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CN116080191A - High-barrier packaging material and preparation method thereof - Google Patents

High-barrier packaging material and preparation method thereof Download PDF

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Publication number
CN116080191A
CN116080191A CN202310117221.6A CN202310117221A CN116080191A CN 116080191 A CN116080191 A CN 116080191A CN 202310117221 A CN202310117221 A CN 202310117221A CN 116080191 A CN116080191 A CN 116080191A
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China
Prior art keywords
packaging material
parts
barrier
layer
bonding layer
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Granted
Application number
CN202310117221.6A
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Chinese (zh)
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CN116080191B (en
Inventor
林伟强
张道静
陶加祥
高勇
金伟浩
朱杭丽
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Zhejiang Pengyuan New Material Technology Group Co ltd
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Zhejiang Pengyuan New Material Technology Group Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00Producing flat articles, e.g. films or sheets
    • B29D7/01Films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered 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
    • B32B15/08Layered 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
    • B32B15/082Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered 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
    • B32B15/08Layered 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
    • B32B15/085Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/40Applications of laminates for particular packaging purposes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02Synthetic macromolecular fibres
    • B32B2262/0253Polyolefin fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • B32B2307/7242Non-permeable
    • B32B2307/7244Oxygen barrier
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/726Permeability to liquids, absorption
    • B32B2307/7265Non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised 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
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised 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
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/346Clay
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/16Solid spheres
    • C08K7/18Solid spheres inorganic

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

The application discloses high separation packaging material and preparation method thereof, this packaging material is including aluminium foil, PE adhesive linkage, barrier layer, PE adhesive linkage, substrate and PE membrane that compound in proper order, the aluminium foil passes through the adhesive linkage and weaves cloth complex, the barrier layer includes the raw materials of following parts by mass: polyethylene: 100 parts; ethylene-vinyl alcohol copolymer: 20-30 parts; lamellar nanomaterial: 10-20 parts; spherical alumina particles: 5-10 parts; dispersion modifier: 1-3 parts; acetylated chitosan nanofibers: 10-20 parts. The packaging material can effectively improve the blocking capability to oxygen and moisture on the premise of keeping good tensile property.

Description

High-barrier packaging material and preparation method thereof
Technical Field
The application relates to the field of packaging materials, in particular to a high-barrier packaging material and a preparation method thereof.
Background
The high-barrier packaging material is an aluminum-plastic packaging material and is formed by compounding aluminum foil and plastic. It has better mechanical properties such as stiffness, tensile strength, tear resistance, wear resistance and the like, and has good blocking effect on ultraviolet light, oxygen and moisture, so that the packaging material is commonly used for precisely packaging noble articles such as precise industrial equipment, medicines and the like.
The existing aluminum-plastic packaging material generally comprises an aluminum foil reflecting layer positioned on a surface layer, a PE film sealing layer positioned on an inner layer, and a plastic woven cloth base material positioned on an intermediate layer. The PE film and the plastic woven cloth base material are compounded by hot pressing, the aluminum foil reflecting layer and the plastic woven cloth base material are compounded by an adhesive, and the adhesive is usually made of polyethylene materials for convenient production.
However, the barrier capability of polyethylene materials to oxygen and moisture remains difficult to meet the packaging requirements of medical or precision equipment.
Disclosure of Invention
The application provides a high-barrier packaging material and a preparation method thereof, which can effectively improve the barrier property of an aluminum-plastic packaging material to oxygen and moisture and meet the packaging requirements of medicines and precision equipment.
In a first aspect, the application provides a high-barrier packaging material, it includes aluminium foil, PE adhesive linkage, barrier layer, PE adhesive linkage, substrate and PE membrane that compound in proper order, the aluminium foil passes through the adhesive linkage and weaves cloth complex, the barrier layer includes the raw materials of following parts by mass:
polyethylene: 100 parts;
ethylene-vinyl alcohol copolymer: 20-30 parts;
lamellar nanomaterial: 10-20 parts;
spherical alumina particles: 5-10 parts;
dispersion modifier: 1-3 parts;
acetylated chitosan nanofibers: 10-20 parts.
According to the technical scheme, the base material of the barrier layer adopts polyethylene and ethylene-vinyl alcohol with high barrier property, so that the gas and water barrier property of the adhesive layer can be effectively improved, and the sealing property is ensured. Further, the application adopts the two forms of nano filler of the lamellar nano material and the spherical alumina particles to be matched together, so that a more compact barrier layer can be formed, the diffusion path of moisture is effectively prolonged, and the moisture barrier capability is improved. In addition, the spherical alumina can reduce friction resistance and promote dispersion and tape casting extrusion of the bonding layer.
