CN107119491B - A kind of preparation method of the fresh-keeping coating paper of fruits and vegetables - Google Patents
A kind of preparation method of the fresh-keeping coating paper of fruits and vegetables Download PDFInfo
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- CN107119491B CN107119491B CN201710374418.2A CN201710374418A CN107119491B CN 107119491 B CN107119491 B CN 107119491B CN 201710374418 A CN201710374418 A CN 201710374418A CN 107119491 B CN107119491 B CN 107119491B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 65
- 238000000576 coating method Methods 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 235000012055 fruits and vegetables Nutrition 0.000 title claims abstract description 24
- 229920001661 Chitosan Polymers 0.000 claims abstract description 94
- 230000004048 modification Effects 0.000 claims abstract description 59
- 238000012986 modification Methods 0.000 claims abstract description 59
- 239000000123 paper Substances 0.000 claims abstract description 27
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 23
- 239000011087 paperboard Substances 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 11
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 4
- 239000012530 fluid Substances 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000007792 addition Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 230000006196 deacetylation Effects 0.000 claims description 8
- 238000003381 deacetylation reaction Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- FIKFOOMAUXPBJM-UHFFFAOYSA-N hepta-2,5-dienediamide Chemical class NC(=O)C=CCC=CC(N)=O FIKFOOMAUXPBJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 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 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000005022 packaging material Substances 0.000 abstract description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 9
- 229940068984 polyvinyl alcohol Drugs 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000003385 bacteriostatic effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- HPDJTIHXXASMDB-UHFFFAOYSA-N CC(=CC)C.C(COCCOCCO)O Chemical class CC(=CC)C.C(COCCOCCO)O HPDJTIHXXASMDB-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical group O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000013456 study Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000123650 Botrytis cinerea Species 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 2
- 235000019398 chlorine dioxide Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000001408 fungistatic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241001478240 Coccus Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 102000007982 Phosphoproteins Human genes 0.000 description 1
- 108010089430 Phosphoproteins Proteins 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical class [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pest Control & Pesticides (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Paper (AREA)
- Storage Of Fruits Or Vegetables (AREA)
Abstract
The invention belongs to field of packaging material, and in particular to a kind of preparation method of the fresh-keeping coating paper of fruits and vegetables.The present invention is with 2,3 epoxypropyltrimethylchloride chlorides and triethylene glycol dimethacrylate are that raw material carries out quaternization and graft modification to chitosan, then modified chitosan and polyvinyl alcohol are formed into coating solution and prepare antibacterial coating paper in art post paperboard, antibacterial coating paper prepared by the present invention can be used for the anti-corrosions of a variety of fruits and vegetables with it is fresh-keeping.
Description
Technical field
The invention belongs to field of packaging material, and in particular to a kind of preparation method of the fresh-keeping coating paper of fruits and vegetables.
Background technology
In recent years, fruits and vegetables production development in China's is rapid, and yield is extremely abundant.But it is apt to deteriorate rotten after fruit and vegetable picking,
Seriously affect the transport, storage and food quality of fruits and vegetables, therefore, fruits and vegetables it is fresh-keeping particularly important.
Tin foil is as a kind of environmentally protective, easily biological-degradable Perserving materials, it has also become domestic and international researcher's grinds
Study carefully emphasis.The preparation of tin foil is that antistaling agent is added in paper substrate or is coated on paper substrate surface, there is chlorine dioxide guarantor at present
The correlative studys such as fresh paper, fresh-keeping paper made from tourmaline, Chinese herbal medicine tin foil and activated carbon tin foil.Although chlorine dioxide safety,
Its smell is difficult to be accepted by the public, and other agriculture chemicals fungicides are there are certain pesticide residue or carcinogenic teratogenesis equivalent risk,
So being also not suitable for using as antistaling agent.
Abroad in Recent Years has investigated some novel dippings or application type antistaling agent, as multi-vitamins C derivatives are fresh-keeping
Agent, phosphoprotein family macromolecule protein preservative film etc., but since greatly improving for cost is not appropriate for large-scale use.
So a kind of antistaling agent of green of exploitation, the inexpensive preservation method of research and development have great importance.
Invention content
The purpose of the present invention is overcoming, there are security risks and fresh-keeping of high cost for traditional chemical antistaling agent in the prior art
Problem, the present invention provide a kind of preparation method of the fresh-keeping coating paper of fruits and vegetables.
