CN115975386A - Packaging film material for preservation and preparation method thereof - Google Patents
Packaging film material for preservation and preparation method thereof Download PDFInfo
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- CN115975386A CN115975386A CN202310114007.5A CN202310114007A CN115975386A CN 115975386 A CN115975386 A CN 115975386A CN 202310114007 A CN202310114007 A CN 202310114007A CN 115975386 A CN115975386 A CN 115975386A
- Authority
- CN
- China
- Prior art keywords
- packaging film
- parts
- film material
- polylactic acid
- chitosan
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Links
- 239000012785 packaging film Substances 0.000 title claims abstract description 93
- 229920006280 packaging film Polymers 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 68
- 238000004321 preservation Methods 0.000 title claims abstract description 28
- 239000000835 fiber Substances 0.000 claims abstract description 95
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 69
- 239000004626 polylactic acid Substances 0.000 claims abstract description 69
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 53
- 229920001661 Chitosan Polymers 0.000 claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 108010010803 Gelatin Proteins 0.000 claims abstract description 22
- 239000008273 gelatin Substances 0.000 claims abstract description 22
- 229920000159 gelatin Polymers 0.000 claims abstract description 22
- 235000019322 gelatine Nutrition 0.000 claims abstract description 22
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 22
- 239000003755 preservative agent Substances 0.000 claims abstract description 21
- 230000002335 preservative effect Effects 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 57
- 239000010902 straw Substances 0.000 claims description 46
- 241001075517 Abelmoschus Species 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229920000728 polyester Polymers 0.000 claims description 16
- -1 2,5-furandicarboxylic acid glycol ester Chemical class 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 229920000954 Polyglycolide Polymers 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- 239000004633 polyglycolic acid Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229920001046 Nanocellulose Polymers 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 9
- CHTHALBTIRVDBM-UHFFFAOYSA-N dehydromucic acid Natural products OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002074 melt spinning Methods 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229940074391 gallic acid Drugs 0.000 claims description 5
- 235000004515 gallic acid Nutrition 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 229940049964 oleate Drugs 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 3
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 claims description 3
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 claims description 3
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 claims description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 20
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 16
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 235000004936 Bromus mango Nutrition 0.000 description 15
- 235000014826 Mangifera indica Nutrition 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 235000009184 Spondias indica Nutrition 0.000 description 15
- 230000004580 weight loss Effects 0.000 description 15
- 241001093152 Mangifera Species 0.000 description 14
- 235000013399 edible fruits Nutrition 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002985 plastic film Substances 0.000 description 8
- 229920006255 plastic film Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 241000238675 Periplaneta americana Species 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000005068 transpiration Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229920002101 Chitin Polymers 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001550 time effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- 241000249058 Anthracothorax Species 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000003544 deproteinization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the field of packaging film materials, and particularly discloses a packaging film material for preservation and a preparation method thereof. The packaging film material for preservation comprises the following raw materials in parts by weight: 3-8 parts of gelatin, 1.5-4 parts of chitosan, 0.06-0.1 part of plasticizer, 0.05-0.08 part of antioxidant, 0.08-0.1 part of heat stabilizer, 0.2-0.4 part of silane coupling agent, 1-2 parts of antibacterial preservative, 1-2 parts of modified polylactic acid fiber and 0.3-0.8 part of titanium dioxide. The packaging film material for preservation has the advantages of good mechanical property and barrier property, easy biodegradation, good antibacterial and preservation durability and capability of prolonging the shelf life of fruits and vegetables.
Description
Technical Field
The application relates to the technical field of packaging film materials, in particular to a packaging film material for fresh keeping and a preparation method thereof.
Background
As is well known, food packaging films are polymeric materials used to wrap the surface of food, primarily to isolate the entry of microbial bacteria and foreign contaminants, preventing and prolonging the deterioration of food. The most common food packaging films in the world today are typically man-made polymeric materials (e.g., polyethylene, polypropylene, etc.), primarily from the petroleum industry, commonly known as plastic films. The membrane has low cost, no toxicity and excellent physical and chemical properties, but has two serious defects. Firstly, the method comprises the following steps: the plastic film is extremely difficult to degrade, the waste plastic film causes serious environmental problems, and the earth is deeply harmed by white pollution caused by waste plastic products nowadays. Therefore, developing new food packaging films to reduce or even replace the use of plastic films is one of the hot spots of future research. Secondly, the method comprises the following steps: the plastic film has weak fresh-keeping capacity and antibacterial effect, and the two performances are required by food packaging, particularly fruit and vegetable products, and the stronger the two performances, the longer the service life of the packaged food.
The Chinese invention patent document with the application number of CN2021112590207 discloses a food packaging film material, which comprises chitosan and American cockroach extracts, wherein the mass ratio of the chitosan to the American cockroach extracts is 1.1-0.4; wherein the chitosan is prepared by the following steps: adding NaOH solution into the periplaneta americana dregs for deproteinization, removing inorganic salt in the dregs by hydrochloric acid after drying, then adding a bleaching agent to complete decolorization, obtaining chitin by freeze-drying treatment, and then adding concentrated alkali liquor into the chitin for deacetylation treatment to obtain chitosan.