The acetylated chitosan nanofiber is added in the method, so that on one hand, the toughening and reinforcing effects can be achieved, and the reduction of toughness and tensile property of the barrier layer caused by the addition of the filler is compensated; on the other hand, the fiber form can be matched with the lamellar nano material and the spherical alumina particles to form a denser barrier layer, so that the barrier effect on oxygen and moisture is improved.
And as the molecular chain of the chitosan nanofiber contains more hydroxyl groups, the chitosan nanofiber has stronger hydrophilicity and is unfavorable for improving the water blocking capacity of the bonding layer, so that the chitosan nanofiber modified by the acetylation and the hydrophobicity is adopted, and the problem is effectively solved.
The above lamellar nano material refers to a carbon material or silicate material having lamellar structure, such as graphite, graphene, montmorillonite, bentonite.
Preferably, the substrate is PE woven cloth, PP woven cloth or PE and PP composite woven cloth.
Preferably, the PE bonding layer is a tape casting layer made of PE material, and the bonding effect is achieved by a tape casting (laminating) process.
Preferably, the D50 particle diameter of the spherical alumina particles is less than 500nm, more preferably the D50 particle diameter of the spherical alumina particles is 50 to 100nm.
Preferably, the average length of the chitosan nanofiber is 30 nm-50 nm.
Preferably, the acetylated chitosan nanofiber consists of the following components in percentage by mass: (4-6): and (2-4) reacting chitosan nanofiber, acetic anhydride and concentrated sulfuric acid.
In the acetylation modification, concentrated sulfuric acid can activate hydroxyl groups of chitosan nanofibers, an esterification reaction is carried out to obtain a sulfuric acid ester intermediate, and then acetic anhydride acyl is substituted to form acetic ester, so that the acetylation hydrophobic modification is completed.
Preferably, the concentration of the concentrated sulfuric acid is 98wt%.
The preparation method of the preferable acetylated chitosan nanofiber comprises the following steps: dispersing chitosan nano fibers in anhydrous acetic acid, and dropwise adding concentrated sulfuric acid under the conditions of heating and stirring to perform esterification reaction; then dripping acetic anhydride for acetylation reaction, filtering and separating out fiber after the reaction is finished, and washing with absolute ethyl alcohol.
Preferably, the heating temperature is 50-60 ℃;
and/or the esterification reaction time is 10-30 min;
and/or the time of the acetylation reaction is 1-2 h.
Preferably, the lamellar nano material is selected from one or more of montmorillonite, mica, kaolin, graphene and graphene oxide.
Preferably, the particle size of the lamellar nanomaterial is 100 to 500nm, more preferably 100 to 300nm.
Preferably, the dispersion modifier comprises one or more of a long-chain alkyl silane coupling agent, a phenyl silane coupling agent and an epoxy silane coupling agent.
The inorganic nano filler with small particle diameter and specific surface area has the tendency of agglomeration and precipitation in a system, and is difficult to disperse uniformly. Therefore, by adding a proper hydrophobic silane coupling agent, the filler can be fully dispersed on the premise of ensuring the hydrophobicity of the packaging material, and the water-moisture blocking capability of the packaging material is improved.
Preferably, the dispersion modifier contains 20 to 30wt% of trimethylmethoxysilane.
The ethylene-vinyl alcohol copolymer added in the application contains a certain polar hydroxyl group, which is not beneficial to improving the compatibility with polyethylene and affecting the exertion of barrier property; on the other hand, the permeability of moisture to the adhesive layer is increased. For this purpose, a small amount of trimethylmethoxysilane is incorporated, and its monomethoxy group can be hydrolyzed into a silylhydroxyl group in the raw material blending step before the casting extrusion, thereby being capable of reacting with the hydroxyl group of the ethylene-vinyl alcohol copolymer to reduce the polarity thereof. More importantly, compared with the silane coupling agent, the adhesive has small molecular weight and high permeability, can infiltrate into ethylene-vinyl alcohol copolymer molecules to fully consume hydroxyl, and promotes the improvement of the moisture barrier property of the adhesive layer. Of course, the steric hindrance and dispersion effect of trimethylmethoxysilane are poor, and the use amount of the silane coupling agent needs to be ensured to promote uniform distribution of the nanofiller.
In a second aspect, the present application provides a method for preparing a high barrier packaging material, which is characterized by the following steps: extruding to obtain a barrier layer through a casting process, obtaining a PE bonding layer through the casting process, and distributing the PE bonding layer on a substrate in parallel, then compositing the barrier layer and the substrate, and compositing a PE film on one side of the substrate far away from the barrier layer through the casting process to obtain a composite sheet; and (3) obtaining a PE bonding layer through a tape casting process, and spreading the PE bonding layer on the surface of the barrier layer of the first composite sheet material in parallel, and compositing the aluminum foil with the composite sheet material to obtain the high-barrier packaging material.