A kind of fruits and vegetables preparation method of fresh-keeping coating paper, includes the following steps：
1) quaternization of chitosan：16.1g chitosans are added in 200ml water, and 0.03g detergent alkylates are then added
Sodium sulfonate is warming up to 70 DEG C of stirring 10min, is added at one time 5.2-10.5g 2, and the heat preservation of 3- epoxypropyltrimethylchloride chlorides is stirred
Reaction 12h is mixed, room temperature is then cooled to 200ml methanol is added and settle 2h in 0 DEG C or less, is then filtered, dry quaternization
Chitosan；The present invention is that modifying agent is modified with chitosan using 2,3- epoxypropyltrimethylchloride chlorides, makes chitosan
The amino of middle part reacts with epoxide ring, introduces ionic group, and water solubility greatly enhances；
2) graft modification of chitosan：The chitosan of 10g quaternizations is added in 100ml aqueous solutions, nitrogen atmosphere
Enclose lower 70 DEG C of stirrings 30min；Then 0.1g ammonium persulfates are added and are stirred to react 15min, 2 ~ 4g triethylene glycol dimethyl propylenes are added
Olefin(e) acid ester, 0.2g methylene-bisacrylamides carry out graft copolymerization, react 6h, are then cooled to room temperature, filtering, washing,
It after product impregnates 30min with the ammonia spirit of 0.2mol/L, filters, filter cake is washed with absolute ethyl alcohol, then dry, mechanical crushing
It is 5 μm of chitosans for obtaining graft modification to grain size；The present invention is graft modification agent to season using triethylene glycol dimethacrylate
Active amino carries out graft modification in salified chitosan, since triethylene glycol dimethacrylate is oxygen ether structure, system
Enhanced for the chitosan hygroscopicity after the graft modification gone out；
3) preparation of modification of chitosan coating fluid：It takes 10g polyvinyl alcohol 17-92 to be scattered in 200ml water, is warming up to poly-
Vinyl alcohol 17-92 is completely dissolved, and then the chitosan, 0.3g emulsifier op-10s of addition 0.3-1.2g graft modifications stir for 24 hours,
It is cooled to room temperature and modification of chitosan coating fluid is obtained using sodium dihydrogen phosphate adjusting pH to 5.5-6.0；
4) modification of chitosan coating fluid is taken uniformly to be coated on art post paperboard single side using coating machine, 50 after coating
Dry 20min obtains fruits and vegetables with fresh-keeping coating paper at DEG C.
Preferably, step 1）The deacetylation of the chitosan is more than 90%, bonded restorations 2.3-
2.9x105；The present invention studies the physicochemical property of raw materials of chitosan, finds only have deacetylation to be more than 90%, glues homogeneous
It is 2.3-2.9x10 to molecular mass5The fruits and vegetables prepared of chitosan with fresh-keeping coating paper to Escherichia coli and golden yellow grape
Coccus inhibition is just best, it may be possible to since active amino exposed in the chitosan of low deacetylation is less, follow-up quaternary ammonium
The graft modification effect of salinization and acrylic acid is undesirable, causes follow-up antibacterial activity poor.
Preferably, step 1）Described 0 DEG C or less refers to -10~-20 DEG C, and temperature is at 0 DEG C or more, the chitosan of quaternization
Be unable to fully be precipitated, have part be dissolved in the system of first alcohol and water, temperature is too low, freeze it is of high cost, so the present invention it is excellent
- 10~-20 DEG C of choosing；
Preferably, step 1）In 2,3- epoxypropyltrimethylchloride chloride additions be 6.8g, step 2）Middle triethylene glycol
The addition of dimethylacrylate is 3.2g；Pass through the reason of quaternization and graft modification bidirectional modulation chitosan in the present invention
Change property and its bacteriostatic activity；
Preferably, step 3）The chitosan addition of middle graft modification is 0.5-0.8g, more preferably 0.6g；
Preferably, step 4）The dosage of middle modification of chitosan coating fluid is 8-15g/m2, i.e., every square metre of art post paperboard painting
The modification of chitosan coating fluid of cloth 8-15g.
Chitosan is the product after chitin deacetylation, it is unique existing alkaline kation polysaccharide in nature,
It is colourless, tasteless, nontoxic, and there is good biocidal property and biological degradability, but its filming performance is poor, the present invention is with 2,3-
Epoxypropyltrimethylchloride chloride and triethylene glycol dimethacrylate, which are modified chitosan, not only increases film forming
Can, and modified chitosan bacteriostatic activity greatly enhances.