The packaging film material has degradable, nontoxic and harmless, antibacterial and antioxidant effects, and also utilizes periplaneta americana dregs, so that waste utilization is realized, but aiming at the related technologies, the inventor finds that when the packaging material is used for packaging fruits and vegetables, the freshness and the durability of the fruits and vegetables are poor, and the freshness retaining capacity needs to be improved.
Disclosure of Invention
In order to improve the fresh-keeping capacity of the packaging film material and prolong the freshness durability of fruits and vegetables, the application provides the packaging film material for keeping fresh and the preparation method thereof.
In a first aspect, the present application provides a packaging film material for fresh-keeping, which adopts the following technical scheme:
a packaging film material for fresh keeping comprises the following raw materials in parts by weight: 3-8 parts of gelatin, 1.5-4 parts of chitosan, 0.06-0.1 part of plasticizer, 0.05-0.08 part of antioxidant, 0.08-0.1 part of heat stabilizer, 0.2-0.4 part of silane coupling agent, 1-2 parts of antibacterial preservative, 1-2 parts of modified polylactic acid fiber and 0.3-0.8 part of titanium dioxide.
By adopting the technical scheme, the gelatin is used as a substrate of the packaging film, the gelatin is a degradable substance which is easily soluble in water, is a product of partial hydrolysis of collagen, contains functional groups such as amino, hydroxyl, carboxyl and the like, and has the property of gel, the formed film has the characteristic of softer texture, the chitosan is a biological macromolecule and has certain antibacterial and antiviral capabilities, the structure of the chitosan is stable, a hydrogen bond can be formed with the gelatin, and a certain binding force can be generated, so that the tensile strength and the breaking elongation of the packaging film are improved.
Optionally, the preparation method of the antibacterial preservative comprises the following steps:
mixing okra straw fibers, polyvinyl alcohol and deionized water, performing ultrasonic dispersion, adding silver nitrate and citric acid, uniformly mixing, drying at 40-50 ℃ for 20-24 hours, and irradiating under an ultraviolet lamp for 3-5 hours to obtain silver-loaded okra straw fibers;
mixing the silver-loaded okra straw fibers with modified polyester and sodium bicarbonate, extruding, granulating and grinding.
By adopting the technical scheme, the okra straw fiber is mainly prepared from okra straw skins through processes of boiling, bleaching and the like, the degumming effect of the okra straw fiber is improved, the okra straw fiber is rough in surface, has longitudinal gaps and transverse branches, has better cohesive force, and is favorable for absorbing silver nitrate and citric acid, the okra straw fiber is used as a carrier, the silver nitrate and the citric acid are loaded in and on the surface of the okra straw fiber through impregnation and adhesion of polyvinyl alcohol, and the silver nitrate is reduced into nano silver under the irradiation of an ultraviolet lamp, so that nano silver particles which are uniformly distributed, small in particle size and antibacterial are formed in the inner part and the surface of the okra straw fiber, hydrogen ions in the citric acid are strong in polarity, ethylene molecules are easier to generate polarization effect and are adsorbed, and the okra straw fiber loaded with the citric acid has physical adsorption effect and chemical adsorption effect on the ethylene molecules, the adsorption capacity is large, the influence of ethylene on the quality of fruits and vegetables can be reduced, and fruits and vegetables are prevented from being rotten; finally, the silver-loaded okra straw fibers are coated by using the modified polyester as an outer layer, and the sodium bicarbonate is used as a pore-forming agent to form micropores on the outer layer, so that nano silver and citric acid on the silver-loaded okra straw fibers can be slowly and effectively released, the nano silver can continuously resist bacteria and prolong the antibacterial aging, and the citric acid can continuously adsorb ethylene, so that the fruits and vegetables are not easy to mature and rot quickly due to the generation of ethylene gas after being coated, and therefore, the long-acting fresh-keeping effect and the fresh-keeping aging of the fruits and vegetables can be prolonged.
Optionally, the antibacterial preservative comprises the following components in parts by weight: 5-10 parts of okra straw fiber, 2-3 parts of silver nitrate, 1-2 parts of polyvinyl alcohol, 100 parts of deionized water, 0.5-2 parts of citric acid, 1-3 parts of modified polyester and 0.3-0.8 part of sodium bicarbonate.
By adopting the technical scheme, the antibacterial preservative capable of slowly and effectively releasing the nano-silver and the citric acid can be prepared from the raw materials, and the mechanical strength of the packaging film can be improved by the antibacterial preservative under the action of the modified polyester outer layer.
Optionally, the preparation method of the modified polylactic acid fiber comprises the following steps:
mixing polylactic acid, poly 2,5-furandicarboxylic acid glycol ester, nano cellulose whisker and coupling modified zinc oxide, and carrying out melt spinning to obtain polylactic acid fiber;
dissolving polyglycolic acid with hexafluoroisopropanol, adding sodium chloride, graphene oxide and a micron-sized molecular sieve, uniformly mixing, soaking the polylactic acid fiber in the solution for 30-40min, washing with deionized water, and drying in the air.