Preferably, in the casting process of the barrier layer, the temperature of the heating section is 180+/-5 ℃; the temperature of the plasticizing section is 220+/-5 ℃; the homogenization section temperature was 230.+ -. 5 ℃.
The packaging material sequentially comprises an aluminum foil, a PE bonding layer, a barrier layer, a PE bonding layer, a PE woven cloth and a PE film from outside to inside, wherein the PE woven cloth and the PE film are the same in material, the aluminum foil layer plays a role in reflection and barrier, and the PE film plays a role in sealing.
In summary, the application has the following beneficial effects:
1. the polyethylene and ethylene-vinyl alcohol copolymer are used as base materials, the lamellar nano material, the spherical alumina particles and the acetylated chitosan nano fibers are used as fillers, and the blocking capacity of the adhesive layer and the packaging material to oxygen and moisture can be improved on the premise of guaranteeing the tensile property and tensile strength of the adhesive layer.
2. The silane coupling agent and the trimethylmethoxysilane are used as the dispersion modifier, so that the water blocking capability of the adhesive layer can be improved while the filler dispersion is promoted.
Detailed Description
Examples of preparation of starting materials and/or intermediates
Preparation example 1, acetylated chitosan nanofiber, was prepared according to the following steps:
dispersing 1 kg of chitosan nanofiber (average length of 30 nm) in 5 kg of anhydrous acetic acid, dropwise adding 0.3 kg of concentrated sulfuric acid under stirring under the heating of a water bath at 50 ℃, and continuously stirring for 20min after the dropwise adding is finished to perform esterification reaction; then 0.5 kg of acetic anhydride is dripped, stirred for 1h, acetylation reaction is carried out, fiber is separated by filtration after the reaction is finished, and the fiber is obtained after 3 times of washing with absolute ethyl alcohol.
Preparation example 2, acetylated chitosan nanofibers, were prepared according to the following steps:
dispersing 1 kg of chitosan nanofiber (average length of 30 nm) in 5 kg of anhydrous acetic acid, dropwise adding 0.4 kg of concentrated sulfuric acid under stirring under the heating of a water bath at 50 ℃, and continuously stirring for 10min after the dropwise adding is finished to perform esterification reaction; then 0.6 kg of acetic anhydride is dripped, stirred for 1h, acetylation reaction is carried out, fiber is separated by filtration after the reaction is finished, and the fiber is obtained after 3 times of washing with absolute ethyl alcohol.
Preparation example 3 acetylated chitosan nanofibers were prepared according to the following steps:
dispersing 1 kg of chitosan nanofiber (average length of 30 nm) in 5 kg of anhydrous acetic acid, dropwise adding 0.2 kg of concentrated sulfuric acid under stirring under the heating of a water bath at 50 ℃, and continuously stirring for 20min after the dropwise adding is finished to perform esterification reaction; then 0.4 kg of acetic anhydride is dripped, stirred for 1h, acetylation reaction is carried out, fiber is separated by filtration after the reaction is finished, and the fiber is obtained after 3 times of washing with absolute ethyl alcohol.
Examples
Example 1, a high barrier packaging material, was prepared as follows:
step 1: 10 kg of polyethylene (LDPE, brand 2426H), 2 kg of ethylene-vinyl alcohol copolymer (the molar content of ethylene is 30%), 1.5 kg of nano montmorillonite (the granularity of D50 is 200 nm), 0.5 kg of spherical alumina particles (the granularity of D50 is 100 nm), 0.3 kg of dispersion modifier (comprising 0.06 kg of trimethylmethoxysilane and 0.14 kg of hexadecyltrimethoxysilane), 1 kg of acetylated chitosan nanofiber obtained in preparation example 1 are taken, added into a mixer, stirred and mixed, and after 1H, the uniformly mixed raw materials are added into a casting machine for plasticizing and melting. Wherein the temperature of the heating section is 180+/-5 ℃; the temperature of the plasticizing section is 215+/-5 ℃; the temperature of the homogenization section is 225+/-5 ℃; and casting to obtain the barrier layer after plasticizing.
LDPE (brand 1C7A, coating grade) is used as a raw material, the raw material is added into a casting machine, two layers of films are obtained through casting at 330+/-5 ℃, one layer is a PE film, the other layer is a PE bonding layer, the PE film and the PE bonding layer are respectively arranged on two sides of a PE woven cloth (substrate), then the obtained barrier layer is compounded on the PE bonding layer, and the composite sheet is obtained through cooling.
