CN113321834B - Intelligent humidity-control barrier composite film and preparation method and application thereof - Google Patents

Intelligent humidity-control barrier composite film and preparation method and application thereof Download PDF

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Publication number
CN113321834B
CN113321834B CN202010088535.4A CN202010088535A CN113321834B CN 113321834 B CN113321834 B CN 113321834B CN 202010088535 A CN202010088535 A CN 202010088535A CN 113321834 B CN113321834 B CN 113321834B
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composite film
barrier composite
control barrier
intelligent
additional layer
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CN113321834A (en
Inventor
张杨
宋建会
郑萃
唐毓婧
姚雪容
潘国元
刘轶群
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154—Organic compounds; Microorganisms; Enzymes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/157—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B65D65/42—Applications of coated or impregnated materials
    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/26—Cellulose ethers
    • C09D101/28—Alkyl ethers
    • C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
    • 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
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • 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
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/04—Alginic acid; Derivatives thereof
    • 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
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/04—Alginic acid; Derivatives thereof
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/00—Specific properties of additives
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Abstract

The invention relates to an intelligent humidity control barrier composite film and a preparation method and application thereof. The intelligent humidity control barrier composite film comprises a base layer and an additional layer, wherein the additional layer is positioned on one side of the base layer; wherein, the base layer is a porous film made of at least one of polyethylene, polypropylene, polystyrene, polyethylene terephthalate and polycaprolactam; the additional layer comprises a cross-linked polymer of a polyhydroxypolymer and an acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer, and further comprises an optional antimicrobial agent. 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.

