CN113201160A - 一种控湿阻隔复合薄膜及其制备方法和应用 - Google Patents
一种控湿阻隔复合薄膜及其制备方法和应用 Download PDFInfo
- Publication number
- CN113201160A CN113201160A CN202010077822.5A CN202010077822A CN113201160A CN 113201160 A CN113201160 A CN 113201160A CN 202010077822 A CN202010077822 A CN 202010077822A CN 113201160 A CN113201160 A CN 113201160A
- Authority
- CN
- China
- Prior art keywords
- additional layer
- composite film
- gas
- control barrier
- barrier composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 alkali metal salt Chemical class 0.000 claims abstract description 55
- 239000002585 base Substances 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 23
- 239000004599 antimicrobial Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- 235000002639 sodium chloride Nutrition 0.000 claims description 28
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 26
- 239000004743 Polypropylene Substances 0.000 claims description 19
- 229920001155 polypropylene Polymers 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 12
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000003242 anti bacterial agent Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000006136 alcoholysis reaction Methods 0.000 claims description 4
- 229940015043 glyoxal Drugs 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 108010013296 Sericins Proteins 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000004302 potassium sorbate Substances 0.000 claims description 2
- 235000010241 potassium sorbate Nutrition 0.000 claims description 2
- 229940069338 potassium sorbate Drugs 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002229 francium Chemical class 0.000 claims 1
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 24
- 239000012528 membrane Substances 0.000 abstract description 21
- 230000035699 permeability Effects 0.000 abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000009920 chelation Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 87
- 238000000576 coating method Methods 0.000 description 18
