CN114957748A - Antibacterial food packaging film and preparation method thereof - Google Patents
Antibacterial food packaging film and preparation method thereof Download PDFInfo
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- CN114957748A CN114957748A CN202210552795.1A CN202210552795A CN114957748A CN 114957748 A CN114957748 A CN 114957748A CN 202210552795 A CN202210552795 A CN 202210552795A CN 114957748 A CN114957748 A CN 114957748A
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- food packaging
- packaging film
- antibacterial
- zinc
- mixture
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- 235000013305 food Nutrition 0.000 title claims abstract description 73
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 64
- 229920006280 packaging film Polymers 0.000 title claims abstract description 64
- 239000012785 packaging film Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 40
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 34
- 239000000725 suspension Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 39
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 19
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 16
- 235000011187 glycerol Nutrition 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 229940044658 gallium nitrate Drugs 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002258 gallium Chemical class 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 claims description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 description 29
- 239000010408 film Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003242 anti bacterial agent Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical class [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical class NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
-
- 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 belongs to the technical field of food packaging, and particularly relates to an antibacterial food packaging film and a preparation method thereof. The preparation method of the antibacterial food packaging film specifically comprises the following steps: (1) ag and Zn co-modified C 3 N 4 (ii) a (2) Ag and Ga co-modify ZnO; (3) co-modifying C with Ag and Zn obtained in the step (1) 3 N 4 Dispersing the Ag and Ga co-modified ZnO obtained in the step (2) in a solvent, and ultrasonically stirring for 20-40 min to obtain a suspension; then adding a certain amount of mixture of PVA and glycerol into the suspension, heating at 85-95 ℃ for 2-4 h, and then coating the solution on a substrateDrying the materials for 10-14h at 50-70 ℃, and then uncovering the film to obtain the food packaging film. The antibacterial food packaging film prepared by the invention has excellent mechanical property and antibacterial property, and has excellent application prospect.
Description
Technical Field
The invention belongs to the technical field of food packaging. More particularly, to an antibacterial food packaging film and a preparation method thereof.
Background
The food contains rich nutrient sources, provides nutrient substance guarantee for human health, and provides a favorable place for the growth and reproduction of bacteria. With the importance of people on food quality and safety, antibacterial packaging is carried forward, and antibacterial packaging refers to a packaging technology in which an antibacterial substance (an antibacterial agent) is added into a packaging material, and the antibacterial substance can be gradually released from the packaging material to the surface of food to control the growth of microorganisms in the food.
Natural antibacterial agents, organic antibacterial agents and inorganic antibacterial agents are the most commonly used species of antibacterial agents. The natural antibacterial agent has few varieties, limited antibacterial effect, poor heat resistance and low sterilization rate, and cannot be used in a broad-spectrum long-acting manner; the organic antibacterial agent has the problems of toxic and side effects, poor heat resistance, easy hydrolysis, short effective period and the like. These disadvantages of natural antibacterial agents and organic antibacterial agents have prompted intense attention to the development and application of new antibacterial agents, including inorganic antibacterial materials.
Compared with natural antibacterial agents and organic antibacterial agents, the inorganic antibacterial agents have the advantages of broad antibacterial spectrum, good heat resistance, lasting antibacterial effect, higher safety, low toxicity and no drug resistance. Metal or metal oxide nanoparticles (e.g., silver, copper, titanium, magnesium, zinc, etc.) are currently the primary research direction for inorganic antimicrobial agents.
Zhao Dong Mei and other researches on preparation of nano Ag/TiO by taking butyl titanate as precursor 2 Compounding the PE antibacterial film. The prepared powder and composite membrane structures are characterized by analysis methods such as scanning electron microscope analysis and the like, and the photocatalytic sterilization performance of the nano Ag/TiO2/PE composite membrane on escherichia coli is investigated by adopting a flat plate colony counting method. The results show that: the PE composite membrane with 5 wt% of powder additive amount has good sterilization effect on escherichia coli, and can fully exert nano Ag and TiO 2 The synergistic bactericidal effect of the silver film can not only resist bacteria with broad spectrum, but also inhibit the color change of the silver film.