By adopting the technical scheme, the poly 2,5-furandicarboxylic acid glycol ester has higher gas barrier property to oxygen, carbon dioxide and steam, higher mechanical strength and more excellent physical-mechanical property, can improve the barrier property and mechanical strength of polylactic acid, the nanocellulose whisker can improve the elongation at break and flexibility of polylactic acid fiber, and increase the crystallinity of polylactic acid, so that the difficulty of small molecule gas permeating a packaging film is increased, the barrier property of the packaging film material is improved, the zinc oxide modified by coupling is uniformly dispersed in the polylactic acid, the tensile strength and elongation at break of the polylactic acid fiber can be improved, and the antibacterial capacity of the polylactic acid fiber is increased; polyglycolic acid has the characteristics of good degradability, flexibility and biocompatibility, and is uniformly mixed with a micron-sized molecular sieve, graphene oxide and the like after being dissolved, the polyglycolic acid forms a film on polylactic acid fibers, the tensile strength and the tear resistance of the polylactic acid fibers are improved, sodium chloride is used as a pore-forming agent, and pores are formed on a polyglycolic acid outer film, so that zinc oxide loaded on the polylactic acid fibers can continuously release antibacterial capacity, the antibacterial and fresh-keeping time effects are prolonged, the graphene oxide contained on the polyglycolic acid outer film can increase the barrier property of the polyglycolic acid to oxygen and water vapor, the micron-sized molecular sieve has good compatibility with the polylactic acid, and the modified polylactic acid fibers have strong adsorption force to ethylene, so that the modified polylactic acid fibers have strong barrier property and mechanical property, can absorb ethylene, and have long fresh-keeping time effect and durable antibacterial property.
Optionally, the modified polylactic acid fiber comprises the following raw materials in parts by weight: 1-3 parts of polylactic acid, 0.5-1 part of 2,5-furandicarboxylic acid glycol ester, 0.6-1.2 parts of nano cellulose whisker, 0.3-0.6 part of coupled modified zinc oxide, 0.5-1.5 parts of polyglycolic acid, 10 parts of hexafluoroisopropanol, 0.1-0.5 part of sodium chloride, 0.3-0.5 part of graphene oxide and 0.3-0.7 part of micron-sized molecular sieve.
By adopting the technical scheme, the modified polylactic acid fiber with durable antibacterial and fresh-keeping performances can be prepared from the raw materials, so that the water transpiration effect of fruits and vegetables is reduced, and the fruits and vegetables are prevented from being rotted.
Optionally, the melt spinning temperature is 190-200 ℃, the spinning speed is 100-150m/min, the diameter of a spinneret orifice is 0.5-0.6mm, and the spinning voltage is 30-40KV.
Optionally, the chitosan is selected from at least one of gallic acid grafted chitosan, vanillic acid grafted chitosan and syringic acid grafted chitosan.
By adopting the technical scheme, although the chitosan is a biopolymer which can be used for food packaging and has hydrophilicity, water vapor is easier to adsorb on a packaging film, so that the diffusion effect of the water vapor is enhanced, and the barrier effect is weakened, therefore, gallic acid, vanillic acid or syringic acid are grafted on the chitosan to form covalent bonds, so that the hydrophilicity of the chitosan is greatly limited, and the affinity of the packaging film for the water vapor is reduced.
Optionally, the plasticizer is at least one of tributyl citrate, acetyl tributyl citrate and glycerol.
Optionally, the heat stabilizer is at least one of calcium epoxy oleate and zinc epoxy stearate.
In a second aspect, the application provides a preparation method of a packaging film material for fresh-keeping, which adopts the following technical scheme: a preparation method of a packaging film material for fresh keeping comprises the following steps:
adding gelatin into deionized water, soaking at normal temperature for 20-30min, heating to 60-65 deg.C, stirring for 30-40min to obtain gelatin solution with concentration of 8-10 wt%;
dissolving chitosan in 2-3wt% acetic acid solution to obtain 3-5wt% chitosan solution;
dissolving a silane coupling agent, adding an antibacterial preservative, titanium dioxide and modified polylactic acid fibers, mixing uniformly, mixing with a gelatin solution and a chitosan solution, adding a plasticizer, a heat stabilizer and an antioxidant, mixing uniformly, casting, drying and cooling to obtain the packaging film material.
By adopting the technical scheme, the interaction of the gelatin solution and the chitosan solution is utilized to form hydrogen bonds, so that the packaging film has better tensile strength and elongation at break, and the silane coupling agent is utilized to improve the compatibility of the antibacterial preservative, the titanium dioxide and the modified polylactic acid with the gelatin solution and the chitosan solution, so that the raw materials are uniformly dispersed in the blend of the gelatin solution and the chitosan solution, and the smooth and compact packaging film is formed.
In summary, the present application has the following beneficial effects:
1. according to the application, gelatin is used as a substrate of the packaging film, the tensile strength and the elongation at break of the packaging film are improved by utilizing chitosan, the antibacterial property and the fresh-keeping capacity of the packaging film are improved, in addition, titanium dioxide is added as a photocatalyst to decompose ethylene generated by fruits and vegetables, the influence of the ethylene on the fruits and vegetables is reduced, the fruits and vegetables are prevented from being rotted, in addition, an antibacterial fresh-keeping agent and modified polylactic acid fibers are also used, the antibacterial fresh-keeping agent has long-acting antibacterial and fresh-keeping capacity, the modified polylactic acid fibers can improve the barrier capacity of the packaging film, the integral action of moisture is hindered, the fruits and vegetables are prevented from being infected by exogenous bacteria or the time of disease generation of germs hidden in the fruits is delayed, the rotting is effectively inhibited, and the tensile strength and the elongation at break of the packaging film can be improved.
