CN113843937A - Migration-resistant hydrogel-based freshness colorimetric indication label and preparation method thereof - Google Patents
Migration-resistant hydrogel-based freshness colorimetric indication label and preparation method thereof Download PDFInfo
- Publication number
- CN113843937A CN113843937A CN202111172153.0A CN202111172153A CN113843937A CN 113843937 A CN113843937 A CN 113843937A CN 202111172153 A CN202111172153 A CN 202111172153A CN 113843937 A CN113843937 A CN 113843937A
- Authority
- CN
- China
- Prior art keywords
- indicator
- sodium alginate
- pvdf
- solution
- hydrogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000013508 migration Methods 0.000 title claims abstract description 11
- 230000005012 migration Effects 0.000 title description 2
- 238000004806 packaging method and process Methods 0.000 claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims description 60
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 24
- 229910052708 sodium Inorganic materials 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 21
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 15
- 239000000661 sodium alginate Substances 0.000 claims description 15
- 235000010413 sodium alginate Nutrition 0.000 claims description 15
- 229940005550 sodium alginate Drugs 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000090 biomarker Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004410 anthocyanin Substances 0.000 claims description 4
- 235000010208 anthocyanin Nutrition 0.000 claims description 4
- 229930002877 anthocyanin Natural products 0.000 claims description 4
- 150000004636 anthocyanins Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000004148 curcumin Substances 0.000 claims description 2
- 235000012754 curcumin Nutrition 0.000 claims description 2
- 229940109262 curcumin Drugs 0.000 claims description 2
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000003283 colorimetric indicator Substances 0.000 claims 3
- 235000013305 food Nutrition 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 102000004310 Ion Channels Human genes 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 12
- 239000000975 dye Substances 0.000 description 9
- 239000012528 membrane Substances 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920002148 Gellan gum Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- -1 biogum Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000000216 gellan gum Substances 0.000 description 2
- 235000010492 gellan gum Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003364 biologic glue Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000009450 smart packaging Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS 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
- B65D43/00—Lids or covers for rigid or semi-rigid containers
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
-
- 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
The invention discloses an anti-migration hydrogel based freshness colorimetric indication label and a preparation method thereof, and belongs to the technical field of intelligent food packaging. The hydrogel solid matrix load dye is prepared from the biogel, provides a good ion channel, and improves the chemical response speed of the dye. However, the hydrogel is usually easy to swell so that the dye is separated out, the stability of the intelligent label is adversely affected, and the antibacterial intelligent label with quick chromogenic response, air permeability and hydrophobicity can be obtained by using the method provided by the invention.
Description
Technical Field
The invention belongs to the technical field of intelligent food packaging, and relates to an anti-migration hydrogel-based freshness colorimetric indication label and a preparation method thereof.
Background
Fresh food is easily affected by physical, chemical and biological aspects in the processes of transportation, sale and storage, and is slightly decayed, so that the quality of the product is affected. The traditional package can not monitor the quality change of the product in real time, which causes the waste of the product. Therefore, the problem which is urgently solved in the field of intelligent packaging is that the change of the food quality and state is visually monitored and detected. Factors such as how to balance functions, sizes and preparation cost of the sensor are technical limits of application of the intelligent indicator label for realizing visual food freshness in packaged products.
The colorimetric sensor is a solution for realizing visualization of food freshness parameters simply, efficiently and at low cost. Colorimetric sensors are typically constructed of two parts, a solid substrate and a chemical/biological dye supported on the solid substrate. By correlating the color change of the chemically responsive dye with the freshness and spoilage of the food product.
The current research for solid matrix materials has mainly focused on polyvinyl alcohol, polysaccharides (cellulose, biogum, chitosan, etc.) and protein degradable materials. Dyes are directly incorporated into these solid substrates by hydrogen bonding or ionic reactions. The hydrogen bond between polysaccharide and anthocyanin plays a stabilizing role in anthocyanin. The biological glue is a natural polysaccharide biological material and has the characteristics of environmental friendliness, unique optical performance, good rheological property and the like. The biological gel is prepared into hydrogel solid matrix loaded with dye, so that a good ion channel is provided, and the chemical response speed of the dye is improved. However, hydrogels are generally very swelling, which causes dyes to precipitate, which adversely affects the stability of the smart tag.
PVDF is a material with biocompatibility, easy processing, polarity and stable performance. PVDF can be prepared into specific porous materials through process regulation. The Ag nano-particle composite PVDF porous material, the sodium alginate and other materials have the antibacterial effect.