Zhang Meng et al research and analysis of feasibility of silver-based metal organic framework (Ag @ MOF) for food packaging, and casting method for preparing four different polyvinyl alcohol (PVA) -based food packaging films (PVA/Ag @ MOF, PVA/H) 2 PYDC, PVA/Ag, PVA), and their mechanical properties, thermodynamic properties, water barrier properties, antibacterial properties, cytotoxicity, and the like were studied. The results show that the polymer is compatible with PVA and PVA/H 2 Compared with the PYDC film, the mechanical property of the film is improved by adding Ag @ MOF, and the maximum tensile strength of the film is increased to 36.21 MPa. With PVA, PVA/H 2 Compared with PYDC and PVA/AgNPs membranes, the addition of Ag @ MOF enhances the thermal stability of the membrane. With PVA, PVA/H 2 Compared with the PYDC film, the rigid structure of AgNPs and Ag @ MOF prevents water from diffusing and improves the water resistance. The PVA/Ag @ MOF film has good antibacterial activity on staphylococcus aureus and escherichia coli, the antibacterial activity of the PVA/Ag @ MOF film is far greater than that of AgNPs and H2PYDC composite films, and the PVA/Ag @ MOF film has low cytotoxicity. Therefore, the PVA/Ag @ MOF film is a promising food packaging material, can reduce the interference of environmental microorganisms to food, has low cytotoxicity, and can effectively improve the safety and the storage period of the food.
CN109370129A discloses a food packaging film, which comprises the following raw materials in parts by weight: 80-100 parts of polyvinyl alcohol, 70-90 parts of starch, 60-80 parts of low-density polyethylene, 10-16 parts of white carbon black, 9-15 parts of modified muscovite, 1-4 parts of calcium carbonate, 0.4-0.7 part of oleic acid, 1-3 parts of antibacterial agent, 30-50 parts of plasticizer, 0.5-1.2 parts of mildew preventive and 0.5-1.5 parts of stabilizer; the modified muscovite comprises raw materials of muscovite, ricinoleic acid, soybean protein and a disodium hydrogen phosphate buffer solution. The food packaging film has good mechanical property, antibacterial property, water resistance and heat sealing capability, and can play a role in improving food safety and prolonging food storage period.
CN109233001B discloses an edible food packaging film, which is characterized by being prepared from the following raw materials in parts by weight: 90-120 parts of carrageenan-tea polyphenol-glucomannan, 30-50 parts of modified casein film forming agent, 10-30 parts of bacteriostatic agent, 10-20 parts of antioxidant, 10-25 parts of plasticizer, 5-15 parts of glycerol, 10-15 parts of tween, 5-10 parts of natural pigment and 120 parts of deionized water. The edible food packaging film prepared by the invention is soft in film forming, good in bending resistance and water resistance, good in glossiness and natural touch, good in antibacterial performance, and good in oxygen permeability, water vapor permeability, moisture content and solubility, and has a good application prospect.
Although the antibacterial performance of the food packaging film is researched in the prior art, the strength or antibacterial performance of the food packaging film prepared in the prior art is still insufficient, and how to develop an antibacterial food packaging film with excellent performance is a problem to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provide an antibacterial food packaging film and a preparation method thereof. The method specifically comprises the following steps: (1) ag and Zn co-modified C 3 N 4 (ii) a (2) Ag and Ga co-modified ZnO; (3) co-modifying C with Ag and Zn obtained in the step (1) 3 N 4 Dispersing the Ag and Ga co-modified ZnO obtained in the step (2) in a solvent, and ultrasonically stirring for 20-40 min to obtain a suspension; and then adding a certain amount of mixture of PVA and glycerol into the suspension, heating at 85-95 ℃ for 2-4 h, coating the solution on a base material, drying at 50-70 ℃ for 10-14h, and uncovering the film after drying to obtain the food packaging film. The antibacterial food packaging film prepared by the invention has excellent mechanical property and antibacterial property, and has excellent application prospect.
The invention aims to provide a preparation method of an antibacterial food packaging film.
Another object of the present invention is to provide an antibacterial food packaging film.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of an antibacterial food packaging film specifically comprises the following steps:
(1) ag and Zn co-modified C 3 N 4
(2) Ag and Ga co-modified ZnO
(3) Co-modifying C with Ag and Zn obtained in the step (1) 3 N 4 Dispersing the Ag and Ga co-modified ZnO obtained in the step (2) in a solvent, and ultrasonically stirring for 20-40 min to obtain a suspension; and then adding a certain amount of mixture of PVA and glycerol into the suspension, heating at 85-95 ℃ for 2-4 h, coating the solution on a base material, drying at 50-70 ℃ for 10-14h, and uncovering the film after drying to obtain the food packaging film.
