CN115975386B - Packaging film material for fresh keeping and preparation method thereof - Google Patents
Packaging film material for fresh keeping and preparation method thereof Download PDFInfo
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- CN115975386B CN115975386B CN202310114007.5A CN202310114007A CN115975386B CN 115975386 B CN115975386 B CN 115975386B CN 202310114007 A CN202310114007 A CN 202310114007A CN 115975386 B CN115975386 B CN 115975386B
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- packaging film
- film material
- polylactic acid
- chitosan
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- 239000012785 packaging film Substances 0.000 title claims abstract description 97
- 229920006280 packaging film Polymers 0.000 title claims abstract description 97
- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 62
- 239000000835 fiber Substances 0.000 claims abstract description 93
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 66
- 239000004626 polylactic acid Substances 0.000 claims abstract description 66
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 58
- 229920001661 Chitosan Polymers 0.000 claims abstract description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003755 preservative agent Substances 0.000 claims abstract description 34
- 230000002335 preservative effect Effects 0.000 claims abstract description 34
- 108010010803 Gelatin Proteins 0.000 claims abstract description 23
- 229920000159 gelatin Polymers 0.000 claims abstract description 23
- 239000008273 gelatin Substances 0.000 claims abstract description 23
- 235000019322 gelatine Nutrition 0.000 claims abstract description 23
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 23
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000002994 raw material 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
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 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 47
- 241001075517 Abelmoschus Species 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 34
- 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
- 229920000728 polyester Polymers 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 229920000954 Polyglycolide Polymers 0.000 claims description 15
- 239000004633 polyglycolic acid Substances 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 14
- 239000002808 molecular sieve 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
- 230000008878 coupling Effects 0.000 claims description 12
- 238000010168 coupling process Methods 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- -1 polyethylene 2, 5-furandicarboxylate Polymers 0.000 claims description 12
- 238000009987 spinning 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
- 238000005406 washing Methods 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940074391 gallic acid Drugs 0.000 claims description 7
- 235000004515 gallic acid Nutrition 0.000 claims description 7
- 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
- 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
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002074 melt spinning Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 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
- DVVGBNZLQNDSPA-UHFFFAOYSA-N 3,6,11-trioxabicyclo[6.2.1]undeca-1(10),8-diene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1O2 DVVGBNZLQNDSPA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 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 4
- 238000010345 tape casting Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 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
- 235000009499 Vanilla fragrans Nutrition 0.000 claims description 2
- 235000012036 Vanilla tahitensis Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 244000263375 Vanilla tahitensis Species 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 20
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 19
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000002829 reductive effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 235000004936 Bromus mango Nutrition 0.000 description 14
- 241001093152 Mangifera Species 0.000 description 14
- 235000014826 Mangifera indica Nutrition 0.000 description 14
- 235000009184 Spondias indica Nutrition 0.000 description 14
- 230000004580 weight loss Effects 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 235000013399 edible fruits Nutrition 0.000 description 13
- 230000035699 permeability Effects 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 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
- 230000000052 comparative effect Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000003795 chemical substances by application Substances 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
- 238000004321 preservation Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920006255 plastic film Polymers 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 6
- 239000000126 substance Substances 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
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 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
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 241000238675 Periplaneta americana Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 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
- ZCZLQYAECBEUBH-UHFFFAOYSA-L calcium;octadec-9-enoate Chemical compound [Ca+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O ZCZLQYAECBEUBH-UHFFFAOYSA-L 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003860 storage 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
- 230000009471 action Effects 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007789 sealing Methods 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
- 238000001179 sorption measurement Methods 0.000 description 2
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 2
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000003487 anti-permeability 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal 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
- 238000005266 casting 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
- 230000007547 defect Effects 0.000 description 1
- 230000003544 deproteinization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental 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
- 239000011521 glass 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
- 230000003993 interaction Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial 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
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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 fresh keeping and a preparation method thereof. The 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. The packaging film material for fresh-keeping has the advantages of good mechanical property and barrier property, easiness in biodegradation, good antibacterial property and fresh-keeping 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
It is well known that food packaging films are polymeric materials used to coat the surface of food, and are primarily used to isolate the entry of decomposing microbial bacteria and foreign contaminants, and to prevent and prolong the deterioration of the food. The most common food packaging film in the world today is generally an artificial polymeric material (e.g. polyethylene, polypropylene, etc.), mainly from the petroleum industry, commonly known as plastic film. The membrane has the advantages of low cost, no toxicity and excellent physical and chemical properties, but has two serious defects. First: plastic films are extremely difficult to degrade, and waste plastic films can cause serious environmental problems, and today the earth is deeply injured by white pollution caused by waste plastic products. Therefore, the development of new food packaging films reduces or even replaces the use of plastic films, which is one of the hot spots for future research. Second,: the plastic film has weak fresh-keeping capability and antibacterial effect, and the two performances are required by food packaging, especially fruit and vegetable products, and the stronger the two performances are, the longer the service life of the packaged food is.
