CN110305361A - It is a kind of intelligently to control dampness barrier composite film and its preparation method and application - Google Patents
It is a kind of intelligently to control dampness barrier composite film and its preparation method and application Download PDFInfo
- Publication number
- CN110305361A CN110305361A CN201810231471.1A CN201810231471A CN110305361A CN 110305361 A CN110305361 A CN 110305361A CN 201810231471 A CN201810231471 A CN 201810231471A CN 110305361 A CN110305361 A CN 110305361A
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- China
- Prior art keywords
- composite film
- barrier composite
- control barrier
- film
- intelligent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 230000004888 barrier function Effects 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 polyethylene Polymers 0.000 claims abstract description 43
- 239000004743 Polypropylene Substances 0.000 claims abstract description 25
- 229920001155 polypropylene Polymers 0.000 claims abstract description 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000004698 Polyethylene Substances 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 10
- 239000004793 Polystyrene Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229920002223 polystyrene Polymers 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 7
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 6
- 238000006136 alcoholysis reaction Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- 229940015043 glyoxal Drugs 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
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- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims description 2
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 108010013296 Sericins Proteins 0.000 claims description 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
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- 229940069338 potassium sorbate Drugs 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
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- 229920000092 linear low density polyethylene Polymers 0.000 claims 1
- 239000004707 linear low-density polyethylene Substances 0.000 claims 1
- 229940118019 malondialdehyde Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 24
- 239000012528 membrane Substances 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
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- 238000009833 condensation Methods 0.000 abstract description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract 1
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- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 9
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/309—Sulfur containing acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention belongs to function film field, it is related to a kind of intelligence control dampness barrier composite film and its preparation method and application.The intelligence control dampness barrier composite film includes base and extra play, and the extra play is located at base one or both sides；Wherein, the base is porous membrane, and material is at least one of polyethylene, polypropylene, polystyrene, poly terephthalic acid diol ester and polycaprolactam；The extra play is dense film, and material contains polyvinyl alcohol and metal salt and optional crosslinking agent and/or antibacterial agent.There is intelligence control dampness barrier composite film of the invention intelligence to control wet ability, fruits and vegetables humidity is kept when relative humidity is lower, increase moisture-inhibiting when relative humidity is higher to prevent fruit and vegetable moisture condensation from festering, and there is oxygen barrier property, the fruit and vegetable box that can be used for having fresh-keeping function and the refrigerator with fruit and vegetable preservation box.
Description
Technical Field
The invention belongs to the field of functional films, and particularly relates to an intelligent humidity control barrier composite film and a preparation method and application thereof.
Background
Fruits and vegetables are important food products for humans and are the main source from which people obtain basic nutrients (vitamins, minerals, complex carbohydrates, etc.). With the increasing living standard of people, the requirement on the freshness of fresh fruits and vegetables is higher and higher. The fruits and vegetables can continue to breathe and transpire after being harvested, and water dispersion and nutrient substance consumption can occur in the storage process. The respiration intensity of the fruits and vegetables is doubled when the temperature is increased by 10 ℃. The household fruit and vegetable fresh-keeping method is to put the fruits and vegetables in a refrigerator for refrigeration to slow down the respiration of the fruits and vegetables. In fruits and vegetables, moisture is an important ingredient, affecting the tenderness, freshness and taste of fruits and vegetables. Too low ambient humidity can result in water loss and weight loss in fruits and vegetables, but too high humidity can cause condensation of water on the surfaces of fruits and vegetables, growth of fungi, and acceleration of rotting and deterioration of fruits and vegetables. Therefore, the control of the storage humidity of the fresh fruits and vegetables is very important, and the preservation time of the fruits and vegetables can be prolonged. The barrier film can prevent the permeation of oxygen and other gases, inhibit the respiration of fresh fruits and vegetables and prolong the fresh-keeping time of fruits and vegetables.
The effects of several functional films, namely a temperature-sensitive moisture-permeable film, a silicon filter film and a moisture-sensitive moisture-permeable film, on the fruit and vegetable box for reducing the water loss in the market are not satisfactory. The temperature-sensitive moisture-permeable film is easy to dewet on the surface of the film under high humidity and low temperature; the silicon filter membrane has the function of moisture retention, but the moisture permeability cannot be changed along with the humidity; the moisture-sensitive and moisture-permeable membrane is formed by coating an adhesive solution on a paper-based substrate, the performance meets the requirement, but the preparation process is not environment-friendly, the process is complex, and the problem that the chlorine content exceeds the standard possibly exists in the processing process.
CN105986511A discloses a technique of applying natural high molecular polymer with good hydrophilic water retention and film forming property on base paper with high dry and wet strength, but the cost is high. CN104029449B discloses a coating film with large moisture permeability, wherein the base layer is an expanded polytetrafluoroethylene film layer, the coating is a polyurethane emulsion copolymerization coating containing hemp stem core superfine micropowder, and the film is used for an automobile lamp shell but does not have intelligent moisture control performance. CN103507339A discloses a moisture-sensitive and moisture-permeable film which retains regenerated cellulose in a substrate of nonwoven fabric, but does not have gas barrier properties. CN103107301A discloses an inorganic coating lithium ion battery diaphragm, contains multilayer structure, is porous flexible basement membrane and the coating of coating in basement membrane both sides respectively, and the coating contains polyvinyl alcohol and zeolite particle, and the auxiliary component of this coating does not have the metal salt composition, and the complex film does not have the function of intelligent accuse humidity. CN1864829A discloses a hydrophilic-hydrophobic bipolar composite membrane and a preparation method thereof, the membrane has a double-layer structure, the bottom layer is a porous support layer, the upper layer is a hydrophilic membrane containing lithium chloride, the membrane has high moisture permeability and strong barrier effect on other gas molecules, but does not have intelligent moisture control property. WO2013066012a1 discloses a porous membrane containing inorganic particles and a polymer binder layer containing hydrophilic and hydrophobic substances, which membrane is used to improve the thermal stability of a lithium battery separator and does not have intelligent humidity control properties. WO2012133805a1 discloses a moisture-permeable film whose porous substrate is preferably polytetrafluoroethylene, which is expensive, and whose high moisture-permeability is not good. US20030054155a1 discloses a waterproof moisture-permeable composite film, the hydrophobic layer being polytetrafluoroethylene and the hydrophilic layer being polyurethane, which has high moisture permeability but does not have intelligent moisture control properties.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an intelligent humidity control barrier composite film which can keep moisture under the condition of low humidity, has strong humidity removal capability under the condition of high humidity and has carbon dioxide barrier property. The invention further provides a preparation method of the film, and the method is simple in process and low in cost. Therefore, the film provided by the invention is particularly suitable for being applied to fresh-keeping packaging of vegetables and fruits.
The invention provides an intelligent humidity control barrier composite film, which comprises a base layer and additional layers, wherein the additional layers are positioned on one side or two sides of the base layer; wherein,
the base layer is a porous film and is made of at least one of polyethylene, polypropylene, polystyrene, polyethylene terephthalate and polycaprolactam;
the additional layer is a compact film, and the material of the additional layer contains polyvinyl alcohol and metal salt, and optional cross-linking agent and/or antibacterial agent.
In the invention, in order to realize intelligent humidity control, the base layer needs to be a porous film, and the additional layer needs to be a compact film. The concepts and terminology categories of porous and dense membranes are well known to those skilled in the art. Dense films as additional layers can be produced by applying a solution containing the additional layer components to the surface of the base layer and drying.
According to the invention, the intelligent humidity control barrier composite film is multilayer, when the intelligent humidity control barrier composite film is two layers, the additional layer is positioned on one side of the base layer, when the intelligent humidity control barrier composite film is three layers, the additional layer is positioned on two sides of the base layer, under the condition of requirement, the intelligent humidity control barrier composite film can also be more than three layers, and the additional layer and the base layer can be arranged at intervals. Wherein the base layer is preferably a single-layer structure.
In the present invention, the pore diameter of the porous membrane is preferably 0.02 to 10 micrometers, more preferably 0.05 to 5 micrometers, and still more preferably 0.1 to 2 micrometers; the porosity is 30-80%, preferably 40-70%; pores with a pore diameter within plus or minus one order of magnitude of the average pore diameter account for more than 50% of the total pores, preferably more than 80% of the total pores.
According to the invention, the polyethylene is preferably at least one of High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE) and Low Density Polyethylene (LDPE); the polypropylene is preferably at least one of homo-polypropylene, random co-polypropylene, block co-polypropylene and impact co-polypropylene.
According to the invention, the relative amounts of polyvinyl alcohol and metal salt are limited to such an extent that a dense film can be formed, preferably the amount of polyvinyl alcohol is from 50 to 99 wt.%, preferably from 66 to 98 wt.%, and more preferably from 70 to 95 wt.%, based on the total weight of the additional layer; the content of the metal salt is 1 to 50 wt%, preferably 2 to 34 wt%, and more preferably 5 to 30 wt%.
According to the present invention, the polyvinyl alcohol with higher molecular weight and alcoholysis degree is more favorable for forming a compact film, preferably, the weight average molecular weight of the polyvinyl alcohol is 10000-500000, more preferably 20000-200000; the alcoholysis degree is preferably 70% to 100%, and more preferably 88% to 99%.
According to the present invention, preferably, the metal salt is a soluble sulfate and/or a soluble halide salt, preferably at least one of sodium sulfate, calcium chloride, lithium chloride, cesium fluoride, lithium bromide and lithium fluoride, and more preferably at least one of sodium sulfate, calcium chloride, lithium chloride and lithium fluoride.
According to the invention, the crosslinking agent and the antibacterial agent are optional components, the addition of the crosslinking agent can enable the intelligent humidity control film to have better oxygen barrier property, and the addition of the antibacterial agent can enable the intelligent humidity control film to have antibacterial property.
The amount of the crosslinking agent is preferably 0 to 10 wt%, more preferably 0.1 to 7 wt%, and still more preferably 2 to 6 wt%, based on the total weight of the additional layer. The cross-linking agent is preferably at least one of formaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, maleic acid, maleic anhydride and sulfuric acid, is more preferably at least one of formaldehyde, glutaraldehyde and sulfuric acid, is more preferably formaldehyde and sulfuric acid, or is glutaraldehyde and sulfuric acid, and the cross-linking agent used in combination can further improve the cross-linking efficiency and the cross-linking effect, wherein the dosage ratio of the formaldehyde or the glutaraldehyde to the sulfuric acid can be 2-5: 1.
the antimicrobial agent is preferably present in an amount of 0 to 20 wt%, more preferably 0.1 to 10 wt%, based on the total weight of the additional layer. The antibacterial agent is preferably at least one of nano zinc oxide, nano titanium oxide, nano silver, nano copper, sericin, quaternary ammonium salt, methylparaben, potassium sorbate and chitosan, and is further preferably at least one of nano zinc oxide, nano silver and quaternary ammonium salt, wherein the quaternary ammonium salt is cetylpyridinium chloride.
The above-mentioned preferred components can give a film superior in moisture permeability and gas barrier properties.
The thickness of the base layer and the additional layer may be determined as desired according to the present invention, and in general, the thickness of the base layer may be 5 to 1000 micrometers, preferably 10 to 100 micrometers, and further preferably 60 to 90 micrometers; the thickness of the additional layer may be in the range of 0.5 to 100 microns, preferably 2 to 20 microns.
The second aspect of the invention provides a preparation method of an intelligent humidity control barrier composite film, which comprises the following steps:
(1) fully dissolving or dispersing all components of the additional layer of the intelligent humidity control barrier composite film in water to prepare solution or dispersion liquid;
(2) coating the solution or dispersion obtained in the step (1) on one surface or two surfaces of the base layer of the intelligent humidity control barrier composite film; and drying to obtain the intelligent humidity control barrier composite film.
The solution or dispersion obtained in step (1) may be applied to a substrate using any conventional coating method, including but not limited to: brushing, curtain coating and spraying.
According to the present invention, the mass concentration of the solution or dispersion in step (1) may be 0.5% to 30%, preferably 1% to 10%, and more preferably 5% to 10%.
According to the present invention, the temperature for drying in step (2) may be 50 ℃ to 100 ℃, preferably 60 ℃ to 90 ℃. The drying step may be accomplished in a variety of conventional heating devices, such as an oven. The drying time can be determined according to the needs, for example, 5-30 min.
According to the invention, the crosslinker can be added during the preparation of the solution or dispersion of the additional layer, or can be applied separately after drying, or can be added in two steps at both times. The step of separately coating after drying includes: independently preparing a cross-linking agent into a solution or a dispersion liquid, coating the solution or the dispersion liquid containing the cross-linking agent on one surface or two surfaces of the dried film in the step (2), and drying again to obtain the intelligent humidity control barrier composite film; the mass concentration of the solution or dispersion containing the crosslinking agent is preferably 0.5% to 10%, and more preferably 1% to 5%. The condition of the re-drying may be the same as the first drying condition.
The third aspect of the invention provides the application of the intelligent humidity control barrier composite film and/or the intelligent humidity control barrier composite film prepared by the preparation method in the fresh-keeping packaging of vegetables and fruits.
The intelligent humidity control barrier composite film has intelligent humidity control capability, can keep the humidity of fruits and vegetables when the relative humidity is low, can increase the moisture permeability when the relative humidity is high so as to prevent the fruits and vegetables from dewing and festering, has oxygen barrier performance, and can be used for fruit and vegetable boxes with fresh-keeping functions and refrigerators with fresh-keeping fruit and vegetable boxes.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below.
The thicknesses of the base layer and the additional layer of the intelligent humidity control film are measured by a Shanghai Heishizi thickness meter; the pore structure including pore size and porosity was measured by mercury intrusion using an instrument, model autopore iii-9420 mercury intrusion gauge.
Polypropylene, F1002B, medium petrochemical Yangtze river petrochemical.
Polyethylene, L501(5000S), medium petrochemical actinolite.
Polystyrene, GH-660, China petrochemical Guangzhou petrochemical.
Polyethylene terephthalate, FR530, dupont, usa.
Polycaprolactam, B4, BASF.
Dense biaxially oriented polypropylene film, medium petrochemical and marine refinery, F280Z.
Polyvinyl alcohol A, chemical industry of Xilonggan, with a trademark of PVA124, a weight average molecular weight of 105000 and an alcoholysis degree of 99%.
Polyvinyl alcohol B, chemical industry of Xilong, with a trademark of PVA1788, a weight-average molecular weight of 74800, and an alcoholysis degree of 88%.
Lithium chloride, carbofuran, 99%.
Lithium fluoride, carbofuran, 99%.
Sodium sulfate, national pharmaceutical group chemical reagents, ltd, analytical grade.
Calcium chloride, carbofuran, purity 98%.
Alumina, carbofuran, purity 90%.
99.5 percent of nano zinc oxide and carbofuran, and the grain diameter is 10-30 nm.
99.5 percent of nano silver and carbofuran, and the grain diameter is 10-30 nm.
Formaldehyde, carbofuran, 50% aqueous solution.
Glutaraldehyde, carbofuran, 50% aqueous solution.
Glyoxal, carbofuran, 50% aqueous solution.
Sulfuric acid, national drug group chemical reagents ltd, analytical grade.
Film uniaxial stretcher, common in Guangzhou, MESI-LL.
Example 1
2kg of polypropylene was stretched on a film uniaxial stretcher to form a polypropylene porous film.
7g of polyvinyl alcohol A was added to 100mL of distilled water and sufficiently dissolved. 2.1g of sodium sulfate, 0.2g of nano zinc oxide, 0.35g of glutaraldehyde and 0.1g of sulfuric acid were added to the obtained solution, and sufficiently stirred until uniformly mixed, to obtain a coating solution. Uniformly brushing the coating solution on one surface of a polypropylene porous film, then placing the polypropylene porous film in a drying oven, and drying for 10min at 70 ℃ to obtain an intelligent humidity control barrier composite film A1, wherein the thickness of a base layer is 70 microns, the pore diameter is 0.25 micron, the porosity is 50%, and the pores with the pore diameter within the range of plus or minus one order of magnitude of average pore diameter account for more than 85% of all pores; the additional layer has a thickness of 9 microns.
Comparative example 1
A film was produced in the same manner as in example 1, except that sodium sulfate was not contained in the coating liquid, to obtain film D1.
Comparative example 2
A film was produced in the same manner as in example 1, except that a polypropylene porous film was not used, but a dense polypropylene biaxially oriented film was used, to obtain a film D2.
Example 2
2kg of polypropylene was stretched on a film uniaxial stretcher to form a polypropylene porous film.
7g of polyvinyl alcohol A was added to 100mL of distilled water and sufficiently dissolved. 1.4g of lithium fluoride, 0.2g of nano zinc oxide, 0.4g of formaldehyde and 0.1g of sulfuric acid were added to the obtained solution, and sufficiently stirred until uniformly mixed, to obtain a coating solution. Uniformly brushing the coating solution on one surface of a polypropylene porous film, then placing the polypropylene porous film in a drying oven, and drying for 12min at 60 ℃ to obtain an intelligent humidity control barrier composite film A2, wherein the thickness of a base layer is 70 microns, the pore diameter is 0.25 micron, the porosity is 50%, and the pores with the pore diameter within the range of plus or minus one order of magnitude of average pore diameter account for more than 85% of all pores; the additional layer has a thickness of 9 microns.
Example 3
2kg of polyethylene was stretched on a film uniaxial stretcher to form a polyethylene porous film.
6g of polyvinyl alcohol A were added to 100mL of distilled water, and sufficiently stirred until completely dissolved. Then 0.8g of calcium chloride and 0.2g of nano silver are added, and the mixture is fully stirred until the mixture is uniformly mixed, so that the coating liquid is obtained. Uniformly brushing the coating solution on two sides of a polyethylene porous film, then placing the polyethylene porous film in a drying oven, drying for 8min at 80 ℃ to obtain a dried film, uniformly brushing 10mL of aqueous solution containing 0.2g of formaldehyde and 0.1g of sulfuric acid on two sides of the dried film, and drying for 8min at 80 ℃ to obtain an intelligent humidity-controlling barrier composite film A3, wherein the thickness of a base layer is 75 micrometers, the pore diameter is 0.18 micrometers, the porosity is 42%, and pores with the pore diameter within the range of plus or minus one order of magnitude of average pore diameter account for more than 75% of all pores; the additional layer has a thickness of 9 microns.
Example 4
A film was prepared according to the same method as in example 1, except that glutaraldehyde and sulfuric acid were not contained in the coating solution, to obtain an intelligent moisture control barrier composite film a 4.
Example 5
Adding 6.5g of polyvinyl alcohol B into 100mL of distilled water, fully dissolving, adding 1g of sodium sulfate, 0.2g of nano zinc oxide, 0.3g of glutaraldehyde and 0.1g of sulfuric acid, and fully stirring until the mixture is uniformly mixed to obtain a coating solution. Uniformly brushing the coating solution on one surface of a polypropylene porous film, then placing the polypropylene porous film in a drying oven, and drying for 10min at 70 ℃ to obtain an intelligent humidity control film A5, wherein the thickness of a base layer is 70 micrometers, the pore diameter is 0.25 micrometers, the porosity is 50%, and pores with the pore diameter within the range of plus or minus one order of magnitude of average pore diameter account for more than 85% of all pores; the additional layer has a thickness of 10 microns.
Comparative example 3
A film was prepared in the same manner as in example 5, except that sodium sulfate was replaced with an equal weight of alumina to give a film D3.
Example 6
A film was prepared in the same manner as in example 2, except that formaldehyde was replaced with glyoxal in an equal weight to obtain an intelligent humidity-controlling film a 6.
Example 7
2kg of polystyrene was stretched on a film uniaxial stretcher to obtain a polystyrene porous film.
Adding 6.5g of polyvinyl alcohol B into 100mL of distilled water, fully dissolving, adding 1g of lithium chloride, 0.2g of nano zinc oxide, 0.3g of glutaraldehyde and 0.1g of sulfuric acid, and fully stirring until the mixture is uniformly mixed to obtain a coating solution. Uniformly brushing the coating solution on one surface of a polystyrene porous film, then placing the polystyrene porous film in a drying oven, and drying the polystyrene porous film for 10min at 70 ℃ to obtain an intelligent humidity control film A7, wherein the thickness of a base layer is 82 microns, the pore diameter is 0.15 micron, the porosity is 35%, and the pores with the pore diameter within the range of plus or minus one order of magnitude of average pore diameter account for more than 80% of all pores; the additional layer has a thickness of 10 microns.
Example 8
A film was prepared in the same manner as in example 2, except that the polyethylene terephthalate porous film was used as the base layer in an equal weight, to obtain an intelligent moisture control film A8.
Test example
The above films were subjected to a water vapor transmission rate test according to GB/T1037-1988, and the water vapor transmission rate per square meter of film per day (g/m) was obtained under test conditions of a test temperature of 25 ℃ and a transmission surface humidity of 50% and 90%, respectively2Day), data results are shown in table 1.
The gas barrier performance of the film is detected according to GB/T19789-3·cm/(cm2·s·Pa)]The data results are shown in table 1.
Table 1: test results of moisture permeability and gas barrier property of film
| Serial number | Moisture permeability (50% RH) | Moisture permeability (90% RH) | Gas barrier property (O)2) |
| A1 | 140 | 1573 | 4.4×10-5 |
| D1 | 31 | 320 | 1.8×10-5 |
| D2 | 8 | 13 | 4.1×10-6 |
| A2 | 128 | 1470 | 4.5×10-5 |
| A3 | 115 | 1421 | 4.6×10-5 |
| A4 | 153 | 1630 | 2.5×10-4 |
| A5 | 122 | 1528 | 4.8×10-5 |
| D3 | 95 | 1273 | 4.7×10-5 |
| A6 | 119 | 1353 | 4.9×10-5 |
| A7 | 127 | 1499 | 4.5×10-5 |
| A8 | 109 | 1355 | 5.0×10-5 |
As can be seen from table 1, the intelligent moisture control barrier composite film of the present invention has good oxygen barrier property and intelligent moisture control capability, i.e., when the humidity is low, the moisture permeability of the intelligent moisture control barrier composite film is reduced, the intelligent moisture control barrier composite film has moisture retention capability, and the humidity of fruits and vegetables can be maintained; on the contrary, when the humidity is higher, the moisture permeability of the intelligent moisture-control barrier composite film is improved, and the intelligent moisture-control barrier composite film has strong moisture-removing capacity, so that the fruit and vegetable can be prevented from dewing and festering.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (16)
1. An intelligent humidity control barrier composite film comprises a base layer and additional layers, wherein the additional layers are positioned on one side or two sides of the base layer; wherein,
the base layer is a porous film and is made of at least one of polyethylene, polypropylene, polystyrene, polyethylene terephthalate and polycaprolactam;
the additional layer is a compact film, and the material of the additional layer contains polyvinyl alcohol and metal salt, and optional cross-linking agent and/or antibacterial agent.
2. The intelligent moisture control barrier composite film of claim 1, wherein the porous film has a pore size of 0.02-10 microns, preferably 0.05-5 microns; the porosity is 30-80%, preferably 40-70%; pores with a pore diameter within plus or minus one order of magnitude of the average pore diameter account for more than 50% of the total pores, preferably more than 80% of the total pores.
3. The intelligent moisture control barrier composite film of claim 1, wherein the polyethylene is at least one of high density polyethylene, linear low density polyethylene, and low density polyethylene; the polypropylene is at least one of homopolymerized polypropylene, random copolymerization polypropylene, block copolymerization polypropylene and impact copolymerization polypropylene.
4. The intelligent moisture control barrier composite film of claim 1, wherein the polyvinyl alcohol is present in an amount of 50 to 99 wt%, preferably 66 to 98 wt%, and the metal salt is present in an amount of 1 to 50 wt%, preferably 2 to 34 wt%, based on the total weight of the additional layer.
5. The intelligent humidity control barrier composite film according to claim 1, wherein the weight average molecular weight of the polyvinyl alcohol is 10000-500000, preferably 20000-200000; the alcoholysis degree is 70-100%, preferably 88-99%.
6. The intelligent moisture control barrier composite film of claim 1, wherein the metal salt is a soluble sulfate and/or a soluble halide salt, preferably at least one of sodium sulfate, calcium chloride, lithium chloride, cesium fluoride, lithium bromide and lithium fluoride, and further preferably at least one of sodium sulfate, calcium chloride, lithium chloride and lithium fluoride.
7. The intelligent moisture control barrier composite film of any one of claims 1 to 6, wherein the crosslinker is present in an amount of 0 to 10 wt%, preferably 0.1 to 7 wt%, based on the total weight of the additional layer.
8. The intelligent moisture control barrier composite film of any one of claims 1-6, wherein the cross-linking agent is at least one of formaldehyde, glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, maleic acid, maleic anhydride, and sulfuric acid, preferably at least one of formaldehyde, glutaraldehyde, and sulfuric acid.
9. The intelligent moisture control barrier composite film of any one of claims 1-6, wherein the antimicrobial agent is present in an amount of 0-20 wt%, preferably 0.1-10 wt%, based on the total weight of the additional layer.
10. The intelligent moisture control barrier composite film of any one of claims 1-6, wherein the antibacterial agent is at least one of nano zinc oxide, nano titanium oxide, nano silver, nano copper, sericin, quaternary ammonium salt, methyl hydroxybenzoate, potassium sorbate and chitosan, preferably at least one of nano zinc oxide, nano silver and quaternary ammonium salt.
11. The intelligent moisture control barrier composite film of any one of claims 1-6, wherein the base layer has a thickness of 5-1000 microns, preferably 10-100 microns; the thickness of the additional layer is 0.5 to 100 microns, preferably 2 to 20 microns.
12. A preparation method of an intelligent humidity control barrier composite film comprises the following steps:
(1) fully dissolving or dispersing the components of the additional layer of the intelligent humidity control barrier composite film according to any one of claims 1 to 11 in water to prepare a solution or dispersion;
(2) applying the solution or dispersion obtained in step (1) to one or both sides of the base layer of the intelligent moisture control barrier composite film according to any one of claims 1-11; and drying to obtain the intelligent humidity control barrier composite film.
13. The production method according to claim 12, wherein the solution or dispersion in step (1) has a mass concentration of 0.5% to 30%, preferably 1% to 10%.
14. The preparation method according to claim 12, wherein the temperature of the drying in the step (2) is 50 ℃ to 100 ℃, preferably 60 ℃ to 90 ℃.
15. The preparation method according to any one of claims 12 to 14, wherein a cross-linking agent is prepared into a solution or a dispersion liquid separately, the solution or the dispersion liquid containing the cross-linking agent is coated on one side or two sides of the dried film in the step (2), and the dried film is dried again to obtain the intelligent humidity control barrier composite film; the mass concentration of the solution or dispersion containing the crosslinking agent is preferably 0.5% to 10%, and more preferably 1% to 5%.
16. Use of the intelligent moisture control barrier composite film according to any one of claims 1 to 11 and/or the intelligent moisture control barrier composite film prepared by the preparation method according to any one of claims 12 to 15 in fresh-keeping packaging of vegetables and fruits.
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| CN113831585A (en) * | 2020-06-08 | 2021-12-24 | 中国石油化工股份有限公司 | Humidity control barrier film and preparation method and application thereof |
| CN113831585B (en) * | 2020-06-08 | 2023-07-21 | 中国石油化工股份有限公司 | Moisture-control barrier film and preparation method and application thereof |
| CN114426699A (en) * | 2020-09-24 | 2022-05-03 | 中国石油化工股份有限公司 | Sandwich type air-blocking moisture-permeable composite film and preparation method and application thereof |
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Application publication date: 20191008 |