CN109422983A - starch/PVA composite antibacterial preservative film and preparation method thereof - Google Patents
starch/PVA composite antibacterial preservative film and preparation method thereof Download PDFInfo
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- CN109422983A CN109422983A CN201710740388.2A CN201710740388A CN109422983A CN 109422983 A CN109422983 A CN 109422983A CN 201710740388 A CN201710740388 A CN 201710740388A CN 109422983 A CN109422983 A CN 109422983A
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- starch
- preservative film
- composite antibacterial
- pva composite
- film
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- 229920002472 Starch Polymers 0.000 title claims abstract description 54
- 235000019698 starch Nutrition 0.000 title claims abstract description 54
- 239000008107 starch Substances 0.000 title claims abstract description 54
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 31
- 239000003755 preservative agent Substances 0.000 title claims abstract description 29
- 230000002335 preservative effect Effects 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 46
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 12
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229960000304 folic acid Drugs 0.000 claims description 7
- 235000019152 folic acid Nutrition 0.000 claims description 7
- 239000011724 folic acid Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- -1 tertiary amino alkyl ether Chemical class 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 244000189799 Asimina triloba Species 0.000 claims description 2
- 235000006264 Asimina triloba Nutrition 0.000 claims description 2
- 235000009467 Carica papaya Nutrition 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 2
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229940008099 dimethicone Drugs 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229960005150 glycerol Drugs 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 2
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 1
- 240000008042 Zea mays Species 0.000 claims 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- 235000005822 corn Nutrition 0.000 claims 1
- 238000004945 emulsification Methods 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- 239000013049 sediment Substances 0.000 claims 1
- 229920002545 silicone oil Polymers 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003292 glue Substances 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 1
- 239000002671 adjuvant Substances 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 abstract 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 14
- 241000287828 Gallus gallus Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 5
- 241000220225 Malus Species 0.000 description 5
- 239000008120 corn starch Substances 0.000 description 5
- 229940099112 cornstarch Drugs 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000012055 fruits and vegetables Nutrition 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000017060 Arachis glabrata Nutrition 0.000 description 3
- 244000105624 Arachis hypogaea Species 0.000 description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 description 3
- 235000018262 Arachis monticola Nutrition 0.000 description 3
- 240000007124 Brassica oleracea Species 0.000 description 3
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 3
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 3
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000366676 Justicia pectoralis Species 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 235000021016 apples Nutrition 0.000 description 3
- 235000013622 meat product Nutrition 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 235000020232 peanut Nutrition 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- 241000207199 Citrus Species 0.000 description 2
- 235000009917 Crataegus X brevipes Nutrition 0.000 description 2
- 235000013204 Crataegus X haemacarpa Nutrition 0.000 description 2
- 235000009685 Crataegus X maligna Nutrition 0.000 description 2
- 235000009444 Crataegus X rubrocarnea Nutrition 0.000 description 2
- 235000009486 Crataegus bullatus Nutrition 0.000 description 2
- 235000017181 Crataegus chrysocarpa Nutrition 0.000 description 2
- 235000009682 Crataegus limnophila Nutrition 0.000 description 2
- 235000004423 Crataegus monogyna Nutrition 0.000 description 2
- 240000000171 Crataegus monogyna Species 0.000 description 2
- 235000002313 Crataegus paludosa Nutrition 0.000 description 2
- 235000009840 Crataegus x incaedua Nutrition 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 235000011430 Malus pumila Nutrition 0.000 description 2
- 235000015103 Malus silvestris Nutrition 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
- 240000006365 Vitis vinifera Species 0.000 description 2
- 235000014787 Vitis vinifera Nutrition 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 2
- 235000020971 citrus fruits Nutrition 0.000 description 2
- 235000021022 fresh fruits Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- SXFBQAMLJMDXOD-UHFFFAOYSA-N (+)-hydrogentartrate bitartrate salt Chemical compound OC(=O)C(O)C(O)C(O)=O.OC(=O)C(O)C(O)C(O)=O SXFBQAMLJMDXOD-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000013594 poultry meat Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a starch/PVA composite antibacterial preservative film and a preparation method thereof. The preservative film is formed by adding a cross-linking agent, a plasticizer, a defoaming agent and a film-forming assistant into a framework structure formed by starch, cationic starch and polyvinyl alcohol. The preparation method comprises the following steps: preparing starch and cationic starch into a water solution with a certain concentration, heating and gelatinizing, adding polyvinyl alcohol, heating and stirring until the polyvinyl alcohol is completely dissolved; adding a cross-linking agent, heating, stirring and reacting for a certain time; adding plasticizer, defoaming agent and film-forming adjuvant to prepare uniform aqueous solution (glue) whose solid content is 15-25%; and pouring the uniformly mixed aqueous solution (glue) into a mold for molding, and drying to form a film. The antibacterial preservative film has high barrier property to oxygen, nitrogen and carbon dioxide, moderate water vapor transmission capacity and certain sterilization capacity; the antibacterial group is connected on the macromolecular skeleton, so that the performance is more stable, the volatilization is difficult, and the service life is long.