Disclosure of Invention
In order to overcome the defect that the freshness indication label in the prior art cannot develop color due to dissolution failure of an indicator caused by the fact that the freshness indication label is poor in hydrophobicity and easy to absorb water, the invention aims to provide a hydrophilic-hydrophobic PVDF freshness indication label and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a migration-proof hydrogel-based freshness colorimetric indication label comprises a transparent packaging box cover, a sodium alginate-indicator composite film, a bracket and a PVDF porous film;
the support is arranged at the outer edge of the upper surface of the transparent packaging box cover, the sodium alginate-indicator composite film is assembled on the upper surface of the transparent packaging box cover and is positioned inside the support, and the PVDF porous film is positioned on the upper surface of the sodium alginate-indicator composite film;
the height of the sodium alginate-indicator composite film is the same as that of the bracket.
Preferably, the PVDF porous film is of a sponge structure, the sponge structure further comprises a plurality of conical through holes inside, each conical through hole is arranged along the vertical direction,
one end of the conical through hole is provided with a large hole, the other end of the conical through hole is provided with a small hole, the small hole is positioned on the lower surface of the PVDF porous film and is in contact with the sodium alginate-indicator composite film, and the large hole is positioned on the upper surface of the PVDF porous film.
A preparation method of the migration-proof hydrogel based freshness colorimetric indication label comprises the following steps:
step 1) mixing PVDF powder, an additive and a solvent, adding silver nitrate after heating reaction, and stirring for reaction to obtain a casting solution;
step 2) standing the casting solution, performing reverse phase film formation, and drying to obtain a PVDF porous film;
step 3) mixing sodium alginate, plasticizer and deionized water to obtain a mixed solution, adding an indicator into the mixed solution to obtain an indicating solution, and placing the indicating solution in CaCL2Performing crosslinking reaction in the solution to obtain a sodium alginate-indicator composite film;
step 4), uniformly coating the GG glue solution on a transparent packaging box cover to obtain a support;
and 5) encapsulating the sodium alginate-indicator composite film in the bracket, and encapsulating the PVDF porous film on the upper surface of the sodium alginate-indicator composite film.
Preferably, the additive is any one of polyvinylpyrrolidone, polyethylene glycol, polymethyl methacrylate, titanium dioxide, silicon dioxide and cyanoethyl cellulose;
the solvent is DMF;
the plasticizer is glycerol;
the indicator is a biological indicator, bromothymol blue or methyl red;
the biological indicator is anthocyanin, alizarin or curcumin.
Preferably, when the indicator is a biological indicator, the mass percentage of the indicator in the indicating solution is 1-5%;
when the indicator is bromothymol blue or methyl red, the mass percentage of the indicator in the indicating solution is 0.1-0.2%.
Preferably, the mass fraction of PVDF in the casting solution is 6-10 wt%;
the mass ratio of the additive to PVDF is (10-30): 100, respectively;
the mass ratio of the sodium alginate to the plasticizer is 5: (0.1 to 1);
preferably, the GG glue solution is 1-3% by mass.
Preferably, the heating reaction condition of the step 1) is heating for 50-60 ℃ for 12 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a hydrophilic-hydrophobic PVDF freshness indication label, which comprises a transparent packaging box cover, a sodium alginate-indicator composite film, a bracket and a PVDF porous film, wherein one surface of the PVDF porous film is hydrophilic and the other surface is hydrophobic, a hydrophilic sodium alginate indicator layer is firmly attached to a hydrophilic pore hydrophilic side, and the hydrophobic side of a macropore is directly contacted with the internal environment of a packaging material, so that the antibacterial intelligent label with quick chromogenic response, air permeability and hydrophobicity is obtained.
The invention also discloses a preparation method of the hydrophilic-hydrophobic PVDF freshness indication label, which prepares the biogel into hydrogel solid matrix loaded dye, provides a good ion channel and improves the chemical response speed of the dye. However, hydrogels are generally very swelling, which causes dyes to precipitate, which adversely affects the stability of the smart tag. PVDF is a material with biocompatibility, easy processing, polarity and stable performance. PVDF can be prepared into a specific porous material through process regulation, and specifically, a certain amount of pore-forming agent is added into PVDF membrane casting solution, uniformly stirred, spread on a hydrophobic substrate, placed into a coagulating bath together with the substrate for reverse phase film formation, taken out, dried and demoulded to obtain a regularly-arranged tapered-pore spongy porous structure film.