- 210000004379 membrane Anatomy 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000021022 fresh fruits Nutrition 0.000 description 3
- 230000029058 respiratory gaseous exchange Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052730 francium Inorganic materials 0.000 description 2
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical class [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000258971 Brachiopoda Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052891 actinolite Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940045110 chitosan Drugs 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 229960002216 methylparaben Drugs 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/154—Organic compounds; Microorganisms; Enzymes
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/157—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Food Science & Technology (AREA)
- Zoology (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Microbiology (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Plant Pathology (AREA)
- Laminated Bodies (AREA)
Abstract
本发明涉及一种控湿阻隔复合薄膜及其制备方法和应用。所述控湿阻隔复合薄膜包括基层和附加层,所述附加层位于基层的一侧;其中,所述基层为多孔薄膜;所述附加层包含聚乙烯醇和聚乙二醇,以及任选的抗菌剂,而且所述附加层的表面含有碱金属盐,是通过与聚乙二醇的螯合作用固定在附加层表面。本发明可以显著提高复合膜的透湿性,而且采用的表面螯合技术,不会破坏附加层的分子排列结构,从而不会影响膜阻气性。本发明的控湿阻隔复合薄膜具有智能控湿能力,在相对湿度较低时保持果蔬湿度,在相对湿度较高时增大透湿从而防止水果蔬菜结露溃烂,并且具有氧气阻隔性能,可用于具有保鲜功能的果蔬盒及具有保鲜果蔬盒的冰箱。
Description
技术领域
本发明涉及功能薄膜领域,具体地说,是涉及一种控湿阻隔复合薄膜及其制备方法和应用。
背景技术
水果和蔬菜是人类重要的食品,是人们取得基本营养物(维生素、矿物质、复合碳水化合物等)的主要来源。随着人们生活水平的日益提高,对新鲜水果和蔬菜的保鲜度要求越来越高。果蔬在收获之后仍能继续进行呼吸和蒸腾等生命活动,在存储过程中会发生水分散失和营养物质的消耗。温度每升高10℃,果蔬呼吸强度就增加一倍。家庭果蔬保鲜方法是将果蔬放置在冰箱中冷藏,减缓果蔬呼吸。在果蔬中,水分是重要成分,影响着水果和蔬菜嫩度、鲜度和味道。周围湿度过低会导致果蔬水分丧失和失重,但湿度过高会使得果蔬表面水分凝结,使真菌生长,加速水果和蔬菜腐烂和变质。因此控制新鲜果蔬储存湿度是非常重要的,将有利于延长果蔬的保鲜时间。使用阻隔性薄膜,可防止由于氧气等气体的渗透,抑制新鲜果蔬呼吸作用,有利于延长果蔬的保鲜时间。
市场上用于减少水分散失的果蔬盒上的几种功能性薄膜“感温透湿膜”、“硅滤膜”、“感湿透湿膜”的效果并不令人满意。感温透湿膜在高湿低温下膜表面容易结露;硅滤膜具有保湿功能,但透湿性无法随湿度而改变;感湿透湿膜是在纸基基材上施涂黏胶溶液,性能符合要求但是制备过程不环保,工艺复杂,且在加工工艺中有可能存在氯含量超标的问题。