Preferably, in the step (1), Ag and Zn co-modify C 3 N 4 The preparation method comprises the following steps: mixing urea, silver salt and zinc salt as raw materials to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in an inert atmosphere, and cooling the mixture to a temperature ofAt room temperature, Ag and Zn modified C is obtained 3 N 4 A catalytic material.
Preferably, the silver salt is silver nitrate; the zinc salt is at least one of zinc nitrate, zinc chloride and zinc acetate; the inert atmosphere is at least one of nitrogen, argon and helium.
Preferably, the molar ratio of the urea to the silver salt to the zinc salt is 1: 0.005-0.015: 0.005-0.015; the calcination conditions are as follows: the calcining temperature is 500-600 ℃, the heating rate is 3-7 ℃/min, and the constant-temperature calcining time is 3-6 h.
Preferably, in the step (2), the preparation method of Ag and Ga co-modified ZnO comprises the following steps: and (3) sequentially dispersing CTAB, a gallium salt, a silver salt, a zinc source and glycol in a solvent, transferring to a high-pressure hydrothermal reaction kettle for hydrothermal reaction, washing and drying the obtained solid product after the reaction is finished, namely the Ag and Ga modified ZnO.
Preferably, the gallium salt is at least one of gallium nitrate, gallium acetate and gallium chloride; the silver salt is silver nitrate; the zinc salt is at least one of zinc nitrate, zinc chloride and zinc acetate; the solvent is at least one of water, ethanol and methanol.
Preferably, the ratio of CTAB, gallium salt, silver salt, zinc source, glycol and solvent is 0.3-0.5 mol: 0.02-0.04 mol: 0.01-0.03 mol: 1 mol: 30-50 mL: 30-50 mL; the drying is carried out at the temperature of 80-100 ℃ for 12-18 h.
Preferably, the hydrothermal reaction temperature is 150-170 ℃, and the reaction time is 24-30 h.
Preferably, in the step (3), the Ag and Zn co-modify C 3 N 4 The mass ratio of Ag and Ga co-modified ZnO to PVA to glycerol is 0.01-0.03: 1: 0.3-0.5, and the solvent is water.
The antibacterial food packaging film is prepared based on the preparation method of the antibacterial food packaging film.
The invention has the following beneficial effects:
(1) co-modification of C by Ag and Zn 3 N 4 By utilizing the interaction between Ag and Zn, the lighting stripUnder the condition, the utilization rate of sunlight can be improved, and oxidizing radicals are generated by illumination for oxidizing sterilization, so that the antibacterial performance of the packaging film is improved;
(2) by adopting Ag and Ga to co-modify ZnO, the antibacterial property of the packaging film can be improved by utilizing the interaction between Ag and Ga.
(3) By modification of C 3 N 4 And the interaction between the modified ZnO, the mechanical property and the antibacterial property of the food packaging film are modified.
(4) The preparation method has the advantages of simple preparation process, low cost and excellent application prospect.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A preparation method of an antibacterial food packaging film specifically comprises the following steps:
(1) ag and Zn co-modified C 3 N 4
Mixing 1mol of urea, 0.01mol of silver nitrate and 0.01mol of zinc nitrate as raw materials to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in a nitrogen atmosphere at 550 ℃, at a heating rate of 5 ℃/min and at a constant temperature for 5 hours, and cooling the mixture to room temperature to obtain Ag and Zn modified C 3 N 4 A catalytic material;
(2) ag and Ga co-modified ZnO
Sequentially dispersing 0.4mol CTAB, 0.03mol of gallium nitrate, 0.02mol of silver nitrate, 1mol of zinc nitrate and 40mL of ethylene glycol in 40mL of ethanol, transferring the mixture to a high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction at the temperature of 160 ℃ for 28 h; and after the reaction is finished, washing and drying the obtained solid product at 90 ℃ for 16h to obtain the Ag and Ga modified ZnO.