Drawings
FIG. 1 is a schematic representation of a porous PVDF membrane;
FIG. 2 is a schematic view of a sodium alginate indicator layer poured on a package box;
FIG. 3 is a schematic view of a package box spin-on adhesive poured with a sodium alginate indicator layer;
FIG. 4 is a schematic structural view of a porous PVDF film sealed and adhered to a packaging box poured with a sodium alginate indicator layer and an adhesive;
FIG. 5 is an SEM image of a PVDF porous membrane, which is a through hole section (a), an upper surface (b) and a lower surface (c) in this order;
FIG. 6 is a graph showing contact angles of the upper surface (a) and the lower surface (b) of a PVDF porous membrane;
FIG. 7 is a stress-strain curve of a PVDF porous film.
Wherein: 1-transparent packing box cover; 2-sodium alginate-indicator composite film; 3-a scaffold; 4-PVDF porous film.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
the first embodiment is as follows:
the preparation method of the PVDF hydrophilic-hydrophobic film/biological hydrogel double-layer colorimetric type intelligent label in the experimental mode comprises the following steps: the assembly is performed according to the flow structure as shown in figures 2, 3 and 4,
firstly, dissolving 3.6g of PVDF in 55.8g of DMF solvent to obtain a membrane casting solution;
secondly, 0.6g of PVP is weighed and dissolved in the membrane casting solution obtained in the first step;
thirdly, measuring 2ml AgNO3Slowly dripping into the solution in the second step, and ultrasonically stirring for 12h under the conditions that the rotating speed is 400r/min, the heating temperature is 50 ℃ and the power is 100%;
fourthly, standing the casting film liquid chamber, pouring the casting film liquid chamber into a polytetrafluoroethylene hydrophobic mold, uniformly spreading the casting film liquid chamber, putting the casting film liquid chamber and the casting film liquid chamber into a deionized water coagulating bath at 50 ℃ together for reverse phase film forming, taking out the casting film liquid chamber, and performing vacuum drying at 50 ℃ for 8 hours to obtain the PVDF porous antibacterial film;
fifthly, 3.6g of sodium alginate and 0.48g of glycerol are weighed and dissolved in 60ml of deionized water, and the mixture is stirred at the temperature of 35 ℃ until the mixture is dissolved;
sixthly, mixing 0.2% methyl red and 0.1% bromothymol blue solution 1: 1 to obtain a mixed indicator, adding 0.1ml of the mixed indicator into the fifth step to obtain an indicating solution, spreading the indicating solution on the porous membrane obtained in the fourth step, and using 5% w/vCaCl2Crosslinking for 5min in the solution to obtain a double-layer indicating label;
seventhly, weighing 3% of gellan gum (GG gum) and dissolving in deionized water to be uniformly stirred to obtain a bracket;
and eighthly, assembling the double-layer indicating label obtained in the step six and the bracket obtained in the step seven on the surface of the transparent plastic packaging box.
Example two
The difference between the embodiment and the embodiment one is that the additive added in the step two is PMMA, and the mass ratio of PMMA to PVDF is 2.5: 10, the mass ratio of sodium alginate to glycerol is 5: 0.1, the temperature of the coagulation bath in the fourth step is room temperature, the mass fraction of PVDF in the casting solution is 10%, and the mass percentage of GG gel solution is 2.5%, and the rest is the same as that of the first embodiment.
EXAMPLE III
The difference between the embodiment and the embodiment one is that the additive added in the step two is PEG, and the mass ratio of the PEG to the PVDF is 1.5: 10, the mass ratio of sodium alginate to glycerol is 5: 1, heating the third step to 60 ℃, wherein the mass fraction of PVDF in the casting solution is 7%, the mass fraction of GG colloidal solution is 1.5%, and the GG colloidal solution is prepared by heating at 60 ℃, and the rest is the same as the first step in the example.
Example four
The difference between the embodiment and the embodiment one is that the additive added in the step two is titanium dioxide, and the mass ratio of the titanium dioxide to the PVDF is 2: 10, the mass ratio of sodium alginate to glycerol is 5: 0.3, the glycerol amount added in the step five is 0.3g, the mass fraction of PVDF in the membrane casting solution is 8%, the mass fraction of GG gum solution is 3%, and the GG gum solution is prepared by heating at 100 ℃, and the rest is the same as the embodiment one.