CN105986511A公开了在干湿强度较高的原纸上施涂亲水保水及成膜性好的天然高分子聚合物的技术,但成本比较高。CN104029449A公开了一种大透湿量涂层膜,基础层为膨体聚四氟乙烯膜层,涂层为含有汉麻杆芯超细微粉的聚氨基甲酸酯乳液共聚涂层,该膜用于汽车车灯壳体,但不具有智能控湿性能。CN103507339A公开了一种感湿透湿膜,该膜将再生纤维素保持在无纺布的基材中,但不具备阻隔气体性能。CN103107301A公开了一种无机涂层锂离子电池隔膜,包含多层结构,分别为多孔柔性底膜和涂覆于底膜两侧的涂层,涂层包含聚乙烯醇和沸石粒子,该涂层的辅助成分并没有金属盐成分,且复合膜不具备智能控湿的功能。CN1864829A公开了一种亲水-憎水双极复合膜及其制备方法,该膜具有双层结构,底层为多孔支撑层,上层为含氯化锂的亲水膜,该膜具有高透湿和对其它气体分子强阻挡作用,但是并不具备智能控湿性。WO2013066012A1公开了一种含有无机粒子的多孔膜和包含亲水和疏水物质聚合物粘结层,该膜用于提高锂电池隔膜的热稳定性,并不具备智能控湿性能。WO2012133805A1公开了一种透湿膜,其多孔基材优选聚四氟乙烯,价格贵,且该膜的高透湿性能不佳。US20030054155A1公开了一种防水透湿复合膜,疏水层为聚四氟乙烯,亲水层为聚氨酯,该膜具有高透湿性,但并不具备智能控湿性能。
发明内容
本发明的目的是为了克服现有技术存在的上述缺陷,提供一种智能控湿阻隔复合薄膜,在低湿度的情况下保湿,在高湿度的情况下具有强排湿能力,并且具有氧气阻隔性能。本发明进一步提供所述该薄膜的制备方法,该方法工艺简单、成本低。因此,本发明提供的薄膜特别适合应用于蔬菜水果的保鲜包装。
本发明目的之一为提供一种控湿阻隔复合薄膜,包括基层和附加层,所述附加层位于基层的一侧,其中,
所述基层为多孔薄膜;
所述附加层包含聚乙烯醇和聚乙二醇,以及任选的抗菌剂;
所述附加层的表面含有碱金属盐。
本发明中,为实现智能控湿,所述基层需为多孔薄膜,所述附加层需为致密(薄)膜。所述多孔薄膜和致密(薄)膜的概念和术语范畴为本领域技术人员公知。作为附加层的致密薄膜可通过将含有附加层组分的溶液涂布至基层表面并干燥的方式制得。
其中基层可以为单层或两层复合结构,优选单层结构。所述基层为多孔薄膜,其材料为聚乙烯、聚丙烯、聚苯乙烯、聚对苯二甲酸二醇酯、聚己内酰胺中的至少一种,优选为聚乙烯和/或聚丙烯。
根据本发明,所述聚乙烯优选为高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)和低密度聚乙烯(LDPE)中的至少一种;所述聚丙烯优选为均聚聚丙烯、无规共聚聚丙烯、嵌段共聚聚丙烯和抗冲共聚聚丙烯中的至少一种。
所述附加层为致密薄膜,其包含聚乙烯醇与聚乙二醇,以及任选的抗菌剂,而且在附加层的表面含有碱金属盐,所述碱金属盐是通过与聚乙二醇的螯合作用固定在附加层表面的。
根据本发明,所述聚乙烯醇、聚乙二醇的相对含量以可形成致密薄膜为限,优选地,以附加层重量为基准,所述聚乙烯醇的含量为50~99wt%,优选为75~95wt%;所述聚乙二醇的含量为0.5~25wt%,优选为2.5~20wt%;所述碱金属盐的含量为0.5~25wt%,优选为2.5~10wt%。
根据本发明,所述聚乙烯醇的重均分子量为10000~500000,优选为20000~200000;醇解度为50~100%,优选为80~99%。
根据本发明,所述聚乙二醇的分子量为100~100000,优选为1000~20000。
根据本发明,所述碱金属盐为锂、钠、钾、铷、铯、钫的盐中的至少一种,优选为锂、钠、钾的盐中的至少一种。
根据本发明,所述碱金属盐优选为锂、钠、钾、铷、铯、钫的卤素盐、硫酸盐中的至少一种。所述碱金属盐具体可以为但不限于以下盐类中的至少一种,氯化钠、硫酸钠、氢氧化钠、氯化钾、硫酸钾、氢氧化钾、磷酸钠、磷酸钾、磷酸氢二钠、磷酸氢二钾、磷酸二氢钾、磷酸二氢钠、溴化钠、溴化钾、碘化钠、碘化钾、氯化锂、溴化锂、碘化锂、硫酸锂、磷酸锂。
根据本发明,所述抗菌剂的加入可使智能控湿薄膜具有抗菌性能。
所述抗菌剂可选择本领域中通常的抗菌剂,优选为纳米氧化锌、纳米氧化钛、纳米银、纳米铜、丝胶、季铵盐、羟苯甲酯、山梨酸钾、壳聚糖中的至少一种,进一步优选为纳米氧化锌、纳米银、季铵盐中的至少一种,所述季铵盐例如为西吡氯铵。
以所述附加层重量为基准,所述抗菌剂的含量优选为0.5~10wt%,更优选为1~5wt%。
根据本发明,所述附加层还可以为交联结构。当所述附加层为交联结构,附加层的凝胶含量为50~99wt%,优选为70~95wt%。
所述交联结构可以通过在附加层中加入交联剂得到,交联剂的加入可使智能控湿薄膜具有更好的氧气阻隔性能。
所述交联剂可选择本领域中通常的醛类交联剂,优选为甲醛、乙二醛、丙二醛、丁二醛、戊二醛、马来酸、马来酸酐中的至少一种,进一步优选为甲醛、戊二醛中的至少一种。
优选地,以所述附加层的重量为基准,所述交联剂的含量为0.5~20wt%,优选为1~10wt%。
上述优选的组分可获得更优透湿度和阻气性的薄膜。
本发明中,所述基层多孔薄膜的孔径优选为0.02~10微米,进一步优选为0.05~5微米,更优选为0.1~2微米;孔隙率为30%~80%,优选为40%~70%;孔径在平均孔径正负一个数量级范围内的孔占全部孔的50%以上,优选占全部孔的80%以上。