The Chinese patent document with the application number of CN2021112590207 discloses a food packaging film material which comprises chitosan and American cockroach extract, wherein the mass ratio of the chitosan to the American cockroach extract is 1:0.1-0.4; wherein, the chitosan is prepared by the following steps: adding NaOH solution into the American cockroach dregs for deproteinization, drying, removing inorganic salt in the dregs by hydrochloric acid, adding bleaching agent for decoloring, freeze-drying to obtain chitin, and adding concentrated alkali liquor into the chitin for deacetylation to obtain chitosan.
The packaging film material has the advantages of degradability, innocuity, antibiosis and antioxidation, and realizes waste utilization by utilizing the American cockroach dregs, but aiming at the related technology, the inventor discovers that when the packaging material is used for packaging fruits and vegetables, the freshness durability of the fruits and vegetables is poor, and the fresh-keeping capability is to be improved.
Disclosure of Invention
In order to improve the fresh-keeping capability of the packaging film material and prolong the freshness durability of fruits and vegetables, the application provides the packaging film material for fresh keeping and a preparation method thereof.
In a first aspect, the present application provides a packaging film material for fresh-keeping, which adopts the following technical scheme:
the 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, gelatin is used as a substrate of the packaging film, the gelatin is a degradable and water-soluble substance, is a product of partial hydrolysis of collagen, contains amino, hydroxyl, carboxyl and other functional groups, has the characteristic of gel property, and the formed film has the characteristic of softer texture, the chitosan is a biological macromolecule, has certain antibacterial and antiviral capabilities, has a relatively stable structure, can form a hydrogen bond with gelatin and can generate a certain binding force, so that the tensile strength and elongation at break of the packaging film are improved, the compatibility of the modified polylactic acid fiber and the antibacterial preservative with chitosan and gelatin is good under the action of the silane coupling agent, the modified polylactic acid fiber can be uniformly dispersed, the tensile strength and toughness of the packaging film can be enhanced, the antibacterial preservative can improve the antibacterial property and the preservative capability of the packaging film, and when the packaging film is used for packaging fruits and vegetables, the titanium dioxide can decompose the ethylene into carbon dioxide and water due to the respiratory action of the fruits and vegetables, and the titanium dioxide can also have the self-cleaning activity, the self-cleaning activity can be generated, the titanium dioxide can inhibit the self-cleaning activity and the self-cleaning activity of the fruits and vegetables, the titanium dioxide can be prevented from being in the packaging film, and the film can not be wrapped by the film, and the film has the moisture absorption coefficient can be prolonged, and the film has the anti-cleaning effect when the film is wrapped by the film is improved, and the film has the anti-cleaning property, and anti-permeability properties when the film is 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 20-24h, and irradiating under an ultraviolet lamp for 3-5h to obtain silver-loaded okra straw fibers;
mixing the silver-carrying okra straw fiber with modified polyester and sodium bicarbonate, extruding, granulating and grinding.
According to the technical scheme, the okra straw fiber is mainly prepared from okra straw skin through the processes of boiling, bleaching and the like, so that the degumming effect of the okra straw fiber is improved, the surface of the okra straw fiber is rough, longitudinal gaps are formed, branches are formed transversely, the adhesive force is good, the absorption of silver nitrate and citric acid is facilitated, the okra straw fiber is used as a carrier, the silver nitrate and the citric acid are carried in the interior and the surface of the okra straw fiber through the adhesion of dipping and polyvinyl alcohol, the silver nitrate is reduced into nano silver under the irradiation of an ultraviolet lamp, nano silver particles which are uniformly distributed and have small particle sizes and antibacterial property are formed in the interior and the surface of the okra straw fiber, the polarity of hydrogen ions in the citric acid is strong, so that ethylene molecules are more easily polarized to be absorbed, the load citric acid on the okra straw fiber has a physical absorption effect on ethylene molecules, the chemical absorption effect is also high, the influence of ethylene on fruit and vegetable quality can be reduced, and fruit and vegetable rot is prevented; finally, the silver-carrying okra straw fiber is coated by using the modified polyester as an outer layer, and the sodium bicarbonate is used as a pore-forming agent to form fine pores on the outer layer, so that the nano silver and citric acid on the silver-carrying okra straw fiber can be slowly and effectively released, the nano silver can continuously resist bacteria, the antibacterial aging is prolonged, the citric acid can continuously adsorb ethylene, and the bacteria and ethylene are adsorbed, so that after fruits and vegetables are coated, the fruits and vegetables are not easy to be quickly ripened and rotten due to the generation of ethylene gas, the long-acting fresh-keeping effect can be achieved, and the fresh-keeping aging of the fruits and vegetables is 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 raw materials can be prepared into the antibacterial preservative with the function of slowly and effectively releasing nano silver and citric acid, and the antibacterial preservative can improve the mechanical strength of the packaging film under the action of the outer layer of the modified polyester.