The present invention provides a kind of fruits and vegetables preparation methods of fresh-keeping coating paper, and the present invention is with 2,3- epoxies
Ammonium chloride and triethylene glycol dimethacrylate are that raw material carries out quaternization and graft modification to chitosan, then will be modified
Chitosan afterwards forms coating solution with polyvinyl alcohol and prepares antibacterial coating paper in art post paperboard, and antibacterial prepared by the present invention applies
Cloth paper can be used for the anti-corrosions of a variety of fruits and vegetables with it is fresh-keeping.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Chitosan comes from Zhejiang Yuhuan marine biochemistry Co., Ltd in the embodiment of the present invention；Emulsifier op-10 source
In West Asia reagent, the quantification of 200g/m of art post paperboard2, remaining raw material is commercially available convenient source.
Embodiment 1
1）The quaternization of chitosan：16.1g chitosans are added in three mouthfuls of glass reaction bottles of 1L（Deacetylation is
92%）, 200ml water, then be added 0.03g neopelexes be warming up to 70 DEG C stirring 10min, be added at one time 10.5g
2,3- epoxypropyltrimethylchloride chloride insulated and stirreds react 12h, are then cooled to 20-30 DEG C and instill 200ml methanol in -10 DEG C
Lower sedimentation 2h, then filtering, be dried in vacuo at 60 DEG C quaternization chitosan；Dropwise addition is preferably taken in infall process
Methanol is added in mode, and the product that if being added at one time methanol, will produce clustering phenomena, and settle out is attached at reaction bottle wall
On, it is unfavorable for the filtering transfer in later stage；
2）The graft modification of chitosan：The chitosan of 10g quaternizations is added in 100ml aqueous solutions, nitrogen atmosphere
Enclose lower 70 DEG C of stirrings 30min；Then 0.1g ammonium persulfates are added and are stirred to react 15min, 2.0g triethylene glycol dimethyl propylenes are added
Olefin(e) acid ester, 0.2g methylene-bisacrylamides carry out graft copolymerization, react 6h, are then cooled to 20-30 DEG C, filter, water
Filter wash cake filters after filter cake impregnates 30min with the ammonia spirit of 20ml 0.2mol/L, and filter cake is washed with absolute ethyl alcohol, then
Vacuum drying, mechanical mill are crushed to the chitosans that grain size obtains graft modification for 5 μm at 45 DEG C；
3）The preparation of modification of chitosan coating fluid：It takes 10g polyvinyl alcohol 17-92 to be scattered in 200ml water, is warming up to poly-
Vinyl alcohol 17-92 is completely dissolved, be then added 0.3 graft modification chitosan, 0.3g emulsifier op-10s stirring for 24 hours, be cooled to
Room temperature adjusts pH to 5.5-6.0 using sodium dihydrogen phosphate and obtains modification of chitosan coating fluid；
4）Modification of chitosan coating fluid is taken uniformly to be coated on art post paperboard single side using coating machine, 50 after coating
Dry 20min obtains the fresh-keeping coating paper of fruits and vegetables at DEG C, and the dosage of modification of chitosan coating fluid is 8g/m2, i.e. every square metre white
The modification of chitosan coating fluid that paperboard is coated with 8g is not with after drying in terms of the modification of chitosan coating fluid actual amount of moistening
Weightening meter.
Embodiment 2
1）The quaternization of chitosan：16.1g chitosans are added in three mouthfuls of glass reaction bottles of 1L（Deacetylation is
96%）, 200ml water, then be added 0.03g neopelexes be warming up to 70 DEG C stirring 10min, be added at one time 10.5g
2,3- epoxypropyltrimethylchloride chloride insulated and stirreds react 12h, be then cooled to 20-30 DEG C instillation 200ml methanol, -15 DEG C
Lower sedimentation 2h, then filtering, be dried in vacuo at 60 DEG C quaternization chitosan；
2）The graft modification of chitosan：The chitosan of 10g quaternizations is added in 100ml aqueous solutions, nitrogen atmosphere
Enclose lower 70 DEG C of stirrings 30min；Then 0.1g ammonium persulfates are added and are stirred to react 15min, 4.0g triethylene glycol dimethyl propylenes are added
Olefin(e) acid ester, 0.2g methylene-bisacrylamides carry out graft copolymerization, react 6h, are then cooled to 20-30 DEG C, filter, water
Filter wash cake filters after filter cake impregnates 30min with the ammonia spirit of 20ml 0.2mol/L, and filter cake is washed with absolute ethyl alcohol, then
Vacuum drying, mechanical mill are crushed to the chitosans that grain size obtains graft modification for 5 μm at 45 DEG C；
3）The preparation of modification of chitosan coating fluid：It takes 10g polyvinyl alcohol 17-92 to be scattered in 200ml water, is warming up to poly-
Vinyl alcohol 17-92 is completely dissolved, and the chitosan of 1.2g graft modifications is then added, 0.3g emulsifier op-10s stir for 24 hours, cooling
PH to 5.5-6.0 is adjusted using sodium dihydrogen phosphate to room temperature and obtains modification of chitosan coating fluid；
4）Modification of chitosan coating fluid is taken uniformly to be coated on art post paperboard single side using coating machine, 50 after coating
Dry 20min obtains the fresh-keeping coating paper of fruits and vegetables at DEG C, and the dosage of modification of chitosan coating fluid is 15g/m2, i.e. every square metre white
The modification of chitosan coating fluid that paperboard is coated with 15g is not with after drying in terms of the modification of chitosan coating fluid actual amount of moistening
Weightening meter.