(3) 0.2g of Ag and Zn obtained in step (1)Co-modified C 3 N 4 And 0.2g of Ag and Ga co-modified ZnO obtained in the step (2) are dispersed in 40mL of water, and ultrasonic stirring is carried out for 30min to obtain a suspension; then, a mixture of 10g of PVA and 4g of glycerin was added to the above suspension, heat-treated at 90 ℃ for 3 hours, and then the above solution was coated on a substrate, followed by drying at 60 ℃ for 12 hours, and after drying, the film was peeled off to obtain a food packaging film.
Example 2
A preparation method of an antibacterial food packaging film specifically comprises the following steps:
(1) ag and Zn co-modified C 3 N 4
Mixing 1mol of urea, 0.015mol of silver nitrate and 0.005mol of zinc chloride as raw materials to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in an argon atmosphere at the temperature of 600 ℃, at the heating rate of 7 ℃/min for 3h at the constant temperature, and cooling the mixture to room temperature to obtain Ag and Zn modified C 3 N 4 A catalytic material.
(2) Ag and Ga co-modified ZnO
Sequentially dispersing 0.5mol of CTAB, 0.02mol of gallium acetate, 0.03mol of silver nitrate, 1mol of zinc chloride and 50mL of ethylene glycol in 30mL of water, and transferring the mixture to a high-pressure hydrothermal reaction kettle to perform hydrothermal reaction at the temperature of 170 ℃ for 24 hours; and after the reaction is finished, washing and drying the obtained solid product at 100 ℃ for 12h to obtain the Ag and Ga modified ZnO.
(3) 0.3g of Ag and Zn obtained in the step (1) are co-modified with C 3 N 4 And 0.1g of Ag and Ga co-modified ZnO obtained in the step (2) are dispersed in 40mL of water, and ultrasonic stirring is carried out for 40min to obtain a suspension; then, a mixture of 10g of PVA and 5g of glycerin was added to the above suspension, heat-treated at 95 ℃ for 2 hours, and then the above solution was coated on a substrate, and then dried at 70 ℃ for 10 hours, and after drying, the film was peeled off to obtain a food packaging film.
Example 3
A preparation method of an antibacterial food packaging film specifically comprises the following steps:
(1) ag and Zn co-modified C 3 N 4
1mol of urea, 0.005mol of silver nitrate and 0.015mol of acetic acidMixing zinc as a raw material to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in a helium atmosphere at 500 ℃ at a heating rate of 3 ℃/min for 6h at a constant temperature, and cooling to room temperature to obtain Ag and Zn modified C 3 N 4 A catalytic material.
(2) Ag and Ga co-modified ZnO
Sequentially dispersing 0.3mol CTAB, 0.04mol gallium chloride, 0.01mol silver nitrate, 1mol zinc acetate and 30mL ethylene glycol in 50mL methanol, transferring to a high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction at the temperature of 150 ℃ for 30 h; and after the reaction is finished, washing and drying the obtained solid product at 80 ℃ for 18h to obtain the Ag and Ga modified ZnO.
(3) 0.1g of Ag and Zn obtained in the step (1) are co-modified with C 3 N 4 And 0.3g of Ag and Ga co-modified ZnO obtained in the step (2) are dispersed in 40mL of water, and the mixture is ultrasonically stirred for 20min to obtain a suspension; then, a mixture of 10g of PVA and 3g of glycerin was added to the suspension, heat-treated at 85 ℃ for 4 hours, and then the solution was coated on a substrate, and then dried at 50 ℃ for 14 hours, and after drying, the film was peeled off to obtain a food packaging film.
Comparative example 1
A preparation method of an antibacterial food packaging film specifically comprises the following steps:
(1) ag modified C 3 N 4
Mixing 1mol of urea and 0.02mol of silver nitrate as raw materials to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in a nitrogen atmosphere at 550 ℃, at a heating rate of 5 ℃/min for 5h at a constant temperature, and cooling the mixture to room temperature to obtain Ag modified C 3 N 4 A catalytic material;
(2) ag and Ga co-modified ZnO
Sequentially dispersing 0.4mol CTAB, 0.03mol of gallium nitrate, 0.02mol of silver nitrate, 1mol of zinc nitrate and 40mL of ethylene glycol in 40mL of ethanol, transferring the mixture to a high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction at the temperature of 160 ℃ for 28 h; and after the reaction is finished, washing and drying the obtained solid product at 90 ℃ for 16h to obtain the Ag and Ga modified ZnO.