Optionally, the preparation method of the modified polylactic acid fiber comprises the following steps:
mixing polylactic acid, poly (ethylene 2, 5-furandicarboxylate), nanocellulose whisker and coupling modified zinc oxide, and carrying out melt spinning to obtain polylactic acid fibers;
dissolving polyglycolic acid with hexafluoroisopropanol, adding sodium chloride, graphene oxide and a micron-sized molecular sieve, uniformly mixing, immersing the polylactic acid fiber in the mixture for 30-40min, washing with deionized water, and airing.
By adopting the technical scheme, the polyethylene 2, 5-furandicarboxylate has higher gas barrier property to oxygen, carbon dioxide and steam, has higher mechanical strength and excellent physical-mechanical properties, can improve the barrier property and mechanical strength of polylactic acid, and 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 permeation of micromolecular gas through a packaging film is increased, the barrier property of the packaging film material is improved, the zinc oxide subjected to coupling modification is uniformly dispersed in the polylactic acid, the tensile strength and elongation at break of polylactic acid fiber can be improved, and the antibacterial capability of the polylactic acid fiber is increased; the polyglycolic acid has the characteristics of good degradability, flexibility and biocompatibility, after the polyglycolic acid is dissolved, the polyglycolic acid is uniformly mixed with a micron-sized molecular sieve, graphene oxide and the like, the polyglycolic acid is formed into a film on polylactic acid fibers, the tensile strength of the polylactic acid fibers is improved, the tear strength is 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 capability, antibacterial and fresh-keeping aging 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 compatibility of the micron-sized molecular sieve and the polylactic acid is good, the adsorption force to ethylene is strong, and the modified polylactic acid fibers with strong barrier property and mechanical property can absorb ethylene and long fresh-keeping aging and durable antibacterial property are prepared.
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 polyethylene 2, 5-furandicarboxylate, 0.6-1.2 parts of nano cellulose whisker, 0.3-0.6 part of coupling 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 raw materials can be prepared into the modified polylactic acid fiber with durable antibacterial and fresh-keeping properties, so that the water transpiration effect of fruits and vegetables is reduced, and the decay of the fruits and vegetables is prevented.
Optionally, the melt spinning temperature is 190-200 ℃, the spinning speed is 100-150m/min, the diameter of a spinning hole is 0.5-0.6mm, and the spinning voltage is 30-40KV.
Optionally, the chitosan is at least one selected from gallic acid grafted chitosan, vanilla acid grafted chitosan and syringic acid grafted chitosan.
By adopting the technical scheme, although the chitosan is a biopolymer capable of being used for food packaging, the chitosan has hydrophilicity, water vapor is more easily adsorbed on a packaging film, so that the diffusion effect of the water vapor is enhanced, the barrier effect is weakened, so that gallic acid, vanillic acid or syringic acid are grafted on the chitosan to form covalent bonds, the hydrophilicity of the chitosan is greatly limited, the affinity of the packaging film to moisture is reduced, a large number of benzene ring structures contained in the grafted chitosan also weaken the intramolecular and intermolecular hydrogen bonding effect of the chitosan, the water vapor permeation coefficient of the packaging film is lower, the barrier property of the packaging film to the water vapor is enhanced, in addition, the intermolecular hydrogen bonding effect formed by grafting gallic acid on the chitosan and the physical connection between polymer networks can reduce the mobility of molecules, the degree of freedom of the packaging film, and the tensile strength and toughness of the packaging film are enhanced, and the gallic acid, the vanillic acid and the syringic acid have antibacterial property, so that the antibacterial property of the chitosan can be enhanced, and the antibacterial property of the packaging film is improved.
Optionally, the plasticizer is at least one of tributyl citrate, acetyl tributyl citrate and glycerin.
Optionally, the heat stabilizer is at least one of epoxy calcium oleate and epoxy zinc stearate.