Embodiment 3
1）The quaternization of chitosan：16.1g chitosans are added in three mouthfuls of glass reaction bottles of 1L（Deacetylation is
98%, bonded restorations 2.9x105）, 200ml water, then be added 0.03g neopelexes be warming up to 70
DEG C stirring 10min, is added at one time 6.8g 2,3- epoxypropyltrimethylchloride chloride insulated and stirreds react 12h, are then cooled to
20-30 DEG C of instillation 200ml methanol, settles 2h at -15 DEG C, then filtering, be dried in vacuo at 60 DEG C quaternization chitosan；
2）The graft modification of chitosan：The chitosan of 10g quaternizations is added in 100ml aqueous solutions, nitrogen atmosphere
Enclose lower 70 DEG C of stirrings 30min；Then 0.1g ammonium persulfates are added and are stirred to react 15min, 3.2g triethylene glycol dimethyl propylenes are added
Olefin(e) acid ester, 0.2g methylene-bisacrylamides carry out graft copolymerization, react 6h, are then cooled to 20-30 DEG C, filter, water
Filter wash cake filters after filter cake impregnates 30min with the ammonia spirit of 20ml 0.2mol/L, and filter cake is washed with absolute ethyl alcohol, then
Vacuum drying, mechanical mill are crushed to the chitosans that grain size obtains graft modification for 5 μm at 45 DEG C；
3）The preparation of modification of chitosan coating fluid：It takes 10g polyvinyl alcohol 17-92 to be scattered in 200ml water, is warming up to poly-
Vinyl alcohol 17-92 is completely dissolved, and the chitosan of 0.6g graft modifications is then added, 0.3g emulsifier op-10s stir for 24 hours, cooling
PH to 5.5-6.0 is adjusted using sodium dihydrogen phosphate to room temperature and obtains modification of chitosan coating fluid；
4）Modification of chitosan coating fluid is taken uniformly to be coated on art post paperboard single side using coating machine, 50 after coating
Dry 20min obtains the fresh-keeping coating paper of fruits and vegetables at DEG C, and the dosage of modification of chitosan coating fluid is 10g/m2, i.e. every square metre white
The modification of chitosan coating fluid that paperboard is coated with 10g is not with after drying in terms of the modification of chitosan coating fluid actual amount of moistening
Weightening meter.
Comparative example 1
Compared with Example 3, the present invention is modified only with the quaternization of chitosan（Also powder after quaternization
It is 5 microns or less to be broken to grain size）, and be modified without the graft modificationization of chitosan, remaining raw material and preparation method and implementation
Example 3 is identical.
Comparative example 2
Compared with Example 3, the present invention does not use the quaternization of chitosan to be modified, i.e., is directly carried out to chitosan
Graft modificationization is modified, remaining raw material and preparation method are same as Example 3.
Fruits and vegetables that embodiment 1-3 and its comparative example 1-2 are prepared are carried out to the detection of fungistatic effect with fresh-keeping coating paper,
Middle detection method is as follows：The fruits and vegetables of preparation are cut into the disc-shaped of a diameter of 80cm with fresh-keeping coating paper, are killed using ultraviolet lamp
Bacterium 30min, aseptically preserves；By 10-15ml potato dextrose agars after heating（PDA）Pour into culture dish
In, 100 microlitres of bacteria suspension is coated with after solidification on culture medium（A concentration of 2X107CFU/ml）, then by the coating paper of preservation
It is placed in culture dish, it is 10mm so that antibacterial cardboard is coated with distance with bacteria suspension, and culture dish is then put into 28 DEG C of constant temperature incubations
Bacteriostasis rate is tested after cultivating 48h in case, is expressed as a percentage, numerical value is the average value measured three times, and the results are shown in table below 1：
1 coating paper bacteriostatic activity test result of table
The above test results show that fruits and vegetables prepared by the present invention have good fungistatic effect, comparison with fresh-keeping coating paper
Example 1 and 2 shows that quaternization and graft modification are all effective to bacteriostatic activity in the modifying process of chitosan, and the two has one
Fixed synergistic function.