Step 2: LDPE (brand 1C 7A) is taken as a raw material, the raw material is added into a casting machine, another PE bonding layer is obtained through casting at 330+/-5 ℃, the PE bonding layer is spread on a barrier layer of a composite sheet, and aluminum foil is compositely fixed on the composite sheet through the PE bonding layer, so that the high-barrier packaging material is obtained.
In the high-barrier packaging material, the thickness of the aluminum foil is 6 mu m, the thickness of the PE bonding layer is 10 mu m, the thickness of the barrier layer is 20 mu m, the thickness of the substrate is 1mm, and the thickness of the PE film is 10 mu m.
Example 2, a high barrier packaging material, was prepared as follows:
step 1: 10 kg of polyethylene (LDPE, brand 2426H), 2 kg of ethylene-vinyl alcohol copolymer (the molar content of ethylene is 30%), 1 kg of nano mica powder (the granularity of D50 is 200 nm), 1 kg of spherical alumina particles (the granularity of D50 is 100 nm), 0.4 kg of dispersion modifier (comprising 0.12 kg of trimethylmethoxysilane and 0.28 kg of hexadecyltrimethoxysilane) and 1 kg of acetylated chitosan nanofiber obtained in preparation example 2 are taken, added into a mixer, stirred and mixed, and after 1H, the uniformly mixed raw materials are added into a casting machine for plasticizing and melting. Wherein the temperature of the heating section is 190+/-5 ℃; the temperature of the plasticizing section is 210+/-5 ℃; the temperature of the homogenization section is 225+/-5 ℃; and casting to obtain the barrier layer after plasticizing.
LDPE (brand 1C7A, coating grade) is used as a raw material, the raw material is added into a casting machine, two layers of films are obtained through casting at 330+/-5 ℃, one layer is a PE film, the other layer is a PE bonding layer, the PE film and the PE bonding layer are respectively arranged on two sides of a PE woven cloth (substrate), then the obtained barrier layer is compounded on the PE bonding layer, and the composite sheet is obtained through cooling.
Step 2: LDPE (brand 1C 7A) is taken as a raw material, the raw material is added into a casting machine, another PE bonding layer is obtained through casting at 330+/-5 ℃, the PE bonding layer is spread on a barrier layer of a composite sheet, and aluminum foil is compositely fixed on the composite sheet through the PE bonding layer, so that the high-barrier packaging material is obtained.
In the high-barrier packaging material, the thickness of the aluminum foil is 6 mu m, the thickness of the PE bonding layer is 10 mu m, the thickness of the barrier layer is 20 mu m, the thickness of the substrate is 1mm, and the thickness of the PE film is 10 mu m.
Example 3, a high barrier packaging material, differs from example 1 in the raw materials of the barrier layer, specifically as follows:
step 1: 10 kg of polyethylene (LDPE, brand 2426H), 3 kg of ethylene-vinyl alcohol copolymer (the molar content of ethylene is 30%), 1.5 kg of nano montmorillonite (the granularity of D50 is 200 nm), 0.5 kg of spherical alumina particles (the granularity of D50 is 100 nm), 0.2 kg of dispersion modifier (comprising 0.05 kg of trimethylmethoxysilane and 0.15 kg of hexadecyltrimethoxysilane) and 2 kg of acetylated chitosan nanofiber obtained in preparation example 3 are taken, added into a mixer, stirred and mixed, and after 1H, the uniformly mixed raw materials are added into a casting machine for plasticizing and melting. Wherein the temperature of the heating section is 180+/-5 ℃; the temperature of the plasticizing section is 215+/-5 ℃; the temperature of the homogenization section is 225+/-5 ℃; and casting to obtain the barrier layer after plasticizing.
Example 4, a high barrier packaging material, differs from example 1 in that in the dispersion modifier, an equivalent amount of long chain silane coupling agent is used instead of trimethylmethoxysilane.
Example 5, a high barrier packaging material, differs from example 1 in that in the dispersion modifier, an equivalent amount of trimethylmethoxysilane is used instead of the long chain silane coupling agent.
Comparative example
Comparative example 1, a high barrier packaging material, differs from example 1 in that an equivalent amount of unmodified chitosan nanofibers was used instead of acetylated chitosan nanofibers.
Comparative example 2, a high barrier packaging material, differs from example 1 in that an equivalent amount of nano montmorillonite was used instead of acetylated chitosan nanofibers.
Comparative example 3, a high barrier packaging material, differs from example 1 in that an equivalent amount of nano montmorillonite was used instead of spherical alumina particles.