(3)Modifying 0.2g of Ag obtained in the step (1) with C 3 N 4 And 0.2g of Ag and Ga co-modified ZnO obtained in the step (2) are dispersed in 40mL of water, and ultrasonic stirring is carried out for 30min to obtain a suspension; then, a mixture of 10g of PVA and 4g of glycerin was added to the above suspension, heat-treated at 90 ℃ for 3 hours, and then the above solution was coated on a substrate, and then dried at 60 ℃ for 12 hours, and after drying, the film was peeled off to obtain a food packaging film.
Comparative example 2
The preparation method of the antibacterial food packaging film specifically comprises the following steps:
(1) zn modified C 3 N 4
Mixing 1mol of urea and 0.02mol of zinc nitrate as raw materials to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in a nitrogen atmosphere at 550 ℃, at a heating rate of 5 ℃/min for 5h at a constant temperature, and cooling the mixture to room temperature to obtain Zn-modified C 3 N 4 A catalytic material;
(2) ag and Ga co-modified ZnO
Sequentially dispersing 0.4mol CTAB, 0.03mol gallium nitrate, 0.02mol silver nitrate, 1mol zinc nitrate and 40mL ethylene glycol in 40mL ethanol, and transferring to a high-pressure hydrothermal reaction kettle to perform hydrothermal reaction at 160 ℃ for 28 h; and after the reaction is finished, washing and drying the obtained solid product at 90 ℃ for 16h to obtain the Ag and Ga modified ZnO.
(3) Modifying 0.2g of Zn obtained in the step (1) with C 3 N 4 And 0.2g of Ag and Ga co-modified ZnO obtained in the step (2) are dispersed in 40mL of water, and ultrasonic stirring is carried out for 30min to obtain a suspension; then, a mixture of 10g of PVA and 4g of glycerin was added to the above suspension, heat-treated at 90 ℃ for 3 hours, and then the above solution was coated on a substrate, and then dried at 60 ℃ for 12 hours, and after drying, the film was peeled off to obtain a food packaging film.
Comparative example 3
A preparation method of an antibacterial food packaging film specifically comprises the following steps:
(1) ag and Zn co-modified C 3 N 4
Mixing 1mol of urea, 0.01mol of silver nitrate and 0.01mol of zinc nitrate as raw materialsMixing to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in a nitrogen atmosphere at 550 ℃, at a heating rate of 5 ℃/min for 5h at a constant temperature, and cooling to room temperature to obtain Ag and Zn modified C 3 N 4 A catalytic material;
(2) ag modified ZnO
Sequentially dispersing 0.4mol CTAB, 0.05mol of silver nitrate, 1mol of zinc nitrate and 40mL of ethylene glycol in 40mL of ethanol, and transferring the mixture to a high-pressure hydrothermal reaction kettle to perform hydrothermal reaction at the temperature of 160 ℃ for 28 h; and after the reaction is finished, washing the obtained solid product, and drying at 90 ℃ for 16h to obtain the Ag modified ZnO.
(3) 0.2g of Ag and Zn obtained in the step (1) are co-modified with C 3 N 4 And 0.2g of Ag co-modified ZnO obtained in the step (2) are dispersed in 40mL of water, and ultrasonic stirring is carried out for 30min to obtain a suspension; then 10g of a mixture of PVA and 4g of glycerol was added to the suspension, heat treated at 90 ℃ for 3 hours, and then the solution was coated on a substrate, and then dried at 60 ℃ for 12 hours, and after drying, the film was peeled off to obtain a food packaging film.
Comparative example 4
A preparation method of an antibacterial food packaging film specifically comprises the following steps:
(1) ag and Zn co-modified C 3 N 4
Mixing 1mol of urea, 0.01mol of silver nitrate and 0.01mol of zinc nitrate as raw materials to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in a nitrogen atmosphere at 550 ℃, at a heating rate of 5 ℃/min and at a constant temperature for 5 hours, and cooling the mixture to room temperature to obtain Ag and Zn modified C 3 N 4 A catalytic material;
(2) ga-modified ZnO
Sequentially dispersing 0.4mol CTAB, 0.05mol of gallium nitrate, 1mol of zinc nitrate and 40mL of ethylene glycol in 40mL of ethanol, transferring the mixture to a high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction at the temperature of 160 ℃ for 28 h; after the reaction is finished, the obtained solid product is washed and dried for 16h at 90 ℃, and the Ga modified ZnO is obtained.
(3) 0.2g of Ag and Zn obtained in the step (1) are co-modified with C 3 N 4 And 0.2g of Ga modified ZnO obtained in the step (2) is dispersed in 40mL of water, and ultrasonic stirring is carried out for 30min to obtain suspension; then, a mixture of 10g of PVA and 4g of glycerin was added to the above suspension, heat-treated at 90 ℃ for 3 hours, and then the above solution was coated on a substrate, and then dried at 60 ℃ for 12 hours, and after drying, the film was peeled off to obtain a food packaging film.
Comparative example 5
A preparation method of an antibacterial food packaging film specifically comprises the following steps:
(1) co-modified C of Ag and Zn 3 N 4
Mixing 1mol of urea, 0.01mol of silver nitrate and 0.01mol of zinc nitrate as raw materials to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in a nitrogen atmosphere at 550 ℃, at a heating rate of 5 ℃/min and at a constant temperature for 5 hours, and cooling the mixture to room temperature to obtain Ag and Zn modified C 3 N 4 A catalytic material;
(3) 0.4g of Ag and Zn obtained in the step (1) are co-modified with C 3 N 4 Dispersing in 40mL of water, and ultrasonically stirring for 30min to obtain a suspension; then, a mixture of 10g of PVA and 4g of glycerin was added to the above suspension, heat-treated at 90 ℃ for 3 hours, and then the above solution was coated on a substrate, and then dried at 60 ℃ for 12 hours, and after drying, the film was peeled off to obtain a food packaging film.
Comparative example 6
A preparation method of an antibacterial food packaging film specifically comprises the following steps:
(2) ag and Ga co-modified ZnO
Sequentially dispersing 0.4mol CTAB, 0.03mol of gallium nitrate, 0.02mol of silver nitrate, 1mol of zinc nitrate and 40mL of ethylene glycol in 40mL of ethanol, transferring the mixture to a high-pressure hydrothermal reaction kettle, and carrying out hydrothermal reaction at the temperature of 160 ℃ for 28 h; after the reaction is finished, the obtained solid product is washed and dried for 16h at 90 ℃, and the Ag and Ga modified ZnO is obtained.
(3) Dispersing 0.4g of Ag and Ga co-modified ZnO obtained in the step (2) in 40mL of water, and ultrasonically stirring for 30min to obtain a suspension; then, a mixture of 10g of PVA and 4g of glycerin was added to the above suspension, heat-treated at 90 ℃ for 3 hours, and then the above solution was coated on a substrate, followed by drying at 60 ℃ for 12 hours, and after drying, the film was peeled off to obtain a food packaging film.
The antibacterial food packaging films of examples 1-3 and comparative examples 1-6 were tested for mechanical properties and antibacterial properties, and the specific test results are shown in table 1.
And (3) testing mechanical properties: the Tensile Strength (TS) of food packaging films was determined using a tensile tester based on ASTM standard method D882-12. The samples used for the test were cut into dumbbell-shaped test specimens having dimensions of 20mm × 60mm × 1mm (width × length × thickness). Each sample was measured 3 times repeatedly to obtain an average value.
And (3) testing antibacterial performance: the antibacterial properties of the food packaging films were measured by testing the antibacterial activity of the food packaging films against escherichia coli (ATCC25922) and staphylococcus aureus (ATCC6538) using a plate colony counting method. All food packaging films were cut into circular specimens of 10mm diameter and placed at the bottom of the wells of a 24-well plate. Subsequently, 100. mu.L of diluted bacterial suspension (about 10. mu.L) was dropped into each well 5 CFU/m L) and dispersed uniformly over the surface of the film. The 24-well plate was then placed in a bacterial incubator and incubated at 37 ℃ for 6 hours. Then, each sample was taken out and soaked in a tube containing a PBS solution added to 10m L, and then all the tubes were placed in a water bath constant temperature shaker (150rpm) and shaken for 10 minutes. Subsequently, 60. mu.L of the diluted bacterial suspension was spread on nutrient agar plates, cultured at 37 ℃ for 24 hours, counted for the number of viable colonies, and the experiment was repeated three times.