2. Preferably adopt okra straw fiber as the carrier in this application, at its inside and surperficial load nanometer silver and citric acid, make silver-carrying okra straw fiber to cladding modified polyester skin on silver-carrying okra straw fiber, utilize sodium bicarbonate as the pore-forming agent, form the micropore on modified polyester skin, thereby make nanometer silver and citric acid slowly release, prolonged the antibiotic and the fresh-keeping persistence of antibiotic antistaling agent, modified polyester and okra straw fiber can improve the mechanical strength of packaging film in addition.
3. In the application, polylactic acid, poly 2,5-ethylene glycol furanoate, nano cellulose whiskers and coupled modified zinc oxide are preferably adopted to prepare polylactic acid fibers through melt spinning, then an outer membrane which takes polyglycolic acid as a film forming substance is impregnated on the polylactic acid fibers, and sodium chloride is taken as a pore-forming agent to form micropores on the polyglycolic acid outer membrane, so that the zinc oxide continuously releases antibacterial capacity to achieve a long-acting antibacterial effect, graphene oxide on the outer membrane can also achieve the antibacterial effect and can also improve the barrier property of the polylactic acid fibers, the micron-sized molecular sieve can adsorb ethylene, the fresh-keeping capacity of the modified polylactic acid fibers is improved, and the freshness of fruits and vegetables is prolonged.
Detailed Description
Preparation examples 1 to 6 of antibacterial and antistaling agents
Preparation example 1: (1) Mixing 10kg of okra straw fiber, 2kg of polyvinyl alcohol and 100 parts of deionized water, ultrasonically dispersing for 20min at the power of 400W, adding 3kg of silver nitrate and 2kg of citric acid, uniformly mixing, drying at 50 ℃ for 20h, and irradiating under an ultraviolet lamp for 5h to obtain the silver-loaded okra straw fiber, wherein the okra straw fiber is prepared by the following method: peeling okra straws to obtain straw skins, heating the straw skins in 2.5g/L hydrochloric acid in a water bath at 60 ℃ for 2 hours, washing with water, boiling for 3 hours by using sodium hydroxide with the concentration of 15wt%, boiling for 30 minutes by using 1.5g/L hydrogen peroxide and 3g/L alkali liquor (consisting of rare earth, sodium carbonate and sodium silicate according to the mass ratio of 1;
(2) Mixing silver-loaded okra straw fiber with 3kg of modified polyester and 0.8kg of sodium bicarbonate, extruding at 220 ℃, granulating, and grinding to 10nm nanometer, wherein the intrinsic viscosity of the modified polyester is 0.68dl/g, and is selected from Wujiang Fudong Shunhexing chemical fiber factories.
Preparation example 2: (1) Mixing 5kg of okra straw fiber, 1kg of polyvinyl alcohol and 100 parts of deionized water, ultrasonically dispersing for 20min at the power of 400W, adding 2kg of silver nitrate and 0.5kg of citric acid, uniformly mixing, drying for 24h at 40 ℃, and irradiating for 3h under an ultraviolet lamp to obtain the silver-loaded okra straw fiber, wherein the okra straw fiber is prepared by the following method: peeling okra straws to obtain straw skins, heating the straw skins in 2.5g/L hydrochloric acid in a water bath at 60 ℃ for 2 hours, washing with water, boiling for 3 hours by using sodium hydroxide with the concentration of 15wt%, boiling for 30 minutes by using 1.5g/L hydrogen peroxide and 3g/L alkali liquor (consisting of rare earth, sodium carbonate and sodium silicate according to the mass ratio of 1;
(2) Mixing silver-loaded okra straw fiber with 1kg of modified polyester and 0.3kg of sodium bicarbonate, extruding at 220 ℃, granulating, and grinding to 20nm, wherein the intrinsic viscosity of the modified polyester is 0.68dl/g, and is selected from Wujiang Dongfeng Shunhxing chemical fiber factory.
Preparation example 3: the difference from preparation example 1 is that silver nitrate was not added.
Preparation example 4: the difference from preparation example 1 is that citric acid was not added.
Preparation example 5: the difference from preparation example 1 is that sodium bicarbonate was not added.
Preparation example 6: the difference from the preparation example 1 is that the step (2) is not carried out, and the silver-loaded okra straw fiber is used as the antibacterial preservative.
Preparation examples 7 to 13 of modified polylactic acid fiber
Preparation example 7: (1) Mixing 3kg of polylactic acid, 1kg of poly 2,5-furandicarboxylic acid glycol ester, 1.2kg of nano cellulose whisker and 0.6kg of coupling modified zinc oxide, and carrying out melt spinning at 200 ℃ to obtain the polylactic acid fiber, wherein the spinning speed is 100m/min, the diameter of a spinneret orifice is 0.6mm, the spinning voltage is 40KV, the type of the polylactic acid is 4032D, the type of the poly 2,5-furandicarboxylic acid glycol ester is selected from jiulong, the type is JFL, and the preparation method of the coupling modified zinc oxide comprises the following steps: refluxing zinc oxide in 40 deg.C ethanol for 1h, ultrasonically dispersing for 20min, adjusting pH to 2 with hydrochloric acid, adding silane coupling agent KH550 with concentration of 2.5wt%, stirring and refluxing at 40 deg.C for 1h, adjusting pH to 10 with sodium hydroxide, refluxing for 2h, centrifuging for 5min, and drying at 80 deg.C;
(2) Dissolving 1.5kg of polyglycolic acid with 10kg of hexafluoroisopropanol, adding 0.5kg of sodium chloride, 0.5kg of graphene oxide and 0.7kg of ZSM-5 type micron-sized molecular sieve, uniformly mixing, soaking the polylactic acid fiber in the mixture for 40min, washing with deionized water and drying in the air.