根据本发明,所述基层和附加层的厚度可根据需要确定,一般地,所述基层的厚度可以为5~1000微米,优选为10~100微米,进一步优选为60~90微米;所述附加层的厚度可以为0.5~100微米,优选为2~20微米。
本发明的目的之二为提供所述控湿阻隔复合薄膜的制备方法,包括以下步骤:
(1)将包括聚乙烯醇和聚乙二醇在内的所述附加层的组分溶解或者分散到溶剂中,配制成溶液或者分散液;
(2)将步骤(1)中得到的溶液或者分散液附着于所述基层的一面,加热烘干,在基层上形成附加层;
(3)将步骤(2)中得到的附加层接触碱金属盐溶液,排液,烘干,得到所述控湿阻隔复合薄膜。
所述基层多孔薄膜为单层时可市售而得,也可以采用现有技术中的常用制膜方法制得。比如,采用现有技术中的薄膜拉伸机将聚乙烯、聚丙烯、聚苯乙烯、聚对苯二甲酸二醇酯和聚己内酰胺或它们的组合物采用通常的薄膜拉伸工艺进行拉伸而制得所述支撑层的薄膜。薄膜拉伸机可以是单向或双向拉伸机。
当所述基层为两层时,两层的材质可以不同,如聚乙烯与聚丙烯复合而成的多孔薄膜。所述基层可市售而得,也可以采用现有技术中的复合薄膜的常用制膜方法制得。
步骤(1)中所述附加层组分可包括交联剂,以所述附加层的重量为基准,所述交联剂的含量为0.5~20wt%,优选为1~10wt%。
所述交联剂可选择本领域中通常的醛类交联剂,优选为甲醛、乙二醛、丙二醛、丁二醛、戊二醛、马来酸、马来酸酐中的一种或几种混合,进一步优选为甲醛、戊二醛中的至少一种。
步骤(1)中所用的溶剂可以采用通常的溶剂,优选为蒸馏水。
可以采用任何常规的涂布方法将步骤(1)中得到的溶液或者分散液涂布于基层,包括但不限于:刷涂、淋涂、喷涂。
根据本发明,步骤(1)中的溶液或者分散液中,聚乙烯醇的质量浓度为0.5~15%,优选为1~10%;聚乙二醇的质量浓度为0.05~5%,优选为0.1~2%;和/或步骤(1)中所述附加层组分包括抗菌剂,所述抗菌剂的质量浓度为0.001~0.5%,优选为0.01~0.3%;和/或步骤(1)中所述附加层组分包括交联剂,所述交联剂的质量浓度为0.05~1%,优选为0.1~0.5%。
步骤(1)中,调节溶液或分散液的pH为0~6,优选为1~4。
根据本发明,步骤(2)中烘干的温度可以为50~100℃,优选为60~90℃。可在常规的各种加热装置中完成烘干步骤,如烘箱。烘干的时间可根据需要确定,优选为1~60min,更优选3~30min。
根据本发明,步骤(3)中所述碱金属盐为氯化钠、硫酸钠、氢氧化钠、氯化钾、硫酸钾、氢氧化钾、磷酸钠、磷酸钾、磷酸氢二钠、磷酸氢二钾、磷酸二氢钾、磷酸二氢钠、溴化钠、溴化钾、碘化钠、碘化钾、氯化锂、溴化锂、碘化锂、硫酸锂、磷酸锂中的一种或几种混合,优选为氯化锂、溴化锂中的至少一种。
根据本发明,步骤(3)中,碱金属盐的质量浓度为0.1~10%,优选为0.5~5%。
根据本发明,步骤(3)中复合膜附加层与碱金属盐溶液接触的时间为10s~10min,优选为30s~5min。
步骤(3)中可在常规的各种加热装置中完成烘干步骤,如烘箱。烘干的温度为50~100℃,优选为60~90℃,烘干时间优选为1~60min,更优选为5~20min。
本发明的目的之三为提供所述控湿阻隔复合薄膜或由上述制备方法制得的控湿阻隔复合薄膜在蔬菜水果保鲜包装中的应用。
经发明人的深入研究发现,利用聚乙二醇将碱金属盐螯合至聚乙烯醇附加层表面,可以提高复合膜的吸湿能力,从而增强膜的透湿性能;另一方面,由于碱金属盐是通过化学键螯合至附加层表面,并没有破坏附加层的分子排列结构,从而不会影响膜的阻气性能。
下式给出了以碱金属盐氯化锂为例,附加层中聚乙二醇螯合氯化锂的机理:
本发明的控湿阻隔复合薄膜在环境湿度低的时候,复合膜功能层的分子链排列紧密,阻止了湿气的透过;当环境湿度高时,分子链间的自由体积增大,湿气透过量增大;由此,本发明的控湿阻隔复合薄膜具有智能控湿能力,在相对湿度较低时保持果蔬湿度,在相对湿度较高时增大透湿从而防止水果蔬菜结露溃烂,并且具有氧气阻隔性能,可用于具有保鲜功能的果蔬盒及具有保鲜果蔬盒的冰箱。
具体实施方式
下面将更详细地描述本发明的优选实施方式。
智能控湿薄膜的基层和附加层的厚度通过上海六菱测厚仪测定;孔结构包括孔径和孔隙率通过压汞法测量,采用仪器AutoporeIII-9420型压汞仪。
聚丙烯,F1002B,中石化扬子石化。
聚乙烯,L501(5000S),中石化扬子石化。
聚苯乙烯,GH-660,中石化广州石化。
聚对苯二甲酸乙二醇酯,FR530,美国杜邦。
聚己内酰胺,B4,BASF。
致密的聚丙烯双向拉伸薄膜,中石化镇海炼化,F280Z。
聚乙烯醇A,西陇化工,牌号为PVA124,重均分子量为105000,醇解度为99%。
聚乙烯醇B,西陇化工,牌号为PVA1788,重均分子量为74800,醇解度为88%。
