CN117304594A - PE (polyethylene) moisture absorption film, preparation method, packaging composite film and cold aluminum - Google Patents

PE (polyethylene) moisture absorption film, preparation method, packaging composite film and cold aluminum Download PDF

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Publication number
CN117304594A
CN117304594A CN202311228150.3A CN202311228150A CN117304594A CN 117304594 A CN117304594 A CN 117304594A CN 202311228150 A CN202311228150 A CN 202311228150A CN 117304594 A CN117304594 A CN 117304594A
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parts
moisture
titanium dioxide
nano titanium
layer
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Inventor
张华江
袁代群
朱欣星
孙碧颖
姜全刚
张娟
周小又
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Sichuan Huili Industrial Co Ltd
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Sichuan Huili Industrial Co Ltd
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Priority to CN202311228150.3A priority Critical patent/CN117304594A/en
Publication of CN117304594A publication Critical patent/CN117304594A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • 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
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

Abstract

The invention discloses a PE (polyethylene) moisture absorption film, a preparation method, a packaging composite film and cold aluminum, wherein the PE moisture absorption film comprises the following components in parts by weight: 100-110 parts of polyethylene resin, 30-40 parts of polyolefin resin, 10-15 parts of mesoporous modified nano titanium dioxide, 8-10 parts of calcium oxide, 5-8 parts of mannitol, 8-10 parts of tertiary butanol, 2-3 parts of chitosan and 5-6 parts of L-cysteine, wherein the mesoporous modified nano titanium dioxide is nano titanium dioxide with micro-nano mesopores on the surface, and the surface of the nano titanium dioxide is activated and modified by a methanesulfonic acid solution. The invention can greatly improve the hygroscopicity and the capability of blocking water from the end side surface to carry out the inner cavity of the package by improving the composition of the components of the heat-seal PE film layer, and can ensure the dryness of the inner cavity of the package.

Description

PE (polyethylene) moisture absorption film, preparation method, packaging composite film and cold aluminum
Technical Field
The invention relates to the technical field of medicine packaging materials, in particular to a PE (polyethylene) moisture absorption film, a preparation method, a packaging composite film and cold aluminum.
Background
Humidity is a common environmental index in life, and the relative humidity in the building has great influence on human health and living comfort. It has been found that when the relative humidity of the indoor air is less than 40% or greater than 65%, the breeding rate of bacteria and viruses is greatly increased, and diseases in respiratory system are easily initiated or aggravated. Along with the increasing of the living standard of people, people also pay attention to the humidity regulation and control problem.
Moisture absorbing packages are used to prevent spoilage of food and pharmaceutical products by blocking the ingress of outside moisture into the package and removing moisture from the package. At present, composite films with aluminum foil structures are commonly adopted for packaging or preventing moisture from affecting contents in industrial packages such as foods, medicines, medical devices and 5G electronics, and as aluminum has strong barrier, the possibility that oxygen and moisture enter the package from the front of the package is very small, so that the side face of the package heat sealing PE film is a main channel for moisture and oxygen to enter an internal cavity. In order to prevent deterioration of the contained food or medicine due to moisture, it is common practice to put a desiccant inside the package, which has a safety risk of reacting with the desiccant due to contact with the medicine and food; in addition, the conventional drying agent can re-emit the water after absorbing the water, so that the moisture absorption effect is reversible, and the long-term storage of the packaged medicines and foods is not facilitated.
In view of this, the present application is specifically proposed.
Disclosure of Invention
The invention aims to provide a PE hygroscopic film, a preparation method, a packaging composite film and cold aluminum, which can greatly improve the hygroscopicity and the capability of blocking water from an end side surface to a packaging cavity by improving the component composition of a heat-sealing PE film layer, and can ensure the dryness of the packaging internal cavity.
The invention is realized by the following technical scheme:
the PE moisture absorption film comprises the following components in parts by weight: 100-110 parts of polyethylene resin, 30-40 parts of polyolefin resin, 10-15 parts of mesoporous modified nano titanium dioxide, 8-10 parts of calcium oxide, 5-8 parts of mannitol, 8-10 parts of tertiary butanol, 2-3 parts of chitosan and 5-6 parts of L-cysteine.
