CN115366513A - Transparent high-barrier composite material and preparation method thereof - Google Patents

Transparent high-barrier composite material and preparation method thereof Download PDF

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Publication number
CN115366513A
CN115366513A CN202210954989.4A CN202210954989A CN115366513A CN 115366513 A CN115366513 A CN 115366513A CN 202210954989 A CN202210954989 A CN 202210954989A CN 115366513 A CN115366513 A CN 115366513A
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China
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layer
composite material
barrier
transparent high
antibacterial
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CN115366513B (en
Inventor
游国强
刘晓明
施遥
施虎林
金潮
蘧艳峰
吴尧
赵怀璞
郝杰
刘凯
马跃峰
郑建国
路文芳
杜旭红
路晶
赵凯杰
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China Institute for Radiation Protection
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China Institute for Radiation Protection
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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Abstract

The invention discloses a transparent high-barrier composite material and a preparation method thereof, wherein the composite material comprises a transparent protective layer, a barrier layer and an antibacterial layer, wherein the protective layer is positioned outside the barrier layer and plays a role in protecting the barrier layer, so that the weather resistance and the chemical resistance of the composite material are improved, and the good moisture absorption resistance, corrosion resistance and the like of the composite material are effectively maintained in the climates of cold, high temperature, high humidity, high salt fog, sea and the like, and the environments of high humidity and high salt concentration; the barrier layer improves the performance of the composite material for blocking water vapor and oxygen, improves the moisture absorption resistance, oxidation resistance and sealing performance of the composite material package, and prolongs the environmental state in the package to be unchanged; the antibacterial layer improves the antibacterial performance of the composite material, reduces the propagation of bacteria in the composite material package, and ensures the performance of the composite material package under extreme conditions; the preparation method of the transparent high-barrier composite material provided by the invention is simple and convenient.