TABLE 1
| Tensile Strength (MPa) | Escherichia coli inhibitory rate (%) | Staphylococcus aureus inhibitory rate (%) | |
| Example 1 | 37.35 | 99.3 | 98.9 |
| Example 2 | 37.12 | 98.3 | 98.1 |
| Example 3 | 37.27 | 98.7 | 98.6 |
| Comparative example 1 | 37.03 | 96.2 | 95.7 |
| Comparative example 2 | 37.05 | 96.3 | 96.0 |
| Comparative example 3 | 37.10 | 96.9 | 96.6 |
| Comparative example 4 | 37.08 | 96.6 | 96.2 |
| Comparative example 5 | 36.25 | 95.3 | 94.1 |
| Comparative example 6 | 36.17 | 94.9 | 93.6 |
As can be seen from Table 1, the antibacterial food packaging films prepared by the invention have excellent mechanical properties and antibacterial properties due to the synergistic effect of the components, namely the antibacterial food packaging films prepared by the invention have excellent application prospects through the comparative examples of examples 1-3 and comparative examples 1-6.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of an antibacterial food packaging film is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) ag and Zn co-modified C 3 N 4
(2) Ag and Ga co-modified ZnO
(3) Co-modifying C with Ag and Zn obtained in the step (1) 3 N 4 Dispersing the Ag and Ga co-modified ZnO obtained in the step (2) in a solvent, and ultrasonically stirring for 20-40 min to obtain a suspension; and then adding a certain amount of mixture of PVA and glycerol into the suspension, heating at 85-95 ℃ for 2-4 h, coating the solution on a base material, drying at 50-70 ℃ for 10-14h, and uncovering the film after drying to obtain the food packaging film.
2. The method for preparing an antibacterial food packaging film according to claim 1, characterized in that: in the step (1), Ag and Zn co-modify C 3 N 4 The preparation method comprises the following steps: mixing urea, silver salt and zinc salt serving as raw materials to obtain a mixture, ball-milling and uniformly mixing the mixture, calcining the mixture in an inert atmosphere, and cooling the mixture to room temperature to obtain Ag and Zn modified C 3 N 4 A catalytic material.
3. The method for preparing an antibacterial food packaging film according to claim 2, characterized in that: the silver salt is silver nitrate; the zinc salt is at least one of zinc nitrate, zinc chloride and zinc acetate; the inert atmosphere is at least one of nitrogen, argon and helium.
4. The method for preparing an antibacterial food packaging film according to claim 2, characterized in that: the molar ratio of the urea to the silver salt to the zinc salt is 1: 0.005-0.015; the calcination conditions are as follows: the calcining temperature is 500-600 ℃, the heating rate is 3-7 ℃/min, and the constant-temperature calcining time is 3-6 h.
5. The method for preparing an antibacterial food packaging film according to claim 1, characterized in that: in the step (2), the preparation method of Ag and Ga co-modified ZnO comprises the following steps: and (3) sequentially dispersing CTAB, a gallium salt, a silver salt, a zinc source and glycol in a solvent, transferring to a high-pressure hydrothermal reaction kettle for hydrothermal reaction, washing and drying the obtained solid product after the reaction is finished, namely the Ag and Ga modified ZnO.
6. The method for preparing an antibacterial food packaging film according to claim 5, characterized in that: the gallium salt is at least one of gallium nitrate, gallium acetate and gallium chloride; the silver salt is silver nitrate; the zinc salt is at least one of zinc nitrate, zinc chloride and zinc acetate; the solvent is at least one of water, ethanol and methanol.
7. The method for preparing an antibacterial food packaging film according to claim 5, characterized in that: the ratio of CTAB, gallium salt, silver salt, zinc source, glycol and solvent is 0.3-0.5 mol: 0.02-0.04 mol: 0.01-0.03 mol: 1 mol: 30-50 mL; the drying is carried out at the temperature of 80-100 ℃ for 12-18 h.
8. The method for preparing an antibacterial food packaging film according to claim 5, characterized in that: the hydrothermal reaction temperature is 150-170 ℃, and the reaction time is 24-30 h.
9. The method for preparing an antibacterial food packaging film according to claim 1, characterized in that: in the step (3), the Ag and Zn co-modify C 3 N 4 The mass ratio of Ag and Ga co-modified ZnO to PVA to glycerin is 0.01-0.03: 1: 0.3-0.5, and the solvent is water.
10. An antibacterial food packaging film prepared by the method for preparing an antibacterial food packaging film according to any one of claims 1 to 9.
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