Further, the mesoporous modified nano titanium dioxide is nano titanium dioxide with micro-nano mesopores on the surface and the surface is activated and modified by methanesulfonic acid solution.
Further, the PE moisture-absorbing film specifically comprises the following components in parts by weight: 100 parts of polyethylene resin, 30 parts of polyolefin resin, 12 parts of mesoporous modified nano titanium dioxide, 8 parts of calcium oxide, 7 parts of mannitol, 8 parts of tertiary butanol, 3 parts of chitosan and 5 parts of L-cysteine.
Further, the PE moisture-absorbing film specifically comprises the following components in parts by weight: 105 parts of polyethylene resin, 35 parts of polyolefin resin, 10 parts of mesoporous modified nano titanium dioxide, 9 parts of calcium oxide, 5 parts of mannitol, 10 parts of tertiary butanol, 2 parts of chitosan and 6 parts of L-cysteine.
Further, the PE moisture-absorbing film specifically comprises the following components in parts by weight: 1110 parts of polyethylene resin, 40 parts of polyolefin resin, 15 parts of mesoporous modified nano titanium dioxide, 10 parts of calcium oxide, 8 parts of mannitol, 9 parts of tertiary butanol, 3 parts of chitosan and 6 parts of L-cysteine.
The invention also provides a preparation method of the PE moisture-absorbing film, which comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methanesulfonic acid solution with the temperature of 85-95 ℃ for activation modification for 2-2.5h to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) Washing, drying, mixing the powder with mannitol and tert-butanol, heating to 35-40deg.C, and stirring for 15-20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) And (5) putting the moisture-absorbing film master batch into an extruder to obtain the PE moisture-absorbing film.
The PE moisture-absorbing film adopts polyethylene resin and polyolefin resin as main components of the film layer, and the polyolefin resin has excellent barrier property, and the capability of blocking oxygen and moisture entering from the end face of the film layer can be improved by being doped into the polyethylene resin.
According to the invention, mesoporous modified nano titanium dioxide and calcium oxide are added into a PE film, calcium oxide can react with moisture entering from the end face of the film to generate calcium hydroxide, so that a good moisture absorption effect is realized, moisture in an external environment is prevented from entering the package to influence medicine or food to be wetted, meanwhile, calcium oxide in the film layer can also absorb moisture in the package to ensure the dryness of medicine or food in the package, wherein the mesoporous modified nano titanium dioxide is nano titanium dioxide with micro-nano mesopores on the surface, and the surface is activated and modified by methanesulfonic acid solution, so that calcium oxide molecules are adsorbed in micropores and nanopores on the surfaces of nano titanium dioxide particles during preparation, and as the nano titanium dioxide particles have higher specific surface area, the film layer can be well dispersed, so that calcium oxide is loaded on the nano titanium dioxide particles, the uniformity of dispersing calcium oxide in the film layer can be improved, calcium oxide can be locked, and calcium oxide is prevented from being free in the film layer, and the precipitate generated by the reaction with water is prevented from covering the pores on the surfaces of the titanium dioxide particles, and the molecular volume expansion caused by the reaction can lead the film layer to deform; in addition, calcium oxide reacts with water to generate calcium hydroxide which is an irreversible chemical reaction, so that the situation that the film layer absorbs water and then releases the water into the packaging cavity can be avoided;
in addition, the surface of the nano titanium dioxide is activated by the methanesulfonic acid solution, and a large number of hydroxyl groups can be enriched on the surface of the nano titanium dioxide, so that on one hand, the adsorption capacity to calcium oxide can be improved, and on the other hand, the hydroxyl groups have good hydrophilicity, so that moisture can be adsorbed on the surface of the nano titanium dioxide particles, and the nano titanium dioxide particles and the calcium oxide can be fully reacted.