Description

Transparent high-barrier composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of packaging materials, and particularly relates to a transparent high-barrier composite material and a preparation method thereof.
Background
Packaging is an organic component of weaponry systems. The container, the materials and the auxiliary objects are generally named according to a certain technical method for protecting weapons and equipment in a flow process, and facilitating storage, transportation and supply guarantee. The packaging is one of important technical means for realizing the protection of the weaponry, and directly influences the reliability, safety and guarantee capability of the weaponry storage.
With the wide application of new technologies and materials in weaponry, the performance of equipment systems is improved, and the demand for environmental protection is also increasing. Higher requirements are made on modern military packaging.
Under the conditions of severe environment or difficult storage, particularly severe environments such as northern cold, southern high-temperature high-humidity, coastal high-salt fog, offshore extreme weather and the like of the frontier defense line in China, and the phenomena of functional failure, moisture rusting or mold corrosion of a plurality of military products such as ammunition and electronic instruments are easily caused by moisture absorption. It is required that military packaging systems should have good moisture sealing properties to provide a dry, sealed interior environment for weapons while scientifically packaging and storing vehicle equipment that is temporarily or permanently unused, thereby extending equipment life, reducing maintenance costs, saving equipment investment, and ensuring that equipment is ready for use at any time.
In the prior art, polyvinyl chloride is used as a main component of a packaging material, but the polyvinyl chloride material has poor heat resistance and aging resistance, and is easy to deform and age quickly in a high-temperature environment. The addition of lignin to polyvinyl chloride improves the anti-aging performance and strength of the polyvinyl chloride material. But it has no antibacterial property and high water vapor transmission rate.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a transparent high-barrier composite material with antibacterial property and low water vapor transmission rate and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: a transparent high-barrier composite material comprises a transparent protective layer, a barrier layer and an antibacterial layer which are sequentially arranged from top to bottom; the protective layer is made of chlorinated polyethylene, polyvinyl chloride and acrylic acid impact modifier materials; the barrier layer is made of polyvinylidene chloride or polytetrafluoroethylene or polypropylene material; the antibacterial layer is composed of chlorinated polyethylene, polyvinyl chloride, acrylic acid impact modifier and nano zinc oxide material.
Furthermore, the composite material also comprises a transition layer, wherein the transition layer is composed of ethyl acetate, vinyl acetate-ethylene copolymer and ethylene-vinyl alcohol copolymer.
The invention also provides a preparation method of the transparent high-barrier composite material, which comprises the following steps: the method comprises the following steps:
(1) Respectively granulating the composition materials of the protective layer, the barrier layer and the antibacterial layer by using granulation equipment;
(2) And co-extruding the granulated protective layer, the barrier layer and the antibacterial layer material to form the transparent high-barrier composite material.
Further, in the step (1), a granulation device is used for granulating the transition layer material; in the step (2), the granulated transition layer, the protective layer, the barrier layer and the antibacterial layer material are co-extruded to form the transparent high-barrier composite material.
The technical scheme provided by the invention has the beneficial effects that the transparent high-barrier composite material comprises a transparent protective layer, a barrier layer and an antibacterial layer, wherein the protective layer is made of chlorinated polyethylene, polyvinyl chloride and acrylic acid impact modifier; the barrier layer is made of polyvinylidene chloride or polytetrafluoroethylene and polypropylene materials; the protective layer is positioned outside the barrier layer, plays a role in protecting the barrier layer, improves the weather resistance and chemical resistance of the composite material, and effectively maintains good moisture absorption resistance, corrosion resistance and the like of the composite material in climates such as cold, high temperature and humidity, high salt fog, sea and the like, and environments with high humidity and high salt concentration; the barrier layer improves the performance of the composite material for blocking water vapor and oxygen, improves the moisture absorption resistance, oxidation resistance and sealing performance of the composite material package, and prolongs the environment state in the package; the antibacterial layer consists of chlorinated polyethylene, polyvinyl chloride, acrylic acid impact modifier and nano zinc oxide material; the antibacterial layer improves the antibacterial performance of the composite material, reduces the propagation of bacteria in the composite material package, and ensures the performance of the composite material package under extreme conditions. The preparation method of the transparent high-barrier composite material provided by the invention is simple and convenient.
Drawings
Fig. 1 is a schematic structural view of a transparent high-barrier composite material according to an embodiment of the invention.
Wherein, the protective layer 1, the barrier layer 2 and the antibacterial layer 3.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example one