Preparation example 8: (1) 1kg of polylactic acid, 0.5kg of poly 2,5-furandicarboxylic acid glycol ester, 0.6kg of nano cellulose whisker and 0.3kg of coupling modified zinc oxide are mixed and melt-spun at 190 ℃ to prepare the polylactic acid fiber, wherein the spinning speed is 150m/min, the diameter of a spinneret orifice is 0.5mm, the spinning voltage is 30KV, the type of the polylactic acid is 4032D, the poly 2,5-furandicarboxylic acid glycol ester is selected from jifenglong, the type is JFL, and the preparation method of the coupling modified zinc oxide is as follows: refluxing zinc oxide in 40 deg.C ethanol for 1h, ultrasonically dispersing for 20min, adjusting pH to 2 with hydrochloric acid, adding silane coupling agent KH550 with concentration of 2.5wt%, stirring and refluxing at 40 deg.C for 1h, adjusting pH to 10 with sodium hydroxide, refluxing for 2h, centrifuging for 5min, and drying at 80 deg.C; (2) Dissolving 0.5kg of polyglycolic acid with 10kg of hexafluoroisopropanol, adding 0.1kg of sodium chloride, 0.3kg of graphene oxide and 0.3kg of ZSM-5 type micron-sized molecular sieve, uniformly mixing, soaking the polylactic acid fiber in the mixture for 40min, washing with deionized water and drying in the air.
Preparation example 9: the difference from preparation example 7 is that no graphene oxide was added in step (2).
Preparation example 10: the difference from preparation example 7 is that micron-sized molecular sieves are not added in step (2).
Preparation example 11: the difference from preparation example 7 is that coupling modified zinc oxide was not added in step (1).
Preparation example 12: the difference from preparation example 7 is that no nanocellulose whiskers were added in step (1).
Preparation example 13: the difference from preparation example 7 is that no polyethylene 2,5-furandicarboxylate was added in step (1).
Examples
Example 1: a packaging film material for fresh-keeping is prepared from chitosan as gallic acid grafted chitosan, plasticizer as glycerin, antioxidant 1010, heat stabilizer as calcium epoxy oleate, silane coupling agent KH550, antibacterial antistaling agent as prepared in preparation example 1, modified polylactic acid fiber as prepared in preparation example 7, and titanium dioxide with particle size of 10nm, as shown in Table 1.
The preparation method of the packaging film material for fresh-keeping comprises the following steps:
s1, adding gelatin into deionized water, soaking at normal temperature for 30min, then heating to 65 ℃, and stirring for 30min to prepare a gelatin solution with the concentration of 10 wt%;
s2, dissolving chitosan in an acetic acid solution with the concentration of 2wt% to prepare a chitosan solution with the concentration of 5 wt%;
s3, dissolving a silane coupling agent by using ethanol until the concentration is 5wt%, adding an antibacterial preservative, titanium dioxide and modified polylactic acid fibers, mixing uniformly, mixing with a gelatin solution and a chitosan solution, adding a plasticizer, a heat stabilizer and an antioxidant, mixing uniformly, and then carrying out tape casting, drying and cooling to obtain the packaging film material.
TABLE 1 consumption of raw materials for the fresh-keeping wrapping film materials in examples 1-3
Example 2: a packaging film material for fresh-keeping, the consumption of raw materials is shown in Table 1, chitosan is gallic acid grafted chitosan, plasticizer is tributyl citrate, antioxidant 1010, heat stabilizer is calcium epoxy oleate, silane coupling agent KH550, antibacterial antistaling agent is prepared by preparation example 2, modified polylactic acid fiber is prepared by preparation example 8, the particle size of titanium dioxide is 10nm;
the preparation method of the packaging film material for fresh-keeping comprises the following steps:
s1, adding gelatin into deionized water, soaking at normal temperature for 20min, then heating to 60 ℃, and stirring for 40min to prepare gelatin solution with the concentration of 8 wt%;
s2, dissolving chitosan in an acetic acid solution with the concentration of 3wt% to prepare a chitosan solution with the concentration of 3 wt%;
s3, dissolving a silane coupling agent in ethanol until the concentration is 5wt%, adding an antibacterial preservative, titanium dioxide and modified polylactic acid fibers, mixing uniformly, mixing with a gelatin solution and a chitosan solution, adding a plasticizer, a heat stabilizer and an antioxidant, mixing uniformly, casting, drying and cooling to obtain the packaging film material.
Example 3: a packaging film material for freshness retaining, which is different from that in example 1 in that the degree of deacetylation of chitosan is 90% and the molecular weight is 1.5X 10 5 Da。
Example 4: a packaging film material for freshness preservation, which is different from that of example 1, an antibacterial freshness-keeping agent was prepared by the preparation example 3.
Example 5: a packaging film material for freshness preservation, which is different from example 1 in that an antibacterial freshness-retaining agent was prepared by preparation example 4.