Mannitol, tertiary butanol, chitosan and L-cysteine are added into a PE film, in the film preparation process, mannitol and tertiary butanol are uniformly mixed with CaO-loaded nano titanium dioxide, so that tertiary butanol and mannitol are wrapped on the outer surface of CaO-loaded nano titanium dioxide, the coating protection effect on calcium oxide can be achieved, the calcium oxide reaction caused by excessive contact with water in the air in the preparation process is avoided, in addition, the hygroscopicity of mannitol and tertiary butanol is small, and the absorption of water and the re-emission of water in the film preparation, transportation and packaging material preparation processes can be avoided; in addition, the chitosan is added to improve the bonding firmness of the PE film when being compounded with other film layers, and the L-cysteine is sulfur-containing amino acid, has ionized sulfhydryl side chains and has hydrophilicity, so that the water entering from the end face of the film can be locked.
The invention also provides a packaging moisture absorption composite film which comprises a PET layer, an Al layer and a PE moisture absorption film layer which are sequentially arranged from outside to inside.
Further, the Al layer and the PE moisture absorption film layer are connected through an adhesive layer, and the adhesive layer contains 3,4, 5-trihydroxybenzoic acid.
According to the invention, the adhesive layer containing 3,4, 5-trihydroxybenzoic acid is used for bonding the Al layer and the PE moisture absorption film layer, and the 3,4, 5-trihydroxybenzoic acid has an antibacterial and disinfectant function and can react with oxygen to absorb the same, so that the packaging composite film has an oxygen isolation function, and the 3,4, 5-trihydroxybenzoic acid is used for an adhesive component of a medical packaging material.
The invention also provides moisture-absorbing cold aluminum for packaging, which comprises a PA layer, an Al layer and a PE moisture-absorbing film layer which are sequentially arranged from outside to inside.
Further, a PVC layer is further arranged between the Al layer and the PE moisture absorption film layer, the PVC layer is connected with the PE moisture absorption film layer through an adhesive layer, and 3,4, 5-trihydroxybenzoic acid is contained in the adhesive layer.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the PE moisture-absorbing film and the preparation method provided by the embodiment of the invention, polyethylene resin and polyolefin resin are selected as main components of the film layer, and the polyolefin resin has excellent barrier property, and the capability of blocking oxygen and moisture entering from the end face of the film layer can be improved by being doped into the polyethylene resin;
2. according to the PE moisture absorption film and the preparation method, mesoporous modified nano titanium dioxide and calcium oxide are added, calcium oxide can react with moisture entering from the end face of the film to generate calcium hydroxide, so that a good moisture absorption effect is achieved, moisture in an external environment is prevented from entering the package to influence the moisture of medicines or foods, meanwhile, the calcium oxide in the film layer can also adsorb the moisture in the package to ensure the dryness of the medicines or foods in the package, and in addition, calcium oxide reacts with water to generate calcium hydroxide to be an irreversible chemical reaction, so that the situation that the film layer absorbs the moisture and then releases the moisture into a package cavity can be avoided;
3. according to the PE moisture absorption film and the preparation method, the mesoporous modified nano titanium dioxide is the nano titanium dioxide with micro-nano mesopores on the surface, and the surface is activated and modified by the methanesulfonic acid solution, so that calcium oxide molecules are adsorbed in micropores and nanopores on the surface of nano titanium dioxide particles during preparation, and the nano titanium dioxide particles have higher specific surface area, so that the nano titanium dioxide particles can be well dispersed in film preparation, and calcium oxide is loaded on the nano titanium dioxide particles, so that the uniformity of the dispersion of the calcium oxide in the film can be improved, the calcium oxide can be locked, the calcium oxide is prevented from being 'dissociated' in the film, calcium hydroxide precipitation generated by the reaction of the calcium oxide with water is prevented from covering the mesopores on the surface of the titanium dioxide particles, and the film can be prevented from being deformed due to molecular volume expansion caused by the reaction;
4. in the preparation process of the film layer, mannitol and tertiary butanol are uniformly mixed with CaO-loaded nano titanium dioxide, so that the tertiary butanol and mannitol are wrapped on the outer surface of CaO-loaded nano titanium dioxide, the coating protection effect on calcium oxide can be achieved, the calcium oxide reaction caused by excessive contact with water in the air in the preparation process is avoided, in addition, the hygroscopicity of the mannitol and the tertiary butanol is small, and the moisture absorption and re-emission of the mannitol and the tertiary butanol in the film layer preparation, transportation and packaging material preparation processes can be avoided;
5. according to the PE moisture-absorbing film and the preparation method provided by the embodiment of the invention, the bonding firmness performance of the PE film during compounding with other film layers can be improved by adding chitosan, and the L-cysteine is sulfur-containing amino acid and has an ionized sulfhydryl side chain and hydrophilicity, so that moisture entering from the end face of the film can be locked.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: no such specific details are necessary to practice the invention. In other instances, well-known methods have not been described in detail in order to avoid obscuring the present invention.