Description
Technical field
The invention belongs to food material fields, and in particular to a kind of starch/PVA composite antibacterial preservative film and its preparation side
Method.
Background technique
Fresh fruit of vegetables, meat product contain sufficient moisture and nutritional ingredient, therefore are the ideal breeding bases of microorganism;
Existing fresh fruit of vegetables, meat product use antibacterial agent to inhibit the mass propagation of microorganism mostly, but are easy absorption and remain in fruit
Vegetable, meat product surface, influence food safety.
Polyvinyl alcohol is a kind of biodegradable synthesis type high molecular material, has many excellent performances, such as water-soluble
Property, film forming, ability is penetrated to the barrier property of the gases such as oxygen, carbon dioxide and ethylene and higher steam.Starch is a kind of
Renewable biodegradable natural macromolecular material, it is from a wealth of sources, it is renewable, it is cheap.Starch/PVA film is used for fruits and vegetables
It is fresh-keeping, safe and non-toxic, complete biodegradable, completely it is water-soluble, have strong barrier property to oxygen, carbon dioxide, ethylene etc., moreover it is possible to protect
The features such as holding aqueous vapor penetration appropriate;But it has the following problems: 1, without anti-microbial property, relies primarily on and adjust fresh-keeping object environment
Atmosphere reaches fresh-keeping effect, and only obvious to strong breathing preserving fruit and vegetable utilizing effect, application range is restricted;2, hydrophilic dampness, film surface
Microorganism easy to breed influences preserving fruit and vegetable utilizing effect.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that provide a kind of starch/PVA multiple
Close antimicrobial preservative film.The present invention use from the natural plants such as citrus, hawthorn, apple and grape organic acid as starch,
The reagent of cationic starch, PVA co-crosslinking is implanted into antibacterial group (quaternary ammonium salt) on starch/PVA film, widens preservative film application
Space;Antibacterial group is fixed on starch/PVA film by chemical bond, avoids the loss of antibacterial group, and it is relatively permanent to be able to maintain
Antibacterial activity, on the other hand food will not be polluted, use is safer;Unreacted organic acid is starch, PVA
Plasticizer, defoaming agent, coalescing agent direct formation of film at surface, high production efficiency can be added without processing after cross-linking reaction in good plasticizer;
Water resistance improves, and reduces film surface microbial growth, improves preserving fruit and vegetable utilizing effect.
Another object of the present invention is to provide above-mentioned starch/PVA composite antibacterial preservative film preparation methods.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of starch/PVA composite antibacterial preservative film, with being total to for starch, polyvinyl alcohol and starch, polyvinyl alcohol and crosslinking agent
Cross-linking products are basic framework, and plasticizer, defoaming agent and coalescing agent is added and is made;According to parts by weight, original is mainly prepared
Material matches
The polyvinyl alcohol is the polyvinyl alcohol that alcoholysis degree is less than or equal to 88%, and specific is preferably polyvinyl alcohol
1788, polyvinyl alcohol 0588 or polyvinyl alcohol 0580.
The starch is at least one of cornstarch, sweet potato starch and pawpaw starch etc..