Referring to the attached figure 1, the transparent high-barrier composite material comprises a transparent protective layer 1, a barrier layer 2 and an antibacterial layer 3 which are sequentially arranged from top to bottom; the protective layer 1 is made of chlorinated polyethylene, polyvinyl chloride and acrylic acid impact modifier; the barrier layer 2 is made of polyvinylidene chloride or polytetrafluoroethylene or polypropylene material; the antibacterial layer 3 is composed of chlorinated polyethylene, polyvinyl chloride, acrylic acid impact modifier and nano zinc oxide material.
Preferably, the protective layer 1 comprises, by mass, 2 to 70% of chlorinated polyethylene, 25 to 97% of polyvinyl chloride and 1 to 5% of acrylic acid impact modifier, the barrier layer 2 comprises, by mass, 100% of polyvinylidene chloride or 1 to 97% of polytetrafluoroethylene and 3 to 99% of polypropylene, and the antibacterial layer 3 comprises, by mass, 2 to 85% of chlorinated polyethylene, 3 to 85% of polyvinyl chloride, 1 to 5% of acrylic acid impact modifier and 0 to 10% of nano zinc oxide.
Preferably, the barrier layer 2 is provided with 2 layers.
Preferably, a transition layer is arranged among the protective layer 1, the barrier layer 2 and the antibacterial layer 3, and the transition layer is arranged between the adjacent barrier layers 2.
Preferably, the transition layer comprises 75-85% of vinyl acetate-ethylene copolymer, 5-15% of ethyl acetate and 10-20% of ethylene-vinyl alcohol copolymer by mass percentage.
The performance index detection data of the transparent high-barrier composite material disclosed by the embodiment of the invention are shown in table 1.
Table 1 performance index of transparent high-barrier composite material of the embodiment of the present invention
Figure BDA0003790969530000041
As can be seen from Table 1, the transparent high-barrier composite material disclosed by the embodiment of the invention has the advantages of good performance indexes, thin total thickness, good acid and alkali resistance, small water vapor and oxygen transmission rate and effective antibiosis; the packaging material used as a military material can have good moisture absorption resistance, corrosion resistance, water vapor and oxygen resistance and the like in the environments of low temperature, high humidity, high salt mist, high humidity, high salt concentration and the like, and effectively maintains the internal environment state of the composite material packaging.
The invention also provides a preparation method of the transparent high-barrier composite material, which comprises the following steps: the method comprises the following steps:
(1) Respectively granulating the above-mentioned components of protective layer 1, barrier layer 2 and antibacterial layer 3 by using granulating equipment;
(2) And co-extruding the granulated materials of the protective layer 1, the barrier layer 2 and the antibacterial layer 3 to form the transparent high-barrier composite material.
Preferably, in the step (1), the transition layer composition material is granulated by using a granulating device; in the step (2), the granulated transition layer, the protective layer 1, the barrier layer 2 and the antibacterial layer 3 are co-extruded to form the transparent high-barrier composite material.
Example two
The embodiment of the invention provides a transparent high-barrier composite material, which comprises a transparent protective layer 1, a barrier layer 2 and an antibacterial layer 3 which are sequentially arranged from top to bottom; the protective layer 1 comprises 35% of chlorinated polyethylene, 60% of polyvinyl chloride and 5% of acrylic acid impact modifier by mass percentage; the component content of the barrier layer 2 is calculated by mass percent and consists of 100 percent of polyvinylidene chloride; the antibacterial layer 3 comprises 32 mass percent of chlorinated polyethylene, 61 mass percent of polyvinyl chloride, 4 mass percent of acrylic acid impact modifier and 3 mass percent of nano zinc oxide.
Preferably, the composite material further comprises a transition layer, and the composition content of the transition layer is calculated by mass percent and consists of 82% of vinyl acetate-ethylene copolymer, 6% of ethyl acetate and 12% of ethylene-vinyl alcohol copolymer.
The performance index detection data of the transparent high-barrier composite material of the embodiment of the invention are shown in table 2.
Table 2 performance index of the transparent high-barrier composite material of the embodiment of the present invention
Figure BDA0003790969530000061
The rest is the same as the first embodiment.
EXAMPLE III
The embodiment of the invention provides a transparent high-barrier composite material, which comprises a transparent protective layer 1, a barrier layer 2 and an antibacterial layer 3 which are sequentially arranged from top to bottom; the protective layer 1 comprises 25 mass percent of chlorinated polyethylene, 70 mass percent of polyvinyl chloride and 5 mass percent of acrylic acid impact modifier; the component content of the barrier layer 2 is calculated by mass percent and consists of 50 percent of polytetrafluoroethylene and 50 percent of polypropylene; the antibacterial layer 3 comprises 61% of chlorinated polyethylene, 31% of polyvinyl chloride, 5% of acrylic acid impact modifier and 3% of nano zinc oxide by mass percentage.
Preferably, the composite material further comprises a transition layer, and the component content of the transition layer is calculated by mass percent and consists of 75% of vinyl acetate-ethylene copolymer, 13% of ethyl acetate and 12% of ethylene-vinyl alcohol copolymer.
The performance index detection data of the transparent high-barrier composite material of the embodiment of the invention are shown in table 3.
Table 3 performance index of the transparent high-barrier composite material of the embodiment of the present invention
Figure BDA0003790969530000071
The rest is the same as the first embodiment.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.