纳米氧化锌,百灵威,99.5%,粒径10-30nm。
纳米银,百灵威,99.5%,粒径10-30nm。
甲醛,百灵威,50%水溶液。
戊二醛,百灵威,50%水溶液。
乙二醛,百灵威,50%水溶液。
硫酸,国药集团化学试剂有限公司,分析纯。
薄膜单向拉伸机,广州普同,MESI-LL。
实施例1
将2kg聚丙烯在薄膜单向拉伸机上拉伸成聚丙烯多孔薄膜。
将5g聚乙烯醇A,0.5g聚乙二醇(分子量为10000)加入94.15g蒸馏水中,充分溶解。将0.1g纳米氧化锌、0.25g戊二醛加至所得溶液中,充分搅拌至混合均匀,并用硫酸调节溶液的pH为2,得到涂覆液。将此涂覆液均匀地刷涂在聚丙烯多孔薄膜一面,然后将其置于烘箱中,在70℃下烘干10min。再将复合膜聚乙烯醇的附加层与质量浓度为1%的氯化锂水溶液接触1min后,排液,在90℃下烘干5min,得到智能控湿阻隔复合薄膜A1,其基层厚度为70微米,孔径为0.25微米,孔隙率为50%,孔径在平均孔径正负一个数量级范围内的孔占全部孔的85%以上;附加层厚度为15微米;附加层的凝胶含量为90%,附加层表面的氯化锂含量为2.5wt%。
实施例2
将2kg聚丙烯在薄膜单向拉伸机上拉伸成聚丙烯多孔薄膜。
将7.5g聚乙烯醇B,2.0g聚乙二醇(分子量为20000)加入90g蒸馏水中,充分溶解。将0.25g纳米氧化锌、0.25g戊二醛加至所得溶液中,充分搅拌至混合均匀,并用硫酸调节溶液的pH为2,得到涂覆液。将此涂覆液均匀地刷涂在聚丙烯多孔薄膜一面,然后将其置于烘箱中,在70℃下烘干10min。再将复合膜聚乙烯醇的附加层与质量浓度为5%的溴化锂水溶液接触1min后,排液,在70℃下烘干10min,得到智能控湿阻隔复合薄膜A2,其基层厚度为70微米,孔径为0.25微米,孔隙率为50%,孔径在平均孔径正负一个数量级范围内的孔占全部孔的85%以上;附加层厚度为19微米;附加层的凝胶含量为95%,附加层表面的溴化锂含量为9.1wt%。
实施例3
将2kg聚乙烯在薄膜单向拉伸机上拉伸成聚乙烯多孔薄膜。
将2.5g聚乙烯醇A,0.3g聚乙二醇(分子量为5000)加入97g蒸馏水中,充分溶解。将0.1g纳米氧化锌、0.1g戊二醛加至所得溶液中,充分搅拌至混合均匀,并用硫酸调节溶液的pH为2,得到涂覆液。将此涂覆液均匀地刷涂在聚乙烯多孔薄膜一面,然后将其置于烘箱中,在70℃下烘干10min。再将复合膜聚乙烯醇的附加层与质量浓度为5%的硫酸锂水溶液接触5min后,排液,在60℃下烘干20min,得到智能控湿阻隔复合薄膜A3,其基层厚度为70微米,孔径为0.25微米,孔隙率为50%,孔径在平均孔径正负一个数量级范围内的孔占全部孔的85%以上;附加层厚度为10微米;附加层的凝胶含量为83%,附加层表面的硫酸锂含量为9.8wt%。
实施例4
根据与实施例1相同的方法制备薄膜,不同的是,将附加层处理液氯化锂替换成碘化锂,得到智能控湿阻隔复合薄膜A4。
实施例5
根据与实施例1相同的方法制备薄膜,不同的是,将附加层处理液氯化锂替换成氯化钠,得到智能控湿阻隔复合薄膜A5。
实施例6
根据与实施例1相同的方法制备薄膜,不同的是,将附加层处理液氯化锂替换成氯化钾,得到智能控湿阻隔复合薄膜A6。
对比例1
根据与实施例1相同的方法制备薄膜,不同的是,附加层不经过碱金属盐溶液的处理,得到智能控湿阻隔复合薄膜D1。
对比例2
将2kg聚丙烯在薄膜单向拉伸机上拉伸成聚丙烯多孔薄膜。
将5g聚乙烯醇A,0.5g聚乙二醇(分子量为10000)以及0.5g氯化锂加入93.65g蒸馏水中,充分溶解。将0.1g纳米氧化锌、0.25g戊二醛加至所得溶液中,充分搅拌至混合均匀,并用硫酸调节溶液的pH为2,得到涂覆液。将此涂覆液均匀地刷涂在聚丙烯多孔薄膜一面,然后将其置于烘箱中,在70℃下烘干10min。得到智能控湿阻隔复合薄膜D2,其基层厚度为70微米,孔径为0.25微米,孔隙率为50%,孔径在平均孔径正负一个数量级范围内的孔占全部孔的85%以上;附加层厚度为16微米;附加层的凝胶含量为90%。
测试例
根据GB/T 1037-1988,对上述薄膜进行水蒸气透过率测试,在测试温度为25℃,透过面湿度为分别为50%和90%的测试条件下,得到每天每平方米薄膜的水蒸气透过量(g/m2/day),数据结果见表1。
根据GB/T 19789-2005对上述薄膜进行气体阻隔性能检测,得到氧气透过率[cm3·cm/(cm2·s·Pa)],数据结果见表1。
表1:薄膜的透湿性和气体阻隔性能测试结果
序号 | 透湿度(50%RH) | 透湿度(90%RH) | 阻气性(O<sub>2</sub>) |
A1 | 385 | 1869 | 2.4×10<sup>-6</sup> |
A2 | 267 | 1750 | 1.5×10<sup>-6</sup> |
A3 | 482 | 1930 | 8.6×10<sup>-6</sup> |