The cationic starch is at least one of starch tertiary amino alkyl ether, quaternary alkyl ammonium starch ether.
The crosslinking agent is from the organic acid of the natural plants such as citrus, hawthorn, apple and grape, specially 2- hydroxyl fourth
At least one of diacid (malic acid), 2,3 dihydroxybutanedioic acid (tartaric acid) and pteroylglutamic acid (folic acid) etc..
The plasticizer is polyhydroxy plasticizer, preferably ethylene glycol, glycerine, polyethylene glycol-400, polyethylene glycol-
1000, at least one of Polyethylene glycol-2000, polyethylene glycol-6000 and sorbierite.
The defoaming agent is glycerin monostearate or phosphoric acid ester.
The coalescing agent is at least one of tackifier, levelling agent and release agent etc..The tackifier are disproportionation pine
At least one of perfume, hydrogenated rosin, terpene resin, xanthan gum and cation guar gum;The levelling agent is modified poly- silicon oxygen
At least one of alkane, acrylate;At least one of the release agent dimethicone, silicone emulsion.
Above-mentioned starch/PVA composite antibacterial preservative film preparation method, comprising the following steps:
(1) starch, cationic starch are made into certain density aqueous solution Heat Gelatinization, polyvinyl alcohol heating stirring is added
To being completely dissolved;
(2) crosslinking agent is added into the solution that step (1) obtains and is stirred to react certain time, obtain uniform mixed solution
Or colloidal sol (the small degree of cross linking is solution, is colloidal sol when larger);
(3) plasticizer, defoaming agent, coalescing agent, high-speed stirring are added into the mixed solution or colloidal sol that step (2) obtains
It mixes, it is cooling, it is configured to homogeneous aqueous solution or colloidal sol that solid content is 15-25%;
(4) aqueous solution made from step (3) or colloidal sol are poured into die for molding, drying and forming-film.
Step (1) the Heat Gelatinization temperature is 60-75 DEG C, and heating stirring, which refers to, is heated to 80-90 DEG C with 1500~2500
Turn/min speed stirs to being completely dissolved;Step (2) mixing speed is 500 turns/min, and reaction time 30-90min is obtained
The solid content of homogeneous solution or colloidal sol is 15-25%;Step (3) is cooled to after mixing evenly with 1500~3500 turns/min speed
40-50℃。
Step (1) the Heat Gelatinization temperature is that 60-75 DEG C of starch makes to be gelatinized completely, and heating stirring, which refers to, is heated to 80-90
DEG C be completely dissolved polyvinyl alcohol with the stirring of 1500~2500 turns/min speed, guarantee step (2) cross-linking reaction and step (2) at
The smooth efficient implementation of membrane process.
The control of step (2) cross-linking reaction temperature is advisable at 70-90 DEG C, is lower than 70 DEG C, it is relatively low to eventually lead to the degree of cross linking;It is higher than
90 DEG C, obtained solution (glue) can not sprawl film forming because of poor fluidity;The stirring 30-90min is cross-linking reaction time, low
In 30min, cross-linking reaction is not yet complete, and the degree of cross linking is lower;Higher than 90min, the degree of cross linking is excessively high, and the solution (glue) of formation may be because
Poor fluidity can not sprawl film forming.
Step (3) solution or colloidal sol solid content must be controlled in 15%-25%, and too high solution (glue) viscosity is big, it is difficult to it sprawls,
Solid content too low filming low efficiency.
The temperature of step (4) described drying and forming-film is 110-150 DEG C.
Cationic starch adds 0.5-1 parts by weight in the above process, and too low antibacterial effect is unobvious, excessively high increase cost,
The introducing of excess antimicrobial agent also can bring side effect to food hygiene and safety;The crosslinking agent adds 0.5-3 parts by weight, is lower than
0.5 part, cross-linking reaction can not occur;Higher than 3 parts, no longer has a significant effect to the degree of cross linking, will increase cost on the contrary.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) the present invention relates to raw material it is biodegradable, crosslinking agent used be natural plants in extract it is natural
Acid finally will be degraded to carbon dioxide and water in natural environment, be a kind of environmentally protective preservative film;
(2) it is fixed compared to compound, coating, coordination, antibacterial group is connected on macromolecular scaffold, and performance is more stable, no
Food hygiene and safety can be endangered because of the volatilization migration stain food of antibacterial agent.