Throughout the specification, references to "one embodiment," "an embodiment," "one example," or "an example" mean: a particular feature, structure, or characteristic described in connection with the embodiment or example is included within at least one embodiment of the invention. Thus, the appearances of the phrases "in one embodiment," "in an example," or "in an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combination and/or sub-combination in one or more embodiments or examples.
Example 1
The preparation method of the PE moisture absorption film provided by the embodiment of the invention comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution at 90 ℃ for activation modification for 2 hours to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) After cleaning and drying, mixing the powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein, 100 parts of polyethylene resin, 30 parts of polyolefin resin, 12 parts of mesoporous modified nano titanium dioxide, 8 parts of calcium oxide, 7 parts of mannitol, 8 parts of tertiary butanol, 3 parts of chitosan and 5 parts of L-cysteine.
Example 2
The preparation method of the PE moisture absorption film provided by the embodiment of the invention comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution at 90 ℃ for activation modification for 2 hours to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) After cleaning and drying, mixing the powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
105 parts of polyethylene resin, 35 parts of polyolefin resin, 10 parts of mesoporous modified nano titanium dioxide, 9 parts of calcium oxide, 5 parts of mannitol, 10 parts of tertiary butanol, 2 parts of chitosan and 6 parts of L-cysteine.
Example 3
The preparation method of the PE moisture absorption film provided by the embodiment of the invention comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution with the temperature of 95 ℃ for activation modification for 2.5 hours to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) After cleaning and drying, mixing the powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein 1110 parts of polyethylene resin, 40 parts of polyolefin resin, 15 parts of mesoporous modified nano titanium dioxide, 10 parts of calcium oxide, 8 parts of mannitol, 9 parts of tertiary butanol, 3 parts of chitosan and 6 parts of L-cysteine.
Example 4
The moisture absorption composite film for packaging provided by the embodiment of the invention comprises a PET layer, an Al layer and a PE moisture absorption film layer which are sequentially arranged from outside to inside, wherein the PET layer, the Al layer and the PE moisture absorption film layer are bonded through an adhesive, and the adhesive comprises 3,4, 5-trihydroxybenzoic acid;
the preparation method of the PE moisture absorption film layer comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution at 90 ℃ for activation modification for 2 hours to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) After cleaning and drying, mixing the powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein, 100 parts of polyethylene resin, 30 parts of polyolefin resin, 12 parts of mesoporous modified nano titanium dioxide, 8 parts of calcium oxide, 7 parts of mannitol, 8 parts of tertiary butanol, 3 parts of chitosan and 5 parts of L-cysteine.
And preparing the moisture absorption composite film into a packaged packaging material for testing.
Example 5
The moisture-absorbing cold aluminum for packaging provided by the embodiment of the invention comprises a PA layer, an Al layer, a PVC layer and a PE moisture-absorbing film layer which are sequentially arranged from outside to inside, wherein the PA layer, the Al layer, the PVC layer and the PE moisture-absorbing film layer are bonded through an adhesive, and the adhesive comprises 3,4, 5-trihydroxybenzoic acid;
the preparation method of the PE moisture absorption film layer comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution at 90 ℃ for activation modification for 2 hours to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) After cleaning and drying, mixing the powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein, 100 parts of polyethylene resin, 30 parts of polyolefin resin, 12 parts of mesoporous modified nano titanium dioxide, 8 parts of calcium oxide, 7 parts of mannitol, 8 parts of tertiary butanol, 3 parts of chitosan and 5 parts of L-cysteine.