In a second aspect, the present application provides a method for preparing a packaging film material for fresh-keeping, which adopts the following technical scheme: the preparation method of the packaging film material for fresh keeping comprises the following steps:
adding gelatin into deionized water, soaking at normal temperature for 20-30min, heating to 60-65deg.C, and stirring for 30-40min to obtain gelatin solution with concentration of 8-10wt%;
dissolving chitosan in acetic acid solution with the concentration of 2-3wt% to prepare chitosan solution with the concentration of 3-5 wt%;
dissolving a silane coupling agent, adding an antibacterial preservative, titanium dioxide and modified polylactic acid fibers, uniformly mixing, mixing with a gelatin solution and a chitosan solution, adding a plasticizer, a heat stabilizer and an antioxidant, uniformly mixing, and carrying out tape 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 compatibility of the antibacterial preservative, the titanium dioxide and the modified polylactic acid with the gelatin solution and the chitosan solution is improved by utilizing the silane coupling agent, 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. because the application adopts gelatin as the matrix of the packaging film, and utilizes chitosan to improve the tensile strength and the elongation at break of the packaging film, meanwhile, the antibacterial property and the fresh-keeping capability of the packaging film are improved, titanium dioxide is additionally added as a photocatalyst to decompose ethylene generated by fruits and vegetables, so that the influence of the ethylene on the fruits and vegetables is reduced, and the fruits and vegetables are prevented from rotting.
2. In the application, the okra straw fiber is preferably used as a carrier, nano silver and citric acid are loaded in and on the surface of the okra straw fiber to prepare the silver-carrying okra straw fiber, the silver-carrying okra straw fiber is coated with the modified polyester outer layer, and sodium bicarbonate is used as a pore-forming agent to form micropores on the modified polyester outer layer, so that the nano silver and the citric acid can be slowly released, the antibacterial property and the fresh-keeping durability of the antibacterial fresh-keeping agent are prolonged, and in addition, the mechanical strength of the packaging film can be improved by the modified polyester and the okra straw fiber.
3. In the application, polylactic acid, polyethylene 2, 5-furandicarboxylate, nanocellulose whisker and coupling modified zinc oxide are preferably adopted to prepare polylactic acid fibers through melt spinning, then an outer film taking polyglycolic acid as a film forming substance is soaked on the polylactic acid fibers, and micropores are formed on the polyglycolic acid outer film by taking sodium chloride as a pore-forming agent, so that the zinc oxide continuously releases antibacterial capacity to achieve a long-acting antibacterial effect, graphene oxide on the outer film can also achieve the antibacterial effect, barrier property of the polylactic acid fibers can be improved, and the micron-sized molecular sieve can adsorb ethylene, improve the fresh-keeping capacity of the modified polylactic acid fibers and prolong the freshness of fruits and vegetables.
Detailed Description
Preparation examples 1-6 of antibacterial preservative
Preparation example 1: (1) Mixing 10kg of okra straw fibers, 2kg of polyvinyl alcohol and 100 parts of deionized water, performing ultrasonic dispersion for 20min at 400W power, 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 silver-loaded okra straw fibers, wherein the okra straw fibers are prepared by the following steps: peeling okra straw to obtain straw skin, heating the straw skin in 2.5g/L hydrochloric acid at 60 ℃ in a water bath for 2 hours, washing with water, boiling with 15wt% sodium hydroxide for 3 hours, washing with water, boiling with 1.5g/L hydrogen peroxide and 3g/L alkali liquor (consisting of rare soda ash and sodium silicate according to the mass ratio of 1:2:1) at 95 ℃ for 30 minutes, boiling with 5wt% sodium hydroxide and 2wt% sodium carbonate at 100 ℃ for 2 hours, and washing with water;
(2) Mixing silver-carrying 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 the modified polyester is selected from Wu Jiangfu Dongshun chemical fiber factories.
Preparation example 2: (1) Mixing 5kg of okra straw fibers, 1kg of polyvinyl alcohol and 100 parts of deionized water, performing ultrasonic dispersion for 20min at 400W power, adding 2kg of silver nitrate and 0.5kg of citric acid, uniformly mixing, drying at 40 ℃ for 24h, and irradiating under an ultraviolet lamp for 3h to obtain silver-loaded okra straw fibers, wherein the okra straw fibers are prepared by the following steps: peeling okra straw to obtain straw skin, heating the straw skin in 2.5g/L hydrochloric acid at 60 ℃ in a water bath for 2 hours, washing with water, boiling with 15wt% sodium hydroxide for 3 hours, washing with water, boiling with 1.5g/L hydrogen peroxide and 3g/L alkali liquor (consisting of rare soda ash and sodium silicate according to the mass ratio of 1:2:1) at 95 ℃ for 30 minutes, boiling with 5wt% sodium hydroxide and 2wt% sodium carbonate at 100 ℃ for 2 hours, and washing with water;
(2) Mixing silver-carrying 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 the modified polyester is selected from Wu Jiangfu Dongsu chemical fiber factories.
Preparation example 3: the difference from preparation example 1 is that no silver nitrate was added.
Preparation example 4: the difference from preparation example 1 is that no citric acid was 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 performed, and the silver-carrying okra straw fiber is used as an antibacterial preservative.
Preparation examples 7 to 13 of modified polylactic acid fibers
Preparation example 7: (1) 3kg of polylactic acid, 1kg of polyethylene 2, 5-furandicarboxylate, 1.2kg of nanocellulose whisker and 0.6kg of coupling modified zinc oxide are mixed, and melt-spun at 200 ℃ to prepare polylactic acid fiber, wherein the spinning speed is 100m/min, the diameter of a spinning hole is 0.6mm, the spinning voltage is 40KV, the model of the polylactic acid is 4032D, the polyethylene 2, 5-furandicarboxylate is selected from the group consisting of rufenglon, the model is JFL, and the preparation method of the coupling modified zinc oxide comprises the following steps: reflux-extracting zinc oxide in ethanol at 40deg.C for 1 hr, ultrasonic dispersing for 20min, adjusting pH to 2 with hydrochloric acid, adding silane coupling agent KH550 with concentration of 2.5wt%, stirring at 40deg.C for 1 hr, adjusting pH to 10 with sodium hydroxide, refluxing for 2 hr, centrifuging for 5min, and drying at 80deg.C;
(2) 1.5kg of polyglycolic acid is dissolved by 10kg of hexafluoroisopropanol, 0.5kg of sodium chloride, 0.5kg of graphene oxide and 0.7kg of ZSM-5 type micron-sized molecular sieve are added, the mixture is uniformly mixed, and the polylactic acid fiber is immersed in the mixture for 40min, washed by deionized water and then dried.
Preparation example 8: (1) Mixing 1kg of polylactic acid, 0.5kg of poly (ethylene 2, 5-furandicarboxylate), 0.6kg of nanocellulose whisker and 0.3kg of coupling modified zinc oxide, and carrying out melt spinning at 190 ℃ to obtain polylactic acid fiber, wherein the spinning speed is 150m/min, the spinning hole diameter is 0.5mm, the spinning voltage is 30KV, the type of polylactic acid is 4032D, the poly (ethylene 2, 5-furandicarboxylate) is selected from the group consisting of rufenglon, the type is JFL, and the preparation method of the coupling modified zinc oxide comprises the following steps: reflux-extracting zinc oxide in ethanol at 40deg.C for 1 hr, ultrasonic dispersing for 20min, adjusting pH to 2 with hydrochloric acid, adding silane coupling agent KH550 with concentration of 2.5wt%, stirring at 40deg.C for 1 hr, adjusting pH to 10 with sodium hydroxide, refluxing for 2 hr, centrifuging for 5min, and drying at 80deg.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, immersing the polylactic acid fiber in the mixture for 40min, washing with deionized water, and airing.
Preparation example 9: the difference from preparation example 7 is that graphene oxide was not added in step (2).
Preparation example 10: the difference from preparation example 7 is that no micron-sized molecular sieve was added in step (2).
Preparation example 11: the difference from preparation example 7 is that no coupling modified zinc oxide was added in step (1).
Preparation example 12: the difference from preparation example 7 is that no nanocellulose whisker was 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: the fresh-keeping packaging film material is prepared from the raw materials shown in Table 1, wherein the raw materials are gallic acid grafted chitosan, the plasticizer is glycerol, the antioxidant is 1010, the heat stabilizer is epoxy calcium oleate, the silane coupling agent is KH550, the antibacterial fresh-keeping agent is prepared from preparation example 1, the modified polylactic acid fiber is prepared from preparation example 7, and 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 for 30min at normal temperature, then heating to 65 ℃ and stirring for 30min to obtain gelatin solution with the concentration of 10 wt%;
s2, dissolving chitosan in acetic acid solution with the concentration of 2wt% to prepare chitosan solution with the concentration of 5 wt%;
s3, dissolving the silane coupling agent with ethanol until the concentration is 5wt%, adding the antibacterial preservative, titanium dioxide and modified polylactic acid fibers, uniformly mixing, then mixing with gelatin solution and chitosan solution, adding the plasticizer, the heat stabilizer and the antioxidant, uniformly mixing, and then carrying out tape casting, drying and cooling to obtain the packaging film material.
Table 1 raw material amounts of packaging film materials for fresh-keeping in examples 1 to 3
Example 2: the fresh-keeping packaging film material has the raw material dosage shown in table 1, wherein chitosan is gallic acid grafted chitosan, plasticizer is tributyl citrate, antioxidant is 1010, heat stabilizer is epoxy calcium oleate, silane coupling agent is KH550, antibacterial fresh-keeping agent is prepared from preparation example 2, modified polylactic acid fiber is prepared from preparation example 8, and 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 for 20min at normal temperature, then heating to 60 ℃ and stirring for 40min to obtain gelatin solution with the concentration of 8 wt%;
s2, dissolving chitosan in acetic acid solution with the concentration of 3wt% to prepare chitosan solution with the concentration of 3 wt%;
s3, dissolving the silane coupling agent with ethanol until the concentration is 5wt%, adding the antibacterial preservative, titanium dioxide and modified polylactic acid fibers, uniformly mixing, then mixing with gelatin solution and chitosan solution, adding the plasticizer, the heat stabilizer and the antioxidant, uniformly mixing, and then carrying out tape casting, drying and cooling to obtain the packaging film material.
Example 3: a packaging film material for fresh keeping, which is different from example 1 in that chitosan has a deacetylation degree of 90% and a molecular weight of 1.5X10 5 Da。
Example 4: a packaging film material for preservation, which is different from example 1 in that an antibacterial preservative is prepared from preparation example 3.
Example 5: a packaging film material for preservation, which is different from example 1 in that an antibacterial preservative is prepared from preparation example 4.
Example 6: the packaging film material for preservation is different from example 1 in that the antibacterial preservative is prepared from preparation example 5.
Example 7: a packaging film material for preservation, which is different from example 1 in that an antibacterial preservative is prepared from preparation example 6.
Example 8: the packaging film material for fresh keeping was different from example 1 in that the modified polylactic acid fiber was produced from production example 9.
Example 9: the packaging film material for fresh keeping was different from example 1 in that the modified polylactic acid fiber was produced from production example 10.
Example 10: a packaging film material for fresh keeping, which is different from example 1 in that modified polylactic acid fibers were produced from production example 11.
Example 11: the packaging film material for fresh keeping was different from example 1 in that the modified polylactic acid fiber was produced from production example 12.
Example 12: a packaging film material for fresh keeping, which is different from example 1 in that modified polylactic acid fibers were produced from production example 13.
Comparative example
Comparative example 1: a packaging film material for preservation, which is different from example 1 in that no antibacterial preservative is added.
Comparative example 2: a packaging film material for fresh keeping, which is different from example 1 in that no titanium dioxide is added.
Comparative example 3: a packaging film material for fresh keeping, which is different from 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 the 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 by the following steps
Step 1, weighing straw stalk fiber with the mass concentration percentage of 1.00%, corn crosslinked starch with the mass concentration percentage of 3.00%, polyvinyl alcohol-carboxymethyl cellulose mixed solution with the mass concentration percentage of 3.00%, glyoxal with the mass concentration percentage of 2.28%, glycerol with the mass concentration percentage of 3.79% and deionized water with the mass concentration percentage of 86.93%;
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 use amount of the deionized water accounts for half of the total deionized water mass; fully and uniformly mixing the polyvinyl alcohol-carboxymethyl cellulose mixed solution weighed in the step 1, straw stalk fiber and the rest deionized water to obtain a first mixed solution;
step 3, fully and uniformly mixing glyoxal and glycerol weighed in the step 1 with the corn crosslinked starch solution and the first mixed solution in the step 2, and then stirring for 30min in a water bath at 85 ℃ to obtain a second mixed solution;
and 4, casting the second mixed solution onto a glass plate, 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
Packaging film materials were prepared according to the methods in examples and comparative examples, and properties of the packaging film materials were examined with reference to the following methods, and the examination results are recorded in table 2.
1. Tensile strength and elongation at break: detecting according to GB/T13022-91 tensile property test method of plastic film;
2. air permeability: testing according to GB/T1038-2000 "differential pressure method for testing gas permeability of Plastic film and sheet"; 3. fresh-keeping capability: cutting packaging film material into 250mm×250mm film, sealing two ends of the folded film on a sealing machine, and making into fresh-keeping bag; the mango with uniform size, consistent maturity and no disease and mechanical damage is selected and divided into 17 groups, wherein 12 groups are taken as example groups, 4 groups are taken as comparison groups, the mangoes are sealed and preserved, the mangoes which are not sealed by a preservation bag are taken as comparison groups, 18 groups of mangoes are stored at room temperature of 25-28 ℃, each group of tests are repeated 3 times, and the following performances are detected: (1) decay index: the rotting area of the fruits is observed in the test, and the fruits are classified into 5 grades according to the proportion of the rotting area to the total area of the fruits: level 4 rot (fruit rot area greater than 50%); 3-level rot (fruit rot area 30-50%); level 2 rot (10-30% of the rot area of the fruit); level 1 rot (fruit rot area less than 10%); class 0 rot (no rot of fruit), the rot index was calculated from the above rot class: rot index (%) = (rot level×number of mangoes of the rot level)/(highest rot level×total number of mangoes checked) ×100%;
(2) Weight loss ratio: in the process of storing fruits, nutrients are continuously consumed, water is subject to transpiration, the quality of the fruits is reduced, the weight loss rate calculated by adopting a direct weighing method can be used for indicating the quality loss of the fruits, and the weight loss rate is calculated by the following steps: weight loss (%) = (Wo-Wi)/wo×100%, wo is the mass of mango before storage in g, wi is the mass of mango at day i of storage in g.
Table 2 results of performance test of packaging film material for fresh keeping
The antibacterial antistaling agent prepared in preparation example 1 and preparation example 2 are respectively used in the embodiment 1 and the embodiment 2, and the modified polylactic acid fiber prepared in the preparation example 7 and the preparation example 8 is 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 antistaling effect on fruits, and the storage period is prolonged.
In example 3, the packaging film material prepared in example 3 has reduced tensile strength, reduced toughness, reduced barrier ability to water vapor, increased moisture permeability, and reduced fresh-keeping ability compared with example 1, and the mango has a rotting index and a weight loss ratio at 6 th and 12 th days after being sealed and wrapped, which are greater than those of example 1.
In example 4, the antibacterial preservative prepared in preparation example 3 is used, silver nitrate and okra straw fibers are not mixed in preparation example 3, namely nano silver is not loaded on the okra straw fibers, the mechanical strength and barrier property of the packaging film material are not changed greatly, but the rotting index and the weight loss rate are increased, and the fact that the nano silver can improve the antibacterial property and the preservative capability of the packaging film is shown.
Example 5 compared with example 1, the antibacterial preservative prepared in preparation example 4 is used, citric acid is not added into okra straw fibers in preparation example 4, 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, and the rotting index and the weight loss rate are obviously increased, so that the citric acid can improve the preservation capability of the packaging film material.
In example 6, the antibacterial preservative prepared in preparation example 5 is used, wherein sodium bicarbonate is added into modified polyester, micropores cannot be formed on the modified polyester skin layer, nano silver and citric acid loaded on okra straw fibers cannot be released, and the antibacterial and preservative capabilities of packaging film materials are remarkably reduced.
In the embodiment 7, the antibacterial preservative is silver-carrying okra straw fiber, the mechanical strength of the packaging film material is weakened, the decay index and the weight loss rate of mangoes are smaller than those of the embodiment 1 on the 6 th day, the antibacterial preservative capability is strong, the decay index and the weight loss rate are remarkably increased on the 12 th day, and the silver-carrying okra straw fiber has better initial preservative antibacterial capability without adding modified polyester fiber and sodium bicarbonate, but the antibacterial preservative capability is poor along with the time.
In example 8 and example 9, the modified polylactic acid fibers prepared in preparation example 9 and preparation example 10 were used, respectively, and in preparation example 9, when the polylactic acid fibers were immersed, graphene oxide was not contained in the solution, and in example 10, no micron-sized molecular sieve was added, and the moisture permeability and carbon dioxide permeability coefficient of the packaging film material prepared in example 9 were increased, the barrier property was weakened, the fresh-keeping and antibacterial properties were decreased, and the barrier property of the packaging film material prepared in example 10 was improved, but the decay index and the weight loss rate were decreased, which indicated that pores were present in the molecular sieve, and that the addition of the molecular sieve increased the gas permeability coefficient of the film, but increased the adsorption of ethylene by the packaging film, and improved the fresh-keeping ability.
Example 10 the modified polylactic acid fiber prepared by using the preparation example 11, wherein no coupling modified zinc oxide is added in the polylactic acid fiber, the moisture permeability and carbon dioxide permeability coefficient of the packaging film are increased, the decay index and the weight loss rate are obviously increased, and the antibacterial fresh-keeping ability is obviously reduced.
In example 11, when the modified polylactic acid prepared in preparation example 12 is used, no nanocellulose whisker is added in preparation example 12, and compared with example 1, the tensile strength and the elongation at break of the packaging film material in example 11 are weakened, which indicates that the nanocellulose whisker can improve the strength and the modulus of the polylactic acid, and in table 2, the moisture permeability of the packaging film material is increased, the decay index and the weight loss rate of mango are increased, which indicates that the nanocellulose whisker can remarkably increase the barrier property of the polylactic acid fiber and increase the fresh-keeping capability.