(3) good controlled atmosphere function is kept, while possessing certain sterilizing ability, has widened that starch/PVA film is fresh-keeping to answer
Use space;
(4) introducing of antibacterial group slow down because film it is hydrophilic caused by bacteria breed, the safety for further increasing preservative film defends
Natural disposition;
(5) crosslinking agent is the organic acid from the Nature, while being also the plasticizer of polyvinyl alcohol and starch, after being not necessarily to
Processing;Starch, PVA crosslinking are completed while introducing antibacterial group, are improved the compatibility between starch, PVA, are improved the physical machine of film
Tool performance.Film producing industry is environmentally protective, is simple and efficient, and is easy industrialization.
Detailed description of the invention
Fig. 1 is 3 days example photos of the fresh-keeping chicken of starch of the present invention/PVA composite antibacterial preservative film, and wherein a is fresh-keeping preceding new
Freshly-slaughtered poultry meat piece, b are the chicken block after storing 3 days;
Fig. 2 is 3 days example photos of the fresh-keeping chicken of PE preservative film, and wherein a is fresh-keeping preceding fresh chicken block, after b is storage 3 days
Chicken block.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
Specific formula:
Preparation process is as follows:
(1) each component is weighed up according to formula metering, 30g cornstarch, 1g cationic starch is configured to a certain concentration water
It is dissolved in the gelatinization of 75 DEG C of heating water baths, polyvinyl alcohol is added and continues heating stirring to being completely dissolved;
(2) 1.5g folic acid reaction 30min is added toward the solution that step (1) obtains;
(3) coalescing agent and deionized water is added toward step (2) and is heated to being completely dissolved, defoaming agent is then added at a high speed
It is dispersed with stirring, is cooled to 50 DEG C, obtains mixed aqueous solution.
(4) uniformly mixed aqueous solution is equably laid on dry, clean mold, formation thickness is uniform, surface
Bright and clean smooth liquid layer, dries 12h at 110 DEG C.
No. 1 sealed package Fresh-cut Apples of antimicrobial preservative film prepared with the embodiment, in 25 DEG C/relative humidity RH75% item
It is stored 3 days under part, Fresh-cut Apples are without obvious oxidative phenomena, without special bad smell, without obvious corruption;PE preservative film is in phase
With under conditions of, Fresh-cut Apples darken, and can smell alcohol smell.
Embodiment 2
Specific formula:
Preparation process is as follows:
(1) each component is weighed up according to formula metering, 20g cornstarch, 0.5g cationic starch is configured to a certain concentration
It is water-soluble to be gelatinized in 75 DEG C of heating water baths, it adds polyvinyl alcohol and continues heating stirring to being completely dissolved;
(2) 1.5g folic acid reaction 30min is added toward the solution that step (1) obtains;
(3) coalescing agent and deionized water is added toward step (2) and is heated to being completely dissolved, defoaming agent is then added at a high speed
It is dispersed with stirring, is cooled to 50 DEG C, obtains mixed aqueous solution.
(4) uniformly mixed aqueous solution is equably laid on dry, clean mold, formation thickness is uniform, surface
Bright and clean smooth liquid layer, dries 12h at 120 DEG C.
Antibacterial film sealed package cabbage heart is prepared using the embodiment, stores two under the conditions of 5 DEG C/relative humidity RH75%
In week, cabbage heart appearance is without significant change;At identical conditions, cabbage heart turns yellow PE preservative film, the sign that rots occurs.