EXAMPLE five
The difference between the embodiment and the embodiment one is that the additive added in the step two is silicon dioxide, and the mass ratio of the silicon dioxide to the PVDF is 1: 10, the mass ratio of sodium alginate to glycerol is 5: 0.5, the amount of the mixed indicator in the sixth step is 0.2ml, the mass fraction of PVDF in the casting solution is 9%, the mass fraction of GG gum solution is 2%, and the GG gum solution is prepared by heating at 80 ℃, and the rest is the same as that in the first embodiment.
EXAMPLE six
The difference between the embodiment and the embodiment one is that the additive added in the step two is CEC, the mass ratio of CEC to PVDF is 3: 10, the mass ratio of sodium alginate to glycerol is 5: 0.8, the amount of the gellan gum in the step seven is 1%, the mass fraction of PVDF in the casting solution is 6.5%, the mass fraction of GG gum solution is 1%, and the GG gum solution is prepared by heating at 90 ℃, and the other steps are the same as those in the first embodiment.
The migration-proof hydrogel-based freshness colorimetric indication label prepared by the method comprises a transparent packaging box cover 1, a sodium alginate-indicator composite film 2, a bracket 3 and a PVDF porous film 4; the bracket 3 is arranged at the outer edge of the upper surface of the transparent packaging box cover 1, the sodium alginate-indicator composite film 2 is assembled on the upper surface of the transparent packaging box cover 1 and is positioned inside the bracket 3, and the PVDF porous film 4 is positioned on the upper surface of the sodium alginate-indicator composite film 2; the height of the sodium alginate-indicator composite film 2 is the same as that of the bracket 3.
The PVDF porous film 4 is of a sponge structure, a plurality of conical through holes are further arranged inside the sponge structure, each conical through hole is arranged in the vertical direction, one end of each conical through hole is a large hole, the other end of each conical through hole is a small hole, the small holes are located on the lower surface of the PVDF porous film 4 and are in contact with the sodium alginate-indicator composite film 2, and the large holes are located on the upper surface of the PVDF porous film 4.
The prepared PVDF porous film is shown in fig. 1, and SEM characterization of the PVDF porous film prepared in example 1 is performed, and the result is shown in fig. 5, from which it can be seen that tapered pores and sponge-like pores can be seen in the cross-sectional structure in fig. 5a, fig. 5b is a uniform small pore structure on the upper surface, and fig. 5c is a uniform large pore structure on the lower surface. Adding a pore-forming agent and blending with PVDF to obtain a casting solution, and performing reverse phase drying film formation by a tape casting method to obtain the porous film with special hydrophilicity and hydrophobicity. The successful fabrication of tapered pore structures can be seen by cross-sectional and top and bottom surface views. The contact angles of the upper surface and the lower surface of the PVDF porous film prepared in example 1 are detected, and the result is shown in fig. 6, where fig. 6a is a hydrophilic upper surface, fig. 6b is a hydrophobic lower surface, and the result of electron microscope images shows that the upper surface has a small pore structure to obtain hydrophilic performance, and the lower surface has a large pore structure to obtain hydrophobic performance. The strain properties of the PVDF porous film prepared in example 1 were investigated, and the results are shown in fig. 7, which shows that the mechanical properties of the film are excellent.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
1. An anti-migration hydrogel-based freshness colorimetric indication label is characterized by comprising a transparent packaging box cover (1), a sodium alginate-indicator composite film (2), a bracket (3) and a PVDF porous film (4);
the support (3) is arranged at the outer edge of the upper surface of the transparent packaging box cover (1), the sodium alginate-indicator composite film (2) is assembled on the upper surface of the transparent packaging box cover (1) and is positioned inside the support (3), and the PVDF porous film (4) is positioned on the upper surface of the sodium alginate-indicator composite film (2);
the height of the sodium alginate-indicator composite film (2) is the same as that of the bracket (3).
2. The anti-migration hydrogel-based freshness colorimetric indication label according to claim 1, wherein the PVDF porous film (4) is of a sponge structure, the sponge structure further comprises a plurality of conical through holes inside, and each conical through hole is arranged along a vertical direction;
one end of the conical through hole is provided with a large hole, the other end of the conical through hole is provided with a small hole, the small hole is positioned on the lower surface of the PVDF porous film (4) and is contacted with the sodium alginate-indicator composite film (2), and the large hole is positioned on the upper surface of the PVDF porous film (4).