Description

Intelligent humidity control barrier composite film and preparation method and application thereof
Technical Field
The invention relates to the field of functional films, in particular 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 rises 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 condense water on the surfaces of fruits and vegetables, cause fungi to grow, and accelerate the 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. CN104029449A 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, the porous substrate of which is preferably polytetrafluoroethylene, which is expensive, and the high moisture permeability of the film 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 elimination capability under the condition of high humidity and has oxygen barrier property. The invention further provides a preparation method of the film, and the method has the advantages of simple process and low cost. Therefore, the film provided by the invention is particularly suitable for being applied to fresh-keeping packaging of vegetables and fruits.
One of the purposes of the invention is to provide an intelligent humidity control barrier composite film, which comprises a base layer and an additional layer, wherein the additional layer is positioned on one side of the base layer; wherein the base layer is a porous film;
the additional layer comprises a cross-linked polymer of a polyhydroxypolymer and an acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.
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 (thin) film. The concept and terminology category of porous and dense (thin) membranes is well known to those skilled in the art. A dense film as an additional layer can be produced by applying a solution containing the additional layer components to the surface of the base layer and drying.
Wherein the base layer can be a single layer or a two-layer composite structure, and the single-layer structure is preferred. The base layer is a porous film made of at least one of polyethylene, polypropylene, polystyrene, polyethylene terephthalate and polycaprolactam, preferably polyethylene and/or polypropylene.
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.
The additional layer is a compact film and is formed by crosslinking a polybasic hydroxyl polymer and an acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, and in addition, the additional layer compact film layer also contains an optional antibacterial agent.
According to the present invention, the mass ratio of the polyhydric hydroxyl polymer to the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer is (1: 20) to (20: 1), and preferably (1: 10) to (10: 1).
According to the invention, the polyhydric hydroxyl-containing polymer is at least one of polyvinyl alcohol, chitosan quaternary ammonium salt, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, gum arabic, sodium alginate and polyether polyol, and preferably gum arabic or polyvinyl alcohol.
According to the invention, the weight average molecular weight of the polyhydric hydroxyl polymer is 10000-500000, preferably 20000-200000.
According to the invention, the addition of the antibacterial agent can enable the intelligent humidity control film to have antibacterial performance.
The antibacterial agent can be selected from antibacterial agents commonly used in the art, 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 more preferably at least one of nano zinc oxide, nano silver and quaternary ammonium salt, such as cetylpyridinium chloride.
The content of the antibacterial agent is 0.1-5 wt%, preferably 0.5-2 wt% based on the weight of the additional layer.
The above-mentioned preferred components can give a film superior in moisture permeability and gas barrier properties.
In the invention, the aperture of the porous film of the base layer is preferably 0.02-10 microns, more preferably 0.05-5 microns, and even more preferably 0.1-2 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.
According to the invention, the thicknesses of the base layer and the additional layer can be determined according to needs, generally, the thickness of the base layer can be 5-1000 micrometers, preferably 10-100 micrometers, and further preferably 60-90 micrometers; the thickness of the additional layer can be 0.5-100 micrometers, and preferably 2-20 micrometers.
The invention also aims to provide a preparation method of the intelligent humidity control barrier composite film, which comprises the following steps:
(1) dissolving or dispersing the components of the additional layer into a solvent to prepare a solution or a dispersion liquid;
(2) and (2) attaching the solution or dispersion liquid obtained in the step (1) to one surface of the base layer, and heating and drying to obtain the intelligent humidity control barrier composite film.
The base porous film may be commercially available as a single layer, or may be prepared by a conventional film-forming method in the prior art. For example, the film of the support layer is obtained by stretching polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polycaprolactam or a combination thereof using a film stretching machine of the prior art by a general film stretching process. The film stretcher may be a unidirectional or bidirectional stretcher.
When the base layer is two layers, the two layers may be made of different materials, such as a porous film formed by compounding polyethylene and polypropylene. The base layer can be obtained commercially or can be prepared by a conventional film-making method of a composite film in the prior art.
The additional layer is formed by crosslinking a polyhydroxy polymer and an acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer. The mass ratio of the polyhydric hydroxyl polymer to the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer is (1: 20) - (20: 1), and preferably (1: 10) - (10: 1).
The solvent used in step (1) may be a conventional solvent, and preferably distilled water.
The solution or dispersion obtained in step (1) may be applied to the substrate using any conventional coating method, including but not limited to: brushing, curtain coating and spraying.
According to the invention, in the solution or dispersion liquid in the step (1), the mass concentration of the polyhydric hydroxyl polymer is 0.5-10%, preferably 1-5%; the mass concentration of the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer is 0.05-5%, preferably 0.1-2.5%; and/or the presence of a gas in the gas,
in the step (1), the additional layer component comprises an antibacterial agent, and the mass concentration of the antibacterial agent is 0.005-0.5%, preferably 0.01-0.1%.
According to the invention, the drying temperature in the step (2) can be 50-100 ℃, and preferably 60-90 ℃. 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, it is preferably 1-60 min, and more preferably 3-30 min.
The invention also 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 inventor finds that the gas barrier performance of the film is improved by utilizing the esterification reaction between hydroxyl in a multi-hydroxyl polymer molecular chain and carboxyl in an acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer molecular chain to form a cross-linked structure; on the other hand, the introduction of sulfonic acid groups in the additional layer can increase the hygroscopicity of the film, thereby increasing the moisture permeability of the film.
When the humidity of the environment is low, molecular chains of the functional layer of the composite film are arranged tightly, so that moisture is prevented from permeating; when the environment humidity is high, the free volume among molecular chains is increased, and the moisture transmission capacity is increased; therefore, the moisture control barrier composite film has intelligent moisture 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 barrier composite 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.
Polyvinyl alcohol (PVA 124), weight average molecular weight 105000, and alcoholysis degree 99%.
Gum arabic, carbofuran.
Hydroxypropyl methylcellulose, carbofuran.
Hydroxyethyl methylcellulose, carbofuran.
Chitosan, carbofuran.
Sodium alginate, carbofuran.
Acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer, Shandong Tai and Water treatment science and technology Co.
99.5 percent of nano zinc oxide and carbofuran, and the grain diameter is 10-30 nm.
Film uniaxial stretcher, general, Guangzhou, MESI-LL.
Example 1
2kg of polypropylene was stretched on a film uniaxial stretcher to form a polypropylene porous film.
4g of gum arabic and 1g of acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer were added to 94.9g of distilled water and sufficiently dissolved. 0.1g of nano zinc oxide is added into the obtained solution, and the solution is fully stirred until the nano zinc oxide and the nano zinc oxide are uniformly mixed, so that the coating solution is obtained. Uniformly brushing the coating solution on one surface of a polypropylene porous film, then placing the film in a drying oven, and drying the film for 15min at 90 ℃ to obtain an intelligent humidity-controlling barrier composite film A1, wherein the thickness of a base layer is 70 microns, the pore diameter is 0.25 micron, the porosity is 40 percent, and the pores with the pore diameters within the range of plus or minus one order of magnitude of the average pore diameter account for more than 85 percent of all pores; the additional layer has a thickness of 16 microns.
Example 2
2kg of polypropylene was stretched on a film uniaxial stretcher to form a polypropylene porous film.
9g of polyvinyl alcohol and 0.9g of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer were added to 90g of distilled water and sufficiently dissolved. 0.1g of nano zinc oxide is added into the obtained solution, and the solution is fully stirred until the nano zinc oxide and the nano zinc oxide are uniformly mixed to obtain the 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 the polypropylene porous film for 30min 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 the average pore diameter account for more than 85% of all the pores; the additional layer has a thickness of 20 microns.
Example 3
2kg of polyethylene was stretched on a film uniaxial stretcher to obtain a polyethylene porous film.
0.2g of chitosan and 2g of acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer were added to 97.7g of distilled water and sufficiently dissolved. 0.1g of nano zinc oxide is added into the obtained solution, and the solution is fully stirred until the nano zinc oxide and the nano zinc oxide are uniformly mixed, so that the coating solution is obtained. 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 20min at 70 ℃ to obtain an intelligent humidity control barrier composite film A3, wherein the thickness of a base layer is 70 microns, the pore diameter is 0.25 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 85% of all pores; the additional layer has a thickness of 10 microns.
Example 4
A film was prepared according to the same method as in example 1, except that hydroxypropylmethylcellulose was used instead of gum arabic, to obtain a smart moisture-controlling barrier composite film a 4.
Example 5
A film was prepared according to the same method as in example 1, except that hydroxyethyl methylcellulose was used instead of gum arabic, to obtain an intelligent moisture-control barrier composite film a 5.
Example 6
A film was prepared according to the same method as in example 1, except that sodium alginate was used instead of gum arabic, to obtain an intelligent moisture-controlling barrier composite film a 6.
Comparative example 1
4g of gum arabic was dissolved in 95.9g of distilled water, and sufficiently dissolved. 0.1g of nano zinc oxide is added into the obtained solution, and the solution is fully stirred until the nano zinc oxide and the nano zinc oxide are uniformly mixed to obtain the 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 15min at 90 ℃ 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 40%, 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 14 microns.
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%, respectively 2 Day), data results are shown in table 1.
The gas barrier performance of the film is detected according to GB/T19789- 3 ·cm/(cm 2 ·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 538.7 1450.9 2.9×10 -6
A2 482.6 1289.0 1.7×10 -6
A3 565.9 1489.3 4.5×10 -6
A4 512.9 1398.5 6.5×10 -6
A5 500.6 1400.0 6.8×10 -6
A6 580.5 1535.0 2.8×10 -5
D1 325.6 976.2 8.7×10 -3
As can be seen from Table 1, the cross-linked structure is formed by the esterification reaction of the hydroxyl in the molecular chain of the multi-hydroxyl polymer and the carboxyl in the molecular chain of the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, so that the gas barrier property of the film is improved; on the other hand, the introduction of sulfonic acid groups in the additional layer can increase the hygroscopicity of the film, thereby increasing the moisture permeability of the film. In addition, the intelligent moisture control barrier composite film has good intelligent moisture control capability, namely when the humidity is lower, the moisture permeability of the intelligent moisture control barrier composite film is reduced, the intelligent moisture control barrier composite film has the moisture retention capability, and the humidity of fruits and vegetables can be kept; 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 (19)

1. An intelligent humidity control barrier composite film, which is characterized in that the composite film comprises a base layer and an additional layer, wherein the additional layer is positioned on one side of the base layer,
the base layer is a porous film;
the additional layer comprises a cross-linked polymer of a polyhydroxypolymer and an acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.
2. The intelligent moisture control barrier composite film of claim 1, wherein:
the base layer is made of at least one of polyethylene, polypropylene, polystyrene, polyethylene terephthalate and polycaprolactam; and/or the presence of a gas in the gas,
the multi-hydroxyl polymer is at least one of polyvinyl alcohol, chitosan quaternary ammonium salt, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, gum arabic, sodium alginate and polyether polyol.
3. The intelligent moisture control barrier composite film of claim 1, wherein:
the weight average molecular weight of the multi-hydroxyl polymer is 10000-500000.
4. The intelligent moisture control barrier composite film of claim 3, wherein:
the weight average molecular weight of the multi-hydroxyl polymer is 20000-200000.
5. The intelligent moisture control barrier composite film of claim 1, wherein:
the additional layer comprises an antibacterial agent, and the content of the antibacterial agent is 0.1-5 wt% of the weight of the additional layer.
6. The intelligent moisture control barrier composite film of claim 5, wherein:
the content of the antibacterial agent is 0.5-2 wt% based on the weight of the additional layer.
7. The intelligent moisture control barrier composite film of claim 5, 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.
8. The intelligent moisture control barrier composite film of claim 1, wherein:
the thickness of the base layer is 5-1000 microns; the thickness of the additional layer is 0.5-100 microns.
9. The intelligent moisture control barrier composite film of claim 8, wherein:
the thickness of the base layer is 10-100 microns; the thickness of the additional layer is 2-20 micrometers.
10. The intelligent moisture control barrier composite film of claim 1, wherein:
the aperture of the porous film of the base layer is 0.02-10 microns; the porosity is 30% -80%; pores with a pore diameter within plus or minus one order of magnitude of the average pore diameter account for more than 50% of all pores.
11. The intelligent moisture control barrier composite film of claim 10, wherein:
the aperture of the base porous film is 0.05-5 microns; the porosity is 40% -70%; the pores with the pore diameter within plus or minus one order of magnitude of the average pore diameter account for more than 80 percent of all the pores.
12. A method for preparing an intelligent moisture control barrier composite film according to any one of claims 1 to 11, which is characterized by comprising the following steps:
(1) dissolving or dispersing the components of the additional layer into a solvent to prepare a solution or a dispersion liquid;
(2) and (2) attaching the solution or dispersion liquid obtained in the step (1) to one surface of the base layer, and heating and drying to obtain the intelligent humidity control barrier composite film.
13. The preparation method of the intelligent humidity control barrier composite film according to claim 12, wherein:
in the step (1), the mass ratio of the polyhydric hydroxyl polymer to the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer is (1: 20) - (20: 1).
14. The preparation method of the intelligent humidity control barrier composite film according to claim 13, wherein:
the mass ratio of the polyhydric hydroxyl polymer to the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer is (1: 10) - (10: 1).
15. The preparation method of the intelligent humidity control barrier composite film according to claim 12, wherein:
in the solution or dispersion liquid in the step (1), the mass concentration of the polyhydric hydroxyl polymer is 0.5-10%; the mass concentration of the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer is 0.05-5%; and/or the presence of a gas in the gas,
in the step (1), the additional layer component comprises an antibacterial agent, and the mass concentration of the antibacterial agent is 0.005-0.5%.
16. The preparation method of the intelligent humidity control barrier composite film according to claim 15, wherein:
in the solution or dispersion liquid in the step (1), the mass concentration of the polyhydric hydroxyl polymer is 1-5%; the mass concentration of the acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer is 0.1-2.5%; and/or the presence of a gas in the atmosphere,
the mass concentration of the antibacterial agent is 0.01-0.1%.
17. The preparation method of the intelligent humidity control barrier composite film according to claim 12, wherein:
in the step (2), the drying temperature is 50-100 ℃; the drying time is 1-60 min.
18. The preparation method of the intelligent humidity control barrier composite film according to claim 17, wherein:
in the step (2), the drying temperature is 60-90 ℃; the drying time is 3-30 min.
19. Use of the intelligent moisture control barrier composite film of any one of claims 1 to 11 or the intelligent moisture control barrier composite film prepared by the preparation method of any one of claims 12 to 18 in fresh-keeping packaging of vegetables and fruits.
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JP2002206031A (en) * 2001-01-10 2002-07-26 Mitsui Chemicals Inc Gas barrier film and method for producing the same
CN102481597A (en) * 2009-08-24 2012-05-30 巴斯夫欧洲公司 Use of polyelectrolyte complexes for producing polymer films having oxygen barrier properties
CN105968405A (en) * 2016-05-30 2016-09-28 天津工业大学 Antimicrobial moisturizing degradable porous gel preservative film and preparation method and application thereof

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JP2002206031A (en) * 2001-01-10 2002-07-26 Mitsui Chemicals Inc Gas barrier film and method for producing the same
CN102481597A (en) * 2009-08-24 2012-05-30 巴斯夫欧洲公司 Use of polyelectrolyte complexes for producing polymer films having oxygen barrier properties
CN105968405A (en) * 2016-05-30 2016-09-28 天津工业大学 Antimicrobial moisturizing degradable porous gel preservative film and preparation method and application thereof

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