Embodiment 3
Specific formula:
Preparation process is as follows:
(1) each component is weighed up according to formula metering, 40g cornstarch, 0.8g cationic starch is configured to a certain concentration
It is water-soluble to be gelatinized in 75 DEG C of heating water baths, it adds polyvinyl alcohol and continues heating stirring to being completely dissolved;
(2) 1.5g folic acid reaction 45min is added toward the solution that step (1) obtains;
(3) coalescing agent and deionized water is added toward step (2) and is heated to being completely dissolved, defoaming agent is then added at a high speed
It is dispersed with stirring, is cooled to 50 DEG C, obtains mixed aqueous solution;
(4) uniformly mixed aqueous solution is equably laid on dry, clean mold, formation thickness is uniform, surface
Bright and clean smooth liquid layer, dries 12h at 120 DEG C.
The fresh peanut of antibacterial film sealed package prepared using the embodiment, under the conditions of 20 DEG C/relative humidity RH60%
It stores 10 days, without significantly different before peanut surface dry, with 10 days;At identical conditions, peanut surface goes out PE preservative film
Now obvious mildew.
Embodiment 4
Specific formula:
Preparation process is as follows:
(1) each component is weighed up according to formula metering, 20g cornstarch, 1g self-control cationic starch is configured to certain dense
Spend it is water-soluble be gelatinized in 75 DEG C of heating water baths, add polyvinyl alcohol and continue heating stirring to being completely dissolved;
(2) 1.5g folic acid reaction 60min is added toward the solution that step (1) obtains;
(3) coalescing agent and deionized water is added toward step (2) and is heated to being completely dissolved, defoaming agent is then added at a high speed
It is dispersed with stirring, is cooled to 50 DEG C, obtains mixed aqueous solution;
(4) uniformly mixed aqueous solution is equably laid on dry, clean mold, formation thickness is uniform, surface
Bright and clean smooth liquid layer, dries 12h at 120 DEG C.
The fresh chicken block of antibacterial film sealed package prepared using the embodiment, under the conditions of 5 DEG C/relative humidity RH75%
Storage 3 days, film is interior without bad smell, and chicken block is not corrupt.Under identical environment, PE film sealed package chicken block, chicken block are used
It darkens, there is a large amount of mucus in film, there is bad smell, corruption is serious.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of starch/PVA composite antibacterial preservative film, which is characterized in that it prepares raw material and includes:
2. starch according to claim 1/PVA composite antibacterial preservative film, which is characterized in that the polyvinyl alcohol is alcoholysis
Degree is less than or equal to 88% polyvinyl alcohol.
3. starch according to claim 1/PVA composite antibacterial preservative film, which is characterized in that the starch is corn shallow lake
At least one of powder, sweet potato starch and pawpaw starch.
4. starch according to claim 1/PVA composite antibacterial preservative film, which is characterized in that the cationic starch is to form sediment
At least one of powder tertiary amino alkyl ether, quaternary alkyl ammonium starch ether.
5. starch according to claim 1/PVA composite antibacterial preservative film, which is characterized in that the crosslinking agent is 2- hydroxyl
At least one of succinic acid, 2,3 dihydroxybutanedioic acid and pteroylglutamic acid.
6. starch according to claim 1/PVA composite antibacterial preservative film, which is characterized in that the plasticizer is polyhydroxy
Plasticizer, the coalescing agent are at least one of tackifier, levelling agent and release agent.
7. starch according to claim 6/PVA composite antibacterial preservative film, which is characterized in that the plasticizer is second two
In alcohol, glycerine, polyethylene glycol-400, polyethylene glycol-1000, Polyethylene glycol-2000, polyethylene glycol-6000 and sorbierite
It is at least one;The tackifier be disproportionated rosin, hydrogenated rosin, terpene resin, xanthan gum and cation guar gum at least
It is a kind of;The levelling agent is at least one of modified polyorganosiloxane, acrylate;The release agent dimethicone, emulsification
At least one of silicone oil.
8. starch according to claim 1/PVA composite antibacterial preservative film, which is characterized in that the defoaming agent is single stearic
Acid glyceride or phosphoric acid ester.