3. A method of making the anti-migration hydrogel-based freshness colorimetric indicator label of claim 1 or 2, comprising the steps of:
step 1) mixing PVDF powder, an additive and a solvent, adding silver nitrate after heating reaction, and stirring for reaction to obtain a casting solution;
step 2) standing the casting solution, performing reverse phase film formation, and drying to obtain a PVDF porous film (4);
step 3) mixing sodium alginate, plasticizer and deionized water to obtain a mixed solution, adding an indicator into the mixed solution to obtain an indicating solution, and placing the indicating solution in CaCL2Performing cross-linking reaction in the solution to obtain a sodium alginate-indicator composite film (2);
step 4), uniformly coating GG glue solution on the transparent packaging box cover (1) to obtain a support (3);
and 5) encapsulating the sodium alginate-indicator composite film (2) in the support (3), and encapsulating the PVDF porous film (4) on the upper surface of the sodium alginate-indicator composite film (2).
4. The preparation method of the migration-proof hydrogel-based freshness colorimetric indication label according to claim 3, wherein the additive is any one of polyvinylpyrrolidone, polyethylene glycol, polymethyl methacrylate, titanium dioxide, silicon dioxide, and cyanoethyl cellulose;
the solvent is DMF;
the plasticizer is glycerol;
the indicator is a biological indicator, bromothymol blue or methyl red;
the biological indicator is anthocyanin, alizarin or curcumin.
5. The preparation method of the anti-migration hydrogel-based freshness colorimetric indicator label according to claim 4, wherein when the indicator is a biological indicator, the mass percentage of the indicator in the indicator solution is 1-5%;
when the indicator is bromothymol blue or methyl red, the mass percentage of the indicator in the indicating solution is 0.1-0.2%.
6. The preparation method of the anti-migration hydrogel-based freshness colorimetric indication label according to claim 3, wherein the mass fraction of PVDF in the casting solution is 6-10%;
the mass ratio of the additive to PVDF is (10-30): 100, respectively;
the mass ratio of the sodium alginate to the plasticizer is 5: (0.1 to 1).
7. The preparation method of the anti-migration hydrogel based freshness colorimetric indication label according to claim 3, wherein the mass percentage of the GG gel solution is 1-3%.
8. The preparation method of the anti-migration hydrogel-based freshness colorimetric indicator label according to claim 3, wherein the heating reaction condition in the step 1) is heating at 50-60 ℃ for 12 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111172153.0A CN113843937B (en) | 2021-10-08 | 2021-10-08 | Migration-resistant hydrogel-based freshness colorimetric indication label and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111172153.0A CN113843937B (en) | 2021-10-08 | 2021-10-08 | Migration-resistant hydrogel-based freshness colorimetric indication label and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113843937A true CN113843937A (en) | 2021-12-28 |
CN113843937B CN113843937B (en) | 2024-02-06 |
Family
ID=78977703
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111172153.0A Active CN113843937B (en) | 2021-10-08 | 2021-10-08 | Migration-resistant hydrogel-based freshness colorimetric indication label and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113843937B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115447222A (en) * | 2022-06-07 | 2022-12-09 | 武汉理工大学 | Preparation method of compact PVDF (polyvinylidene fluoride) -based composite membrane |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4629563A (en) * | 1980-03-14 | 1986-12-16 | Brunswick Corporation | Asymmetric membranes |
CN101293185A (en) * | 2008-01-30 | 2008-10-29 | 清华大学 | Method for producing polyvinylidene fluoride porous membrane |
CN102198374A (en) * | 2011-05-16 | 2011-09-28 | 杭州费尔过滤技术有限公司 | Asymmetric polyvinylidene fluoride microporous membrane with high intensity and preparation method thereof |
CN104568933A (en) * | 2014-12-26 | 2015-04-29 | 山东商业职业技术学院 | Detection method for freshness of chilled fresh meat |
CN104897663A (en) * | 2015-05-21 | 2015-09-09 | 北京大学深圳研究生院 | Thin film sensor for detecting carbon dioxide and application of thin film sensor |
US20150377791A1 (en) * | 2014-06-27 | 2015-12-31 | Samsung Electronics Co., Ltd. | Gas sensor, refrigerator having the gas sensor and method of controlling the refrigerator |