In the preparation process of modification of chitosan coating fluid, the present invention takes single-factor variable method to have studied in detail graft modification
Chitosan additive amount（Only change the step 3）The chitosan additive amount of middle graft modification, the additive amount of other materials and preparation
Method is same as Example 3）With finally prepare relationship of the fruits and vegetables with fresh-keeping coating paper antibacterial activity, only with botrytis cinerea bacteriostasis rate
For evaluation object, the results are shown in Table 2：
2 modification of chitosan additive amount of table and antibacterial activity relationship
| Additive amount/g | 0 | 0.2 | 0.3 | 0.5 | 0.6 | 0.8 | 1.0 | 1.2 | 1.5 | 2.0 | 3.0 |
| Bacteriostasis rate/%（Botrytis cinerea） | <2 | 85 | 89 | 98 | 100 | 99 | 99 | 98 | 98 | 92 | 90 |
The above result shows that starting to increase with modification of chitosan additive amount, bacteriostatic activity increases, when addition is 0.6g
When bacteriostatic activity reach maximum, behind have downward trend instead, it may be possible to the film forming of coated film is affected since additive amount is excessive
Performance adequately cannot be embodied and be expressed so as to cause bacteriostatic activity, so additive amount is advisable with 0.3-1.0g, most preferably
Near 0.6g.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, can embodiments of the present invention be made with various changes, replacement and change.
Claims (7)
1. a kind of fruits and vegetables preparation method of fresh-keeping coating paper, includes the following steps：
1) quaternization of chitosan：16.1g chitosans are added in 200ml water, and 0.03g dodecyl benzene sulfonic acid is then added
Sodium is warming up to 70 DEG C of stirring 10min, is added at one time 5.2-10.5g 2,3- epoxypropyltrimethylchloride chloride insulated and stirreds are anti-
12h is answered, room temperature is then cooled to 200ml methanol is added and settle 2h in 0 DEG C or less, is then filtered, the shell of dry quaternization
Glycan；
2) graft modification of chitosan：The chitosan of 10g quaternizations is added in 100ml aqueous solutions, under nitrogen atmosphere
70 DEG C of stirring 30min；Then 0.1g ammonium persulfates are added and are stirred to react 15min, 2 ~ 4g triethylene glycol dimethacrylates are added
Ester, 0.2g methylene-bisacrylamides carry out graft copolymerization, react 6h, are then cooled to room temperature, filtering, washing, product
It after impregnating 30min with the ammonia spirit of 0.2mol/L, filters, filter cake is washed with absolute ethyl alcohol, then dry, mechanical crushing to grain
Diameter is 5 μm of chitosans for obtaining graft modification；
3) preparation of modification of chitosan coating fluid：It takes 10g polyvinyl alcohol 17-92 to be scattered in 200ml water, is warming up to polyethylene
Alcohol 17-92 is completely dissolved, and the chitosan of 0.3-1.2g graft modifications is then added, 0.3g emulsifier op-10s stir for 24 hours, cooling
PH to 5.5-6.0 is adjusted using sodium dihydrogen phosphate to room temperature and obtains modification of chitosan coating fluid；
4) modification of chitosan coating fluid is taken uniformly to be coated on art post paperboard single side using coating machine, after coating at 50 DEG C
Dry 20min obtains fruits and vegetables with fresh-keeping coating paper.
2. preparation method according to claim 1, it is characterised in that：Step 1）The deacetylation of the chitosan is more than
90%, bonded restorations are 2.3~2.9 × 105。
3. preparation method according to claim 1, it is characterised in that：Step 1）Described 0 DEG C or less is -10~-20 DEG C.
4. preparation method according to claim 1, it is characterised in that：Step 1）Middle 2,3- epoxypropyltrimethylchloride chlorides
Addition is 6.8g, step 2）The addition of middle triethylene glycol dimethacrylate is 3.2g.
5. preparation method according to claim 1, it is characterised in that：Step 3）The chitosan addition of middle graft modification is
0.5-0.8g。
6. preparation method according to claim 5, it is characterised in that：Step 3）The chitosan addition of middle graft modification is
0.6g。
7. preparation method according to claim 1, it is characterised in that：Step 4）The dosage of middle modification of chitosan coating fluid is
8-15g/m2, i.e., the modification of chitosan coating fluid of every square metre of art post paperboard coating 8-15g.
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| BR112023004156A2 (en) | 2020-09-22 | 2023-04-04 | Swimc Llc | COATING COMPOSITION, COATED ARTICLE, AND METHOD FOR PRODUCING A COATING COMPOSITION |
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