A4 | 280 | 1716 | 2.9×10<sup>-6</sup> |
A5 | 215 | 1479 | 3.6×10<sup>-6</sup> |
A6 | 187 | 1320 | 3.1×10<sup>-6</sup> |
D1 | 36 | 879 | 2.7×10<sup>-6</sup> |
D2 | 252 | 1678 | 4.5×10<sup>-5</sup> |
由表1可见,利用碱金属盐离子与聚乙二醇之间的螯合作用将其固定在附加层聚乙烯醇的表面,可以显著提高复合膜的透湿性;而且与直接向附加层中引入碱金属盐相比,本发明采用的表面螯合技术,不会破坏附加层的分子排列结构,从而不会影响膜阻气性。此外,本发明的智能控湿阻隔复合薄膜具有良好的智能控湿能力,即在湿度较低时,该智能控湿阻隔复合薄膜的透湿度降低,具有保湿的能力,可保持果蔬湿度;反之,在湿度较高时,该智能控湿阻隔复合薄膜的透湿度提高,具有强排湿能力,从而可防止水果蔬菜结露溃烂。
以上已经描述了本发明的各实施例,上述说明是示例性的,并非穷尽性的,并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下,对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。
Claims (14)
1.一种控湿阻隔复合薄膜,其特征在于所述复合薄膜包括基层和附加层,所述附加层位于基层的一侧,其中,
所述基层为多孔薄膜;
所述附加层包含聚乙烯醇和聚乙二醇,以及任选的抗菌剂;
所述附加层的表面含有碱金属盐。
2.根据权利要求1所述的控湿阻隔复合薄膜,其特征在于:
以所述附加层重量为基准,所述聚乙烯醇的含量为50~99wt%,优选为75~95wt%;所述聚乙二醇的含量为0.5~25wt%,优选为2.5~20wt%;所述碱金属盐的含量为0.5~25wt%,优选为2.5~10wt%;和/或,
以所述附加层重量为基准,所述抗菌剂的含量为0.5~10wt%,优选为1~5wt%。
3.根据权利要求1所述的控湿阻隔复合薄膜,其特征在于:
当所述附加层为交联结构,附加层的凝胶含量为50~99wt%,优选为70~95wt%。
4.根据权利要求1所述的控湿阻隔复合薄膜,其特征在于:
所述基层的材料为聚乙烯、聚丙烯、聚苯乙烯、聚对苯二甲酸二醇酯、聚己内酰胺中的至少一种;和/或,
所述聚乙烯醇的重均分子量为10000~500000,优选为20000~200000;醇解度为50~100%,优选为80~99%;和/或,
所述聚乙二醇的分子量为100~100000,优选为1000~20000;和/或,
所述碱金属盐为锂、钠、钾、铷、铯、钫的盐中的至少一种;和/或,
所述抗菌剂为纳米氧化锌、纳米氧化钛、纳米银、纳米铜、丝胶、季铵盐、羟苯甲酯、山梨酸钾、壳聚糖中的至少一种,优选为纳米氧化锌、纳米银、季铵盐中的至少一种。
5.根据权利要求1所述的控湿阻隔复合薄膜,其特征在于:
所述碱金属盐为氯化钠、硫酸钠、氢氧化钠、氯化钾、硫酸钾、氢氧化钾、磷酸钠、磷酸钾、磷酸氢二钠、磷酸氢二钾、磷酸二氢钾、磷酸二氢钠、溴化钠、溴化钾、碘化钠、碘化钾、氯化锂、溴化锂、碘化锂、硫酸锂、磷酸锂中的至少一种。
6.根据权利要求1所述的控湿阻隔复合薄膜,其特征在于:
所述基层的厚度为5~1000微米,优选为10~100微米;所述附加层的厚度为0.5~100微米,优选为2~20微米。
7.根据权利要求1所述的控湿阻隔复合薄膜,其特征在于:
所述基层多孔薄膜的孔径为0.02~10微米,优选为0.05~5微米;孔隙率为30%~80%,优选为40%~70%;孔径在平均孔径正负一个数量级范围内的孔占全部孔的50%以上,优选占全部孔的80%以上。
8.一种根据权利要求1~7之任一项所述的控湿阻隔复合薄膜的制备方法,其特征在于包括以下步骤:
(1)将包括聚乙烯醇和聚乙二醇在内的所述附加层的组分溶解或者分散到溶剂中,配制成溶液或者分散液;
(2)将步骤(1)中得到的溶液或者分散液附着于所述基层的一面,加热烘干,在基层上形成附加层;
(3)将步骤(2)中得到的附加层接触碱金属盐溶液,烘干,得到所述控湿阻隔复合薄膜。
9.根据权利要求8所述的控湿阻隔复合薄膜的制备方法,其特征在于:
步骤(1)中所述附加层组分包括交联剂,以所述附加层的重量为基准,所述交联剂的含量为0.5~20wt%,优选为1~10wt%。
10.根据权利要求9所述的控湿阻隔复合薄膜的制备方法,其特征在于:
所述交联剂为甲醛、乙二醛、丙二醛、丁二醛、戊二醛、马来酸、马来酸酐中的至少一种。
11.根据权利要求8所述的控湿阻隔复合薄膜的制备方法,其特征在于:
步骤(1)中的溶液或者分散液中,聚乙烯醇的质量浓度为0.5~15%,优选为1~10%;聚乙二醇的质量浓度为0.05~5%,优选为0.1~2%;和/或,