Example 6: a packaging film material for freshness preservation, which is different from example 1 in that an antibacterial freshness-retaining agent was prepared by preparation example 5.
Example 7: a packaging film material for freshness preservation, which is different from example 1 in that an antibacterial and freshness-retaining agent was prepared by preparation example 6.
Example 8: a packaging film material for freshness preservation, which is different from example 1 in that modified polylactic acid fibers are prepared according to preparation example 9.
Example 9: a packaging film material for freshness preservation, which is different from example 1 in that a modified polylactic acid fiber was produced in preparation example 10.
Example 10: a packaging film material for freshness preservation, which is different from example 1 in that a modified polylactic acid fiber was produced in preparation example 11.
Example 11: a packaging film material for freshness preservation, which is different from example 1 in that a modified polylactic acid fiber was produced in preparation example 12.
Example 12: a packaging film material for freshness preservation, which is different from example 1 in that a modified polylactic acid fiber was produced in preparation example 13.
Comparative example
Comparative example 1: a packaging film material for freshness preservation is different from that in example 1 in that an antibacterial freshness-keeping agent is not added.
Comparative example 2: a packaging film material for freshness preservation which is different from that of example 1 in that titanium dioxide is not added.
Comparative example 3: a packaging film material for freshness preservation, which is different from that in example 1 in that modified polylactic acid fibers are not added.
Comparative example 4: the degradable packaging film material is prepared from 1.00% of straw stalk fiber, 3.00% of corn crosslinked starch, 3.00% of polyvinyl alcohol-carboxymethyl cellulose mixed solution, 2.28% of glyoxal, 3.79% of glycerol and 86.93% of deionized water according to mass concentration percentage, wherein the polyvinyl alcohol-carboxymethyl cellulose mixed solution is prepared by mixing polyvinyl alcohol and carboxymethyl cellulose according to the mass ratio of 1:2, and the degradable packaging film material is specifically prepared according to the following steps
Step 1, weighing 1.00 mass percent of straw stalk fiber, 3.00 mass percent of corn crosslinked starch, 3.00 mass percent of polyvinyl alcohol-carboxymethyl cellulose mixed solution, 2.28 mass percent of glyoxal, 3.79 mass percent of glycerol and 86.93 mass percent of deionized water;
step 2, fully and uniformly mixing the corn crosslinked starch weighed in the step 1 and part of deionized water, and stirring in a constant-temperature water bath at 90 ℃ until gelatinization to obtain a corn crosslinked starch solution, wherein the using amount of the deionized water accounts for half of the mass of the total deionized water; fully and uniformly mixing the polyvinyl alcohol-carboxymethyl cellulose mixed solution weighed in the step 1, straw stalk fibers and the rest part of deionized water to obtain a first mixed solution;
step 3, fully and uniformly mixing the glyoxal and the glycerol weighed in the step 1 with the corn crosslinked starch solution and the first mixed solution in the step 2, and stirring in a water bath at 85 ℃ for 30min to obtain a second mixed solution;
and 4, casting the second mixed solution onto a glass plate, keeping the liquid thickness on the glass plate to be 2.55mm, standing for 15min, drying at 80 ℃ for 3h, cooling to room temperature, and finally removing the packaging film to obtain the degradable packaging film material, wherein the thickness of the degradable packaging film material is 0.158mm.
Performance test
The packaging film materials were prepared according to the methods in examples and comparative examples, and the properties of the packaging film materials were examined with reference to the following methods, and the examination results are reported in table 2.
1. Tensile strength and elongation at break: detecting according to GB/T13022-91 'Plastic film tensile property test method';
2. air permeability: testing according to GB/T1038-2000 pressure differential method for testing gas permeability of plastic films and sheets; 3. fresh-keeping capacity: cutting the packaging film material into a film with the thickness of 250mm multiplied by 250mm, and sealing two ends of the folded film on a sealing machine to prepare a freshness protection package; selecting mangoes with uniform size, consistent maturity, no diseases and no mechanical damage, dividing the mangoes into 17 groups, wherein 12 groups are taken as an example group, 4 groups are taken as a comparative example group, sealing and preserving the mangoes, taking the mangoes which are not sealed by a preservative bag as a control group, placing 18 groups of mangoes at the room temperature of 25-28 ℃ for storage, repeating the test of each group for 3 times, and detecting the following properties: (1) rot index: the size of the rotten area of the fruit is observed during the experiment, and the fruit is divided into 5 grades according to the proportion that the rotten area is adhered to the total area of the fruit: grade 4 rot (the rotted area of the fruit is more than 50%); grade 3 rot (the rotten area of the fruit is 30-50%); grade 2 rot (10-30% of the rotten area of the fruit); grade 1 rot (the rotten area of the fruit is less than 10%); grade 0 decay (no decay of fruit), decay index calculated from the above decay levels: rot index (%) = (rot level × number of mangoes of the rot level)/(highest rot level × number of inspection total mangoes) × 100%;
(2) Weight loss ratio: during the storage process of fruits, nutrient substances are continuously consumed, water also can generate transpiration, the quality of the fruits can be reduced, the weight loss of the fruits can be represented by calculating the weight loss rate by adopting a direct weighing method, and the weight loss rate is calculated by the following method: weight loss (%) = (Wo-Wi)/Wo × 100%, wo being the mass of mango before storage in g, wi being the mass of mango at the i-th day of storage in g.
