CN110055820B - Preparation method of composite reinforced slow-release functional preservative paper base material - Google Patents
Preparation method of composite reinforced slow-release functional preservative paper base material Download PDFInfo
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- CN110055820B CN110055820B CN201910167901.2A CN201910167901A CN110055820B CN 110055820 B CN110055820 B CN 110055820B CN 201910167901 A CN201910167901 A CN 201910167901A CN 110055820 B CN110055820 B CN 110055820B
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- essential oil
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- 239000003755 preservative agent Substances 0.000 title claims abstract description 34
- 230000002335 preservative effect Effects 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000000123 paper Substances 0.000 claims abstract description 75
- 239000000341 volatile oil Substances 0.000 claims abstract description 71
- 238000000576 coating method Methods 0.000 claims abstract description 62
- 239000011248 coating agent Substances 0.000 claims abstract description 61
- 239000000243 solution Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003094 microcapsule Substances 0.000 claims abstract description 37
- 229920002472 Starch Polymers 0.000 claims abstract description 35
- 239000008107 starch Substances 0.000 claims abstract description 35
- 235000019698 starch Nutrition 0.000 claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 claims abstract description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920001661 Chitosan Polymers 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000005303 weighing Methods 0.000 claims abstract description 21
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 235000013305 food Nutrition 0.000 claims abstract description 11
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 10
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 10
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 10
- 229960004853 betadex Drugs 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 244000223760 Cinnamomum zeylanicum Species 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 235000017803 cinnamon Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 244000223014 Syzygium aromaticum Species 0.000 claims description 4
- 235000016639 Syzygium aromaticum Nutrition 0.000 claims description 4
- 235000009024 Ceanothus sanguineus Nutrition 0.000 claims description 3
- 235000013628 Lantana involucrata Nutrition 0.000 claims description 3
- 240000003553 Leptospermum scoparium Species 0.000 claims description 3
- 235000015459 Lycium barbarum Nutrition 0.000 claims description 3
- 235000006679 Mentha X verticillata Nutrition 0.000 claims description 3
- 235000002899 Mentha suaveolens Nutrition 0.000 claims description 3
- 235000001636 Mentha x rotundifolia Nutrition 0.000 claims description 3
- 235000006677 Monarda citriodora ssp. austromontana Nutrition 0.000 claims description 3
- 240000007673 Origanum vulgare Species 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 9
- 239000001110 calcium chloride Substances 0.000 abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 2
- 235000012055 fruits and vegetables Nutrition 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 238000004321 preservation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000009172 bursting Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- -1 aluminosilicate compound Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
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- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- AZJQQNWSSLCLJN-UHFFFAOYSA-N 2-ethoxyquinoline Chemical compound C1=CC=CC2=NC(OCC)=CC=C21 AZJQQNWSSLCLJN-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- 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
-
- 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
-
- 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
- D21H21/50—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 form
- D21H21/52—Additives of definite length or shape
- D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paper (AREA)
Abstract
The invention discloses a preparation method of a composite reinforced slow-release functional preservative paper base material, which comprises the following steps: (1) weighing beta-cyclodextrin and essential oil to prepare an essential oil microcapsule; (2) mixing the essential oil microcapsules and the mesoporous molecular sieve, adding water, and oscillating at a high speed to prepare the essential oil microcapsule-loaded molecular sieve; (3) respectively preparing starch solution, chitosan solution and inorganic salt solution, wherein the inorganic salt is NaCl and MgCl2、CaCl2、Na2SO4、MgSO4One or more of the above; (4) mixing and stirring the molecular sieve loaded with the essential oil microcapsules, the starch solution, the chitosan solution and the inorganic salt solution according to a ratio, adding deionized water to ensure that the solid content of the mixture is 5-10%, and preparing into a coating solution; (5) uniformly coating the coating liquid on the surface of the food packaging base paper; (6) and fully drying the coated paper at room temperature to obtain the functional preservative paper base material. The preservative paper prepared by the preparation method can prolong the storage period of the preserved objects and can prolong the service life of the preservative paper.
Description
(I) technical field
The invention belongs to the technical field of packaging paper, and particularly relates to a preparation method of a composite reinforced slow-release preservative paper base material.
(II) technical background
China is a big country for fruit and vegetable production, but the loss rate of fruit and vegetable storage and preservation reaches 25% -30% every year, which causes serious economic loss. At present, the plastic film is the most common packaging material in the aspect of preserving fruits and vegetables, and is widely applied in the market due to the advantages of transparency, low price, convenient use and the like, but the defects of the plastic preservative film are obvious: the fruits and vegetables are easy to cause oxygen deficiency and carbon dioxide poisoning after being stored for a long time, so that the fruits and vegetables have peculiar smell and are rotten; the film has poor water vapor permeability, and the evaporation of the water in the fruits and vegetables can cause condensation in the package, cause microbial pollution and cause decay and deterioration; plastic films are inedible and not biodegradable, and thus the problems of environmental pollution and food safety are very serious, and have attracted great attention from society. Therefore, a new packaging material is required to replace it.
Paper, a biodegradable material, has been widely used in the field of food packaging due to its low cost and environmental friendliness. The cellulose fiber used for papermaking is microporous and porous, so that the cellulose fiber has high permeability to gas and water vapor and has good application prospect in the aspect of fruit and vegetable preservation. The traditional preservative paper is coated with the preservative by smearing, spraying, dipping and other modes, and has short action time and poor preservation effect.
Patent CN104472671A discloses a method for preparing fruit and vegetable fresh-keeping paper bags, wherein an antistaling agent is prepared by compounding ethoxyquinoline, gelatin, citric acid, eugenol and sodium carbonate, and the antistaling agent is uniformly coated on the paper bags to prepare the fresh-keeping paper bags. Patent CN106884360A discloses a method for preparing safe and highly efficient mildew-proof food wrapping paper, which uses kraft paper as base paper, plant extract as mildew preventive, sprays the mildew preventive on the inner surface of the base paper, and coats adhesive and waterproof layer to form the mildew-proof wrapping paper. The mildew preventive can not be uniformly distributed through simple spraying, and the active ingredients are easy to lose.
The invention adopts the microcapsule specific carrier embedding technology, coats the plant functional factors with the antibacterial and bactericidal effects, is compounded with the inorganic porous carrier molecular sieve, and is uniformly distributed on the surface of paper, thereby realizing the slow release in the storage period and improving the bioavailability of active substances. Meanwhile, the surface of the preservative paper is ensured not to grow mildews, the preserved objects are not polluted, the preservative paper is prevented from being corroded and damaged by microorganisms, and the service life of the preservative paper is prolonged, so that the optimal effect of fruit and vegetable preservation is achieved, and the preservative paper has very important significance for promoting the development of the fruit and vegetable preservation industry in China.
Disclosure of the invention
Aiming at the problems, the invention aims to provide a preparation method of a composite reinforced slow-release functional preservative paper base material, which can increase the loading capacity of preservative essential oil, prolong the release time of the essential oil, enhance the slow-release effect of the essential oil, is favorable for the stability of the environment in a package and prolong the storage period of a preserved object; meanwhile, the propagation of microorganisms on the surface of the preservative paper can be prevented, the mechanical properties (ring crush strength, bursting strength and the like) of the paper can be improved, and the service life of the preservative paper can be prolonged.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a preservative paper base material, which comprises the following steps:
(1) weighing a certain amount of beta-cyclodextrin, dissolving the beta-cyclodextrin in deionized water according to the mass ratio of 1:4-5, and fully stirring to prepare a saturated cyclodextrin aqueous solution; weighing essential oil which is one or more of cinnamon essential oil, oregano essential oil, clove essential oil, tea tree essential oil and mint essential oil, and dissolving the essential oil in absolute ethyl alcohol according to the mass ratio of 1:10-15 to obtain an essential oil solution; slowly pouring the essential oil solution into the cyclodextrin aqueous solution at a constant speed to ensure that the mass ratio of the essential oil solution to the cyclodextrin aqueous solution is 1:5-8, stirring at the temperature of 45-55 ℃ for 4-6h after adding, taking out, cooling to room temperature, standing at the temperature of 0-4 ℃ for 24-48h, taking out, performing vacuum filtration on the essential oil solution, and drying at the temperature of 50-60 ℃ to constant weight to obtain a white powdery substance, namely the essential oil microcapsule;
(2) mixing the essential oil microcapsules and the mesoporous molecular sieve according to the mass ratio of 1-3:1-2, adding water to ensure that the mass ratio of the mixture of the essential oil microcapsules and the mesoporous molecular sieve to the water is 1:8-10, and oscillating at a high speed of 1000rpm for 10-15min at 800-;
(3) weighing a certain amount of starch, adding the starch into deionized water to enable the mass ratio of the starch to the deionized water to be 1:20-25, heating to 90-95 ℃, fully stirring to obtain a gelatinized starch solution, cooling to 50-60 ℃, and preserving heat for later use; weighing chitosan, adding acetic acid solution with the concentration of 0.05-0.1 mol/L, wherein the volume dosage of the acetic acid solution is 50-70ml/g based on the dosage of the chitosan, and mixing and stirring to prepare chitosan solution; weighing a certain amount of inorganic salt, and adding deionized water to obtain an inorganic salt solution with the concentration of 0.05-0.1 mol/L, wherein the inorganic salt is NaCl or MgCl2、CaCl2、Na2SO4、MgSO4One or more of the above;
(4) mixing and stirring the molecular sieve loaded with the essential oil microcapsules, the starch solution, the chitosan solution and the inorganic salt solution according to the mass ratio of 1:3-5:1-3:0.1-1, adding deionized water to ensure that the solid content of the mixture is 5-10%, and preparing coating liquid;
(5) uniformly coating the coating liquid on the surface of food packaging base paper, wherein the coating weight is controlled to be 1.5-2g/m2;
(6) And fully drying the coated paper at room temperature (preferably 23 +/-2 ℃) to obtain the base material of the preservative paper.
In step (5) of the present invention, there is no particular requirement for the coating method as long as "uniform coating" can be achieved, and the following operations can be generally performed: the food packaging base paper is arranged on a coating machine, fixed by a coating rod, a certain volume of coating liquid is taken from one end of the paper, and the coating machine is started to uniformly coat the coating liquid on the paper.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1. the invention takes beta-cyclodextrin as raw material and essential oil as preservative, and the prepared essential oil microcapsule is combined with mesoporous molecular sieve, thus increasing the coating amount of the microcapsule, prolonging the release time of the essential oil, improving the slow release effect of the essential oil, being beneficial to the stability of the environment in the package and prolonging the storage period of fruits and vegetables.
Specifically, the beta-cyclodextrin is a cyclic compound, which contains a hollow cavity inside and can form a microcapsule inclusion compound with plant essential oil, and the particle size ranges from 0.7 nm to 0.8 nm. The mesoporous molecular sieve is an aluminosilicate compound with cubic lattice, has high adsorption capacity and uniform mesoporous structure, and has uniform hole diameter, and the general particle size range is 2-50 nm. Through high-speed oscillation, the molecular sieve can adsorb a large amount of microcapsules in a mesoporous structure due to the strong adsorption capacity and the large specific surface area of the molecular sieve.
Compared with the traditional preservative paper, the coating of the molecular sieve loaded with the essential oil microcapsules greatly increases the coating amount of the microcapsules, thereby increasing the loading amount of the plant essential oil; the active ingredients can be better protected, the release time of the essential oil is prolonged, and the slow release effect of the essential oil is enhanced; meanwhile, the molecular sieve can also adsorb gas and impurities, such as ethylene, carbon dioxide, water vapor and the like, is beneficial to the stability of the environment in the package, and prolongs the storage period of fruits and vegetables.
2. The starch, the chitosan and the inorganic salt act together to improve the mechanical properties (ring crush strength, bursting strength and the like) of the paper and prevent the propagation of microorganisms on the surface of the preservative paper, thereby prolonging the service life of the preservative paper; and the added inorganic salt can improve the stability of a coating system and enable the coating to be more uniform.
Specifically, starch is a polysaccharide substance, which is renewable and easily biodegradable, but the formed coating is brittle, has low strength, is easy to grow bacteria and mildew, and has a very limited application. The chitosan has stronger broad-spectrum antibacterial property and film forming property. The starch and the chitosan are combined for use, so that the mechanical property of the preservative paper can be improved, and the propagation of microorganisms on the surface of the preservative paper can be prevented.
The interaction of starch, chitosan molecules and inorganic salt can improve the compatibility of the coating liquid and improve the mechanical property of paper. Starch belongs to a high-polarity polymer material, a large number of hydrogen bonds exist between molecules, and the addition of inorganic salt can break the hydrogen bonds between the starch and chitosan, so that rigid molecules become soft, the activity of molecular chains of the starch and the chitosan is enhanced, the intermolecular force is increased, and the compatibility becomes good. The amino groups on the chitosan molecular chain have stronger interaction with metal ions, so that a relatively stable complex can be formed, small crystals are formed in the paper after drying, and the ring crush strength of the paper is integrally improved. The inorganic salt is dispersed in the fiber, can compensate the reinforcement of the substituted starch on the base paper bursting strength to a certain extent, forms hydrogen bonds with the fiber, overcomes the brittleness of the starch-based material, and enables the starch/chitosan composite coating to show better mechanical properties.
Inorganic salt is added into the reaction system, and the stability of the coating system can be improved. The coating starch needs high-temperature gelatinization, the molecular sieve has weaker hydrothermal stability, and the inorganic salt is added, so that the hole wall thickness of the molecular sieve is improved, the polymerization degree of silicate anions is increased, and the distortion resistance of a mesoporous structure are effectively improved, so that the hydrothermal stability is improved, and the microcapsule-loaded molecular sieve can be uniformly and stably distributed in a coating system.
(IV) description of the drawings
FIG. 1 is a technical scheme of a conventional scheme
FIG. 2 is a technical scheme of the invention
(V) detailed description of the preferred embodiments
The following examples are set forth in order to provide a thorough understanding of the invention and to provide a further understanding of the invention. However, the present invention is not limited by the following examples.
Example 1
(1) 100g of beta-cyclodextrin was weighed, dissolved in 400ml of deionized water and stirred well to prepare a saturated aqueous cyclodextrin solution. Then 7g of cinnamon essential oil and 3g of mint essential oil are weighed and dissolved in 100g of absolute ethyl alcohol according to the mass ratio of 1:10 to obtain an essential oil solution. Slowly pouring 50g of the essential oil solution into 250g of the cyclodextrin saturated solution at a constant speed, stirring at 45 ℃ for 4h, taking out, cooling to room temperature, and standing in a refrigerator at 4 ℃ for 24 h. Taking out, carrying out vacuum filtration on the microcapsule, and drying the microcapsule to constant weight by using a drying oven at 50 ℃ to obtain a white powdery substance, namely the essential oil microcapsule;
(2) mixing 5g of essential oil microcapsules and 5g of mesoporous molecular sieve according to the mass ratio of 1:1, adding 90g of water, and oscillating at a high speed of 800rpm for 10min to prepare the molecular sieve loaded with the essential oil microcapsules;
(3) weighing 20g of starch, adding 400g of deionized water, wherein the mass ratio of the starch to the deionized water is 1:20, heating for 30min at 95 ℃ under stirring to obtain a gelatinized starch solution, and cooling to 60 ℃ for heat preservation for later use. 1g of chitosan was weighed, and 60ml of an acetic acid solution having a concentration of 0.05mol/L was added thereto, followed by mixing and stirring to prepare a chitosan solution. Weighing 3g of NaCl, and adding 100ml of deionized water to obtain a NaCl solution with the concentration of 0.5 mol/L;
(4) weighing 10g of microcapsule-loaded molecular sieve, 30g of starch solution, 10g of chitosan solution and 5g of NaCl solution, mixing according to the mass ratio of 1:3:1:0.5, adding deionized water, and uniformly stirring to prepare a coating liquid with the solid content of 5%;
(5) coating the coating liquid on the surface of food packaging base paper, mounting the base paper on a multifunctional coating machine, fixing the base paper by a coating rod, taking 10ml of the coating liquid at one end of the paper, starting the coating machine to uniformly coat the coating liquid on the paper, wherein the coating weight is 1.5g/m2。
(6) And drying the coated paper at room temperature (23 ℃) for 24 hours to obtain the preservative paper.
Example 2
(1) 100g of beta-cyclodextrin was weighed, dissolved in 450ml of deionized water and stirred well to prepare a saturated aqueous cyclodextrin solution. Then weighing 5g of cinnamon essential oil and 5g of clove essential oil, mixing, and dissolving the cinnamon essential oil and the clove essential oil in 150g of absolute ethyl alcohol according to the mass ratio of 1:15 to obtain an essential oil solution. Slowly pouring 50g of the essential oil solution into 300g of the cyclodextrin saturated solution at a constant speed, stirring at 50 ℃ for 5h, taking out, cooling to room temperature, and placing in a refrigerator at 4 ℃ for standing for 36 h. Taking out, carrying out vacuum filtration on the microcapsule, and drying the microcapsule to constant weight by using a drying oven at 60 ℃ to obtain a white powdery substance, namely the essential oil microcapsule;
(2) mixing 6.7g of essential oil microcapsules and 3.3g of mesoporous molecular sieve according to the mass ratio of 2:1, adding 90g of water, and oscillating at high speed of 900rpm for 12min to prepare the molecular sieve for loading the essential oil microcapsules;
(3) weighing 20g of starch, adding 460g of deionized water, wherein the mass ratio of the starch to the deionized water is 1:23, heating for 30min under stirring at 95 ℃ to obtain a gelatinized starch solution, and cooling to 60 ℃ for heat preservation for later use. 1g of chitosan was weighed, and 50ml of an acetic acid solution having a concentration of 0.05mol/L was added thereto, followed by mixing and stirring to prepare a chitosan solution. Weighed 1.11gCaCl2And 100ml of deionized water is added to obtain CaCl with the concentration of 0.1mol/L2A solution;
(4) weighing 10g of the mixed solution of the microcapsule-loaded molecular sieve, 40g of the starch solution, 20g of the chitosan solution and 7g of CaCl2Mixing the solution according to the mass ratio of 1:4:2:0.7, adding deionized water, and uniformly stirring to prepare a coating liquid with the solid content of 7%;
(5) coating the coating liquid on the surface of food packaging base paper, mounting the base paper on a multifunctional coating machine, fixing the base paper by a coating rod, taking 12ml of the coating liquid at one end of the paper, starting the coating machine to uniformly coat the coating liquid on the paper, wherein the coating weight is 2g/m2。
(6) And drying the coated paper at room temperature (23 ℃) for 24 hours to obtain the preservative paper.
Example 3
(1) 100g of beta-cyclodextrin was weighed, dissolved in 500ml of deionized water and stirred well to prepare a saturated aqueous cyclodextrin solution. Then weighing 4g of cinnamon essential oil, 3g of oregano essential oil and 3g of tea tree essential oil, mixing, and dissolving in 100g of absolute ethyl alcohol according to the mass ratio of 1: 10. Slowly pouring 50g of the essential oil solution into 350g of the cyclodextrin saturated solution at a constant speed, stirring at 45 ℃ for 6h, taking out, cooling to room temperature, and placing in a refrigerator at 4 ℃ for standing for 24 h. Taking out, carrying out vacuum filtration on the microcapsule, and drying the microcapsule to constant weight by using a drying oven at 50 ℃ to obtain a white powdery substance, namely the essential oil microcapsule;
(2) mixing 6g of essential oil microcapsules and 4g of mesoporous molecular sieve according to the mass ratio of 3:2, adding 90g of water, and oscillating at a high speed of 1000rpm for 15min to prepare the molecular sieve loaded with the essential oil microcapsules;
(3) weighing 20g of starch, adding 500g of deionized water, wherein the mass ratio of the starch to the deionized water is 1:25, and heating for 30min at 95 ℃ under stirring to obtain gelatinized starchCooling the starch solution to 60 ℃, and preserving the temperature for later use. 1g of chitosan was weighed, and 50ml of an acetic acid solution having a concentration of 0.1mol/L was added thereto, followed by mixing and stirring to prepare a chitosan solution. Weighed 4.8g MgCl2And 100ml of deionized water was added to obtain MgCl at a concentration of 0.5mol/L2A solution;
(4) weighing 10g of microcapsule-supporting molecular sieve, 50g of starch solution, 30g of chitosan solution and 10g of MgCl2Mixing the solution according to the mass ratio of 1:5:3:1, adding deionized water, and uniformly stirring to prepare a coating liquid with the solid content of 10%;
(5) coating the coating liquid on the surface of food packaging base paper, mounting the base paper on a multifunctional coating machine, fixing the base paper by using a coating rod, taking 15ml of the coating liquid at one end of the paper, starting the coating machine to uniformly coat the coating liquid on the paper, wherein the coating weight is 2g/m2。
(6) And drying the coated paper at room temperature (23 ℃) for 24 hours to obtain the preservative paper.
The test of the preservative paper comprises the following steps:
1. and (3) testing mechanical properties:
sampling the paper to be tested according to GB/T450-.
Ring crush strength: referring to GB/T2679.8-1995, the ring crush strength of paper sheets was measured by a ring crush strength compression apparatus and expressed as a ring crush strength index, and three groups were made for each sample and averaged.
The ring crush strength index Rd is 1000R/W, wherein Rd represents the ring crush index (N.m/g); r represents ring crush strength (kN/m); w represents the quantitative amount (g/m) of the sample2)
Burst strength: with reference to GB/T454-.
2. Smoothness testing:
with reference to GB/T456-2002, smoothness of paper is measured by a smoothness tester, and three sets of smoothness values are obtained for each sample, and the average value is represented by s.
3. Essential oil release test:
the preservative paper is analyzed by using gas chromatography and mass spectrometry every day, wherein the gas chromatography conditions comprise that a chromatographic column is HP-5MS (30m multiplied by 0.25 mu m multiplied by 0.25mm), carrier gas is high-purity helium, the flow rate is 0.91mL/min, and split-flow sample injection is not performed. The injection port temperature was 250 ℃ and the injection amount was 1. mu.L. The temperature programming mode is adopted, wherein the column temperature is 80 ℃, the temperature is kept for 3min, and then the temperature is raised to 280 ℃ at the speed of 8 ℃/min, and the temperature is kept for 30 min. The mass spectrum conditions comprise that the ion source temperature is 230 ℃, the interface temperature is 250 ℃, the solvent delay is 2min, the EI electron source and the electron energy are 70e V, and the m/z scanning range is 35-500 amu.
4. Fresh-keeping test:
the preservative paper was cut to the same size, covered on the surface of the mushroom, and stored at room temperature (25. + -. 2 ℃ C., 50% RH). Storing for 3 days, and testing its weight loss, hardness and membrane permeability
Weight loss: weight loss was determined by weighing the entire mushroom before and after the storage period. Body weight loss is expressed as percent weight loss relative to initial weight.
Weight loss ratio W (%) ═ m1-m2)/m1X 100%, wherein m1Is the mass of the mushroom before storage, m2Is the quality of the mushrooms after 3 days of storage.
Hardness: the hardness of the mushrooms is analyzed by using a fruit hardness meter, a proper probe is selected, and a supporting ring of the impact device is tightly pressed on the surface of the test sample according to a selected measuring direction, wherein the impact direction is vertical to the test surface. Each site was tested 5 times and the average was taken.
Membrane permeability: the conductivity was measured with a digital conductivity meter. Cutting 4 cylinders with a 1cm diameter puncher at equator of different fruits, placing in a small beaker, adding 40ml deionized water, immediately measuring the conductivity, and recording as P010min later the conductivity was again determined and recorded as P1Boiling for 10min, cooling to room temperature, adding water to the scale, and measuring the conductivity P2。
Relative membrane permeability P (%) ═ P1-P0)/(P2-P0)×100%
The results of the tests, as shown in table 1 below:
TABLE 1
Claims (2)
1. A preparation method of a preservative paper base material comprises the following steps:
(1) weighing a certain amount of beta-cyclodextrin, dissolving the beta-cyclodextrin in deionized water according to the mass ratio of 1:4-5, and fully stirring to prepare a saturated cyclodextrin aqueous solution; weighing essential oil which is one or more of cinnamon essential oil, oregano essential oil, clove essential oil, tea tree essential oil and mint essential oil, and dissolving the essential oil in absolute ethyl alcohol according to the mass ratio of 1:10-15 to obtain an essential oil solution; slowly pouring the essential oil solution into the cyclodextrin aqueous solution at a constant speed to ensure that the mass ratio of the essential oil solution to the cyclodextrin aqueous solution is 1:5-8, stirring at the temperature of 45-55 ℃ for 4-6h after adding, taking out, cooling to room temperature, standing at the temperature of 0-4 ℃ for 24-48h, taking out, performing vacuum filtration on the essential oil solution, and drying at the temperature of 50-60 ℃ to constant weight to obtain a white powdery substance, namely the essential oil microcapsule;
(2) mixing the essential oil microcapsules and the mesoporous molecular sieve according to the mass ratio of 1-3:1-2, adding water to ensure that the mass ratio of the mixture of the essential oil microcapsules and the mesoporous molecular sieve to the water is 1:8-10, and oscillating at a high speed of 1000rpm for 10-15min at 800-;
(3) weighing a certain amount of starch, adding the starch into deionized water to enable the mass ratio of the starch to the deionized water to be 1:20-25, heating to 90-95 ℃, fully stirring to obtain a gelatinized starch solution, cooling to 50-60 ℃, and preserving heat for later use; weighing chitosan, adding acetic acid solution with the concentration of 0.05-0.1 mol/L, wherein the volume dosage of the acetic acid solution is 50-70ml/g based on the dosage of the chitosan, and mixing and stirring to prepare chitosan solution; weighing a certain amount of inorganic salt, and adding deionized water to obtain an inorganic salt solution with the concentration of 0.05-0.1 mol/L, wherein the inorganic salt is NaCl and MgCl2、Na2SO4、MgSO4One or more of the above;
(4) mixing and stirring the molecular sieve loaded with the essential oil microcapsules, the starch solution, the chitosan solution and the inorganic salt solution according to the mass ratio of 1:3-5:1-3:0.1-1, adding deionized water to ensure that the solid content of the mixture is 5-10%, and preparing coating liquid;
(5) uniformly coating the coating liquid on the surface of food packaging base paper, wherein the coating weight is controlled to be 1.5-2g/m2;
(6) And fully drying the coated paper at room temperature to obtain the base material of the preservative paper.
2. The method of claim 1, wherein: in the step (5), the coating is carried out according to the following operations: the food packaging base paper is arranged on a coating machine, fixed by a coating rod, a certain volume of coating liquid is taken from one end of the paper, and the coating machine is started to uniformly coat the coating liquid on the paper.
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