步骤(1)中所述附加层组分包括抗菌剂,所述抗菌剂的质量浓度为0.001~0.5%,优选为0.01~0.3%;和/或,
步骤(1)中所述附加层组分包括交联剂,所述交联剂的质量浓度为0.05~1%,优选为0.1~0.5%。
12.根据权利要求8所述的控湿阻隔复合薄膜的制备方法,其特征在于:
步骤(3)中,碱金属盐的质量浓度为0.1~10%,优选为0.5~5%。
13.根据权利要求8所述的控湿阻隔复合薄膜的制备方法,其特征在于:
步骤(1)中,调节溶液或分散液的pH为0~6,优选为1~4;和/或,
步骤(2)中,烘干的温度为50~100℃,优选为60~90℃,烘干时间为1~60min,优选3~30min;和/或,
步骤(3)中,所述附加层与碱金属盐溶液接触的时间为10s~10min,优选为30s~5min;烘干的温度为50~100℃,优选为60~90℃,烘干时间为1~60min,优选5~20min。
14.权利要求1~7之任一项所述的控湿阻隔复合薄膜或由权利要求8~13之任一项所述的制备方法制得的控湿阻隔复合薄膜在蔬菜水果保鲜包装中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010077822.5A CN113201160B (zh) | 2020-02-01 | 2020-02-01 | 一种控湿阻隔复合薄膜及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010077822.5A CN113201160B (zh) | 2020-02-01 | 2020-02-01 | 一种控湿阻隔复合薄膜及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113201160A true CN113201160A (zh) | 2021-08-03 |
CN113201160B CN113201160B (zh) | 2022-08-19 |
Family
ID=77024909
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010077822.5A Active CN113201160B (zh) | 2020-02-01 | 2020-02-01 | 一种控湿阻隔复合薄膜及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113201160B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4273318A1 (en) * | 2022-05-04 | 2023-11-08 | B&T Entwicklungs- und Vermarktungsgesellschaft mbH | Layered structure |
PL442888A1 (pl) * | 2022-11-19 | 2024-05-20 | Folpak Spółka Z Ograniczoną Odpowiedzialnością | Folia opakowaniowa, trójwarstwowa |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030124365A1 (en) * | 2001-11-14 | 2003-07-03 | Robert Posey | Oxygen barrier coating and coated film |
CN109562865A (zh) * | 2016-08-12 | 2019-04-02 | 太阳化学公司 | 增强阻隔的涂料 |
CN109721905A (zh) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | 聚乙烯醇薄膜及其组合物和制备方法 |
CN110305361A (zh) * | 2018-03-20 | 2019-10-08 | 中国石油化工股份有限公司 | 一种智能控湿阻隔复合薄膜及其制备方法和应用 |
-
2020
- 2020-02-01 CN CN202010077822.5A patent/CN113201160B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030124365A1 (en) * | 2001-11-14 | 2003-07-03 | Robert Posey | Oxygen barrier coating and coated film |
CN109562865A (zh) * | 2016-08-12 | 2019-04-02 | 太阳化学公司 | 增强阻隔的涂料 |