In example 12, when the modified polylactic acid fiber prepared in preparation example 13 was used, polyethylene 2, 5-furandicarboxylate was not added, and the tensile strength and elongation at break of the packaging film material prepared in example 12 were reduced as compared with example 1, and the barrier property against carbon dioxide was reduced, and the decay index and the weight loss were larger than those of example 1, and the freshness retaining ability was reduced.
In comparative example 1, no antibacterial preservative is added, the mechanical strength of the packaging film material is reduced, the barrier property is weakened, and the fresh-keeping capability is reduced; in comparative example 2, no titanium dioxide was added, and the mechanical strength of the packaging film material was not greatly changed, but the barrier property was weakened, and the fresh-keeping ability was lowered.
In comparative example 3, modified polylactic acid fiber was not added, mechanical properties such as tensile strength and the like of the packaging film material were lowered, barrier property was weakened, and fresh-keeping ability was lowered.
Comparative example 4 is a degradable packaging film material prepared by the prior art, which has better mechanical strength, but the moisture permeability and carbon dioxide permeability coefficient are larger than those of example 1, the barrier property is inferior to that of example 1, and the preservation capacity of mango is inferior to that of example 1.
The mango in the control group is not sealed by using a fresh-keeping bag, the rot index of the mango is large at the 6 th day, and the rot index is as high as 90.2% at the 12 th day, which indicates that the packaging film material can reduce the rot index, inhibit the transpiration and reduce the weight loss rate of fruits.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (5)
1. The packaging film material for fresh-keeping 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;
the chitosan is at least one selected from gallic acid grafted chitosan, vanilla acid grafted chitosan and syringic acid grafted chitosan;
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 20-24h, and irradiating under an ultraviolet lamp for 3-5h to obtain silver-loaded okra straw fibers;
mixing the silver-carrying okra straw fibers with modified polyester and sodium bicarbonate, extruding, granulating and grinding;
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;
the preparation method of the modified polylactic acid fiber comprises the following steps:
mixing polylactic acid, poly (ethylene 2, 5-furandicarboxylate), nanocellulose whisker and coupling modified zinc oxide, and carrying out melt spinning to obtain polylactic acid fibers;
dissolving polyglycolic acid with hexafluoroisopropanol, adding sodium chloride, graphene oxide and a micron-sized molecular sieve, uniformly mixing, immersing the polylactic acid fiber in the mixture for 30-40min, washing with deionized water, and airing;
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 polyethylene 2, 5-furandicarboxylate, 0.6-1.2 parts of nano cellulose whisker, 0.3-0.6 part of coupling 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.
2. The packaging film material for fresh keeping according to claim 1, wherein the melt spinning temperature is 190-200 ℃, the spinning speed is 100-150m/min, the diameter of the spinning hole is 0.5-0.6mm, and the spinning voltage is 30-40KV.
3. The packaging film material for fresh keeping according to claim 1, wherein the plasticizer is at least one of tributyl citrate, acetyl tributyl citrate, and glycerin.
4. The packaging film material for fresh keeping according to claim 1, wherein the heat stabilizer is at least one of calcium epoxyoleate and zinc epoxystearate.
5. The method for producing a packaging film material for fresh keeping according to any one of claims 1 to 4, comprising the steps of:
adding gelatin into deionized water, soaking at normal temperature for 20-30min, heating to 60-65deg.C, and stirring for 30-40min to obtain gelatin solution with concentration of 8-10wt%;
dissolving chitosan in acetic acid solution with the concentration of 2-3wt% to prepare chitosan solution with the concentration of 3-5 wt%;
dissolving a silane coupling agent, adding an antibacterial preservative, titanium dioxide and modified polylactic acid fibers, uniformly mixing, mixing with a gelatin solution and a chitosan solution, adding a plasticizer, a heat stabilizer and an antioxidant, uniformly mixing, and carrying out tape 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 |
| CN112981600A (en) * | 2019-12-16 | 2021-06-18 | 荣雷 | Anti-allergy polyester fiber |
| CN115449199A (en) * | 2022-10-15 | 2022-12-09 | 深圳市鼎力盛科技有限公司 | Novel polymer material bacterium-resistant plastic bubble bag and preparation method thereof |
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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 |
| CN115449199A (en) * | 2022-10-15 | 2022-12-09 | 深圳市鼎力盛科技有限公司 | Novel polymer material bacterium-resistant plastic bubble bag and preparation method thereof |
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