9. the described in any item starch of claim 1 to 8/PVA composite antibacterial preservative film preparation method, which is characterized in that packet
Include following steps:
(1) starch, cationic starch are made into certain density aqueous solution Heat Gelatinization, polyvinyl alcohol heating stirring is added to complete
Fully dissolved;
(2) crosslinking agent is added into the solution that step (1) obtains and is stirred to react certain time, obtain solution or colloidal sol;
(3) plasticizer, defoaming agent, coalescing agent are added into the solution or colloidal sol that step (2) obtains, high-speed stirred is cooling, matches
The homogeneous aqueous solution or colloidal sol that solid content is 15-25% is made;
(4) aqueous solution made from step (3) or colloidal sol are poured into die for molding, drying and forming-film.
10. starch according to claim 9/PVA composite antibacterial preservative film preparation method, which is characterized in that step (1)
The Heat Gelatinization temperature be 60-75 DEG C, heating stirring refer to be heated to 80-90 DEG C with 1500~2500 turns/min speed stir to
It is completely dissolved;Step (2) mixing speed is 500 turns/min, reaction time 30-90min, and obtained solution or consolidating for colloidal sol contain
Amount is 15-25%;Step (3) is cooled to 40-50 DEG C with 1500~3500 turns/min speed after mixing evenly.
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Cited By (8)
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CN110367246A (en) * | 2019-07-10 | 2019-10-25 | 邱张云 | A kind of natural plants specially treated technique |
CN111057251A (en) * | 2019-12-31 | 2020-04-24 | 浙江工业大学 | Preparation method of cationic hydrogel |
CN112358655A (en) * | 2020-11-09 | 2021-02-12 | 绍兴兆丽新材料科技有限公司 | Environment-friendly medicine packaging material and preparation method thereof |
CN112515085A (en) * | 2020-11-30 | 2021-03-19 | 四川农业大学 | Novel preservation card and preparation method thereof |
CN113004643A (en) * | 2021-03-18 | 2021-06-22 | 浙江农林大学 | starch/PVA composite antibacterial preservative film and preparation method thereof |
CN113388135A (en) * | 2021-04-25 | 2021-09-14 | 广西民族大学 | Preparation of PVA/cassava starch/LAE active composite membrane and application of PVA/cassava starch/LAE active composite membrane in food packaging bacteriostasis |
WO2022027607A1 (en) * | 2020-08-07 | 2022-02-10 | 南京五瑞生物降解新材料研究院有限公司 | Novel fresh-keeping bag capable of being dissolved in seawater and preparation method therefor |
WO2024145455A1 (en) * | 2022-12-28 | 2024-07-04 | Monosol, Llc | Hybrid starch/pvoh water-soluble films |
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CN110367246A (en) * | 2019-07-10 | 2019-10-25 | 邱张云 | A kind of natural plants specially treated technique |
CN111057251A (en) * | 2019-12-31 | 2020-04-24 | 浙江工业大学 | Preparation method of cationic hydrogel |
CN111057251B (en) * | 2019-12-31 | 2024-02-13 | 浙江工业大学 | Preparation method of cationic hydrogel |
WO2022027607A1 (en) * | 2020-08-07 | 2022-02-10 | 南京五瑞生物降解新材料研究院有限公司 | Novel fresh-keeping bag capable of being dissolved in seawater and preparation method therefor |
CN112358655A (en) * | 2020-11-09 | 2021-02-12 | 绍兴兆丽新材料科技有限公司 | Environment-friendly medicine packaging material and preparation method thereof |
CN112515085A (en) * | 2020-11-30 | 2021-03-19 | 四川农业大学 | Novel preservation card and preparation method thereof |
CN113004643A (en) * | 2021-03-18 | 2021-06-22 | 浙江农林大学 | starch/PVA composite antibacterial preservative film and preparation method thereof |
CN113388135A (en) * | 2021-04-25 | 2021-09-14 | 广西民族大学 | Preparation of PVA/cassava starch/LAE active composite membrane and application of PVA/cassava starch/LAE active composite membrane in food packaging bacteriostasis |
CN113388135B (en) * | 2021-04-25 | 2023-08-29 | 广西民族大学 | Preparation of PVA/tapioca starch/LAE active composite film and application of PVA/tapioca starch/LAE active composite film in food packaging bacteriostasis |
WO2024145455A1 (en) * | 2022-12-28 | 2024-07-04 | Monosol, Llc | Hybrid starch/pvoh water-soluble films |
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