TABLE 2 Performance test results of the packaging film materials for freshness preservation
In the embodiment 1 and the embodiment 2, the antibacterial and antistaling agent prepared in the preparation example 1 and the preparation example 2 are respectively used, and the modified polylactic acid fibers prepared in the preparation example 7 and the preparation example 8 are adopted, and as can be seen from the data in the table 2, the packaging film materials prepared in the embodiment 1 and the embodiment 2 have better barrier property and high mechanical strength, and have better fresh-keeping effect on fruits and longer storage period.
In example 3, the non-grafted chitosan was used, and compared with example 1, the packaging film material prepared in example 3 was reduced in tensile strength and toughness, reduced in water vapor barrier property and increased in moisture permeability, and after mango was hermetically wrapped, the rot index and weight loss rate were greater on days 6 and 12 than those of example 1, and the freshness-keeping ability was reduced.
In example 4, the antibacterial preservative prepared in preparation example 3 is used, and in preparation example 3, silver nitrate is not mixed with okra straw fibers, that is, nano silver is not loaded on the okra straw fibers, so that the mechanical strength and barrier property of the packaging film material are not greatly changed, but the rot index and the weight loss rate are increased, which shows that the nano silver can improve the antibacterial property and the preservation capability of the packaging film.
Example 5 compared with example 1, using the antimicrobial preservative prepared in preparation example 4, citric acid was not added to okra straw fibers in preparation example 4, and the test results of tensile strength, elongation at break, moisture permeability and the like of the packaging film material prepared in example 5 are similar to those of example 1, while the rot index and weight loss rate are significantly increased, which shows that citric acid can improve the fresh-keeping ability of the packaging film material.
In example 6, the antibacterial preservative prepared in preparation example 5 was used, wherein sodium bicarbonate was added to the modified polyester, and micropores were not formed on the modified polyester skin layer, and the nano silver and citric acid loaded on the okra straw fiber could not be released, resulting in a significant decrease in the antibacterial and preservative capabilities of the packaging film material.
In example 7, the antibacterial preservative is silver-loaded okra straw fibers, the mechanical strength of a packaging film material is weakened, and in day 6, the rot index and the weight loss rate of mangos are smaller than those in example 1, the antibacterial preservation capability is strong, but in day 12, the rot index and the weight loss rate are remarkably increased, and in the absence of the modified polyester fibers and the sodium bicarbonate, the silver-loaded okra straw fibers have better initial preservation antibacterial capability, but the antibacterial preservation capability is deteriorated along with the prolonging of time.
In example 8 and example 9, compared with example 1, the modified polylactic acid fibers prepared in preparation example 9 and preparation example 10 are respectively used, graphene oxide is not contained in the solution in the impregnation of the polylactic acid fibers in preparation example 9, the micron-sized molecular sieve is not added in example 10, the moisture permeability and the carbon dioxide transmission coefficient of the packaging film material prepared in example 9 are increased, the barrier property is weakened, and the freshness keeping and antibacterial abilities are reduced, but the barrier property of the packaging film material prepared in example 10 is rather improved, but the rot index and the weight loss rate are reduced, which shows that pores exist in the molecular sieve, and the gas transmission coefficient of the film is increased by adding the molecular sieve, but the adsorption of the packaging film to ethylene is increased, and the freshness keeping ability is improved.
Example 10 the modified polylactic acid fiber prepared in preparation example 11, in which no coupling modified zinc oxide was added to the polylactic acid fiber, was used, the moisture permeability and carbon dioxide permeability coefficient of the packaging film were increased, the decay index and weight loss rate were significantly increased, and the antibacterial freshness-retaining ability was significantly reduced.
In example 11, the modified polylactic acid prepared in preparation example 12 was used, and when the polylactic acid fiber prepared in preparation example 12 was used, the nanocellulose whiskers were not added, compared with example 1, the tensile strength and elongation at break of the packaging film material in example 11 were reduced, which indicates that the nanocellulose whiskers can improve the strength and modulus of the polylactic acid, and table 2 shows that the moisture permeability of the packaging film material is increased, the rot index and weight loss rate of mangoes are increased, which indicates that the nanocellulose whiskers can significantly increase the barrier property of the polylactic acid fiber and increase the fresh-keeping ability.
In example 12, the modified polylactic acid fiber prepared in preparation example 13 was used, and polyethylene 2,5-furandicarboxylate was not added in the preparation of the polylactic acid fiber, so that the tensile strength and elongation at break of the packaging film material prepared in example 12 were reduced as compared with example 1, the barrier property against carbon dioxide was reduced, the rot index and weight loss rate were greater than those of example 1, and the freshness-keeping ability was reduced.
In the comparative example 1, no antibacterial preservative is added, the mechanical strength of a packaging film material is reduced, the barrier property is weakened, and the preservation capability is reduced; in comparative example 2, titanium dioxide is not added, the mechanical strength of the packaging film material is not changed greatly, but the barrier property is weakened to some extent, and the fresh-keeping capacity is reduced.
In the comparative example 3, the modified polylactic acid fiber is not added, the mechanical properties of the packaging film material, such as tensile strength and the like, are reduced, the barrier property is weakened, and the fresh-keeping capacity is reduced.