CN109721905A (zh) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | 聚乙烯醇薄膜及其组合物和制备方法 |
CN110305361A (zh) * | 2018-03-20 | 2019-10-08 | 中国石油化工股份有限公司 | 一种智能控湿阻隔复合薄膜及其制备方法和应用 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4273318A1 (en) * | 2022-05-04 | 2023-11-08 | B&T Entwicklungs- und Vermarktungsgesellschaft mbH | Layered structure |
WO2023213956A1 (en) | 2022-05-04 | 2023-11-09 | B&T Entwicklungs- Und Vermarktungsgesellschaft Mbh | Layered structure |
PL442888A1 (pl) * | 2022-11-19 | 2024-05-20 | Folpak Spółka Z Ograniczoną Odpowiedzialnością | Folia opakowaniowa, trójwarstwowa |
Also Published As
Publication number | Publication date |
---|---|
CN113201160B (zh) | 2022-08-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113201160B (zh) | 一种控湿阻隔复合薄膜及其制备方法和应用 | |
Tual et al. | Transport properties of chitosan membranes: influence of crosslinking | |
Wiles et al. | Water vapor transmission rates and sorption behavior of chitosan films | |
Despond et al. | Barrier properties of paper–chitosan and paper–chitosan–carnauba wax films | |
CN112300438A (zh) | 一种阻气透湿薄膜及其制备方法和应用 | |
Schnell et al. | Films from xylan/chitosan complexes: preparation and characterization | |
CN110305361A (zh) | 一种智能控湿阻隔复合薄膜及其制备方法和应用 | |
CN113717415A (zh) | 一种多孔透气的纳米抗菌果蔬保鲜膜的制备方法 | |
CN107746470B (zh) | 防霉保鲜膜及其制备方法 | |
CN113292753A (zh) | 一种缓控释抗菌性壳聚糖基复合膜的制备方法及其应用 | |
CN113321834B (zh) | 一种智能控湿阻隔复合薄膜及其制备方法和应用 | |
CN113831585A (zh) | 一种控湿阻隔薄膜及其制备方法和应用 | |
CN110607715A (zh) | 一种无氟防油纸及其制备方法与应用 | |
CN114426699A (zh) | 一种三明治型阻气透湿复合膜及其制备方法和应用 | |
CN111718508B (zh) | 一种包含醋酸纤维素的阻气透湿薄膜及其制备方法和应用 | |
CN112538188B (zh) | 一种智能控湿阻隔复合薄膜及其制备方法和应用 | |
CN111013402B (zh) | 一种智能控湿薄膜及制备方法与应用 | |
US20220305446A1 (en) | Selectively permeable polymeric membrane | |
CN113278192B (zh) | 一种控湿复合薄膜及其制备方法和应用 | |
CN115584659B (zh) | 一种高阻隔性保鲜材料及其制备方法 | |
CN112538189B (zh) | 一种包含磺化聚乙烯醇和聚乙二醇的智能控湿阻隔复合薄膜及其制备方法和应用 | |
CN110305351A (zh) | 一种可全生物降解的智能控湿薄膜及其制备方法和应用 | |
CN112755804B (zh) | 一种智能控湿薄膜及其制备方法和应用 | |
CN110302679A (zh) | 一种智能控湿薄膜及其制备方法和应用 | |
CN113637210B (zh) | 一种阻气透湿膜及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |