CN117511291A - Alkali-controlled high-temperature-resistant modified cyclopropene, fresh-keeping gloss oil and fresh-keeping packaging product - Google Patents
Alkali-controlled high-temperature-resistant modified cyclopropene, fresh-keeping gloss oil and fresh-keeping packaging product Download PDFInfo
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- CN117511291A CN117511291A CN202311462057.9A CN202311462057A CN117511291A CN 117511291 A CN117511291 A CN 117511291A CN 202311462057 A CN202311462057 A CN 202311462057A CN 117511291 A CN117511291 A CN 117511291A
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- Prior art keywords
- fresh
- keeping
- cyclopropene
- gloss oil
- modified
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- 239000003513 alkali Substances 0.000 title claims abstract description 38
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 13
- 125000000298 cyclopropenyl group Chemical class [H]C1=C([H])C1([H])* 0.000 title 1
- 150000001943 cyclopropenes Chemical class 0.000 claims abstract description 39
- -1 cyclopropene compound Chemical class 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 22
- 230000007935 neutral effect Effects 0.000 claims abstract description 17
- 150000003961 organosilicon compounds Chemical group 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- OOXWYYGXTJLWHA-UHFFFAOYSA-N cyclopropene Chemical compound C1C=C1 OOXWYYGXTJLWHA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 239000004480 active ingredient Substances 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 102
- 239000000839 emulsion Substances 0.000 claims description 50
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 45
- 238000007639 printing Methods 0.000 claims description 42
- 239000000123 paper Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 19
- 239000011087 paperboard Substances 0.000 claims description 18
- SHDPRTQPPWIEJG-UHFFFAOYSA-N 1-methylcyclopropene Chemical compound CC1=CC1 SHDPRTQPPWIEJG-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000005022 packaging material Substances 0.000 claims description 12
- 239000003755 preservative agent Substances 0.000 claims description 12
- 230000002335 preservative effect Effects 0.000 claims description 12
- 229920001353 Dextrin Polymers 0.000 claims description 11
- 239000004375 Dextrin Substances 0.000 claims description 11
- 235000019425 dextrin Nutrition 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 229920000858 Cyclodextrin Polymers 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000001116 FEMA 4028 Substances 0.000 claims description 6
- 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 description 6
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 6
- 229960004853 betadex Drugs 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000005969 1-Methyl-cyclopropene Substances 0.000 claims description 5
- 239000000017 hydrogel Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 38
- 239000007789 gas Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000012065 filter cake Substances 0.000 description 18
- 235000012055 fruits and vegetables Nutrition 0.000 description 16
- 238000000576 coating method Methods 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- 244000298697 Actinidia deliciosa Species 0.000 description 12
- 235000009436 Actinidia deliciosa Nutrition 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000008247 solid mixture Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000011111 cardboard Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
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- 230000029058 respiratory gaseous exchange Effects 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 241000270288 Gekko Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000003854 Surface Print Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 101710121996 Hexon protein p72 Proteins 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 101710125418 Major capsid protein Proteins 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000021022 fresh fruits Nutrition 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound 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 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nutrition Science (AREA)
- Health & Medical Sciences (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Paper (AREA)
Abstract
The invention discloses an alkali-regulated high-temperature-resistant modified cyclopropene, fresh-keeping gloss oil and fresh-keeping packaging product, wherein the modified cyclopropene is in a solid state and comprises an active ingredient cyclopropene compound, a curing coating agent and a high-temperature-resistant modifier; the high temperature resistant modifier is an organosilicon compound. The application adopts the organosilicon compound and the curing inclusion agent to carry out modification treatment on the cyclopropene compound, so that the heat stability and the oxidation resistance stability of the cyclopropene compound can be obviously enhanced, and the condition that the corrugated board production needs 180 ℃ can be satisfied; and has the characteristic of alkali regulation and release, can be stably stored in a neutral system with pH of 6.5-8.5, and can activate and release cyclopropene gas in an alkaline system with pH of more than 8.5, so that the modified MCP and other products prepared from the modified MCP, such as fresh-keeping gloss oil, fresh-keeping cartons and the like, can be stored for a long time in a conventional environment.
Description
Technical Field
The invention belongs to the technical field of preservation, and particularly relates to alkali-controlled high-temperature-resistant modified cyclopropene, preservation gloss oil and a preservation packaging product.
Background
In the prior art, the drying agent or the preservative adopted by fruits and vegetables and other fresh foods is generally packaged by a single-sided water-locking breathable paper-plastic material and put into a fresh packaging box, so that the contact area is small, and the fresh-keeping effect is limited. Although the fruit and vegetable respiration inhibition type preservative has good preservation effect, the fruit and vegetable respiration inhibition type preservative is usually used for preserving fruits and vegetables in a refrigerator in a fumigation mode, and is not applied to fresh transportation.
The prior art researches are mainly focused on antibacterial fresh-keeping, mildew-proof fresh-keeping coating or adsorption coating, some of the technical operations are complicated and cannot be applied on a large scale, and some of the technical effects are limited and cannot be applied to perishable fruits such as cherry, banana and kiwi fruits.
1-methyl cyclopropene (1-MCP for short) is a cyclopropene compound, exists in a gas state under normal temperature, is nontoxic and odorless, has a boiling point of about 10 ℃, is unstable in a liquid state, can be combined with ethylene in a competitive manner because of similar molecular structure, inhibits various biochemical reactions related to after ripening, and is practically used for fumigating and preserving warehouses.
In order to solve the problems of storage and transportation of the cyclopropene liquid preservative in the prior art, an inclusion agent such as dextrin is generally adopted for solidification, and 1-MCP gas can be released only by absorbing a small amount of water during use.
The packaging material most often adopted in fruit and vegetable transportation is a carton, and particularly the cured MCP inclusion compound can be manufactured into a bagged preservative in application and directly put into the carton for use, but the method has the problems of small contact area and limited preservation effect as described above.
Another method is that as described in patent CN201610637567.9, the MCP inclusion compound is prepared into a coating, then the coating is coated on the surface of the raw paper layer, and then the raw paper layer is dried at 40-60 ℃ to obtain preservative paper, then the preservative paper is used as a paper box, before the fruits and vegetables are not put into the paper box, the moisture in the air is insufficient to cause release of gas MCP, and after the fruits and vegetables are directly put into the paper box, the water vapor generated by respiration of the fruits and vegetables induces slow release of MCP gas. Or as described in patent CN201710283918.5, adding cyclodextrin-coated MCP into monomer, pore-forming agent, cross-linking agent, initiator and the like to prepare premix, drying, using the premix in printing ink of a packaging carton, adding fruits and vegetables, and slowly releasing gas MCP by utilizing water vapor breathed by the fruits and vegetables. The method has convenient use and good fresh-keeping effect. However, there are certain problems with both of these patents: 1. although under the conventional condition, the moisture in the air is insufficient to enable the solidified MCP to release MCP gas, when the carton is stored for a long time and not used, the storage environment is complex and changeable, and the release of gas MCP is still easy to cause under the humid environment, so that the preservation effect is affected. 2. The paper box obtained by directly coating and drying the patent CN201610637567.9 has poor coating binding force and is easy to fall off, while the paper box obtained by adopting a printing mode in the patent CN201710283918.5 can instantaneously generate high temperature of more than 120 ℃ in the ink printing process, so that a large amount of gas MCP is released, the existing paper box preprinting technology is more and more popular, corrugated boards are produced by passing through a 160-180 ℃ flat line after preprinting, and therefore, the cured MCP is required to be capable of tolerating the high temperature of more than 180 ℃, and the two patent products cannot meet.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide an alkali-regulated high-temperature-resistant modified cyclopropene, fresh-keeping gloss oil and fresh-keeping packaging product.
The invention aims at realizing the following technical scheme:
an alkali-controlled high-temperature-resistant modified cyclopropene is in a solid state and comprises an active ingredient cyclopropene compound, a curing and inclusion agent and a high-temperature-resistant modifier; the high-temperature resistant modifier is an organic silicon compound; the content of the organosilicon compound is 1-50% of the mass of the cyclopropene compound.
Preferably, the modified cyclopropene can withstand high temperature of more than or equal to 180 ℃ and stably store in a neutral system with pH of 6.5-8.5 without releasing the cyclopropene gas, and activate and release the cyclopropene gas in an alkaline system with pH of more than 8.5.
Preferably, the cyclopropene compound is 1-methylcyclopropene;
preferably, the organosilicon compound is selected from ethyl orthosilicate and/or silicic acid hydrogel obtained by hydrolysis of ethyl orthosilicate;
preferably, the curing inclusion agent is one or more selected from beta-cyclodextrin, yellow dextrin and white dextrin.
Preferably, in the modified cyclopropene, the content of the curing inclusion agent is 8-12 times of the mass of the cyclopropene compound.
The preparation method of the alkali-regulated high-temperature-resistant modified cyclopropene comprises the following steps:
s1, uniformly mixing a cyclopropene compound stock solution with a certain proportion with an organosilicon compound to obtain a first mixture; uniformly mixing the curing inclusion compound and quantitative water to obtain a second mixture;
s2, mixing the first mixture and the second mixture for reaction;
s3, carrying out solid-liquid separation on the reacted mixture to obtain the modified cyclopropene;
step S1 and step S2 are performed at a temperature less than the boiling point of the cyclopropene compound.
The pH value of the fresh-keeping gloss oil is 6.5-8.5, and the fresh-keeping gloss oil comprises water-based resin and the modified cyclopropene; the mass percentage of the modified cyclopropene in the fresh-keeping gloss oil is 0.1-5%;
the resin type in the aqueous resin system is selected from resins which can resist high temperature of more than or equal to 180 ℃ and are not decomposed and are stable under the condition that the pH is more than or equal to 6.5.
Preferably, the resin is one or more selected from styrene-acrylic emulsion, sulfonated polyester and sulfonic acid type aqueous polyurethane.
Preferably, the resin is a mixture selected from the group consisting of high hardness styrene-acrylic emulsion, medium hardness styrene-acrylic emulsion and low hardness styrene-acrylic soft emulsion; the dosages of the high-hardness styrene-acrylic emulsion, the medium-hardness styrene-acrylic emulsion and the low-hardness styrene-acrylic soft emulsion are respectively 10-35%, 30-70% and 10-35% of the total mass of the resin.
Preferably, the fresh-keeping gloss oil further comprises a defoaming agent and water;
the fresh-keeping gloss oil comprises, by mass, 0.5-12% of water, 0.3-0.5% of defoamer and the balance of resin.
A fresh-keeping packaging product comprises a packaging material body layer and a fresh-keeping gloss oil layer positioned on at least one side surface of the packaging material body layer;
the fresh-keeping gloss oil layer is formed by curing the fresh-keeping gloss oil with alkali; the consumption of the alkali is 2-6% of the mass of the fresh-keeping gloss oil.
Preferably, the packaging material is paper; the fresh-keeping packaging product is prepared by any one of the following processes:
A. preprinting process: firstly, uniformly mixing neutral fresh-keeping gloss oil with alkali to be used as printing ink, immediately printing by a preprinting machine to obtain a fresh-keeping gloss oil paper roll, and preparing a paperboard containing a fresh-keeping gloss oil layer by a flat line;
B. the common process comprises the following steps: firstly, common base paper is used to obtain a common paperboard through a flat line, then the common paperboard is used as a substrate, neutral fresh-keeping gloss oil and alkali are uniformly mixed to be used as printing ink, and the paperboard containing a fresh-keeping gloss oil layer is immediately printed by a watermark printer.
The application adopts the organosilicon compound and the curing inclusion agent to carry out modification treatment on the cyclopropene compound, so that the thermal stability and the oxidation resistance stability of the cyclopropene compound can be obviously enhanced, and the condition that the printing (preprinting) needs 180 ℃ can be satisfied; and has the characteristic of alkali regulation and release, can be stably stored in a neutral system with pH of 6.5-8.5, and can activate and release cyclopropene gas in an alkaline system with pH of more than 8.5, so that the modified MCP and other products prepared from the modified MCP, such as fresh-keeping gloss oil, fresh-keeping cartons and the like, can be stored for a long time in a conventional environment.
Drawings
FIG. 1 is a graph showing the heated gas release profile of the modified MCP solid powder obtained in example 1 and a conventional dextrin-modified MCP;
FIG. 2 is a graph showing the results of stability tests of the neutral fresh-keeping gloss oil obtained in example 1 and a fresh-keeping gloss oil added with sodium hydroxide and having a pH of 11;
FIG. 3 is a diagram of a freshness test process for a freshness protection carton;
fig. 4 is a graph showing the hardness change of kiwi fruits stored in fresh-keeping cartons and ordinary cartons;
fig. 5 is a graph showing the weight change of kiwi fruits stored in fresh-keeping cartons and ordinary cartons.
Detailed Description
The application provides alkali-controlled high-temperature-resistant modified cyclopropene which is in a solid state and comprises an active ingredient cyclopropene compound, a curing inclusion agent and a high-temperature-resistant modifier; the high temperature resistant modifier is an organosilicon compound; the content of the organic silicon compound is 1-50% of the mass of the cyclopropene compound.
In the prior art, the MCP solidified by inclusion of substances such as dextrin can release gas MCP in a neutral system, so that the subsequent application, such as the preparation of a fresh-keeping carton made by the patent 201710283918.5 and the patent 201610637567.9, is likely to absorb excessive moisture during normal preservation to release the MCP in advance, and the application of the solidified MCP is limited. In addition, conventional inclusion cured MCPs have poor high temperature resistance and cannot withstand the high temperatures of conventional printing such as watermarking and preprinting.
According to the application, through intensive researches, the method adopts the organosilicon compound and the curing inclusion compound to carry out modification treatment on the cyclopropene compound (such as 1-MCP), on the basis of the silicon-oxygen bond with strong thermal stability and oxidation stability in organosilicon molecules, the thermal stability and oxidation stability of the modified gas MCP can be obviously enhanced, the modified gas MCP is hardly released at 180 ℃ as measured by a thermal release curve, a large amount of release temperature is between 250 and 350 ℃, and the condition that the corrugated board production needs 180 ℃ can be met; and has the characteristic of alkali regulation and release, can be stably stored in a neutral system with pH of 6.5-8.5, and can activate and release cyclopropene gas in an alkaline system with pH of more than 8.5, so that the modified MCP and other products prepared from the modified MCP, such as fresh-keeping gloss oil, fresh-keeping cartons and the like, can be stored for a long time in a conventional environment. The base-mediated release mechanism, applicants speculate that the modified cyclopropenes have the characteristics of a Lewis base, which can be destroyed by the strong base, resulting in the release of the encapsulated gas. However, in the absence of water vapor, the strong base is solid and has limited destructive power to the coating structure, and thus is relatively stable in the dry state without release of cyclopropene gas.
By adjusting the amount of the organosilicon compound, the heat release profile can be adjusted, and in general, the heat release temperature is relatively high when the amount of the organosilicon compound is large within a limited range.
Preferably, the cyclopropene compound is 1-methylcyclopropene which is widely used or a cyclopropene derivative which has similar performance to 1-methylcyclopropene.
Preferably, the organosilicon compound is selected from ethyl orthosilicate, and/or silicic acid hydrogel obtained by hydrolysis of ethyl orthosilicate.
Preferably, the curing inclusion agent is one or more combinations selected from beta-cyclodextrin, yellow dextrin and white dextrin, and further preferably is the most common and most widely used beta-cyclodextrin.
Preferably, in the modified cyclopropene, the content of the curing inclusion agent is 8-12 times of the mass of the cyclopropene compound.
The preparation method of the alkali-regulated high-temperature-resistant modified cyclopropene comprises the following steps:
s1, uniformly mixing a cyclopropene compound stock solution with a certain proportion with an organosilicon compound to obtain a first mixture; uniformly mixing the curing inclusion compound and quantitative water to obtain a second mixture;
s2, mixing the first mixture and the second mixture for reaction;
s3, carrying out solid-liquid separation on the reacted mixture to obtain the modified cyclopropene.
The proportion is as follows: the usage amount of the organosilicon compound is 1-50% of the mass of the cyclopropene compound, and the usage amount of the curing inclusion compound is 8-12 times of the mass of the cyclopropene compound.
Step S1 and step S2 are carried out at a temperature less than the boiling point of the cyclopropene compound, so that the preservative gas is prevented from being released in advance under the condition of higher temperature.
Preferably, when the cyclopropene compound is 1-MCP, the raw solution of the cyclopropene compound and the organosilicon compound are stirred and mixed for 60-90 min at the temperature of minus 5 ℃ to minus 10 ℃, the curing inclusion compound and quantitative water are ground and mixed at the temperature of 1-5 ℃, and the water consumption is 1.5-2.5 times of the mass of the curing inclusion compound; and S2, pouring the first mixture into the second mixture, and continuously grinding and mixing for 90-120 min.
And S3, carrying out suction filtration on the ground solid mixture, washing a filter cake with ethanol for more than 2 times, then placing the filter cake into a vacuum drying oven at 40-60 ℃ for vacuum drying for 18-30 h, and then taking out and grinding to obtain the modified cyclopropene.
The modified cyclopropene can be applied as a conventional cyclopropene preservative, such as a preservative bag, and is beneficial to the excellent high temperature resistance of the modified cyclopropene, the modified cyclopropene can be stored for a long time in a high temperature drying environment, and the modified cyclopropene can be directly placed in a fruit and vegetable transport case when in use, and then is wetted by alkali liquor, so that the cyclopropene gas can be released. The modified cyclopropene and alkali powder can be uniformly mixed to prepare a fresh-keeping bag, and the fresh-keeping bag is directly placed in a fruit and vegetable transport case when in use, and then is wetted by water.
In order to fully utilize the advantages of high temperature resistance and alkali regulation release of the modified cyclopropene, the application provides the fresh-keeping gloss oil which is stable under a neutral condition and can resist the high temperature of more than 180 ℃, and the fresh-keeping gloss oil can be used as printing ink to directly print and produce fruit and vegetable packaging boxes. Specifically, the pH of the fresh-keeping gloss oil is 6.5-8.5, and the fresh-keeping gloss oil comprises water-based resin and the modified cyclopropene; the mass percentage of the modified cyclopropene in the fresh-keeping gloss oil is 0.1-5%. When the dosage of the modified cyclopropene in the gloss oil is too small, the corresponding fresh-keeping effect cannot be achieved, and when the dosage is too large, the cost is high.
The fresh-keeping gloss oil resin system can adopt a conventional aqueous resin system, adopts an aqueous coating, has higher safety performance, is suitable for fresh-keeping of fresh fruits and vegetables, and is favorable for absorbing moisture and releasing fresh-keeping gas in the subsequent application. However, the resin is required to be resistant to high temperature of not less than 180 ℃ and stable under neutral and alkaline conditions at pH not less than 6.5, and preferably the resin is a combination of a plurality of types selected from styrene-acrylic emulsion, sulfonated polyester and sulfonic acid aqueous polyurethane. Further preferred is a low cost styrene-acrylic emulsion suitable for mass production.
In the prior art, the styrene-acrylic emulsion has more products, and the styrene-acrylic emulsion with different hardness can be obtained respectively by adjusting the proportion of styrene and other acrylic functional monomers, and the styrene-acrylic emulsion preferably adopts the mixture of high-hardness styrene-acrylic emulsion, medium-hardness styrene-acrylic emulsion and low-hardness styrene-acrylic soft emulsion, wherein the dosages of the high-hardness styrene-acrylic emulsion, the medium-hardness styrene-acrylic emulsion and the low-hardness styrene-acrylic soft emulsion are respectively 10 to 35 percent, 30 to 70 percent and 10 to 35 percent of the total mass of the resin. The technical characteristics of the high-hardness styrene-acrylic emulsion, the medium-hardness styrene-acrylic emulsion and the low-hardness styrene-acrylic soft emulsion in the application are shown in table 1 (the hardness mainly refers to Tg value, and the higher the Tg value is, the higher the emulsion hardness is).
TABLE 1
The higher the styrene-acrylic emulsion hardness is, the worse the film forming property is, after printing and solidification, tiny cracks are generated, the entering of water vapor and the release of fresh-keeping gas are facilitated, but the printing technology has certain requirements on the ink hardness, the hardness is too high, and the printing property is poor, so on the basis of considering the printing property, the stability and the release, the styrene-acrylic emulsion with different hardness is preferably mixed for use, and compared with the styrene-acrylic emulsion with single hardness, the styrene-acrylic emulsion with single hardness has better technical effect.
As will be appreciated by those skilled in the art, when other resin systems are employed, the principle is similar to that of styrene-acrylic emulsions, and it is also preferred to use a blend of resins of different hardness.
Preferably, the fresh-keeping gloss oil further comprises a defoaming agent and water; the fresh-keeping gloss oil comprises 0.5-12% of water by mass, 0.3-0.5% of defoamer by mass and the balance of resin by mass. The defoamer is preferably BYK-019 defoamer. The water content can be adjusted according to the water content in the resin, so as to keep the viscosity of the fresh-keeping gloss oil within a range suitable for printing, and the total water content in the gloss oil is generally kept between 30 and 60 percent.
The fresh-keeping gloss oil can be directly coated on the surface of a packaging material for use as in patent 201610637567.9, and because the modified MCP in the fresh-keeping gloss oil is alkali for regulating and releasing fresh-keeping gas, a certain amount of alkali needs to be added into the fresh-keeping gloss oil before coating, so that excessive release of the fresh-keeping gas in the coating and drying process is reduced, and the fresh-keeping gloss oil is uniformly mixed and then is required to be immediately coated and dried quickly. The packaging material needs to be able to quickly absorb the moisture in the coating and to be able to quickly cure the coating, such as paper, foam, etc.
Therefore, the application also provides a fresh-keeping packaging product, which comprises a packaging material body layer and a fresh-keeping gloss oil layer positioned on at least one side surface of the packaging material body layer;
the fresh-keeping gloss oil layer is formed by curing the fresh-keeping gloss oil by adding alkali; the consumption of the alkali is 2-6% of the quality of the fresh-keeping gloss oil.
The paper box is the most widely used fruit and vegetable packaging box, has low price and excellent water absorption performance, therefore, the preferred packaging material is paper, the application firstly proposes that a small amount of alkali, preferably sodium hydroxide/potassium hydroxide, is manually added before printing, and then is immediately used for printing, and the paper box can be stably stored for a plurality of months under the condition that the paper box is dried at room temperature, and the active ingredient 1-MCP is slowly released. When in use, the coating is sprayed by a sprayer, and then the 1-MCP can be activated to start releasing after the fruits and vegetables are packaged. Specifically, the fresh-keeping carton can be prepared by adopting any one of the following processes:
A. preprinting process: firstly, uniformly mixing neutral fresh-keeping gloss oil with alkali to be used as printing ink, immediately printing by a preprinting machine to obtain a fresh-keeping gloss oil paper roll, and preparing a paperboard containing a fresh-keeping gloss oil layer by a flat line; as will be appreciated by those skilled in the art, the fresh-keeping gloss oil layer is located on the inner layer of the board, and on the outer side of the board conventional top layer printing can also be performed by a watermark printer.
B. The common process comprises the following steps: firstly, common base paper is used to obtain a common paperboard through a flat line, then the common paperboard is used as a substrate, neutral fresh-keeping gloss oil and alkali are uniformly mixed to be used as printing ink, and the printing ink is immediately printed by a watermark printer to obtain the paperboard containing the fresh-keeping gloss oil layer. As will be appreciated by those skilled in the art, the fresh-keeping gloss oil layer is located on the inner layer of paperboard and the substrate may be a conventional paperboard printed with a conventional top layer.
In order to fully and uniformly mix the fresh-keeping gloss oil and the alkali, the solid alkali can be diluted by a small amount of water and then added into the fresh-keeping gloss oil, and in order to reduce the release of MCP gas, the mixture should be printed immediately.
The preprinting process is adopted, so that the production efficiency is high, and the printing is uniform; the common process is simple in process and slightly poor in uniformity, but due to complicated steps, the efficiency is low, the cost is relatively high, and the process can be selected for printing production according to actual production conditions. The preprinting process and the common process are only required by adopting a conventional corrugated board production printing process, and are not repeated in the application.
The dry fresh-keeping paper box can be stored for a long time in a dry room temperature environment, when the paper box is used, the interior of the paper box is sprayed with water to be wet, and fresh-keeping effect can be obtained after fruits and vegetables are filled in the paper box, the length of the fresh-keeping period can be adjusted by adjusting the alkali content and the printing amount of the coating, and in addition, the fresh-keeping period is related to the environmental temperature and the air humidity of the paper box.
Example 1
(1) Preparation of modified MCP solids
(a) Setting the temperature of a low-temperature reactor to minus 10 ℃, sequentially pouring 10g of 1-MCP stock solution into a split four-neck flask, 0.5g of tetraethoxysilane, and keeping low-temperature stirring for 60min at 360 r/min.
(b) Setting the temperature of a low-temperature dispersing device at 3 ℃, after the dispersing device is fully cooled, sequentially adding 100g of beta-cyclodextrin and 200g of distilled water, grinding into paste, adding the mixed solution obtained in the step (1), and continuously grinding for 120min.
(c) Filtering the ground solid mixture, washing the filter cake with 30ml ethanol for 3 times, putting the filter cake into a vacuum drying oven (vacuum degree-0.09 Mpa) at 50 ℃, taking out the filter cake after 24 hours, and grinding the filter cake to obtain modified MCP solid powder.
(2) Preparation of fresh-keeping gloss oil
Under the room temperature condition, 15g of high-hardness styrene-acrylic emulsion, 60g of medium-hardness styrene-acrylic emulsion, 15g of low-hardness styrene-acrylic soft emulsion, 9.5g of deionized water, 0.1g of modified MCP and 0.4g of BYK-019 defoamer are sequentially added into a high-speed dispersing machine, and the fresh-keeping gloss oil with the pH of 7.8 can be obtained after high-speed dispersion for 60min. (wherein 0590 emulsion and 1207 emulsion are from the natural product of Gekko ink, BYK-019 from Pick chemical).
(3) Printing of fresh-keeping cartons
And adding 2wt% of sodium hydroxide solid powder (which can be diluted by a small amount of water and uniformly mixed with the fresh-keeping gloss oil) into the fresh-keeping gloss oil, fully and uniformly stirring, pouring into a preprinting machine for printing, and winding to obtain the fresh-keeping gloss oil layer paper roll. The fresh-keeping gloss oil layer paper roll passes through a 180 ℃ flat line to obtain a paperboard with a fresh-keeping gloss oil layer (the printing quantity of the fresh-keeping gloss oil layer is 3 g/m) 2 ). The cardboard is subjected to surface printing by a watermark printer to obtain the fresh-keeping cardboard box.
Example 2
(1) Preparation of modified MCP solids
(a) Setting the temperature of a low-temperature reactor to be minus 5 ℃, sequentially pouring 10g of 1-MCP liquid into the split four-neck flask, 5g of silicic acid hydrogel, and stirring at a low temperature for 90min at 800 r/min.
(b) Setting the temperature of a low-temperature dispersing device at 3 ℃, after the dispersing device is fully cooled, sequentially adding 80g of yellow dextrin and 160g of distilled water, grinding into paste, adding the mixed solution obtained in the step (1), and continuously grinding for 90min.
(c) Filtering the ground solid mixture, washing the filter cake with 30ml ethanol for 3 times, putting the filter cake into a vacuum drying oven (vacuum degree-0.09 Mpa) at 50 ℃, taking out the filter cake after 24 hours, and grinding the filter cake to obtain modified MCP solid powder.
(2) Preparation of fresh-keeping gloss oil
Under the room temperature condition, sequentially adding 30g of high-hardness styrene-acrylic emulsion, 30g of medium-hardness styrene-acrylic emulsion and 30g of styrene-acrylic soft emulsion into a high-speed dispersing machine, 9.3g of deionized water, 0.3g of modified MCP (micro-control board), 0.4g of BYK-019 defoamer and high-speed dispersing for 90min to obtain fresh-keeping gloss oil, wherein the pH value of the gloss oil is 7.6.
(3) Printing of fresh-keeping cartons:
(a) And (3) using common base paper to prepare a common corrugated board through a 180 ℃ flat line, and carrying out surface layer printing through a watermark printer.
(b) Adding 3wt% sodium hydroxide solid powder into the fresh-keeping gloss oil, fully and uniformly stirring,
(c) Pouring into a watermark printer to print the fresh-keeping gloss oil layer on the back of the paper board with the surface layer printed as a substrate to obtain a fresh-keeping paper box (the printing quantity of the fresh-keeping gloss oil layer is 3 g/m) 2 )。
Example 3
(1) Preparation of modified MCP solids
(a) Setting the temperature of a low-temperature reactor at-3 ℃, sequentially pouring 10g of 1-MCP stock solution into a split four-neck flask, 0.1g of tetraethoxysilane, and keeping stirring at a low temperature for 30min 720 r/min.
(b) Setting the temperature of the low-temperature dispersing device to 3 ℃, after the dispersing device is fully cooled, sequentially adding 100g of dextrin and 200g of distilled water, grinding into paste, adding the mixed solution obtained in the step (1), and continuously grinding for 120min.
(c) Filtering the ground solid mixture, washing the filter cake with 30ml ethanol for 3 times, putting the filter cake into a vacuum drying oven (vacuum degree-0.09 Mpa) at 50 ℃, taking out the filter cake after 24 hours, and grinding the filter cake to obtain modified MCP solid powder.
(2) Preparation of fresh-keeping gloss oil
Under the room temperature condition, 10g of high-hardness styrene-acrylic emulsion, 60g of medium-hardness styrene-acrylic emulsion, 20g of low-hardness styrene-acrylic soft emulsion, 9.1g of deionized water, 0.5g of modified MCP, 0.4g of BYK-019 defoamer and 120min of high-speed dispersion are sequentially added into a high-speed dispersing machine, so that the fresh-keeping gloss oil with the pH of 7.9 can be obtained. (wherein 0590 emulsion and 1207 emulsion are from the natural product of Gekko ink, BYK-019 from Pick chemical).
(3) Printing of fresh-keeping cartons
And adding 2wt% of sodium hydroxide solid powder into the fresh-keeping gloss oil, fully and uniformly stirring, pouring into a preprinting machine for printing, and rolling to obtain the fresh-keeping gloss oil layer paper roll. The fresh-keeping gloss oil layer paper roll passes through a 180 ℃ flat line to obtain a paperboard with a fresh-keeping gloss oil layer (the printing quantity of the fresh-keeping gloss oil layer is 3 g/m) 2 ). The cardboard is subjected to surface printing by a watermark printer to obtain the fresh-keeping cardboard box.
Example 4
(1) Preparation of modified MCP solids
(a) Setting the temperature of a low-temperature reactor to be minus 5 ℃, sequentially pouring 10g of 1-MCP liquid into the split four-neck flask, and keeping the silicic acid hydrogel at a low temperature for 90min under stirring at 800 r/min.
(b) Setting the temperature of a low-temperature dispersing device at 3 ℃, after the dispersing device is fully cooled, sequentially adding 120g of beta-cyclodextrin and 200g of distilled water, grinding into paste, adding the mixed solution obtained in the step (1), and continuously grinding for 90min.
(c) Filtering the ground solid mixture, washing the filter cake with 30ml ethanol for 3 times, putting the filter cake into a vacuum drying oven (vacuum degree-0.09 Mpa) at 50 ℃, taking out the filter cake after 24 hours, and grinding the filter cake to obtain modified MCP solid powder.
(2) Preparation of fresh-keeping gloss oil
Under the room temperature condition, 30g of high-hardness styrene-acrylic emulsion, 40g of medium-hardness styrene-acrylic emulsion, 20g of styrene-acrylic soft emulsion, 8.6g of deionized water, 1g of modified MCP, 0.4g of BYK-019 defoamer and high-speed dispersion for 90min are sequentially added into a high-speed dispersion machine, so that the fresh-keeping gloss oil with the pH of 8.2 can be obtained.
(3) Printing of fresh-keeping cartons:
(a) And (3) using common base paper to prepare a common corrugated board through a 180 ℃ flat line, and carrying out surface layer printing through a watermark printer.
(b) Adding 6wt% sodium hydroxide solid powder into the fresh-keeping gloss oil, fully and uniformly stirring,
(c) Pouring into a watermark printer to print the fresh-keeping gloss oil layer on the back of the paper board with the surface layer printed as a substrate to obtain a fresh-keeping paper box (the printing quantity of the fresh-keeping gloss oil layer is 3 g/m) 2 )。
Experimental example
1. Modified MCP solid thermal stability test
The modified MCP solid powder obtained in example 1 was taken and tested for heated gas release profile under the following test conditions using conventional dextrin-modified MCP solid powder (no silicone modification added) as a control, and the results are shown in fig. 1 (x-axis is temperature, unit deg.c; y-axis is weight residual percentage).
Test conditions: thermal weight loss test, 5mg is sampled, 30-800 ℃ and N 2 Atmosphere, heating rate 10 ℃/min.
As can be seen from fig. 1, when the temperature reaches 200 ℃, the conventional dextrin modified MCP has more than 10% of gas release, but the modified cyclopropene gas release in the application is less than 5%, and the gas release reaches 10% only when the temperature reaches about 250 ℃, so that it can be proved that the modified MCP obtained in the application can completely resist the printing high temperature of 180 ℃.
2. Stability test of fresh-keeping gloss oil
100g of the neutral fresh-keeping gloss oil obtained in example 1 (the addition amount of the fresh-keeping agent is increased from 0.1wt% to 5wt% in order to improve the test precision, and the water consumption is correspondingly reduced) and the fresh-keeping gloss oil added with 2wt% of sodium hydroxide (pH is 11) are respectively filled into metal cans for sealing. The sealed pot is put into a 60 ℃ oven for heat storage, one pot is taken out every 24 hours and cooled, the seal is opened, the sealed pot is weighed after being slightly stirred, and the quality change is recorded, and the result is shown in figure 2.
As can be seen from fig. 2, the fresh-keeping gloss oil prepared by the method can be stably stored under a neutral condition, almost has no loss of quality, and slowly releases fresh-keeping gas under an alkaline condition.
3. Fresh-keeping test for fresh-keeping carton
Test conditions: the kiwi fruits picked in the same weight and batch are respectively stored in a fresh-keeping gloss oil layer (fresh-keeping paper box obtained in the example 1) and a paper box without the fresh-keeping gloss oil layer (common paper box obtained without printing the fresh-keeping gloss oil layer under the same production process condition), the kiwi fruits are stored for 6 days under the environment of 25 ℃ and 70% RH, the hardness change and the weight change of the kiwi fruits are compared and tested, the pictures of the test process are shown in fig. 3, and the results are shown in fig. 4-5.
From fig. 4, it can be seen that the hardness of the kiwi fruits stored in the cartons with the fresh-keeping gloss oil layer is higher than that of the cartons without the coating layer in the test time, so that the cartons with the fresh-keeping gloss oil layer can delay the maturation of the kiwi fruits, and the fresh-keeping effect is achieved.
As can be seen from fig. 5, the loss of weight of kiwi fruits in the cartons with the fresh-keeping gloss oil layer starts to approach to the uncoated cartons at 4 to 5 days of storage, and the fresh-keeping gloss oil starts to lose efficacy in this period, so that the rate of organic matter consumption of kiwi fruits becomes high. Therefore, the inhibition time of the ethylene inhibition type water-based paint on the breathing action of the kiwi fruits is about 4-5 days, and the fresh-keeping effect of the carton on the kiwi fruits is about 4-5 days.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The alkali-controlled high-temperature-resistant modified cyclopropene is characterized by being in a solid state and comprising an active ingredient cyclopropene compound, a curing inclusion agent and a high-temperature-resistant modifier; the high-temperature resistant modifier is an organic silicon compound; the content of the organosilicon compound is 1-50% of the mass of the cyclopropene compound.
2. The alkali-controlled high-temperature-resistant modified cyclopropene as claimed in claim 1, wherein the modified cyclopropene can resist high temperature of more than or equal to 180 ℃ and stably store in a neutral system with pH of 6.5-8.5 without releasing cyclopropene gas, and activate and release cyclopropene gas in an alkaline system with pH of more than 8.5.
3. The alkali-controlled high temperature-resistant modified cyclopropene of claim 1, wherein the cyclopropene compound is 1-methylcyclopropene;
preferably, the organosilicon compound is selected from ethyl orthosilicate and/or silicic acid hydrogel obtained by hydrolysis of ethyl orthosilicate;
preferably, the curing inclusion agent is one or more selected from beta-cyclodextrin, yellow dextrin and white dextrin.
4. The alkali-controlled high temperature-resistant modified cyclopropene of claim 1,
in the modified cyclopropene, the content of the curing inclusion agent is 8-12 times of the mass of the cyclopropene compound.
5. The method for preparing the alkali-controlled high-temperature-resistant modified cyclopropene as claimed in any one of claims 1 to 4, comprising the steps of:
s1, uniformly mixing a cyclopropene compound stock solution with a certain proportion with an organosilicon compound to obtain a first mixture; uniformly mixing the curing inclusion compound and quantitative water to obtain a second mixture;
s2, mixing the first mixture and the second mixture for reaction;
s3, carrying out solid-liquid separation on the reacted mixture to obtain the modified cyclopropene;
step S1 and step S2 are performed at a temperature less than the boiling point of the cyclopropene compound.
6. A preservative gloss oil characterized in that the preservative gloss oil has a pH of 6.5 to 8.5 and comprises an aqueous resin and the modified cyclopropene of any one of claims 1 to 4; the mass percentage of the modified cyclopropene in the fresh-keeping gloss oil is 0.1-5%;
the resin type in the aqueous resin system is selected from resins which can resist high temperature of more than or equal to 180 ℃ and are not decomposed and are stable under the condition that the pH is more than or equal to 6.5.
7. The fresh-keeping gloss oil according to claim 6, wherein,
the resin is one or a combination of more selected from styrene-acrylic emulsion, sulfonated polyester and sulfonic acid type aqueous polyurethane.
Preferably, the resin is a mixture selected from the group consisting of high hardness styrene-acrylic emulsion, medium hardness styrene-acrylic emulsion and low hardness styrene-acrylic soft emulsion; the dosages of the high-hardness styrene-acrylic emulsion, the medium-hardness styrene-acrylic emulsion and the low-hardness styrene-acrylic soft emulsion are respectively 10-35%, 30-70% and 10-35% of the total mass of the resin.
8. The fresh-keeping gloss oil according to claim 6, wherein,
the fresh-keeping gloss oil also comprises a defoaming agent and water;
the fresh-keeping gloss oil comprises, by mass, 0.5-12% of water, 0.3-0.5% of defoamer and the balance of resin.
9. A freshness package product, characterized by: comprises a packaging material body layer and a fresh-keeping gloss oil layer positioned on at least one side surface of the packaging material body layer;
the fresh-keeping gloss oil layer is formed by curing the fresh-keeping gloss oil according to any one of claims 6 to 8 with alkali; the consumption of the alkali is 2-6% of the mass of the fresh-keeping gloss oil.
10. The freshness package product of claim 9, wherein: the packaging material is paper; the fresh-keeping packaging product is prepared by any one of the following processes:
A. preprinting process: firstly, uniformly mixing neutral fresh-keeping gloss oil with alkali to be used as printing ink, immediately printing by a preprinting machine to obtain a fresh-keeping gloss oil paper roll, and preparing a paperboard containing a fresh-keeping gloss oil layer by a flat line;
B. the common process comprises the following steps: firstly, common base paper is used to obtain a common paperboard through a flat line, then the common paperboard is used as a substrate, neutral fresh-keeping gloss oil and alkali are uniformly mixed to be used as printing ink, and the paperboard containing a fresh-keeping gloss oil layer is immediately printed by a watermark printer.
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| CN202311462057.9A CN117511291A (en) | 2023-11-06 | 2023-11-06 | Alkali-controlled high-temperature-resistant modified cyclopropene, fresh-keeping gloss oil and fresh-keeping packaging product |
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| CN202311462057.9A CN117511291A (en) | 2023-11-06 | 2023-11-06 | Alkali-controlled high-temperature-resistant modified cyclopropene, fresh-keeping gloss oil and fresh-keeping packaging product |
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