Comparative example 4 is a degradable packaging film material prepared by the prior art, which has better mechanical strength, but has larger moisture permeability and carbon dioxide permeability coefficient than example 1, barrier property inferior to example 1, and preservation capability on mango inferior to example 1.
The mango in the control group is not sealed by a freshness protection package, the rot index of the mango is large on the 6 th day, and the rot index is as high as 90.2% on the 12 th day, which indicates that the packaging film material can reduce the rot index, inhibit transpiration and reduce the weight loss rate of the fruit.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The packaging film material for preservation is characterized by comprising the following raw materials in parts by weight: 3-8 parts of gelatin, 1.5-4 parts of chitosan, 0.06-0.1 part of plasticizer, 0.05-0.08 part of antioxidant, 0.08-0.1 part of heat stabilizer, 0.2-0.4 part of silane coupling agent, 1-2 parts of antibacterial preservative, 1-2 parts of modified polylactic acid fiber and 0.3-0.8 part of titanium dioxide.
2. The wrap material for freshness preservation according to claim 1, characterized in that: the preparation method of the antibacterial preservative comprises the following steps:
mixing okra straw fibers, polyvinyl alcohol and deionized water, performing ultrasonic dispersion, adding silver nitrate and citric acid, uniformly mixing, drying at 40-50 ℃ for 20-24 hours, and irradiating under an ultraviolet lamp for 3-5 hours to obtain silver-loaded okra straw fibers;
mixing the silver-loaded okra straw fibers with modified polyester and sodium bicarbonate, extruding, granulating and grinding.
3. The packaging film material for fresh keeping according to claim 2, wherein the antibacterial and antistaling agent comprises the following components in parts by weight: 5-10 parts of okra straw fiber, 2-3 parts of silver nitrate, 1-2 parts of polyvinyl alcohol, 100 parts of deionized water, 0.5-2 parts of citric acid, 1-3 parts of modified polyester and 0.3-0.8 part of sodium bicarbonate.
4. The packaging film material for fresh keeping according to claim 1, wherein the modified polylactic acid fiber is prepared by the following method:
mixing polylactic acid, 2,5-furandicarboxylic acid glycol ester, nano cellulose whisker and coupling modified zinc oxide, and carrying out melt spinning to obtain polylactic acid fiber;
dissolving polyglycolic acid with hexafluoroisopropanol, adding sodium chloride, graphene oxide and a micron-sized molecular sieve, uniformly mixing, soaking the polylactic acid fiber in the solution for 30-40min, washing with deionized water, and drying in the air.
5. The packaging film material for fresh keeping according to claim 4, wherein the modified polylactic acid fiber comprises the following raw materials in parts by weight: 1-3 parts of polylactic acid, 0.5-1 part of poly 2,5-furandicarboxylic acid glycol ester, 0.6-1.2 parts of nano cellulose whisker, 0.3-0.6 part of coupled modified zinc oxide, 0.5-1.5 parts of polyglycolic acid, 10 parts of hexafluoroisopropanol, 0.1-0.5 part of sodium chloride, 0.3-0.5 part of graphene oxide and 0.3-0.7 part of micron-sized molecular sieve.
6. The packaging film material for freshness preservation according to claim 4, wherein the melt spinning temperature is 190-200 ℃, the spinning speed is 100-150m/min, the diameter of the spinneret orifice is 0.5-0.6mm, and the spinning voltage is 30-40KV.
7. The packaging film material for freshness protection as claimed in claim 1, wherein the chitosan is at least one selected from gallic acid grafted chitosan, vanillic acid grafted chitosan and syringic acid grafted chitosan.
8. The freshness-retaining packaging film material according to claim 1, wherein the plasticizer is at least one of tributyl citrate, acetyl tributyl citrate and glycerol.
9. The packaging film material for fresh keeping according to claim 1, wherein the heat stabilizer is at least one of calcium epoxy oleate and zinc epoxy stearate.
10. The method for producing a packaging film material for freshness protection as claimed in any one of claims 1 to 9, characterized by comprising the steps of:
adding gelatin into deionized water, soaking at normal temperature for 20-30min, heating to 60-65 deg.C, stirring for 30-40min to obtain gelatin solution with concentration of 8-10 wt%;
dissolving chitosan in 2-3wt% acetic acid solution to obtain 3-5wt% chitosan solution;
dissolving a silane coupling agent, adding an antibacterial preservative, titanium dioxide and modified polylactic acid fibers, mixing uniformly, mixing with a gelatin solution and a chitosan solution, adding a plasticizer, a heat stabilizer and an antioxidant, mixing uniformly, casting, drying and cooling to obtain the packaging film material.
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| CN105885110A (en) * | 2016-05-27 | 2016-08-24 | 黑龙江八农垦大学 | Degradable packaging film material and preparing method and application thereof |
| CN212268997U (en) * | 2020-04-08 | 2021-01-01 | 上海博阳包装技术有限公司 | Tension adjusting device is used in packaging film processing |
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| CN105885110A (en) * | 2016-05-27 | 2016-08-24 | 黑龙江八农垦大学 | Degradable packaging film material and preparing method and application thereof |
| CN112981600A (en) * | 2019-12-16 | 2021-06-18 | 荣雷 | Anti-allergy polyester fiber |
| CN212268997U (en) * | 2020-04-08 | 2021-01-01 | 上海博阳包装技术有限公司 | Tension adjusting device is used in packaging film processing |
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