Comparative example 4, a high barrier packaging material, differs from example 1 in that an equivalent amount of spherical alumina particles was used instead of nano montmorillonite.
Comparative example 5, a high barrier packaging material, differs from example 1 in that the raw material of the barrier layer was not added with platelet nanomaterial, spherical alumina particles, and acetylated chitosan nanofibers.
Performance test
1. Barrier properties: the high barrier packaging material was tested for its barrier ability to oxygen and water vapour at 23 ℃ and 50RH% according to the specifications in GB/T1038-2000.
2. Tensile property test: the barrier layer was tested for tensile strength (MPa) and elongation at break (%) as specified in GB/T13022-1991.
TABLE 1 Experimental results
Figure BDA0004078976110000061
Analysis of results:
(1) It can be seen from the combination of examples 1 to 5 and comparative examples 1 to 5 and table 1 that the present application can improve the barrier ability of the packaging material of the present application to oxygen and moisture by using the platelet nanomaterial, the spherical alumina particles, and the acetylated chitosan nanofibers, and effectively compensate for the loss of tensile properties by the acetylated chitosan nanofibers.
(2) As can be seen from the combination of examples 1 and examples 4 to 5 and table 1, the present application uses a complex of a hydrophobic coupling agent such as trimethylmethoxysilane and a long-chain alkyl coupling agent as a dispersion modifier, which can effectively reduce the oxygen and water vapor transmission rate of the packaging material. The reason for this may be that the long-chain alkyl coupling agent may be attached to the nano-sized surface, and the long-chain alkyl plays a role in steric hindrance, inhibits aggregation, makes the nano-filler uniformly dispersed, and fully exerts the barrier effect. The trimethyl methoxy silane has the advantages of steric hindrance, no obvious dispersion effect and good permeability, and the hydrolyzed silicon hydroxyl can react with the hydroxyl of the ethylene-vinyl alcohol copolymer, so that the polarity of the ethylene-vinyl alcohol copolymer is reduced, and the compatibility and the blocking effect on moisture are improved.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (8)

1. The high-barrier packaging material is characterized by comprising an aluminum foil, a PE bonding layer, a barrier layer, a PE bonding layer, a substrate and a PE film which are sequentially compounded, wherein the aluminum foil is compounded with woven cloth through the bonding layer, and the barrier layer comprises the following raw materials in parts by mass:
polyethylene: 100 parts;
ethylene-vinyl alcohol copolymer: 20-30 parts;
lamellar nanomaterial: 10-20 parts;
spherical alumina particles: 5-10 parts;
dispersion modifier: 1-5 parts;
acetylated chitosan nanofibers: 10-20 parts.
2. The high-barrier packaging material according to claim 1, wherein the acetylated chitosan nanofibers are formed from a blend of 10: (4-6): and (2-4) reacting chitosan nanofiber, acetic anhydride and concentrated sulfuric acid.
3. The high-barrier packaging material according to claim 2, wherein the preparation method of the acetylated chitosan nanofiber comprises the following steps: dispersing chitosan nano fibers in anhydrous acetic acid, and dropwise adding concentrated sulfuric acid under the conditions of heating and stirring to perform esterification reaction; then dripping acetic anhydride for acetylation reaction, filtering and separating out fiber after the reaction is finished, and washing with absolute ethyl alcohol.
4. A high barrier packaging material according to claim 3, wherein the heating temperature is 50-60 ℃;
and/or the esterification reaction time is 10-30 min;
and/or the time of the acetylation reaction is 1-2 h.
5. The high-barrier packaging material according to claim 1, wherein the lamellar nano material is one or more selected from montmorillonite, mica, kaolin, graphene and graphene oxide.
6. The high-barrier packaging material according to claim 1, wherein the dispersion modifier comprises one or more of a long-chain alkyl silane coupling agent, a phenyl silane coupling agent and an epoxy silane coupling agent.
7. The high barrier packaging material of claim 6, wherein the dispersion modifier comprises 20 to 30wt% of trimethylmethoxysilane.
8. The method of producing a high barrier packaging material according to any one of claims 1 to 7, characterized by the steps of:
extruding to obtain a barrier layer through a casting process, obtaining a PE bonding layer through the casting process, and distributing the PE bonding layer on a substrate in parallel, then compositing the barrier layer and the substrate, and compositing a PE film on one side of the substrate far away from the barrier layer through the casting process to obtain a composite sheet;
and (3) obtaining a PE bonding layer through a tape casting process, and spreading the PE bonding layer on the surface of the barrier layer of the first composite sheet material in parallel, and compositing the aluminum foil with the composite sheet material to obtain the high-barrier packaging material.
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