Claims (10)

1. A transparent high-barrier composite material is characterized in that: comprises a transparent protective layer (1), a barrier layer (2) and an antibacterial layer (3) which are arranged from top to bottom in sequence; the protective layer (1) is composed of chlorinated polyethylene, polyvinyl chloride and acrylic acid impact modifier materials; the barrier layer (2) is made of polyvinylidene chloride or polytetrafluoroethylene or polypropylene material; the antibacterial layer (3) is composed of chlorinated polyethylene, polyvinyl chloride, acrylic acid impact modifier and nano zinc oxide material.
2. The transparent high-barrier composite material as claimed in claim 1, wherein: the protective layer (1) comprises 2-70% of chlorinated polyethylene, 25-97% of polyvinyl chloride and 1-5% of acrylic acid impact modifier by mass percent; the component content of the barrier layer (2) is calculated by mass percent and consists of 100 percent of polyvinylidene chloride or 1 to 97 percent of polytetrafluoroethylene and 3 to 99 percent of polypropylene; the antibacterial layer (3) comprises, by mass, 2-85% of chlorinated polyethylene, 3-85% of polyvinyl chloride, 1-5% of acrylic acid impact modifier and 0-10% of nano zinc oxide.
3. The transparent high-barrier composite material as claimed in claim 1, wherein: the barrier layer (2) is provided with 2 layers; transition layers are arranged among the protective layer (1), the barrier layers (2) and the antibacterial layers (3), and the transition layers are arranged among the adjacent barrier layers (2).
4. A transparent high-barrier composite material according to claim 3, wherein: the transition layer comprises 75-85% of vinyl acetate-ethylene copolymer, 5-15% of ethyl acetate and 10-20% of ethylene-vinyl alcohol copolymer by mass percentage.
5. The transparent high-barrier composite material as claimed in claim 1, wherein: the protective layer (1) comprises 35% of chlorinated polyethylene, 60% of polyvinyl chloride and 5% of acrylic acid impact modifier by mass percentage; the component content of the barrier layer (2) is calculated by mass percent and consists of 100 percent of polyvinylidene chloride; the antibacterial layer (3) comprises, by mass, 32% of chlorinated polyethylene, 61% of polyvinyl chloride, 4% of acrylic acid impact modifier and 3% of nano zinc oxide.
6. A transparent high-barrier composite according to claim 3, wherein: the transition layer comprises 82% of vinyl acetate-ethylene copolymer, 6% of ethyl acetate and 12% of ethylene-vinyl alcohol copolymer in percentage by mass.
7. The transparent high-barrier composite material as claimed in claim 1, wherein: the protective layer (1) comprises 25% of chlorinated polyethylene, 70% of polyvinyl chloride and 5% of acrylic acid impact modifier by mass percentage; the component content of the barrier layer (2) is calculated by mass percent and consists of 50 percent of polytetrafluoroethylene and 50 percent of polypropylene material; the antibacterial layer (3) comprises 61% of chlorinated polyethylene, 31% of polyvinyl chloride, 5% of acrylic acid impact modifier and 3% of nano zinc oxide by mass percentage.
8. A transparent high-barrier composite according to claim 3, wherein: the transition layer comprises 75% of vinyl acetate-ethylene copolymer, 13% of ethyl acetate and 12% of ethylene-vinyl alcohol copolymer in percentage by mass.
9. The method for preparing the transparent high-barrier composite material according to any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:
respectively granulating the materials of the protective layer (1), the barrier layer (2) and the antibacterial layer (3) by using granulation equipment;
(2) And sequentially co-extruding the materials of the protective layer (1), the barrier layer (2) and the antibacterial layer (3) after granulation into a transparent high-barrier composite material.
10. The method for preparing the transparent high-barrier composite material as claimed in claim 9, wherein the method comprises the following steps: in the step (1), the transition layer material is granulated; in the step (2), the granulated transition layer, the protective layer (1), the barrier layer (2) and the antibacterial layer (3) are sequentially co-extruded into the transparent high-barrier composite material.
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