CN105833742A (en) * | 2016-04-26 | 2016-08-10 | 上海应用技术学院 | Preparation method for hydrophilic polyvinylidene fluoride (PVDF) antibacterial ultrafiltration membrane |
-
2021
- 2021-10-08 CN CN202111172153.0A patent/CN113843937B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4629563A (en) * | 1980-03-14 | 1986-12-16 | Brunswick Corporation | Asymmetric membranes |
US4629563B1 (en) * | 1980-03-14 | 1997-06-03 | Memtec North America | Asymmetric membranes |
CN101293185A (en) * | 2008-01-30 | 2008-10-29 | 清华大学 | Method for producing polyvinylidene fluoride porous membrane |
CN102198374A (en) * | 2011-05-16 | 2011-09-28 | 杭州费尔过滤技术有限公司 | Asymmetric polyvinylidene fluoride microporous membrane with high intensity and preparation method thereof |
US20150377791A1 (en) * | 2014-06-27 | 2015-12-31 | Samsung Electronics Co., Ltd. | Gas sensor, refrigerator having the gas sensor and method of controlling the refrigerator |
CN104568933A (en) * | 2014-12-26 | 2015-04-29 | 山东商业职业技术学院 | Detection method for freshness of chilled fresh meat |
CN104897663A (en) * | 2015-05-21 | 2015-09-09 | 北京大学深圳研究生院 | Thin film sensor for detecting carbon dioxide and application of thin film sensor |
CN105833742A (en) * | 2016-04-26 | 2016-08-10 | 上海应用技术学院 | Preparation method for hydrophilic polyvinylidene fluoride (PVDF) antibacterial ultrafiltration membrane |
Non-Patent Citations (1)
Title |
---|
卜海军;于莲;陈鸣才;许凯;: "指状和海绵状聚偏氟乙烯多孔膜的制备及表征", 高分子材料科学与工程, no. 03 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115447222A (en) * | 2022-06-07 | 2022-12-09 | 武汉理工大学 | Preparation method of compact PVDF (polyvinylidene fluoride) -based composite membrane |
Also Published As
Publication number | Publication date |
---|---|
CN113843937B (en) | 2024-02-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3846404A (en) | Process of preparing gelled cellulose triacetate products and the products produced thereby | |
CN103531736B (en) | A kind of high heat-resisting lithium ion battery separator and preparation method thereof | |
Zhuang et al. | Development and characterization of nano-bilayer films composed of polyvinyl alcohol, chitosan and alginate | |
CN101811596B (en) | Edible polysaccharide-protein composite packaging film and preparation method thereof | |
US3963442A (en) | Colorimetric indicator compositions and method of manufacture | |
KR100715867B1 (en) | Method for manufacture of films containing insoluble solids embedded in cellulose-based films | |
AU2170102A (en) | Paste, which can undergo screen printing, for producing a porous polymer membrane for a biosensor | |
CN108783554A (en) | A kind of leakage of efficient anti-seepage carries capsule with diuresis promoting function and preparation method thereof | |
CN113843937B (en) | Migration-resistant hydrogel-based freshness colorimetric indication label and preparation method thereof | |
FR2702046A1 (en) | Heat-sensitive indicator | |
CN112266502B (en) | Multi-response nano-cellulose composite membrane and preparation method thereof | |
US11407866B2 (en) | Water-soluble polyvinyl alcohol blend film, related methods, and related articles | |
EP3578631B1 (en) | Water-soluble unit dose articles made from extruded films and containing household care compositions and methods for making the same | |
JPH0822802B2 (en) | Soluble sachet | |
US11453754B2 (en) | Water-soluble polyvinyl alcohol blend film, related methods, and related articles | |
CN108041674A (en) | A kind of impermeable capsule and preparation method thereof that efficiently blocks water | |
CN108409988A (en) | A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel | |
JP2011011164A (en) | Microcapsule and method for manufacturing the same | |
Hidayati et al. | Development of biodegradable smart packaging from chitosan, polyvinyl alcohol (PVA) and butterfly pea flower’s (Clitoria ternatea L.) anthocyanin extract | |
JP2023175789A (en) | Compositions and articles comprising complexes of 1-methylcyclopropene and alpha-cyclodextrin | |
BE1013079A3 (en) | Envelope a hard capsules plant and manufacturing method thereof. | |
CN102585263B (en) | Preparation method of organic montmorillonite-modified gelatin/PVA (polyvinyl acetate) composite film | |
CN101324530B (en) | Time process indicating device and its forming method | |
US20230139423A1 (en) | Humidity controlling material and humidity controlling apparatus | |
CN110511416A (en) | A kind of food Package is with stablizing the fresh-keeping plastic foil of moisture absorption and preparation method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |