering while the solution is hot to obtain pink solution, and slowly evaporating at room temperature for one day to precipitate pink crystals;
(2) preparation of semi-dehydrated-activated-bacterial cellulose membranes
Placing the bacterial cellulose membrane into a container filled with 100mL of sodium hydroxide solution with the mass concentration of 20g/L, stirring at 75-80 ℃ for 0.5-1 h, and carrying out mercerization treatment to obtain an activated bacterial cellulose membrane; washing the activated-bacterial cellulose membrane with ultrapure water to a pH of 7; then placing the obtained activated-bacterial cellulose membrane into an ethanol water solution containing 100mL, controlling the stirring speed to be 160-200 r/min, and continuously stirring for 1-2 h; taking out the membrane, sucking the membrane with filter paper, adding the membrane into ethanol again, continuously stirring and extracting for 1-2 hours, and sucking the membrane with filter paper again to obtain the semi-dewatering-activating-bacterial cellulose membrane;
(3) preparation of elastic and adsorbable cellulose membranes
At N 2 In the method, 15-20 g of adsorption crystal solution and semi-dewatering-activating-bacterial cellulose membrane are mixed in a four-mouth flask and are vigorously stirred for 1-2h under mechanical stirring; after pouring out the residual solution from the four-necked flask, 100mL of NaBH was added dropwise 4 The white film turns black rapidly, and after the solution is added dropwise within 30-45 min, the reaction is kept for 1-2 h; an elastic, adsorbable cellulose film is subsequently obtained.
2. The heat-insulating packaging bag for cooling and preventing condensation of quick-frozen foods according to claim 1, wherein the heat-insulating packaging bag is characterized in that: the antibacterial substance is prepared as follows:
accurately weighing 0.2-0.5 g of zirconium tetrachloride, dissolving 0.15-0.25 g of 2-amino terephthalic acid into 30-50 mLN, adding 5-6 mL of acetic acid and 0.05-0.06 mL of hydrochloric acid, stirring uniformly, transferring into a 100mL hydrothermal reaction kettle, carrying out microwave for 15-20 min, reacting for 10-12 h at 120 ℃, pouring the solution into a centrifuge tube after the reaction is finished, centrifuging for 15-20 min at 9000r/min, washing for 3 times with DMF, soaking for 20-24 h with acetone, centrifuging, and vacuum drying the product for 12h at 60 ℃;
weighing 350-400 mg of the product, soaking in 50mg/mL of thymol methanol solution, sealing and stirring for one night, fully adsorbing thymol by a metal organic frame, centrifuging at a rotating speed of 9000r/min, pouring out the solution, standing and drying the residual solid in a fume hood, and thus obtaining the antibacterial substance.
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