And preparing the moisture-absorbing cold aluminum into a packaged packaging material for testing.
Comparative example 1
This comparative example provides a process for preparing a PE hygroscopic film comprising the steps of:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution at 90 ℃ for activation modification for 2 hours to obtain mesoporous modified nano titanium dioxide;
2) After cleaning and drying, mixing the powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
3) Adding the mixture prepared in the step 2) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein, 100 parts of polyethylene resin, 30 parts of polyolefin resin, 12 parts of mesoporous modified nano titanium dioxide, 7 parts of mannitol, 8 parts of tertiary butanol, 3 parts of chitosan and 5 parts of L-cysteine.
This comparative example does not contain CaO in the PE hygroscopic film on the basis of example 1.
Comparative example 2
The preparation method of the PE hygroscopic film provided by the comparative example comprises the following steps:
1) Mixing CaO powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
2) Adding the mixture prepared in the step 1) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
3) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein, 100 parts of polyethylene resin, 30 parts of polyolefin resin, 8 parts of calcium oxide, 7 parts of mannitol, 8 parts of tertiary butanol, 3 parts of chitosan and 5 parts of L-cysteine.
This comparative example was based on example 1, in which the PE hygroscopic film did not contain mesoporous modified nano titania.
Comparative example 3
The preparation method of the PE hygroscopic film provided by the comparative example comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution at 90 ℃ for activation modification for 2 hours to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) After cleaning and drying, adding the powder into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
4) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein, polyethylene resin 100 parts, polyolefin resin 30 parts, mesoporous modified nano titanium dioxide 12 parts, calcium oxide 8 parts, chitosan 3 parts and L-cysteine 5 parts.
This comparative example does not contain mannitol and t-butanol in the PE hygroscopic film on the basis of example 1.
Comparative example 4
The preparation method of the PE hygroscopic film provided by the comparative example comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution at 90 ℃ for activation modification for 2 hours to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) After cleaning and drying, mixing the powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein, 100 parts of polyethylene resin, 30 parts of polyolefin resin, 12 parts of mesoporous modified nano titanium dioxide, 8 parts of calcium oxide, 7 parts of mannitol, 8 parts of tertiary butanol and 5 parts of L-cysteine.
This comparative example was based on example 1, in which the PE hygroscopic film did not contain chitosan.
Comparative example 5
The preparation method of the PE hygroscopic film provided by the comparative example comprises the following steps:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methane sulfonic acid solution at 90 ℃ for activation modification for 2 hours to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) After cleaning and drying, mixing the powder with mannitol and tertiary butanol, heating to 40 ℃ and stirring for 20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding chitosan, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) Putting the moisture-absorbing film master batch into an extruder to obtain a PE moisture-absorbing film;
wherein, polyethylene resin 100 parts, polyolefin resin 30 parts, mesoporous modified nano titanium dioxide 12 parts, calcium oxide 8 parts, mannitol 7 parts, tertiary butanol 8 parts and chitosan 3 parts.
This comparative example does not contain L-cysteine in the PE hygroscopic film on the basis of example 1.
Comparative example 6
The comparative example is a common PE film.
Comparative example 7
This comparative example does not include 3,4, 5-trihydroxybenzoic acid in the adhesive based on example 4.
Comparative example 8
This comparative example does not include 3,4, 5-trihydroxybenzoic acid in the adhesive based on example 5.
Comparative example 9
This comparative example is based on example 4, and the PE film is a general PE film.
The film bodies of examples 1-3, comparative examples 1-6, and the composite films of examples 4-5 and comparative examples 7-9 were subjected to moisture absorption performance test with cold aluminum. Normal temperature test conditions: the temperature is 25 ℃ and the humidity is 50%; high temperature and high humidity test conditions: the temperature is 40 ℃ and the humidity is 75%.
TABLE 1
As can be seen from table 1 above, the hygroscopic PE films of examples 1 to 3 of the present invention have good hygroscopic properties, and the packaging hygroscopic composite film and hygroscopic cold aluminum prepared therefrom also have good hygroscopic and moisture and oxygen permeation barrier abilities.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. The PE moisture absorption film is characterized by comprising the following components in parts by weight: 100-110 parts of polyethylene resin, 30-40 parts of polyolefin resin, 10-15 parts of mesoporous modified nano titanium dioxide, 8-10 parts of calcium oxide, 5-8 parts of mannitol, 8-10 parts of tertiary butanol, 2-3 parts of chitosan and 5-6 parts of L-cysteine.
2. The PE moisture absorbing film according to claim 1, wherein the mesoporous modified nano titanium dioxide is nano titanium dioxide with micro-nano mesopores on the surface and the surface is activated and modified by a methanesulfonic acid solution.
3. The PE moisture-absorbing film according to claim 1, which is characterized by comprising the following components in parts by weight: 100 parts of polyethylene resin, 30 parts of polyolefin resin, 12 parts of mesoporous modified nano titanium dioxide, 8 parts of calcium oxide, 7 parts of mannitol, 8 parts of tertiary butanol, 3 parts of chitosan and 5 parts of L-cysteine.
4. The PE moisture-absorbing film according to claim 1, which is characterized by comprising the following components in parts by weight: 105 parts of polyethylene resin, 35 parts of polyolefin resin, 10 parts of mesoporous modified nano titanium dioxide, 9 parts of calcium oxide, 5 parts of mannitol, 10 parts of tertiary butanol, 2 parts of chitosan and 6 parts of L-cysteine.
5. The PE moisture-absorbing film according to claim 1, which is characterized by comprising the following components in parts by weight: 1110 parts of polyethylene resin, 40 parts of polyolefin resin, 15 parts of mesoporous modified nano titanium dioxide, 10 parts of calcium oxide, 8 parts of mannitol, 9 parts of tertiary butanol, 3 parts of chitosan and 6 parts of L-cysteine.
6. A process for the preparation of a PE absorbent film according to any one of claims 1 to 3, characterized in that it comprises the steps of:
1) Placing nano titanium dioxide powder with micro-nano mesopores on the surface into 2% methanesulfonic acid solution with the temperature of 85-95 ℃ for activation modification for 2-2.5h to obtain mesoporous modified nano titanium dioxide;
2) Putting mesoporous modified nano titanium dioxide into ethanol solution, then adding calcium oxide powder, and fully stirring to enable CaO to be loaded and adsorbed in micro-nano mesopores on the surface of the titanium dioxide;
3) Washing, drying, mixing the powder with mannitol and tert-butanol, heating to 35-40deg.C, and stirring for 15-20min;
4) Adding the mixture prepared in the step 3) into a screw machine, sequentially adding chitosan, L-cysteine, polyethylene resin and polyolefin resin, and mixing and granulating to obtain a moisture-absorbing film master batch;
5) And (5) putting the moisture-absorbing film master batch into an extruder to obtain the PE moisture-absorbing film.
7. A moisture-absorbing composite film for packaging, which is characterized by comprising a PET layer, an Al layer and a PE moisture-absorbing film layer as claimed in any one of claims 1 to 3, which are sequentially arranged from outside to inside.
8. The composite film according to claim 7, wherein the Al layer and the PE moisture-absorbing film layer are connected by an adhesive layer, and the adhesive layer contains 3,4, 5-trihydroxybenzoic acid.
9. A moisture-absorbing cold aluminum for packaging, which is characterized by comprising a PA layer, an Al layer and a PE moisture-absorbing film layer as claimed in any one of claims 1 to 3, which are sequentially arranged from outside to inside.
10. The absorbent cold aluminum for packaging according to claim 9, wherein a PVC layer is further provided between the Al layer and the PE absorbent film layer.
CN202311228150.3A 2023-09-22 2023-09-22 PE (polyethylene) moisture absorption film, preparation method, packaging composite film and cold aluminum Pending CN117304594A (en)

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